Interactions of cells with their chemical microenvironments are critical to many polarized processes, including differentiation, migration, and pathfinding. To investigate such cellular events, tools are required that can rapidly reshape the microscopic chemical landscapes presented to cultured cells. Existing chemical dosing technologies rely on use of pre-fabricated chemical gradients, thus offering static cell-reagent interactions. Such interactions are particularly limiting for studying migration and chemotaxis, during which cells undergo rapid changes in position, morphology, and intracellular signaling. This dissertation describes the use of laminar streams, containing cellular effector molecules, for precise delivery of effectors to selected subcellular regions. In this approach, cells are grown on an ultra-thin polymer membrane that serves as a barrier to an underlying reagent reservoir. By using a tightly-focused pulsed laser beam, micron-diameter pores can be ablated in the membrane upstream of desired subcellular dosing sites. Emerging through these pores are well-defined reagent streams, which dose the targeted regions. Multiple pores can be ablated to allow parallel delivery of effector molecules to an arbitrary number of targets. Importantly, both the directionality and the composition of the reagent streams can be changed on-the-fly under a second to present dynamically changing chemical signals to cells undergoing migration. These methods are applied to study the chemotactic responses of neutrophil precursor cells. The subcellular localization of the chemical signals emerging through pores is found to influence the morphological evolution of these motile cells as they polarize and migrate in response to rapidly altered effector gradients. / text

Complex interactions between topographic heterogeneity and steep gradients in climate and environmental conditions are commonly assumed to promote biotic diversification. Using tropical frogs as a model, I investigate the nature of these interactions that disrupt migration between populations, causing genetic divergence and speciation. I determine the role of several putative factors that affect gene flow (Euclidean distances, Least Cost Path (LCP) distances, topographic complexity, and elevation difference) and promote genetic structure (FST) between populations of three tropical Andean frog species. Moreover, I investigate, from an intraspecific perspective, whether montane frog species display on average larger genetic distances per kilometer relative to lowland species. Finally, I test if recent genetic divergence caused by topographic barriers to gene flow is paralleled by independent character systems such as acoustics and morphological traits in the high Andean frog Dendropsophus labialis. Even though the effect of geographic features on migration (and conversely, FST) was species-specific, LCP and Euclidean distances had the strongest effect on migration rate. Topographic complexity also reduced migration rate whereas elevation difference did not have an effect. I found that indeed highland species show larger genetic distances per kilometer between haplotypes than do lowland species. Also, genetic divergence is strongly associated with topographic heterogeneity, which is an intrinsic characteristic of montane regions. Finally, I found that acoustic variation in D. labialis diverges according to genealogical history, but external morphology does not follow this relationship. Stochastic processes due to genetic drift appear to be a better explanatory mechanism for the divergence in calls than adaptive variation. The strong and congruent divergence observed in acoustic and genetic characters indicates that these two groups correspond to morphologically cryptic parapatric species. Overall, the results of this study suggest some of the mechanisms that allow tropical mountains to promote intraspecific genetic divergence. The combined effect of ridges (promoting allopatric differentiation) and environmental gradients across elevation (promoting parapatric differentiation) are effective forces that are present mostly in highland biomes. Unfortunately, such biomes are critically threatened by habitat destruction and climate change, possibly more than any other biome on earth. / text

No description available.

Either tropical niche divergence or tropical niche conservatism could drive the latitudinal diversity gradient. Greater niche divergence in the tropics could accelerate reproductive isolation leading to more rapid species formation. Alternatively, latitudinal asymmetry in niche conservatism, whereby tropical species are more conserved than high latitude species, could promote more dispersal in to than out of the tropics, leading to greater tropical richness. Here I test whether rates of climatic niche evolution vary across the latitudinal gradient for 164 closely related pairs of species. Using the evolutionary ages at which sister species diverge, and the niche divergence between them, I applied Brownian motion models to test whether rates of climatic niche evolution varied with latitude. My results indicate that climatic niche conservatism is strongest in the tropics. This suggests that the latitudinal diversity gradient is driven by the inability of tropical to adapt to temperate climates and colonize non-tropical latitudes.

Either tropical niche divergence or tropical niche conservatism could drive the latitudinal diversity gradient. Greater niche divergence in the tropics could accelerate reproductive isolation leading to more rapid species formation. Alternatively, latitudinal asymmetry in niche conservatism, whereby tropical species are more conserved than high latitude species, could promote more dispersal in to than out of the tropics, leading to greater tropical richness. Here I test whether rates of climatic niche evolution vary across the latitudinal gradient for 164 closely related pairs of species. Using the evolutionary ages at which sister species diverge, and the niche divergence between them, I applied Brownian motion models to test whether rates of climatic niche evolution varied with latitude. My results indicate that climatic niche conservatism is strongest in the tropics. This suggests that the latitudinal diversity gradient is driven by the inability of tropical to adapt to temperate climates and colonize non-tropical latitudes.

