Strong hydrogen bonding in organic synthesis

The preparation of phenacyl and para-phenylphenacyl esters, the reactions of carboxylic acids, phenols, 2-nitropropane and alcohols with alkyl halides in the presence of fluoride anion are described. The reactions are thought to be accelerated by the formation of hydrogen bonds between the fluoride anion and the organic electron acceptor. The fluoride ,carboxylic acids, fluoride-phenols and fluoride-2-nitropropane are better reaction systems than the fluoride-alcohol. The source of the fluoride anion and the choice of solvents are also discussed.

The generation effect and word learning: a test of the effect of the language experience approach versus the text approach in the acquisition of new reading vocabulary

A class of twenty-two grade one children was tested to determine their reading levels using the Stanford Diagnostic Reading Achievement Test. Based on these results and teacher input the students were paired according to reading ability. The students ages ranged from six years four months to seven years four months at the commencement of the study. Eleven children were assigned to the language experience group and their partners became the text group. Each member of the language experience group generated a list of eight to be learned words. The treatment consisted of exposing the student to a given word three times per session for ten sessions, over a period of five days. The dependent variables consisted of word identification speed, word identification accuracy, and word recognition accuracy. Each member of the text group followed the same procedure using his/her partner's list of words. Upon completion of this training, the entire process was repeated with members of the text group from the first part becoming members of the language experience group and vice versa. The results suggest that generally speaking language experience words are identified faster than text words but that there is no difference in the rate at which these words are learned. Language experience words may be identified faster because the auditory-semantic information is more readily available in them than in text words. The rate of learning in both types of words, however, may be dictated by the orthography of the to be learned word.

The importance of hydrogen bonding in the alkylation of phenols

Hydrogen bond assisted alkylation of phenols is compared with the classical base assisted reactions. The influence of solvents on the fluoride assisted reactions is discussed,· with emphasis on the localization of hydrogen bond charge density. Polar aprotic solvents such as DMF favour a-alkylation, and nonpolar aprotic solvents such as toluene favourC-alkylation of phenol. For more reactive and soluble fluorides, such as tetrabu~ylammoniumfluoride, the polar aprotic solvent favours a-alkylation and nonpolar aprotic solvent favours fluorination. Freeze-dried potassium fluoride is a better catalytic agent in hydrogen bond assisted alkylation reactions of phenol than the oven-dried fluoride. The presence of water in the alkylation reactions reduces the expected yield drastically. The tolerance of the reaction to water has also been studied. The use ofa phase transfer catalyst such as tetrabutylammonium bromide in the alkylation reactions of phenol in the presence of potassium fluoride is very effective under anhydrous conditions. Sterically hindered phenols such as 2,6-ditertiarybutyl-4-methyl phenol could not be alkylated even by using the more reactive fluorides, such as tetrabutylammonium fluoride in either polar or nonpolar aprotic solvents. Attempts were also made to alkylate phenols in the presence of triphenylphosphine oxide.

Hydrogen sulphide as inhibitor and substrates for the cytochrome c-cytochrome c oxidase system /

It has previously been recognized that the major biochemical toxicity induced by sulphide is due to an inhibition of cytochrome ~ oxidase. Inhibition of this enzyme occurs at 30°C and pH 7.4 with a Ki of approximately 0.2 ~M, and a kon of 104 M-1 s-l, under catalytic conditions. However, the equimo1ar mixture of sulphide and the enzyme shows identical catalytic behaviour to that of the native enzyme. This cannot readily be attributed to rapid dissociation of sulphide, as both spectroscopic and plot analysis indicate the koff value is low. The addition of stoichiometric sulphide to the resting oxidized enzyme gives rise to the appearance of a low-spin ferric-type spectrum not identical with that seen on the addition of excess sulphide to the enzyme aerobically. Sulphide added to the enzyme anaerobically gives rise to another low-spin, probably largely ferric, form which upon admission of oxygen is then converted into a 607 nm species closely resembling Compound C. The 607 nm form is probably the precursor of oxyferricytochrome aa3. The addition of successive a1iquots of Na2S solution to the enzyme induces initial uptake of approximately 3 moles of oxygen per mole of the enzyme. Thus, it is concluded that: 1. the initial product of sulphide-cytochrome c oxidase interaction is not an inhibited form of the enzyme, but the low-spin (oxyferri) ~3+~+ species; 2. a subsequent step in which sulphide reduces cytochrome ~ occurs; 3. the final inhibitory step, in which a further molecule of sulphide binds to the cytochrome ~ iron centre in the cytochrome ~2+~+ species, gives the cytochrome a2+~+-H2S form which is a half-reduced fully inhibited species;4. a 607 run form of the enzyme is produced which may be converted into a catalytically active low-spin (oxyferri) state; and therefore 5. liganded sulphide may be able to reduce the cytochrome 33 -Cu centre without securing the prior reduction of the cytochrome a_ haem group or the Cud centre associated with it.

