Friedreich Ataxia

Friedreich's ataxia (FRDA) is the most common autosomal recessive hereditary ataxia in Caucasians. Neurological symptoms dominate the clinical picture. The underlying neuropathology affects the dorsal root ganglia, the spinal cord, and the deep cerebellar nuclei. In addition, most cases present a hypertrophic cardiomyopathy that may cause premature death. Other problems include a high risk of diabetes, skeletal abnormalities such as kyphoscoliosis, and pes cavus. Most patients carry a homozygous expansion of GAA trinucleotide repeat within the first intron of the FXN gene, leading to repressed transcription through epigenetic mechanisms. The encoded protein, frataxin, is localized in mitochondria and participates in the biogenesis of iron-sulfur clusters. Frataxin deficiency leads to mitochondrial dysfunction, altered iron metabolism, and oxidative damage. Thanks to progress in understanding pathogenesis and to the development of animal and cellular models, therapies targeted to correct frataxin deficiency or its downstream consequences are being developed and tested in clinical trials.

Friedreich Ataxia

Friedreich ataxia (FRDA) is an autosomal recessive disease characterized by progressive neurological and cardiac abnormalities. It has a prevalence of around 2×10⁵ in whites, accounting for more than one-third of the cases of recessively inherited ataxia in this ethnic group. FRDA may not exist in nonwhite populations.The first symptoms usually appear in childhood, but age of onset may vary from infancy to adulthood. Atrophy of sensory and cerebellar pathways causes ataxia, dysarthria, fixation instability, deep sensory loss, and loss of tendon reflexes. Corticospinal degeneration leads to muscular weakness and extensor plantar responses. A hypertrophic cardiomyopathy may contribute to disability and cause premature death. Other common problems include kyphoscoliosis, pes cavus, and, in 10% of patients, diabetes mellitus.The FRDA gene (FXN) encodes a small mitochondrial protein, frataxin, which is produced in insufficient amounts in the disease, as a consequence of the epigenetic silencing of the gene triggered by a GAA triplet repeat expansion in the first intron of the gene. Frataxin deficiency results in impaired iron-sulfur cluster biogenesis in mitochondria, in turn leading to widespread dysfunction of iron-sulfur center containing enzymes (in particular respiratory complexes I, II and III, and aconitase), impaired iron metabolism, oxidative stress, and mitochondrial dysfunction. Therapy aims to restore frataxin levels or to correct the consequences of its deficiency.

Faint Galaxies in the Megaparsec-Scale Environments of Hyperluminous QSOs at Redshifts 2 < z < 3

This thesis presents detailed observational studies of the extended distributions of gas, galaxies, and dark matter around hyperluminous quasars (HLQSOs) at high redshift. Taken together, these works aim to coherently describe the relationships between these massive, accreting black holes and their environments: the nature of the regions that give rise to such massive black holes, the effect of HLQSO radiation on their surrounding galaxies and gas, and the ability of both galaxies and black holes to shed new light on the formation and evolution of the other.

Chapter 2 focuses on the continuum-color-selected galaxies drawn from the Keck Baryonic Structure Survey (KBSS). The KBSS is a uniquely deep spectroscopic survey of star-forming galaxies in the same volumes of space as 15 HLQSOs at 2.5 < z < 2.9. The three-dimensional distribution of these galaxies among themselves and the nearby HLQSOs is used to infer the extent to which these black holes are associated with overdense peaks in the dark matter and galaxy distribution as quantified by clustering statistics. In conjunction with recent dark-matter simulations, these data provide the first estimates of the host dark-matter halo masses for HLQSOs, providing new insight into the formation and evolution of the most massive black holes at high redshift.

Chapter 3 describes the first results from a new survey (KBSS-Lyα) conducted for this thesis. The KBSS-Lyα survey uses narrowband imaging to identify Lyα-emitters (LAEs) in the ~Mpc regions around eight of the KBSS HLQSOs. Many of these LAEs show the effect of reprocessed HLQSO radiation in their emission through the process known as Lyα fluorescence. In this chapter, these fluorescent LAEs are used to generate a coarse map of the average HLQSO ionizing emission on Mpc scales, thereby setting the first direct constraints of the lifetime and angular distribution of activity for a population of these uniquely luminous black holes.

