Les cellules solaires à colorant (DSSC) sont une alternative sérieuse aux cellules à base de silicium. Le principe de fonctionnement repose sur la photosensibilisation d'un semi-conducteur par un colorant qui est en général un complexe polypyridinique du ruthénium (II). La modulation des propriétés de ces complexes permet d'optimiser les performances des cellules solaires correspondantes. Dans cette thèse, nous avons synthétisé et étudié l'effet de nouveaux ligands bipyridiniques à substituants électro-donneurs [pi]-délocalisés à base de dithiénylpyrroles (DTP). Ces motifs induisent, dans les complexes homoleptiques, bis- et tris-hétéroleptiques du Ru(II), des effets bathochromes (lorsque les motifs DTP sont liés par leur cycle thiophénique à la bipyridine) et d'importantes augmentations des coefficients d'extinction molaires. Les nouveaux composés ont été caractérisés par spectroscopies, électrochimie, photophysique et calcul théorique. Deux complexes hétéroleptiques ont été testés en cellule DSSC. Si la collecte de photons est excellente, les performances restent en dessous de celles de colorants de référence. Comme en attestent les courbes J/V et les courbes IPCE. Ce résultat peut-être dû à une limitation lors de l'injection dans la bande de conduction ou encore à une gêne stéréo-électronique provoquée par le ligand lors de la réduction du colorant oxydé (Ru(III) par le médiateur / Dye-sensitized Solar Cells (DSSC) appear to be promising devices. Operation principle relies on the photosensitization of a wide-gap semiconductor with a dye, the latter typically being a polypyridinyl ruthenium(II) complex. Modulation of the properties of such complexes enables the optimization of the corresponding solar cells' performances. In the present work, we synthesized and investigated the effect of new bipyridine ligands bearing electron-donating dithienylpyrroles (DTP). These moieties induced red-shifts of the absorption spectra in homoleptic, bis- and tris-heteroleptic Ru(II) complexes especially when the DTP was bound by its thiophene unit to the bipyridine ligand. A notable increase of the molar extinction coefficients was also obtained. All new compounds have been characterized by using spectroscopic, electrochemical, photophysical and computational chemistry techniques. Two heteroleptic complexes have been tested in DSSCs. Despite excellent light harvesting properties, performances were found lower than those of standard dyes as revealed by J/V and IPCE curves. Stereoelectronic effects could be involved since the bulky DTP moiety could impede an efficient access of the mediator to Ru(III) centers

Les lipides représentent une classe essentielle de biomolécules au fonctionnement normal des organismes vivants. Étant donné leur complexité et leur très grande diversité, les analyses du lipidome combinent généralement une méthode de séparation analytique et une détection par spectrométrie de masse. Bien que ces méthodes d’analyses présentent plusieurs avantages, elles requièrent généralement une homogénéisation de l’échantillon préalablement à l’analyse. La conséquence est la perte de l’information spatiale des analytes au travers de l’échantillon. L’imagerie par spectrométrie de masse (IMS) est une technologie de pointe permettant de cartographier au niveau moléculaire des sections tissulaires minces sans homogénéisation préalable de l’échantillon. Cette technique d’analyse permet de caractériser une vaste gamme d’analyte d’intérêt sans l’utilisation de marqueurs spécifiques. Ainsi, cette cartographie moléculaire peut être combinée à des méthodes de coloration tissulaires ou de microscopie optique afin de corréler précisément les résultats obtenus avec les histologies des sections. En revanche, la délocalisation potentielle des analytes d’intérêt au travers de la section entraîne de graves erreurs d’interprétation et prévient la corrélation exacte des résultats IMS avec les régions histologiques d’intérêt. Les travaux mis en évidence dans ce mémoire présentent le développement, la caractérisation et l’utilisation d’une nouvelle lame d’analyse pour l’IMS permettant de drastiquement réduire la délocalisation des triacylglycérols (TAG) présents dans le gras viscéral. Dans un premier temps, ces travaux montrent la délocalisation des TAG sur et hors-section tissulaire ainsi que leur induction sur la migration conjointe de plusieurs classes de phospholipides (PL) dans leurs déplacements. Par la suite, l’amplitude de la délocalisation des TAG fut étudiée sur 12 types de lames différentes, et la caractérisation de la topographie et de l’hydrophobicité de ces lames à permis de mieux comprendre la relation entre la surface et l’ampleur de la délocalisation des TAG. Pour finir, le potentiel antidélocalisation d’une nouvelle lame en aluminium oxydé fut étudié avec deux tissus comprenant une large proportion de gras