A kinetic model of electronic energy migration within pairs of photophysically non-identical fluorophores has been developed. The model applies to fluorescent groups that exhibit different photophysical and spectral properties when attached to different positions in a macromolecule. The energy migration within such asymmetric pairs is partially reversible, which leads to the case of partial donor-donor energy migration (PDDEM). The model of PDDEM is an extension of the recently developed donor-donor energy migration model (DDEM, F. Bergström et al, PNAS 96 (1999) 12477), and applies to quantitative measurements of energy migration rates and distances within macromolecules. One important distinction from the DDEM model is that the distances can be obtained from fluorescence lifetime measurements. A model of fluorescence depolarisation in the presence of PDDEM is also presented. To experimentally test the PDDEM approach, different model systems were studied. The model was applied to measure distances between rhodamine and fluorescein groups within on-purpose synthesised molecules that were solubilised in lipid bilayers. Moreover, distances were measured between BODIPY groups in mutant forms of the plasminogen activator inhibitor of type 2 (PAI-2). Measurements of both the fluorescence intensity decays and the time-resolved depolarisation were performed. The obtained distances were in good agreement with independent determinations. Finally, the PDDEM within pairs of donors is considered, for which both donors exhibit a nonexponential fluorescence decay. In this case it turns out that the fluorescence relaxation of a coupled system contains distance information even if the photophysics of the donors is identical. It is also demonstrated that the choice of relaxation model has a negligible effect on the obtained distances. The latter conclusion holds also for the case of donor-acceptor energy transfer.

Title: Modelling Dependent Lives Author: Eva Pavčová Department: Department of Probability and Mathematical Statistics Supervisor: RNDr. Lucie Mazurová, Ph.D., Department of Probability and Mathematical Statistics Abstract: In this thesis, we model the dependence between the remaining lifetimes of a husband and wife using a specific Markov model. We examined the impact of the dependence on the net single premium using the specific Markov model that captures the long-term dependence between lifetimes of the two considered lives. Using this model we have calculated 10-year joint-life annuity due and 10-year last-survivor annuity due considering the age rage (37, 80) in case of dependence and also independence of the two considered lives. The calculations were based on the dataset related to the Czech population in 2015. The impact of the dependence between the remaining lifetimes of the husband and wife was found to be not significant. Keywords: positive quadrant depedence, multiple life insurance premiums, depen- dent lifetimes, joint-life annuity, last-survivor annuity, joint-life and last-survivor models

Master´s thesis is focused on diagnostics of semiconductor materials by EBIC method (measuring of currents induced beam), determination of the lifetime of minority carriers, or their diffusion length. The theoretical part is aimed at the principle of scanning electron microscopy, the characteristic properties of the microscope and the signals generated by the interaction of the primary electron beam with the sample. The thesis describes a structure of semiconducting silicon, band models, types of lattice defects and doped of semiconductor structures. After that it is described the theory of calculation of the diffusion length of minority carriers in semiconductors of type N and P. The aim of the experiment part of the thesis is to measure the properties of the semiconductor structure by EBIC and determination of diffusion length and lifetime of minority charge carriers based on the measured data The aim of the experiment part of the thesis is to measure the properties of the semiconductor structure by EBIC and determination of diffusion length and lifetime of minority charge carriers on the basis of the measured data.

Since C^C* cyclometalated Pt(II) complexes with N-heterocyclic carbene (NHC) ligands have been identified as potential emitter materials in organic light-emitting devices (OLEDs), very promising results regarding quantum yields, colour and stability have been presented. Herein, we report on four nitrile substituted complexes with a chelating NHC ligand (1-(4-cyanophenyl)-3-isopropyl-1H-benzo[d]imidazole or 4-(tert-butyl)-1-(4-cyanophenyl)-3-methyl-1H-imidazole) and a bidentate monoanionic auxiliary ligand (acetylacetone or dimesitoylmethane). The complexes have been fully characterized including extensive 2D NMR studies (COSY, HSQC, HMBC, NOESY, 195Pt NMR), three of them also by solid-state structures. Photophysical measurements in amorphous PMMA films and pure emitter films at room temperature reveal the impact of the mesityl groups in the auxiliary ligand, which led to a significant increase of the quantum yield, while the decay lifetimes decreased. The electron withdrawing nitrile groups shift the emission towards blue colour coordinates.

