Application of NMR RDC’s, relaxation and self-diffusion for the study of dynamic processes of small molecules in solution

Spin-lattice Relaxation, self-Diffusion coefficients and Residual Dipolar Couplings (RDC’s) are the basis of well established Nuclear Magnetic Resonance techniques for the physicochemical study of small molecules (typically organic compounds and natural products with MW < 1000 Da), as they proved to be a powerful and complementary source of information about structural dynamic processes in solution. The work developed in this thesis consists in the application of the earlier-mentioned NMR techniques to explore, analyze and systematize patterns of the molecular dynamic behavior of selected small molecules in particular experimental conditions. Two systems were chosen to investigate molecular dynamic behavior by these techniques: the dynamics of ion-pair formation and ion interaction in ionic liquids (IL) and the dynamics of molecular reorientation when molecules are placed in oriented phases (alignment media). The application of NMR spin-lattice relaxation and self-diffusion measurements was applied to study the rotational and translational molecular dynamics of the IL: 1-butyl-3-methylimidazolium tetrafluoroborate [BMIM][BF4]. The study of the cation-anion dynamics in neat and IL-water mixtures was systematically investigated by a combination of multinuclear NMR relaxation techniques with diffusion data (using by H1, C13 and F19 NMR spectroscopy). Spin-lattice relaxation time (T1), self-diffusion coefficients and nuclear Overhauser effect experiments were combined to determine the conditions that favor the formation of long lived [BMIM][BF4] ion-pairs in water. For this purpose and using the self-diffusion coefficients of cation and anion as a probe, different IL-water compositions were screened (from neat IL to infinite dilution) to find the conditions where both cation and anion present equal diffusion coefficients (8% water fraction at 25 ºC). This condition as well as the neat IL and the infinite dilution were then further studied by 13C NMR relaxation in order to determine correlation times (c) for the molecular reorientational motion using a mathematical iterative procedure and experimental data obtained in a temperature range between 273 and 353 K. The behavior of self-diffusion and relaxation data obtained in our experiments point at the combining parameters of molar fraction 8 % and temperature 298 K as the most favorable condition for the formation of long lived ion-pairs. When molecules are subjected to soft anisotropic motion by being placed in some special media, Residual Dipolar Couplings (RDCs), can be measured, because of the partial alignment induced by this media. RDCs are emerging as a powerful routine tool employed in conformational analysis, as it complements and even outperforms the approaches based on the classical NMR NOE or J3 couplings. In this work, three different alignment media have been characterized and evaluated in terms of integrity using 2H and 1H 1D-NMR spectroscopy, namely the stretched and compressed gel PMMA, and the lyotropic liquid crystals CpCl/n-hexanol/brine and cromolyn/water. The influence that different media and degrees of alignment have on the dynamic properties of several molecules was explored. Different sized sugars were used and their self-diffusion was determined as well as conformation features using RDCs. The results obtained indicate that no influence is felt by the small molecules diffusion and conformational features studied within the alignment degree range studied, which was the 3, 5 and 6 % CpCl/n-hexanol/brine for diffusion, and 5 and 7.5 % CpCl/n-hexanol/brine for conformation. It was also possible to determine that the small molecules diffusion verified in the alignment media presented close values to the ones observed in water, reinforcing the idea of no conditioning of molecular properties in such media.

Âges K-Ar de glauconites des environs de Luz de Tavira, Algarve

Glauconite K-Ar ages (6.88±0.4; 7.03±0.4 MY) confirm earlier reports to Upper Tortonian of silt beds near Morgadinho, Luz de Tavira and Tavira. Taking stratigraphical position and age into account it is possible now to correlate these beds with similar ones at Quelfes and Cacela (Formação de Cacela, lower member, ascribed to the upper part of N16 or to NI7 Blow's zone, Globorotalia humerosa - G. dutertrei; Tortonian to Messinian, according to the ostracod fauna). Limit between the above quoted zones is thus placed at about 7 MY. New K-Ar ages greatly improve the knowledge about Upper Miocene in eastern Algarve, and on regional tectonic evolution. This is particulary so in what concerns an intra-Tortonian phase.