viscéral soit un échantillon de muscle de boeuf présentant des stries de gras internes et un rein de souris bordé de gras. Cette nouvelle lame permet une forte ségrégation des TAG comparativement aux résultats obtenus sur les lames commerciales couramment utilisées et ainsi augmenter la fidélité des analyses IMS obtenues. Cette nouvelle méthode permettra entre autres l’analyse de plusieurs organes et tissus d’intérêt très gras autrement difficile à analyser tel que le rein, la médulla surrénale, certains muscles et cancer du sein. / Lipids represent an essential class of biomolecules for the normal functioning of living organisms. Because of their high complexity and diversity, lipid analysis generally requires the combination of an analytical separation method with mass spectrometry detection. Although these methods present many advantages, they also generally require sample homogenization prior to analysis. This implies the loss of analyte spatial localization information within the sample. Imaging mass spectrometry (IMS) is a frontier technology that allows to generate molecular cartography of thin tissue sections without prior homogenization of the sample. This technique allows to characterize a vast variety of analyte without the use of any specific markers. IMS molecular cartography can be combined to staining methods for optic microscopy to precisely correlate results with the underlaying histological features. On the other hand, potential delocalization of analytes throughout the section would prevent correlation of the IMS results with any histological landmarks and lead to severe misinterpretation by an unaware analyst. The work in this master’s thesis presents the development, characterization and use of a new slide for IMS analyses allowing a drastic decrease the delocalization of triglycerides (TAG) abundant in visceral fat. In the first part of this work, TAG delocalization on and off tissue section and its effect on phospholipids (PL) delocalization was characterized. Subsequently, the extend of TAG delocalization was evaluated on 12 different slides and both surface topography and hydrophobicity studies allowed to better understand the relationship between surface chemistry and TAG delocalization. Finally, the ability of an optimal aluminum oxide slide to decrease visceral fat delocalization was investigated using fat-marbled beef sections and kidneys surrounded by significant fat bundles. This new aluminum oxide slide presents a strong segregation for TAG in comparison to commercially available ITO-coated slides. Overall, this new aluminum oxide slide can considerably limit TAG delocalization and improve IMS fidelity and will enable the analyses of multiples organs and samples presenting large amounts of fat such as kidney, adrenal medulla, muscles, and breast cancer, otherwise very difficult to analyze using traditional slides.

<p>   </p> <p>Colloidal cesium lead bromide (CsPbBr₃) quantum dots (QDs) have emerged as an exciting class of quantum emitters due to their near-unity quantum yields, large oscillator strengths, and long coherence time. Ordered superlattices (SLs) grown from these QDs exhibit emergent properties resulting from their assembly. In this work, we explore the self-assembly, disorder, and superradiant properties of 3D superlattices of CsPbBr₃ to understand how structural heterogeneity influences optical properties.</p> <p>A thorough understanding of the competition between coherence and dephasing from phonon scattering and energetic disorder is currently lacking in the literature. Here, we present an investigation of exciton coherence in perovskite QD solids using temperature-dependent photoluminescence linewidth and lifetime measurements. The properties of perovskite QDS described above should also enable them to overcome hurdles experienced by other materials that limit solid-state superradiance, such as fast dephasing processes from inherent disorder and thermal fluctuations. Our results demonstrate that excitons can coherently delocalize in highly ordered CsPbBr₃ superlattices leading to superradiant emission. We observe loss of coherence and exciton localization to a single QD at higher temperatures, resulting from scattering by optical phonons. At low temperatures, static disorder and defects limit exciton coherence, and a wide range of coherence numbers are observed across a self-assembled sample of SLs. These results highlight the promise and challenge in achieving long-range coherence in perovskite QD solids.</p> <p>A thorough understanding of structural heterogeneity in CsPbBr₃ quantum dot superlattices is necessary for the realization of robust exciton coherence in these systems. 