Neste trabalho realizou-se uma analise detalhada das vantagens e desvantagens da sequencia de Precessao Livre no Estado Estacionario (Steady State Free Precession - SSFP) para aquisicao rapida de espectros de Ressonancia Magnetica Nuclear (RMN) de 13C. O regime de SSFP e obtido atraves da aplicacao de um trem de pulsos de mesma fase, duracao e intensidade, separados por um intervalo de tempo (Tp) menor que os tempos de relaxacao longitudinal (T1) e transversal (T2) da amostra. Nestas condicoes e possivel acumular dezenas de espectros por unidade de T1, proporcionando um incremento significativo na razao sinal/ruido (s/r) do espectro. Ao comparar os resultados obtidos com as sequencias de SSFP e convencional (pulsos de 90 graus e T 5T1 p >= ), verificou-se que a SSFP apresentou um ganho medio de 30 vezes no tempo de analise para uma mesma s/r. No entanto, os espectros obtidos com a SSFP apresentam anomalias de fase e amplitude do sinal, decorrente da refocalizacao da magnetizacao na forma de um eco de spin. Comparou-se tambem a SSFP com a sequencia padrao usada para obtencao de espectros de 13C, que utiliza pulsos de 30 graus e Tp = 1.38s. Neste caso os ganhos da SSFP foram menores (5,5 vezes no tempo de analise para uma mesma s/r) verificando que a sequencia padrao utiliza a vantagem da SSFP (Tp < T1, T2). A formacao do eco e, consequente das anomalias de fase nao sao observadas na sequencia padrao, pois a aquisicao do sinal e truncada em 0,9s, e a ciclagem de fase dos pulsos reduz a formacao do eco, por levar a uma perda de coerencia do sinal SSFP. Neste trabalho tambem analisou-se os metodos propostos por Rudakov, Freeman e Hill e Schwenk para supressao destas anomalias nos espectros de RMN 13C quando adquiridos no regime de SSFP. Os resultados demonstraram que a aplicacao destas metodologias proporciona uma melhora significativa na qualidade do espectro. No entanto, verificou-se que nenhum metodo foi capaz de suprimir totalmente as anomalias de fase e amplitude do sinal. / It was performed a detailed analysis of the advantages and disadvantages of Steady State Free Precession (SSFP) sequence for a rapid acquisition of 13C Nuclear Magnetic Resonance (NMR) spectra. The SSFP regime is obtained by the application of a pulse train with the same phase, duration and intensity, separated by a time interval (Tp) shorter than the transverse (T2) and longitudinal (T1) relaxation times. In these conditions it is possible to accumulate tens of spectra per units of T1, providing a significant increase in the spectrum signal-to-noise ratio (s/n). By comparing the spectra obtained by SSFP and conventional pulse sequence (90 degree pulse and T 5T1 p >= ) it was noted that SSFP shows an average gain of 30 times in analysis time for the same s/n. However, the SSFP spectra show phase and intensity anomalies due to the refocusing of the magnetization, generating a spin echo. We also compared the SSFP with the standard 13C pulse sequence, that uses a 30 degree pulses and Tp = 1.38 s. In this comparison the SSFP gain were small (5,5 times in analysis time for the same s/n), because the standard sequence also uses the advantage of SSFP (Tp < T1, T2). The echo signal and the phase anomalies are not observed in the standard sequence because the signal acquisition is truncated at 0.9s and the cycling of the pulse phase, that partially destroy the SSFP coherence. We also analyzed the methods proposed by Rudakov, Freeman and Hill and Schwenk to suppress those anomalies in the 13C NMR spectrum when acquired in SSFP regime. The results showed that the application of these methodologies provides a significant improvement in the spectrum quality. However, it was verified that none of the methods were able to completely eliminate the phase and intensity anomalies.