Depósitos messinianos do sul de Portugal, mamíferos (incluindo Rodentia e Logomorpha) e idades K-Ar

In the southern part of Tagus basin, North of paleozoic rocks of Valverde-Senhor das Chagas (near Alcácer do Sal) horst, a marine transgression has been recognized, Upper Serravallian, and maybe Lower Tortonian in age. There are no earlier marine deposits, and no younger ones are known either. Paleozoic behaved as a barrier separating two basins, distinct at least since Middle Miocene until Upper Pleistocene. Until now, both were regarded as a single entity, the so-called «Sado basin» Southwards (Alvalade basin) there has been a single transgression. It was assummed that it was the same one as the former. Indeed it is not definitely so. Later transgression accounts for Esbarrondadoiro Formation, whose deposits have been ascribed to Tortonian or even to Middle Miocene. However they are Upper Messinian to Lower Zanclean. Esbarrondadoiro Formation is younger than Lower Member of Cacela Formation in Algarve and, with even stronger reason, than the upper-most well dated marine levels in Tagus basin. Age of Miocene units dealt with here has been based on small mammals found in marine sands.

Production of recombinant protein hLIF in static and dynamic systems of animal cell culture

Thesis for the Degree of Master of Science in Biotechnology Universidade Nova de Lisboa, Faculdade de Ciências e Tecnologia

Multi-bit sigma-delta modulators with enhanced dynamic-range using non-linear DAC for hearing aids

15th IEEE International Conference on Electronics, Circuits and Systems, Malta

An implementation of dynamic fully compressed suffix trees

Dissertação apresentada na Faculdade de Ciências e Tecnologia da Universidade Nova de Lisboa para obtenção do grau de Mestre em Engenharia Informática

L’instabilité dynamique pendant le Toarcien dans le Moyen Atlas (Maroc): mise en évidence de glissements synsédimentaires dans le synclinal de Bou Angar

During the Toarcian, shelves undergo block-faulting with mechanisms of tilting. It results the break up of the Middle Atlas basin in subsident sectors separated by resistant ridges. This device is highlighted by strong variations of facies, more or less extended lacunar zones, reefs aligned on the ridges and of synsedimentary tectonics structures. Within the framework of mapping survey carried out in the south-west of Middle Atlas, a meticulous prospection of Bou Angar synclinal allowed the description of a new outcrop of Toarcian. This one offers good examples of extensional structures and bio-accumulations. These data, supplemented by other witnesses of the dynamic instability in the rest of the Middle Atlas, permit to propose a paleogeographic map of the Middle Atlas basin during the Toarcian.

Simple and stable dynamic traffic engineering for provider scale ethernet

Trabalho apresentado no âmbito do Mestrado em Engenharia Informática, como requisito parcial para obtenção do grau de Mestre em Engenharia Informática

A lightweight distributed super peer election algorithm for unstructured dynamic P2P systems

Dissertação apresentada na Faculdade de Ciências e Tecnologia da Universidade Nova de Lisboa para obtenção do grau de Mestre em Engenharia Electrotécnica e de Computadores

A middleware for service oriented computing in dynamic environments

Dissertação apresentada na Faculdade de Ciências e Tecnologia da Universidade Nova de Lisboa para a obtenção do Grau de Mestre em Engenharia Informática

Static laws in dynamic environments (bridging science to legislation)

Proceedings of the First International Conference on Coastal Conservation and Management in the Atlantic and Mediterranean, p. 193-200

Intelligent decision support systems for collaboration in industrial plants

Dissertação apresentada para obtenção do Grau de Doutor em Sistemas de Informação Industriais, Engenharia Electrotécnica, pela Universidade Nova de Lisboa, Faculdade de Ciências e Tecnologia

Dynamic and interaction of cytochrome c with Pf1 virus

Dissertação apresentada na Faculdade de Ciências e Tecnologia da Universidade Nova de Lisboa para obtenção do grau de Mestre em BioOrgânica

Imagens da Técnica na Ficção Científica. A Obra de Philip K. Dick no Contexto Sociotécnico

Dissertação para obtenção do grau de Doutor em Ciências da Comunicação Especialidade de Comunicação e Cultura

Organising interoperability information on highly dynamic and heterogeneous environments

Dissertação para obtenção do Grau de Mestre em Engenharia Electrotécnica e de Computadores