Herein we report the synthesis of an RGD-ruthenium bipyridine [Ru(Bpy)2(BpyRGD)]2+ complex aimed at the detection of angiogenesis. Angiogenesis plays a critical role in many pathophysiological processes, such as tumor growth. The αv-integrins (αv[beta]3, αv[beta]5) are currently used as molecular targeting sites for anti-angiogenic therapies. The [Ru(Bpy)2(BpyRGD)]2+ complex is an organometallic luminescent probe, which enables noninvasive, in vitro imaging of αv[beta]3 expression. Peptides containing the arginine-glycine-aspartic acid (RGD) sequence have been shown to bind strongly to the αvb3 integrin. The RuBpy probes are soluble in water, display long lifetimes, and are photochemically stable. These properties enable the Ru(tris-bpy) complexes to be useful in numerous applications in biophysical and cell biology. The [Ru(Bpy)2(BpyRGD)]2+ complex was synthesized by combining the succinimidyl ester on the RuBpy complex with the lysine of the c(RGDfK) peptide. The results of the one-photon fluorescence bioimaging showed selective binding of the cyclic RGD to αv[beta]3 integrin, which supports previous literature. The high luminescence intensity, long lifetimes, and low cell toxicity levels of dye [Ru(Bpy)2(BpyRGD)]2+, illustrates the potential usage of this probe for future biological applications.

Estados Nucleares isoméricos são estados que decaem com vidas-médias longas ( T1/2 > 10 ns) e revelam, em geral, uma grande mudança no momento angular no seu decaimento, um pequeno elemento de matriz ou uma baixa energia de transição. Através da medida da vida-média de estados nucleares é possível obter informações sobre a função de onda desse estado, representando um teste rigoroso para modelos nucleares. Neste trabalho foi utilizado um sistema desenvolvido no Laboratório Aberto de Física Nuclear (LAFN) da Universidade de São Paulo chamado SIStema para Medida de Estados Isoméricos (SISMEI), que utiliza coincidência atrasada entre partículas evaporadas numa reação nuclear e raios gama emitidos pelo estado isomérico. O SISMEI consiste de cintiladores plásticos para detecção das partículas, detectores de germânio hiperpuro (HPGe) e iodeto de sódio (NaI(Tl)) para raios gama, associados a uma eletrônica de coincidência, instalado no acelerador Pelletron (8UD) do LAFN. Neste trabalho, realizou-se um experimento para medir o estado isomérico 7(-) (E = 1229,87(4) keV) do 68Ga. A tomada de dados durou cerca de 80 horas com uma taxa de eventos de aproximadamente 80000 contagens por hora. O resultado obtido foi T 1/2 = 60, 8(11) ns, que é compatível com os resultados experimentais de outros trabalhos, porém, mais preciso. A estrutura desse núcleo foi calculada através do Modelo de Camadas em Larga Escala considerando-se duas interações residuais diferentes FPG e JUN45; os resultados foram comparados entre si, juntamente com os valores obtidos em outros trabalhos. Os cálculos realizados com o Modelo de Camadas reproduziram relativamente bem a energia e a ordem dos estados excitados do 68Ga, a interação FPG conseguiu descrever melhor a probabilidade de transição quadrupolar elétrica B(E2) diretamente ligada à vida-média do estado. / Isomeric nuclear states are nuclear states which decay with long lifetimes (T1/2 > 10 ns); their study generally reveals, a large change in angular momentum in its decay, a small matrix element or a small transition energy. By measuring lifetimes of isomeric states it is possible to obtain information about this states wave function, being a robust test for nuclear models. In this work, a system developed at the Laboratório Aberto de Fsica Nuclear (LAFN) of University of São Paulo called System for the Measurement of Isomeric States (SISMEI) was utilized. Delayed coincidence between evaporated particles in a nuclear reaction and the delayed gamma-rays emitted from the isomeric state was used to measure lifetimes. SISMEI is composed of plastic scintillators for particle detection, hiperpure germanium detectors (HPGe) and sodium iodide (NaI(Tl)) for gamma-ray detection, coupled to a coincidence system, located on 30A beam line of the Pelletron (8UD) accelerator - LAFN. In the present work, an experiment to measure the 7 (-) (E = 1229.87(4) keV) isomeric state of 68Ga was performed. The experiment took about 80 hours with an event rate of about 80000 counts per second. The measured value was T 1/2 = 60.8(11) ns, which is compatible, but more accurate, with experimental results of other authors. The nuclear structure of this nucleus was calculated with the Large Scale Shell Model by using two different residual interactions FPG and JUN45; the results were compared with the known values. The structure calculated with LSSM described the energy states and the order of excited states relatively well; the FPG interaction was capable to describe better the quadrupolar electrical transition probability B(E2), which is direct related to predicting the state lifetime.

