Les acides carboxyliques aliphatiques sont utilisés dans de nombreux secteurs industriels et leur importance économique augmente. Ils sont actuellement produits en grande quantité, grâce à des procédés utilisant le C0 qui est principalement non- renouvelable. L'anhydride carbonique est une molécule potentiellement écologique, renouvelable et abondante. Cette thèse décrit l'étude et l'optimisation d'un système catalytique homogène de Rh, utilisé pour produire des acides carboxyliques aliphatiques à partir de substrats oxygénés, C02 et H2. Le système consiste en un précurseur de Rh, un additif à base d'iodure et un ligand PPh3, fonctionnant dans un réacteur discontinu sous une pression de C02 et de H2. Les conditions de réaction ont été optimisées pour chaque classe de substrats étudiés: alcools primaires et secondaires, cétones, aldéhydes et époxydes. 30 molécules différentes ont été converties en acides carboxyliques, conduisant à des rendements jusqu'à 80%. En plus, le système a été étudié avec une approche de « Design of Experiment », ce qui a permis d'obtenir des informations supplémentaires concernant les paramètres étudiés. Le mécanisme de réaction et les espèces catalytiques actives ont été étudiés par différentes manipulations comme des réactions compétitives, des expériences de RMN et l'utilisation de molécules marquées. La réaction est composée de transformations non catalytiques et de deux étapes catalytiques. La réaction se déroule à travers une réaction de reverse Water Gas Shift (rWGSR) transformant le C02 et l'H2 en C0 et H20, qui sont consommés dans l'hydrocarboxylation suivante de l'alcène formé in situ pour livrer l'acide carboxylique. Le système catalytique est similaire aux catalyseurs traditionnels à base du Rh pour les réactions de carbonylation et de Water Gas Shift. Le PPh3 est nécessaire pour fournir des ligands supplémentaires, permettant au catalyseur de fonctionner avec une quantité minimale de ligand toxique de C0. En plus, un système catalytique hétérogène a été étudié pour la même réaction. « Single Atom Catalysts » (SACs) reçoit beaucoup plus d'attention que les solutions catalytiques, car il présente à la fois les avantages des catalyseurs homogènes (sélectivité, haute activité) et des catalyseurs hétérogènes (séparation et recyclage faciles). Des atomes de rhodium simples dispersés sur du graphène dopé avec l'N ont été synthétisés et caractérisés, obtenant des informations concernant la structure chimique et physique du matériau. Finalement, ils ont été testés ainsi que les catalyseurs pour l'activation du C02, la production d'acides carboxyliques, les réactions d'hydrogénation et d'hydrogénolyse / Aliphatic carboxylic acids are used in many industrial sectors and their importance from an economical point of view is increasing. They are currently produced in large quantities, through processes exploiting the mostly non-renewable C0 as C1 synthon. Carbon dioxide is a potential environmentally friendly, renewable and abundant C1 building block. The aim of this work is to provide a catalytic protocol converting C02, H2 and oxygenated substrates to obtain useful chemicals, like carboxylic acids.To this end a homogeneous catalytic Rh system, used to produce aliphatic carboxylic acids starting from oxygenated substrates, C02 and H2 was investigated and optimized. The system consists of a Rh precursor, iodide additive and PPh3 ligand working in a batch reactor under C02 and H2 pressure. The reaction conditions were optimized for each class of investigated substrates: primary alcohols, secondary alcohols, ketones, aldehydes and epoxides. The reaction scope was investigated and 30 different molecules were converted into carboxylic acids, leading to yields of up to 80%. ln addition, the system was studied using a Design of Experiment approach, obtaining additional information regarding the studied parameters.The reaction mechanism and the catalytically active species were studied, by different experiments like competitive reactions, NMR and labelling experiments. This investigation resulted in a deeper knowledge of the reaction pathway, composed of some non-catalytic transformations and two catalytic steps. The reaction proceeds through a reverse Water Gas Shift Reaction (rWGSR) transforming C02 and H2 into C0 and H20, which are consumed in the following hydrocarboxylation of the in-situ formed alkene to give the final carboxylic acid product. The catalytic system is similar to traditional Rh carbonylation and Water Gas Shift catalysts. The PPh3 is needed to supply additional ligands allowing the catalyst to work in reaction conditions with