Chapter 4 contains a more detailed description of the KBSS-Lyα survey itself and the detailed properties of the star-forming and fluorescent objects selected therein. Using imaging and spectroscopic data covering rest-frame UV and optical wavelengths, including spectra from the new near-infrared spectrometer MOSFIRE, we characterize this population of nascent galaxies in terms of their kinematics, enrichment, gas properties, and luminosity distribution while comparing and contrasting them with previously-studied populations of continuum-selected galaxies and LAEs far from the effects of HLQSO emission.

At the conclusion of this thesis, I briefly present future directions for the continuation of this research. In Appendix A, I provide background information on the instrumentation used in this thesis, including my own contributions to MOSFIRE.

Graphene and Semicondutor or Metallic Nanoparticles for Energy Conversion

The purpose of the present PhD thesis is to investigate the properties of innovative nano- materials with respect to the conversion of renewable energies to electrical and chemical energy. The materials have been synthesized and characterized by means of a wide spectrum of morphological, compositional and photophysical techniques, in order to get an insight into the correlation between the properties of each material and the activity towards different energy conversion applications. Two main topics are addressed: in the first part of the thesis the light harvesting in pyrene functionalized silicon nanocrystals has been discussed, suggesting an original approach to suc- cessfully increase the absorption properties of these nanocrystals. The interaction of these nanocrystals was then studied, in order to give a deeper insight on the charge and energy extraction, preparing the way to implement SiNCs as active material in optoelectronic devices and photovoltaic cells. In addition to this, the luminescence of SiNCs has been exploited to increase the efficiency of conventional photovoltaic cells by means of two innovative architectures. Specifically, SiNCs has been used as luminescent downshifting layer in dye sensitized solar cells, and they were shown to be very promising light emitters in luminescent solar concentrators. The second part of the thesis was concerned on the production of hydrogen by platinum nanoparticles coupled to either electro-active or photo-active materials. Within this context, the electrocatalytic activity of platinum nanoparticles supported on exfoliated graphene has been studied, preparing an high-efficiency catalyst and disclosing the role of the exfoliation technique towards the catalytic activity. Furthermore, platinum nanoparticles have been synthesized within photoactive dendrimers, providing the first proof of concept of a dendrimer-based photocatalytic system for the hydrogen production where both sensitizer and catalyst are anchored to a single scaffold.

Theoretical Rationalization of the Singlet–Triplet Gap in OLEDs Materials: Impact of Charge-Transfer Character

New materials for OLED applications with low singlet–triplet energy splitting have been recently synthesized in order to allow for the conversion of triplet into singlet excitons (emitting light) via a Thermally Activated Delayed Fluorescence (TADF) process, which involves excited-states with a non-negligible amount of Charge-Transfer (CT). The accurate modeling of these states with Time-Dependent Density Functional Theory (TD-DFT), the most used method so far because of the favorable trade-off between accuracy and computational cost, is however particularly challenging. We carefully address this issue here by considering materials with small (high) singlet–triplet gap acting as emitter (host) in OLEDs and by comparing the accuracy of TD-DFT and the corresponding Tamm-Dancoff Approximation (TDA), which is found to greatly reduce error bars with respect to experiments thanks to better estimates for the lowest singlet–triplet transition. Finally, we quantitatively correlate the singlet–triplet splitting values with the extent of CT, using for it a simple metric extracted from calculations with double-hybrid functionals, that might be applied in further molecular engineering studies.

Surface photochemistry: photodegradation study of pyrene adsorbed onto microcrystalline cellulose and silica

Ground-state diffuse reflectance, time resolved laser-induced luminescence, diffuse reflectance laser flash-photolysis transient absorption and chromatographic techniques were used to elucidate the photodegradation processes of pyrene adsorbed onto microcrystalline cellulose and silica. Ground-state diffuse reflectance showed that on both substrates low concentrations display absorption of pyrene monomers. At high concentrations spectral changes attributed to aggregate formation were observed. Laser induced fluorescence showed that pyrene onto microcrystalline cellulose mainly presents fluorescence from monomers, while for silica, excimer-like emission was observed from low surface loadings (greater than or equal to 0.5 mumol g(-1)). Transient absorption and photodegradation studies were performed at concentrations where mainly monomers exist. On silica, pyrene presents transient absorption from its radical cation. On microcrystalline cellulose both radical cation, radical anion and pyrene triplet-triplet absorption were detected. Irradiation followed by chromatographic analysis showed that pyrene decomposes on both substrates. For pyrene on microcrystalline cellulose 1-hydroxypyrene was the main identified photoproduct since in the absence of oxygen further oxidation of 1-hydroxypyrene was very slow. For pyrene on silica photodegradation was very efficient. Almost no 1-hydroxypyrene was detected since in the presence of oxygen it is quickly oxidized to other photooxidation products. On both substrates, pyrene radical cation is the intermediate leading to photoproducts and oxygen it is not involved in its formation.