Estados Nucleares isoméricos são estados que decaem com vidas-médias longas ( T1/2 > 10 ns) e revelam, em geral, uma grande mudança no momento angular no seu decaimento, um pequeno elemento de matriz ou uma baixa energia de transição. Através da medida da vida-média de estados nucleares é possível obter informações sobre a função de onda desse estado, representando um teste rigoroso para modelos nucleares. Neste trabalho foi utilizado um sistema desenvolvido no Laboratório Aberto de Física Nuclear (LAFN) da Universidade de São Paulo chamado SIStema para Medida de Estados Isoméricos (SISMEI), que utiliza coincidência atrasada entre partículas evaporadas numa reação nuclear e raios gama emitidos pelo estado isomérico. O SISMEI consiste de cintiladores plásticos para detecção das partículas, detectores de germânio hiperpuro (HPGe) e iodeto de sódio (NaI(Tl)) para raios gama, associados a uma eletrônica de coincidência, instalado no acelerador Pelletron (8UD) do LAFN. Neste trabalho, realizou-se um experimento para medir o estado isomérico 7(-) (E = 1229,87(4) keV) do 68Ga. A tomada de dados durou cerca de 80 horas com uma taxa de eventos de aproximadamente 80000 contagens por hora. O resultado obtido foi T 1/2 = 60, 8(11) ns, que é compatível com os resultados experimentais de outros trabalhos, porém, mais preciso. A estrutura desse núcleo foi calculada através do Modelo de Camadas em Larga Escala considerando-se duas interações residuais diferentes FPG e JUN45; os resultados foram comparados entre si, juntamente com os valores obtidos em outros trabalhos. Os cálculos realizados com o Modelo de Camadas reproduziram relativamente bem a energia e a ordem dos estados excitados do 68Ga, a interação FPG conseguiu descrever melhor a probabilidade de transição quadrupolar elétrica B(E2) diretamente ligada à vida-média do estado. / Isomeric nuclear states are nuclear states which decay with long lifetimes (T1/2 > 10 ns); their study generally reveals, a large change in angular momentum in its decay, a small matrix element or a small transition energy. By measuring lifetimes of isomeric states it is possible to obtain information about this states wave function, being a robust test for nuclear models. In this work, a system developed at the Laboratório Aberto de Fsica Nuclear (LAFN) of University of São Paulo called System for the Measurement of Isomeric States (SISMEI) was utilized. Delayed coincidence between evaporated particles in a nuclear reaction and the delayed gamma-rays emitted from the isomeric state was used to measure lifetimes. SISMEI is composed of plastic scintillators for particle detection, hiperpure germanium detectors (HPGe) and sodium iodide (NaI(Tl)) for gamma-ray detection, coupled to a coincidence system, located on 30A beam line of the Pelletron (8UD) accelerator - LAFN. In the present work, an experiment to measure the 7 (-) (E = 1229.87(4) keV) isomeric state of 68Ga was performed. The experiment took about 80 hours with an event rate of about 80000 counts per second. The measured value was T 1/2 = 60.8(11) ns, which is compatible, but more accurate, with experimental results of other authors. The nuclear structure of this nucleus was calculated with the Large Scale Shell Model by using two different residual interactions FPG and JUN45; the results were compared with the known values. The structure calculated with LSSM described the energy states and the order of excited states relatively well; the FPG interaction was capable to describe better the quadrupolar electrical transition probability B(E2), which is direct related to predicting the state lifetime.

