Dissertations / Theses on the topic 'Cycle redox'

Les recherches présentées dans cette thèse portent sur l'étude et l'évaluation d'un nouveau procédé de génération d'hydrogène. De nos jours, la production d'hydrogène est principalement basée sur le reformage du gaz naturel ou de naphta. Des procédés moins énergivores et plus durables pour la production d'hydrogène sont attractifs aussi bien pour l'industrie que pour les applications domestiques. Une voie très intéressante est le reformage de bio-alcools, en principe CO2-neutre. Des procédés de séparation coûteux peuvent être évités en séparant le procédé en deux étapes successives (combustion en boucle chimique), dans le but de réaliser deux flux séparés de H2 et de COx. De plus, un avantage supplémentaire en termes de durabilité est l'utilisation du bioéthanol comme source d'hydrogène, au lieu du gaz naturel.Le principe essentiel du cycle de boucle thermochimique est qu'un matériau de stockage d'oxygène est d'abord réduit par un courant d'éthanol, puis ré-oxydé par l'eau, afin de produire de l'hydrogène et de restaurer l'état d'oxydation d'origine du matériau en boucle.L’objectif initial du projet était de définir des conditions et des matériaux qui pourraient conduire à un processus optimisé, permettant de produire un flux d'hydrogène qui ne nécessite aucun traitement supplémentaire de purification ou de séparation. Différents oxydes mixtes de type spinelle modifiés TYPE I – MFe2O4 et TYPE II – M0,6Fe2,4Oy avec : (M = Cu, Co, Mn, Mg, Ca et Cu / Co, Cu / Mn, Co / Mn), en tant que matériaux potentiellement intéressants pour l’oxygène ionique et le bouclage de porteurs d'électrons, ont été préparés par co-précipitation et testés à la fois afin d’étudier leurs propriétés redox et de leur activité catalytique pour générer de l'hydrogène par oxydation à la vapeur d'eau, après une étape de réduction réalisée avec de l'éthanol. En particulier, nous nous sommes focalisés sur le comportement de réactivité des matériaux binaires/ternaires qui se traduit par leur capacité à former des oxydes de spinelle thermodynamiquement stables qui permettent de réobtenir la phase spinelle initiale lors du cycle et, à son tour, d'augmenter la stabilité du matériau en boucle par lui-même. De plus, ces travaux de recherche incluent des analyses DRIFTS in situ et des études XPS in situ qui ont permis d'extraire des informations au niveau moléculaire et de suivre les changements de surface dans les processus de réduction / réoxydation pendant le reformage d'éthanol en boucle chimique. Plusieurs caractérisations ont été effectuées à l'aide de techniques DRX, TPR / O, MET / MEB / EDS, mesures magnétiques et techniques spectroscopiques Raman / Mössbauer. De plus, nous avons effectué une modification du procédé CLR conventionnel avec l’addition d’une 3ème étape de régénération (réalisée avec de l'air) afin d'augmenter la stabilité du matériau en boucle et de résoudre les problèmes de désactivation tels que: dépôt / accumulation de coke et la réoxydation incomplète de M0 au cours de la 2ème étape
The current research is focused on the study and evaluation of a new process for the hydrogen generation. Nowadays, hydrogen production is mainly based on the reforming of natural gas or naphtha. Less energy intensive and more sustainable processes for hydrogen production are appealing for both industry and consumer applications. A highly attractive route is steam reforming of bio-alcohols, in principle CO2 neutral. Costly separation processes can be avoided by splitting the process into two alternated steps (chemical-loop reforming), in the aim of achieving two separate streams of H2 and COx. Moreover, an additional advantage in terms of sustainability is the use of bio-ethanol as the source of hydrogen, instead of natural gas.The main principle of the thermochemical-loop cycle is that an oxygen-storage material is first reduced by an ethanol stream, and then re-oxidized by water, in order to produce hydrogen and restore the original oxidation state of the looping-material.The initial task of the project was to define conditions and materials that may lead to an optimized process, allowing producing a hydrogen stream that does not require any additional purification or separation treatment. Different M-modified spinel-type mixed oxides: TYPE I – MFe2O4 and TYPE II – M0.6Fe2.4Oy viz. modified ferrospinels (where M=Cu, Co, Mn, Mg, Ca and Cu/Co, Cu/Mn, Co/Mn), as potentially attractive ionic oxygen and electron carrier looping materials, were prepared via co-precipitation method and tested in terms of both redox properties and catalytic activity to generate hydrogen by oxidation with steam, after a reductive step carried out with ethanol. Particularly, the focus on the reactivity behaviour of binary/ternary materials explained by their ability to form thermodynamically stable spinel oxides which allow us to re-obtain the initial spinel phase upon cycling and in turn increase the stability of looping material itself. In addition, the research includes in-situ DRIFTS and in-situ XPS studies that allowed to extract information at molecular level and to follow surface changes within the reduction/re-oxidation processes during ethanol chemical-loop reforming. Bulk characterizations have been done using XRD, TPR/O, TEM/SEM/EDS, Magnetic measurements and Raman/Mössbauer spectroscopic techniques. Moreover, a modification of the conventional CLR process with an addition of the 3rd regeneration step (carried out with air) was done in order to increase the stability of the looping material and to overcome the deactivation problems, such as: a coke deposition/accumulation and an incomplete re-oxidation of M0 during the 2nd step

Seed germination is critical for plant establishment but little is known about how the reduction-oxidation (redox) environment of the cells in the emerging root meristem influences cell division. The glutathione redox potentials of the nuclei and cytosol were determined using redox-sensitive green fluorescent protein (roGFP2) in the Arabidopsis root apical meristem, in which cell cycle had been synchronised using hydroxyurea, within the period immediately after germination, in order to characterise the relationships between cellular redox status and cell cycle progression. The average glutathione redox potentials of the nuclei and cytosol were -297.5 mV ± 0.7 and -292.8 mV ± 0.6 respectively. However, a transient oxidation occurred in compartments during the G1 phase of the cell cycle, as determined by the expression of cell cycle markers (CYCB1;1-GUS, cytrap and cyclins). The effect of low antioxidant buffering capacity on the gene expression profiles of dry and imbibed seeds as well as the redox potentials of the nuclei and cytosol was determined using the ascorbate deficient vtc2-1 and vtc2-4 mutants. The glutathione redox potentials of the nuclei in the proliferation zone of vtc2-1 radicles expressing roGPF2 were -282.3 mV ± 0.5 and the cytosol was -282.9 mV ± 0.5. These increased levels of oxidation persisted throughout the period of measurement, a feature that was linked to changes in cell cycle progression. The transcriptome profiles of vtc2-1 and vtc2-4 dry seeds compared with that of wild-type seeds revealed large changes in the abundance of transcripts encoding transcription factors, redox components, and proteins involved in cell cycle and secondary metabolism. Fewer differences were shown for the transcriptome profiles of vtc2-1 and vtc2-4 imbibed seeds. Taken together these data show that antioxidant buffering capacity exerts a strong influence on cell cycle progression and gene expression without having marked effects on germination.

Photocatalytic reactions mediated by semiconductors such as ZnS, TiO2, ZnO, etc. can harvest solar energy into chemical bonds, a process with important prebiotic and environmental chemistry applications. The recycling of CO2 into organic molecules (e.g., formate, methane, and methanol) facilitated by irradiated semiconductors such as colloidal ZnS nanoparticles has been demonstrated. ZnS can also drive prebiotic reactions from the reductive tricarboxylic acid (rTCA) cycle such as the reduction of fumarate to succinate. However, the mechanism of photoreduction by ZnS of the previous reaction has not been understood. Thus, this thesis reports the mechanisms for heterogeneous photocatalytic reductions on ZnS for two model reactions in water with sulfide hole scavenger. First the reduction of CO2 is carried out under variable wavelength of irradiation and proposed to proceed thorough five steps resulting in the exclusive formation of formate. Second the reduction of the double bond of fumaric acid to succinic acid is reported in detail and compared to the previous conversion of CO2 to formic acid. Both reactions are carried out under variable wavelength of irradiation and proposed to proceed thorough one electron transfer at a time. In addition, a new method to measure the bandgap of colloidal ZnS suspended in water is established. Furthermore, the time scales of electron transfer and oxidizing hole loss during irradiation of ZnS for both reactions are reported and interpreted in terms of the Butler-Volmer equation. The sunlight promoted production of succinate introduced above, provides a connection of this prebiotic chemistry work to explore if central metabolites of the rTCA cycle can catalyze the synthesis of clay minerals. Clay minerals are strong adsorbents that can retain water and polar organic molecules, which facilitate the polymerization of biomolecules and conversion of fatty acid micelles into vesicles under prebiotic conditions relevant to the early Earth. While typical clay formation requires high temperatures and pressures, this process is hypothesized herein to be accelerated by central metabolites. A series of synthesis are designed to last only 20 hours to study the crystallization of sauconite, an Al- and Zn-rich model clay, at low temperature and ambient pressure in the presence of succinate as a catalyst. Succinate promotes the formation of the trioctahedral 2:1 layer silicate at ≥ 75 °C, 6.5 ≤ pH ≤ 14, [succinate] ≥ 0.01 M. Cryogenic and conventional transmission electron microscopies, X-ray diffraction, diffuse reflectance Fourier transformed infrared spectroscopy, and measurements of total surface area and cation exchange capacity are used to study the time evolution during the synthesis of sauconite. While the studies with ZnS presented above advanced the fundamental understanding of photocatalysis with single semiconductors, the environmental applications of this material appear limited. A common limitation to photocatalysis with single semiconductors is the rapid recombination of photogenerated electron-hole pairs, which reduces significantly the efficiency of the process that in the case of ZnS also suffers from photocorrosion in the presence of air. In order to overcome the fast charge recombination and the limited visible-light absorption of semiconductor photocatalysts, an effective strategy is developed in this work by combining two semiconductors into a nanocomposite. This nanocomposite is solvothermally synthesized creating octahedral cuprous oxide covered with titanium dioxide nanoparticles (Cu2O/TiO2). The nanocomposite exhibits unique surface modifications that provide a heterojunction with a direct Z-scheme for optimal CO2 reduction. The band structure of the nanocomposite is characterized by diffused reflectance UV-visible spectroscopy, X-ray photoelectron spectroscopy (XPS) and ultraviolet photoelectron spectroscopy. The photoreduction of CO2(g) to CO(g) on the nanocomposite is investigated in the presence water vapor as the hole scavenger that generates the quantifiable hydroxyl radical (). The quantum efficiency of CO production under irradiation at λ ≥ 305 nm with the nanocomposite is 2-times larger than for pure Cu2O. The detection of and XPS analysis contrasting the stability of Cu2O/TiO2 vs Cu2O during irradiation prove that TiO2 prevents the photocorrosion of Cu2O. Overall, the studies of photocatalytic reductions on single component semiconductors reveal new knowledge needed for developing future photocatalytic application for fuel production, wastewater treatment, reducing air pollution, and driving important prebiotic chemistry reactions. Furthermore, the design of a photocatalyst operating under a Z-scheme mechanism provides a new proof of concept for the design of systems that mimic photosynthesis. Finally, this work also demonstrates how molecules obtained by mineral mediated photochemistry can catalyze clay formation; highlighting the important role that photochemistry may have played for the origin of life on the early Earth and other rocky planets.

In photosynthetic organisms the redox-dependent modification of thiols belonging to enzymes of the photosynthetic cycle, plays a prominent role in the regulation of metabolism and signalling. An important regulatory mechanism is represented by light that acts through a ferredoxin-thioredoxin system. The system permits the reduction/oxidation of disulfide bridges of the target enzymes. Moreover, cysteines residues can undergo other modifications such as glutathionylation and nitrosylation. Proteomic studies have allowed the identification of new putative targets of redox modifications, including Calvin Benson cycle enzymes. The aim of the studies was to investigate whether phosphoglycerate kinase, triose phosphate isomerase and glyceraldehyde-3-phosphate dehydrogenase from Chlamydomonas reinhardtii undergo redox modifications. All enzymes and their mutants (i.e. cysteines variants) were purified and the treatments with alkylating and oxidative agents have permitted to confirm the presence of reactive cysteine(s). The sensitivity of recombinant proteins to redox modifications and the cysteine(s) involved were analyzed by biochemical approcheas. The structural features were analyzed, and the crystallography structure of CrTPI and CrGPA were solved. The three enzymes result all redox regulated although with different biochemical features. The CrPGK contains two cysteines sensitive to redox treatments, although the inhibitor effects of these modifications are different, indeed glutathionylation slightly affected the enzymatic activity compare to nitrosylation. Moreover, the crystallographic structure of CrTPI was determined at a resolution of 1.1.Å, showing a homodimeric conformation containing the typical α/β- barrel fold. No evidence for CrTPI Trx-dependent regulation was obtained but was found to undergo glutathionylation and nitrosylation with a moderate down-regulation on activity. Furthermore, the CrGAPA shows an extreme sensitivity to oxidant molecules and the crystallographic structure of CrGAPA was determined at a resolution of 1.8.Å, confirming the tetrameric fold of the enzyme. the results suggest that redox modifications could constitute a mechanism for the regulation of the Calvin-Benson cycle under oxidative stress conditions.

La phosphoribulokinase (PRK) et la glycéraldéhyde 3-phosphate déshydrogénase (GAPDH) sont deux enzymes-clés du cycle de Calvin-Benson. Leurs activités sont régulées par l’intermédiaire de la CP12, une protéine intrinsèquement désordonnée. Au cours de la transition lumière-obscurité, la GAPDH, la CP12 et la PRK forment un complexe supramoléculaire au sein duquel l’activité des enzymes est inhibée. Dans les travaux présentés ici, nous nous sommes intéressés à la formation de ce complexe et à la dynamique de ses composants. Nous avons montré pour la première fois que les résidus cystéine Cys243 et Cys249 de la PRK sont essentiels à la formation du complexe GAPDH-CP12-PRK et qu’ils peuvent former un pont disulfure en présence de CP12. Nous avons également étudié la dynamique de la CP12 en présence de ses partenaires, et observé que la CP12 adopte une conformation beaucoup plus compacte en présence de GAPDH et de PRK. La glutathionylation (formation d’un pont disulfure mixte entre une molécule de glutathion et un résidu cystéine appartenant à une protéine) est une modification post-traductionnelle associée au stress oxydant qui affecte dix enzymes du cycle de Calvin-Benson, y compris la GAPDH et la PRK. Nous avons étudié l’impact de la glutathionylation sur ces enzymes, et montré que l’inactivation de la PRK naît de l’encombrement du site de fixation de l’ATP.Enfin, la dernière partie de ces travaux est centrée sur l’adénylate kinase 3 de C. reinhardtii, une enzyme impliquée dans le métabolisme de l’ATP et qui possède une extension similaire à la CP12. Cette première étude montre que cette extension augmente la stabilité de l’ADK 3 et intervient dans sa glutathionylation
Phosphoribulokinase (PRK) and glyceraldehyde 3-phosphate dehydrogenase (GAPDH) are two key enzymes of the Calvin-Benson and their activities are redox-regulated through the intervention of CP12, a intrinsically disordered protein. During the light-to-dark transitions, GAPDH, CP12 and PRK form a supramolecular complex in which the enzymes are strongly inhibited; this complex is dissociated during the dark-to-light transition and the active enzymes are released.In the work presented here, we studied the formation of the complex and the dynamics of its components. For the first time, we showed that two cysteine residues of PRK, Cys243 and Cys249, are essential to the assembly of the GAPDH-CP12-PRK complex, and can form a disulfide bridge in presence of CP12.Glutathionylation (the formation of a mixed disulfide bridge linking one glutathione molecule and a cysteine residue from a protein) is a post-translational modification associated with oxidative stress that affects ten of the Calvin-Benson enzymes, including GAPDH and PRK, and we show that the inactivation of PRK by glutathionylation is caused by the blockage of the ATP binding site by glutathione.The last part of this work is centered around adenylate kinase 3 from C. reinhardtii, an enzyme tied to the energetic metabolism of the cells that presents a CP12-like C-terminal extension. Our results suggest that this CP12-like “tail” improve the stability of ADK 3 and participates in tis glutathionylation