a minimal amount of toxic C0 ligand. ln addition, a heterogeneous catalytic system was investigated for the same reaction. Single atom catalysts (SACs) are receiving much attention as catalytic solution, since they have both the advantages of homogeneous (selectivity, high activity) and heterogeneous (easy separation and recycling) catalysts. Single Rh atoms dispersed on N-doped graphene were synthesized and characterized, obtaining information regarding the chemical and physical structure of the material. Eventually, they were tested as catalysts for C02 activation, carboxylic acid production, hydrogenation and hydrogenolysis reactions / Aliphatische Carbonsauren werden in vielen industriellen Bereichen verwendet und ihre wirtschaftliche Bedeutung nimmt zu. Sie werden derzeit in gror.en Mengen hergestellt, indem das meistens nicht erneuerbare Kohlenmonoxid als C1-Synthon genutzt wird. Kohlendioxid ist ein potenziell umweltfreundlicher, erneuerbarer und abundanter C1-Baustein. Das Ziel dieser Arbeit ist die Entwicklung eines Protokolls zur katalytischen Umwandlung von C02, H2 und sauerstoffhaltigen Substraten, um nützliche Chemikalien, wie Carbonsauren zu erhalten. Zu diesem Zweck wird ein homogenes Rh-Katalysatorsystems zur Herstellung aliphatischer Carbonsauren aus sauerstoffhaltigen Substraten, C02 und H2 untersucht und optimiert. Das System besteht aus Rh-Prakursor, lodid-Additiv und PPh3 als Ligand, die in einem Batchreaktor unter C02 und H2 eingesetzt werden. Die Reaktionsbedingungen wurden für folgende Substratklassen optimiert: primare Alkohole, sekundare Alkohole, Ketone, Aldehyde und Epoxide. Es wurden insgesamt 30 verschiedene Substrate mit Ausbeuten bis zu 80% zu Carbonsauren umgesetzt. Darüber hinaus wurde das System mit einem ,,Statistische Versuchsplanung"-Ansatz untersucht, um zusatzliche lnformationen zu den untersuchten Parametern zu erhalten. Mechanismus und katalytisch aktive Spezies wurden durch verschiedene Experimente wie Konkurrenzreaktionen, NMR- und Markierungsexperimenten untersucht. Dies erschloss den Reaktionsweg, der aus mehreren nicht-katalytischen Transformationen und zwei katalytischen Schritten besteht. Die Reaktion verlauft durch eine ,,reverse Wassergas-Shift-Reaktion" (rWGSR), die C02 und H2 in C0 und H20 umwandelt. Diese werden wiederum bei der nachfolgenden Hydrocarboxylierung des in-situ gebildeten Alkens unter Bildung der Carbonsaure verbraucht. Das katalytische System ahnelt herkômmlichen Rh-Carbonylierungs- und WGSR-Katalysatoren. PPh3 fungiert als zusatzlicher Ligand, der es dem Katalysator ermôglicht unter den gleichen Reaktionsbedingungen mit minimaler Menge toxischen C0 als Liganden zu arbeiten. Zusatzlich wurde ein heterogenes katalytisches System für die gleiche Reaktion untersucht. ,,Single atom catalysts" (SACs) erhalten gror.e Aufmerksamkeit als neue Katalysatorklasse. Sie kombinieren die Selektivitat und hohe Aktivitat homogener und die einfache Abtrennung und Recycling heterogener Katalysatoren Verschiedene Katalysatoren aus auf N-dotiertem Graphen dispergierten Rh-Atomen, wurden synthetisiert und charakterisiert. Dadurch wurden lnformationen über die chemische und physikalische Struktur des Materials gewonnen und als Katalysatoren für C02-Aktivierung, Carbonsauresythese, Hydrierung und Hydrogenolyse getestet

No description available.

The objective of this study was to assess low to high levels of Cognitive Workload by measuring heart rate and cortical blood flow in real-time. Four conditions were implemented into a within-subjects experimental design. Two conditions of difficulty and two conditions of trial order were used to illicit different levels of workload which will be analyzed with psychophysiological equipment. Functional Near-Infrared Spectroscopy (fNIRS) has become more prominent for measuring the blood oxygenation levels in the prefrontal cortex of individuals operating in hazardous work environments, students with learning disabilities, and in research for military training. This is due to the fNIR device being highly mobile, inexpensive, and able to produce a high-spatial resolution of the dorsolateral prefrontal cortex during executive functioning. Heart Rate will be measured by an Electrocardiogram, which will be used in concordance with fNIR oxygenation levels to predict if an individual is in a condition that produces low or high mental workload. Successfully utilizing heart rate and blood oxygenation data as predictors of cognitive workload may validate implementing multiple physiological devices together in real-time and may be a more accurate solution for preventing excessive workload.

