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Modeling Transition Metal Chemistry for Catalytic Functionalization of MoleculesMorello, Glenn 08 1900 (has links)
The diversity of transition metal complexes allows for a wide range of chemical processes to be mediated by the metal, from catalysis to surface chemistry. Investigations into the structure and electronic configuration of transition metal complexes allow for tuning of desired species by modifications to the ligands and/or metals to achieve more efficient thermodynamics and kinetics for the process of interest. Transition metals, often used in catalysts for a number of important processes, require detailed descriptions of intermediates, transition states and products to fully characterize a reaction mechanism(s) in order to design more active and efficient catalysts. Computational investigations into inorganic catalysts are explored with the aim of understanding the activity of each species and how modifications of supporting ligands, co-ligands and metals vary the interaction along the reaction pathway. Reported results give important insight into the development of the most active complexes in addition to determining the least active complexes to aid experimental development. This report first investigates the mechanisms of two unique transfer reactions: 1) formation of low coordinate nickel-nitrene ((P~P)Ni=NR; P~P = 1,2-bis(dihydrophosphino)-ethane or 1,2-bis(difluoromethylphosphino)-ethane) complexes as catalysts for nitrogen atom transfer and 2) oxidation of a triphosphorus niobium complex, [(η2-P3SnPh3)Nb(OMe)3], for the transfer of the phosphorus synthon, Ph3SnP3. These reactions have utility in the synthesis of nitrogen and phosphorus containing molecules, respectively, and the results presented provide mechanistic insight into the synthesis of the organometallic intermediates. Additionally, a computational approach towards rational catalyst design was performed on the ruthenium based hydroarylation catalyst TpRu(CO)(Ph) [Tp = hydrido-tris(pyrazolyl)borate]. Targeted modifications at the Tp, metal and co-ligand (CO) sites were studied in order to tune the electronics and sterics of the catalyst. Modifications, through computational methods, provided a more cost- and time-efficient way to study the impact of modifications, which provided direct input into attractive synthetic targets. The research described heir in highlights the use of computational chemistry methodologies, specifically DFT, in collaboration with experimental results, for the accurate description of reaction geometries and factors influencing the thermodynamics and kinetics of the systems. Valuable insight is gained by treating inorganic complexes with theoretical methods and additionally provides a fast, cheap way to predict and understand the chemistry of such complex systems.
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Exploring Photocatalytic and Electrocatalytic Reduction of CO2 with Re(I) and Zn(II) Complexes and Attempts to Employ a Novel Carbene Ligand to this EndeavorBerro, Patrick 07 January 2021 (has links)
With the blend of addressing issues of sustainable energy with the environmental worries regarding emission of greenhouse gases, there is a motivation to target the efficient chemical reduction of CO2. Re(I) integrated photosensitizers and catalysts, synthesized from commercially available ligands, are introduced with the selective CO2 reduction of formic acid, making for a unique class of Re(I) catalysts typically selective for CO as a reduction product. Furthermore, synthesized Zn(II) phosphino aminopyridine complexes are structurally and computationally characterized as well as observed to function as unprecedented electrocatalysts for the reduction of CO2 to formic acid and CO. Lastly, with the importance and popularity of N-heterocyclic carbenes (NHCs) as a class of ligands in the field of organometallic catalysis, six-membered perimidine based carbenes are further explored. Synthesis of a chelating pyridyl-perimidine NHC in addition to potential transition metal catalysts are also attempted.