O objetivo deste trabalho consistiu na caracterização das zeólitas Y e ZSM-5, usando a técnica de Espectroscopia de Alta resolução em sólidos por Ressonância Magnética Nuclear (RMN). Os espectros de alta resolução do 13C e 27Al foram obtidos usando, simultaneamente, as técnicas de desacoplamento em alta potência (DEC) e rotação da amostra em torno de ângulo mágico (MAS). Utilizamos os espectros de alta resolução dos núcleos de 27Al para analisarmos a coordenação e a quantificação dos alumínios estruturais e extra-estruturais em zeólitas Y e de 13C para analisarmos o posicionamento de moléculas direcionadas localizadas nos canais da ZSM-5 / The objective of this work consisted of the characterization of zeolites Y and ZSM-5, using Solid State High Resolution Nuclear Magnetic Resonance Spectrsocopy. The 13C and 27Al high resolution spectra were obtained using simultaneously, High Power Decoupling (DEC) and Magic Angle Spinning (MAS). The high resolution 27Al spectra were used to distinguish and quantify framework and non-framework aluminium in zeolites Y. The high resolution 13C spectra were used to probe the position and configuration of the guest organic molecules within the framework of the ZSM-5 zeolite

Amyloidogenic neurodegenerative disorders such as Alzheimer's disease (AD) and Parkinson's disease (PD) are an important health issue. However, the underlying molecular mechanisms of the disease-related protein aggregates, that are present in humans, are only understood partially. I have used and developed biophysical methods to study the structural and biological properties of individual aggregates of Amyloid β peptide and α-Synuclein, proteins whose aggregation is associated with the development of Alzheimer's and Parkinson's disease respectively. I expanded the single aggregate visualisation through enhancement (SAVE) technique, which is a method based on the fluorescent dye Thioflavin T (ThT) that reversibly bind to the aggregates and whose fluorescence increases upon binding. I firstly explored the use of other dyes for these experiments and found that a ThT dimer has higher affinity to α-Synuclein aggregates in vitro. I then applied the SAVE method to the cerebral spinal fluid (CSF) of a cohort of AD patients and control CSF and observed no clear difference in aggregate number. However, these experiments provided insights into how antibodies bind the aggregates in human CSF. I could show, that despite altering the Ca2+ influx into both cells and vesicles, the antibody did not measurably affect the aggregate structure. To study the size specific effects of the Amyloid β 42 (Aβ42) peptide in more detail, I used and optimised gradient ultracentrifugation combined with single aggregate imaging to study the structural properties of the isolated aggregates. This aggregation kinetic independent method allowed me to compare the properties of fluorescently labelled and unlabelled Aβ42 and characterize the size dependent properties of aggregates in a single experiment. Since I could measure the relative concentration of different size aggregates it was also possible to compare the properties of single aggregates of different sizes. I then used biological assays to examine the ability of aggregates to permeabilise membranes resulting in the entry of calcium ions, and their ability to induce TNFα production in microglia cells. Both processes are thought to play key roles in the development of AD. I found that small soluble oligomers are most potent at inducing Ca2+ influx, whereas longer protofilaments are the most potent inducers of TNFα production. My results suggest that the mechanism by which aggregates damage cells changes as aggregation proceeds, as longer aggregates with different structures are formed. Protofilaments with a diameter of 1 nm or less have a structure that could make them particularly potent at causing the signalling of toll-like receptors, providing a molecular basis for their ability to induce TNFα production.

