Search results for: Clémence Hauduc

Authors: Guillaume Bélanger, Jean-Philippe Fontaine, Clémence Hauduc

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There is an undeniable thirst from organic chemists and from the pharmaceutical industry to access complex alkaloids with short syntheses. While medicinal chemists are interested in the fascinating wide range of biological properties of alkaloids, synthetic chemists are rather interested in finding new routes to access these challenging natural products of often low availability from nature. To synthesize complex polycyclic cores of natural products, reaction cascades or sequences performed one-pot offer a neat advantage over classical methods for their rapid increase in molecular complexity in a single operation. In counterpart, reaction cascades need to be run on substrates bearing all the required functional groups necessary for the key cyclizations. Chemoselectivity is thus a major issue associated with such a strategy, in addition to diastereocontrol and regiocontrol for the overall transformation. In the pursuit of synthetic efficiency, our research group developed an innovative one-pot transformation of linear substrates into bi- and tricyclic adducts applied to the construction of Aspidospermatan-type alkaloids. The latter is a rich class of indole alkaloids bearing a unique bridged azatricyclic core. Despite many efforts toward the synthesis of members of this family, efficient and versatile synthetic routes are still coveted. Indeed, very short, non-racemic approaches are rather scarce: for example, in the cases of aspidospermidine and aspidospermine, syntheses are all fifteen steps and over. We envisaged a unified approach to access several members of the Aspidospermatan alkaloids family. The key sequence features a highly chemoselective formamide activation that triggers a Vilsmeier-Haack cyclization, followed by an azomethine ylide generation and intramolecular cycloaddition. Despite the high density and variety of functional groups on the substrates (electron-rich and electron-poor alkenes, nitrile, amide, ester, enol ether), the sequence generated three new carbon-carbon bonds and three rings in a single operation with good yield and high chemoselectivity. A detailed study of amide, nucleophile, and dipolarophile variations to finally get to the successful combination required for the key transformation will be presented. To complete the indoline fragment of the natural products, we developed an original approach. Indeed, all reported routes to Aspidospermatan alkaloids introduce the indoline or indole early in the synthesis. In our work, the indoline needs to be installed on the azatricyclic core after the key cyclization sequence. As a result, typical Fischer indolization is not suited since this reaction is known to fail on such substrates. We thus envisaged a unique photocatalyzed decarboxylative radical cyclization. The development of this reaction as well as the scope and limitations of the methodology, will also be presented. The original Vilsmeier-Haack and azomethine ylide cyclization sequence as well as the new photocatalyzed decarboxylative radical cyclization will undoubtedly open access to new routes toward polycyclic indole alkaloids and derivatives of pharmaceutical interest in general.

Keywords: Aspidospermatan alkaloids, azomethine ylide cycloaddition, decarboxylative radical cyclization, indole and indoline synthesis, one-pot sequential cyclizations, photocatalysis, Vilsmeier-Haack Cyclization

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Authors: Jabulani Sibanda, Clemence Chikiwa

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This paper traces diverse language practices representative of equally diverse conceptions of language. To be dynamic with languaging practices, one needs to appreciate nuanced languaging practices, their challenges, prospects, and opportunities. The paper presents what we envision as three major conceptions of language that give impetus to diverse language practices. It examines theoretical models of the bilingual mental lexicon and how they inform language practices. The paper explores classroom languaging practices that have been promulgated and experimented with. The paper advocates the deployment of multisensory semiotic systems to complement linguistic classroom communication and the acknowledgement of learners’ linguistic and semiotic resources as valid in the learning enterprise. It recommends the enactment of specific clauses on language in education policies and curriculum documents that empower classroom interactants to exercise discretion in languaging practices.

Keywords: languaging, monolingual, multilingual, semiotic and linguistic repertoire

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Authors: Jabulani Sibanda, Clemence Chikiwa

Abstract:

This paper traces diverse language practices representative of equally diverse conceptions of language. To be dynamic with languaging practices, one needs to appreciate nuanced languaging practices, their challenges, prospects, and opportunities. The paper presents what we envision as three major conceptions of language that give impetus to diverse language practices. It examines theoretical models of the bilingual mental lexicon and how they inform language practices. The paper explores classroom languaging practices that have been promulgated and experimented with. The paper advocates the deployment of multisensory semiotic systems to complement linguistic classroom communication and the acknowledgement of learners’ linguistic and semiotic resources as valid in the learning enterprise. It recommends the enactment of specific clauses on language in education policies and curriculum documents that empower classroom interactants to exercise discretion in languaging practices.

