No description available.

Ce projet de recherche mené en collaboration industrielle avec St-Jean Photochimie Inc. / PCAS Canada vise le développement et la caractérisation de dérivés dipyrrométhène pour des applications dans le domaine du photovoltaïque. La quête du récoltage des photons se situant dans le proche-infrarouge a été au centre des modifications structurales explorées afin d’augmenter l’efficacité de conversion des cellules solaires de type organique et à pigments photosensibles. Trois familles de composés intégrant le motif dipyrrométhène ont été synthétisées et caractérisées du point de vue spectroscopique, électrochimique, structural ainsi que par modélisation moléculaire afin d’établir des relations structures-propriétés. La première famille comporte six azadipyrrométhènes au potentiel de coordination tétradentate sur des centres métalliques. Le développement d’une nouvelle voie synthétique asymétrique combinée à l’utilisation d’une voie symétrique classique ont permis d’obtenir l’ensemble des combinaisons de substituants possibles sur les aryles proximaux incluant les noyaux 2-hydroxyphényle, 2-méthoxyphényle et 2- pyridyle. La modulation du maximum d’absorption dans le rouge a pu être faite entre 598 et 619 nm. De même, la présence de groupements méthoxyle ou hydroxyle augmente l’absorption dans le violet (~410 nm) tel que démontré par modélisation. La caractérisation électrochimique a montré que les dérivés tétradentates étaient en général moins stables aux processus redox que leur contre-parti bidentate. La deuxième famille comporte dix dérivés BODIPY fusionnés de façon asymétrique en position [b]. L’aryle proximal a été modifié de façon systématique afin de mieux comprendre l’impact des substituents riches en électron et de la fusion de cycles aromatiques. De plus, ces dérivés ont été mis en relation avec une vaste série de composés analogues. Les résultats empiriques ont montré que les propriétés optoélectroniques de la plateforme sont régies par le degré de communication électronique entre l’aryle proximal, le pyrrole sur lequel il est attaché et le noyau indolique adjacent à ce dernier. Les maximums d’absorption dans le rouge sont modulables entre 547 et 628 nm et la fluorescence des composés se situe dans le proche- infrarouge. L’un des composé s’est révélé souhaitable pour une utilisation en photovoltaïque ainsi qu’à titre de sonde à pH. La troisième famille comporte cinq complexes neutres de RuII basés sur des polypyridines et portant un ligand azadipyrrométhène cyclométalé. Les composés ont montré une forte absorption de photons dans la région de 600 à 800 nm (rouge à proche- infrarouge) et qui a pu être étendue au-delà de 1100 nm dans le cas des dérivés portant un ligand terpyridine. L’analyse des propriétés optoélectroniques de façon empirique et théorique a montré un impact significatif de la cyclométalation et ouvert la voie pour leur étude en tant que photosensibilisateurs en OPV et en DSSC. La capacité d’un des complexes à photo-injecter un électron dans la bande de conduction du semi-conducteur TiO2 a été démontré en collaboration avec le groupe du Pr Gerald J. Meyer à University of North Carolina at Chapel Hill, premier pas vers une utilisation dans les cellules solaires à pigments photosensibles. La stabilité des complexes en solution s’est toutefois avérée problématique et des pistes de solutions sont suggérées basées sur les connaissances acquises dans le cadre de cette thèse. / This research project carried out in industrial collaboration with Saint-Jean Photochemicals Inc. / PCAS Canada aims at the development and characterization of dipyrromethene derivatives for photovoltaic applications. The quest for harvesting near- infrared photons was the central focus and various structural modifications were explored to improve the power conversion efficiency of organic and dye-sensitized solar cells (OPV and DSSC, respectively). Three families of chromophores which embedded a dipyrromethene motif were synthesized and characterized through spectroscopy, electrochemistry, X-ray diffraction and computationnal modelization in order to establish their structure-properties relationship. The first family includes six azadipyrromethenes with potential for tetradentate coordination on metallic centers. The development of a new asymmetric synthetic route together with the classical symmetric one allowed access to