No description available.

Em muitos países e principalmente no Brasil, compostos oxigenados tais como etanol e metil terta-butil-éter (MTBE) têm sido adicionados à gasolina em cerca de 26% do seu volume para aumentar a octanagem do motor e diminuir a emissão de monóxido de carbono e os níveis de ozônio na atmosfera. O derramamento de tais gasolinas, referidas como gasolina oxigenada tem um efeito cosolvente, provocando um aumento da concentração dos hidrocarbonetos na água subterrânea. A taxa de dissolução em água da gasolina oxigenada, que é dependente das propriedades químicas dos compostos orgânicos, determinam o grau e a severidade de contaminação da água subterrânea nas vizinhanças do derramamento. O objetivo do trabalho foi analisar e quantificar o potencial de contaminação da água subterrânea e de solos arenosos residuais dos arenitos da Formação Botucatu por derramamento de gasolina oxigenada. As análises realizadas buscam fornecer dados para a modelagem numérica em casos envolvendo derramamento de gasolina. Ensaios de equilíbrio em lote e de dissolução em colunas foram realizados objetivando a determinação da concentração aquosa de hidrocarbonetos da gasolina em equilíbrio de fases e a avaliação do tempo estimado para total dissolução em água dos hidrocarbonetos da gasolina pura. Ambos os ensaios analisaram também o efeito cosolvente do etanol na mistura. Verificou-se a validade da lei de Raoult e do modelo log-linear na determinação da concentração aquosa da gasolina pura e oxigenada. Em colunas de solos não saturados avaliou-se a difusão na fase vapor dos compostos orgânicos da gasolina em função do tempo. Finalizando as análises, fez-se uma simulação numérica do transporte da gasolina em zonas não saturadas fazendo-se uso do programa R-UNSAT. / In many countries and mainly in Brazil oxygenated compounds such as ethanol and MTBE have been added to gasoline up to 26% to increase the octane level and to reduce carbon monoxide and ozone levels in the air. The spill of such gasolines, referred as oxygenated gasoline has a potential cosolvent effect, resulting in an increased groundwater concentration of hydrocarbons. The rate of oxygenated gasoline dissolution, which is dependent of the chemical properties of the compounds, determines the degree and severity of groundwater contamination in the vicinity of the spill. The goal of this research was to analyze and to quantify the potential of contamination of the groundwater and of the residual sandy soils from Botucatu sandstone due to the spill of oxigenated gasoline. The performed analysis supply data to the numerical model in case of gasoline spills. Laboratory batch and column leaching tests were carried out in order to determine the equilibrium aqueous concentration of the hydrocarbons compounds of gasoline and to evaluate the time scale for aqueous dissolution of the hydrocarbons compounds. Both tests have analyzed the cosolvent effect of ethanol in the mixture. It was verified the validity of the Raoult's law and the log-linear cosolvency model to estimate the solubility of the hydrocarbons compounds from unamended gasoline and from oxygenated gasoline. Column tests with unsaturated undisturbed soil samples were carried out to investigate the vapor-phase diffusion of aromatic hydrocarbons compounds with time. Finally the transport of gasoline in unsaturated zones was simulated with the R-UNSAT model.