3D SLs self-assemble from a colloidal solution of cubic QDs as the solvent evaporates, leading to SLs ranging widely in macroscopic size, shape, and aspect ratio. Scanning transmission electron microscopy (STEM) coupled to fast-Fourier transform (FFT) analysis is utilized to characterize the structural properties of individual SLs, such as the average constituent quantum dot size, size dispersity, and number of crystalline domains. Analysis reveals that SLs are structurally heterogeneous but tend to have a narrower size distribution than the precursor solution due to size selection that occurs during evaporative self-assembly. We directly correlate STEM-FFT structural properties to low-temperature photoluminescence spectra for individual SLs, demonstrating that substructure in the photoluminescence peak arises from multiple, locally-ordered domains within the SL. In addition, we show that long-range structural disorder in a SL does not necessarily impact short-range phenomena such as exciton delocalization.</p> <p>  </p>

Dans cette thèse nous analysons dans quelle mesure le concept de mobilité peut être pris en compte dans la démarche d'analyse et de conception de systèmes de production. Notre apport vise à formaliser la démarche d'analyse et de conception de ce dernier, explicitant les décisions à prendre, les informations nécessaires et les critères de décision à mettre en place. Dans cet objectif, deux niveaux d'analyse ont été distingués : un niveau local concernant un site de production et un niveau global comprenant un ensemble de sites.Le premier niveau local considère un seul site de production. A ce niveau nous avons proposé une approche prenant en compte les caractéristiques du site de production. Dans notre contexte, le choix de la localisation géographique de production est imposé par le client. De ce fait, la conception du système de production doit s'adapter à cette contrainte. D'un point de vue conception, quatre questions sont abordées : (1) dans quelle mesure le concept de mobilité peut être intégré dans une démarche de conception de système de production mobile ? (2) quelles caractéristiques de l'environnement de production doivent être prises en compte ? (3) comment déterminer ce qu'il faut produire sur site ou ce qu'il serait opportun d'externaliser ? et (4) compte tenu des informations obtenues quelle est la meilleure configuration du SPM à envisager et selon quels critères de choix ? La réponse à ces questions conduit à la proposition d'une configuration du SPM adaptée pour un seul site de production.Le deuxième niveau global traite la problématique de mobilité successive multi sites. En effet, pour être rentabilisé le système de production doit être mobilisé sur plusieurs sites de production. A chaque changement de site de production, une reconfiguration du système de production s'impose en se basant sur la configuration existante (version i-1). LaThèse de Youssef BENAMAreconfigurabilité concerne d'une part l'architecture interne du système (choix des machines, recrutement de nouvelles équipes locales, etc) et d'autre part l'organisation de la chaîne d'approvisionnement du SPM (faire en interne ou externaliser, fournisseur local, etc.). A ce niveau global d'analyse, nous proposons deux modèles d'analyse : (1) un premier modèle pour l'analyse de la reconfigurabilité interne. Ce modèle d'analyse permet d'adapter le nombre de lignes de production et le nombre d'équipes en fonction d'un scénario de demande (localisations géographiques, capacité nécessaire par site). L'originalité de notre proposition consiste d'une part en l'évaluation des coûts de reconfiguration nécessaires et d'autre part l'appréciation du niveau d'adéquation de la configuration proposée avec le contexte du site de production via l'utilisation de l'indicateur de mobilité. (2) Le deuxième modèle d'analyse concerne la reconfigurabilité de la chaîne d'approvisionnement amont du SPM. Il consiste en une adaptation du modèle d'aide à la décision "faire ou faire faire" par l'intégration d'un côté de l'importance du site de production et d'un autre côté des spécificités de chaque site de production.La démarche d'analyse proposée est illustrée sur le cas industriel concernant la conception d'une usine mobile pour la fabrication et l'installation sur site de composants de centrales solaires thermodynamiques. / In this thesis we analyse how the concept of mobility can be taken into account in the analysis and design of production systems. Our contribution aims to formalize the analysis and design process, explaining the decisions, the necessary information and decision criteria to be taken into account. For this purpose, two levels of analysis were distinguished: a local level concerning one production site and a global level including a set of sites.The first level considers one production site. At this level we have proposed an approach that takes into account the characteristics of the production site. In our context, the choice of the geographical location of production is imposed