Automatic Structure Generation using Genetic Programming and Fractal Geometry

Three dimensional model design is a well-known and studied field, with numerous real-world applications. However, the manual construction of these models can often be time-consuming to the average user, despite the advantages o ffered through computational advances. This thesis presents an approach to the design of 3D structures using evolutionary computation and L-systems, which involves the automated production of such designs using a strict set of fitness functions. These functions focus on the geometric properties of the models produced, as well as their quantifiable aesthetic value - a topic which has not been widely investigated with respect to 3D models. New extensions to existing aesthetic measures are discussed and implemented in the presented system in order to produce designs which are visually pleasing. The system itself facilitates the construction of models requiring minimal user initialization and no user-based feedback throughout the evolutionary cycle. The genetic programming evolved models are shown to satisfy multiple criteria, conveying a relationship between their assigned aesthetic value and their perceived aesthetic value. Exploration into the applicability and e ffectiveness of a multi-objective approach to the problem is also presented, with a focus on both performance and visual results. Although subjective, these results o er insight into future applications and study in the fi eld of computational aesthetics and automated structure design.

Locating home : the diverse experiences of recent newcomer youth and first generation youth within Ontario's education system

This study has found that youth who or whose parents had left their home country for fear-based reasons were less involved within their school and wider community than youth who left or whose parents left for reasons concerning their social mobility. Many existing studies focus on the challenges newcomer youth experience within the education system (see Anisef, Brown, Phythian, & Sweet, 2010), however through the use of qualitative methodologies this study expanded on the current literature by further examining why it is some youth are successful in overcoming such challenges, while others are not. This study supported what has been demonstrated in the literature regarding challenges faced by newcomer youth and resources to address such challenges. Despite challenges experienced within the education system, youth planned to complete secondary school and attend a postsecondary institution. However, not all youth anticipated remaining in Canada upon completion of their education, with youth or youth whose parents left their home country for fear-based reasons frequently discussing the possibility of returning to their or their parents' home country. Thus, perhaps these youth were less involved within their school, as their goal was not necessarily to establish or maintain connections within their community as they may have viewed residing in Canada as temporary. This finding has important implications, as there are benefits to involvement in extracurricular activities, which may assist youth in overcoming challenges encountered within the education system. Therefore, it would seem that youth who had or whose parents had left their home country for reasons concerning their social mobility may have be at an advantage within the education system with respect to their involvement in school. Perhaps then this differential involvement may at least partially explain why it is some newcomer youth are able to overcome challenges they experience in the education system, while others are not. Both policy and theoretical implications are discussed.

Experiences with cultural capital in education : exploring the educational life stories of first-generation postsecondary students

This study used a life history research design to explore first-generation university students' educational life stories and experiences with cultural capital. The project sought to examine how 3 first-generation university students experience cultural capital that is privileged in Ontario's education system and how the interactions between capital acquired through experiences within the home and school and capital privileged by the education system affect these students' educational experiences and perceptions. Using Pierre Bourdieu's (1984; 1986) theory of cultural capital as a framework, 3 firstgeneration, first-year university students participated in two 1- to 2-hour interviews. A focus on each participant's experiences with culture, capital, and education revealed themes corresponding to navigating, utilizing, and confronting familial, institutional, economic, and embodied forms of cultural capital. The study highlights the importance of recognizing how cultural capital influences the education system and how firstgeneration students can recreate normative pathways and achieve academic success despite challenges posed by the cultural capital privileged within the education system. Given cultural capital's effect on academic success, understanding first-generation students' educational life stories sheds light on the complex challenges facing students who confront and deal with privileged culture in the education system.