No description available.

No description available.

Les symétries géométriques jouent un rôle important dans la compréhension de la stabilité de tout système physique. En structure nucléaire, elles sont reliées à la forme du champ moyen utilisé pour décrire les propriétés des noyaux atomiques. Dans le cadre de cette thèse, nous avons utilisé les prédictions obtenues avec l'aide du Hamiltonien du champ moyen nucléaire avec le potentiel de Woods-Saxon Universel pour étudier les effets des symétries dites de « Haut-Rang ». Ces symétries ponctuelles mènent à des dégénérescences des états nucléaires d’ordre 4. Il est prédit que la symétrie tétraédrique influence la stabilité des noyaux proches des nombres magiques tétraédriques [Z,N]=[32,40,56,64,70,90-94,136]. Nous avons sélectionné la région des Terres-Rares proche du noyau doublement magique tétraédrique 154Gd pour notre étude. Dans cette région, il existe des structures de parité négative qui sont mal comprises. Or la symétrie tétraédrique, en tant que déformation octupolaire non-axiale, brise la symétrie par réflexion et doit produire des états de parité négative. Après une étude systématique des propriétés expérimentales des noyaux de la région, nous avons sélectionné le 156Gd comme objet de notre étude des modes d’excitation octupolaire. Nous avons utilisé les probabilités réduites de transition gamma pour discerner ces différents modes. Pour atteindre cet objectif, nous avons réalisé trois expériences de spectroscopie gamma à l’ILL de Grenoble avec les détecteurs EXILL et GAMS afin de mesurer les durées de vie et les intensités des transitions gamma des états candidats. L'analyse de nos résultats montre que notamment la forme tétraédrique aide à comprendre les probabilités des transitions dipolaires. Ce résultat ouvre de nouvelles perspectives expérimentales et théoriques. / Geometrical symmetries play an important role in the understanding of all physical systems. In nuclear structure they are linked to the shape of the mean-field used to describe the atomic nuclei properties. In the framework of this thesis, we have used the predictions obtained with the help of the nuclear mean-field Hamiltonian with the Universal Woods-Saxon potential to study the effects of the so-called “High-Rank” symmetries. These point-group symmetries lead to a nuclear state degeneracy of the order of 4. It is predicted that the tetrahedral symmetry affects the stability of nuclei close to the tetrahedral magic numbers [Z,N]=[32,40,56,64,70,90-94,136]. We have selected the Rare-Earth region close to the tetrahedral doubly magic nucleus 154Gd for our study. In this region, there exists negative parity structures poorly understood. Yet the tetrahedral symmetry, as related to a non-axial octupole deformation, breaks the reflection symmetry and leads to the negative parity states. Following a systematics of experimental properties of the nuclei in this region, we have selected 156Gd as the object of our study for the octupole excitation modes. We have used the reduced transitions probabilities to discriminate between these modes. To achieve this goal, we have performed three gamma spectroscopy experiments at the ILL in Grenoble with the EXILL and GAMS detectors to measure the lifetimes and the gamma transition intensities from the candidate states. The analysis of our results shows that including the tetrahedral shape helps to understand the dipole transition probabilities. This result will open new experimental and theoretical perspectives.