La quinone réductase 2 ou QR2 est une enzyme qui, comme son homologue QR1, joue un rôle de détoxification des quinones, molécules fortement réactives, en les réduisant en hydroquinones. Cependant, il a été observé au niveau cellulaire et tissulaire que l'activité de cette flavoprotéine pouvait avoir des effets délétères en déclenchant une surproduction d'espèces réactives de l'oxygène (ROS). D'autre part, on observe une surexpression ou une sous expression de QR2 dans certaines maladies neurodégénératives comme la maladie de Parkinson et la maladie d'Alzheimer. Dans ce contexte, ce travail a porté sur l'étude des espèces oxygénées réactives produites lors du cycle redox quinone / QR2 et leurs variations en fonction de la nature de la quinone, sur protéine purifiée et sur modèles cellulaires comparativement à QR1. Les propriétés d'oxydo-réduction des substrats, co-substrats et inhibiteurs de QR2 étudiées par électrochimie ont permis de les classer en fonction de leur capacité à être réduits. L'activité enzymatique de la protéine, qu'elle soit purifiée ou intracellulaire, a été suivie par différentes méthodologies (résonance paramagnétique électronique, spectroscopie UV-visible et de fluorescence, U(H)PLC-MS, microscopie confocale de fluorescence). La production du radical superoxyde est observée en présence de lignées cellulaires surexprimant ou non QR1 et QR2. Les quinones sont réduites enzymatiquement pour donner des hydroquinones via l'activité des quinones réductases (QR1 et QR2) et des semiquinones via l'activité de réductases à un électron (CytP540 réductase par exemple). La réoxydation de ces produits est responsable d'une production plus ou moins forte de radicaux superoxydes selon la structure initiale de la quinone et l'affinité pour les différentes réductases. La ménadione provoque une production cellulaire de superoxyde plus importante en l'absence de QR1 et QR2. Ces analyses ont également démontré que, comme son homologue QR1, QR2 est capable de réduire les ortho-quinones dont certaines catécholquinones (aminochrome, dopachrome, adrénochrome) reconnues pour leur toxicité neuronale
Quinone reductase 2 or QR2 is an enzyme that, like its counterpart QR1, plays a role in detoxification of the highly reactives quinones by reducing them into hydroquinones. On one hand, it has been observed at the cellular and tissue level that the activity of this flavoprotein could have deleterious effects by triggering an overproduction of reactive oxygen species (ROS). On the other hand, overexpression or under expression of QR2 has been observed in some neurodegenerative diseases such as Parkinson's disease and Alzheimer's disease. In this context, this work focused on the study of reactive oxygen species produced during the quinone / QR2 redox cycle and their variations depending on the nature of the quinone, on both purified protein and cell models, in comparison to QR1. The redox properties of the substrates, co-substrates and inhibitors ok QR2 studied by electrochemistry allowed to classify them according to their capacity to be reduced. The enzymatic activity of the protein, either purified or intracellular, was followed by various methodologies (electron paramagnetic resonance, UV-visible and fluorescence spectroscopy, U(H)PLC-MS, confocal fluorescence microscopy). Production of superoxide radical is observed in the presence of cell lines overexpressing or not QR1 and QR2. Quinones are reduced enzymatically to form hydroquinones via the activity of quinone reductase (QR1 and QR2) and semiquinone via the activity of one electron reductases (e.g. CytP540 reductase). Reoxidation of these products is responsible for a greater or lesser production of the superoxide radical, according to the initial structure of the quinone and the affinity for different reductases. Menadione causes a higher production of cellular superoxide in the absence of QR1 and QR2. These analyzes have also shown that, like its counterpart QR1, QR2 is capable of reducing ortho-quinones including catecholquinones (aminochrome, dopachrome, adrenochrome) known for their neuronal toxicity

The emergence of tamoxifen or aromatase inhibitor resistance is a major problem in the treatment of breast cancer. The molecular signaling mechanism of antiestrogen resistance is not clear. Understanding the mechanisms by which resistance to these agents arise could have major clinical implications for preventing or circumventing it. Therefore, in this dissertation we have investigated the molecular mechanisms underlying antiestrogen resistance by studying the contributions of reactive oxygen species (ROS)-induced redox signaling pathways in antiestrogen resistant breast cancer cells. Our hypothesis is that the conversion of breast tumors to a tamoxifen-resistant phenotype is associated with a progressive shift towards a pro-oxidant environment of cells as a result of oxidative stress. The hypothesis of this dissertation was tested in an in vitro 2-D cell culture model employing state of the art biochemical and molecular techniques, including gene overexpression, immunoprecipitation, Western blotting, confocal imaging, ChIP, Real-Time RT-PCR, and anchorage-independent cell growth assays. We observed that tamoxifen (TAM) acts like both an oxidant and an antioxidant. Exposure of tamoxifen resistant LCC2 cell to TAM or 17 beta-estradiol (E2) induced the formation of reactive oxidant species (ROS). The formation of E2-induced ROS was inhibited by co-treatment with TAM, similar to cells pretreated with antioxidants. In LCC2 cells, treatments with either E2 or TAM were capable of inducing cell proliferation which was then inhibited by biological and chemical antioxidants. Exposure of LCC2 cells to tamoxifen resulted in a decrease in p27 expression. The LCC2 cells exposed to TAM showed an increase in p27 phosphorylation on T157 and T187. Conversely, antioxidant treatment showed an increase in p27 expression and a decrease in p27 phosphorylation on T157 and T187 in TAM exposed cells which were similar to the effects of Fulvestrant. In line with previous studies, we showed an increase in the binding of cyclin E–Cdk2 and in the level of p27 in TAM exposed cells that overexpressed biological antioxidants. Together these findings highly suggest that lowering the oxidant state of antiestrogen resistant LCC2 cells, increases LCC2 susceptibility to tamoxifen via the cyclin dependent kinase inhibitor p27.

An indigenous mixed culture of bacteria collected from a Wastewater Treatment Plant (Brits, North West Province, South Africa), biocatalytically reduced Cr(VI) in the presence of As(III). Both the reduced chromium (Cr(III)) and the oxidised arsenic (As(V)) readily form amorphous hydroxides that can be easily separated or precipitated from the aqueous phase as part of the treatment process. Treatment of Cr(VI) and As(III) before disposal of wastewater is critical since both compounds are known to be carcinogenic and mutagenic at very low concentrations, and acutely toxic at high concentrations. Batch experiments were conducted to evaluate the rate of Cr(VI) reduction under anaerobic condition in the presence of its co-contaminant As(III) typically found in the groundwater and mining effluent. Results showed near complete Cr(VI) reduction under initial Cr(VI) concentrations up to 70 mg/L in a batch amended with 20 mg/L As(III). However, increasing Cr(VI) concentrations up to 100 mg/L resulted in the inhibition of Cr(VI) reduction activity. Further investigation was conducted in a batch reactor amended with 70 mg/L Cr(VI) concentration at different As(III) concentrations ranging from 5-70 mg/L to evaluate the effect of varying As(III) concentration on Cr(VI) reduction efficiency. Results showed that Cr(VI) reduction efficiency increased as As(III) concentrations increased from 5-40 mg/L. However, further increase in As(III) concentration up to 50 mg/L resulted in incomplete Cr(VI) reduction and decrease in Cr(VI) reduction efficiency. These results suggest that the rate of Cr(VI) reduction depends on the redox reaction of As(III) and As(V) with Cr(VI). Moreover, the inhibitory effect observed at high Cr(VI) and As(III) concentration may also be attributed to the dual toxicity effect of Cr(VI) and As(III) on microbial cell. From the above batch kinetic studies lethal concentration of Cr(VI) and As(III) for these strains was evaluated and established. Initial evaluation of the bacteria using 16S rRNA partial sequence method showed that cells in the mixed culture comprised predominantly of the Gram-positive species: Staphylococcus sp., Enterobacter sp., and Bacillus sp. The biokinetic parameters of these strains were estimated using a non-competitive inhibition model with a computer programme for simulation of the Aquatic System “AQUASIM 2.0”. Microbial reduction of Cr(VI) in the presence of As(III) was further investigated in continuous-flow bioreactors (biofilm reactor) under varying Cr(VI) loading rates. The reactor achieved Cr(VI) removal efficiency of more than 96 % in the first three phases of continuous operation at lower Cr(VI) concentration ranging from 20-50 mg/L. However, 20 % decrease in Cr(VI) removal efficiency was observed as Cr(VI) concentration increase up to 100 mg/L. The reactor was able to recover from Cr(VI) and As(III) overloading phase after establishing the resilient nature of the microorganism. Similarly to the batch reactor studies the overall performance of the reactor also demonstrated that the presence of As(III) greatly enhance Cr(VI) reduction in a bioreactor. This was evident by near complete removal of Cr(VI) concentration up to 50 mg/L. The basic mass balance expressions on Cr(VI) along with the non-competitive inhibition model were used to estimate the biokinetic parameters in the continuous flow bioreactor system. Cr(VI) reduction efficiency along the longitudinal column was also evaluated in this study. Results showed that Cr(VI) efficiency increased as Cr(VI) concentration travels along the longitudinal column. Other important factors such as oxygen and pH during biological Cr(VI) reduction in the presence of As(III) oxidation were also evaluated.
Dissertation (MEng)--University of Pretoria, 2014.
tm2015
Chemical Engineering
MEng
Unrestricted

Ce manuscrit présente une étude sur les facteurs structuraux qui modulent les différences d'activité enzymatique et de comportement vis-à-vis de métaux lourds de certaines oxydoréductases à disulfure et nicotinamide (Glutathion réductase (GR), Thiorédoxine réductase (TrxR), et NADH peroxydase (NPX)). Des approches complémentaires combinant des expériences de biochimie à des spectroscopies d'absorption électronique et diffusion Raman de résonance (DRR) ont été utilisées. La réduction de la GR à deux électrons par le substrat (NADPH) ou par le produit (GSH)de la réaction aboutit à la formation de deux espèces différentes. L'étude par DRR de ces deux états réduits a montré que le noyau isoalloxazine du FAD imposait à l'enzyme un contrôle redox et une régulation de son activité via une modulation de la force d'une liaison hydrogène sur l'atome N5. L'inhibition provoquée par l'association de sels métalliques (Hg2+, Cd2+) au dithiol du site actif de la GR est expliquée par le découplage des deux centres redox de la GR (dithiol et FAD) et par une forte distorsion du noyau isoalloxazine, qui engendre des modifications profondes dans les interactions FAD-protéine. Les effets sont tout aussi importants sur la TrxR puisque l'association de ces sels déplace fortement la seconde réduction du FAD de 1 à 3 équivalents de NADPH. Elle permet également de stabiliser beaucoup plus facilement une forme semiquinonique bleue, qui serait un intermédiaire dans une voie de régulation pour cette classe d'enzymes. Les spectres de DRR des différentes espèces redox de la NPX montrent que le cycle isoalloxazine possède connue dans la GR une densité électronique faible. Elle permet la stabilisation de l'acide cystéine-sulfénique et celle du complexe de transfert de charge formé après la réduction de l'enzyme par le NADH
This manuscript presents a study on the characterization of structural factors modulating enzymatic activity and reactivity with metallic ions from members of the pyridine nucleotide disulfide-oxidoreductase family (Glutathione reductase (GR), Thioredoxin reductase (TrxR) and NADH peroxidase (NPX). Complementary techniques combining biochemical experiments, electronic absorption and resonance Raman (RR) spectroscopies have been used. The two-electron reduction of GR by the substrate (NADPH) or the product (GSH) of the enzyme reaction gives rise to the formation of two different species. RR studies of these two-electron reduced states show that isoalloxazine ring of the FAD imposes a redox control and a regulation, of enzyme activity via a hydrogen bond modulation on the N5 atom of FAD. The enzyme inhibition induced by the binding of metallic ions (Hg2+, Cd2+) on the active site dithiol of GR is explained by both an elimination of the redox coupling between the two active centers of GR (dithiol and FAD) and a strong out-of-plane distortion of isoalloxazine moiety that generates strong alterations in FAD-protein interactions. Association of the heavy metal to TrxR produces a displacement of the second redaction step of FAD from 1 to 3 equivalents of NADPH. Moreover, the formation of a blue semiquinone is stabilized. The stabilization of this radical is proposed to be a regulation way for this enzyme class. RR spectra obtained for different redox states of NPX show that the isoalloxazine ring has a low electronic density, as in the case of GR. A direct consequence is the stabilization, of the cysteine-sulfenic acid as well as a charge transfer complex formed after the enzyme redaction by NADH. For the three enzymes, this study showed an intimate electronic coupling between the two redox centers for the two electron-reduced enzymes