all possible combinations of derivatives including 2-hydroxyphenyl, 2-methoxyphenyl and 2-pyridyl substituents in the proximal position of the dipyrromethene. Modulation of the absorption maxima in the red ranged between 598 and 619 nm. Also, having methoxy or hydroxy substituents provided an increase of the violet absorption (~410 nm) as established by modelization. Electrochemical characterization showed that the tetradentate azadipyrromethenes were generally less stable towards redox processes as compared to their bidentate counter- parts. The second family includes ten asymmetric benzo[b]-fused BODIPYs where the proximal aryl was systematically modified in order to assess the impact of electron-rich substituents and fused aromatic cycles. The derivatives were further compared to a wide series of related BODIPYs. Empirical results showed the optoelectronic properties are dictated by the extend of electronic communication between the proximal aryl, the pyrrol to which it is attached and the adjacent indolic moiety. Absorption maxima in the red were modulated between 547 nm and 628 nm and the fluorescence was in the near-infrared. One compound proved to be a potential candidate for photovoltaic and pH probe applications. The third family includes five neutral RuII polypyridine complexes bearing a cyclometalated azadipyrromethene ligand. The compounds exhibit strong light absorption in the 600 – 800 nm range (red to near-infrared) that tails beyond 1100 nm in the terpyridine-based adducts. Analysis of the optoelectronic properties showed a significant impact of this novel cyclometalation strategy for dipyrromethene derivatives and paved the way for further incorporation of the resulting complexes as photosensitizers in OPV and DSSC. In collaboration with the group of Pr Gerald J. Meyer at the University of North Carolina at Chapel Hill, the capacity of one compound to photo-inject its electron into the conduction band of the TiO2 semiconductor was established, a first step towards their use in dye-sensitized solar cells. The structural instability in solution of the complexes hindered their full potential for photovoltaic applications and suggestions to improve them are proposed based on the knowledge acquired in the course of this thesis.

This thesis describes the synthesis, characterisation and application of artificial metalloenzymes as catalysts. The focus was on two mutants of SCP-2L (SCP-2L A100C and SCP-2L V83C) both of which possess a hydrophobic tunnel in which apolar substrates can accumulate. The crystal structure of SCP-2L A100C was determined and discussed with a special emphasis on its hydrophobic tunnel. The SCP-2L mutants were covalently modified at their unique cysteine with two different N-ligands (phenanthroline or dipicolylamine based) or three different phosphine ligands (all based on triphenylphosphine) in order to increase their binding capabilities towards metals. The metal binding capabilities of these artificial proteins towards different transition metals was determined. Phenanthroline modified SCP-2L was found to be a promising scaffold for Pd(II)-, Cu(II)-, Ni(II)- and Co(II)-enzymes while dipicolylamine-modified SCP-2L was found to be a promising scaffold for Pd(II)-enzymes. The rhodium binding capacity of two additional phosphine modified protein scaffolds was also investigated. Promising scaffolds for Rh(I)- and Ir(I)-enzymes were identified. Rh-enzymes of the phosphine modified proteins were tested in the aqueous-organic biphasic hydroformylation of linear long chain 1-alkenes and compared to the Rh/TPPTS reference system. Some Rh-enzymes were found to be several orders of magnitude more active than the model system while yielding comparable selectivities. The reason for this remarkable reactivity increase could not be fully elucidated but several potential modes of action could be excluded. Cu-, Co-, and Ni-enzymes of N-ligand modified SCP-2L A100C were tested in the asymmetric Diels-Alder reaction between cyclopentadiene and trans-azachalcone. A promising 29% ee for the exo-product was found for the phenanthroline modified protein in the presence of nickel. Further improvement of these catalyst systems by chemical means (e.g. optimisation of ligand structure) and bio-molecular tools (e.g. optimisation of protein environment) can lead to even more active and (enantio)selective catalysts in the future.

