Grätzel cells or Dye-Sensitized Solar Cells (DSSCs) are considered one of the most promising methods to convert the sun's energy into electricity due to their low cost and simple technology of production. The Grätzel cell is based on a photosensitizer adsorbed on a low band gap semiconductor. The photosensitizer can be a metal complex or an organic dye. Organic dyes can be produced on a large scale resulting in cheaper dyes than complexes based on rare elements. However, the performance of Grätzel cells based on metal-free, organic dyes is not high enough yet. The dye's performance depends primarily on the electron dynamics. The electron dynamics in Grätzel cells includes electron injection, recombination, and regeneration. Different deactivation processes affect the electron dynamics and the cells’ performance. In this thesis, the electron dynamics was explored by various time-resolved spectroscopic techniques, namely time-correlated single photon counting, streak camera, and femtosecond transient absorption. Using these techniques, new deactivation processes for organic dyes used in DSSCs were uncovered. These processes include photoisomerization, and quenching through complexation with the electrolyte. These deactivation processes affect the performance of organic dyes in Grätzel cells, and should be avoided. For instance, the photoisomerization can compete with the electron injection and produce isomers with unknown performance. Photoisomerization as a general phenomenon in DSSC dyes has not been shown before, but is shown to occur in several organic dyes, among them D149, D102, L0 and L0Br. In addition, D149 forms ground state complexes with the standard iodide/triiodide electrolyte, which directly affect the electron dynamics on TiO2. Also, new dyes were designed with the aim of using ferrocene(s) as intramolecular regenerators, and their dynamics was studied by transient absorption. This thesis provides deeper insights into some deactivation processes of organic dyes used in DSSCs. New rules for the design of organic dyes, based on these insights, can further improve the efficiency of DSSCs.

<p>In this thesis, regioregularpoly( 3-hexylthiophene) (rr-P3HT) polymer was used as a light absorption and electron donating material, while the C60 fullerene and its derivative [6,6]-phenyl C61-butyric acid methyl ester (PCBM) were used as electron acceptor materials. The effect of solvent to control the degree of mixing of the polymer and fullerene components, as well as the domain size and charge transport properties of the blends were investigated in detail using P3HT:C60 films. The photo-physical, structural and electrical transport properties of the polymer blends were carried out according to their ratios. A distinctive photoluminescence (PL) quenching effect was observed indicating a photo-induced electron transfer. In this thesis, the effect of solvents on the crystallization and interchain interaction of P3HT and C60 fullerene films were studied using XRD, UV-vis, PL, Raman and FTIR spectroscopy. The polymer blends formed with non-aromatic solvents exhibited an improved crystallinity and polymer morphology than that formed with aromatic solvents. An improved ordering was demonstrated in the polymer films spin coated from non-aromatic solvents. This indicates that the limited solubility of rr P3HT in a marginal solvent such as non-aromatic solvents can offer a strategy to obtain highly ordered crystal structures and lead directly to optimal morphologies on the films.</p>

L'identification, chez divers organismes, d'enzymes de dégradation des N-acyl homosérineslactones (NAHLs) impliquées dans la signalisation QS pose la question de leurs rôles dans lesinteractions bactéries-eucaryotes. Dans une première partie, une synthèse bibliographique analyse lesconnaissances acquises sur ces enzymes dégradant les NAHLs. Dans une seconde partie, la croissancedes bactéries dégradant les signaux NAHLs a été stimulée par l'application de g-caprolactone (GCL)dans la rhizosphère de plants de pommes de terre à des fins de phytoprotection. L'effet de cetraitement sur la diversité des communautés bactériennes rhizosphériques a été évalué en combinantdifférentes approches d'écologie microbienne moléculaire comme la DGGE, le pyroséquençaged'amplicons rrs, et la métagénomique fonctionnelle. Cette dernière approche appliquée à une banquede 30 000 clones environ a conduit à l'identification d'un gène qsdB codant la dégradation des signauxNAHL. Ce travail révèle ainsi l'existence d'une nouvelle classe d'enzymes de dégradation des NAHLsappartenant à la famille des enzymes possédant une signature amidase (AS) dont des membres sontpar ailleurs impliqués dans la dégradation de composés xénobiotiques. Dans une troisième partie, unsystème expérimental a été développé afin de mesurer le transfert conjugatif du plasmide de virulenceTi (tumor inducing) chez des dérivés du pathogène Agrobacterium tumefaciens, appelés "tricheurs",incapables de produire des signaux NAHLs mais utilisateurs de ceux produits par les autres bactéries.Ce modèle a permis de montrer l'effet modérateur de lactonases dégradant les NAHLs exprimées chezdes agrobactéries produisant les NAHLs, chez des bactéries réceptrices du plasmide Ti, ou des planteshôtes des agrobactéries sur le transfert conjugatif initié par les tricheurs. L'ensemble de ce travailrévèle à la fois une nouvelle famille d'enzymes impliquées dans la dégradation des NAHLs, ainsiqu'un nouveau rôle de ces enzymes dans la modulation des flux de gènes entre bactériesphytopathogènes en interaction avec une plante hôte.

