NCube/papyrus huggingface dataset:
Enantiopure 3-substituted piperidines via an
aziridinium ion ring expansion

This thesis describes the development of a novel methodology of irreversible ring expansion from N-alkyl-3,4-dehydroprolinols to N-alkyl-3-substituted tetrahydropyridines through a bicyclic aziridinium ion intermediate. This method allows a wide variety of substituents at the 3-position, and also permits substitution at the 2- and 6-positions of the tetrahydropyridine giving mono-, di- or tri-substituted piperidines with excellent diasterocontrol. Complete transfer of the stereogenic information of the 3,4- dehydroprolinol to the tetrahydropyridine product is demonstrated. Also, a methodology was developed to prepare the 3,4-dehydroprolinol starting materials in enantiopure form, with the possibility of substitution at the 2- and 5-positions with excellent diasterocontrol. The first chapter presents the literature background, including a brief summary of methodologies for the synthesis of 3-substituted piperidines, and an overview of aziridinium ion chemistry. Also presented is the original hypothesis of the project, and our reasoning for undertaking this project. The second chapter describes the synthesis of N-alkyl-3,4-dehydroprolinols used as precursors for the ring expansion to 3-substituted tetrahydropyridines, including two different synthetic routes. The first route route converts L-trans-4-hydroxyproline to enantioenriched N-benzyl-3,4-dehydroprolinol in 6 steps. The second synthetic route was developed using a variant of the Petasis-Mannich reaction and a ring closing metathesis,making the precursors more readily available and simple to synthesize. The third chapter presents the proof of concept of the viability of the project and optimization studies. Moreover, the transfer of stereogenic information to the resulting product is demonstrated. The fourth chapter demonstrates the broad scope of the ring expansion and mechanistic insight is given based on the relative configuration of the products. An expedient divergent enantioselective synthesis of a 2,3-disubstituted tetrahydropyridine is also shown, with both substituents being chosen from a common intermediate in 3 steps.

Keyphrases: Piperidine, Tetrahydropyridine, Aziridinium, Aziridinium, Enantioselective synthesis, Diastereoselective synthesis
Évidence génétique de populations sympatriques de la perchaude (Perca flavescens) dans le Lac Saint-Pierre

Yellow perch (Perca flavescens) is a commercially-exploited freshwater fish species in Lake Saint-Pierre (Quebec, Canada). Even if this fluvial lake is designated as a biosphere reserve by UNESCO, the yellow perch status is of concern. To ensure the persistence of species facing to anthropogenic pressures, understanding dynamics and mechanism that structure populations are of major importance. Because the habitat characteristics are spatially structured and this species is known to display natal site fidelity, a subdivision of the species in multiple populations and local adaptations may occur. It is possible to detect these processes according to genetic signal associated with individuals’ reproduction. However, low genetic differentiation is hypothesised due to the recent colonization of the system (< 8 K years). This study aims at determining if there are multiple populations of yellow perch in Lake Saint-Pierre. Simulations was first performed to confirm that population differentiation is better depicted by amplified fragment length polymorphism (AFLP) than microsatellite markers. In order to associate individuals to their site of birth, larvae captured after hatching were used. A survey of the variation throughout the entire genome was then performed by using the AFLP approach and variations at microsatellite loci were used to further investigate the organization of these populations. Three distinct AFLP analyses indicated a correlation between genetic composition of individuals and spawning sites, and thus confirmed the presence of multiple sympatric populations in Lake Saint-Pierre, resulting likely from natal site fidelity. At the opposite, the lack of genetic differentiation reported by microsatellites markers confirms the importance of the choice of genetic markers. While the genetic differentiation is very low, the management of this species should take into account the existence of distinct population structures in this system.

Keyphrases: AFLP, microsatellites, Perca flavescens, AFLP, microstellites, genetic differentiation, fishery management plan, natal site fidelity, Perca flavescens, Lake Saint-Pierre
Regards d’aînés sur le vieillissement : justice, autonomie et responsabilité partagée

Until now, the health of the elderly has been studied primarily in terms of loss of autonomy, health policy and the difficulties raised by the allocation of resources, and these problems were usually handled by technocrats, specialists and rarely by older people themselves. In addition, it pays little attention to the perceptions of seniors according to points of view's which can be theirs. The originality of this thesis comes precisely because it focuses on the experience of aging as experienced by older people and the representations they make with health services, experiences, expectations and needs, all considered from the perspective of ethical issues and respect for personal autonomy, justice and equity, shared responsibility. It comes out from thirty interviews with people aged between 70 and 91 years experience of aging is always unique, singular, although some categorizations and models can be built based on health status, ruptures and losses, links maintained or not. Preserve their autonomy appears as an important and sometimes central to the comments received, saying the efforts granted to this end. However, when weakened the autonomy needs, to still be able to live themselves and exerted in spite of the limitations and constraints related to age or illness, of an effective solidarity, assistance of close relatives and wider support. The division of responsibilities and tasks between relatives and social services is seen as unfair. Also one question, in conclusion of the thesis, the will of the State and his contribution in the implementation of the policy of home support and practical devices, and well founded in light of the heterogeneity aging.