A diffuse reflectance comparative study of benzil inclusion within microcrystalline cellulose and beta-cyclodextrin

Diffuse reflectance and laser-induced techniques were used to study photochemical and photophysical processes of benzil adsorbed on two solid powdered supports, microcrystalline cellulose and beta-cyclodextrin. In both substrates, a distribution of ground-state benzil conformers exists, largely dominated by skew conformations where the carbonyl groups are twisted one to the other. Room temperature phosphorescence was observed in air-equilibrated samples in both cases. The decay times vary greatly and the largest lifetime was obtained for benzil/beta-cyclodextrin, showing that this host's cavity accommodates benzil well, enhancing its room temperature phosphorescence. Triplet - triplet absorption of benzil entrapped in cellulose was detected and benzil ketyl radical formation also occurred. With benzil included into beta-cyclodextrin, and following laser excitation, benzoyl radicals were detected on the millisecond timescale. Product analysis and identification of laser-irradiated benzil samples in the two hosts clearly showed that the main degradation photoproducts were benzoic acid and benzaldehyde. The main differences were a larger benzoic acid/benzaldehyde ratio in the case of cellulose and the formation of benzyl alcohol in this support.

Novel laser-induced luminescence resulting from benzophenone/O-propylated p-tert-butylcalix[4]arene complexes. A diffuse reflectance study

Laser-induced room temperature luminescence of air-equilibrated benzophenone/O-propylated p-tert-butylcalix[ 4] arene solid powdered samples revealed the existence of a novel emission, in contrast with benzophenone/p-tertbutylcalix[ 4] arene complexes, where only benzophenone emits. This novel emission was identified as phosphorescence of 1-phenyl-1,2-propanedione, which is formed as the result of an hydrogen atom abstraction reaction of the triplet excited benzophenone from the propoxy substituents of the calixarene. Room temperature phosphorescence was obtained in air-equilibrated samples in all propylated hosts. The decay times of the benzophenone emission vary greatly with the degree of propylation, the shortest lifetimes being obtained in the tri- and tetrapropylated calixarenes. Triplet - triplet absorption of benzophenone was detected in all cases, and is the predominant absorption in the p-tert-butylcalix[ 4] arene case, where an endo-calix complex is formed. Benzophenone ketyl radical formation occurs with the O-propylated p-tert-butylcalix[ 4] arenes hosts, suggesting a different type of host/guest molecular arrangement. Diffuse reflectance laser. ash photolysis and gas chromatography - mass spectrometry techniques provided complementary information, the former about transient species and the latter regarding the final products formed after light absorption. Product analysis and identification clearly show that the two main degradation photoproducts following laser excitation in the propylated substrates are 1-phenyl-1,2- propanedione and 2- hydroxybenzophenone, although several other minor photodegradation products were identified. A detailed mechanistic analysis is proposed. While the solution photochemistry of benzophenone is dominated by the hydrogen abstraction reaction from suitable hydrogen donors, in these solid powdered samples, the alpha-cleavage reaction also plays an important role. This finding occurs even with one single laser pulse which lasts only a few nanoseconds, and is apparently related to the fact that scattered radiation exists, due to multiple internal reflections possibly trapping light within non-absorbing microcrystals in the sample, and is detected until at least 20 mus after the laser pulse. This could explain how photoproducts thus formed could also be excited with only one laser pulse.

A diffuse reflectance comparative study of benzil inclusion within p-tert-butylcalix[n]arenes (n=4, 6, and 8) and silicalite