Keywords: languaging, monolingual, multilingual, semiotic and linguistic repertoire

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Authors: Clemence Collon, Didier Poracchia

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The manipulation of sports competitions is a new type of sports integrity problem. While doping has become an organized, institutionalized struggle, the manipulation of sports competitions is gradually building up. This study aims to describe and understand how the soft Olympic and Paralympic law was gradually built. It also summarizes the legal tools for prevention, detection, and sanction developed by the international Olympic movement. Then, it analyzes the impact of this soft law on the law of the States, in particular in French law. This study is mainly based on an analysis of existing legal literature and non-binding law in the International Olympic and Paralympic movement and on the French National Olympic Committee. Interviews were carried out with experts from the Olympic movement or experts working on combating the manipulation of sports competitions; the answers are also used in this article. The International Olympic Committee has created a supranational legal base to fight against the manipulation of sports competitions. This legal basis must be respected by sports organizations. The Olympic Charter, the Olympic Code of Ethics, the Olympic Movement Code on the prevention of the manipulation of sports competitions, the rules of standards, the basic universal principles, the manuals, the declarations have been published in this perspective. This sports soft law has influences or repercussions in each state. Many states take this new form of integrity problem into account by creating state laws or measures in favor of the fight against sports manipulations. France has so far only a legal basis for manipulation related to betting on sports competitions through the infraction of sports corruption included in the penal code and also created a national platform with various actors to combat this cheating. This legal study highlights the progressive construction of the sports law rules of the Olympic movement in the fight against the manipulation of sports competitions linked to sports betting and their impact on the law of the states.

Keywords: integrity, law and ethics, manipulation of sports competitions, olympic, sports law

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Authors: Clémence Royer, Stéphane Mazouffre

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Nowadays, electric propulsion systems play a crucial role in space exploration missions due to their high specific impulse and long operational life. The Hall thrusters are one of the most mature EP technologies. It is a gridless ion thruster that has proved reliable and high-performance for decades in various space missions. Operation of HT relies on electron emissions through a cathode placed outside a hollow dielectric channel that includes an anode at the back. Negatively charged particles are trapped in a magnetic field and efficiently slow down. By collisions, the electron cloud ionizes xenon atoms. A large electric field is generated in the axial direction due to the low electron transverse mobility in the region of a strong magnetic field. Positive particles are pulled out of the chamber at high velocity and are neutralized directly at the exhaust area. This phenomenon leads to the acceleration of the spacecraft system at a high specific impulse. While HT’s architecture and operating principle are relatively simple, the physics behind thrust is complex and still partly unknown. Current and voltage oscillations, as well as electron properties, have been captured over a 30 mn time period after ignition. The observed low-frequency oscillations exhibited specific frequency ranges, amplitudes, and stability patterns. Correlations between the oscillations and plasma characteristics we analyzed. The impact of these instabilities on thruster performance, including thrust efficiency, has been evaluated as well. Moreover, strategies for mitigating and controlling these instabilities have been developed, such as filtering. In this contribution, in addition to presenting a summary of the results obtained in the transient regime, we will present and discuss recent advances in Hall thruster plasma discharge filtering and control.

Keywords: electric propulsion, Hall Thruster, plasma diagnostics, low-frequency oscillations

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Authors: Marine Reymond, Michael Descostes, Marie Muguet, Clemence Besancon, Martine Leermakers, Catherine Beaucaire, Sophie Billon, Patricia Patrier