Les propriétés intrinsèques, photophysiques, électrochimiques et cristallographiques des molécules fluorescentes 4,4'-bis(2-benzoxazolyle)stilbène (BBS) et 2,5-bis(5-tert-butyl-2-benzoxazolyle)thiophène (BBT) ont été étudiées en solution et dans les polymères semi-cristallins : poly(butylène succinate) (PBS) et polylactide (PLA). Les deux fluorophores sont caractérisés par de hauts rendements quantiques absolus de fluorescence. Toutefois, une désactivation de la fluorescence peut se produire par croisement intersystème vers l'état triplet pour le BBT, et par photoisomérisation trans-cis pour le BBS. La cinétique de ce dernier processus dépend de la concentration, résultant en un pur isomère cis photo-induit à faibles concentrations, qui est accompagné à des concentrations élevées par l'apparition d'un composé acide après photo-clivage suivi d'une oxydation. Cette étude a révélé des changements spectroscopiques prononcés suite à l’augmentation de la concentration des fluorophores, en particulier à l'état solide, spécifiques à l'agrégation des molécules à l'état fondamental pour le BBT et à la formation d’excimères pour le BBS, permettant ainsi de corréler les propriétés fluorescentes avec les caractéristiques du monocristal pour chaque fluorophore. En outre, le passage d’une dispersion moléculaire à une séparation de phases dans le cas du BBS est accompagné d'un changement de couleur du bleu au vert, qui est sensible à la déformation, à la température et au temps, affectant les rendements quantiques absolus de fluorescence et fournissant une large opportunité à la création d'une grande variété de polymères intelligents indicateurs capables d'auto-évaluation. D’autre part, la solubilité élevée du BBT dans les solvants courants, combinée à ses propriétés optoélectroniques élevées, en font un candidat en tant que référence universelle de fluorescence et matériau intelligent à la fois pour les études de polymères et en solution. Similairement aux mélanges comprenant des polymères miscibles, l'orientation du PBS augmente après ajout d'une molécule fluorescente, dont les monomères ont tendance à être orientés dans des films étirés, contrairement aux excimères ou agrégats. / The intrinsic, photophysical, electrochemical and crystallographic properties of the fluorescent molecules 4,4'-bis(2-benzoxazolyl)stilbene (BBS) and 2,5-bis(5-tert-butyl-2-benzoxazolyl)thiophene (BBT) have been investigated in solution as well as in semi-crystalline poly(butylene succinate) (PBS) and polylactide (PLA). Both fluorophores were found to be characterized by high fluorescence absolute quantum yields. However, fluorescence quenching was found to occur by intersystem crossing to the triplet state for BBT, and by trans-cis photoisomerization for BBS. The latter process was kinetically concentration-dependent, resulting in a pure photoinduced cis-isomer at low concentrations, which is accompanied at high concentrations by the appearance of an acidic compound after photocleavage followed by oxidation. This study revealed pronounced spectroscopic changes upon an increase of the fluorophore concentration, especially in the solid-state, specific to aggregation of ground state molecules for BBT or excimer formation for BBS, thus correlating the fluorescent features with the single crystal characteristics for each fluorophore. Moreover, the transformation from molecular dispersion to phase separation, occurring for BBS, is accompanied by a significant colour change from blue to green, which is sensitive to deformation, time and temperature, thus affecting the absolute fluorescence quantum yields and providing a broad opportunity for the creation of a wide variety of smart polymers with self-assessing capabilities. On the other hand, the BBT’s high solubility in common solvents combined with its measured enhanced optoelectronic properties make it a candidate as a universal fluorophore reference and smart material for both polymeric and solution studies. Similarly to blends comprising miscible polymers, the PBS orientation was found to increase by adding a fluorescent molecule, whose monomers tend to be oriented in stretched films, contrary to excimers or aggregates.