Keyphrases: justice, elderly, solidarity, autonomy, aging, health care, gerontology, ethic, justice
La mise en nourrice en Nouvelle-France : l'île de Montréal, 1680-1768

The physicians and other Ancien-Régime writers who denounced the harmful effects of wetnursing assigned part of the blame for high rates of infant mortality to the practice. The habit of entrusting the nursing and care of one’s child to a woman other than its mother had taken hold among French aristocrats by the thirteenth century. Bourgeois and other city-dwellers had followed suit by the seventeenth century. Brought across the Atlantic by the colonists of Canada, wet-nursing left many traces in the colony’s parish, notarial and judicial records. Demographers and historians have investigated the phenomenon in studies on different social groups (nobility, « bourgeoisie ») or populations (Quebec City or French-Régime Canada as a whole). They were particularly interested in the infants and their families. This thesis studies wet-nursing in and around Montréal from the 1680s to the 1760s. It begins by following the trajectory of 436 nursed children, most of whom died in infancy : the socio-professional group of the parents (when known), demographic profile, place of residence of the wet-nurse to whom they were entrusted. It then examines 245 women who took care of these children : their migration patterns and the different socio-demographic parameters of their lives. Although they offer a Montréal perspective on wet-nursing, several of the observations correspond to (or at least do not contradict) the results of other studies. New findings include the eighteenth-century widening of the range of infants’ fathers’ professions, as well as the existence of more than one profile of wet-nurse, from the point of view of age (and capacity to nurse), marital status, and degree of vulnerability.

Keyphrases: Montréal, History, Childhood, Infant Mortality, Wet-Nursing, Feeding Techniques, Women, Motherhood, Family, New France, Montreal
L’opération 5000/15000 logements sociaux et communautaires : une réponse au besoin en logements des ménages immigrants récents à Montréal, le cas de Côte-des-Neiges

Immigration in big cities like Montreal is a phenomenon which is growing in recent years. However, if households recent immigrants are an important positive contribution in the population growth, social, cultural and economic development of our society, improving their socioeconomic situation and conditions of housing they occupy, do not seem to be the priority housing policies of the government. Despite abundance of statistical data on immigration, it turns out that we know little about the housing conditions of such households and Quality of public support for their social housing are intended.  Our research, by a quantitative method and analysis technique Statistics conducted empirical research on population Greater Montreal, especially that of Côte-des-Neiges, for analyze the socioeconomic situation of households and recent immigrants their housing conditions. This to know if households Recent immigrants have a lower socioeconomic level than the average of households in the city, to constitute the poorest households poor, and if their housing conditions are unfavorable report to those of average households in the city and so are among the most poorly housed.  In our search for a second time, by a graphical method and mapping technique, we want to illustrate and then understand the logic implementation of housing, developed by the operation 5000/15000 housing community. Understanding this logic in its decision considering the initial choice of accommodation of households recent immigrants and in its uniformity of distribution of its units on the agglomeration of Montreal.

Keyphrases: immigrants, households, social housing, geographical location
Programme d’intervention pour les parents d’enfants autistes âgés de 2 à 6 ans

Over the years, several programs of intervention were built, in order to meet the particular needs of autistic children. An important component of these interventions should be the parent-mediated treatment; this guidance made it possible for the parents to feel more qualified and the children were able to generalize their gains throughout their daily living.  The purpose of this program was to evaluate an intervention for the parents of autistic children. During the study the parents received knowledge of the characteristics of their child.  They took part in specific activities that taught them to be more responsive to the needs of their child. The quasi-experimental design with pre and a post test with a non-equivalent control group was used to evaluate the effects of this program.  The sample for this study consists of 14 families. They were distributed into groups according to their arrival in the program. The parents and the children of the experimental group took part in an individual weekly session during five weeks. The parents and the children, from the two groups showed a significant improvement or a tendency to improve at the time of the post test. This improvement was not significantly different between the two groups as there were several non-controlled variables that can explain these results. The results are promising enough to encourage the continuation of this study.