Les minéraux absorbent la lumière proche des UV (comme TiO2, Fe2O3, MgO) présents dans les aérosols minéraux interagissent avec les gaz traces présents dans l'atmosphère et peuvent initier une nouvelle chimie hétérogène photo-induite potentiellement significative et actuellement peu documentée. Cette thèse vise à aborder différentes questions sur la réactivité des poussières minérales vers les composés organiques et évaluer l'impact de ces interactions sur plusieurs aspects des sciences de l'atmosphère. Nous avons étudié expérimentalement l'interaction physico-chimique d'aérosols minéraux, purs ou revêtus de matériaux organiques/inorganiques avec des gaz traces de plusieurs familles chimiques (alcools, cétones, acides carboxyliques), dans des conditions simulées proches de l'environnement reel (concernant l'humidité, la concentration en phase gazeuse, la longueur d'onde et l'intensité de l'irradiation, la pression et la température) évaluant les effets des conditions ambiantes sur la cinétique de capture et la génération de produits en phase gazeuse. Dans l'ensemble, nos résultats montrent clairement que les reactions photochimique des poussières minérales doit être considéré comme une source de composés réactifs et comme un processus clé affectant leur action sur la nucléation de la glace et les noyaux de condensation des nuages / Minerals that absorb light near UV/Vis present in dust aerosols interact with trace gases in the atmosphere and can initiate a new and potentially significant photo-induced heterogeneous chemistry, which is currently poorly documented. This thesis aims to address different issues of mineral dust reactivity towards organic compounds and, therefore, assesses the impact of these interactions on several aspects of atmospheric sciences. We investigated experimentally the physicochemical interaction of mineral aerosols (synthetic and natural), pure or coated with organic/inorganic materials with trace gases from several chemical families (alcohols, ketones, carboxylic acids, etc.), under simulated conditions close to the real environment (regarding to humidity, concentration in the gas phase, wavelength and intensity of irradiation, pressure and temperature). In a first approach, we studied the uptake of oxygenated organics onto different dust proxies such as SiO2, TiO2 and Arizona test dust (ATD) evaluating the effects of ambient conditions on the uptake kinetics and product generation. Then, we discussed the chemistry of 5 dicarboxylic acids (C4-C8) on ATD particles upon UV-A irradiation monitoring products in the gas phase as well as those whose stay adsorbed on the particulate phase. Lastly, we investigated the influence of nitrate anions on the uptake of acetone on ATD and SiO2 and in the photochemical product formation of glutaric acid on ATD. Overall, our results clearly show that photochemical processing of dust aerosols should be considered as a source of reactive compounds and as a key process affecting their action as ice nucleation and cloud condensation nuclei

The homoaldol reaction is one of the most powerful methods for the construction of C–C bonds as well as 1,4-oxygenated compounds yet this reaction remains in challenging tasks due to the instability of homoenolates which spontaneously cyclize to the cyclopropanolate. A regioselective catalytic homoaldol equivalent reaction of 3-bromo vinyl acetate with aldehydes under Cr(III)-Mn(0) redox condition was developed. This homoaldol equivalent reaction allows access to the 1,4-oxygenated compounds that are not possible by a conventional aldol process. Mild hydrolysis of the vinyl acetate and reduction of the homoaldol adducts generated diols and lactols in high yield (99%). Further manipulation including stereoselective epoxidation and cyclopropanation was achieved in an efficient manner. Furans, found in many natural products and utilized in drug discovery, have been well studied but current synthetic methods toward furans have some limitations in functional group tolerance, substrate scope, and low product yield in many cases. A highly efficient and catalytic cycloisomerization reaction that transforms acetylenic α,β-epoxides to 2,3,5-tri-substituted furans under InCl3 catalysis was developed. This reaction sequence allows access to rapid construction of highly valuable, tri-substituted furan derivatives. Cross-coupling reactions utilizing transition metals and Lewis acids are important synthetic tools for the formation of C–C and C–N bonds and a number of cross-coupling reactions between α-bromo carbonyl compounds and metal reagents such as aryl metals, alkenyl metals, and alkyl metals have been reported. Transition metal-catalyzed cross-coupling reaction for the construction of α-alkynyl carbonyl compounds has reported in a limited case. The first approach to secondary α-alkynyl carbonyl compounds from secondary α-bromo esters and amides with tributyl(phenylethynyl)stannane under palladium-catalyzed cross-coupling reaction conditions was developed. This synthetic method allows access to secondary α-alkynyl carbonyl compounds which are valuable precursors in pharmaceuticals and agricultural applications.