Introdução: A Bronquiolite Obliterante Pós-infecciosa (BOPI) é uma síndrome clínica rara e grave caracterizada por sinais e sintomas persistentes de obstrução crônica das pequenas vias aéreas. Objetivos: o objetivo do presente estudo é avaliar a evolução da função pulmonar de uma coorte de acompanhamento de pacientes com BOPI de Porto Alegre, Brasil. Métodos: Foram incluídas crianças, adolescentes com BOPI, de ambos os sexos, em acompanhamento de longo prazo nos ambulatórios de pneumologia pediátrica dos hospitais da Criança Santo Antônio e Materno-Infantil Presidente Vargas, ambos de Porto Alegre, Brasil. Resultados: Quanto à análise das variáveis da função pulmonar, as médias globais dos pontos analisados no tempo para cada variável foram: da CVF foi de 68,8% ± 17,7, do VEF1 foi 48% ± 15, do VEF1/CVF foi 66% ± 17, e do FEF25-75 foi 25,4% ± 14. Longitudinalmente, encontramos que houve melhora estatística e clínica, significativa, da CVF (p=0,04). Já as variáveis VEF1 e o FEF25-75, que refletem melhor o componente obstrutivo, não apresentaram mudanças significativas tanto estatisticamente (p=0,708 e p=0,873 respectivamente) quanto clinicamente, mantendo valores similares no percentual do predito ao longo do tempo. A relação VEF1/CVF sofreu uma mudança estatisticamente significativa (p=0,015), clinicamente explicável pela maior melhora da CVF comparado com o VEF1. Conclusões: Em conclusão, os resultados do nosso estudo sugerem que, em crianças e adolescentes com bronquiolite obliterante pós-infecciosa, o componente obstrutivo da função pulmonar (VEF1 e FEF25-75) sofre poucas modificações significativas, deletérias ou benéficas, ao longo do tempo. A capacidade vital forçada, por outro lado, sofre um aumento progressivo ao longo do tempo que pode ser de grande importância como fator de proteção quando iniciar o declínio fisiológico da função pulmonar na idade adulta. / Introduction: The Post-Infectious Bronchiolitis Obliterans (PIBO) is a rare and serious clinical syndrome characterized by persistent signs and symptoms of small airways’ chronic obstruction. Objectives: The objetive of this study is evaliate the evoluction of pulmonary function in a monitoring cohort of patients with PIBO from Porto Alegre, Brazil. Methods: Children, adolescents with PIBO, of both sexes were included, in long-term monitoring in pediatric pneumology clinics of Santo Antônio children’s hospital and Presidente Vargas maternal and child hospital, both from Porto Alegre, Brazil. Results: Regarding the analysis of the variables of pulmonar function, the global average of ten points analyzed in the time for each variable were: from CVF was 68,8% ± 17,7, from VEF1 was 48% ± 15, from VEF1/CVF was 66% ± 17 and from FEF25-75 was 25,4% ± 14. Lengthwise, we found that there was an statistical and clinical improvement, significant, from CVF (p=0,04). However, the variables VEF1 and the FEF25-75, which better reflect the osbstructive component, don’t show significant changes as statistically (p=0,708 and p=0,873 respectively) as clinically, keeping similar values in percentage of the predicted over time. The relation VEF1/CVF suffered a statistically significant change (p=0,015), clinically explained by the greatest improvement in CVF compared with VEF1. Conclusões: In conclusion, the results of our study suggest that, in children and adolescents with post-infectious bronchiolitis obliterans, the obstructive component of pulmonary function (FEV 1 and FEF 25-75) suffers few significant changes, deleterious or beneficial, over time. The forced vital capacity, on the other hand, suffers a progressive increase over time which can be of great importance as protective factor when start the physiological decline of pulmonary function in adult age.

No description available.