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Synthesis, characterization and application studies of ionic platinum(II) complexesLi, Jun 01 September 2017 (has links)
This thesis is dedicated to developing novel charged Pt(II) complexes and exploring their applications in electroluminescence, bio-imaging and the preparation of soft salts. At the beginning, a brief introduction about the development of ionic transition metal complexes and an overview of their applications in electroluminescence, bio-imaging and soft salts are presented. In chapter 2, a series of anionic Pt(II) complexes were successfully synthesized and fully characterized for their application in electroluminescence with relatively small current density. All the complexes show highly intense emission from blue to red in the solid state but is almost non-emissive in solution. The obtained single crystal data show that the anionic Pt(II) complexes exhibit very large Pt-Pt separation of over 10 Å in the crystal packings due to the bulky counterion [N(n-C4H9)4]+. The strong interactions between adjacent [Pt(C^N)(CN)2]- is thus absent in the solid state and this is considered as the main reason for the different properties in solution and solid state of these anionic complexes. This kind of Pt(II) anionic complexes has also found application in electroluminescence with relatively small current density. A series of novel water-soluble cationic Pt(II) complexes have also been designed and synthesized in chapter 3. Their photophysical properties in both water solution and solid state were investigated. Some of the cationic Pt(II) complexes have been selected to be applied in cell imaging in both live human hepatoma cells (BEL-7402) and mouse embryonic fibroblast (MEF) cells. The results show that these complexes have a much higher cellular uptake in BEL-7402 cells (tumor cells) than in MEF cells (normal cells), indicating these complexes are promising probes for tumor cell imaging. All of the cationic Pt(II) complexes show very low cytotoxicity at low concentration and the cell viability is still assessed to be high even when the concentration increases to 10 μM. The localization of the complexes turned out to be in the cytoplasm and accumulate near the cell nucleus. Attempts have been made to obtain efficient deep-red or NIR Pt(II) complexes by taking advantages of the Pt-Pt interactions in chapter 4. Two Pt(II) soft salts, SS1 and SS2 with bright emission at 674 and 718 nm, have been successfully prepared and characterized. The crystal packing shows a short separation between the two Pt atoms of 3.476 Å and the average distance of two planes of the cyclometalated ligands is 3.360 Å, indicating the existence of strong intramolecular Pt-Pt and π-π interactions. It is the first examples of Pt(II) soft salts bearing strong Pt-Pt interactions and π-π stacking and this has opened a versatile and facile avenue to prepare efficient NIR Pt(II) emitters by taking advantages of the Pt-Pt interactions. SS2 shows different emission in PEG with different concentration and excitation wavelength, indicating their potential application in optical data storage. The electrochromic properties of SS2 have also been investigated considering that the soft salt consists of ions with opposite charges, which suggests the soft salt could be promising candidate for electrochromic and optoelectronic material. The Pt(II) soft salt has also been used as NIR in-vivo imaging probe. Chapters presents the concluding remarks and points out some further work that could be done in the future. The experimental details are displayed in Chapter 6.
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Synthesis and bio-applications of luminescent iridium (III) and ruthenium (II) bipyridine complexesWang, Haitao 24 August 2020 (has links)
This thesis is based on the past three years of research work including synthesis, characterization of three series of iridium(III) complexes and one series of ruthenium(II) complexes, and their comparative bio-applications of DNA-binding, cell morphology, cytotoxicity, mitochondrial membrane potential, cellular uptake and distribution. Chapter 1 introduces the background and recent studies of transition-metal complexes as biosensors and anti-tumor medicines. Their structure related properties of cytotoxicities, cellular uptake and distributions were also discussed. In chapter 2, five iridium(III) complexes Ir4: [Ir(4-mpp)2DPPZ]+, Ir7: [Ir(4-mpp)2BDPPZ]+, Ir8: [Ir(4-mpp)2MDPPZ]+, Ir115: [Ir(pp)2DBDPPZ]+ and Ir139: [Ir(dpapp)2DBDPPZ]+ were synthesized and characterized. The crystals of complex Ir139 were successfully cultured and analyzed by X-ray crystallography. The HOMO and LUMO energy gaps of complexes Ir4, Ir7 and Ir8 were obtained. The smaller the energy gap is the larger the Stokes shift will be. The DNA binding properties of Ir4, Ir7 and Ir8 were studied to acquire their binding constants and quenching constants. All the five complexes were