This thesis describes the work undertaken by the author in collaboration with Wyman-Gordon Forgings, USA, to assist in the development of a cooling system,based on air assisted atomised water sprays primarily for the quenching of aerospace components from high temperatures. The mechanical properties of forgings used in aircraft engines depend on the rate of cooling from the heat treatment solution temperature. It is well known that water quenching produces high cooling rate. Although, the severity of the quench can sometimes produce unacceptable distortion and high residual stresses in the component. For this reason water quenching is only used when a high cooling rate is definitely needed and it is often replaced by a less severe oil quench. However, over the last 10 years the trend to reduce manufacturing costs has led to the forging of parts that are closer to the net shape. In these cases even oil quenching can lead to residual stresses being developed that result in difficulties during the final machining of the engine component. Forced air cooling has been adopted in problem cases where the part is thin enough to attain the desired cooling rate. In many instances, however, the component is of intermediate size or varying in cross section and fan cooling cannot provide the cooling rate which is needed to obtain the desired mechanical properties, whilst oil quenching produces an unacceptable level of residual stresses. The use of air assisted atomised water sprays can provide heat transfer coefficients whose values lie between those for air cooling and oil quenching. Another advantage is that control of the air pressure enables the spray nozzle to operate with a much wider range of water flow rates so that the cooling rate can be readily controlled over the range. This study describes the investigation of the heat transfer characteristics of air assisted atomised water sprays to quench aeroengine components from temperatures of approximately 850°C. New data were obtained at high temperatures for air assisted atomised water sprays operating over a wide range of water mass fluxes, (8.01>w 0 >0kg/m2 .s). In practice the geometry of a component can be complex in shape. Therefore an investigation was also carried out into the application of spray cooling on recessed surfaces. It was found that the surface recess contributes significantly to the reduction in the rate of heat transfer at low and high water mass fluxes, but had little effect at intermediate flow rates. Pulsed sprays were investigated and proposed as a means of controlling heat transfer coefficients for both plane and recessed surfaces. The use of a pulsed spray makes it possible to control the amount of water impacting on a surface per second. It was found that "water off periods of 5 and 10 seconds resulted in a reduction in heat transfer coefficients at low temperatures and also reduced considerably the differences in cooling previously observed between plane and recessed surfaces. A finite element code was used to predict the residual stresses produced in a forged component for a range of spray parameters, and spray arrangements. The data were compared with cooling rates and stress patterns produced by both air and oil quenching. It was found that spray cooling resulted in cooling rates which met the mechanical property specification and provided residual stresses lower than those obtained during oil quenching. Furthermore, simulations of residual stress formation using two different spray arrangements in a typical forging indicated that spray non uniformities can substantially disturb the resultant residual stress patterns which could result in less predictable distortions during final machining. The study of spray cooling presented here suggests that the use of air assisted atomised water sprays has considerable potential and could provide the required cooling rate for individual forgings.

Philosophiae Doctor - PhD / In this thesis, regioregularpoly( 3-hexylthiophene) (rr-P3HT) polymer was used as a light absorption and electron donating material, while the C60 fullerene and its derivative [6,6]-phenyl C61-butyric acid methyl ester (PCBM) were used as electron acceptor materials. The effect of solvent to control the degree of mixing of the polymer and fullerene components, as well as the domain size and charge transport properties of the blends were investigated in detail using P3HT:C60 films. The photo-physical, structural and electrical transport properties of the polymer blends were carried out according to their ratios. A distinctive photoluminescence (PL) quenching effect was observed indicating a photo-induced electron transfer. In this thesis, the effect of solvents on the crystallization and interchain interaction of P3HT and C60 fullerene films were studied using XRD, UV-vis, PL, Raman and FTIR spectroscopy. The polymer blends formed with non-aromatic solvents exhibited an improved crystallinity and polymer morphology than that formed with aromatic solvents. An improved ordering was demonstrated in the polymer films spin coated from non-aromatic solvents. This indicates that the limited solubility of rr P3HT in a marginal solvent such as non-aromatic solvents can offer a strategy to obtain highly ordered crystal structures and lead directly to optimal morphologies on the films. / South Africa