by the final client. Therefore, the design of the production system should be adapted to this constraint. From a design perspective, four questions are addressed: (1) To what extent the concept of mobility can be integrated into a mobile production system design approach? (2) What characteristics of the production environment must be taken into account? (3) How to determine what to produce on site or that it would be appropriate to outsource? And (4) taking into account all obtained information what is the best configuration of the mobile production system to consider and according towhich criteria? The answer to these questions led to the proposal of a configuration of SPM suitable for a single production site.The second Level of analysis addresses the problem of global mobility. In order to be profitable, the production system must be used on several production locations. every change of production location led to a need of reconfiguration of the Production System. Reconfigurability Concerns the internal architecture of the system (machine selection, recruitment News local teams, etc.) as well as the organization of the SPM supply chain. Fot this global level, we propose two analytical models: (1) the first model for the analysis of internal reconfigurability. This analysis model is used to adapt the number of production lines and the number of teams according to a production scenario (Geographical locations, necessary capacity per site). The originality of our proposal consists on the assessment of costs to support reconfiguration and the appreciation the convenience level with the context of the production site by using the mobility indicator. (2) Second model to analyse Concerns reconfigurability of the upstream supply chain of PMS. It Consists in June adaptation of the model using the decision "to do ou do" by integrating A side of the importance of the production site and another side Specifics Each of the production site.The proposed approach is illustrated on an industrial case concerning the design of a mobile manufacturing plant used to produce in-site and Install components of solar plant

La present tesi doctoral s'emmarca dins el camp de la química teòrica icomputacional. El primer objectiu, que va ser el de partida, consistia a veure si els índexosbielectrònics derivats de la teoria AIM podien ser útils per estudiar la reorganitzacióelectrònica al llarg d'una reacció. De forma paral·lela es va plantejar un objectiumetodològic, el càlcul dels índexos mencionats a altres nivells de teoria, com podia serDFT o CI. CI. Aquests dos objectius varen portar a molts d'altres, tot i que els principals són:Objectiu 1. Estudi de la reorganització de parells d'electrons al llarg d'unareacció.Objectiu 2. Efecte de la solvatació sobre l'estructura de parells d'electrons d'unamolècula.Objectiu 3. Càlcul dels índexos de localització i deslocalització als nivells de teoriadel funcional de la densitat i post-Hartree-Fock.Objectiu 4. Caracterització de l'enllaç per pont d'hidrogen per mitjà del'estructura dels parells d'electrons.Objectiu 5. L'índex de deslocalització: nou criteri electrònic d'aromaticitat.

In this thesis we analyse a problem of the real economic adjustment between two countries, one of which is an emerging market and the other is a developed economy. When they form a monetary union the only possible adjustment to asymmetric shocks transmitted internationally is through the real variables. We take into account existing asymmetries in the foreign direct investment (FDI) intensity and FDI relations. The issues of FDI and differences in the FDI intensity are real aspects of functioning of economies and relations between them. They reveal some problem from the macroeconomic perspective. However, the problem relates also to microeconomic foundations. The given trade and FDI relations between countries depend on decisions of firms that are heterogeneous. To study the effect of plant delocalization and FDI on output fluctuations between two countries we use a framework that accounts for all this issues, that means dynamic stochastic general equilibrium (DSGE) models with heterogeneity in firm productivity. We add a new dimension to the existing literature on DSGE models with heterogeneous firms. First, we complete goods market with a new segment of production, namely products offered by multinationals which produce abroad and export back to their economy of origin. Second, we account for asymmetries in the FDI intensity and differences in production structures that occur between two economies forming a monetary union. Summing things up, the analysis allows us to state that the real aspects of economy functioning, such as trade connections between countries and differences in production structures, determine economic performance and behaviour of economies in terms of output fluctuations.