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²²⁶Ra is one of the radionuclides resulting from the disintegration of ²³⁸U. Due to its half-life (1600 y) and its high specific activity (3.7 x 1010 Bq/g), ²²⁶Ra is found at the ultra-trace level in the natural environment (usually below 1 Bq/L, i.e. 10-13 mol/L). Because of its decay in ²²²Rn, a radioactive gas with a shorter half-life (3.8 days) which is difficult to control and dangerous for humans when inhaled, ²²⁶Ra is subject to a dedicated monitoring in surface waters especially in the context of uranium mining. In natural waters, radionuclides occur in dissolved, colloidal or particular forms. Due to the size of colloids, generally ranging between 1 nm and 1 µm and their high specific surface areas, the colloidal fraction could be involved in the transport of trace elements, including radionuclides in the environment. The colloidal fraction is not always easy to determine and few existing studies focus on ²²⁶Ra. In the present study, a complete multidisciplinary approach is proposed to assess the colloidal transport of ²²⁶Ra. It includes water sampling by conventional filtration (0.2µm) and the innovative Diffusive Gradient in Thin Films technique to measure the dissolved fraction (<10nm), from which the colloidal fraction could be estimated. Suspended matter in these waters were also sampled and characterized mineralogically by X-Ray Diffraction, infrared spectroscopy and scanning electron microscopy. All of these data, which were acquired on a rehabilitated former uranium mine, allowed to build a geochemical model using the geochemical calculation code PhreeqC to describe, as accurately as possible, the colloidal transport of ²²⁶Ra. Colloidal transport of ²²⁶Ra was found, for some of the sampling points, to account for up to 95% of the total ²²⁶Ra measured in water. Mineralogical characterization and associated geochemical modelling highlight the role of barite, a barium sulfate mineral well known to trap ²²⁶Ra into its structure. Barite was shown to be responsible for the colloidal ²²⁶Ra fraction despite the presence of kaolinite and ferrihydrite, which are also known to retain ²²⁶Ra by sorption.

Keywords: colloids, mining context, radium, transport

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Authors: Mohamed Dakki, Genevieve Robin, Marie Suet, Abdeljebbar Qninba, Mohamed A. El Agbani, Asmâa Ouassou, Rhimou El Hamoumi, Hichem Azafzaf, Sami Rebah, Claudia Feltrup-Azafzaf, Nafouel Hamouda, Wed a.L. Ibrahim, Hosni H. Asran, Amr A. Elhady, Haitham Ibrahim, Khaled Etayeb, Essam Bouras, Almokhtar Saied, Ashrof Glidan, Bakar M. Habib, Mohamed S. Sayoud, Nadjiba Bendjedda, Laura Dami, Clemence Deschamps, Elie Gaget, Jean-Yves Mondain-Monval, Pierre Defos Du Rau

Abstract:

In biodiversity monitoring, large datasets are becoming more and more widely available and are increasingly used globally to estimate species trends and con- servation status. These large-scale datasets challenge existing statistical analysis methods, many of which are not adapted to their size, incompleteness and heterogeneity. The development of scalable methods to impute missing data in incomplete large-scale monitoring datasets is crucial to balance sampling in time or space and thus better inform conservation policies. We developed a new method based on penalized Poisson models to impute and analyse incomplete monitoring data in a large-scale framework. The method al- lows parameterization of (a) space and time factors, (b) the main effects of predic- tor covariates, as well as (c) space–time interactions. It also benefits from robust statistical and computational capability in large-scale settings. The method was tested extensively on both simulated and real-life waterbird data, with the findings revealing that it outperforms six existing methods in terms of missing data imputation errors. Applying the method to 16 waterbird species, we estimated their long-term trends for the first time at the entire North African scale, a region where monitoring data suffer from many gaps in space and time series. This new approach opens promising perspectives to increase the accuracy of species-abundance trend estimations. We made it freely available in the r package ‘lori’ (https://CRAN.R-project.org/package=lori) and recommend its use for large- scale count data, particularly in citizen science monitoring programmes.

Keywords: biodiversity monitoring, high-dimensional statistics, incomplete count data, missing data imputation, waterbird trends in North-Africa

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Authors: Nishimwe Clemence, Mchunu Gugu, Mukamusoni Dariya