Explorações educacionais (educational explorations) : schooling experiences of second-generation Portuguese Canadian students

This study explores the stories and experiences of second-generation Portuguese Canadian secondary school students in Southern Ontario, Canada. The purpose of this research was to understand the educational experiences of students, specifically the successes, challenges, and struggles that the participants faced within the education system. Questions were also asked about identity issues and how participants perceived their identities influencing their educational experiences. Six Portuguese Canadian students in grades 9 to 11 were interviewed twice. The interviews ranged from 45 minutes to 90 minutes in length. Data analysis of qualitative, open-ended interviews, research journals, field notes and curricular documents yielded understandings about the participants' experiences and challenges in the education system. Eight themes emerged from data that explored the realities of everyday life for second-generatiop Portuguese Canadian students. These themes include: influences of part-time work on schooling, parental involvement, the teacher is key, challenges and barriers, the importance of peers, Portuguese Canadian identity, lack of focus on identity in curricul:um content, and the dropout problem. Recommendations in this study include the need for more community-based programs to assist students. Furthermore, teachers are encouraged to utilize strategies and curriculum resources that engage learners and integrate their histories and identities. Educators are encouraged to question power dynamics both inside and outside the school system. There is also a need for further research with Portuguese Canadian students who are struggling in the education system as well as an examination of the number of hours that students work.

Creating a Generation of Upstanders: Curriculum Resource to Help Ontario Educators Build Safe Schools

This project focuses on the bullying found in the 21st century elementary classrooms, more specifically in grades 4-8. These grades were found to have high levels of bullying because of major shifts in a student’s life that may place a student of this age at risk for problems with their peer relationships (Totura et al., 2009). Supporting the findings in the literature review, this handbook was created for Ontario grade 4-8 classroom teachers. The resource educates teachers on current knowledge of classroom bullying, and provides them with information and resources to share with their students so that they can create a culture of upstanders. Upstanders are students who stand up for the victims of bullying, and have the self-esteem and strategies to stand up to classroom bullies. These upstanders, with the support of their classroom teachers and their peers, will be a force strong enough to build the government-mandated Safe School environment.

Creating a Generation of Upstanders: Curriculum Resource to Help Ontario Educators Build Safe Schools

This project focuses on the bullying found in the 21st century elementary classrooms, more specifically in grades 4-8. These grades were found to have high levels of bullying because of major shifts in a student’s life that may place a student of this age at risk for problems with their peer relationships (Totura et al., 2009). Supporting the findings in the literature review, this handbook was created for an Ontario grade 4-8 classroom teachers. The resource educates teachers on current knowledge of classroom bullying, and provides them with information and resources to share with their students so that they can create a culture of upstanders. Upstanders are students who stand up for the victims of bullying, and have the self-esteem and strategies to stand up to classroom bullies. These upstanders, with the support of their classroom teachers and their peers, will be a force strong enough to build the government-mandated Safe School environment.

Towards Equitable Access to Postsecondary Education: Learning From the Voices of First Generation Students

This qualitative, phenomenological study investigated first generation students’ perceptions of the challenges they experienced in the process of accessing higher education and the type of school-based support that was received. Particular emphasis was placed on the impact of parental education level on access to postsecondary education (PSE) and how differences in support at the primary and secondary levels of schooling influenced access. Purposeful, homogenous sampling was used to select 6 first generation students attending a postsecondary institution located in Ontario. Analysis of the data revealed that several interrelated factors impact first generation students’ access to postsecondary education. These include familial experiences and expectations, school streaming practices, secondary school teachers’ and guidance counselors’ representations of postsecondary education, and the nature of school-based support that participants received. The implications for theory, research, and practice are discussed and recommendations for enhancing school-based support to ensure equitable access to postsecondary education for first generation students are provided.

Educational Attainment of Second-Generation Immigrants in Belgium: an Estimation of the Assimilation Degree of Immigrants Based on Cross Section Analysis.

Rapport de recherche

Spectro-imagerie optique à faible flux et comparaison de la cinématique Ha et HI d'un échantillon de galaxies proches

