NCube/papyrus huggingface dataset:
Approche pour la synthèse diastéréosélective d’analogues a-nucléosidiques et synthèse de nouveaux analogues de nucléosides C2'-désoxy

Natural nucleotides are the constituent monomers of DNA and RNA, and are necessary for the proliferation of cancer cells and viruses. The use of nucleoside analogues as anti-cancer and/or antiviral agents quickly aroused great therapeutic interest. Several analogues containing an all-carbon quaternary center in the C3' position have been synthesized by the Guindon laboratory and have interesting biological activities. A new acyclic approach has been developed in order to gain efficient and selective access to a multitude of these novel targeted nucleoside analogues. This strategy is distinguished by the development of a new enantioselective Mukaiyama aldol reaction starting from a protected alpha-alkoxy aldehyde and a chiral complex. The stereoselective addition of the nucleobase on an acyclic dithioacetal precursor, followed by an intramolecular SN2-like cyclization, allows the direct synthesis of alpha-anomers in the (D) -1',2'-trans series bearing a fluorine atom at the C2' position and a quaternary center at C3'. The differentiation of the two primary alcohols throughout the synthetic routes is necessary to selectively functionalize the C3' or C5' position at the end of the synthesis to potentially confer enhanced biological properties on such analogues. The application of this strategy has also made it possible to easily and efficiently synthesize a new family of C2'-deoxy analogues bearing a C3' quaternary center. The differentiation of the C3' and C5' primary alcohols facilitates the separation of the glycosylation products through the selective deprotection of one of these two positions. It has been determined that when the glycosylation precursor contains an acetylglycine at the C3' position, a bêta-directing effect is induced. Finally, new C2'-deoxy analogues have been prepared and are currently being tested against a series of viruses and polymerase enzymes.

Keyphrases: Glycosylation, Virus, Mukaiyama aldol, Quaternary center, Enantioselectivity, C2'-deoxy analogues, Bêta-directing effect, Viruses
Transition metal-free desulfinative cross-coupling of 2-pyridyl sulfonates with organolithium reagents : mild access to 2-substituted pyridines

Biaryl compounds containing the pyridine moiety represent a ubiquitous structure in both organic and medicinal chemistry. Therefore, finding new and reliable approaches for their synthesis is still of interest. Traditionally, azine containing biaryls are efficiently synthesized via transition-metal catalyzed cross-coupling reactions. However, due to its π-deficient nature, pyridine cannot be easily functionalized at the C-2 position to serve as nucleophile partner. For examples, in the Suzuki-Miyaura cross-coupling reaction, 2-pyridyl boronates are well known for their instability. 2-Pyridyl organometallics undergo electrophilic aromatic substitution poorly. Thus, the synthesis of 2-substituted pyridines remains a challenging task. The first part of the thesis focuses on the recent methods to address the coupling issues of 2-pyridyl nucleophiles in cross-coupling reactions. Of note, the classical methods including Suzuki-Miyaura cross-coupling reactions, C-H activation of N-activated pyridinium species, and direct coupling reaction of pyridine are presented. Alternative approaches using the pyridine moiety as an electrophilic entity in the coupling with organometallic reagents are also discussed. In the second part of the thesis, a transition metal-free desulfinative cross-coupling reaction of 2-pyridyl sulfonates with organolithium reagents is reported. A variety of 2-substituted pyridines were successfully synthesized in good yields, by treatment of neopentyl 2-pyridyl sulfonates and phenyl 2-pyridyl sulfonate with aryl, alkyl, and heteroaryl-lithium reagents at low temperature. Mechanistic studies showed that the coupling reaction with lithium reagents undergoes an SNAr pathway. However, a ligand coupling process of a σ-sulfurane intermediate may be involved in the reaction with Grignard reagents to form the biaryl.