Quantum mechanics became a foundation for incessant development of versatile computational methods for analysis of chemical and physical properties of molecules and crystals. A huge progress has been made in the fifield of density functional theory, since nowadays this theory offers the best compromise between precision of results and efficiency fiof computation. The chemical bonding analysis can be easily performed with real space methods based on chemical concepts introduced via partitioning of real space into chemically meaningful domains, since the orbital based approach is not well applicable due to the delocalized nature of plane waves. However the practical usage of those methods often requires a signifificant amount of computational resources. Some methods require the evaluation of so called domain overlap matrices, that is a formidable task for complex and low-symmetry systems. In the present research the author enables the investigation of complex solid compounds with real space chemical bonding indicators by introducing the derivation of the expression for the evaluation of the domain overlap matrix elements from the projected-augmented wave method. The corresponding program module was developed, which is capable to perform the real space chemical bonding analysis with a number of methods, like electron localizability indicators, electron localization function, localization/delocalization indices and domain averaged Fermi hole orbitals. The efficiency and the accuracy of the developed implementation is demonstrated by the comparison with the domain overlap matrix elements evaluation from the full-potential linearized augmented plane wave method on a set of simple compounds with three atoms per primitive cell at most. A set of complex periodic structures is analyzed and the capability of the present implementation to unravel intricate chemical bonding patterns is demonstrated.

<p>Noble metal nanostructures display collective oscillation of the surface conduction electrons upon light irradiation as a form of localized surface plasmon resonance (LSPR) properties. Size, shape and the refractive index of surrounding environment are the key features that controls the LSPR properties. Surface passivating ligands have the ability to modify the charge density of nanostructures to allow resonant wavelength to match that of the incident light, a phenomenon called “plasmoelectric effect,”. According to the drude model Red and blue shifts of LSPR peak of nanostructures are observed in the event of reducing and increasing charge density, respectively. However, herein we report unusual LSPR properties of gold triangular nanoprisms (Au TNPs) upon functionalization with para-substituted thiophenols (X-Ph-SH, X = -NH₂, -OCH₃, -CH₃, -H, -Cl, -CF₃, and -NO₂). Accordingly, we hypothesized that an appropriate energy level alignment between the Au Fermi energy and the HOMO or LUMO of ligands allows delocalization of surface plasmon excitation at the hybrid inorganic-organic interface, and thus provides a thermodynamically driven plasmoelectric effect. We further validated our hypothesis by calculating the HOMO and LUMO levels and also work function changes of Au TNPs upon functionalization with para substituted thiol. We further utilized our unique finding to design ultrasensitive plasmonic substrate for biosensing of cancer microRNA in bladder cancer and owe to unpresidential sensitivity of the developed Au TNPs based LSPR sensor, for the first time we have been utilized to analysis the tumor suppressor microRNA for more accurate diagnosis of BC. Additionally, we have been advancing our sensing platform to mitigate the false positive and negative responses of the sensing platform using surface enhanced fluorescence technique. This noninvasive, highly sensitive, highly specific, also does not have false positives technique provide strong key to detect cancer at very early stage, hence increase the cancer survival rate. Moreover, the electromagnetic field enhancement of Surface-Enhanced Raman Scattering (SERS) and other related surface-enhanced spectroscopic processes resulted from the LSPR property. This dissertation describes the design and development of entirely new SERS nanosensors using flexible SERS substrate based on unique LSPR property of Au TNPs and developed sensors shows excellent SERS activity (enhancement factor = ~6.0 x 106) and limit of detection (as low as 56 parts-per-quadrillions) with high selectivity by chemometric analyses among three commonly used explosives (TNT, RDX, and PETN). Further we achieved the programable self-assembly of Au TNPs using molecular tailoring to form a 3D supper lattice array based on the substrate effect. Here we achieved the highest reported sensitivity for potent drug analysis, including opioids and synthetic cannabinoids from human plasma obtained from the emergency room. This exquisite sensitivity is mainly due to the two reasons, including molecular resonance of the adsorbate molecules and the plasmonic coupling among the nanoparticles. Altogether we are highly optimistic that our research will not only increase the patient survival rate through early detection of cancer but also help to battle the “war against drugs” that together is expected to enhance the quality of human life. </p> <p> </p>