This thesis comprises of diverse projects all focused towards analysis of mitochondrial translation in unicellular parasites. As only two mitochondrially encoded genes are required during the life cycle stage when Trypanosoma brucei resides in the bloodstream of a mammalian host, this protist provides a simplified background in which to study mitochondrial translation termination phase. The leading project utilizes T. brucei to examine mitochondrial translation termination factor TbMrf1 by gene knockout. Subsequently, it is suggested that the peptidyl-tRNA hydrolase TbPth4 is able to abate the TbMrf1 knockout phenotype by its ability to rescue mitoribosomes that become stalled when TbMrf1 is absent. Additionally, modifying methyltransferase of TbMrf1, the TbMTQ1, was characterized. And finally, this work contributed to the development of the protein expression regulation method in Leishmania parasites, a protocol for measurement of proton pumping activity of FoF1 ATPase complex in native mitochondria, and optimization of purification protocol for hydrophobic recombinant proteins.

Nonphotochemical quenching and state transitions are an important photoprotective mechanism against excessive irradiation. In this work I studied changes in the size of the effective crosssection of photosystem II antennae in regard to the level of nonphotochemical quenching (state transitions) under different levels of light induced stress.

Submitted by Maike Costa (maiksebas@gmail.com) on 2016-05-11T11:38:41Z No. of bitstreams: 1 arquivo total.pdf: 5689290 bytes, checksum: 55be9a3cf14a111bd7b7407cbca5df8e (MD5) / Made available in DSpace on 2016-05-11T11:38:41Z (GMT). No. of bitstreams: 1 arquivo total.pdf: 5689290 bytes, checksum: 55be9a3cf14a111bd7b7407cbca5df8e (MD5) Previous issue date: 2015-08-07 / The photoluminescence efficiency in compounds of lanthanide ions is a result of the complex balance between absorption of photons, energy transfer and quenching mechanisms, among which the multiphonon decay and suppression mediated by low energy ligand-to-metal charge transfer states (LMCT) which might be generated by ligands that have a low oxidation potential, for instance the NCS–. Less than a decade ago, this process was described mainly in terms of the energy transfer between 4f states and LMCT states, not being considered the participation of intraligands states. In the present study, we investigated the photoluminescent properties of new lanthanide isothiocyanates coordination complexes with N-acetyl-2-aminopyridine, N-benzoyl-2-aminopyridine and N-benzoyl-2- aminopyrimidine as ligands. We also synthesized the well-known complexes of formulas [Ln(NCS)3(phen)3] (H2O), and [Ln(NO3)3(Phen)2] with phen = 1,10-phenanthroline. The complexes were characterized via CHN elemental analysis, vibrational spectroscopy, complexometric titration and thermogravimetric analysis. Their spectroscopic properties were investigated via molecular diffuse reflectance, excitation and emission spectroscopy along with time decay of the emitting states. The results from the analysis of emission spectroscopy and photoluminescence excitation, as well as the lifetimes measurements of the emitting states of the investigated complexes provided what we believe to be the most expressive experimental demonstration of the luminescence quenching via triplet-LMCT energy transfer process in Eu(III) complex so far. / A eficiência na fotoluminescência em compostos de íons lantanídeos é o resultado de um balanço complexo entre absorção de fótons, transferência de energia e mecanismos supressores, dentre os quais se destacam o decaimento multifônon e a supressão mediada por estados de transferência de carga ligante-metal (TCLM) de baixa energia, que pode ser gerado por ligantes que apresentam baixo potencial de oxidação, a exemplo do NCS–. Há menos de uma década, este processo era descrito essencialmente em termos da transferência de energia entre estados 4f e os estados TCLM, não sendo considerada a participação dos estados intraligantes. Neste trabalho, investigamos as propriedades fotoluminescentes de novos compostos de coordenação de isotiocianatos de lantanídeos com os ligantes N-acetil- 2-aminopiridina, N-benzoil-2-aminopiridina e N-benzoil-2-aminopirimidina. Sintetizamos, também, os complexos já conhecidos, de fórmulas gerais [Ln(NCS)3(phen)3] (H2O) e [Ln(NO3)3(phen)2] com phen= 1,10-fenantrolina. Os complexos foram caracterizados por análise elementar de CHN, espectroscopia vibracional na região do infravermelho, análise termogravimétrica e titulação complexométrica e suas propriedades espectroscópicas foram investigadas por espectroscopias molecular de reflectância difusa e de excitação e emissão bem como os tempos de decaimento dos estados emissores. Os resultados obtidos a partir das análises de espectroscopia de emissão e excitação da fotoluminescência, assim como as medidas de tempos de vida dos estados emissores dos complexos investigados proporcionaram o que acreditamos ser a demonstração experimental mais expressiva, até então, do processo de supressão da luminescência mediada pelo processo de transferência de energia tripleto-TCLM em complexos do íon Eu(III).

