Zastosowanie modelu hantli w badaniach właściwości fizykochemicznych i strukturalnych układów homo- i heterogenicznych metodą Monte Carlo

Wydział Chemii

Room temperature photo-response of titanium supersaturated silicon at energies over the bandgap

Silicon samples were implanted with high Ti doses and subsequently processed with the pulsed-laser melting technique. The electronic transport properties in the 15–300 K range and the room temperature spectral photoresponse at energies over the bandgap were measured. Samples with Ti concentration below the insulator-metal (I-M) transition limit showed a progressive reduction of the carrier lifetime in the implanted layer as Ti dose is increased. However, when the Ti concentration exceeded this limit, an extraordinary recovery of the photoresponse was measured. This result supports the theory of intermediate band materials and is of utmost relevance for photovoltaic cells and Si-based detectors.

Homo-quê? Expressão de atitudes implícitas e explicitas face à homoparentalidade – Moderação motivacional

Dissertação de Mestrado apresentada ao Instituto Superior de Psicologia Aplicada para obtenção de grau de Mestre na especialidade de Psicologia Social e das Organizações.

Impacto ambiental associado à utilização intensive de algumas energies renováveis – Pequeno contributo

A utilização da energia hídrica, obtida em grandes barragens, é uma prática muito antiga, em Portugal. Nas ultimas décadas de anos , o seu número tem aumentado, existindo ou estando em fase de conclusão, 57 grandes barragens, no Alentejo. Os problemas associados a este tipo de barragens são conhecidos. Iremos falar de um, extremamente importante, na região. Devido à profundidade atingida, existe pouco oxigénio no fundo destes reservatórios, e a decomposição de matéria morta origina grandes quantidades de metano. Em termos de efeito de estufa o metano é 30 vezes mais potente que o CO2. O facto de não ter havido limpeza do solo antes do enchimento das albufeiras e de algumas se encontrarem com problemas de eutrofização, vem aumentar este problema. Outro tipo de energia muito utilizada é a energia solar, existindo grandes centrais fotovoltaicas em funcionamento e prevendo-se a construção de novas centrais com uma potência total de 1300 MW para o país. Em Évora, Ourique, Alcoutim e Nisa já foi anunciada a construção de novas centrais com uma potência total de 155 MW. Os problemas associados a este tipo de centrais, são de vários tipos. Iremos debruçar-nos sobre os produtos tóxicos que as células solares contêm e que variam com o tipo de célula. Estando algumas centrais já em funcionamento e outras em fase de montagem, importa refletir sobre o que fazer depois de a central deixar de funcionar. O que fazer com os resíduos tóxicos, as toneladas de aço e outros materiais envolvidos, formação de pessoal que saiba manusear os produtos tóxicos, custos associados às soluções possíveis, etc. Não se conhecendo informação relativa a estes problemas, por parte da comunicação social, importa refletir sobre a informação fornecida à população e autoridades locais envolvidas.

Impacto ambiental associado à utilização intensive de algumas energies renováveis – Pequeno contributo

A utilização da energia hídrica, obtida em grandes barragens, é uma prática muito antiga, em Portugal. Nas ultimas décadas de anos , o seu número tem aumentado, existindo ou estando em fase de conclusão, 57 grandes barragens, no Alentejo. Os problemas associados a este tipo de barragens são conhecidos. Iremos falar de um, extremamente importante, na região. Devido à profundidade atingida, existe pouco oxigénio no fundo destes reservatórios, e a decomposição de matéria morta origina grandes quantidades de metano. Em termos de efeito de estufa o metano é 30 vezes mais potente que o CO2. O facto de não ter havido limpeza do solo antes do enchimento das albufeiras e de algumas se encontrarem com problemas de eutrofização, vem aumentar este problema. Outro tipo de energia muito utilizada é a energia solar, existindo grandes centrais fotovoltaicas em funcionamento e prevendo-se a construção de novas centrais com uma potência total de 1300 MW para o país. Em Évora, Ourique, Alcoutim e Nisa já foi anunciada a construção de novas centrais com uma potência total de 155 MW. Os problemas associados a este tipo de centrais, são de vários tipos. Iremos debruçar-nos sobre os produtos tóxicos que as células solares contêm e que variam com o tipo de célula. Estando algumas centrais já em funcionamento e outras em fase de montagem, importa refletir sobre o que fazer depois de a central deixar de funcionar. O que fazer com os resíduos tóxicos, as toneladas de aço e outros materiais envolvidos, formação de pessoal que saiba manusear os produtos tóxicos, custos associados às soluções possíveis, etc. Não se conhecendo informação relativa a estes problemas, por parte da comunicação social, importa refletir sobre a informação fornecida à população e autoridades locais envolvidas.