Ce travail de thèse s’inscrit dans une démarche d’approfondissement des connaissances du fonctionnement des aquifères karstiques. Pour cela, le site pilote des Sources du Toulon, siège d’une alimentation multiréservoirs, a été choisi et offre une fenêtre d’observation privilégiée sur les relations hydrogéologiques entre les aquifères de la marge Nord du Bassin aquitain. Elles sont utilisées depuis 1832 pour l’alimentation en eau potable de la ville de Périgueux, et constituent actuellement son unique ressource.L’objectif de ce travail a été de tester une approche multi-traceurs et un suivi haute-résolution pour caractériser le fonctionnement et la vulnérabilité d’un aquifère karstique multicouche.L’utilisation d’une approche couplée hydrodynamique et hydrochimie a mis en évidence l’alimentation des Sources du Toulon par une ressource profonde et captive en complément d’un aquifère libre plus superficiel. Ces informations ont été intégrées dans le contexte hydrogéologique global de la zone d’étude pour proposer une nouvelle délimitation du bassin d’alimentation des Sources du Toulon.L’utilisation d’un suivi haute-résolution a permis de préciser le fonctionnement hydrogéologique du système karstique étudié. Il en ressort des fonctionnements différents suivants les crues, avec des transferts de masse pouvant s’étendre de quelques jours à quelques semaines.L’apport des isotopes des nitrates (δ15N-NO3- ; δ18O-NO3-) a permis d’identifier deux origines des nitrates mesurés dans les eaux de surface et souterraines : les fertilisants minéraux de synthèse utilisés pour l’agriculture, et les rejets d’assainissement individuels.L’évaluation temporelle de la vulnérabilité spécifique des Sources du Toulon à certains marqueurs de contamination tels que les particules, les éléments bactériologiques et les nitrates a permis de distinguer plusieurs masses d’eau superficielles et subsuperficielles participant à l’alimentation pendant les crues, et jouant un rôle différent dans le transfert des contaminants. / This work is included in an approach for a better knowledge of karst aquifers. For this, the Toulon Springs pilot site was chosen, and provides the opportunity to study relationships between multilayered karst aquifers of the northern edge of the Aquitaine sedimentary basin. Toulon Springs are major regional springs and are located in Périgueux (Dordogne County, France). They have been supplying water to the metropolitan area of Périgueux since 1832.This work aim to test an innovative multitracer approach coupled with a physicochemical high-resolution auto-monitoring to characterize functioning and vulnerability of a multilayered karst aquifer.The use of a coupled hydrodynamic and hydrochemical approach has highlighted Toulon Springs supply by a deep and captive aquifer, in addition to a more subsuperficial aquifer. This information has been incorporated into the global hydrogeological situation of the study area to propose a new delineation of Toulon Springs hydrogeological cathment.The use of a high-resolution monitoring enables to specify the hydrogeological functioning of the studied karst system. The analysis performed on several flood events, identify that mass transfer can range from a few days to a few weeks.The use of nitrate isotope (δ15N-NO3- ; δ18O-NO3-) enables to identify two main nitrate sources in both surface water and groundwater: (i) inorganic fertilizer; (ii) sewage from individual house.The last part of this work was to analyse Toulon Springs temporal vulnerability during floods to marker of contamination such as particles, dissolved organic carbon, nitrate, and bacteria. Hence, several water type from surface runoff, unsaturated zone and saturated zone were identify as responsible of contaminant transfer: (i) water from saturated zone is responsible of vulnerability to mineral particles ; (ii) water from unsaturated zone is responsible of vulnerability to nitrare ; (iii) water from surface runoff is responsible of vulnerability to bacteria contamination.

The Gulf of Mexico commercial reef fish fishery has experienced significant management changes and disturbance in recent years, including transitioning two major fisheries from a traditional open access system into a limited entry individual fishing quota (IFQ) system in 2007 and 2010. Also in 2010, the Deepwater Horizon oil spill (DWH) released an estimated 4.9 million barrels of oil into the Gulf (~206 million U.S. gallons), and is still the largest U.S. environmental disaster to date. Emergency fishing closures initiated shortly after the oil spill began were successful in keeping tainted seafood from reaching markets. However, effects of DWH closures on fisher decision making, fishery productivity, and distribution of fishing effort all remain poorly understood. Understanding the range and magnitude of fishers’ responses to perturbations — including regulatory change and human-induced environmental disasters — is critical for designing effective management and disaster response policies that can meet