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Background: Community health workers and extension workers can play an important role in supporting families to adopt health practices, encourage delivery in a health care facility, and ensure time referral of mothers and newborns if needed. Saving the lives of neonates should, therefore, be a significant health outcome in any maternal and newborn health program that is being implemented. Furthermore, about half of a million mothers die from pregnancy-related causes. Maternal and newborn deaths related to the period of postnatal care are neglected. Some authors emphasized that in developing countries, newborn mortality rates have been reduced much more slowly because of the lack of many necessary facility-based and outreach service. The aim of this review was to critically analyze the implementation and integration process of the maternal and newborn health care program by maternal community health workers, into the health care system, in Africa. Furthermore, it aims to reduce maternal and newborn mortality. We addressed the following review question: (1) what process is involved in the implementation and integration of the maternal and newborn health care program by maternal community health workers during antenatal, delivery and postnatal care into health system care in Africa? Methods: The database searched was from Health Source: Nursing/Academic Edition through academic search complete via EBSCO Host. An iterative approach was used to go through Google scholarly papers. The reviewers considered adapted Preferred Reporting Items for Systematic Reviews and Meta-Analysis (PRISMA) guidance, and the Mixed Methods Appraisal Tool (MMAT) was used. Synthesis method in integrative review following elements of noting patterns and themes, seeing plausibility, clustering, counting, making contrasts and comparisons, discerning commons and unusual patterns, subsuming particulars into general, noting relations between variability, finding intervening factors and building a logical chain of evidence, using data–based convergent synthesis design. Results: From the seventeen of studies included, results focused on three dimensions inspired by the literature on antenatal, delivery, and postnatal interventions. From this, further conceptual framework was elaborated. The conceptual framework process of implementation and integration of maternal and newborn health care program by maternal community health workers was elaborated in order to ensure the sustainability of community based intervention. Conclusions: the review revealed that the implementation and integration of maternal and newborn health care program require planning. We call upon governments, non-government organizations, the global health community, all stakeholders including policy makers, program managers, evaluators, educators, and providers to be involved in implementation and integration of maternal and newborn health program in updated policy and community-based intervention. Furthermore, emphasis should be placed on competence, responsibility, and accountability of maternal community health workers, their training and payment, collaboration with health professionals in health facilities, and reinforcement of outreach service. However, the review was limited in focus to the African context, where the process of maternal and newborn health care program has been poorly implemented.

Keywords: Africa, implementation of integration, maternal, newborn

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Authors: Wondale Getinet Alemu, Lillian Mwanri, Clemence Due, Telake Azale, Anna Ziersch

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Background: Mental illness is one of the most severe, chronic, and disabling public health problems that affect patients' Quality of life (QoL). Improving the QoL for people with mental illness is one of the most critical steps in stopping disease progression and avoiding complications of mental illness. Therefore, we aimed to assess the QoL and its determinants in patients with mental illness in outpatient clinics in Northwest Ethiopia in 2023. Methods: A facility-based cross-sectional study was conducted among people with mental illness in an outpatient clinic in Ethiopia. The sampling interval was decided by dividing the total number of study participants who had a follow-up appointment during the data collection period (2400) by the total sample size of 638, with the starting point selected by lottery method. The interviewer-administered WHOQOL BREF-26 tool was used to measure the QoL of people with mental illness. The domains and Health-Related Quality of Life (HRQoL) were identified. The indirect and direct effects of variables were calculated using structural equation modeling with SPSS-28 and Amos-28 software. A p-value of < 0.05 and a 95% CI were used to evaluate statistical significance. Results: A total of 636 (99.7%) participants responded and completed the WHOQOL-BREF questionnaire. The mean score of overall HRQoL of people with mental illness in the outpatient clinic was (49.6 ± 10 Sd). The highest QoL was found in the physical health domain (50.67 ±9.5 Sd), and the lowest mean QoL was found in the psychological health domain (48.41±10 Sd). Rural residents, drug nonadherence, suicidal ideation, not getting counseling, moderate or severe subjective severity, the family does not participate in patient care, and a family history of mental illness had an indirect negative effect on HRQoL. Alcohol use and psychological health domain had a direct positive effect on QoL. Furthermore, objective severity of illness, having low self-esteem, and having a history of mental illness in the family had both direct and indirect effects on QoL. Furthermore, sociodemographic factors (residence, educational status, marital status), social support-related factors (self-esteem, family not participating in patient care), substance use factors (alcohol use, tobacco use,) and clinical factors (objective and subjective severity of illness, not getting counseling, suicidal ideation, number of episodes, comorbid illness, family history of mental illness, poor drug adherence) directly and indirectly affected QoL. Conclusions: In this study, the QoL of people with mental illness was poor, with the psychological health domain being the most affected. Sociodemographic factors, social support-related factors, drug use factors, and clinical factors directly and indirectly, affect QoL through the mediator variables of physical health domains, psychological health domains, social relation health domains, and environmental health domains. In order to improve the QoL of people with mental illnesses, we recommend that emphasis be given to addressing the scourge of mental health, including the development of policy and practice drivers that address the above-identified factors.

Keywords: quality of life, mental wellbeing, mental illness, mental disorder, Ethiopia

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