cultured with hepatocellular carcinoma cell (hep-G2) in different concentrations for cell morphologies and MTT assays. The IC50 values were calculated and the structure-activity relationship (SAR) was discussed. Properties of Ir115 and Ir139 for photodynamic therapy under the visible light were studied, and moderate light-enhanced cytotoxicities were discovered. The live and dead cell assay and mitochondrial transmembrane potential (ΔΨM) testing were performed and a similar cytotoxicity order to IC50 values was obtained. Some interesting interactions between complex and calcein or propidium iodide (PI) dye were observed and discussed. Cellular uptake and distribution assay showed that the fluorescence of iridium complex was closely related to its toxicity. The obvious cellular uptake at 4 ℃ indicated that all the complexes could transfer into cell through a passive transport mode of facilitated diffusion without the consumption of ATP. The greatest change in uptake intensity of Ir115 implied that the ATP could assist the transport of Ir115 at 37.5 ℃. The efficiency of uptake and distribution of complexes in paraformaldehyde (PFA) fixed cells was found to be strictly related to their size and the hydrophobicity. The rigidity of dipyrido[3,2-a:2',3'-c]phenazine based bipyridine ligands in this chapter contributed to the main cytotoxcities of those iridium complexes. Most of the iridium complexes in chapter 2 have similar structures to their classic ruthenium analogues while their activities have largely improved due to the higher cellular uptake and more biocompatibility. Chapter 3 presented five iridium complexes with rotatable 1H-imidazo [4,5-f] [1,10] (phenanthroline) based bipyridine ligands, which are Ir79: [Ir(pp)2MTPIP]+, Ir80: [Ir(pp)2EIPP]+, Ir116: [Ir(piq)2APIP]+, Ir119: [Ir(piq)2PPIP]+ and Ir134: [Ir(iqdpba)2PPIP]+. Cell morphology and proliferation assay, MTT assay indicated that most of them were not quite toxic for hep-G2 cell lines except for Ir116 which contained an amino group and was assumed to be very active to the carboxyl group in the protein residues in cells. Under the irradiation of visible light, Ir80 and the Ir119 were found to be quite photo-toxic with the light IC50 value of 8.08 μM and 6.14 μM respectively. They could become the potential candidates for the promising drugs of photo-dynamic therapy. The cytotoxicities of those five complexes were further investigated by the live and dead assay using calcein AM (acetoxymethyl) and propidium iodide (PI) double stain method. JC-1 aggregates observation and analysis in the mitochondrial transmembrane potential (ΔΨM) testing proved the lower cytotoxicities of those five complexes than those in chapter 2. Fluorescence and cytotoxicity relationship (FCR) was also uncovered in chapter 3 in which the stronger macromolecular binding to complex could lead to its higher fluorescence intensity. Without the metabolic activity and the assistance of ATP at low temperature of 4 ℃, little Ir80 and Ir134 were found in cells, and the moderate uptake for Ir79 and higher volume of Ir116 and Ir119 were detected. A novel strategy of cold-shock enhanced cellular uptake pathway was discovered in Ir119 and its cold-shock caused cytotoxicity would be further evaluated. The volumes of uptake for those complexes in paraformaldehyde fixed cells were all very low due to their higher hydrophilicity and lower structural rigidity than those in chapter 2. Chapter 4 reported the investigation of six iridium complexes of Ir105: [Ir(4-mpp)2CDYP]+, Ir107: [Ir(piq)2CDYP]+, Ir108: [Ir(3-mpp)2CDYP]+, Ir123: [Ir(4-mpp)2CDYMB]+, Ir125: [Ir(piq)2CDYMB]+ and Ir133: [Ir(dpapp)2CDYMB]+ with rotatable 5H-cyclopenta[2,1-b:3,4-b']dipyridin Schiff-base ligands. Most of them were rather toxic to hep-G2 cell lines from the MTT assay, cell morphology and proliferation assay due to the Schiff-base N^N ligands. Those rotatable Schiff-base ligands seemed to have more cytotoxicity than the flexible 1H-imidazo[4, 5-f] [1, 10](phenanthroline) ligands in chapter 3. The planar and rigid structure of piq C^N ligands in Ir107 and Ir125 were supposed to contribute to the highest cytotoxicity in chapter 4. The dead (red PI) to live (green calcein) cell area ratios and the ΔΨM assay were in accordance with the cytotoxocity sequence in MTT assay. Most of the complexes in chapter 4 demonstrated characteristics of one kind of programmed cell death (PCD), namely apoptosis and the typical features of another cell death mode of oncosis including cellular dwelling and cytoplasm vacuolation have been discovered from Hep-G2 cell lines in the incubation with Ir107. The JC-1 aggregates have disappeared when the two most toxic complexes Ir107 and Ir125 were cultured with the cells at 5 μmol/L, indicating the ΔΨM lost repidly under the damage of iridium complexes. All the complexes were distributed in the cellular nuclei when the incubation time reached 120 minutes at the concentration of 20 and 40 μmol/L. The