O desenvolvimento de métodos de simulação física e numérica tem criado novas possibilidades de otimização dos processos relacionados à estampagem com inclusão de processos industriais reais. Portanto, recorrendo à aplicação destes métodos de análise, é possível avaliar a transformação mecânica e as transformações de fase que ocorrem no material e prever as interações entre as propriedades dos materiais no processo de conformação, o comportamento constitutivo do material, as variáveis de otimização do processo, bem como a previsão das tensões e deformações a fim de estabelecer a melhor relação material-processo-desempenho. A introdução e crescente utilização de aços avançados de alta resistência (AHSS) em aplicações automotivas exige uma maior compreensão dos fenômenos físicos envolvidos no processamento termomecânico a fim de otimizar a performance da peça final fabricada. O presente trabalho teve como objetivo avaliar experimentalmente o processo de estampagem a quente, com posterior tratamento térmico de têmpera e partição e analisar as microestruturas formadas e suas propriedades mecânicas. A formação de microestruturas durante o processo de estampagem a quente e de têmpera e partição foi avaliada neste trabalho por simulação física em simulador termomecânico Gleeble, acoplado à uma linha de difração de raios X (XTMS) de feixe de luz síncrotron no Laboratório Nacional de Nanotecnologia (LNNano). Foram avaliadas a partição do carbono, a estabilidade térmica da austenita retida e a formação de microconstituintes resultantes da transformação da austenita durante resfriamento forçado (têmpera), seguido de partição de carbono em patamares isotérmicos. Foram utilizadas técnicas de caracterização com apoio de microscopia eletrônica (MEV-FEG e STEM), EBSD, tomografia de sonda atômica (APT) e avaliação de propriedades mecânicas por ensaios de tração e indentação instrumentada. A análise numérica foi realizada por meio do método dos elementos finitos (MEF) e por elementos finitos orientada a objetos (OOF, Object Oriented Finite Element Analysis) visando estabelecer correlações entre microestrutura e propriedades mecânicas, comparando com resultados experimentais. Os resultados e conclusões obtidos no projeto, além de possibilitarem a identificação dos mecanismos fundamentais de geração de microestruturas durante o processo, auxiliam no projeto de aços AHSS estampados a quente, usados principalmente na indústria automobilística, na busca pela redução do consumo de combustível, através da redução do peso, e pelo aumento da segurança dos passageiros. / The development of numerical and physical simulation methods has created new possibilities regarding the optimization of metal forming processes, taking into account real industrial forming processes. Therefore, by applying such methods of analysis it is now possible to assess the material phase transformations and predict the interactions between material properties and the forming process, the constitutive behavior of the material, and optimize process variables as well as predicting the best material-process-performance relationship. The increasing usage of Advanced High Strength Steels (AHSS) in automotive applications demands a better insight of the physical phenomena involved in the thermomechanical processing in order to optimize the performance of the final manufactured part. Thermomechanical simulation of the hot stamping, quenching and partitioning process was carried out in a Gleeble machine coupled to the XTMS Synchrotron X-ray diffraction line at the National Nanotechnology Laboratory (LNNano). Carbon partitioning, carbon contents, and amount of retained austenite, martensite, bainite and ferrite was assessed online during the experiments. In addition, characterization techniques by optical, electron microscopy (FEG-SEM and STEM), EBSD, and Atom Probe Tomography (APT) were applied. Mechanical testing of subsize specimens of the processed steels was performed by means of tensile tests and macro and nanoindentation tests. The numerical analysis was performed using the finite element method (FEM) and object-oriented finite element technique (OOF). The results were compared with the experimental results of mechanical testing of specimens used in the thermomechanical simulations and with hot stamped sheets, where quenching and partitioning were carried out. The results and conclusions obtained in this project allow the identification of the fundamental mechanisms of the process, helping the design of the hot stamping process for AHSS steels used primarily in the automotive industry, seeking weight reduction to improve fuel economy and increased passenger safety.