Keyphrases: Autism, Early intervention, Parent-mediated treatment
La dynamique de la déviance : comparaison entre les trajectoires de vie de délinquants et de joueurs excessifs

This thesis explores the trajectories of two types of deviance, that of excessive gamblers (N = 100) and of persistent offenders (N = 172). The questionnaire used in each case has an important component to collect information chronologically on different themes; the life history calendar method.  The interest of a calendar analysis is that it takes into account the specific changes in behaviour and evaluates the short-term effects during their deviant careers.  The demonstration is based on the three dimensions of the trajectories: the intensity of the commitment, the episodes of voluntary abstinence and relapse episodes.  The major result of my thesis demonstrates that the circumstances of life (dynamic factors) have a greater influence on the dimensions of the trajectories, whereas the individual characteristics (fixed or static factors) often have very little explanatory power.  A careful analysis of the indirect effects illustrates the relevance of maintaining an interest in these factors.  Indeed, the impact of dynamic characteristics is often conditional on certain static variables.  No study, either American or Canadian, has examined the dynamic trajectories of excessive gamblers.  The second chapter examines the monthly fluctuations of amounts spent on gambling and games of chance.  We attempted to understand what motivates gamblers to spend more certain months and less at others.  Particular attention is also devoted to the months when the players cease to gamble, and the factors that promote this provisional abstinence.    The third chapter focuses on the trajectories of persistent offenders. Here, the criminal performance (illegal monthly income), measure the intensity of the criminal commitment. In this chapter, we are interested in the conditions that favour both the success of criminal episodes and episodes of temporary desistance.  The “official” measures of recidivism (new conviction, new admission into therapy) present a problem when it comes to unrecorded events; the actual relapses outnumber the relapse known by the official authorities. The interest of chapter four is to focus on an auto-revealed analysis of relapse and of the “moment in time" when these relapses occur. The second objective of this study is to compare the relapse episodes between the two trajectories. The logic of this chapter follows that of the preceding ones, we are interested in the dynamics surrounding these episodes and we wish to see if it is similar in both deviant trajectories.

Keyphrases: Deviance, Jeu excessif, Gambling, Crime, Criminal performance, Abstinence, Temporary desistance, Relapses
Détection de points chauds de déforestation à Bornéo de 2000 à 2009 à partir d'images MODIS

Borneo’s forests are priceless. Beyond the richness and diversity of its fauna and flora, its natural habitats constitute efficient carbon reservoirs. Unfortunately, the vast forests of the island are rapidly being cut down, both by the forestry industry and the rapidly expanding oil palm industry. In this context, we’ve developed methods to detect deforestation and forest degradation in order to better understand and monitor the phenomena. In doing so, the peculiarities of Borneo, such as the persistent cloud cover, had to be accounted for. Nevertheless, we succeeded in producing a time series of the yearly forest degradation and deforestations hotspots for the year 2000 through the year 2009.

Keyphrases: MODIS, EVI, REDD-plus, PEST, Borneo, Oil palm, Change detection
Questionnaire d'attitudes et de préférences éducatives des intervenants (QAPÉI) :
structure factorielle et relations avec les traits de personnalité

Psychoeducation and several clinical psychology theoretical approaches suggest that the interventionist constitute a fundamental active ingredient of psychosocial interventions for individuals with adjustment problems.  Among the various characteristics of interventionists there are useful to consider, attitudes and preferences in interventions are important because they can be related to an adequate matching in a given intervention milieu, to professional self-efficacy and, ultimately, to the intervention efficacy.  However, there are very empirically-validated psychometric instrument to asses these important constructs.  The main aim of this study was to make a preliminary evaluation of the psychometric properties of the French-Canadian version of the Counselors’ AIttitudes and Preferences Questionnaire (“Questionnaire d’attitudes et de préférences éducatives des intervenants”, QAPÉI; Jesness & Wedge, 1983; Le Blanc, Trudeau-Le Blanc, & Lanctôt, 1999).  The first objective was to assess if the original theoretical structure could be reproduced empirically, or if an alternative factor structure was necessary.  The second objective was to assess if interventionists’ attitudes and preferences were related to their personality traits.  The sample that was used was composed of interventionists from Boscoville2000, a residential cognitive-behavioral intervention program for adolescents with serious adjustment problems.  Exploratory factor analyses demonstrated that the original theoretical structure was not reproduced empirically.  An alternative five-factor structure was recovered.  This alternative structure was more conceptually coherent and provided a better fit to the data.  The identified factors were labeled Affective distance, Therapeutic Avoidance, Exasperation, Permissiveness, and Coercion.  Correlational analyses demonstrated that attitudes and preferences scales were related in a conceptually coherent way to interventionists’ personality traits, which supported the criterion-related validity of the instrument new structure.