Abstract Lymphomas are a group of more than 70 different malignancies arising from lymphoid tissues and diffuse large B-cell lymphoma (DLBCL) is the most common subtype of lymphoma. More than 70% of DLBCL patients can be cured with modern therapy, but some patients still die of the disease. The recognition of patients with adverse prognosis, justifying deviation from standard treatment and risking severe side effects, is problematic. The aim of this study was to identify potential biological factors for the prediction of poor treatment response and central nervous system (CNS) relapse in DLBCL patients. The study included 263 lymphoma patients. 205 patients had a DLBCL, and 37 of these represented primary CNS lymphoma (PCNSL). Immunohistochemistry was used to determine the expression of oxidative stress markers 8-hydroxydeoxyguanosine (8-OHdG) and nitrotyrosine, as well as antioxidant enzymes manganese superoxide dismutase (MnSOD), thioredoxin (Trx) and gamma cysteine ligase (GCL) from samples representing reactive lymphoid tissue and B-cell derived lymphomas. From DLBCL samples staining was also conducted for cell cycle regulating proteins p16, p53, p21 and p27 and chemokine receptors CXCR4, CXCR5 and CCR7. Immunoelectron microscopy (IEM) for CXCR4 and CXCR5, and their ligands CXCL12 and CXCL13 was performed on additional samples from reactive lymphoid tissue, nodal DLBCL, secondary CNS lymphoma and PCNSL. Factors associated with adverse prognosis included expression of nitrotyrosine, Trx and GCL. A prognostic score reflecting the degree of cell cycle dysregulation within each patient’s tumour identified 3 distinct prognostic groups among DLBCL patients. High cytoplasmic CXCR5 expression was associated with CNS involvement, whereas nuclear CXCR4 expression correlated with nodal disease. These results demonstrate the considerable biological heterogeneity seen within DLBCL, but further research is needed to confirm them. High antioxidant activity and the accumulation of damage to cell cycle regulating pathways separated patient groups with a poor prognosis that might benefit from new types of treatment. Chemokine receptor expression seems to play a role in the CNS tropism of DLBCL, and, if confirmed, could in the future contribute to more effective targeting of CNS prophylactic therapies
Tiivistelmä Lymfoomat ovat yli 70 erilaisen maligniteetin muodostama ryhmä imukudoksen syöpiä, ja diffuusi suurisoluinen B-solulymfooma (engl. DLBCL) on yleisin lymfoomatyyppi. Yli 70 prosenttia DLBCL-potilaista pystytään parantamaan nykyaikaisilla hoidoilla, mutta osa potilaista kuolee edelleen tautiin. Nämä potilaat tarvitsisivat tehokkaampia hoitoja vakavien haittavaikutusten riskistä huolimatta, mutta huonon ennusteen potilaiden tunnistaminen etukäteen on vaikeaa. Tutkimuksen tavoitteena oli löytää biologisia tekijöitä DLBCL-potilaiden hoitovasteen ja taudin keskushermostossa (engl. CNS) uusiutumisen ennustamiseen. Aineisto sisältää 263 lymfoomapotilasta. 205 potilaalla on DLBCL, ja 37:llä näistä primaari aivolymfooma (PCNSL). Immunohistokemiallisilla värjäyksillä määritettiin oksidatiivisen stressin markkereiden 8-hydroksideoksiguanosiinin (8-OHdG) ja nitrotyrosiinin, sekä antioksidanttientsyymien mangaanisuperoksidi-dismutaasin (MnSOD), tioredoksiinin (Trx) ja gammakysteiiniligaasin (GCL) ilmentyminen reaktiivista imukudosta sekä B-soluperäisiä lymfoomia edustavissa näytteissä. DLBCL-näytteistä määritettiin lisäksi solusykliä säätelevien proteiinien p16, p53, p21 ja p27 sekä kemokiinireseptorien CXCR4, CXCR5 ja CCR7 ilmentyminen. Lisäksi reaktiivista imukudosta, imusolmuke-DLBCL:aa, sekundaarista CNS-lymfoomaa ja PCNSL:aa edustavista näytteistä määritettiin immunoelektronimikroskooppisesti reseptorien CXCR4 ja CXCR5 sekä ligandien CXCL12 ja CXCL13 ilmentyminen. Tulosten mukaan voimakas nitrotyrosiini-, Trx- ja GCL-positiivisuus ovat yhteydessä huonoon ennusteeseen. Solusyklin säätelyhäiriön vaikeusastetta kuvaava ennusteellinen pisteytys jaotteli DLBCL-potilaat kolmeen ennusteelliseen ryhmään. Runsas sytoplasminen CXCR5-positiivisuus oli yhteydessä CNS-tautiin, kun taas tumapositiivisuus CXCR4:lle korreloi imusolmuketautiin. Tutkimustulokset kuvaavat DLBCL:n merkittävää biologista heterogeenisyyttä, mutta tulosten varmistamiseksi tarvitaan lisää tutkimuksia. Korkea antioksidanttiaktiivisuus ja solusyklin säätelyhäiriöiden kasautuminen erottivat huonoennusteisia potilasryhmiä, jotka voisivat hyötyä uudenlaisista hoidoista. Kemokiinireseptorien ilmentyminen vaikuttaisi olevan yhteydessä DLBCL:n CNS-hakuisuuteen, ja tulosten varmistuessa ekspressioprofiilien analysointia voitaisiin tulevaisuudessa hyödyntää ennaltaehkäisevien hoitojen tehokkaammassa kohdentamisessa

As renewable energy production becomes more prevalent, the challenge of producing renewable dispatchable fuel for the transportation sector remains unresolved. One promising approach is to produce hydrogen from solar energy with a two step thermochemical cycle which utilizes an oxygen storage material (OSM) to split water through two reversible reactions. Due to the strong coupling between reactor design, operational parameters, and OSM properties, the direct comparison of two OSMs is not straightforward. In order to guide the designs of OSMs for two-step thermochemical hydrogen production, a methodology is developed to model the max performance possible for a two-step thermochemical cycle. The novel contribution of this model considers the strong coupling between reactor operation, OSM properties, and reactor performance. Next, a method for screening and evaluating new OSMs which utilizes thermogravimetric analysis (TGA) is proposed. With this data, the modeling method previously developed is applied to determine maximum reactor efficiency possible with new materials. This allows many materials to be evaluated quickly, and facilitates further characterization new OSMs. Additionally, by comparing the predicted maximum efficiency of a new material with the efficiency of current ones, this method facilitates the comparison of two different OSMs on equal footing.

Causé par un parasite du genre Plasmodium transmis par les moustiques, le paludisme est encore aujourd’hui un fléau causant des centaines de milliers de morts tous les ans. Le développement de nouvelles molécules antipaludiques et/ou l’amélioration des molécules déjà présentes sur le marché est une urgence sanitaire. Des molécules pouvant cibler tous les stades du cycle de vie du parasite seraient idéales. Ces molécules permettraient le traitement symptomatique et la prévention des rechutes mais aussi empêcheraient la transmission de la maladie. Dans ce travail, j’ai étudié le mécanisme d’action de deux molécules à activité antipaludique : la plasmodione et le proguanil. La plasmodione est en cours de développement et cible le parasite à la fois au stade sanguin et sous sa forme gamétocyte responsable de la transmission de l’homme au moustique. Le proguanil est une molécule déjà sur le marché depuis longtemps mais dont le mode d’action n’est pas encore compris bien qu’il soit un excellent partenaire synergique de l’antipaludique atovaquone, un inhibiteur du complexe bc1 de la chaine respiratoire mitochondriale. Pour cette étude, à l’aide du modèle levure, j’ai utilisé une approche génétique (construction, sélection et analyse de mutants) et biochimique (test d’activité enzymatique) afin de décrypter le mode d’action de ces molécules. Les résultats obtenus indiquent que la plasmodione est une ‘pro-drogue’ qui est transformée en métabolites actifs qui entrent ensuite dans un cycle de réactions d’oxydo-réduction (redox) produisant des espèces réactives de l’oxygène (ROS). Le stress oxydant qui en résulte provoque l’arrêt de croissance. Ces résultats sont en accord avec les données venant des études avec le parasite. J’ai montré que des flavoprotéines mitochondriales, principalement de la chaine respiratoire et du cycle de Krebs, jouent un rôle clé dans l’activité de la plasmodione. Ainsi les NADH déshydrogénases catalysent les réactions redox en utilisant les métabolites actifs de la plasmodione comme substrats aboutissant à une production de ROS. La succinate-déshydrogénase pourrait être impliquée dans la transformation de la plasmodione en métabolites actifs. Le fonctionnement de ces enzymes mitochondriales est donc requis pour que l’activité inhibitrice de la plasmodione soit observée. La mitochondrie est aussi un élément clé dans le mode d’action du proguanil. Dans une étude publiée précédemment, les auteurs avaient émis l’hypothèse que le proguanil ciblerait un système enzymatique mitochondrial participant au maintien du potentiel membranaire. Mais les résultats que j’ai obtenus ici ne semblent pas valider ce modèle. Ils conduisent plutôt à l’hypothèse que le proguanil s’accumulerait dans la mitochondrie, peut-être à de fortes concentrations. Cette accumulation affecterait des fonctions mitochondriales essentielles, résultant dans la mort de la cellule. De nombreuses questions restent ouvertes et plus de travail sera requis pour décrypter le mode d’action du proguanil
Malaria is caused by the Plasmodium parasite transmitted by mosquitoes. The disease remains today a major health issue with hundreds of thousands deaths every year. The development of new antimalarial compounds and/or the improvement of already available drugs is urgently needed. Compounds that could target all the stages of the life cycle of the parasite would be the best. Such drugs could be used in symptomatic treatment, for relapse prevention but also to block the transmission of the disease. In this work, I studied the mode of action of two antimalarial compounds, namely plasmodione and proguanil. Plasmodione is a new lead compound that targets the parasite both at the blood stage and at the gametocyte stage responsible for the transmission from human to mosquito. Proguanil has been in use for many years. Yet its mode of action is not understood although it is known to be an efficient synergistic partner of the antimalarial atovaquone that targets the mitochondrial respiratory chain bc1 complex. I used yeast as a model organism and an approach of genetics (construction, selection and analysis of mutants) and biochemistry (enzymatic activity tests) in order to decipher the mode of action of these compounds. The results indicate that plasmodione is a pro-drug transformed into active metabolites that then enter in a cycle of oxido-reductions (redox) producing reactive oxygen species (ROS). The resulting oxidative stress causes growth arrest. These data are in agreement with results obtained with the parasite. I showed that mitochondrial flavoproteins, mainly of the respiratory chain and Krebs cycle, play a key role in plasmodione activity. The NADH-dehydrogenases catalyse the redox reactions using the active plasmodione metabolites as substrates, leading to ROS production. The succinate-dehydrogenase is likely to be involved in the transformation of plasmodione in its active metabolites. Thus the functioning of the mitochondrial enzymes are required for the activity of plasmodione. The mitochondria is also a key element in the mode of action of proguanil. In a previously published report, the authors had hypothesized that proguanil would target a mitochondrial enzymatic system involved in the generation of the membrane potential. However the data I obtained do not seem to validate that hypothesis. They lead rather to the following hypothesis: proguanil would accumulate in the mitochondria, probably to high concentrations, which would affect essential mitochondrial functions leading to cell death. A number of questions remain open and more work are needed to uncover proguanil mode of action

After mineral exploitation the residual grinded and milled material, rich in sulphide minerals and heavy metals, is often left exposed to the atmospheric variables. This weathered mine waste material can lead to the formation of acid mine drainage (AMD) which has negative effects to the environment. The fractionation of stable isotope of metals such as Cu and Fe can be measured using innovative analytical techniques developed recently and could offer a detailed hindsight of the geochemical processes occurring in mine contaminated sites. Tailings profiles from Northern Sweden with high content of Cu and Fe sulphides and in different stages of weathering and/or remediation, along with plant and soil samples from a phytoremediation test site in Ronneburg, Germany were analysed using MC-ICP-MS to measure the isotope ratios of 65Cu/63Cu and 56Fe/54Fe. The analytical method used requires anion exchange chromatography to extract Cu and Fe from a complex matrix prior to the proper isotope ratio measurement. The samples from the tailings profile were useful to interpret the geochemical processes that can lead to a fractionation of Cu and Fe in the field, since redox-driven reactions such as rock oxidation and mineral precipitation are present in such environment. This study shows that precipitation of covellite in a redox-boundary zone in a mine tailings can cause a clear fractionation of Cu (Δ65Curock-covellite= -5.66±0.05‰) and a depletion of the lighter Cu isotope in the oxidised areas of the tailings due to dissolution of the remaining Cu-sulphides. Precipitation of Fe(oxy)hydroxides as a result of the oxidation process of sulphide-bearing rocks can also fractionate Fe, being the precipitated mineral slightly enriched in 56Fe.The influence of soil bacteria and plant uptake in the fractionation of Cu and Fe was investigated in pot and field experiments at the Ronneburg site, where organic amendments were used. The results showed that the plant material was enriched in the lighter Fe isotope compared to the substrate used in the pot and field experiments, in spite of the application of a bacterial consortium. Cu isotope fractionation is more susceptible to the changes in the amendments used, being those bacterial consortium, mychorriza or compost than Fe isotope fractionation. There are differences in the fractionation values in pot and field trials, regardless of the type of organic amendment applied. As an overall view, leaves are enriched in the heavier Cu isotope compared to the soils, regardless of the amendment usedThe application of the results obtained in this work would help not only to offer a view in the cycle of Fe and Cu in the surface environment, and the understanding of the (bio)geochemical processes occurring in sulphide soil surfaces. But also in the way that current remediation techniques of metal contaminated sites could be evaluated, having in mind that simplified systems show a different Cu and Fe fractionation compared to natural systems where more variables are needed to take into account.
Godkänd; 2012; 20120816 (natper); LICENTIATSEMINARIUM Ämnesområde: Tillämpad geologi/Applied Geology Uppsats: Fractionation of Cu and Fe Isotopes in Metal-Rich Mine sites: Biotic and Abiotic Processes Examinator: Professor Björn Öhlander, Institutionen för samhällsbyggnad och naturresurser, Luleå tekniska universitet Diskutant: Dr., Project Manager Magnus Land, Kungliga Vetenskapsakademien Tid: Tisdag den 25 september 2012 kl 10.00 Plats: F341, Luleå tekniska universitet

L'arsenic est un metalloïde toxique et cancérigène. Ubiquiste dans la pedosphere, il est très sensibleaux fluctuations des conditions redox du sol, ce qui influe significativement sa toxicité et mobilité. Nousétudions le cycle biogéochimique global de l'arsenic, en tenant compte de l'usage croissant des ressources, etpassons en revue l'importance respective de l'arsenic geogénique et anthropogénique dans l'environnement.La contamination à l'arsenic est souvent diffuse dans les bassins sédimentaires de l'Europe. Cependant, desconcentrations dans l'eau interstitielle du sol peuvent être élevées lors de périodes de saturation du solcausées par la monté des eaux souterraines ou les inondations, prévues d'augmenter dû aux changementsclimatiques. La spectrométrie de fluorescence X quantitative et sans standard a été utilisée pour analyserl'arsenic dans des sols relativement contaminés de la plaine alluviale de la Saône au moyen de protocoles depréparation d'échantillons conçus pour optimiser la précision d'analyse et l'exactitude in situ aux bassesconcentrations d'arsenic. L'arsenic dans ces sols est associe aux (hydr)oxydes du fer et de manganèse de lataille d'argile colloïdale. Ceux-ci subissent une dissolution réductrice par les microorganismes lors desinondations, libérant une importante concentration d'arsenic dans la phase aqueuse. Si, par la suite, l'arsenicdégagé n'est pas éliminé avec l'eau de crue évacuée, il est ré-immobilisé pendant l'oxydation du sol et lareprécipitation des oxydes métalliques. Grâce à une combinaison novatrice d'analyses chimiques par voiehumide, d'écologie microbienne, de spectroscopie ainsi que de modélisation thermodynamique et cinétique,nous démontrons que les cycles d'oxydo-réduction séquentiels entraînent une atténuation d'arsenic aqueuxdans des conditions réductrices dû à la coprécipitation croissante, et a une diminution de l'activitémicrobienne causée par l'appauvrissement en matière organique labile. Des processus d'atténuationsimilaires sont observés en l'absence d'activité microbienne pour Cr et As dans des argiles pyriteuses lorsquecelles-ci sont exposés aux oscillations redox provoquées par l'ajout de substances humiques réduites. Ainsi,nous montrons que les effets cumulatifs de cycles redox successifs sont extrêmement importants pour lamobilité de divers contaminants dans l'environnement.