Made available in DSpace on 2014-12-17T14:08:50Z (GMT). No. of bitstreams: 1 PauloRMP_capa_ate_pag32.pdf: 5057325 bytes, checksum: bf8da0b02ad06ee116c93344fb67e976 (MD5) Previous issue date: 2012-02-06 / Originally aimed at operational objectives, the continuous measurement of well bottomhole pressure and temperature, recorded by permanent downhole gauges (PDG), finds vast applicability in reservoir management. It contributes for the monitoring of well performance and makes it possible to estimate reservoir parameters on the long term. However, notwithstanding its unquestionable value, data from PDG is characterized by a large noise content. Moreover, the presence of outliers within valid signal measurements seems to be a major problem as well. In this work, the initial treatment of PDG signals is addressed, based on curve smoothing, self-organizing maps and the discrete wavelet transform. Additionally, a system based on the coupling of fuzzy clustering with feed-forward neural networks is proposed for transient detection. The obtained results were considered quite satisfactory for offshore wells and matched real requisites for utilization / Originalmente voltadas ao monitoramento da opera??o, as medi??es cont?nuas de press?o e temperatura no fundo de po?o, realizadas atrav?s de PDGs (do ingl?s, Permanent Downhole Gauges), encontram vasta aplicabilidade no gerenciamento de reservat?rios. Para tanto, permitem o monitoramento do desempenho de po?os e a estimativa de par?metros de reservat?rios no longo prazo. Contudo, a despeito de sua inquestion?vel utilidade, os dados adquiridos de PDG apresentam grande conte?do de ru?do. Outro aspecto igualmente desfavor?vel reside na ocorr?ncia de valores esp?rios (outliers) imersos entre as medidas registradas pelo PDG. O presente trabalho aborda o tratamento inicial de sinais de press?o e temperatura, mediante t?cnicas de suaviza??o, mapas auto-organiz?veis e transformada wavelet discreta. Ademais, prop?e-se um sistema de detec??o de transientes relevantes para an?lise no longo hist?rico de registros, baseado no acoplamento entre clusteriza??o fuzzy e redes neurais feed-forward. Os resultados alcan?ados mostraram-se de todo satisfat?rios para po?os marinhos, atendendo a requisitos reais de utiliza??o dos sinais registrados por PDGs

Les marais de l'Ouest ont été gagnés sur les sédiments fluvio-marins par poldérisation débutée dès le moyen âge. Les aménagements hydrauliques avaient, initialement, des objectifs sanitaires et d'élevage. A partir des endiguements, ils ont divisé les territoires en marais mouillés et marais desséchés. Depuis les années 1970 le développement des cultures intensives de céréales a nécessité un rabaissement complémentaire de la nappe par drainage en partie pour augmenter la désalinisation de surface et limiter l’engorgement des sols. Néanmoins, ces territoires restent caractérisés par des nappes proches de la surface. En conséquence les profils hydriques vont être gouvernés par les conditions météorologiques y compris l'évapotranspiration, la pluviométrie, mais également par les remontées capillaires issues d'une nappe salée. D'autre par la nature argileuse des sols et ses propriétés de retrait conditionnent énormément le fonctionnement hydrodynamique et les évolutions de structure.La première partie du travail a été de suivre les évolutions des profils hydriques et de salinité en parcelles non drainées (prairies) et en parcelles drainées (Maïs, Blé, Tournesol). Ces suivis ont été complétés par les mesures des niveaux de nappes et par des mesures tensiométriques via des bougies poreuses implantées à différentes profondeurs. L'objectif final a été de calculer et modéliser les profils de réserve utile (RU) et de RU "résiduelle" utilisable par les plantes. Dans ces systèmes alimentés par les remontées capillaires, le réseau racinaire puise l'eau dans la zone non saturée de surface (vadose) puis dans la zone saturée sous-jacente. La teneur en eau caractéristique de l'interface zone non saturée - zone saturée a été déterminée par analogie entre les chemins d'état de la matrice argileuse le long de sa courbe de retrait et du sol le long de sa courbe de compaction. Les profils de RU résiduelle utilisable par les plantes ont été calculés à partir des profils de teneurs en eau puis comparés aux profils de RU obtenus via les données de station météorologique. Ces profils de RU résiduelle ont pu être écrits sous forme