biological, ecological, economic, social, and sustainability objectives. This work characterized the spatial and temporal patterns of productivity and fishing effort for the Gulf of Mexico (GoM) commercial reef fish fishery. Patterns of productivity and effort distribution were used to examine the response of fishers to management change and large-scale disturbance, namely the DWH fishing closures. Fisheries-dependent logbook trip reports were used to quantify revenue and catch-per-unit-effort (CPUE) patterns from 2000-2014. Novel to fisheries work in the GoM, complementary vessel monitoring systems (VMS) satellite tracking data were used to quantify high-resolution spatial distribution patterns over time, relative to the DWH fishing closures. A general linear modeling (GLM) approach was also used to examine which variables may have contributed to resilience of fishers after DWH closures. Results suggested that this fishery was largely resilient to the DWH fishing closures in 2010, although exact outcomes varied by region. Overall fleet-level productivity steadily increased over time, but regional patterns were based on major species in catch. Productivity in the western GoM was consistently highest over time, and trips in the west and central GoM were dominated by Red snapper (Lutjanus campechanus) and Vermilion snapper (Rhomboplites aurorubens). Trips in the east were dominated by Red grouper (Epinephelus morio) and Gag grouper (Mycteroperca microlepis). Shifts in spatial distribution to new productive fishing grounds or reduced competition via fewer vessels or trips may explain the increases in productivity observed over the study period. Consolidation in the fleet was apparent, with fewer individual vessels and fewer total trips over time. However, the rate of vessel drop out after DWH (5%) was far below the annual background attrition rate of ~14-20%. Relative productivity patterns inside vs. outside the boundaries of fishing closures did not change over time, and there were even some increases in productivity observed during and after DWH in the eastern GoM. Yet, vessels that dropped out after DWH were concentrated in the north-central and eastern GoM. Distribution of fishing grounds before and after DWH were highly similar, and there were increases in effort along the outer West Florida Shelf. Variability in revenue and CPUE, CPUE magnitude, and magnitude of grouper landings were significant predictors of dropping out of the fishery in the GLMs. Synergies with the Red snapper or Grouper-Tilefish IFQs may have “primed” the fishery for resilience by eliminating inconsistent or marginal fishers before the oil spill, and may further explain some of the spatially varying patterns of productivity and attrition after 2010. Resilience was likely also enhanced by the more than $2 billion in emergency compensation payments made to captains, crew, and vessel owners for lost fishing income and assistance with oil remediation efforts. This work stands to make a significant contribution to our understanding of how the DWH oil spill impacted fisheries and communities in the GoM. The results add to a growing body of literature suggesting that the acute population- and ecosystem-level impacts of the DWH oil spill were not as strong or severe as initially anticipated. This work also stands to make contributions to the broader understanding of how this fishery has performed in the wake of recent management change and major environmental disturbance.

The work presented in this thesis belongs to the domain of theoretical and experimental gas phase molecular spectroscopy. It consists of two parts dedicated to two relatively different aspects in this field. The first part presents a high resolution analysis of the ν5 fundamental band (NO2 in plane bending mode) positions and intensities of D14NO3 (deuterated nitric acid) in the 11 µm spectral region. For this study, we used an infrared spectrum of D14NO3 recorded in the 700−1400 cm−1 region on a Fourier transform spectrometer at Bergische Universität in Wuppertal (Germany). Our analysis demonstrates that the fundamental ν5 band centered at 887.657 cm−1 is strongly perturbed. Indeed, it proves that 5^1 and 7^1+9^1 energy levels of DNO3 are coupled through A and B type Coriolis resonances. The resonance scheme for the isotopologue D14NO3 therefore differs substantially from the schemes of H14NO3 and H15NO3 that feature dominantly Fermi type resonances. The second theme treated in this work is devoted to the lineshapes of pure rotational transitions of CH3F with the study of collisional broadening (collisions CH3F-CH3F and CH3F-He) of optical transitions and their Stark components. The microwave measurements were realised at ICT in Prague. Their analysis enabled to provide collisional parameters using various line profiles (Voigt, Rautian, Speed dependent) for the J, K → J + 1, K (K = 0, ..., J) transitions with J = 1 and J = 3 as well as for their various Stark components J, K, M → J + 1, K, M' (|M| = 0, ..., J ; |M − M'| = 0, 1). Moreover, a correct use of model based on Infinite Order Sudden approximation led to very satisfactory results of the observed line-mixing effects. The retrieved experimental results complete and extend the previous studies and provide the first successful demonstration of the ability of the IOS approximation to model line-mixing effects among Stark transitions