Diffuse reflectance and laser-induced techniques were used to access photochemical and photophysical processes of benzil in solid supports, namely p-tert-butylcalix[n]arenes with n = 4, 6, and 8. A comparative study was performed using these results and those obtained with another electronically inert support, silicalite, which is a hydrophobic zeolite. In the latter substrate, ground-state benzil has the two carbonyl groups in an s-trans planar conformation while in the calixarenes a distribution of conformers exists, largely dominated by skew conformations where the carbonyl groups are twisted one to the other. In all substrates, room-temperature phosphorescence was obtained in air-equilibrated samples. The decay times vary greatly and the largest lifetime was obtained for benzil/p-tert-butylcalix[6]arene, showing that this host cavity well accommodates benzil, enhancing its room-temperature phosphorescence. p-tert-Butylcalix[6] and [8]arene molecules provide larger hydrophobic cavities than silicalite, and inclusion complexes are formed with these hosts and benzil as guest; p-tert-butylcalix[4]arene does not include benzil. This probe is deposited outside the calix[41 cavity, in the form of microcrystals. Triplet-triplet absorption of benzil was detected in all cases and is predominant in the silicalite channel inclusion case. Benzil ketyl radical formation occurs with inclusion in calix[6]arene and calix[8]arene. In the three cases, benzoyl radical was detected at long times (in the millisecond time scale). Product analysis and identification clearly show that the main detected degradation photoproducts in all substrates are benzoyl radical derivatives. Calix[6] and [8]arenes are able to supply hydrogen atoms that allow also another reaction, the reduction to benzoin through benzil ketyl radical formation.

Superior color rendering with a phosphor-converted blue-cyan monolithic light-emitting diode

The future generation of modern illumination should not only be cheap and highly efficient, but also demonstrate high quality of light, light which allows better color differentiation and fidelity. Here we are presenting a novel approach to create a white solid-state light source providing ultimate color rendition necessary for a number of applications. The proposed semi-hybrid device combines a monolithic blue-cyan light emitting diode (MBC LED) with a green-red phosphor mixture. It has shown a superior color rendering index (CRI), 98.6, at correlated color temperature of around 3400 K. The MBC LED epi-structure did not suffer from the efficiency reduction typical for monolithic multi-color emitters and was implemented in the two most popular chip designs: “epi-up” and “flip-chip”. Redistribution of the blue and cyan band amplitudes in the white-light emission spectrum, using the operating current, is found to be an effective tool for fine tuning the color characteristics. (Figure presented.).

Roteiro Tecnológico (roadmap) da Captação, Utilização e Armazenamento de Dióxido de Carbono (CCUS) em Portugal

O objetivo primordial deste trabalho foi estabelecer um roteiro tecnológico para aplicação das tecnologias de “Captação, Utilização e Sequestração de Carbono - CCUS” em Portugal. Para o efeito procedeu-se à identificação da origem das maiores fontes emissoras estacionárias industriais de CO2, adotando como critério o valor mínimo de 1×105 ton CO2/ano e limitado apenas ao território continental. Com base na informação recolhida e referente aos dados oficiais mais recentes (ano de 2013), estimou-se que o volume de emissões industriais de CO2 possível de captar em Portugal, corresponde a cerca de 47 % do valor global das emissões industriais, sendo oriundo de três setores de atividade industrial: produção de cimento, de pasta de papel e centrais termoelétricas a carvão. A maioria das grandes fontes emissoras industriais localiza-se no litoral do país, concentrando-se entre Aveiro e Sines. Pelas condicionantes geográficas do país e, sobretudo pela vantagem de já existir uma rede de gasodutos para o transporte de gás natural, com as respetivas infraestruturas de apoio associadas, admitiu-se que o cenário mais favorável para o transporte do CO2 captado será a criação de um sistema de transporte por gasoduto específico para o CO2. Como critério de compatibilização da proximidade das fontes emissoras de CO2 com potenciais locais para o armazenamento geológico das correntes captadas, adotou-se a distância máxima de 100 km, considerada adequada perante a dimensão do território nacional e as características do tecido industrial nacional. Efetuou-se a revisão das tecnologias de captação de CO2 disponíveis, quer comercialmente, quer em níveis avançados de demonstração e procedeu-se à análise exploratória da adequação desses diferentes métodos de captação a cada um dos setores de atividade industrial previamente identificados com emissões de CO2 suscetíveis de serem captadas. Na perspetiva da melhor integração dos processos, esta análise preliminar tomou em consideração as características das misturas gasosas, assim como o contexto industrial correspondente e o processo produtivo que lhe dá origem. As possibilidades de utilização industrial do CO2 sujeito à captação no país foram tratadas neste trabalho de forma genérica dado que a identificação de oportunidades reais para a utilização de correntes de CO2 captadas exige uma análise de compatibilização das necessidades efetivas de utilização de CO2 por parte de potenciais utilizadores industriais que carece da caracterização prévia das propriedades dessas correntes. Este é um tipo de análise muito específico que pressupõe o interesse mútuo de diferentes intervenientes: agentes emissores de CO2, operadores de transporte e, principalmente, potenciais utilizadores de CO2 como: matéria-prima para a síntese de compostos, solvente de extração supercrítica na indústria alimentar ou farmacêutica, agente corretor de pH em tratamento de efluentes, biofixação por fotossíntese, ou outra das aplicações possíveis identificadas para o CO2 captado. A última etapa deste estudo consistiu na avaliação das possibilidades de armazenamento geológico do CO2 captado e envolveu a identificação, nas bacias sedimentares nacionais, de formações geológicas com características reconhecidas como sendo boas indicações para o armazenamento de CO2 de forma permanente e em segurança. Seguiu-se a metodologia preconizada por organizações internacionais aplicando à situação nacional, critérios de seleção e de segurança que se encontram reconhecidamente definidos. A adequação para o armazenamento de CO2 das formações geológicas pré-selecionadas terá que ser comprovada por estudos adicionais que complementem os dados já existentes sobre as características geológicas destas formações e, mais importante ainda, por testes laboratoriais e ensaios de injeção de CO2 que possam fornecer informação concreta para estimar a capacidade de sequestração e de retenção de CO2 nestas formações e estabelecer os modelos geológicos armazenamento que permitam identificar e estimar, de forma concreta e objetiva, os riscos associados à injeção e armazenamento de CO2.