positive correlation in the fluorescence and cytotoxicity relationship (FCR) were also discovered in chapter 4. The luminescence intensity sequence of the complexes from the cellular uptake and distribution has almost the same order as the previous toxicity results. The two most toxic complexes of Ir107 and Ir125 were found to have the two highest fluorescent intensities inside cells at 4 ℃. Most complexes in this chapter could easily distribute in the fixed cellular nuclei except for Ir125 and Ir133 owing to their large and hydrophobic structures. Generally, the uptake of complexes in paraformaldehyde fixed cells was higher than the live cells at 4 ℃ according to their passive transport mode. Although the simple Schiff base ligands of CDYP and CDYMB in this chapter were rotatable and flexible similar to the 1H-imidazo[4, 5-f][1, 10](phenanthroline) based bipyridine ligands in chapter 3, the cytotoxicities of complexes were much higher than those in chapter 3. The former chapters implied that effective uptake of complexes in nuclei were the results of the cytotoxicities which damaged the integrity of nuclear envelope and leaked into the nucleoplasm. We assumed that there could be another explanation in chapter 4 that the complexes transferred into the nuclei through the nuclear pore on the nuclear envelope and accumulated in the nucleolus, and therefore, triggered the apoptosis of cells. This kind of evidence was discovered for the two most toxic complexes Ir107 and Ir125 that could enter into cellular nuclei when the cell looked quite healthy. There would be another possiblilty that the Schiff base could interrupt the function of intracellular hydrolase enzymes. Chapter 5 compared the properties of five ruthenium(II) complexes of Ru2: [Ru(bpy)2DBDPPZ]2+, Ru7: [Ru(bpy)2MTPIP]2+, Ru8: [Ru(bpy)2EIPP]2+, Ru15: [Ru(phen)2BPDC]2+ and Ru24: [Ru(phen)2CDYMB]2+ with the ligand DBDPPZ from chapter 2, MTPIP and EIPP from chapter 3, CDYMB from chapter 4 and BPDC with two carboxyl groups. Those two positively charged ruthenium complexes indicated very low cytotoxicities from the cell morphology assay and MTT assay. No typical features of cellular apoptosis such as round and shrank cells were observed. However, the light IC50 value of Ru8 was excitingly obtained to be 2.33 μM upon the irradiation of 465 nm which was found to be one of the most promising drugs for photodynamic therapy (PDT) in his thesis. Charge and property relationship (CPR) was discovered to be the most decisive factor in the cytotoxicities of iridium and ruthenium complexes in this thesis which was also supported by a few of the independent literature papers mentioning high cytotoxicity of one positively charged ruthenium complex or low toxicity of two positively charged iridium complex. The DBDPPZ and CDYMB ligands in the ruthenium complexes Ru2 and Ru24 did not add into their cytotoxicity but those ligands greatly enhanced the toxicities of iridium complexes. The calculation of both area and number ratios of dead to live cells stained by the PI and calcein dyes indicated the lowest dark cytotoxicity among the ruthenium complexes could be Ru8 while the Ru24 and Ru7 were more toxic than others. Active JC-1 aggregates were maintained in the cell mitochondria and did not greatly diminish with the increasing concentration of ruthenium complexes. The two positive charges were found to play the important role in the poor cellular uptake of all the ruthenium complexes and the large size of phen ligand further prevented the uptake of Ru24 and reduced its toxicity. The Ru2, Ru7 and Ru8 were found to distribute in fixed cells with much higher luminescence intensities than their corresponding iridium complexes of Ir115, Ir79 and Ir80 with the same N^N ligand respectively which were assigned to be the two positive charges in those ruthenium complexes. The facilitated diffusion was found to be the main passive transport for the five ruthenium complexes in HepG2 cells at 4 ℃ when the ATP functions were considered to be largely inhibited. The low temperature cellular uptake has the similar trend of the cytotoxicities of the five complexes, indicating the structures of complexes were decisive in the process of facilitated diffusion. The enormous difference of cellular uptake and distribution in the fixes cells remind us the normal protocol before the cell-image pictures of fluorescence inverse microscopes (FIM) or confocal laser scanning microscope (CLSM) should be cancelled or very cautiously handled when the luminescent metal complexes were applied. In chapter 6, the further structure-activity relationship (SAR) was discussed based on the different C^N, N^N ligands and metal cores from the previous chapters. The overall research scheme, results and significance were summarized. Highlights were listed and future research plan was also proposed. At last, Chapter 7 described briefly the experiment protocols and supplementary information for the former chapters.