Em muitos países e principalmente no Brasil, compostos oxigenados tais como etanol e metil terta-butil-éter (MTBE) têm sido adicionados à gasolina em cerca de 26% do seu volume para aumentar a octanagem do motor e diminuir a emissão de monóxido de carbono e os níveis de ozônio na atmosfera. O derramamento de tais gasolinas, referidas como gasolina oxigenada tem um efeito cosolvente, provocando um aumento da concentração dos hidrocarbonetos na água subterrânea. A taxa de dissolução em água da gasolina oxigenada, que é dependente das propriedades químicas dos compostos orgânicos, determinam o grau e a severidade de contaminação da água subterrânea nas vizinhanças do derramamento. O objetivo do trabalho foi analisar e quantificar o potencial de contaminação da água subterrânea e de solos arenosos residuais dos arenitos da Formação Botucatu por derramamento de gasolina oxigenada. As análises realizadas buscam fornecer dados para a modelagem numérica em casos envolvendo derramamento de gasolina. Ensaios de equilíbrio em lote e de dissolução em colunas foram realizados objetivando a determinação da concentração aquosa de hidrocarbonetos da gasolina em equilíbrio de fases e a avaliação do tempo estimado para total dissolução em água dos hidrocarbonetos da gasolina pura. Ambos os ensaios analisaram também o efeito cosolvente do etanol na mistura. Verificou-se a validade da lei de Raoult e do modelo log-linear na determinação da concentração aquosa da gasolina pura e oxigenada. Em colunas de solos não saturados avaliou-se a difusão na fase vapor dos compostos orgânicos da gasolina em função do tempo. Finalizando as análises, fez-se uma simulação numérica do transporte da gasolina em zonas não saturadas fazendo-se uso do programa R-UNSAT. / In many countries and mainly in Brazil oxygenated compounds such as ethanol and MTBE have been added to gasoline up to 26% to increase the octane level and to reduce carbon monoxide and ozone levels in the air. The spill of such gasolines, referred as oxygenated gasoline has a potential cosolvent effect, resulting in an increased groundwater concentration of hydrocarbons. The rate of oxygenated gasoline dissolution, which is dependent of the chemical properties of the compounds, determines the degree and severity of groundwater contamination in the vicinity of the spill. The goal of this research was to analyze and to quantify the potential of contamination of the groundwater and of the residual sandy soils from Botucatu sandstone due to the spill of oxigenated gasoline. The performed analysis supply data to the numerical model in case of gasoline spills. Laboratory batch and column leaching tests were carried out in order to determine the equilibrium aqueous concentration of the hydrocarbons compounds of gasoline and to evaluate the time scale for aqueous dissolution of the hydrocarbons compounds. Both tests have analyzed the cosolvent effect of ethanol in the mixture. It was verified the validity of the Raoult's law and the log-linear cosolvency model to estimate the solubility of the hydrocarbons compounds from unamended gasoline and from oxygenated gasoline. Column tests with unsaturated undisturbed soil samples were carried out to investigate the vapor-phase diffusion of aromatic hydrocarbons compounds with time. Finally the transport of gasoline in unsaturated zones was simulated with the R-UNSAT model.

L'infarctus du myocarde constitue la première cause de mortalité cardiovasculaire. Dans ce contexte, depuis plus de 40 ans et les premières études sur les populations du Groenland, il est connu qu'une consommation de poisson riche en acide gras polyinsaturés de type omégas 3 (AGPI n-3) a des effets cardioprotecteurs. De très nombreuses études cliniques, animales et cellulaires ont ensuite confirmé ces résultats cardioprotecteurs des AGPI n-3 qui semblent passer par une prévention des arythmies cardiaques post infarctus.Cependant, du fait de leurs nombreuses doubles liaisons carbone-carbone, les principaux AGPI n-3 que sont l'acide eicosapentaénoïque et l'acide docosahexaénoïque sont très sensibles à l'oxygénation à l'air et peuvent subir une peroxydation non enzymatique spontanée sous condition de stress oxydant qui accompagne notamment l'ischémie/reperfusion lors d'un infarctus du myocarde.Dans ce travail de thèse, nous posons la question de savoir quelle forme d'AGPI a des effets cardioprotecteur : la forme réduite ou oxydée. En effet, les effets des AGPI n-3 sur la fonction cardiaque sont très controversés, notamment due au manque d'information sur les mécanismes impliqués. Particulièrement, on ne sait pas quel lipide est actif : les AGPI n-3 ou un des leurs métabolites oxygénés.Durant l'ischémie reperfusion puis dans les mois qui suivent l'infarctus du myocarde, le stress oxydant est élevé et de nombreux métabolites non enzymatiques dérivés des AGPI n-3 comme les NeuroProstanes sont alors produits à tel point qu'ils sont reconnus comme biomarqueurs du stress oxydant. Ainsi, dans ce travail de recherche, nous spéculons que les NeuroProstanes ne sont pas seulement des biomarqueurs du stress oxydant mais auraient un rôle biologiquement actif qui expliqueraient les effets cardioprotecteurs connus de leurs précurseurs ; les AGPI n-3.Le but de cette thèse est dans un premier temps d'investiguer