<p>We present an investigation of the magnetic field geometries and inhomogeneous distribution of chemical elements in the atmospheres of peculiar A and B stars. Our study combines high-quality spectroscopic and spectropolarimetric stellar observations with the development and application of novel techniques for theoretical interpretation of the shapes and variability of stellar line profiles. In particular, we extend the method of Doppler imaging to the analysis of spectra in the four Stokes parameters, making it possible to derive detailed and reliable stellar magnetic maps simultaneously with the imaging chemical inhomogeneities.</p><p>The magnetic Doppler imaging is applied to study of magnetic topologies and distributions of chemical elements in the peculiar stars α² CVn and 53 Cam. We found that the magnetic field geometry of 53 Cam is considerably more complex than a low-order multipolar topology, commonly assumed for magnetic A and B stars. Our Doppler imaging analysis also led to a discovery and study of spots of enhanced mercury abundance in the atmosphere of α And, a star where the presence of a global magnetic field is unlikely.</p><p>The ESO 3.6-m telescope is used to collect unique, very high spectral- and time-resolution observations of rapidly oscillating peculiar A (roAp) stars and to reveal line profile variations due to stellar pulsations. We present a detailed characterization of the spectroscopic pulsational behaviour and demonstrate a remarkable diversity of pulsations in different spectral lines. The outstanding variability of the lines of rare-earth elements is used to study propagation of pulsation waves through the stellar atmospheres and identify pulsation modes. This analysis led to a discovery of a non-axisymmetric character of pulsations in roAp stars.</p><p>Our study of chemical stratification in the atmosphere of the roAp star γ Equ provides a compelling evidence for significant variation of the chemical composition with depth. We find a combined effect of extreme chemical anomalies and a growth of pulsation amplitude in the outermost atmospheric layers to be the most likely origin of the high-amplitude pulsational variations of the lines of rare-earth elements.</p><p>Observations of cool magnetic CP stars are obtained with the ESO Very Large Telescope and are used for empirical investigation of the anomalies in the atmospheric temperature structure. We show that the core-wing anomaly of the hydrogen Balmer lines observed in some cool CP stars can be attributed to a hot layer at an intermediate atmospheric depth.</p>

In festen azobenzenhaltigen Polymeren wurde bei Bestrahlung mit blauem Licht ein makroskopischer Materialtransport beobachtet. Um die Dynamik der Gitterentstehung zu verfolgen, wurde am Speicherring für Synchrotronstrahlung ein Gitterschreibaufbau errichtet. Damit konnte erstmals in dieser Arbeit die Gitterbildungsgeschwindigkeit in-situ simultan mit Röntgen- und Lichtstreuung untersucht werden. Mit Hilfe einer speziellen Anpassung der Röntgenstreutheorie konnten sehr gute Übereinstimmungen von theoretischen Berechnungen mit den Messergebnissen erzielt werden. Dabei konnte nachgewiesen werden, dass sich zeitgleich mit einem Oberflächengitter auch ein Dichtegitter entwickelt. Durch die Trennung beider Streuanteile ließ sich die Dynamik der Strukturentstehungen bestimmen. Des weiteren konnte erstmals mit Hilfe der Photoelektronenspektroskopie die molekulare Orientierung an der Oberfläche eines Oberflächengitters nachgewiesen werden. Die Bewegungsursache kann auf einen Impulsübertrag während der Isomerisierung zurückgeführt werden, während die Bewegungsrichtung durch den elektrischen Feldvektor festgelegt wird. Die Theorie der Gitterentstehung konnte verbessert werden. / Solid azobenzene containing polymers show a macroscopic material transport under illumination with blue light. A writing setup was constructed at a synchrotron beamline in order to investigate the dynamics of the grating formation. With this setup it was possible to record the grating velocity for the first time simultaneously with x-ray and laser light scattering. <br /> A very good consistency could be achieved between the experiments and a suitable accomodation of the x-ray scattering theory. The theory reveals, that a density grating develops simultaneously with a surface grating. By separation of both parts the dynamics was determined for the density and the surface grating.<br /> The molecular ordering was determined at the surface with photoelectron spectroscopy. A momentum transfer could be identified as the source of the movement while the electric field defines the direction of the movement. The theory of the grating formation was improved.