Les biotechnologies sont un outil puissant permettant d’emprunter les circuits biologiques pour produire des composés aux applications multiples (médecine, alimentation, industries…). Les cyanobactéries possèdent des propriétés génétiques et trophiques précieuses pour réduire les coûts et l’empreinte environnementale de ces procédés (photosynthèse, fixation du CO₂, sources d’azote assimilables...). Elles produisent aussi naturellement certaines molécules énergétiques comme le H₂ dont pourraient émerger de nouvelles filières propres de biocarburants. Cependant, une compréhension globale et approfondie de leur physiologie est nécessaire pour concevoir un châssis biologique performant à partir de ces organismes. Elles sont aisément manipulables génétiquement mais présentent une versatilité favorisant la fixation de mutations bénéfiques mais aussi délétères pour leur exploitation à grande échelle. Au cours de ma thèse, j’ai construit et étudié des mutants d’un régulateur de l’assimilation du CO₂ dont l’activation est liée à la photosynthèse. J’ai montré que l’activité du cycle de Calvin synchronise les flux du carbone et le statut rédox de Synechocystis et que sa dérégulation se répercute de manière pléiotropique sur son métabolisme. Plus spécifiquement, je me suis intéressé au déséquilibre carbone/azote dans cette espèce et à son métabolisme de l’urée qui présente un intérêt biotechnologique considérable. J’ai démontré que ce dernier était en compétition avec l’hydrogénase pour l’insertion du nickel dans leurs centres catalytiques respectifs. L’insuffisance de ce métal a permis de sélectionner des mutants de l’uréase tolérant une exposition prolongée à l’urée et conservant une forte capacité de production de H₂ en présence de ce substrat azoté. L’ensemble de ces résultats montre que le métabolisme de Synechocystis peut être détourné au profit de certains processus cellulaires. Les approches « omiques » permettent d’identifier globalement les réponses physiologiques induites ainsi que les leviers biologiques de compensation. Ces travaux sont discutés au regard des implications biotechnologiques de l’instabilité génétique et de la nécessité de renforcer notre compréhension de la plasticité métabolique et génomique des cyanobactéries
Biotechnology is a powerful tool allowing exploitation of biological circuits to produce compounds with multiple uses (medicine, nutrition, industrial…). Cyanobacteria have valuable genetic and trophic properties which could reduce the costs and the environmental footprint of these processes (photosynthesis, CO₂ fixation, assimilation of diverse nitrogen sources…). They also naturally produce energetic molecules such as H₂ from which new and sustainable biofuels sectors may rise. However, a global and fine understanding of their physiology is required in order to design an efficient biological chassis with these organisms. They are genetically manipulable but also exhibit a strong versatility favoring fixation of mutations that can be either beneficial or harmful to their large-scale cultivation. Over the course of my PhD, I constructed and studied mutants of a CO₂ fixation regulator whose activation is linked to photosynthesis. I showed that the Calvin cycle activity synchronizes carbon fluxes and redox status in Synechocystis and that its deregulation affects the metabolism in a pleiotropic manner. I was specifically interested into the carbon/nitrogen balance in this species and its urea metabolism which is of prime interest in biotechnology. I demonstrated that the latter was in competition with the hydrogenase for the insertion of nickel into their respective catalytic centers. Scarcity of this metal leads to selection of mutants thriving upon prolonged exposure to urea that retained a high capacity of H₂ production in presence of this nitrogenic substrate. This work shows that the metabolism of Synechocystis can be altered in favor of other cellular processes. Omics approaches allow global identification of the physiological responses induced as well as the biological compensation mechanisms. These observations are discussed with regards to biotechnological implications of genetic instability and the need to strengthen our understanding of metabolic and genetic plasticity in cyanobacteria

Cette thèse démontre qu'une approche expérimentale systématique de complexité croissante permet de réévaluer le sens du potentiel redox (EH), et fournit une mise à jour sur l'interprétation de sa valeur dans les assemblages complexes de matrices minérales, des consortiums microbiens, des nutriments et des contaminants sous dynamique, oxydoréduction oscillant conditions. Pour étudier l'utilité des mesures EH dans les systèmes environnementaux saturés d'eau une cascade complète redox 500 à -350 mV (pH ~7.4) a été reproduit dans le laboratoire. Les expériences ont révélé que l'électrode de Pt classique redox répond à des processus microbiens dans une mesure différente en fonction de l'oxygénation et de la présence d'un tampon d'oxydo-réduction physique, chimique et. Les mesures du EH dans des matrices argileuses appauvris dans le tampon redox, tels que le couple électroactif Fe3 + / Fe2 +, par conséquent, se révèlent avoir une utilité limitée. Dans de tels environnements, les couples redox sensible abondantes, cependant, non électroactif, tels que O2 / H2O, CrO42- / Cr (OH) 3, NO3- / NO2- / NH 4 +, Sb (OH) 6- / Sb2O3, et HAsO42 - / H3AsO3 ne pas d'impact mesuré EH. Pour quantifier l'effet de l'oxydation des perturbations sur la mobilité des oxyanions dans la matrice argileuse, j'ai effectué des expériences de traitement par lots sous oscillations redox contrôlées. cycles successifs de conditions oxiques et anoxiques ont été imposées sur les suspensions argileuses modifiées avec un mélange d'oxyde As (V), Sb (V), Cr (VI) et N (V). la mobilité des oxyanions a été étudiée dans des conditions stériles, avec l'addition de carbone organique labile (éthanol), et avec l'addition de microbienne du sol inoculum. Spéciation analyses ont révélé des réactions irréversibles de réduction avec ou sans ajouts d'éthanol. Fraîchement réduite As (III), Sb (III), Cr (III) et N (III) ne sont pas ré-oxydée pendant les périodes subséquentes oxiques démontrant un comportement non-oscillant. Microbiologiquement induit des transformations de réduction a diminué les concentrations aqueuses de Sb et Cr par précipitation, enlevés N par volatilisation, alors préservé Comme dans la solution. En fonction de la diversité microbienne, altérées par l'addition d'inoculum dans le sol, deux types de contaminants imbrications sont caractérisés comme inhibiteurs de réduction et de non-inhibiteurs. Ces données, le représentant de l'environnement souterrain saturé (sous-sol> 20 m), est en outre par rapport à oxyanion mobilité dans l'environnement proche de la surface (la couche arable <0,15 m). Les principales différences entre les systèmes de la couche arable et du sous-sol sont dans la fraction d'oxyhydroxyde Fe-, Mn- et minéraux Al-, la diversité microbienne, pCO2, et la gamme des valeurs EH développées au cours des cycles d'oxydo-réduction. Par exemple, la gamme EH de plus de 900 mV (500 à -300 mV) dans la suspension de la couche arable est opposée à la gamme EH de 100 mV (350-250 mV) dans la suspension du sous-sol. En outre, dans la suspension de la couche arable, fort cycle redox de Fe et Mn coïncide avec la mobilité d'oscillation de As et Sb. Cette corrélation suggère le rôle crucial des minéraux oxyhydroxyde agissant non seulement comme principaux sorbants, mais aussi comme catalyseurs pour des réactions d'oxydation éventuellement contrôlant la réversibilité de la séquestration des contaminants. Par conséquent, appauvri en minéraux oxyhydroxyde, matrice argileuse est révélée environnement propice à la rétention des contaminants, car il peut supporter des oscillations périodiques redox sans libérer les contaminants de retour à la phase aqueuse sur l'échelle de temps expérimental
This thesis demonstrates that a systematic experimental approach of increasing complexity allows reassessing the meaning of the redox potential (EH), and provides an update on the interpretation of its value in complex assemblages of mineral matrices, microbial consortiums, nutrients, and contaminants under dynamic, redox-oscillating conditions. To study the usefulness of EH measurements in water-saturated environmental systems a full redox cascade from +500 to -350 mV (pH ∼7.4) was reproduced in the laboratory. The experiments revealed that conventional Pt redox electrode responds to physical, chemical, and microbial processes to a different extent depending on oxygenation and on the presence of a redox buffer. The measurements of EH in argillaceous matrices depleted in the redox buffer, such as the electroactive Fe3+/Fe2+ couple, thus, are shown to have limited usefulness. In such environments, the abundant redox-sensitive couples, yet non-electroactive, such as O2/H2O, CrO42-/Cr(OH)3, NO3-/NO2-/NH4+, Sb(OH)6-/Sb2O3, and HAsO42-/H3AsO3 do not impact measured EH. To quantify the effect of oxidizing perturbations on the mobility of oxyanions in the argillaceous matrix, I performed batch experiments under controlled redox oscillations. Successive cycles of oxic and anoxic conditions were imposed on the argillaceous suspensions amended with a mixture of oxidized As(V), Sb(V), Cr(VI), and N(V). Oxyanion mobility was investigated under sterile conditions, with the addition of labile organic carbon (ethanol), and with the addition of soil microbial inoculum. Speciation analyses revealed irreversible reduction reactions with and without ethanol additions. Freshly reduced As(III), Sb(III), Cr(III), and N(III) were not re-oxidized during subsequent oxic periods demonstrating non-oscillating behavior. Microbially induced reduction transformations decreased aqueous concentrations of Sb and Cr via precipitation, removed N via volatilization, while preserved As in the solution. Depending on microbial diversity, altered by the addition of soil inoculum, two types of contaminant interplays are characterized as inhibitory and non-inhibitory reductions. These data, the representative of saturated subsurface environment (subsoil > 20 m), is further compared to oxyanion mobility in the near-surface environment (topsoil < 0.15 m). The key differences between the topsoil and subsoil systems are in the fraction of oxyhydroxide Fe-, Mn-, and Al- minerals, microbial diversity, pCO2, and the range of EH values developed during redox cycles. For example, the EH range over 900 mV (from +500 to -300 mV) in the topsoil suspension is contrasted to the EH range of 100 mV (from +350 to +250 mV) in the subsoil suspension. Furthermore, in the topsoil suspension, strong redox cycling of Fe and Mn is coincident with the oscillating mobility of As and Sb. This correlation suggests the crucial role of oxyhydroxide minerals acting not only as major sorbents, but also as catalysts for oxidation reactions eventually controlling the reversibility of contaminant sequestration. Therefore, depleted in oxyhydroxide minerals, argillaceous matrix is shown to be suitable environment for contaminant retention, as it can stand periodical redox oscillations without releasing contaminants back to the aqueous phase on the experimental time scale

Les catalyseurs Pt-Rh supportés ont montré des propriétés intéressantes en ouverture sélective des naphtènes. Les performances catalytiques de ces catalyseurs dépendent, entre autres, de l'interaction entre le rhodium et le platine. L'objectif de ces travaux portait sur l'étude de l'influence de la méthode de préparation sur les interactions Pt-Rh. Dans ce but, plusieurs voies reposant sur des stratégies de synthèse différentes ont été sélectionnées, des plus classiques, comme l'imprégnation, aux plus sophistiquées, comme la modification d'un catalyseur monométallique parent par ajout d'un second métal par réaction de surface, la formation des particules Pt-Rh au sein de microémulsion ou de microsuspension ou encore la réduction des précurseurs métalliques assistée par radiolyse. Les catalyseurs ont été caractérisés par diverses techniques telles que la chimisorption d'hydrogène, la microscopie électronique en transmission, la réduction en température programmée, l'adsorption de molécules sondes (CO ou NO puis CO) suivie par infrarouge ou encore par réactions modèles. Ces caractérisations ont permis de mettre en évidence que (i) les imprégnations classiques ou assistées par radiolyse mènent à un mélange de particules monométalliques et bimétalliques, (ii) les méthodes de modification de surface permettent le dépôt du second métal sur les sites spécifiques des particules métalliques préformées, (iii) la synthèse des particules métalliques en microsuspension ou microémulsion permet également l'obtention de particules bimétalliques, mais avec la présence d'alliages Pt-Rh de surface
Pt-Rh supported catalysts have demonstrated interesting properties in selective ring opening of naphthenic molecules. Their catalytic performances depend on several properties like platinum-rhodium interaction. The aim of this work was to study the influence of the preparation method on Pt-Rh interactions. For this purpose, several preparation ways were selected, from the most classical ones, such as impregnation, to more sophisticated ways such as (1) surface modification of monometallic catalyst by addition of a second metal (surface reactions), (2) formation of Pt-Rh particles in microemulsion or in microsuspension, or (3) impregnation assisted by radiolysis. Catalysts were characterized by various techniques such as hydrogen chemisorption, transmission electron microscopy, temperature programmed reduction, adsorption of probe molecules (CO or NO then CO) followed by infrared spectroscopy, or model reactions.These characterizations allowed demonstrating that (i) the classical impregnation or the one assisted by radiolysis leads to monometallic and bimetallic particles, (ii) metal deposition on specific sites of preformed metallic particles can be obtained by surface modification of monometallic catalysts, (iii) the synthesis of metallic particles in microemulsion or microsuspension yields bimetallic entities with Pt-Rh alloy at the particle surface

Le paludisme reste une des maladies infectieuses les plus importantes au monde. Récemment, le laboratoire de Dr E. Davioud-Charvet a conçu des 3-Benzyl-Ménadiones substituées (benzylMD) comme agents antipaludiques prometteurs. Les études sur le mode d'action ont mis en évidenceque ces molecules déstabilisent l'équilibre redox des érythrocytes infectés en agissant comme agent catalytique redox (redox-Cycler), une stratégie prometteur pour le développement de nouveaux agents antipaludiques. Le travail de thèse présenté a caractérisé l'activité in vitro et le mécanisme d'action de tête de série, la 3-[4-(trifluorométhyl)-Benzyl]-Ménadione 1c, ce qui représente une partie principale du développement des benzylMDs. Une deuxième partie explorait les relations structure-Activité de benzylMD dérivés. Dans l'ensemble, les résultats démontrent l'activité in vitro très prometteuse de la benzylMD 1 cet soutiennent l'amélioration de benzylMDs comme nouveaux candidats-Médicaments antipaludiques
Malaria is still one of the most important infectious diseases worldwide. Previously, the laboratory of Dr. E. Davioud-Charvet presented the chemical design of very promising antimalarial agents, 3-[substituted-Benzyl]-Menadiones (benzylMD). Studies on the mode of action evidenced that these agents disturb the redox balance of the parasitized erythrocyte by acting as redox-Cyclers - a promising strategy for the development of new antimalarial agents. The presented PhD work characterized the in vitro potency and the mechanism of action of the lead agent, the 3-[4-(trifluoromethyl)benzyl]-Menadione 1 c, which represents an essential part of the lead optimization stage of the benzylMD drug development process. A second part of this work focused on the structure-Activity relationships benzylMD derivatives. Overall, the presented findings demonstrate the promising in vitro potency of lead benzylMD 1c and highly support the further development of benzylMDs as antimalarial drug candidates