Un nouveau contrôleur de EMCCD (Electron multiplying Charge Coupled Device) est présenté. Il permet de diminuer significativement le bruit qui domine lorsque la puce EMCCD est utilisé pour du comptage de photons: le bruit d'injection de charge. À l'aide de ce contrôleur, une caméra EMCCD scientifique a été construite, caractérisée en laboratoire et testée à l'observatoire du mont Mégantic. Cette nouvelle caméra permet, entre autres, de réaliser des observations de la cinématique des galaxies par spectroscopie de champ intégral par interférométrie de Fabry-Perot en lumière Ha beaucoup plus rapidement, ou de galaxies de plus faible luminosité, que les caméras à comptage de photon basées sur des tubes amplificateurs. Le temps d'intégration nécessaire à l'obtention d'un rapport signal sur bruit donné est environ 4 fois moindre qu'avec les anciennes caméras. Les applications d'un tel appareil d'imagerie sont nombreuses: photométrie rapide et faible flux, spectroscopie à haute résolution spectrale et temporelle, imagerie limitée par la diffraction à partir de télescopes terrestres (lucky imaging), etc. D'un point de vue technique, la caméra est dominée par le bruit de Poisson pour les flux lumineux supérieurs à 0.002 photon/pixel/image. D'un autre côté, la raie d'hydrogène neutre (HI) à 21 cm a souvent été utilisée pour étudier la cinématique des galaxies. L'hydrogène neutre a l'avantage de se retrouver en quantité détectable au-delà du disque optique des galaxies. Cependant, la résolution spatiale de ces observations est moindre que leurs équivalents réalisés en lumière visible. Lors de la comparaison des données HI, avec des données à plus haute résolution, certaines différences étaient simplement attribuées à la faible résolution des observations HI. Le projet THINGS (The HI Nearby Galaxy Survey a observé plusieurs galaxies de l'échantillon SINGS (Spitzer Infrared Nearby Galaxies Survey). Les données cinématiques du projet THIGNS seront comparées aux données cinématiques obtenues en lumière Ha, afin de déterminer si la seule différence de résolution spatiale peut expliquer les différences observées. Les résultats montrent que des différences intrinsèques aux traceurs utilisées (hydrogène neutre ou ionisé), sont responsables de dissemblances importantes. La compréhension de ces particularités est importante: la distribution de la matière sombre, dérivée de la rotation des galaxies, est un test de certains modèles cosmologiques.

Hydrogen peroxide enhances the expression and function of Giα proteins in aortic vascular smooth muscle cells from Sprague-Dawley rats : role of growth factor receptors transactivation

Nous avons récemment démontré que les espèces réactives oxygénées induisent une augmentation de l’expression des protéines Giα dans les cellules du muscle lisse vasculaire (CMLV) provenant d’aortes de rats spontanément hypertendus (SHR, de l’anglais spontaneously hypertensive rats). La présente étude a pour but d’étudier les effets du peroxyde d’hydrogène (H2O2), un oxydant qui induit le stress oxydatif, sur l’expression de Giα et sur l’activité de l’adénylate cyclase, et d’explorer les voies de signalisation sous-jacentes responsables de cette réponse. Nos résultats montrent que H2O2 induit une augmentation de l’expression des protéines Giα-2 et Giα-3 de manière dose- et temps-dépendante avec une augmentation maximale de 40-50% à 100 µM après 1 heure, sans affecter l’expression de Gsα. L’expression des protéines Giα a été maintenue au niveau normal en presence de AG 1478, AG1295, PD98059 et la wortmannine, des inhibiteurs d’EGF-R (de l’anglais epidermal growth factor receptor), PDGFR-β (de l’anglais platelet-derived growth factor receptor β), de la voie de signalisation ras-ERK1/2 (de l’anglais extracellular regulated kinase1/2), et de la voie de la PI3Kinase-AKT (de l’anglais phosphatidyl inositol-3 kinase), respectivement. En outre, le traitement des CMLV avec H2O2 a induit une augmentation du degré de phosphorylation d’EGF-R, PDGF-R, ERK1/2 et AKT; et cette expression a été maintenue au niveau témoin par leurs inhibiteurs respectifs. Les inhibiteurs d’EGF-R et PDGF-R ont aussi induit une diminution du degré de phosphorylation de ERK1/2, et AKT/PKB. En outre, la transfection des cellules avec le siRNA (de l’anglais, small interfering ribonucleic acid) de EGF-R et PDGFR-β a atténué la surexpression des protéines Giα-2 et Giα-3 induite par le traitement au H2O2. La surexpression des protéines Giα induite par H2O2 a été corrélée avec une augmentation de la fonction de la protéine Giα. L’inhibition de l’activité de l’adénylate cyclase par de faibles concentrations de GTPγS après stimulation par la forskoline a augmenté de 20% dans les cellules traitées au H2O2. En outre, le traitement des CMLV au H2O2 a aussi accru l’inhibition de l’activité de l’adénylate cyclase par les hormones inhibitrices telles que l’angiotensine II, oxotrémorine et C-ANP4-23. D’autre part, la stimulation de l’adénylate cyclase induite par GTPγS, glucagon, isoprotérénol, forskoline, et le fluorure de sodium (NaF) a été atténuée de façon significative dans les cellules traitées au H2O2. Ces résultats suggèrent que H2O2 induit la surexpression des protéines Giα-2 and Giα-3 via la transactivation des récepteurs des facteurs de croissance EGF-R, PDGFR-β et l’activation des voies de signalisation ras-ERK1/2 et PI3K-AKT Mot-cles: Protéines Giα, peroxyde d’hydrogène, stress oxydant, récepteurs des facteurs de croissance, MAP kinases, adénylate cyclase, hypertension