Transfert ultrarapide d’électron et transfert modéré d’énergie au sein d’assemblages supramoléculaires de colorants et d’un cluster de palladium

Résumé : Les transferts d’électrons photo-induits et d’énergie jouent un rôle primordial dans un grand nombre de processus photochimiques et photobiologiques, comme la respiration ou la photosynthèse. Une très grande quantité de systèmes à liaisons covalentes ont été conçus pour copier ces processus de transferts. Cependant, les progrès sont, en grande partie, limités par les difficultés rencontrées dans la synthèse de nouveaux couples de types donneurs-accepteurs. Récemment, des espèces utilisant des liaisons non-covalentes, comme les liaisons hydrogènes, les interactions [pi]-[pi], les liaisons de coordination métal-ligands ou encore les interactions électrostatiques sont le centre d’un nouvel intérêt du fait qu’ils soient plus faciles à synthétiser et à gérer pour obtenir des comportements de transferts d’électrons ou d’énergie plus flexibles et sélectifs. C’est dans cette optique que le travail de cette thèse a été mené, i.e. de concevoir des composés auto-assemblés avec des porphyrines et un cluster de palladium pour l’étude des transferts d’électrons photo-induits et d’énergie. Cette thèse se divise en quatre parties principales. Dans la première section, le chapitre 3, deux colorants porphyriniques, soit le 5-(4-carboxylphényl)-10, 15, 20-tristolyl(porphyrinato)zinc(II) (MCP, avec Na+ comme contre-ion) et 5, 15-bis(4-carboxylphényl)-15, 20-bistolyl(porphyrinato)zinc(II) (DCP, avec Na+ comme contre-ion) ont été utilisés comme donneurs d’électrons, et le [Pd3(dppm)3(CO)]2+ ([Pd32+], dppm = (Ph2P)2CH2, PF6‾ est le contre-ion) a été choisi comme accepteur d’électrons. La structure de l’assemblage [Pd32+]•••porphyrine a été élucidée par l’optimisation des géométries à l’aide de calculs DFT. La spectroscopie d’absorption transitoire (TAS) montre la vitesse de transferts d’électrons la plus rapide (< 85 fs, temps inférieurs à la limite de détection) jamais enregistrée pour ce type de système (porphyrine-accepteur auto-assemblés). Généralement, ces processus sont de l’ordre de l’échelle de la ps-ns. Cette vitesse est comparable aux plus rapides transferts d’électrons rapportés dans le cas de systèmes covalents de type porphyrine-accepteur rapide (< 85 fs, temps inférieurs à la limite de détection). Ce transfert d’électrons ultra-rapide (ket > 1.2 × 1013 s-1) se produit à l’état énergétique S1 des colorants dans une structure liée directement par des interactions ioniques, ce qui indique qu’il n’est pas nécessaire d’avoir de forts liens ou une géométrie courbée entre le donneur et l’accepteur. Dans une deuxième section, au chapitre 4, nous avons étudié en profondeur l’effet de l’utilisation de porphyrines à systèmes π-étendus sur le comportement des transferts d’électrons. Le colorant 9, 18, 27, 36-tétrakis-meso-(4-carboxyphényl)tétrabenzoporphyrinatozinc(II) (TCPBP, avec Na+ comme contre-ion) a été sélectionné comme candidat, et le 5, 10, 15, 20-tétrakis-meso-(4-carboxyphényl)porphyrineatozinc(II) (TCPP, avec Na+ comme contre-ion) a aussi été utilisé à des fins de comparaisons. TCPBP et TCPP ont, tous deux, été utilisés comme donneurs d’électrons pour fabriquer des assemblages supramoléculaires avec le cluster [Pd32+] comme accepteur d’électrons. Les calculs DFT ont été réalisés pour expliquer les structures de ces assemblages. Dans les conditions expérimentales, ces assemblages sont composés principalement d’une porphyrine avec 4 équivalents