Poética homo: propuesta metodológica para el análisis de la sexo-diversidad, con un enfoque en el género masculino, en el teatro. Teatro mexicano s. XX

El trabajo que aquí se presenta surge de una doble inquietud. Por una parte establecer el análisis de las obras de teatro, a partir de entender estas como un producto artístico en cuanto a material literario y hecho escénico se refiere, y por otra la necesidad, no de definir la homosexualidad, sino el entender cuáles han sido los recursos dramáticos a través de los que se ha manifestado la tematización de la diversidad sexual masculina, y cómo han sido empleados en el fenómeno teatral. Los trabajos de investigación y crítica que han sido elaborados sobre el tema homosexual se han llevado a cabo, principalmente, en disciplinas como la psicología y la antropología. En el ámbito de las letras dichos estudios se han centrado tan solo en dos de los géneros literarios: la poesía y la narrativa; haciendo a un lado al otro gran género que es el teatro. Son pocos los estudios que se han realizado en torno al teatro homosexual, por tanto el tesista se atreve a afirmar que dicho terreno de investigación se encuentra despoblado. Para entender la homosexualidad dentro del teatro, es necesario acercarnos a la historia natural de la misma, es decir al recorrido sintagmático que ha presentado en la historia del hombre, de manera que se puedan comprender y comparar así las manifestaciones paradigmáticas que han surgido en la historia del teatro...

Raman Spectroscopy and DFT calculations for the Electronic Structure Characterization of Conjugated Polymers

In the last three decades, there has been a broad academic and industrial interest in conjugated polymers as semiconducting materials for organic electronics. Their applications in polymer light-emitting diodes (PLEDs), polymer solar cells (PSCs), and organic field-effect transistors (OFETs) offer opportunities for the resolution of energy issues as well as the development of display and information technologies1. Conjugated polymers provide several advantages including low cost, light weight, good flexibility, as well as solubility which make them readily processed and easily printed, removing the conventional photolithography for patterning2. A large library of polymer semiconductors have been synthesized and investigated with different building blocks, such as acenes or thiophene and derivatives, which have been employed to design new materials according to individual demands for specific applications. To design ideal conjugated polymers for specific applications, some general principles should be taken into account, including (i) side chains (ii) molecular weights, (iii) band gap and HOMO and LUMO energy levels, and (iv) suited morphology.3-6 The aim of this study is to elucidate the impact that substitution exerts on the molecular and electronic structure of π-conjugated polymers with outstanding performances in organic electronic devices. Different configurations of the π-conjugated backbones are analyzed: (i) donor-acceptor configuration, (ii) 1D lineal or 2D branched conjugated backbones, and (iii) encapsulated polymers (see Figure 1). Our combined vibrational spectroscopy and DFT study shows that small changes in the substitution pattern and in the molecular configuration have a strong impact on the electronic characteristics of these polymers. We hope this study can advance useful structure-property relationships of conjugated polymers and guide the design of new materials for organic electronic applications.