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Orientation and Dimensionality Control of Two-dimensional Transition Metal DichalcogenidesAljarb, Areej 17 January 2021 (has links)
Two-dimensional (2D) transition metal dichalcogenides (TMDs) have attracted significant attention owing to their unique electrical, optical, mechanical, and thermal properties not found in their 3D counterparts. They can be obtained by mechanical, chemical, or electrochemical exfoliation. However, these strategies lack uniformity and produce defect-rich samples, making it impossible for large-scale device fabrication. Chemical vapor deposition (CVD) method emerges as the viable candidate to create atomically thin specimens at the technologically relevant scale. However, the large-scale growth of monolayer TMD films with spatial homogeneity and high electrical performance remains an unsolved challenge. The spatial inhomogeneity and the associated grain boundaries between randomly oriented domains culminate to the deleterious quality of TMDs, breaking of the long-range crystalline periodicity and introduction of insidious strain. Recent research efforts have therefore dedicated to obtaining the single crystallinity of 2D materials by controlling the orientation and dimensionality to obtain a large-scale and grain boundary-free monolayer films for Si-comparable electron mobility and overcoming the scaling limitation of traditional Si-based microelectronics,.
In the first part of this thesis, orientation and dimensionality controlling of TMDs are discussed. To this end, we systematically study the growth of stereotypical molybdenum disulfide (MoS2) monolayer on a c-plane sapphire with CVD to elucidate the factors controlling their orientation. We have arrived at the conclusion that the concentration of precursors- that is, the ratio between sulfur and molybdenum oxide, plays a key role in the size and orientation of seeds, subsequently controlling the orientation of MoS2 monolayers. Later, we demonstrate a ledge-directed epitaxy (LDE) of dense arrays of continuous, self-aligned, monolayer, and single-crystalline MoS2 nanoribbons on β-gallium (iii) oxide (β-Ga2O3) (100) substrates. LDE MoS2 nanoribbons have spatial uniformity over a long-range and transport characteristics on par with those seen in exfoliated benchmarks.
In the second part, we theoretically reveal and experimentally determine the origin of resonant modulation of contrast as a result of the residual 3-fold astigmatism in modern scanning transmission electron microscopy (STEM) and its unintended impact on violating the power-law dependence of contrast on coordination modes between the transition metal and chalcogenide atoms.
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Catalytic and Electronic Activity of Transition Metal Dichalcogenides HeterostructuresLi, Baichang January 2021 (has links)
The synthesis of transition metal dichalcogenides (TMDs) are crucial to realization of their real-world applications in electronic, optoelectronic and chemical devices. However, the fabrication yield in terms of material quality, crystal size, defect density are poorly controlled. In this work, by employing the up-to-date stack-and-transfer and nano fabrication techniques, synthetic TMDs that obtained from different growth methods with various crystal qualities were studied.
In most of the cases, better crystals with lower defect densities and larger crystal domain sizes are preferred. Self-flux method was developed to obtain better quality crystals comparing to the traditional chemical vapor transport, as characterized by lower defect densities. BN encapsulating graphene device platform was utilized and TMDs monolayers with different defect densities was inserted in between the BN/graphene interface, where intrinsic defects from the TMDs disturbed the electronic environment of graphene. With the better TMD crystal insertion, we obtain much better electrical performed device in terms of hysteresis, FWHM of Dirac peak and electron mobility. This device also showed advantage in quantum transport measurements
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On the other hand, the presence of defects are not always undesired, especially when it comes to serve as electrocatalysts, in which most of the reactions take place at vacancy sites. However, similar to most of the MoS2 electronic devices, forming barrier-free metal semiconductor contact is the major challenge. We develop a platform that contact resistance could be monitored simultaneously with electrochemical activity. In this platform, the total device resistance is significantly reduced before electrochemical reaction happens while the intrinsic catalytic activity of the MoS₂ can be extracted. With this platform, we found the intrinsic catalytic activity of MoS₂ strongly correlated to H-coverage on its surface. By adding molecular mediator into electrolytes, H-coverage and the resulting HER activity was enhanced via “Catch and Release” mechanism. Molecular simulation was performed to support our experimental results.