Keyphrases: Ester de 2-pyridine sulfonate, Lithiation, Direct arylation, 2-pyridyl sulfonate esters, Biaryl synthesis, 2-substituted pyridine, Transition metal-free reactions
Nouveaux tétraoxa[8]circulènes ayant une géométrie de double-bol : synthèse, cristallisation et interactions avec invités électropauvres

Aromaticity and antiaromaticity remain important topics of chemical research because these concepts explain the reactivity of various classes of molecules. For instance, certain polycyclic compounds with π-extended conjugation, such as tetraoxa[8]circulenes, contain both aromatic and antiaromatic rings, which affect their physicochemical properties. Oxacirculenes consist of a circular arrangement of four furan and four benzene rings positioned in an alternating fashion, thus creating a formally antiaromatic cyclooctatetraene (COT) core. Despite this, oxacirculenes exhibit great stability. They can serve as components in optoelectronic devices such as electroluminescent diodes, and their molecular organisation in the solid state can be controlled in ways that influence their properties.  The present memoir describes the synthesis of tetraoxa[8]circulenes by a very special acid-catalysed cyclocondensation reaction starting from suitable 1,4-quinones, thereby allowing the preparation of large conjugated molecules in a single step. The compounds prepared have an awkward molecular structure that inhibits efficient packing and creates voids in the crystal structure, allowing the inclusion of guests. In particular, the inclusion of C60, achieved by cocrystallization, appears to create charge-transfer interactions as indicated by uniformization of bond lengths in the COT core. Optical properties studied by UV-vis spectroscopy and fluorescence show that oxacirculenes are sensitive to their local chemical environment, suggesting that they can be used as chemical sensors for the rapid detection of guests.

Keyphrases: PAHs, C60, Aromaticity, π-extended conjugation, Cyclocondensation of 1,4-quinones, Host-guest chemistry, Cocrystallization, Chemical sensors
Enjeux de pouvoir chez le bombo Tamang au Népal

The purpose of this research project is to focus on the Bombo’s awakening, growing into, and mastering his/her powers as a shaman of the Tamang people of Nepal. This is about understanding how the Bombo, who may not have chosen his/her role, first undergoes the call to vocation, then gradually takes ownership of acquired capacities and powers, to eventually get back in control of his/her own life.  We first concentrate on the shamanic call in itself, also in connection with its symbolic significance to the future Bombo. Then, we seek understanding of how, by means of transmission from, and apprenticeship with a guru, the future Bombo grows into control of his/her powers (in this instance, a guru is a Bombo accepting to convey a teaching). Finally, we consider the position of the Bombo in the Tamang social fabric, to seek understanding of his/her power and prominence in the community, feeding back into further development of his/her shamanic self: adding incremental capabilities and enhancing the mastery of his/her shamanic power(s).  The deliberate option is to carry out the research project to this point based on existing – albeit aging – literature: a fruitful field research would have necessitated more time and resources than were available in the context of this work.

Keyphrases: Tamang, Transmission, Shamanism, Agency, Identity, Power
Une poéticisation du langage dans les performances musicales nord-occitanes : l'accessoire-bohème, le capital-intellectuel et le marqueur-local

Beginning in 2019 an ethnographic field in Auvergne (and peripheral regions of the Massif Central in Southern France), several current themes of Endangered Languages - theme increasingly central in contemporary studies of linguistic anthropology - will be presented and discussed. The Auvergnat language is a North-Occitan dialect located in a marginal area of the Occitan cultural area, as well as the centralized French space, which makes it in many ways the "patois of patois”. It is classified by UNESCO among the most endangered languages in Europe. Basing my research work on the question of linguistic usage, I discuss the registers, representations and socio-cultural formations made possible by activity that is both political and poetical. Intellectuals and academicians of normativity, folklorists of the romanticism of last speakers and, above all, natural speakers, the "great absentees of the discourse on language", meet in these linguistic and cultural settings. The fieldwork reported here focused on village festivals, Occitanist political and associative meetings, and urban anarchist or worker cafes in which the Auvergnat language is spoken. This to evoke the contribution of disruptive practices and concerns for linguistic revitalization to the romantic and political potential of Auvergnat Occitan. This study concentrates on the Panoccitanism represented by the performativity of militant and artistic linguistic usages: these manifestations of creation and hybridization which form a revitalized language, a new language, defying the strong monolinguism dominating France. This study has been supplemented by a comparison with the Occitan dialects of Piedmont (Italy), thus making it possible to highlight the influences of a linguistic policy on the use and representation of a language and a culture.