de clusters. Ces systèmes ont aussi été investigués par des mesures de quenching (perte de luminescence), par électrochimie et par d’autres techniques. Les transferts d’électrons (< 85 fs; temps inférieurs à la limite de détection) étaient aussi observés, de façon similaire aux assemblages MCP•••[Pd32+] et [Pd32+]•••DCP•••[Pd32+]. Les résultats nous indiquent que la modification de la structure de la porphyrine vers la tétrabenzoporphyrine ne semble pas influencer le comportement des cinétiques de transferts d’électrons (aller ou retour). Dans la troisième section, le chapitre 5, nous avons synthétisé la porphyrine hautement [pi]-conjuguée: 9, 18, 27, 36-tétra-(4-carboxyphényléthynyl)tétrabenzoporphyrinatozinc(II) (TCPEBP, avec Na+ comme contre-ion) par des fonctionnalisations en positions meso- et β, β-, qui présente un déplacement vers le rouge de la bande de Soret et des bandes Q. TCPEBP était utilisé comme donneur d’électrons pour fabriquer des motifs supramoléculaires avec le [Pd32+] comme accepteur d’électrons. Des expériences en parallèle ont été menées en utilisant la 5, 10, 15, 20-tétra-(4-carboxyphényl)éthynylporphyrinatozinc(II) (TCPEP, avec Na+ comme contre-ion). Des calculs DFT et TDDFT ont été réalisés pour de nouveau déterminer de façon théorique les structures de ces systèmes. Les constantes d’association pour les assemblages TCPEBP•••[Pd32+]x sont les plus élevées parmi tous les assemblages entre des porphyrines et le cluster de palladium rencontrés dans la littérature. La TAS a montré, encore une fois, des processus de transferts d’électrons dans des échelles de l’ordre de 75-110 fs. Cependant, les transferts de retour d’électrons sont aussi très rapides (< 1 ps), ce qui est un obstacle potentiel pour des applications en cellules solaires à pigment photosensible (DSSCs). Dans la quatrième section, le chapitre 6, les transferts d’énergie triplets (TET) ont été étudiés pour les assemblages MCP•••[Pd32+] et [Pd32+]•••DCP•••[Pd32+]. Les analyses spectrales des états transitoires dans l’échelle de temps de la ns-[mu]s démontrent de façon évidente les TETs; ceux-ci présentent des transferts d’énergie lents et/ou des vitesses moyennes pour des transferts d’énergie T1-T1 (3dye*•••[Pd32+] → dye•••3[Pd32+]*) opérant à travers exclusivement le mécanisme de Förster avec des valeurs de kET autour de ~ 1 × 105 s-1 selon les mesures d’absorption transitoires à 298 K. Des forces motrices non-favorables rendent ces types de processus non-opérants ou très lents dans les états T1. L’état T1 de [Pd32+] (~8190 cm-1) a été qualitativement déterminé par DFT et par la mise en évidence de l’émission S0 ← Tn retardée à 680-700 nm provenant de l’annihilation T1-T1, ce qui fait que ce cluster peut potentiellement agir comme un donneur à partir de ses états Tn, et accepteur à partir de T1 à l’intérieur de ces assemblages. Des pertes d’intensités de types statiques pour la phosphorescence dans le proche-IR sont observées à 785 nm. Ce travail démontre une efficacité modérée des colorants à base de porphyrines pour être impliquée dans des TETs avec des fragments organométalliques, et ce, même attachées grâce à des interactions ioniques. En conclusion, les assemblages ioniques à base de porphyrines et de clusters de palladium présentent des propriétés de transferts d’électrons S1 ultra-rapides, et des transferts d’énergie T1 de vitesses modérées, ce qui est utile pour de possibles applications comme outils optoélectroniques. D’autres études, plus en profondeur, sont présentement en progrès.