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Aplikace metodiky PRINCE2 / Application of the PRINCE2 MethodologyCagalová, Eva January 2018 (has links)
The aim of this diploma thesis is to improve onboarding project management by identifying the differences between PRINCE2® methodology and existing transition process of the company. Found differences will be the baseline for new proposals that should make the project management more efficient by cost and time savings. These proposals are intended to rise the level of client‘s satisafacion, which would lead to the possibility of receiving higher volumes of new projects.
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Comme chez soi : le sentiment d’appartenance de diplômés d’écoles secondaires de langue française de l’Ontario lors de leur première année à l’universitéFaubert, Nicholas 23 November 2021 (has links)
Le point de vue des étudiants et les minorités linguistiques sont peu présents dans la recherche sur la transition scolaire et l’expérience étudiante à l’université (Lamoureux, 2007; Lamoureux et coll., 2013; Tinto, 2017). Notre recherche porte sur le sentiment d’appartenance chez des étudiants diplômés d’écoles secondaires de langue française de l’Ontario lors de leur première année universitaire. Dans la présente étude, nous avons fait une utilisation secondaire de données provenant de 17 groupes de discussion réalisés auprès de 88 étudiants. Une analyse de contenu a été effectuée selon trois concepts, soit l’appartenance à l’institution, les relations sociales et le métier d’étudiant. Les résultats montrent qu’au premier trimestre, les étudiants sont en mode de survie et ont de la difficulté à trouver l’équilibre entre leur vie sociale et académique. Au deuxième trimestre, des moments de prise de conscience ont permis à plusieurs participants de comprendre ce sur quoi ils devaient travailler pour se sentir plus à l’aise à l’université. Cette étude contribue à la recherche sur le sentiment d’appartenance à l’université chez une population francophone minoritaire dans la mesure où nous avons montré de quelle façon celui-ci se développe lors de la première année d’études universitaires.
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Socio-anthropologie des énergies marines renouvelables en Basse-Normandie : gouverner (par) l'alternative / Socio-anthropology of marine renewable energy in Lower Normandy : governing (by) the alternativeBourdier, Laure 22 November 2019 (has links)
À la suite du paquet Énergie Climat Européen et des Grenelle de l’Environnement, l’État français lance à partir de 2011 une série d’appels d’offres et d’appels à manifestation d’intérêt pour la construction d’infrastructures d’énergies marines renouvelables (EMR) le long des côtes françaises, en particulier en Basse-Normandie, région fortement marquée par son lien avec le nucléaire civil et militaire. Les parties prenantes du développement des EMR y anticipent des problèmes d’« acceptabilité sociale ». L’objet de cette thèse est, à partir de l’étude des acteurs qui concourent au développement des EMR en Basse-Normandie et des dispositifs d’acceptabilité qu’ils mettent en place, d’appréhender le maintien et le renouvellement d’un système énergétique centralisé fondé sur le nucléaire, en y intégrant l’alternative renouvelable. S’appuyant sur une combinaison de techniques d’enquête (observation directe, entretiens, questionnaires, recueil de productions documentaires, de textes réglementaires et de documents biographiques) dont l’analyse s’appuie sur des méthodes principalement qualitatives, ce travail montre que le maintien du système énergétique opère à travers le gouvernement de la critique. Les acteurs locaux, y compris critiques des projets, sont mobilisés par les entreprises, l’État, les collectivités, et les scientifiques à l’aide de dispositifs visant à construire l’acceptabilité sociale. Avec ces dispositifs d’acceptabilité, on n’assiste pas à une transformation des projets techniques vers l’intégration de dimensions sociales, mais davantage à la translation d’enjeux sociaux en termes techniques. / Following the European Union climate and energy package and le Grenelle de l’Environment, the French State launched, from 2011, a series of calls for tender and for expressions of interest for the construction of infrastructures of Marine Renewable Energy (MRE). The planned infrastructures are located along the French coast, particularly in Lower Normandy, a region characterized by the production of civilian and military nuclear power. Stakeholders in the development of MREs anticipated problems of "social acceptability". This thesis, based on a study of the actors who participated in the development of MREs in Basse-Normandie and of the acceptability mechanisms they have put in place, focuses on maintaining a centralized energy system based on nuclear energy, that has integrated the renewable alternative. Based on a combination of survey techniques (direct observation, interviews, questionnaires, collection of documentary productions, regulatory texts and biographical documents) analysed mainly through qualitative methods, this thesis reveals that the maintaining of the energy system operates through the government of critique. Local actors, including those who oppose the project, are mobilized by companies, the state, regional public authorities, and scientists through mechanisms aiming to build social acceptance. Thus acceptability, as an instrument of governing, does not mean a transformation of technical projects towards a better integration of social dimensions, but rather a translation of social questions into technical terms.