Keyphrases: Occitanism, North-occitan, Linguistic revitalization, Endangered languages, Ethnomusicology, Activism
The impact of mobility and climate on the cross-sectional geometry of long bones : comparing preindustrial Euro-Canadians and Inuit to other archaeological populations

Biomechanical analyses have been used to study the impact of mobility and climate on the skeletal morphology of past human populations through the measure of the cross-sectional geometry of long bones. Behavior and climate are one of the many non-genetic factors that can impact bone functional adaptation by influencing mechanical loads on the skeleton and triggering the bone modeling process. The present study focuses on the structural changes occurring at the macrolevel of long bones, more specifically robusticity and shape, by calculating mechanical properties at several cross-sectional locations. This project consists of creating a reference collection using four Holocene populations from northern Canada including Sadlermiut Inuit and three Euro-Canadian samples from Notre-Dame, Pointe-aux-Trembles and Sainte-Marie. The objective is to control for different environmental factors to better understand the impact of mobility and climate on human postcranial morphology. Cross-sectional properties were measured in the humerus, femur and tibia using a portable peripheral quantitative computed tomography (pQCT). These data were then input into a meta-analysis that included data, drawn from the scientific literature, from other archaeological populations with different modes of subsistence and inhabiting various climate types. The results showed that Sadlermiut Inuit had more robust upper and lower limbs than all three samples of Euro-Canadians who did not differ significantly from one another. The high measures of robusticity among Sadlermiut were attributed to the strenuous physical activity demanded by their hunting and gathering mode of subsistence in cold and harsh environmental conditions. Furthermore, the meta-analysis on mobility demonstrated that the type and intensity of habitual mechanical loading on the skeleton has a significant influence on the upper and lower limbs whereas the meta-analysis pertaining to climate only had a significant relationship with the humerus. Essentially, this project highlights the multifactorial nature of the bone modeling process and that the level of influence of behavioral versus climatic factors is not uniform throughout the skeleton.

Keyphrases: Climat, Mode de subsistance, Human postcranial morphology, Cross-sectional geometry, Robusticity, Mobility, Climate, Subsistence mode
Exploration de la diversité crânienne récente et passée en Afrique centrale : analyses via la morphométrie géométrique tridimensionnelle

The biological diversity of the African continent impels us to explore the multiple sources of variation that shape human morphology. Morphometry, a complementary tool to genetics, explores current and past diversity. Therefore, by exploring various factors (phylogeny, geography, climate, history) this research aims to re-examine the morphological variation in Central Africa, a key geographical region for understanding the history of the continent. Thus far, craniometric studies have been carried out with two-dimensional methods on complete crania, and rarely included fragmentary archaeological collections. The aim of this research is also to overcome this problem, by analyzing the whole cranium versus the temporal bone. The latter has the advantage of an exceptional state of preservation and provides information of phylogenetic nature.  Therefore, a sample of 147 crania from Central Africa was selected. Recent individuals (137 complete crania) originating from various localities spread over a geographical area of 760,000 km2. The archaeological sample (11 temporal bones) originates from two sites: Shum Laka, Cameroon (7,000 – 3,000 BP) (n=2); and Upemba Depression, R.D.C (1,3000 BP) (n=9). After creating a 3D models database using photogrammetry, 3D geometrics morphometrics was performed to analyze separately crania and temporal bones. Results demonstrate a weak influence of sexual dimorphism on morphology and raise four points: I) The analysis of current cranial morphology reflects various phylogenetic (ethnicity), environmental (geography, climate), and possibly histological (movement of populations) aspects. II) The morphology of the temporal bone also reflects a high inter-population variation. However, because distances between groups are relatively short, this could be explained by the fact that the temporal bone reflects mostly phylogeny. III) A continuity of some morphological traits of the temporal bone through time has been detected, particularly in the Iron Age group (Upemba Depression). IV) Finally, a possible anatomical adaptation to environmental pressures (diet, economy) was observed, especially in the shape of the mandibular fossa of the temporal bone, changing from a circular form during the LSA to an ellipsoid form in recent times.