Materials design for ambipolar devices: tuning orbital energetics in oligothiophene-naphthalimides semiconductors

Ambipolar organic field-effect transistors (OFETs), which can efficiently transport both holes and electrons, using a single type of electrode, are currently of great interest due to their possible applications in complementary metal oxide semiconductor (CMOS)-like circuits, sensors, and in light-emitting transistors. Several theoretical and experimental studies have argued that most organic semiconductors should be able to transport both types of carrier, although typically unipolar behavior is observed. One factor that can compromise ambipolar transport in organic semiconductors is poor solid state overlap between the HOMO (p-type) or LUMO (n-type) orbitals of neighboring molecules in the semiconductor thin film. In the search of low-bandgap ambipolar materials, where the absence of skeletal distortions allows closer intermolecular π-π stacking and enhanced intramolecular π-conjugation, a new family of oligothiophene-naphthalimide assemblies have been synthesized and characterized, in which both donor and acceptor moieties are directly conjugated through rigid linkers. In previous works we found that oligothiophene-napthalimide assemblies connected through amidine linkers (NDI derivates) exhibit skeletal distortions (50-60º) arising from steric hindrance between the carbonyl group of the arylene core and the sulphur atom of the neighbored thiophene ring (see Figure 1). In the present work we report novel oligo- and polythiophene–naphthalimide analogues NAI-3T, NAI-5T and poly-NAI-8C-3T, in which the connections of the amidine linkage have been inverted in order to prevent steric interactions. Thus, the nitrogen atoms are directly connected to the naphthalene moiety in NAI derivatives while they were attached directly to the thiophene moiety in the previously investigated NDI-3T and NDI-5T. In Figure 1 is depicted the calculated molecular structure of NAI-3T together with that of NDI-3T showing how the steric interactions are not present in the novel NAI derivative. The planar skeletons in these new family induce higher degree of crystallinity and the carrier charge transport can be switched from n-type to ambipolar behaviour. The highest FET performance is achieved for vapor-deposited films of NAI-3T with mobilities of 1.95x10-4cm2V-1s-1 and 2.00x10-4cm2V-1s-1 for electrons and holes, respectively. Finally, these planar semiconductors are compared with their NDI derivates analogues, which exhibit only n-type mobility, in order to understand the origin of the ambipolarity in this new series of molecular semiconductors.

Agamben, G. (2015), Homo sacer, IV, 2 : L’usage des corps, Paris, Seuil, 393 p.

Compte rendu de l'ouvrage "Agamben, G. (2015), Homo sacer, IV, 2 : L’usage des corps, Paris, Seuil, 393 p."

Agamben, G. (2015), Homo sacer, IV, 2 : L’usage des corps, Paris, Seuil, 393 p.

Compte rendu de l'ouvrage "Agamben, G. (2015), Homo sacer, IV, 2 : L’usage des corps, Paris, Seuil, 393 p."

Sequential alcohol oxidation/putative homo Claisen-Tishchenko-type reaction to give esters: a key process in accessing novel biologically active lactone macrocycles

We report an efficient methodology for the direct oxidative esterification of primary alcohols to diether-esters using pyridinium chlorochromate (PCC). Numerous studies were carried out to probe the reaction mechanism and at the same time optimize the reaction conditions. The reaction could be conducted with 1 equivalent of PCC and 1 equivalent of BF3 center dot OEt2. Indications based on literature precedent were that the reaction may proceed via a sequential alcohol oxidation to the aldehyde followed by a putative Cr or boron catalyzed Claisen-Tishchenko-type reaction. Using this efficient methodology, we synthesized a family of novel diether-esters in very good yields; some of these molecules were subsequently tested against both acetylcholinesterase (AChE) and butyrylcholinesterase (BuChE). In addition, we also disclose a new synthetic strategy for the synthesis of lactam macrocycles with potential biological activity. This methodology included the regioselective borylation of the ester substrate and a subsequent Suzuki-Miyaura coupling to obtain the desired lactam macrocycle.