Nitrate and potassium concentration in fertigated soil cultivated with wine vines.

In the semiarid region of Brazil the use of irrigation systems for applying fertilizers in horticulture is the primary means for incorporating nutrients in the soil. However, this technique still requires its use in wine vines to be assessed. In view of this, this study aimed to assess nitrate and potassium concentrations in soil fertigated with nitrogen and potassium fertilizers in 3 wine grape growing cycles. A field experiment was conducted with ?Syrah? wine grapes, in Petrolina, Pernambuco, Brazil; it assessed five nitrogen doses (0, 15, 30, 60 and 120 kg ha-1) and five K2O doses (0, 15, 30, 60 and 120 kg ha-1) applied by drip irrigation system with two emitters per plant, with a flow rate of 4 L h-1. The experimental design used was the factorial split-plot, making up 13 combinations arranged in 4 randomized blocks. Soil solution samples were collected weekly with the aid of porous cup extractors for all treatments and at depths of 0.4 and 0.6 m by determining nitrate and potassium concentrations and electrical conductivity. Increased levels of both nutrients in the irrigation water increased the availability of nitrate and potassium in the soil solution. The highest nitrate and potassium concentrations were found in the second growing cycle at both depths studied.

Dynamic Modeling and Seasonal Performance Evaluation of Air-to-Water Heat Pump Systems

In this Thesis a series of numerical models for the evaluation of the seasonal performance of reversible air-to-water heat pump systems coupled to residential and non-residential buildings are presented. The exploitation of the energy saving potential linked to the adoption of heat pumps is a hard task for designers due to the influence on their energy performance of several factors, like the external climate variability, the heat pump modulation capacity, the system control strategy and the hydronic loop configuration. The aim of this work is to study in detail all these aspects. In the first part of this Thesis a series of models which use a temperature class approach for the prediction of the seasonal performance of reversible air source heat pumps are shown. An innovative methodology for the calculation of the seasonal performance of an air-to-water heat pump has been proposed as an extension of the procedure reported by the European standard EN 14825. This methodology can be applied not only to air-to-water single-stage heat pumps (On-off HPs) but also to multi-stage (MSHPs) and inverter-driven units (IDHPs). In the second part, dynamic simulation has been used with the aim to optimize the control systems of the heat pump and of the HVAC plant. A series of dynamic models, developed by means of TRNSYS, are presented to study the behavior of On-off HPs, MSHPs and IDHPs. The main goal of these dynamic simulations is to show the influence of the heat pump control strategies and of the lay-out of the hydronic loop used to couple the heat pump to the emitters on the seasonal performance of the system. A particular focus is given to the modeling of the energy losses linked to on-off cycling.

Light & Electron beam - the perfect combination for the observation and application of photo active materials

The aim of the present PhD thesis is to investigate the properties of innovative nanomaterials for energy conversion. The materials have been deeply studied by means of a wide spectrum of different techniques based on both light and electron sources, in order to get an insight into the correlation between the properties of each material and the activity towards different energy conversion applications. The activity has been carried out in the framework of a collaboration between the “G.Ciamician” Chemistry Department of the University of Bologna and the CNR-IMM Bologna. Four main topics have been explored: in the first part, luminescent silicon nanocrystals (SiNCs) have been discussed, suggesting a new approach to improve their optical properties as active material in complementary optoelectronic devices and photovoltaic cells. The luminescence of SiNCs have been exploited to increase the efficiency of conventional photovoltaic cells by means of an innovative architecture. Specifically, SiNCs were shown to be very promising light emitters in luminescent solar concentrators (LSC). The second part of the work has been focused on the study of high phosphorescent molecular chromophores, suggesting a new approach in their use as optical sensors successfully applied to the field of polymeric materials. This is due to the enhanced emission of light that appears in rigid, constrained or crystalline state, that is commonly called: "Aggregation-Induced Emission (AIE)". Such phenomenon is characteristic for molecular structures such as persulfurated benzene chromophores, hereafter named asterisks. The last two parts were focused on conventional and in-situ Transmission Electron Microscopy (TEM) morphological and structural characterization of photoactive and catalytic materials for energetic applications and in particular water splitting.