Keyphrases: Variation, 3D geometric morphometrics, Central Africa, Phylogeny, Temporal bone, Cranium
Le cadrage des débats linguistiques dans la presse anglophone et francophone au Québec : un clivage médiatique? : analyse de la couverture du projet de loi 14

It is generally believed that media messages influence the perceptions of audiences. Thus, they contribute to identity formation and to social cohesion. However, research in Canada has often found discrepancies in coverage by Quebec and English-Canadian media. This media divide has been suspected of amplifying the differences between the two communities. Yet, research on the differences between the Francophone and the Anglophone press in Quebec is limited. This thesis poses the question whether a linguistic divide also exists in the Quebec media landscape. For this purpose, we identified the frames mobilized by French- and English-language newspapers. We understand frames as interpretative schemata proposed by the media to make sense of news events. To verify our hypothesis that frames differ in the English and French language media of Quebec, we analyzed the coverage of Bill 14 by ten newspapers during 50 weeks. Using a mixed method, which combined a computer-assisted and a qualitative analysis using Van Gorp’s (2005) frame matrix, we identified linguistic, social, political, pragmatic and sovereignist frames. Our results show that four of these frames were used by both French- and English-language newspapers and that the media partially took up discourses from the other language community. However, the two groups prefer different frames and articulate them differently. The rapprochement of Anglophone and Francophone media in Quebec is thus limited, among other things, by diverging historic experiences and activism by community newspapers.

Keyphrases: media, framing, media frames, linguistic question, two solitudes, linguistic divide, journalistic cultures, cluster analysis, minority context
Application des méthodes de partitionnement de données fonctionnelles aux trajectoires de voiture

The study of the clustering of functional data has made a lot of progress in the last couple of years. Multiple methods have been proposed and the respective analysis has shown their eÿciency with some benchmark studies. The objective of this Master’s thesis is to compare those clustering algorithms with datasets from traÿc at an intersection of Montreal. The idea behind this is that the manual classification of these data sets is time-consuming. We show that it is possible to obtain adequate clustering and prediction results with several algorithms. One of the methods that we discussed is distclust : a distance-based algorithm that uses a K-means approach. We will also use a Gaussian mixture density clustering method known as mclust. Although those two techniques are quite e˙ective, they are multi-purpose clustering methods, therefore not tailored to the functional case. With that in mind, we apply four functional clustering methods : fitfclust, funmbclust, funclust, and funHDDC. Our results show that there is no loss in the quality of the clustering between the afore-mentioned functional methods and the multi-purpose ones. We prefer to use the functional ones because they provide a detailed estimation of the functional structure of the trajectory curves. One notable detail is the impact of a dimension reduction done with multivari-ate functional principal components analysis. Furthermore, we can use objective selection criteria such as the AIC and the BIC, and avoid using cluster quality indices that use a pre-existing classification of the data.

Keyphrases: B-splines, Bayes, Functional data, Clustering, Principal component analysis, Probabilistic models, Trajectory curves
Tic-tac... Explorer les perceptions de femmes qui vivent un échec du déclenchement du
travail