Development of processes for the valorization of lignocellulosic biomass based on renewable energies

The world grapples with climate change from fossil fuel reliance, prompting Europe to pivot to renewable energy. Among renewables, biomass is a bioenergy and bio-carbon source, used to create high-value biomolecules, replacing fossil-based products. Alkyl levulinates, derived from biomass, hold promise as bio-additives and biofuels, especially via acid solvolysis of hexose sugars, necessitating further exploration. Alkyl levulinate's potential extends to converting into γ-valerolactone (GVL), a bio-solvent produced via hydrogenation with molecular-hydrogen. Hydrogen, a key reagent and energy carrier, aids renewable energy integration. This thesis delves into a biorefinery system study, aligning with sustainability goals, integrating biomass valorization, energy production, and hydrogen generation. It investigates optimizing technologies for butyl levulinate production and subsequent GVL hydrogenation. Sustainability remains pivotal, reflecting the global shift towards renewable and carbon bio-resources. The research initially focuses on experimenting with the optimal technology for producing butyl levulinate from biomass-derived hexose fructose. It examines the solvolysis process, investigating optimal conditions, kinetic modeling, and the impact of solvents on fructose conversion. The subsequent part concentrates on the technological aspect of hydrogenating butyl levulinate into GVL. It includes conceptual design, simulation, and optimization of the fructose-to-GVL process scheme based on process intensification. In the final part, the study applies the process to a real case study in Normandy, France, adapting it to local biomass availability and wind energy. It defines a methodology for designing and integrating the energy-supply system, evaluating different scenarios. Sustainability assessment using economic, environmental, and social indicators culminates in an overall sustainability index, indicating scenarios integrating the GVL biorefinery system with wind power and hydrogen energy storage as promising due to high profitability and reduced environmental impact. Sensitivity analyses validate the methodology's reliability, potentially extending to other technological systems.

Dielectron Mass Spectra From Au+au Collisions At √[s(nn)]=200 gev.

We report the STAR measurements of dielectron (e(+)e(-)) production at midrapidity (|y(ee)|<1) in Au+Au collisions at √[s(NN)]=200  GeV. The measurements are evaluated in different invariant mass regions with a focus on 0.30-0.76 (ρ-like), 0.76-0.80 (ω-like), and 0.98-1.05 (ϕ-like)   GeV/c(2). The spectrum in the ω-like and ϕ-like regions can be well described by the hadronic cocktail simulation. In the ρ-like region, however, the vacuum ρ spectral function cannot describe the shape of the dielectron excess. In this range, an enhancement of 1.77±0.11(stat)±0.24(syst)±0.33(cocktail) is determined with respect to the hadronic cocktail simulation that excludes the ρ meson. The excess yield in the ρ-like region increases with the number of collision participants faster than the ω and ϕ yields. Theoretical models with broadened ρ contributions through interactions with constituents in the hot QCD medium provide a consistent description of the dilepton mass spectra for the measurement presented here and the earlier data at the Super Proton Synchrotron energies.

Beam-energy Dependence Of Charge Separation Along The Magnetic Field In Au+au Collisions At Rhic.

Local parity-odd domains are theorized to form inside a quark-gluon plasma which has been produced in high-energy heavy-ion collisions. The local parity-odd domains manifest themselves as charge separation along the magnetic field axis via the chiral magnetic effect. The experimental observation of charge separation has previously been reported for heavy-ion collisions at the top RHIC energies. In this Letter, we present the results of the beam-energy dependence of the charge correlations in Au+Au collisions at midrapidity for center-of-mass energies of 7.7, 11.5, 19.6, 27, 39, and 62.4 GeV from the STAR experiment. After background subtraction, the signal gradually reduces with decreased beam energy and tends to vanish by 7.7 GeV. This implies the dominance of hadronic interactions over partonic ones at lower collision energies.