With the issue of the rise of anthropogenic CO2, global warming and rise of the primary energy demand, strong measures for the energy transition and the diversification with renewables and existing fossil-based infrastructure are required. Also, carbon capture and utilization of CO2 would also be needed. In that sense, thermochemical redox cycles gain particular interest to produce synthetic fuels, which can be used for energy generation and production of chemicals. In a two-step redox cycles, metal oxides acts as oxygen carriers and undergo looping between two reactors. In the reduction reactor, metal oxide is reduced with release of oxygen (solar-thermal) or produces syngas (for fuel reduction) whereas, in oxidation, CO2/H2O splits for form syngas when in contact with the metal oxide. Ceria being readily available at large scale and due to its nature of undergoing reduction non-stoichiometrically at low temperature makes it a good candidate. In the present thesis, a detailed investigation of thermochemical dissociation of CO2 and H2O considering solar thermal and fuel reduction with a focus on non-structured reactors is carried out. For the solar-driven cycle, an assessment of counter-current flow moving bed reactors for reduction and oxidation is performed and a chemical looping (CL) unit is added to a 100 MW power plant. With an operating temperature of 1600oC and 10-7 bar pressure, a maximum power output of 12.9 MW with solar to electricity efficiency of 25.4% is calculated. This additional power would bring down the efficiency loss due to carbon capture from 11.3 to 6%. Even though a considerable efficiency is obtained on very optimistic operating conditions, it still requires a huge solar field. Economics revealed that with a carbon tax of $40/tone of CO2 the levelized cost of electricity (LCOE) achieved is 17.8 times higher than the existing market price (without carbon capture). If a higher carbon tax of 80$/MWh is considered that it would still be 6.28 times higher for a plant with a carbon tax. As an alternative, methane-driven CL unit is integrated into a power plant to access the overall system efficiency and amount of efficiency regain after carbon capture. Since there exists no solid-state kinetic model in the literature for methane driven CO2/H2O splitting cycle, an experimental investigation was performed which revealed that an Avrami-Erofe’ev (AE3) model fit best to both oxidation and reduction, with activation energies of 283 kJ/mol and 59.7 kJ/mol, respectively. A comparative assessment was performed to investigate the influence of kinetics. A CL unit based on thermodynamics and kinetics (with moving bed reactors) were tested in a power plant. A drop of 20% in the efficiency of the CL unit was observed when the kinetic-based CL unit is considered. However, due to thermal balance within the system, a similar thermal efficiency of the overall plant was achieved as 50.9%. However, when the thermodynamic-based CL unit layout is considered there exists an excess heat which predicts the possibility of improving the efficiency. An economic assessment revealed a specific overnight capital cost of 2455$/kW, a levelized cost of CO2 savings of 96.25 $/tonneCO2, and a LCOE of 128.01 $/MWh. However, with a carbon tax of 6 $/tonneCO2, the LCOE would drop below 50 $/MWh. The methane-driven CL unit is later integrated as an add-on unit to a polygeneration plant that produces electricity and dimethyl ether. The results showed that the plant can produce 103 MWe and 2.15 kg/s of DME with energy and exergy efficiency of 50% and 44%, respectively. The capital investment required for the plantis about $534 million. With the carbon tax of $40/tonne of CO2, a current DME price of $18/GJ and an electricity price of $50/MWh would be achieved. Overall, the integration of the CL unit as an add-on unit to the power plant is more suitable than polygeneration with respect to the existing market price.
El aumento del CO2 antropogénico y el calentamiento global y el aumento de la demanda de energía primaria hace que se requieran medidas para la transición energética y la diversificación con energías renovables e infraestructuras existentes basadas en combustibles fósiles. Además de implementar medidas para la captura y el secuestro de carbono, también se necesita desarrollar métodos para la utilización de CO2. En ese sentido, los ciclos redox termoquímicos son particularmente interesantes para producir combustible sintético que, a su vez, pueden utilizarse para la producción de otras substancias químicas. La rotura de CO2 / H2O (CL) mediante una vía termoquímica de dos pasos está compuesta por dos reacciones redox con un óxido metálico. El primer paso es la reducción de los óxidos metálicos al perder oxígeno y crear vacantes en la red a una temperatura más alta y convertirse en óxido de metal de valencia más baja. Durante la etapa de oxidación, los gases reactivos CO2 / H2O reaccionan con el óxido metálico reducido formando CO y H2. Se ha investigado el uso de diferentes óxidos metálicos en función de su capacidad de transporte de oxígeno y sus propiedades para realizar ciclos redox continuos a distintos valores de temperatura y presión. Después de un examen cuidadoso, se ha seleccionado a la ceria para la división de CO2 / H2O a gran escala. En el presente trabajo, se investigan las divisiones termoquímicas de CO2 / H2O impulsadas por energía solar y la reducción de metano para la producción de gas de síntesis, con especial atención a su aplicación en reactores no estructurados. Se evalúa el uso de reactores de lecho móvil basado en flujo contracorriente y reactores de lecho fluidizado que funcionan en diferentes regímenes de fluidización. Es un reactor de lecho móvil tanto para la etapa de reducción como para la etapa de oxidación se obtienen altas selectividades de CO y H2 con volúmenes óptimos del reactor, mientras que en un reactor de lecho fluidizado el volumen requerido es mucho más alto, lo que lo hace inviable. Los modelos de reactor se han desarrollado en Aspen plus y se validan a partir de la literatura. Un análisis de sensibilidad ha revelado que la unidad CL depende en gran medida de la temperatura y la presión. El análisis se ha ampliado integrando la unidad desarrollada de CL como una unidad adicional a una central eléctrica de 100 MW con captura de carbono. La eficiencia de la planta se ha investigado considerando sólo la división de CO2, sólo la del H2O y la mezcla de CO2 y H2O como alimentación al reactor de oxidación de la unidad CL. El resultado es de una potencia máxima de 12.9 MW con una eficiencia de energía solar a eléctrica de 25.4%. Esta potencia adicional reduciría la pérdida de eficiencia debido a la captura de carbono de 11.3 a 6%. Para lograr esto, el reactor de reducción de la unidad CL debe funcionar a 1600 ° C y 10-7 bar de presión. Estas condiciones necesitarían un enorme campo solar y la operación, en ausencia de almacenamiento térmico, se limitaría a unas pocas horas durante el día. El análisis técnico-económico ha revelado que el coste nivelado de la electricidad es de 1321 $/MWh sin incluir incentivos ni impuestos sobre el carbono. Posteriormente, se ha considerado la reducción del metano como una alternativa a la reducción térmica. Al principio, se realizaron análisis termodinámicos de la unidad de CL impulsada por metano. A partir del análisis, se ha demostrado que la temperatura mínima requerida es de 900°C con 50% de exceso de metano para la reducción, lo que supone una eficiencia de la unidad CL de 62% con un rendimiento óptimo de CO y H2. La división de CO2/H2O en el reactor de oxidación a una mayor temperatura de salida beneficiaría considerablemente la eficiencia energética del ciclo redox CL completo. La variación de la relación H2/CO en la salida con respecto a los parámetros de entrada variables que incluyen la composición del gas al reactor de oxidación se ha estudiado con el fin de especificar las condiciones operativas idóneas. Posteriormente, la unidad CL impulsada por metano se ha integrado como una unidad adicional a una central eléctrica de 500 MW alimentada por oxígeno. Se ha investigado el rendimiento de un sistema con un ciclo combinado de gas natural convencional con o sin captura de carbono. Se ha obtenido una eficiencia de sistema y eficiencia energética de 50.7 y 47.4%, respectivamente. La eficiencia del sistema podría mejorarse a 61.5%, sujeto a la optimización del sistema. La evaluación tecno-económica ha revelado un coste de capital durante la noche de 2455 $/kW con un coste de ahorro de CO2 de 96.25 $/tonelada CO2 y un LCOE de 128.01 $/MWh. Sin embargo, con créditos de carbono de 6 $/tonelada CO2, el LCOE caería por debajo de 50 $/MWh.
Con l'aumento delle emissioni di CO2 antropogenica che contribuiscono al riscaldamento globale e l'incremento della domanda mondiale di energia primaria, sono richieste significative misure per favorire la diversificazione delle fonti e la transizione energetica tramite fonti rinnovabili a partire dalle infrastrutture esistenti basate su combustibili fossili. Prima ancora degli interventi per la cattura e il sequestro dell’anidride carbonica, anche l’utilizzo della CO2 rappresenta una misura necessaria al raggiungimento degli obiettivi di decarbonizzazione. In questo senso, i cicli redox termochimici hanno acquisito particolare interesse per la produzione di combustibile sintetico da utilizzare come intermedio nella produzione di altri prodotti chimici. La separazione chimica di CO2/H2O attraverso un ciclo termochimico – chemical looping splitting (CL) – in due fasi è composta da due reazioni redox con un ossido di metallo. La prima fase del ciclo avviene alla temperatura più elevata e consiste nella riduzione dell’ossido di metallo, che cede ossigeno creando vacanze nel reticolo e diventando ossido di metallo a bassa valenza. Durante la fase di ossidazione, i gas reagenti CO2/H2O reagiscono con l'ossido di metallo ridotto che forma CO e H2. Una mappatura dettagliata dei diversi ossidi di metallo è stata effettuata in base alla loro capacità di trasporto dell’ossigeno e alle proprietà nei cicli di ossido-riduzione a funzionamento continuo in condizioni di variazione di temperatura e pressione. Dopo un attento esame, l’ossido di Cerio - ceria - è stato selezionato per l'applicazione che può essere disponibile per la scissione CO2 / H2O su larga scala. In questo lavoro, sia la separazione termochimica di CO2/H2O alimentata tramite energia solare, sia i cicli con riduzione tramite metano, entrambi finalizzati all produzione di syngas sono stati studiati con particolare attenzione ai reattori non strutturati. Per il ciclo termochimico basato su energia solare, è stata effettuata la valutazione dei reattori a letto mobile a flusso in controcorrente e a letto fluido che operano in diversi regimi di fluidizzazione. Il reattore a letto mobile è stato individuato come il più performante sia per la riduzione che l’ossidazione, con elevate selettività verso CO e H2 e volumi ottimali del reattore, mentre una resa analoga con reattori a letto fluidizzato potrebbe essere ottenuta solo con volumi di reattore molto alti, rendendo questa scelta irrealizzabile nella pratica. I modelli di reattore sono stati sviluppati in Aspen plus e sono stati validati dalla letteratura. Un'analisi di sensitività ha rivelato che la performance dell'unità CL è in larga misura dipendente dalla temperatura e dalla pressione di riduzione. L'analisi è stata estesa integrando l'unità CL sviluppata come unità aggiuntiva di una centrale elettrica a ossicombustione da 100 MW con cattura di carbonio. L'efficienza dell'impianto è stata studiata considerando di alimentare il reattore di ossidazione dell'unità CL sia con CO2, sia con H2O, sia con una miscela di CO2 e H2O. I risultati indicano una potenza massima di 12,9 MW con un rendimento da solare a elettricità del 25,4% generabile grazie all’unità di CL. Questa potenza aggiuntiva ridurrebbe la perdita di efficienza dovuta alla cattura di carbonio dall'11,3 al 6%. Per ottenere ciò, il reattore di riduzione dell'unità CL deve operare a 1600 ° C con una pressione di 10-7 bar. Queste condizioni avrebbero bisogno di un enorme campo solare e l'operazione sarebbe limitata a poche ore durante il giorno senza l’integrazione di un accumulo termico. L'analisi tecno-economica ha rivelato che il costo livellato (levelizad cost) dell'elettricità era di 1321 $ / MWh, senza includere incentivi o tassazione sul carbonio. Successivamente, è stata considerata la riduzione della ceria con metano come alternativa alla riduzione termica. Inizialmente, sono state condotte analisi termodinamiche dell'unità CL con riduzione a metano. Dall'analisi è emerso che la temperatura minima richiesta era 900 °C per la riduzione con un eccesso di metano del 50%, che ha prodotto un'efficienza dell'unità CL del 62% con una resa ottimale di CO e H2. In questo caso, la scissione di CO2/H2O nel reattore di ossidazione consisteva nell'ossidazione completa esotermica della ceria, per cui una temperatura di uscita più elevata avrebbe notevolmente migliorato l'efficienza energetica del ciclo CL redox completo. La variazione del rapporto H2 / CO all'uscita rispetto ai vari parametri di input, compresa la composizione del gas inviato al reattore di ossidazione, è stata studiata per specificare le condizioni operative necessarie. Successivamente, l'unità CL a metano è stata integrata come unità aggiuntiva in una centrale elettrica a ossicombustione da 500 MW. Sono state studiate le prestazioni del sistema in una valutazione comparativa con un ciclo combinato convenzionale a gas naturale, un ciclo a ossicombustione con cattura di carbonio e l'impianto proposto. Sono stati ottenuti per l’impianto rispettivamente un rendimento del sistema e un'efficienza energetica del 50,7% e del 47,4%. L'efficienza del sistema potrebbe essere migliorata fino al 61,5% tramite l'ottimizzazione del recupero termico del sistema, valutata attraverso la pinch analysis del sistema. Una dettagliata valutazione tecno-economica ha rivelato un costo specifico del capitale di 2455 $ / kW (overnight cost), un costo livellato delle emissioni di CO2 evitate 96,25 $ / tonnellata di CO2, e un costo dell’elettricità (LCOE) di 128,01 $ / MWh. Tuttavia, considerando un incentivo di 6 $ / tonnellata di CO2 evitata, il LCOE scenderebbe sotto i 50 $ / MWh. L'unità CL a metano viene successivamente integrata come unità aggiuntiva in un impianto di poligenerazione che produce elettricità e dimetil-etere. I risultati hanno mostrato che l'impianto può produrre 103 MWe e 2,15 kg/s di DME con un’efficienza energetica ed exergetica del 50% e del 44% rispettivamente. L'investimento di capitale richiesto per l'impianto ammonta a 534 M$. Con un valoré per la carbon tax di $ 40 / tonnellata di CO2, il DME e l’elettricità raggiungerebbero la parità con gli attuali prezzi di mercato, pari a $18/GJ per il DME e $50/MWh per l’elettricità. I costi risultanti sono dovuti all'unità di separazione dell'aria richiesta per la centrale elettrica a ossicombustione e può essere ridotta sostituendo l'unità di separazione dell'aria con una tecnologia a membrana per la separazione dell'ossigeno. Poiché in letteratura non esiste un modello completo per cinetica dello stato solido che descriva la riduzione con metano della ceria, esso è stato ricavato per via sperimentale. Sono stati condotti esperimenti in un reattore tubolare orizzontale a letto fisso in un intervallo di temperatura di 900-1100 °C. E’ stata studiata la cinetica della scissione della CO2, essendo una reazione più complessa rispetto alla scissione dell'acqua, la cui cinetica è stata invece ottenuta dalla letteratura. In base all’analisi sperimentale condotta, il modello cinetico Avrami-Erofe'ev (AE3) è risultato essere il migliore per entrambe le reazioni, con le rispettive energie di attivazione ottenute rispettivamente come 283 kJ/mol e 59,68 kJ/mol. L'ordine della reazione è stato ricavato come relazione tra temperatura e concertazione dei reagenti. L'analisi è stata effettuata seguendo un approccio termodinamico, ma la reazione eterogenea dell'ossido di metallo e dei gas reagenti limita il raggiungimento dell'equilibrio durante la reazione e dipende sempre dal tipo di reattore scelto per x l'applicazione. Pertanto, un modello di reattore a letto mobile è stato sviluppato considerando la riduzione del metano ottenuta sperimentalmente e la cinetica di splitting della CO2 è stata incorporata per valutare i due impianti proposti: la centrale elettrica e l'impianto di poligenerazione. È stata osservata una riduzione del 20% nell'efficienza dell'unità CL. Tuttavia, grazie all’integrazione termica interna al sistema, l’efficienza termica dell'impianto complessivo è molto simile a quella raggiunta nell’analisi termodinamica, con un valore del 50,9%. Tuttavia, a differenza del layout termodinamico, non è disponibile calore in eccesso per migliorare ulteriormente l'efficienza del sistema. Oltre al riciclo e all'utilizzo della CO2, come criteri di valutazione della sostenibilità per il layout proposto sono stati analizzati anche l’occupazione del suolo terreno e il fabbisogno idrico. Sia il fabbisogno di terra che di acqua aumentano di 2,5 volte rispetto ad una centrale convenzionale a ciclo combinato a gas naturale. Inoltre, anche l’impianto di poligenerazione con produzione di energia elettrica e dimetil etere (DME) è stato studiato considerando un modello dell’unità CL basato sulla cinetica e ha rilevato che la produzione di DME scenderebbe da 2,15 kg/s a 1,48 kg/s e la potenza elettrica prodotta da 103 a 72 MW. Pertanto, la cinetica ha una forte influenza sulla prestazione complessiva del sistema, e considerarla nell’analisi porta a ridurre la produzione di energia e DME di circa il 30% con un aumento di costo del 30%. Complessivamente, l'integrazione dell'unità CL come unità aggiuntiva ad una centrale elettrica a ossicombustione risulta più adatta rispetto alla poligenerazione, considerando il prezzo di mercato attuale per le commodities prodotte.