d'équation polynomiale du second degré puis modélisés. Dans cet environnement alimenté par les remontées capillaires, ces profils de RU résiduelles peuvent être modélisés à partir d'un paramètre facilement mesurable en surface qui prend en compte la structure du sol et les conditions météorologique : soit la teneur en eau à 10 cm de profondeur. Cette modélisation reste suffisamment réaliste pour être utilisée comme un outil prédictif face à la pédodiversité et/ou les rendements de culture.A ce travail s'ajoute deux études préliminaires : - les mesures des conductivités thermiques effectives de ces sols par la méthode du fil chaud et leurs modélisations dans les systèmes biphasés : eau - argile et air - argile, mais également pour les systèmes triphasés non saturés : eau - air - argile. Les perspectives sont la modélisation des transferts thermiques et hydriques dans le sol à partir de la surface, - et l'élaboration d'un protocole d'imprégnation-polymérisation des sols argileux humides par des résines de type HEMA. Cette imprégnation permet d'envisager la confection de lames minces dans le matériau argileux induré avec conservation de sa structure initiale humide. Les perspectives sont la pétrographie quantitative à l'interface racine - sol le long de profils verticaux dans les environnements argileux à degrés de saturation et structure évolutives. / The coastal marshlands are territories generally reclaimed on primary fluvio-marine sediments. They result from hydraulic managements and/or polderization which may date from the Middle Ages. Historically these hydraulic managements were built for goals of wholesomeness, breeding and farming. They isolate two territories: the dried marshes and the wet marshes. For the intensive cereal crops the slow drying caused by land reclamation was recently improved by the drainage, in part for increase the depth of desalinization and decrease waterlogging. Nevertheless, these territories remain characterized by shallow ground water of initial salt water. Consequently, the hydric profiles are governed by the meteoric conditions including the Evapotranspiration, the rainfall, but also the capillarity rises from the salt groundwater. Moreover, the clay dominated nature of the soils and their drastic shrinkage properties govern the hydrodynamic functioning and the soil structure behavior.The first part of the work was the monitoring of the water content and salinity profiles in drained cereal crops and in undrained grasslands. These measurements have been completed by the ground water level and tensiometric monitoring. The final goal was the calculation and modeling of the available water capacity (AWC) and plant available water (PAW) profiles. In these systems mainly supplied by the capillarity rises, the root network gets water in the subsurface vadose zone and then in the deeper saturated groundwater zone. The water content characteristic of the interface between the vadose and saturated zone was determined by comparison between the clay material state paths along its shrinkage curve and along its compaction curve. The PAW profiles were calculated from the water content profiles and then compared to the AWC profiles. The PAW profiles have been equated as polynomial second degree equations. In these shallow groundwater environments the PAW profiles have been modeled taking into account an easy measurable surface parameter which includes the soil structure behavior and the meteoric conditions: i.e. the water content measured at 10 cm depth. The PAW modelling remains sufficiently realistic to be used as a tool for farming management. Two preliminary studies were added to this work: - the measurement of effective thermal conductivity of the clayey soils by the transient hot wire method, and the modeling of the effective thermal conductivity of biphasic air-clay and water-clay media, but also triphasic unsaturated air-water-clay media. The prospect is the modeling of thermal and hydric transfer from the surface to the depth. - and the elaboration of a protocol of impregnation - hardening for wet clay dominated soils by HEMA resins. This impregnation allows the making of thin sections in these clay materials with conservation of their initial wet structures. The prospective is the quantitative petrography at the root - clay matrix interface along vertical profiles in clayey soils at different degrees of saturation and different structures.