Induction of labor is an obstetric procedure which consists of inducing labor so that women can experience a vaginal birth within 24 to 48 hours after the initiation of the procedure (Leduc et al., 2013). The induction of labor may not work resulting in the need for a caesarean delivery after lasting more than 24 hours. This qualitative study aimed to explore the experience of women who had experienced labor induction failure resulting in an unplanned caesarean section. This study was conducted with 6 women in the postpartum unit during their hospitalisation.  Data were collected from a socio-demographic questionnaire, the participants’ medical chart as well as a semi-structured interview. After participants’ consent, the semi-structured interviews were recorded, transcribed, then analysed using the Braun, Clarke, Hayfield and Terry (2019) thematic analysis approach. Five themes and 12 sub-themes emerged to better capture the experience of women experiencing labor induction failure resulting in a caesarean. Four themes: Expectation of Labor and Delivery: Managing Expectations, Antepartum and Intrapartum Support Received, Comprehensive Information Needed, and Feeling in Control of the Experience emerged as influencing the participant's satisfaction or dissatisfaction towards their Global Experience of a Failed Induction of Labor Resulting in a Ceserean Section. Nurses have a strategic role and are key support professionals in communicating information and supporting women during induction of labor, allowing them to better manage their expectations and have the desired level of control over their experience.

Keyphrases: delivery, obstetric, labor, obstetric, obstetric labor complications, labor, induced, cesarean section, qualitative research, nursing
Implication des proches dans les soins de fin de vie d’une personne âgée vivant en centre d’hébergement : une étude de cas sur les perceptions de proches et d’infirmières

In health care settings, it’s imperative that quality of all services is ensured, including end-of-life (EoL) care. A key role of nurses working in long-term care homes (LTCH) is to promote the involvement of relatives in EoL care to, among others, help relieve a possible suffering of relatives or older adults. Based on Andershed and Ternestedt’s (2001) theory, relatives’ involvement can be described in three categories: their knowledge (to know), their presence (to be) and their participation in tasks or care (to do). However, few studies address relatives’ involvement in LTCH in other aspects than decision-making and care planning. Considering this knowledge gap, we conducted a qualitative case study exploring relatives’ and nurses’ perceptions of relatives’ involvement in this context. Data was collected from a sample of 4 nurses and 3 relatives using individual semi-structured interviews, a reflexive journal and relevant documents from the LTCH. Applying thematic analysis, results showed the scope of relatives’ involvement during the EoL, how relatives wished to be involved, and facilitating strategies to involve relatives in care. These results can guide improvement in LTCH practices and raise awareness in health care professionals of the experience of relatives during the agony phase.

Keyphrases: participation, family, elderly, terminal care, palliative care, long-term care, nursing homes, geriatrics, nursing care, case study
Self-care experiences of Indonesian adults with chronic disease living in Montreal

Background: Self-care is an essential aspect of chronic disease management. This experience is shaped by culture and values, health knowledge/literacy, support from others and access to care. We aimed to explore the chronic illness self-care experiences and various influencing factors among Indonesian immigrants living in Montreal.  Methods:  We used a qualitative descriptive approach. Eight men and women, living with various chronic illnesses, participated. We conducted a thematic analysis. Results: Three broad themes were identified: 1) “What’s Helpful for Indonesian’ Self-care” captures the different sources of support and/or ways of being and doing that helped the participants manage and monitor their illness and feel well and healthy, both physically and emotionally; 2) “Self-care Challenges and Responses to Living with a Chronic Illness” highlights the key challenges that participants faced while living with a chronic illness and provides a description of how participants responded to living with an illness; 3) “Expectations regarding Self-care and Support” reveals some of the participants’ disappointments regarding their own self-care and/or support. Conclusion: Taken together the themes highlight several important points regarding the self-care experiences of Indonesian immigrants that should be considered during care. These include the importance of faith and religion for Indonesians in self-care; being helpful has an important place in self-care; self-care is a learning process; self-care; including family support, is experienced differently in Canada compared to being in Indonesia; social support may continue transnationally; and there is a need for health care professionals to provide more personalized care. Keywords: self-management, self-maintenance, self-monitoring, chronic illness, diabetes, hypertension, arthritis, chronic kidney disease, immigrants

Keyphrases: Self-management, Self-maintenance, Self-monitoring, Hypertension, Diabetes, Arthritis, Chronic Kidney Disease, Immigrants