Microbial metal reduction contributes to biogeochemical cycling, and reductive precipitation provides the basis for bioremediation strategies designed to immobilize radionuclide contaminants present in the subsurface. Facultatively anaerobic ×-proteobacteria of the genus Shewanella are present in many aquatic and terrestrial environments and are capable of respiration on a wide range of compounds as terminal electron acceptor including transition metals, uranium and transuranics. S. putrefaciens is readily cultivated in the laboratory and a genetic system was recently developed to study U(VI) reduction in this organism. U(VI) reduction-deficient S. putrefaciens point mutant Urr14 (hereafter referred to as CCMB1) was found to retain the ability to respire several alternate electron acceptors. In the present study, CCMB1 was tested on a suite of electron acceptors and found to retain growth on electron acceptors with high reduction potential (E¡¬0) [O2, Fe(III)-citrate, Mn(IV), Mn(III)-pyrophosphate, NO3-] but was impaired for anaerobic growth on electron acceptors with low E¡¬0 [NO2-, U(VI), dimethyl sulfoxide, trimethylamine N-oxide, fumarate, ×-FeOOH, SO32-, S2O32-]. Genetic complementation and sequencing analysis revealed that CCMB1 contained a point mutation (H108Y) in a CcmB homolog, an ABC transporter permease subunit required for c-type cytochrome maturation in E. coli. The periplasmic space of CCMB1 contained low levels of cytochrome c and elevated levels of free thiol equivalents (-SH), an indication that redox homeostasis was disrupted. Anaerobic growth ability, but not cytochrome c maturation activity, was restored to CCMB1 by adding exogenous disulfide bond-containing compounds (e.g., cystine) to the growth medium. To test the possibility that CcmB transports heme from the cytoplasm to the periplasm in S. putrefaciens, H108 was replaced with alanine, leucine, methionine and lysine residues via site-directed mutagenesis. Anaerobic growth, cytochrome c biosynthesis or redox homeostasis was disrupted in each of the site-directed mutants except H108M. The results of this study demonstrate, for the first time, that S. putrefaciens requires CcmB to produce c-type cytochromes under U(VI)-reducing conditions and maintain redox homeostasis during growth on electron acceptors with low E¡¬0. The present study is the first to examine CcmB activity during growth on electron acceptors with widely-ranging E¡¬0, and the results suggest that cytochrome c or free heme maintains periplasmic redox poise during growth on electron acceptors with E¡¬0 < 0.36V such as in the subsurface engineered for rapid U(VI) reduction or anoxic environments dominated by sulfate-reducing bacteria. A mechanism for CcmB heme translocation across the S. putrefaciens cytoplasmic membrane via heme coordination by H108 is proposed.

Thesis: Ph. D., Massachusetts Institute of Technology, Department of Mechanical Engineering, 2016.
Cataloged from PDF version of thesis.
Includes bibliographical references (pages 224-229).
A number of CO₂ capture-enabled power generation technologies have been proposed to address the negative environmental impact of CO₂ emission. An important barrier to adopting these technologies is the associated energy and economic penalties. Chemical-looping (CLC) is an oxycombustion technology that can significantly lower such penalties, utilizing a redox process to eliminate the need for an air separation unit and enable better energy integration. Conventional CLC employs two separate reactors, with metal oxide particles circulating pneumatically in-between, leading to significant irreversibility associated with reactor temperature difference. A rotary reactor, on the other hand, maintains near-thermal equilibrium between the two stages by thermally coupling channels undergoing oxidation and reduction. In this thesis, a multiscale analysis for assessing the integration of the rotary CLC reactor technology in power generation systems is presented. This approach employs a sequence of models that successively increase the resolution of the rotary reactor representation, ranging from interacting thermal reservoirs to higher fidelity quasi-steady state models, in order to assess the efficiency potential and perform a robust optimization of the integrated system. Analytical thermodynamic availability and ideal cycles are used to demonstrate the positive impact of reactor thermal coupling on system efficiency. Next, detailed process flow-sheet models in which the rotary reactor is modeled as a set of interacting equilibrium reactors are used to validate the analytical model results, identify best cycle configurations and perform preliminary parametric analysis for between the reactor and the system while maintaining computational efficiency, an intermediate fidelity model is developed, retaining finite rate surface kinetics and internal heat transfer within the reactor. This model is integrated with a detailed system model and used for optimization, parametric analysis and characterization of the relative techno-economic performance of different oxygen carrier options for thermal plants integrated with the rotary CLC reactor. Results show that thermal coupling in the redox process increases the efficiency by up to 2% points for combined, recuperative and hybrid cycles. The studies also show that the thermal efficiency is a function of the reactor purge steam demand, which depends on the reactivity of the oxygen carrier. While purge steam constitutes a monotonic parasitic loss for the combined cycle, for recuperative and hybrid cycles, it raises the efficiency as long as the steam demand is less than a threshold value. This relationship between reactivity and system efficiency provides a useful selection criteria for the oxygen carrier material. Optimization results based on efficiency and levelized cost of electricity (LCOE) identify nickel-based oxygen carriers as the most suitable for the rotary reactor because its high reactivity ensures low steam demand and reactor cost. Compared to nickel, maximum efficiency and minimum LCOE are respectively 7% lower and 40% higher for a copper-based system; iron-based systems have 4% higher maximum efficiency and 7% higher minimum LCOE. This study also showed that optimal efficiency generally has an inverse profile to that for the optimized LCOE.
by Chukwunwike Ogbonnia Iloeje.
Ph. D.

The chemistry of transition metal clusters has been a fast developing area of organometallic research in recent years. Compared to mononuclear metal complexes, polynuclear clusters offer more opportunities to study cooperative effects and electron reservoir properties between contiguous metal centers, in addition to functioning as storehouses for the release of catalytically active small fragments capable of exhibiting heterosite subtrate activation. Theoretically, metal clusters are intermediates between mononuclear complexes and metal surfaces, i.e., they serve as a bridge between molecular and solid-state chemistry. Transition metal clusters are ideal candidates to study M-M interactions stretching from the single bond to the collective metallic behavior found in a three-dimensional network of metal atoms. The reaction between the redox-active diphoshpine ligand bpcd and RU(CO) has been examined under a variety of conditions. The disubstituted cluster Ru3(CO)10(bpcd)(2) has been synthesized and shown to contain a chealating bpcd ligand, on the basis of IR and 31P NMR data. The cluster 2 (chelating isomer) undergoes cluster fragmentation at ambient temperatures in the dark to give the binuclear compound 3 and Ru3(CO)12, with no evidence for the formation of 4. Both 3 and 4 have been isolated and fully characterized in solution by IR and NMR spectroscopy, and the solid-state structure of each new binuclear compound has been established by X-ray diffraction analysis. Independent experiments reveal that dinuclear 3 is converted to 4 by 366 nm light with a quantum efficiency of .0364.

Le relargage de phosphore sédimentaire constitue une source interne de nutriments dans les eaux conduisant à l’eutrophisation des milieux aquatiques, en particulier des retenues. Les connaissances actuelles concernant le relargage du P sédimentaire ne tiennent pas compte de la fraction colloïdale, qui est pourtant considérée comme une importante phase porteuse de P, très mobile et potentiellement biodisponible. Cette thèse souligne le rôle majeur des colloïdes sédimentaires vis-à-vis de leur teneur en phosphore ainsi que leur fort potentiel à être mobilisé dans l’eau. Il a été démontré que les colloïdes sont une composante intrinsèque essentielle des sédiments au sein du barrage de Champsanglard (Creuse, France) et qu’ils peuvent être remobilisés à hauteur de 2.3 % de la masse totale du sédiment lors de la resuspension de ce dernier. Le phosphore colloïdal représentait jusqu’à 6 % du phosphore sédimentaire total et 80 % du phosphore total mobilisable. L’étude des différents protocoles d'extraction, de séparation et de conservation des sédiments a permis de proposer une méthodologie opérationnelle permettant la sélection du protocole le plus approprié. Il est ainsi recommandé de réaliser les extractions de colloïdes sur sédiment humides, par une méthode douce (agitation) et de réaliser la séparation des colloïdes extraits par filtration avec une étape de pré-séparation. Les centrifugations successives sont déconseillées car elles conduisent à une estimation biaisée de la quantité et de la qualité des colloïdes extraits. Au travers de l’étude de la retenue de Champsanglard, il a été mis en évidence une forte hétérogénéité de la répartition spatiale de la quantité et de la qualité des colloïdes sédimentaires et du P associé. La granulométrie des sédiments, l'hydrodynamique des écoulements, la présence d'affluents et le marnage apparaissent comme des facteurs clés. La plus importante quantité de colloïdes mobilisables et en particulier les colloïdes de plus grande taille (0.2 – 1 μm) concerne les sédiments lacustres des zones profondes, en amont de la confluence avec les tributaires. Les sédiments de berge régulièrement impactés par le marnage de l’eau relarguent du phosphore sous une forme biodisponible (forme dissoute et nano/petits colloïdes). En condition anoxique, les sédiments ont la capacité de libérer du phosphore colloïdal, dans des proportions largement supérieures au phosphore dissous. Jusqu’à 40 % du phosphore sédimentaire total a ainsi été remobilisé sous forme colloïdale. Lorsque les conditions redeviennent oxiques, une majeure partie du phosphore mobilisé persiste en solution et notamment sous la forme de colloïdes de tailles petites et intermédiaires (300 KDa - 0.45 μm). En conditions d’oxydo-réduction variables, les processus biogéochimiques impliquant le fer et la matière organique seraient les paramètres clés contrôlant la mobilité du P colloïdale. Ce travail met en évidence la nécessité de considérer la contribution des colloïdes pour l’évaluation de la mobilité et de la biodisponibilité du P, en particulier en contexte de retenue de barrage
The mobilization of phosphorus (P) from sediment is a persistent internal nutrient source sustaining eutrophication, especially in reservoir. Current knowledge about sedimentary P release does not consider colloidal form, although it is well-known for its efficiency as P-carrier, its high mobility and potentially bioavailability. This thesis provides new constraints to place sedimentary colloids and sedimentary colloidal P into light concerning their important stock and release potential in the reservoir. Colloids are shown to be an intrinsic component of reservoir sediment, and their recovery under sediment resuspension indicated the contribution of water mobilizable colloids up to 2.3 % of the sediment mass in Champsanglard dam reservoir (Creuse, France). The amount of P associated with colloids was up to 6 % of total sedimentary P and 80 % of water-mobilizable P. After the application of different protocols for colloid extraction, separation and for sediment storage, a framework for selecting appropriated method for colloid recovering from a sediment is proposed. The recommendation for colloid recovery is to work with wet sediment, avoid using high-power extraction protocol (i.e. sonication), using filtration with pre-separation step instead of successive centrifugation to avoid under or overestimation in quantity and quality of recovered colloids. The quantity and quality of sedimentary colloids and associated P varied spatially in the reservoir according to sediment size grain distribution and the influence of flow hydrodynamics, the presence of tributaries and fluctuations in the water-level. The highest content of water mobilizable colloids and especially large colloids (0.2 - 1 μm) were found in lacustrine bottom sediments, downstream of the tributary confluence. Bank sediments impacted by water-level fluctuations released P in bioavailable forms (dissolved P and small/nano P-colloids). Under anoxic condition, the potential of sediment to mobilize colloidal P was significantly higher than truly dissolved P and represented up to 40 % of total sedimentary P. When condition became oxic subsequently, major portion of released P remained in suspension under small/intermediate size (300 kDa - 0.45 μm). In redox changing conditions, the closely linked biogeochemical cycles of iron and organic matter could be the key parameters involved in mobility of colloidal P. This thesis highlights the need to consider colloids and their contribution in the P mobility at the boundary of sediment-water and associated bioavailability to aquatic plankton, particularly in dam reservoir context

L'élucidation des propriétés du réseau métabolique est fondamentale pour la compréhension du fonctionnement cellulaire et pour l'élaboration de stratégies d'ingénierie métabolique. L'objectif de cette thèse était de mieux comprendre la régulation du métabolisme du NADPH, un métabolite "hub" qui joue un rôle central dans de nombreux processus cellulaires, chez Saccharomyces cerevisiae en fermentation. Nous avons utilisé une démarche systématique couplant modélisation et approches multi-“omics” pour étudier de façon quantitative la réponse à une perturbation de la demande en NADPH. Un système expérimental original, basé sur l'expression d'une butanediol déshydrogénase modifiée NADPH-dépendante a été utilisé pour augmenter de façon contrôlée la demande en NADPH. L'utilisation de ce dispositif, le développement et l'utilisation d'un modèle stœchiométrique de la levure dédié à la fermentation ont permis de prédire la répartition des flux pour différents niveaux de perturbation. Ces analyses ont montré, en premier lieu, la très grande capacité de la levure à faire face à des demandes très importantes de NADPH représentant jusqu'à 40 fois la demande anabolique. Pour des demandes modérées (allant jusqu'à 20 fois la demande anabolique), la perturbation est principalement compensée par une augmentation du flux à travers la voie des pentoses phosphate (VPP) et à moindre titre à travers la voie acétate (Ald6p). Pour une forte demande en NADPH, correspondant à 40 fois la demande anabolique, le modèle prédit la saturation de la VPP ainsi que la mise en place du cycle glycérol-DHA, qui permet l'échange du NADH en NADPH. Des analyses fluxomique (13C), métabolomique et transcriptomique, ont permis de valider ces hypothèses et de les compléter. Nous avons mis en évidence différents niveaux de régulation selon l'intensité de la perturbation : pour les demandes modérées, les flux sont réajustés par un contrôle au niveau enzymatique ; pour de fortes demandes, un contrôle transcriptionnel de plusieurs gènes de la VPP ainsi que de certains gènes des voies de biosynthèse des acides aminés est observé, cet effet résultant probablement de la moindre disponibilité en NADPH. Dans l'ensemble, ce travail a apporté un nouvel éclairage sur les mécanismes impliqués dans l'homéostasie du NADPH et plus généralement dans l'équilibre redox intracellulaire
The elucidation of the properties of metabolic network is essential to increase our understanding of cellular function and to design metabolic engineering strategies. The objective of this thesis was to better understand the regulation of the metabolism of NADPH, a “hub” metabolite which plays a central role in many cellular processes in Saccharomyces cerevisiae during fermentation. We used a systematic approach combining modeling and multi-“omics” analyses to study quantitatively the response to a perturbation of the NADPH demand. An original experimental system, based on the expression of a modified NADPH-dependent butanediol dehydrogenase was used to increase the demand for NADPH in a controlled manner. Through the use of this device and the development and use of a stoichiometric model of yeast dedicated to the fermentation, we predicted the flux distribution for different levels of perturbation. These experiments showed, first, the overwhelming ability of yeast to cope with very high NADPH demand, up to 40 times the anabolic demand. For a moderate level (up to 20 times the anabolic demand), the perturbation is mainly compensated by increased flux through the pentose phosphate pathway (PPP) and to a lesser extent through the acetate pathway (Ald6p). For a high NADPH demand, corresponding to 40 times the anabolic demand, the model predicts the saturation of the PPP as well as the operation of the glycerol-DHA cycle, which allows the exchange of NADH to NADPH. Fluxomics (13C), metabolomics and transcriptomics data were used to validate and to complement these hypotheses. We showed different levels of control depending on the intensity of the perturbation: for moderate demands, flux remodeling is mainly achieved by enzymatic control; for a high demand, a transcriptional control is observed for several genes of the PPP as well as some genes of the amino acids biosynthetic pathways, this latter effect being likely due to the low NADPH availability. Overall, this work has shed new light on the mechanisms governing NADPH homeostasis and more generally the intracellular redox balance