During the race towards the4th generation (4G) cellular-based digital communication systems, a growth in the demand for high capacity, multi-media capable, improved Quality-of-Service (QoS) mobile communication systems have caused the developing mobile communications world to turn towards betterMultiple Access (MA) techniques, like Code Division Multiple Access (CDMA) [5]. The demand for higher throughput and better QoS in future 4G systems have also given rise to a scheme that is becoming ever more popular for use in these so-called ‘bandwidth-on-demand’ systems. This scheme is known as adaptive channel coding, and gives a system the ability to firstly sense changes in conditions, and secondly, to adapt to these changes, exploiting the fact that under good channel conditions, a very simple or even no channel coding scheme can be used for Forward Error Correction(FEC). This will ultimately result in better system throughput utilization. One such scheme, known as incremental redundancy, is already implemented in the Enhanced Data Rates for GSM Evolution (EDGE) standard. This study presents an extensive simulation study of a Multi-User (MU), adaptive channel coded Direct Sequence Spread Spectrum Multiple Access (DS/SSMA) communication system. This study firstly presents and utilizes a complex Base Band(BB) DS/SSMA transmitter model, aimed at user data diversity [6] in order to realize the MU input data to the system. This transmitter employs sophisticated double-sideband (DSB)Constant-Envelope Linearly Interpolated Root-of-Unity (CE-LI-RU) filtered General Chirp-Like (GCL) sequences [34, 37, 38] to band limit and spread user data. It then utilizes a fully user-definable, complex Multipath Fading Channel Simulator(MFCS), first presented by Staphorst [3], which is capable of reproducing all of the physical attributes of realistic mobile fading channels. Next, this study presents a matching DS/SSMA receiver structure that aims to optimally recover user data from the channel, ensuring the achievement of data diversity. In order to provide the basic channel coding functionality needed by the system of this study, three simple, but well-known channel coding schemes are investigated and employed. These are: binary Hamming (7,4,3) block code, (15,7,5) binary Bose-Chadhuri-Hocquenghem (BCH) block code and a rate 1/3 <i.Non-Systematic (NS) binary convolutional code [6]. The first step towards the realization of any adaptive channel coded system is the ability to measure channel conditions as fast as possible, without the loss of accuracy or inclusion of known data. In 1965, Gooding presented a paper in which he described a technique that measures communication conditions at the receiving end of a system through a device called a Performance Monitoring Unit (PMU) [12, 13]. This device accelerates the system’sBit Error Rate (BER) to a so-called Pseudo Error Rate(PER) through a process known as threshold modification. It then uses a simple PER extrapolation algorithm to estimate the system’s true BER with moderate accuracy and without the need for known data. This study extends the work of Gooding by applying his technique to the DS/SSMA system that utilizes a generic Soft-Output Viterbi Algorithm(SOVA) decoder [39] structure for the trellis decoding of the binary linear block codes [3, 41-50], as well as binary convolutional codes mentioned, over realistic MU frequency selective channel conditions. This application will grant the system the ability to sense changes in communication conditions through real-time BER measurement and, ultimately, to adapt to these changes by switching to different channel codes. Because no previous literature exists on this application, this work is considered novel. Extensive simulation results also investigate the linearity of the PER vs. modified threshold relationship for uncoded, as well as all coded cases. These simulations are all done for single, as well as multiple user systems. This study also provides extensive simulation results that investigate the calculation accuracy and speed advantages that Gooding’s technique possesses over that of the classic Monte-Carlo technique for BER estimation. These simulations also consider uncoded and coded cases, as well as single and multiple users. Finally, this study investigates the experimental real-time performance of the fully functional MU, adaptive coded, DS/SSMA communication system over varying channel conditions. During this part of the study, the channel conditions are varied over time, and the system’s adaptation (channel code switching) performance is observed through a real-time observation of the system’s estimated BER. This study also extends into cases with multiple system users. Since the adaptive coded system of this study does not require known data sequences (training sequences), inclusion of Gooding’s technique for real-time BER estimation through threshold modification and PER extrapolation in future 4G adaptive systems will enable better Quality-of-Service (QoS) management without sacrificing throughput. Furthermore, this study proves that when Gooding’s technique is applied to a coded system with a soft-output, it can be an effective technique for QoS monitoring, and should be considered in 4G systems of the future. / Dissertation (MEng (Computer Engineering))--University of Pretoria, 2007. / Electrical, Electronic and Computer Engineering / MEng / unrestricted

No description available.