Keyphrases: Attitudes, Préférences éducatives, Intervenants, Attitudes, Counseling Preferences, Personality Traits, Youth Counselors
Aspects géométriques et intégrables des modèles de matrices aléatoires

This thesis deals with the geometric and integrable aspects associated with random matrix models. Its purpose is to provide various applications of random matrix theory, from algebraic geometry to partial differential equations of integrable systems. The variety of these applications shows why matrix models are important from a mathematical point of view.   First, the thesis will focus on the study of the merging of two intervals of the eigenvalues density near a singular point. Specifically, we will show why this special limit gives universal equations from the Painlevé II hierarchy of integrable systems theory. Then, following the approach of (bi) orthogonal polynomials introduced by Mehta to compute partition functions, we will find Riemann-Hilbert and isomonodromic problems connected to matrix models, making the link with the theory of Jimbo, Miwa and Ueno. In particular, we will describe how the hermitian two-matrix models provide a degenerate case of Jimbo-Miwa-Ueno's theory that we will generalize in this context. Furthermore, the loop equations method, with its central notions of spectral curve and topological expansion, will lead to the symplectic invariants of algebraic geometry recently proposed by Eynard and Orantin. This last point will be generalized to the case of non-hermitian matrix models (arbitrary beta) paving the way to ``quantum algebraic geometry'' and to the generalization of symplectic invariants to ``quantum curves''. Finally, this set up will be applied to combinatorics in the context of topological string theory, with the explicit computation of an hermitian random matrix model enumerating the Gromov-Witten invariants of a toric Calabi-Yau threefold.   Since the range of the applications encountered is large, we try to present every domain in a simple way and explain how random matrix models can bring new insights to those fields. The common element of the thesis being matrix models, each part has been written so that readers unfamiliar with the domains of application but familiar with matrix models should be able to understand it.

Keyphrases: algebraic geometry, loop equations, symplectic invariants, topological string theory, isomonodromy, polynomes orthogonaux, orthogonal polynomials
Développement de l’activité rythmique chez l’embryon du poisson-zébré

Neuronal circuits are capable of generating diverse forms of rhythmic activity. Mechanisms underlying rhythmogenesis can be separated into two main groups. First, pacemaker central pattern generators (CPGs) are composed of neurons that have intrinsic oscillatory properties, such as the lobster stomatogastric ganglion. Second, CPGs driven by network-based dynamics rely on synapse-mediated cell properties, such as locomotion in aquatic vertebrates. Despite an existing wealth of knowledge obtained through studying frog and lamprey swimming CPGs, the means by which a locomotor CPG develops remains elusive. Here, we propose to address this question using the zebrafish embryo, for its rapid development, optical transparency and stereotyped behaviour.  Motor activity in zebrafish embryos begins with spontaneous activity around 17 hours post-fertilization (hpf). Studies have shown that this activity is not sensitive to antagonists of chemical neurotransmission, and does not require the hindbrain. By 28 hpf, they become able to swim, and generate low-amplitude alternating contractions at a rate of 30 Hz. This study explores the developmental window between the onset of motility and the onset of a mature locomotor output, such as swimming, with the objective of uncovering key steps in motor network maturation. By measuring the grouping of contractions rather than overall frequency of spontaneous activity, we uncovered a novel form of spontaneous activity, starting around 22 hpf. This activity consists of two alternating contractions in rapid succession. In contrast to early spontaneous activity, this motor activity requires glutamatergic neurotransmission and input from the hindbrain, as previously shown for swimming at 28 hpf. This intermediate behavior may reveal an important step in the maturation of the motor network.

Keyphrases: rhythmic activity, motor network, developmental neurobiology
Genèse de l’immunopeptidome du CMH de classe I

Self/non-self discrimination is a fundamental requirement of life. Endogenous peptides presented by major histocompatibility complex class I (MHC I) molecules represent the essence of self for CD8 T lymphocytes. These MHC I peptides (MIPs) are collectively referred to as the immunopeptidome. Very little is known about the origin, composition and plasticity of the immunopeptidome. Here, we developed a novel high-throughput mass spectrometry approach that yields an accurate definition of the nature and relative abundance of peptides presented by MHC I molecules. Surprisingly, we found that the immunopeptidome, and therefore the nature of the immune self, is biased toward peptides derived from highly abundant transcripts and conceals a tissue-specific signature. Then, we showed that the immunopeptidome is plastic and moulded by cellular metabolic activity. In fact, we found that altering cellular metabolism via the inhibition of the mammalian target of rapamycin (mTOR) results in dynamic changes in the cell surface MIPs landscape. Importantly, we provide the first systems-level evidence that the immunopeptidome projects at the cell surface a faithful representation of biochemical networks and metabolic events regulated at multiple levels inside the cell. Our discoveries open up new perspectives in systems biology and immunology. Indeed, our work suggests that the composition of the immunopeptidome is modulated in space and time. Therefore, it is imperative to further develop and exploit systems-level quantitative methods that will enable modelling of the immunopeptidome’s plasticity. Simulating and predicting variations in the immunopeptidome in response to cell-intrinsic and -extrinsic factors could be relevant to numerous contexts, including the rational design of immunotherapeutic interventions.

Keyphrases: immunopeptidome, mTOR, major histocompatibility complex, immunopeptidome, mass spectrometry, plasticity