Notre thèse se propose de démontrer dans quelle mesure et par quels procédés Alves Redol s’inspire de la crise viticole du Alto Douro (1907-1915) sous ses aspects humains, politiques et socio-économiques pour élaborer l’architecture de sa trilogie. Cette problématique permet de découvrir combien la possession et la dépossession de la terre sont incontestablement deux axes fondamentaux qui décident du sort des protagonistes. Ce travail consiste à s’interroger sur les différents mécanismes qui sont au début de cette crise viticole, qui ont engendré un déséquilibre économique et par conséquent, d’importants changements tant au niveau de l’organisation sociale qu’au niveau des rapports sociaux. L’objectif de ce travail est de montrer comment la terre schisteuse du Douro, productrice du vin de Porto, façonne foncièrement l’homme dans sa dépendance fatale de la rigueur inexorable des saisons. Les viticulteurs dans la trilogie redolienne, et par le biais de l’intertextualité, sont aux prises avec une multitude de difficultés dues à plusieurs éléments : facteurs législatifs (signature d’un traité de vente de vin avec et en faveur de l’Angleterre) ; facteurs naturels (sous-production avec le phylloxéra et le mildiou) ; facteurs humains (surproduction et mévente avec la concurrence et surtout avec la contrefaçon du vin de Porto). Dans le sillage des théories marxistes-léninistes et du matérialisme dialectique, nous avons tenté de montrer que, malgré les procédés d’animalisation et de perspectives de privations continuelles des viticulteurs et des sans terre par les détenteurs des moyens de production, la masse rurale unie, réussit à se révolter contre l’exploitant et pour un nouvel ordre social
Our thesis intends to prove to what extent and by what processes Alves Redol inspired by the Alto Douro wine-growing crisis (1907-1915) in its human, political and socio-economic dimensions to develop the architecture of his trilogy. Posing the problem in this fashion enables us to highlight that land ownership and dispossession are unquestionably two main axes which have an influence on the protagonists’fate. Our work examines the different mechanisms at the root of the wine-growing crisis, which created an economic imbalance, and consequently important changes in social organization as well as social relationships. This work aims at showing how the Upper Douro’s schistose soil, a key element in Porto wine production, also fundamentally fashions man and makes him dependent on the rigour of the cycle of seasons. In Redol’s trilogy, wine-growers, through the intertextuality process, are confronted with many difficulties due to various elements, whether they be legislative (the signing of a wine sales treaty in favour of England), natural (underproduction caused by phylloxera and mildew), or human (overproduction and bad sales due to competition and counterfeiting of Port wine). In keeping with Marxist-Leninist theories and dialectic materialism, we intend to show that, in spite of the dehumanization process and constant deprivation of wine-growers and landless people by those who control means of production, the united rural world succeeded in rebelling against its exploiters to achieve a new social order

Ce mémoire présente l'étude du fonctionnement des cycles enzymatiques en milieu hétérogène et en milieu homogène. En milieu hétérogène, nous avons développé, en partant de l'analyse SeCDAR et des approches antérieures, l'étude des systèmes enzymatiques de transport actif primaire, transmembranaire d'électrons et de protons. Deux réactions d'oxydo-réduction reliées par un transporteur-médiateur forment le modèle de base; ses variantes sont identifiables par le nombre d'enzymes et de co-facteurs. Nous les avons explorées expérimentalement, par modélisation mathématique électrochimique et cinétique et par simulation numérique. Les corrélations entre les enzymes, le flux de transport actif, les potentiels redox, la concentration des transporteurs, la sélectivité de la membrane, les conditions de transport et de réversibilité de tous les systèmes sont décrites, en utilisant les réactions réversibles et irréversibles. Deux exemples typiques correspondant au modèle théorique sont analysés et expérimentés. En milieu homogène, nous avons montré l'influence de la catalase, du pH et de la superoxyde dismutase (SOD) sur le mécanisme de la réaction de consommation de NADH, catalysée par la peroxydase. A pH 7,5, la linéarité entre la consommation totale de NADH et les concentrations de SOD et H2O2 d'une part, ou la linéarité de la relation cinétique de Lineweaver et Burk d'autre part, donne deux méthodes de dosages de H2O2, produit notamment par les réactions enzymatiques. On les illustre dans le dosage à la glucose oxydase du glucose aqueux et urinaire

On retrouve des contaminations d’aquifèr à l’arsenic dans touts les deltaï de l'Asie du Sud-Est, y compris dans le delta du Mékong, ce qui affecte la santé de millions de personnes. L’arsenic est très sensible aux fluctuations des conditions redox qui sont générés par les cycles alternés humides/secs pendant la saison de mousson. Une étude sur les caractéristiques géophysiques et chimiques du sol et des eaux souterraines dans le district de An Phu, dans le haut du delta du Mékong au Vietnam, suggère une forté contamination à l’As dans cette région. Les données chimiques et géophysiques indiquent une forte corrélation entre concentrations dans les eaux souterraines anoxiques et conductivité des sols. La liberation de l’arsenic est associée à la dissolution réductrice induih par des microorganisms des colloïdes et (oxyhydr)oxydes de fer dans des conditions d'oxydo-réduction oscillantes. La présence de bactéries sulforéductrices a le potentiel de stabiliser l’arsenic dans la phase solide et de l’atténuer dans la phase aqueuse par adsorption / désorption de l’arsenic sur les (oxyhydr)oxydes, et / ou sulfures de fer via la formation de complexes thiols. En raison de la teneur en pyrite élevée dans les sédiments, l'oxydation de la pyrite peut abaisser le pH et conduire à l'inhibition de la réduction microbienne du sulfate et aime empêcher la séquestration de l’arsenic dissous. Bien que le cycle biogéochimique de l’arsenic dans un système dynamique d’oxydoréduction soit une problématique complexe, il a été possible de renforcer notre compréhension de ce système
Aquifer arsenic (As) contamination is occuring throughout deltaic areas of Southeast Asia, including the Mekong Delta, and affects the health of millions of people. As is highly sensitive to fluctuations of redox conditions which are generated by the alternating wet-dry cycles during the monsoonal seasons. A survey of geophysical and chemical characteristics of soil and groundwater in the An Phu district, located in the vicinity of the Mekong Delta in Vietnam, shows the occurrence high As aqueous concentration in this region. Chemical and geophysical data indicate a strong positive correlation between As concentrations in the anoxic groundwater and conductivity of soils. In addition, mechanisms of As release are shown to be associated with colloidal and iron (oxyhydr)oxides which undergo microbial mediated reductive dissolution under redox oscilatting conditions. The presence of sulfate microbial reduction potentially stabilizes As in the solid phase and diminish As in the aqueous phase through the adsorption/desorption of As onto iron (oxyhydr)oxides and/ or sulfides with formation of thiols complexes in solid phase. Because of the high pyrite content in sediment, pyrite oxidation may drop in pH values, leads to inhibition of sulfate reducing bacteria and reduces sequestration of dissolved As. Although the biogeochemical cycling of redox sensitive species such as As in dynamic systems is challenging, it has been possible to strengthen our collective understanding of such system

Cette étude se focalise sur le développement de procédés de dissociation de H2O et CO2 par voie thermochimique utilisant des oxides métalliques non-stœchiométriques et l’énergie solaire concentrée pour la production de carburants solaires. Les procédés redox se décomposent en deux réactions distinctes : tout d’abord, une réduction thermique à haute température de l’oxyde métallique avec la création de lacunes en oxygène dans la structure cristallographique, entrainant une production d’oxygène ; puis, une réoxydation de l’oxyde métallique par H2O et/ou CO2, conduisant à la production de H2 et/ou CO. La cérine et les pérovskites ont été étudiées comme matériaux réactifs pour les cycles thermochimiques. Pour augmenter l’efficacité des cycles thermochimiques, différents paramètres ont été étudiés, comme la composition chimique et la morphologie de l’oxyde réactif, les conditions opératoires, ainsi que la configuration du réacteur solaire. Dans un premier temps, les activités redox, la cinétique et la thermodynamique de différentes pérovskites ont été étudiées expérimentalement pour les cycles redox. Par la suite, les performances thermochimiques de différents matériaux réactifs sous forme de structures poreuses ou de particules ont été étudiées dans des réacteurs solaires (configuration monolithique ou lit fixe) permettant de réaliser des cycles thermochimiques en deux étapes. Une étude paramétrique détaillée a été effectuée pour déterminer les taux et vitesses de production. La vitesse de production de CO la plus élevée (9.9 mL/min/g) a été obtenue avec des mousses réticulées en cérine. Enfin, un réacteur solaire membranaire a été développé pour produire en isotherme et en continu du CO (ou H2) par dissociation de CO2 (ou H2O) avec une membrane réactive et perméable à l’oxygène. La vitesse de production la plus élevée atteint 0.133 µmol/cm2/s à 1550 °C en utilisant une membrane en cérine avec un revêtement en pérovskite
This study is focused on the development of thermochemical H2O and CO2 splitting processes using non-stoichiometric metal oxides and concentrated solar energy to produce solar fuels. The redox process is composed of two distinct reactions: first, a thermal reduction at high temperature of the metal oxide with creation of oxygen vacancies in the crystallographic structure, resulting in released oxygen; second, the re-oxidation of the metal oxide by H2O and/or CO2, leading to H2 and/or CO production. Ceria and perovskite materials have been investigated as reactive oxides for thermochemical cycles. To increase the thermochemical process efficiency, different aspects were investigated, such as chemical composition and morphology of the metal oxide, operating parameters, and solar reactor configuration. The redox activities, kinetics and thermodynamics of different perovskite materials were first experimentally investigated for two-step thermochemical cycles. Then, the thermochemical performances of various reactive materials shaped as porous structures or particulate media were investigated in solar reactors (monolithic or packed-bed configurations) able to perform two-step thermochemical cycles. A detailed parametric study was performed to determine fuel production rates and yields. The highest CO production rate (9.9 mL/min/g) was achieved with ceria reticulated foams. Finally, a solar membrane reactor was developed for isothermal and continuous production of CO (or H2) by CO2 (or H2O) splitting with a reactive and oxygen-permeable membrane. The highest CO production rate reached 0.133 µmol/cm2/s at 1550 °C using a perovskite-coated ceria membrane

La demande croissante d'énergie au niveau mondial fait que les énergies obtenues de ressources renouvelables connaissent un essor important, notamment dans la production globale d'électricité propre (ne générant pas des gaz à effet de serre, tels les combustibles fossiles enrichis en carbone). La nature 'intermittente' de ces ressources renouvelables d'énergie implique l'utilisation des dispositifs de stockage de grande échelle, efficaces et économiquement compétitifs. Les batteries à circulation, tout vanadium (VRFB) sont des dispositifs de stockage prometteurs pour les applications stationnaires. En effet, l'absence de contamination irréversible de l'électrolyte est l'avantage principal de cette batterie dont le nombre de cycles 'charge-décharge' est théoriquement illimité. Le graphite et le feutre de graphite sont des matériaux d'électrodes à faible coût utilisés par les VRFB ; cependant le système V(V)/V(IV) (électrode positive) est cinétiquement lent sur ce matériau et introduit une surtension diminuant la tension délivrée par la batterie. Différentes méthodes (chimiques, thermiques, électrochimiques,...) ont été conçues lors de cette thèse pour activer la surface du graphite commercial, càd. améliorer son activité électrocatalytique vis-à-vis de la réaction (VO2 + ⇌VO2+) ayant lieu à l'électrode positive. Cette amélioration a été caractérisée par voltammétrie linéaire (état quasi-stationnaire) et cyclique (état transitoire). En outre, la morphologie de l'électrode et son état de surface ont été analysés par infrarouge à transformée de Fourier (FTIR) et par microscopie électronique à balayage (SEM). De plus, l'interaction électrode-électrolyte a été quantifiée par des mesures d'angle de contact qui ont permis de déterminer l'énergie libre de surface. L'activation de l'électrode a généré différents groupes oxygénés (C-OH, C = O, COOH) sur sa surface, laquelle a par ailleurs augmenté du fait d'une certaine érosion et donc la création d'une rugosité ; ceci s'est traduit par : i) l'augmentation de 35% de l'amplitude du courant du pic obtenu par voltamétrie cyclique (pour le système VO2+/VO2+) et ii) le rapprochement des pics anodique et cathodique (ΔEpics= 300 mV). Les calculs de la théorie fonctionnelle de la densité (DFT) ont été effectués pour évaluer le rôle de ces groupes oxygénés sur la réactivité du système redox VO2+/VO2+(à l'électrode positive). DFT montre que ces groupes d'oxygéne augmente l'hybridation sp3 dans la structure du graphite, ce qui facilite les réactions redox. La constante de transfert électronique hétérogène intrinsèque (k °) de ce même système redox a augmentée de 2,6 et 6,1 fois pour l'oxydation (V(IV)→V(V)) et la réduction (V(V)→V(IV)), respectivement. Par ailleurs l'augmentation constatée de l'énergie libre de surface du feutre de graphite (de 13,9 mN / m à 53,29 mN / m) traduit l'amélioration, par le traitement, des interactions électrode-électrolyte. La performance de l'électrode a été évaluée dans une demi-cellule classique par des cycles de charge/décharge et les résultats ont montré que la tension aux bornes durant la charge diminue (de 1,18 V à 1,04 V) alors que celle obtenue en décharge augmente (de 0,42 V à 0,75 V), après l'activation de GF. Des cycles charge/décharge ont également été réalisés avec un réacteur électrochimique filtre presse (pile et électrolyseur pour VRFB), ayant une surface géométrique de 100 cm2 de GF dans chaque compartiment électrolytique. Grace au traitement effectué, le rendement énergétique et la tension aux bornes se sont améliorés de 20% et 13% respectivement, dans le cas d'une électrolyse en mode galvanostatique (50 A.m2), ce qui montre que les méthodes d'activation proposées sont efficaces et en outre faciles à mettre en œuvre
Increase of the share of renewable energy in the overall power production can ensure the future energy demand and help to cope with the environmental challenges inherent to the carbon enrich fossil fuels. Due to intermittent nature of these renewable resources, cost competitive and efficient energy storage devices are required. Vanadium redox flow batteries (VRFBs) are promising storage devices for the stationary applications due to its easy scalability, long charge-discharge cycles. The graphite and the graphite felt are low cost electrodes materials used by VRFBs which exhibits low kinetic reversibility of the redox reaction involving the system V(V)/V(IV) in the positive half-cell; this fact is responsible of significant kinetics overpotential decreasing the delivered voltage from the battery. In this work, different methods (chemical, thermal, electrochemical,) were tried to activate the surface of commercial graphite, expecting to enhance its electro-kinetics activity, specifically for the positive half-cell reaction (VO2+⇌VO2+). The enhancement of the electro kinetic activity of the electrode surface was characterized by the cyclic and linear sweep voltammetries. Besides the surface chemistry and morphology were analysed by the Fourier-transform infrared spectroscopy (FTIR) and Scanning electron microscopy (SEM). In another study, the electrode-electrolyte interaction was quantified by contact angle measurements allowing access to the surface free energy determination. The activation method enables to create different oxygenal groups (C-OH, C=O -COOH) on the graphite surface and to increase the surface area. Both effects lead to i) the increase by 35 % of the current magnitude of the peak obtained by cyclic voltammetry (for the system VO2+/VO2+) and ii) the decrease of the ΔEpeaks of the same system by 300 mV. The density functional theory calculations (DFT) were performed to evaluate the individual catalytic role of the these oxygenal groups against the redox couple VO2+/VO2+(in the positive electrode). DFT shows that these oxygenal groups increase sp3 hybridization in the structure of the felt, that are facilitating the redox reactions. The intrinsic heterogeneous electronic transfer constant (k°) of V(V)/V(IV) system is enhanced by 2.6 and 6.1 times for the oxidation (V(IV)→V(V)) and reduction (V(V)→V(IV)) reactions, respectively. The electrode-electrolyte interaction improves because of the increment of the surface free energy of GF from 13.9 mN/m to 53.29 mN/m. The electrode performance was evaluated in the classical half-cell by charge discharge cycles. The charging voltage decrease from 1.18V to 1.04V and the discharge voltage increase from 0.42V to 0.75V, after the activation of GF. Proposed activation methods are novel, easy and effective. The charge discharge cycles of VRFB were performed at stack level, into the electrochemical plug flow reactor, by using 100 cm2 GF in each electrolytic section. At a current density of 50 A.m-2, there is an improvement of 20 % and 13 % in energy and voltage efficiency (VE) of stack respectively, due to treated electrode