l'influence de la peroxydation lipidique du DHA sur ses propriétés antiarythmiques in cellulo sur des cellules ventriculaires cardiaques isolées puis in vivo sur des souris ayant subit un infarctus du myocarde par ligature de l'artère coronaire gauche. De la même manière, nous avons évalué les propriétés antiarythmiques des métabolites non enzymatique des AGPI n-3 et notamment le 4(RS)-4F4t-NeuroProstane. Dans un second temps et de manière plus précoce, nous avons observé si une infusion préventive de 4(RS)-4F4t-NeuroP chez le rat, 20 minutes avant un épisode d'ischémie reperfusion peut protéger le myocarde des dommages ischémiques (morts cellulaires), des arythmies et des altérations morpho-fonctionnelles.L'ensemble de ce travail de thèse a ainsi permis de mettre en évidence que un des médiateurs lipidiques des AGPI n-3 ; le 4(RS)-4-F4t-NeuroP peut exercer des effets biologiquement actifs qui passent par une prévention des arythmies dans les mois qui suivent l'infarctus du myocarde ; effets passant par une prévention des modifications post-translationnelles du RyR2 et in fine d'une régulation de l'homéostasie calcique. De manière plus précoce durant l'ischémie reperfusion, nos résultats montrent que le 4(RS)-4-F4t-NeuroP réduit les arythmies ventriculaires, la taille de la zone infarcie et la dysfonction cardiaque, effets cardioprotecteurs qui passent par des mécanismes mitochondriaux.Le travail de cette thèse démontre pour la première fois que le DHA n'exerce pas d'effets cardioprotecteurs mais que ce serait les produits issus de son oxydation non enzymatique tel le 4(RS)-4-F4t-NeuroP pouvant ainsi expliquer l'ensemble des effets connus des AGPI n-3. Cette découverte ouvre de nouvelles perspectives sur les produits oxydés non enzymatiques des AGPI n-3 comme des potentiels médiateurs dans les maladies comme durant l'infarctus du myocarde ou le stress oxydant qui est généré joue un rôle prépondérant dans les altérations physiopathologiques qui en découlent. / Since 40 years, ω3 poly-unsaturated fatty acids (n-3 PUFA) are known to have cardioprotective properties in ischemic disease such as cardiac infarction following ischemia/reperfusion period. Many studies in isolated cells or in animals confirmed these effects and it has been suggested that n-3 PUFA have direct effects on targeted proteins such as ionic channels. However, due to the abundance of double carbone bounds, the main n-3 PUFA; eicosapentaenoic acid (C20: 5 n-3, EPA) and docosahexaenoic acid (C22: 6 n-3, DHA) are very sensitive to free radical oxidation and can undergo non-enzymatic spontaneous peroxidation under oxidative stress conditions as it occurs in ischemia/reperfusion. In the present work, we addressed the question of the form of DHA having cardioprotective properties: reduced or oxidized. Indeed, the effects of n-3 PUFA on cardiac function are controversial, notably due to the lack of information on the mechanisms involved. Particularly, it is not well understood which is the active lipid: the PUFA or one of its oxygenated metabolites. In the context of oxidative stress, during ischemia/reperfusion and in month following cardiac infarction, a lot of oxygenated metabolites of PUFA like Neuroprostane; 4(RS)-4F4t-NeuroP are produced and used as biomarkers of oxidative stress. This metabolite is associated to a lower atherosclerosis risk suggesting a beneficial role in cardiovascular diseases. In this context we speculate that Neuroprostane are not just a markers of stress conditions but have biological activities.The aim of this thesis was in first time to investigate the influence of DHA peroxidation on its potentially anti-arrhythmic properties in isolated ventricular cardiomyocytes and in vivo in post-myocardial infarcted (PMI) mice. In same way, we investigated in cellulo and in vivo anti-arrhythmic properties of oxygenated metabolites of n-3 PUFA such as 4(RS)-4F4t-NeuroP. In second time we investigated if the pericardial delivery 20 minutes before occlusion of 4F4t-NeuroP protects in prevention the myocardium from ischemic damages and arrhythmias during and following an I/R episode in rats.In this study, we challenged the paradigm that spontaneously formed oxygenated metabolites of lipids are undesirable as they are unconditionally toxic. This study reveals that the lipid mediator 4(RS)-4-F4t-NeuroP derived from non-enzymatic peroxidation of DHA, can counteract such deleterious effects through cardiac anti-arrhythmic properties in month following cardiac infarction by preventing deleterious post-translational modification of RyR2 and thus regulating calcium homeostasis. More early, during ischemia/reperfusion, our results show that pericardial delivery of 4(RS)-4-F4t-NeuroP reduced ischemia-induced ventricular arrhythmias, infarct sizes, and cardiac dysfonction ; cardioprotective effects involving mitchondria mecanisms.This thesis demonstrate for the first time that DHA per se has no anti-arrhythmic effects and 4(RS)-4-F4t-NeuroP as a mediator of the cardioprotection characteristics of DHA. This discovery opens new perspectives for products of non-enzymatic oxidized n-3 PUFA as potent mediators in oxidative stress diseases like during a cardiac infarction, where oxidative stress generated play fundamental role in pathophysiological alterations.