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Couplage magnéto-électrique dans des ferrites et des manganites de structure perovskite / Magnetoelectric coupling in ferrites and manganites with perovskite type structureTrotsenko, Vasily 24 May 2018 (has links)
Le but de la présente thèse est d'étudier la dynamique des réseaux de ferrites Bi1-xAxFeO3(A= Sr, Ca) et de manganites La1-хСахМnОЗ et Pr1-хCaхMnO3. Dans ces systèmes les paramètres d'ordres électrique et magnétique sont en compétition. Afin d'identifier les mécanismes microscopiques de l'ordre magnétique et électrique dans ces systèmes, une étude de diffraction des rayons X a été menée pour mettre en évidence l'effet de la substitution aliovalente sur les changements de la structure. L'évolution de la symétrie cristalline dépend non seulement de la concentration de l'élément de substitution, mais aussi de sa nature (Sr ou Ca). Les spectroscopies Raman, infrarouge, Mössbauer et XPS ont été utilisées comme des techniques appropriées pour étudier les excitations de réseau dans les systèmes étudiés où les ordres polaires et magnétiques devraient coexister. Afin de mieux comprendre les effets de contrainte et de taille sur les mécanismes microscopiques de l'ordre magnétique et électrique dans la même phase, des films épitaxiés de certaines phases sélectionnées ont été élaborés par la technique d'ablation laser pulsé sur des substrats de SrTiO3 (STO), MgO et MgO tamponné par STO. Nos résultats confirment la coexistence de l'état antiferromagnétique de charge-ordonné et de phases ferromagnétiques métalliques avec la compétition entre les interactions de super échange et de double échange. Dans ce travail, les conditions de coexistence des structures magnétiques et électriques se sont avérées dépendre des substitutions de cations ainsi que de la méthode de synthèse des échantillons sous forme céramique ou films minces / The aim of the present thesis is to study the lattice dynamics of ferrites Bi1-xAxFeO3 (A= Sr, Ca) and manganites La1-хСахМnОЗ and Pr1-хCaхMnO3 systems subject of competitive electric and magnetic order parameters. To identify the microscopic mechanisms of both magnetic and electric ordering in these systems, usual x-ray diffraction study has been conducted to highlight the effect of aliovalent substitution on the structural changes. The evolution of crystal symmetry was found to depend not only to the concentration of substituting element but also to its nature (Sr or Ca). Raman and infrared and of sub-THz, Mössbauer, and XPS were used as appropriate spectroscopic techniques for studying the lattice excitations in the studied systems where polar and magnetic orders expected to coexist. In order to shed more light on strain- and size effects on the microscopic mechanisms of both magnetic and electric ordering in the same phase, epitaxial films of some selected phase were grown by pulse laser deposition on SrTiO3(STO), MgO, and MgO buffered STO substrates. Our results confirm the coexistence of charge–ordered antiferromagnetic state and ferromagnetic metallic phases with the competition between super-exchange and double-exchange interactions. In this work, the conditions of coexistence of magnetic and electric structures were found to depend on the cation substitutions as well as on the method of sample elaboration either in ceramics or in thin films forms
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