O homem produz conhecimentos científicos e tecnológicos que interferem em seu cotidiano. Para que todo cidadão possa compreender como essas novas tecnologias vão afetar a sua vida se faz necessária uma compreensão do conhecimento básico a respeito da genética, dos mecanismos de transmissão das características hereditárias, bem como de genética molecular, da estrutura do material genético, o DNA. Nessa fase, o aprendizado, conforme descrito por Kolb (1984) pode ser compreendido como um processo de ressignificação da realidade, que ocorre por meio da relação dialética entre as experiências anteriores e a reflexão com relação a novas informações adquiridas pelo sujeito. Este mesmo autor, com base nesse processo dialético de aprendizagem, desenvolveu o ciclo de aprendizagem experiencial composto por quatro modelos de aprendizagem: experiência concreta (EC), a observação reflexiva (OR), a conceitualização abstrata (CA) até alcançar a experiência ativa (EA). Por meio dos modelos expostos e da relação dialética entre eles, Kolb desenvolveu categorias de estilos de aprendizagem (acomodadores, assimiladores, convergentes, divergentes) nas quais seria possível verificar o perfil que se adequa a cada fase do aprendizado. O ambiente cultural em associação com o ambiente de ensino estabelece o estilo de aprendizado de cada aluno influenciando no modo de aprender. Desta forma, a cultura e os estilos de aprendizagem caminham correlatos e influenciam no comportamento do aluno. Neste sentido, Geert Hofstede (1980) apresentou um método de identificação de dimensões culturais (distância hierárquica, individualismo versus coletivismo, masculinidade versus feminilidade, aversão a incerteza e orientação a longo prazo). Neste contexto, este trabalho foi desenvolvido com alunos de biologia do ensino médio de uma escola particular de Guaratinguetá-SP para trabalhar o conceito do DNA objetivando especificamente: verificar a existência de predominância de algum estilo de aprendizagem, bem como, detectar a existência ou não de congruência entre os estilos de aprendizagem dos alunos e as dimensões culturais de Hofstede. Foi possível também usar a estratégia \"Ensinar ao redor do ciclo de aprendizagem de David Kolb\" para propor ações de melhoria da qualidade e da aprendizagem. Nesta etapa, utilizou-se o sistema de resposta interativa (clikers). O sistema interativo de respostas é uma tecnologia portátil por meio da qual o professor consegue medir o grau de entendimento dos alunos em sala de aula sobre determinado assunto, de forma imediata. Como resultado tem-se que o grupo de alunos em que a aprendizagem foi baseada no ciclo de David Kolb levando em consideração as atividades baseadas no perfil cultural dos alunos apresentou coeficiente de variação menor do que o outro grupo, ou seja, o desempenho dos alunos foi mais homogêneo em termos de nota, provavelmente pela abordagem baseada nos diferentes estilos de aprendizagem destes alunos. Assim, levar em consideração os estilos de aprendizagem e as dimensões culturais do grupo de alunos contribuiu para praticamente duplicar a média final deste grupo em relação ao outro grupo de alunos. Desta forma, acredita-se que a partir do momento que o professor entender que suas atitudes pedagógicas podem ser alteradas em função do grupo ocorrerá uma aproximação do professor e aluno de uma forma mais significativa para melhorias efetivas na educação de nosso país.
Men produce scientific and technological knowledge that interfere in their daily life. In order to have every citizen understand how these technologies will affect their lives, it is necessary a basic genetic understanding, as well as the understanding of the mechanisms of genetic inheritance transmission of traits, molecular genetics and the structure of DNA. In this phase, learning, as described by Kolb (1984), can be understood as a process of resignification of reality, which occurs through a dialectical relation between previous experiences and the thinking regarding new information acquired by the individual. Kolb, based on this dialectical learning process, has developed the four-stage learning cycle: immediate or concrete experience (CE), reflective observation (RO), abstract conceptualization (AC) and the active experimentation (AE). Through the exposed models and the dialectical relation between them, Kolb has developed categories of learning styles (accommodating, assimilating, converging and diverging), in which it would be possible to verify the profile that fits in each phase of the learning process. The cultural environment together with the teaching environment will determine the learning style of each student, influencing his way of learning. Therefore, culture and learning styles are correlated and influence the student\'s behavior. In this way, Geert Hofstede (1980) has presented an identification method of cultural dimensions (power distance, individualism versus collectivism, masculinity versus femininity, uncertainty avoidance and time orientation). Within this context, the current research was developed with biology high school students from a private school in Guaratinguetá - SP, in order to work the concept of DNA, aiming specifically to verify whether there is the existence of prevalence of any learning style, as well as to find out whether the congruence between the learning styles and the cultural dimension of Hosfede exists. It was also possible to use the strategy \"teaching around Kolb learning cycle\" to propose improvement actions in learning quality. This phase used the system of interactive response (clickers). This system of interactive response is a mobile technology through which the teacher is able to immediate measure the students\' level of understanding of a subject in the classroom. As a result, it could be observed that the students who had their learning based on David Kolb learning cycles, taking into account tasks based on the cultural profile of the students, presented a lower variation coefficient. That is, the performance of this group was more homogeneous in terms of grades, which is probably due to the approach based on different learning styles of these students. Therefore, taking into account the learning styles and the cultural dimension of the group of students contributed to increase nearly two times the final average of this group, comparing to the other group of students. It is believed that by the time the teacher understands that his pedagogical attitudes could be modified according to the group, this teacher will get closer to his students in a more substantial way, so as to achieve improvements in the education in our country.

碩士
國立臺中教育大學
科學應用與推廣學系科學教育碩士班
100
The purpose of this study was to use the action research approach to reflect on the results of the process in five stages while the teachers used the 5E learning cycle in science teaching. The study also explored the influence on and experience of the students through learning the concept of oxidation-reduction by using the 5E learning cycle teaching model. The participants of this study were 10 graders’ at a comprehensive high school in the central Taiwan. The researcher is the executor who adopted this teaching method in the process of this study. The material used in this study include “oxidation-reduction concept test”, “the learning cycle teaching behavior checklist”, “the questionnaire of the 5E learning cycle teaching model”, and “the questionnaire of learning perception of the 5E learning cycle”. The findings indicated while the teachers applied the 5E learning cycle in science classroom, the students’ average grades in post-test and pre-test showed significant differences. Moreover, the students’ average grades in delayed tests and pre-test showed significant differences. The approach of learning cycle model did not only improve the student performance, but also it help students to acquire the knowledge. Furthermore, by utilizing action research, the researchers designed the teaching activities to engage student learning during the stages of engagement and exploration. The results indicated that it not only could improve the teacher’s capability of designing teaching activities, but also it help with the teacher’s professional growth. Student learning perception was better during the engagement and exploration stages of the 5E learning cycle teaching model. Through the teaching activities designed by the researcher, 69％ of students focused on the topics during the engagement stage; while 77％ of students could explore deeper into the questions on the subject during the exploration stage. Therefore, using the 5E learning cycle teaching model could attract students to participate and explore in depth the topics. This study encourages teachers to become the researchers as well as suggests teachers to utilize the method of action research to improve instruction. This is because it does help teachers to improve their abilities in instructional design. The study also suggests teachers employing the 5E learning cycle teaching model to attain the goal of improving students learning objectives.

碩士
國立臺灣大學
植物科學研究所
102
The mechanism of how the phase transition from vegetative to bolting stage in Oncidium is still not distinctive. Previous studies have shown that high temperature-induced flowering is regulated by Oncidium cytosolic ascorbate peroxidase 1 (OgcytAPX1) through mediating the redox state of ascorbate (AsA). However, there were no reports on the regulating proteins interacting with AsA in the flowering process. Here, we demonstrate that the effect of AsA redox state underlying flowering induction of Oncidium was correlated with glutathione (GSH) redox state, and this signal transduction is transduced via AsA-GSH cycle. By analyzing over-expression of OgcytAPX1 in Arabidopsis, and Arabidopsis mutant lines, apx1-1, to realize the relationship in redox homeostasis between AsA and GSH under high-temperature. This result indicate that the redox changes in GSH is closely related with AsA redox state, and further to induce flowering. Biochemical assays of the GSH levels, and GSH redox ratio, revealing that the decrease of GSH redox ratio was associated with bolting stage and high-temperature induced flowering. Analysis of transcripts level and enzymatic activity revealed that the GSH biosynthesis enzyme (γ-glutamylcysteine synthetase, GSH1 ; glutathione synthetase, GSH2) and glutathione reductase (GR1), the GSH-redox related enzyme, were decrease during bolting stage and after the high-temperature stress condition. To reconfirm the influence of GSH redox ratio in bolting, we applied glutathione biosynthesis inhibitor, buthionine sulphoximine (BSO), and GSSG (the oxidized form of GSH) in Oncidium. The results demonstrate that GSH redox ratio could strongly influence bolting. Moreover, analysis on the expression profiling of floral genes also demonstrating that GIGANTEA (GI), FLOWERING LOCUS T (FT), LEAFY (LFY), and APETALA 1 (AP1) are highly induced in these treatment, suggesting that GSH redox ratio plays the crucial role on flowering induction in Oncidium.

Continued emission of green house gases has energized research activity worldwide to develop efficient ways to harness renewal energy. The availability of large scale energy storage technologies is essential to make renewal energy a reliable source of energy. Redox flow batteries show potential in this direction. These batteries typically need expensive membranes which need replacement be-cause of fouling. The recently proposed soluble lead redox flow battery (SLRFB), in which lead ions deposit on electrodes in charge cycle and dissolve back in discharge cycle, can potentially cut down the cost of energy storage by eliminating membrane. A number of challenges need to be overcome though. Low cycleability, residue formation, and low efficiencies are foremost among these, all of which require an understanding of the underlying mechanisms. A model of laminar flow-through SLRFB is first developed to understand buildup of residue on electrodes with continued cycling. The model accounts for spatially and temporally growing concentration boundary layers on electrodes in a self consistent manner by permitting local deposition/dissolution rates to be controlled by local ion transport and reaction conditions. The model suggests controlling role for charge transfer reaction on electrodes (anode in particular) and movement of ions in the bulk and concentration boundary layers. The non-uniform current density on electrodes emerges as key to formation of bare patches, steep decrease in voltage marking the end of discharge cycle, and residue buildup with continuing cycles. The model captures the experimental observations very well, and points to improved operational efficiency and decreased residue build up with cylindrical electrodes and alternating flow direction of recirculation. The underlying mechanism for more than an order of magnitude increase in cycle life of a beaker cell battery with increase in stirrer speed is unraveled next. Our experiments show that charging with and without stirring occurs identically, which brings up the hitherto unknown but quite strong role of natural convection in SLRFB. The role of stirring is determined to be dislodgement/disintegration of residue building up on electrodes. The depletion of active material from electrolyte due to residue formation is offset by “internal regeneration mechanism”, unraveled in the present work. When the rate of residue formation, rate of dislodging/disintegration from electrode, and rate of regeneration of active material in bulk of the electrolyte becomes equal, perpetual operation of SLRFB is expected. The identification of strong role of free convection in battery is put to use to demonstrate a battery that requires stirring/mixing only intermittently, during open circuit stages between charge and discharge cycles when no current is drawn. Inspired by our experimental finding that the measured currents for apparently diffusion limited situations (no external flow) are far larger than the maxi-mum possible theoretical value, the earlier model is modified to account for natural convection driven by concentration gradient of lead ions in electrolyte. The model reveals the presence of strong natural convection in battery. The induced flow in the vicinity of the electrodes enhances mass transport rates substantially, to the extent that even in the absence of external flow, normal charge/discharge of battery is predicted. The model predicted electrochemical characteristics are verified quantitatively through voltage-time measurements. The formation of flow circulation loops driven by electrode processes is validated qualitatively through PIV measurements. Natural convection is predicted to play a significant role in the presence of external flow as well. The hitherto unexplained finding in the literature on insensitivity of charge-discharge characteristics to electrolyte flow rate is captured by the model when mixed mode of convection is invoked. Flow reversal and wavy flow are predicted when natural convection and forced convection act in opposite directions in the battery. The effect of the presence of non-conducting material (PbO on anode) on the performance of SLRFB is studied using a simplified approach in the model. The study reveals the presence of charge coup de fouet phenomenon in charge cycle. The phenomenon as well as the predicted effect of depth of discharge on the magnitude of charge coup de fouet are confirmed experimentally.

Continued emission of green house gases has energized research activity worldwide to develop efficient ways to harness renewal energy. The availability of large scale energy storage technologies is essential to make renewal energy a reliable source of energy. Redox flow batteries show potential in this direction. These batteries typically need expensive membranes which need replacement be-cause of fouling. The recently proposed soluble lead redox flow battery (SLRFB), in which lead ions deposit on electrodes in charge cycle and dissolve back in discharge cycle, can potentially cut down the cost of energy storage by eliminating membrane. A number of challenges need to be overcome though. Low cycleability, residue formation, and low efficiencies are foremost among these, all of which require an understanding of the underlying mechanisms. A model of laminar flow-through SLRFB is first developed to understand buildup of residue on electrodes with continued cycling. The model accounts for spatially and temporally growing concentration boundary layers on electrodes in a self consistent manner by permitting local deposition/dissolution rates to be controlled by local ion transport and reaction conditions. The model suggests controlling role for charge transfer reaction on electrodes (anode in particular) and movement of ions in the bulk and concentration boundary layers. The non-uniform current density on electrodes emerges as key to formation of bare patches, steep decrease in voltage marking the end of discharge cycle, and residue buildup with continuing cycles. The model captures the experimental observations very well, and points to improved operational efficiency and decreased residue build up with cylindrical electrodes and alternating flow direction of recirculation. The underlying mechanism for more than an order of magnitude increase in cycle life of a beaker cell battery with increase in stirrer speed is unraveled next. Our experiments show that charging with and without stirring occurs identically, which brings up the hitherto unknown but quite strong role of natural convection in SLRFB. The role of stirring is determined to be dislodgement/disintegration of residue building up on electrodes. The depletion of active material from electrolyte due to residue formation is offset by “internal regeneration mechanism”, unraveled in the present work. When the rate of residue formation, rate of dislodging/disintegration from electrode, and rate of regeneration of active material in bulk of the electrolyte becomes equal, perpetual operation of SLRFB is expected. The identification of strong role of free convection in battery is put to use to demonstrate a battery that requires stirring/mixing only intermittently, during open circuit stages between charge and discharge cycles when no current is drawn. Inspired by our experimental finding that the measured currents for apparently diffusion limited situations (no external flow) are far larger than the maxi-mum possible theoretical value, the earlier model is modified to account for natural convection driven by concentration gradient of lead ions in electrolyte. The model reveals the presence of strong natural convection in battery. The induced flow in the vicinity of the electrodes enhances mass transport rates substantially, to the extent that even in the absence of external flow, normal charge/discharge of battery is predicted. The model predicted electrochemical characteristics are verified quantitatively through voltage-time measurements. The formation of flow circulation loops driven by electrode processes is validated qualitatively through PIV measurements. Natural convection is predicted to play a significant role in the presence of external flow as well. The hitherto unexplained finding in the literature on insensitivity of charge-discharge characteristics to electrolyte flow rate is captured by the model when mixed mode of convection is invoked. Flow reversal and wavy flow are predicted when natural convection and forced convection act in opposite directions in the battery. The effect of the presence of non-conducting material (PbO on anode) on the performance of SLRFB is studied using a simplified approach in the model. The study reveals the presence of charge coup de fouet phenomenon in charge cycle. The phenomenon as well as the predicted effect of depth of discharge on the magnitude of charge coup de fouet are confirmed experimentally.