Highly accurate analysis for the quantification of sulphur compounds and oxygenated volatile organic compounds are crucial for the adherence of the legislation in different environmental sectors. The sulphur compounds and oxygenated volatile organic compounds measurements are challenging, due to various factors such as molecules being adsorbed on the inner surfaces of cylinders. It is therefore important to produce accurate and reliable reference gas mixtures with mole fraction at ambient levels for the air quality monitoring and field of gas sensing in South Africa. The challenges in producing sulphur compounds and oxygenated volatile organic compounds reference gas mixtures are that the overall process from gravimetric preparation steps until the comparison analysis process and the stability of mixture in the gas cylinder, results in the large measurement uncertainties. In order to produce reference gas mixtures of the highest level, three important steps are followed: purity assessment of starting material, gravimetric preparation, and verification/validation of prepared gas mixtures. The purity analysis of high purity starting materials was determined using gas chromatography coupled with various detectors and Karl Fischer for determination of moisture content in high purity chemicals. The sulphur compounds and oxygenated volatile organic compounds to be developed in this study were hydrogen sulphide, sulphur dioxide, acetone, methanol, ethanol, isopropanol, and n-butanol. These components were produced following the International Organisation for Standardisation documents at mole fraction of 10 µmol/mol for sulphur compounds and 5 µmol/mol for oxygenated volatile organic compounds. The preparation of sulphur compounds reference gas mixtures was done with a static gravimetric method using a direct method where a target component was transferred directly into the cylinder. The preparation of oxygenated volatile organic compounds used an indirect method whereby a target liquid component from high purity chemicals was transferred into a cylinder using a gas-tight syringe.The comparison between the reference gas mixtures was validated using Non-Dispersive Ultra-Violet analysers (NDUV), gas chromatograph coupled with pulsed discharge helium ionisation detector (GC-PDHID, UV fluorescence analysers for sulphur compounds and gas chromatograph coupled with flame ionisation detector (GC-FID) for the oxygenated volatile organic compounds. A multi-point calibration method was used to analyse sulphur dioxide and hydrogen sulphide on the NDUV analyser, and the single-point calibration method was used for analysis on the gas chromatography and UV fluorescence where a sample mixture is analysed against a reference mixture with a similar mole fraction. The statistical data considered during analysis included calculation of the instrument drift and percentage relative standard deviation to check measurements repeatability, reliability, and measurement uncertainty. The gravimetric results of prepared sulphur compounds at 10 µmol/mol gave a percentage relative expanded uncertainty of 0.041 % REU for hydrogen sulphide, 0.12 % REU for sulphur dioxide. The gravimetric results of prepared oxygenated volatile organic compounds at 5 µmol/mol showed a percentage relative expanded uncertainty 0.068 to 0.35 % REU for isopropanol and ethanol respectively and less than 2.4 % REU for multi component of oxygenated volatile organic compounds. Finally, the primary standard gas mixtures of sulphur compounds and oxygenated volatile organic compounds were developed with the highest metrological measurement uncertainty level of (k=2). / Environmental Sciences / M. Sc. (Environmental Sciences)