Dans cette thèse, nous analysons la question de l’ajustement réel entre des économies de niveau de développement diffèrent au sein d’une union monétaire. Dans ce, les deux économies représentées – une économie développée et une économie émergente – ne peuvent utiliser le taux de change nominal pour s’ajuster à des chocs asymétriques. Pour étudier les conditions de l’ajustement réel entre ces pays, nous prenons en compte les flux d’investissements directs. En effet, ce type d’investissement a profité largement aux économies d’Europe de l’est non membres de le zone euro. Pour étudier cette question, nous utilisons un modèle DSGE (« dynamic stochastic general equilibrium ») permettant de micro fonder les décisions d’investissement direct sur l’hétérogénéité productive des firmes. Nous complétons la littérature existante dans ce domaine en privilégiant deux aspects : (1) les investissements directs peuvent être à la fois des substituts aux importations ou une solution retenue par les firmes pour réduire leurs coûts de production afin de réimporter des biens sur leur marché national et (2) les pays sont traités de manière asymétrique, afin de relier leur niveau de développement aux types de variétiés de biens (non échangeables, exportables, délocalisables). Nous évaluons de quelle manière ces éléments affectent la dynamique des économies à un choc de productivité asymétrique. De manière générale, on observe que les économies vont répondre de manière différente au niveau macroéconomique en fonction de leur structure productive. En résumé l’analyse proposée dans cette thèse montre que des différences structurelles et la possibilité pour les pays de s’engager dans des investissements directs détermine de manière critique la réaction des variables macroéconomiques à des chocs asymétriques. / In this thesis we analyse a problem of the real economic adjustment between two countries, one of which is an emerging market and the other is a developed economy. When they form a monetary union the only possible adjustment to asymmetric shocks transmitted internationally is through the real variables. We take into account existing asymmetries in the foreign direct investment (FDI) intensity and FDI relations. The issues of FDI and differences in the FDI intensity are real aspects of functioning of economies and relations between them. They reveal some problem from the macroeconomic perspective. However, the problem relates also to microeconomic foundations. The given trade and FDI relations between countries depend on decisions of firms that are heterogeneous. To study the effect of plant delocalization and FDI on output fluctuations between two countries we use a framework that accounts for all this issues, that means dynamic stochastic general equilibrium (DSGE) models with heterogeneity in firm productivity. We add a new dimension to the existing literature on DSGE models with heterogeneous firms. First, we complete goods market with a new segment of production, namely products offered by multinationals which produce abroad and export back to their economy of origin. Second, we account for asymmetries in the FDI intensity and differences in production structures that occur between two economies forming a monetary union. Summing things up, the analysis allows us to state that the real aspects of economy functioning, such as trade connections between countries and differences in production structures, determine economic performance and behaviour of economies in terms of output fluctuations.

Quantum mechanics became a foundation for incessant development of versatile computational methods for analysis of chemical and physical properties of molecules and crystals. A huge progress has been made in the fifield of density functional theory, since nowadays this theory offers the best compromise between precision of results and efficiency fiof computation. The chemical bonding analysis can be easily performed with real space methods based on chemical concepts introduced via partitioning of real space into chemically meaningful domains, since the orbital based approach is not well applicable due to the delocalized nature of plane waves. However the practical usage of those methods often requires a signifificant amount of computational resources. Some methods require the evaluation of so called domain overlap matrices, that is a formidable task for complex and low-symmetry systems. In the present research the author enables the investigation of complex solid compounds with real space chemical bonding indicators by introducing the derivation of the expression for the evaluation of the domain overlap matrix elements from the projected-augmented wave method. The corresponding program module was developed, which is capable to perform the real space chemical bonding analysis with a number of methods, like electron localizability indicators, electron localization function, localization/delocalization indices and domain averaged Fermi hole orbitals. The efficiency and the accuracy of the developed implementation is demonstrated by the comparison with the domain overlap matrix elements evaluation from the full-potential linearized augmented plane wave method on a set of simple compounds with three atoms per primitive cell at most. A set of complex periodic structures is analyzed and the capability of the present implementation to unravel intricate chemical bonding patterns is demonstrated.