In many practical problems in applied sciences, the features of most interest cannot be observed directly, but have to be inferred from other, observable quantities. In particular, many important data acquisition devices provide an access to the measurement of the partial derivatives of a feature of interest rather than sensing its values in a direct way. In this case, the feature has to be recovered through integration which is known to be an ill-posed problem in the presence of noises. Moreover, the problem becomes even less trivial to solve when only a portion of a complete set of partial derivatives is available. In this case, the instability of numerical integration is further aggravated by the loss of information which is necessary to perform the reconstruction in a unique way. As formidable as it may seem, however, the above problem does have a solution in the case when the partial derivatives can be sparsely represented in the range of a linear transform. In this case, the derivatives can be recovered from their incomplete measurements using the theory of compressive sampling (aka compressed sensing), followed by reconstruction of the associated feature/object by means of a suitable integration method. It is known, however, that the overall performance of compressive sampling largely depends on the degree of sparsity of the signal representation, on the one hand, and on the degree of incompleteness of data, on the other hand. Moreover, the general rule is the sparser the signal representation is, the fewer measurements are needed to obtain a useful approximation of the true signal. Thus, one of the most important questions to be addressed in such a case would be of how much incomplete the data is allowed to be for the signal reconstruction to remain useful, and what additional constraints/information could be incorporated into the estimation process to improve the quality of reconstruction in the case of extremely under-sampled data. With these questions in mind, the present proposal introduces a way to augment the standard constraints of compressive sampling by additional information related to some natural properties of the signal to be recovered. In particular, in the case when the latter is defined to be the partial derivatives of a multidimensional signal (e.g. image), such additional information can be derived from some standard properties of the gradient operator. Consequently, the resulting scheme of derivative compressive sampling (DCS) is capable of reliably recovering the signals of interest from much fewer data samples as compared to the case of the standard CS. The signal recovery by means of DCS can be used to improve the performance of many important applications which include stereo imaging, interferometry, coherent optical tomography, and many others. In this proposal, we focus mainly on the application of DCS to the problem of phase unwrapping, whose solution is central to all the aforementioned applications. Specifically, it is shown both conceptually and experimentally that the DCS-based phase unwrapping outperforms a number of alternative approaches in terms of estimation accuracy. Finally, the proposal lists a number of research questions which need to be answered in order to attach strong theoretical guarantees to the practical success of DCS.

Multiconfigurational quantum chemistry methods, and especially the multiconfigurational self-consistent field (MCSCF) and multireference perturbation theory (MRPT2), are powerful tools, particularly suited to the accurate modeling of photochemical processes and transition metal catalysis. However, they are limited by their high computational cost compared to other methods, especially density functional theory. Moreover, there are areas where they would be expected to perform well, but where they are not applied due to lack of experience. This thesis addresses those issues. First, the efficiency of the Cholesky decomposition approximation to reduce the cost of MCSCF and MRPT2 without sacrificing their accuracy is demonstrated. This then motivates the extension of the Cholesky approximation to the computation of MCSCF nuclear gradients, thus strongly improving the ability to perform MCSCF non-adiabatic molecular dynamics. Typically, a tenfold speed-up is observed allowing dynamic simulation of larger systems or over longer times. Finally, multiconfigurational methods are applied to the computation of X-ray spectra of transition metal complexes. The importance of the different parameters in the calculation is systematically investigated, laying the base for wider applications of those accurate methods in the modeling of X-ray spectroscopy. A tool to analyze the resulting spectrum in terms of molecular orbitals is also presented, strengthening the interplay between theory and experiments. With these developments and other significant ones that have happened in recent years, multiconfigurational methods can now reach new grounds and contribute to important new discoveries

Gegenstand der Arbeit ist die PFG NMR (nuclear magnetic resonance with pulsed field gradients), wobei speziell die apparativen und experimentellen Bedingungen untersucht werden, welche sich durch die Verwendung ultra-hoher gepulster magnetischer Feldgradienten von bis zu 35T/m ergeben. Motiv für die Arbeit ist die Untersuchung von Diffusionserscheinungen in mikroporösen Wirtssystemen mit inneren magnetischen Feldgradienten oder/und kurzen T2-Relaxationzeiten. Nach Zusammenstellung der notwendigen Werkzeuge zur mathematischen Beschreibung von PFG NMR-Experimenten werden die aus der Literatur bekannten Impulssequenzen kritisch untersucht und durch eigene Weiterentwicklungen ergänzt. Für wichtige PFG NMR-Impulssequenzen wird eine verallgemeinerte Schreibweise vorgestellt und auf beliebige Formen der gepulsten magnetischen Feldgradienten ausgedehnt. Weiterhin werden Störeinflüsse auf das PFG NMR-Experiment untersucht und zunächst in allgemeiner Form Möglichkeiten zu deren Beseitigung bzw. Unterdrückung dargestellt. Die so gewonnenen Erkenntnisse fanden konkrete Anwendung bei der Konzeption und dem Bau des PFG NMR-Spektrometers Fegris 400 NT. Dieses Gerät wird, soweit es den Gegenstand der Arbeit berührt, ebenfalls beschrieben und in der Anlage dokumentiert. Abschließend sind einige Untersuchungen, die mit dem Fegris 400 NT durchgeführt wurden und in der dargestellten Form erst mit diesem Gerät möglich waren, kurz skizziert, wobei für weitergehende Informationen auf die entsprechenden Veröffentlichungen verwiesen wird.

No description available.

Ce travail porte sur la détection de l’endommagement de matériaux composites. Une première partie concerne l’élaboration de méthodes permettant d’estimer les termes sources de chaleur d’un matériau sollicité mécaniquement. Lors de ce processus, un ensemble de défauts mécaniques mènent à des productions de chaleur. La détection des sources peut permettre la détection de ces défauts. Deux principales méthodes sont présentées : une méthode dite « directe » basée sur une discrétisation du champ de température mesuré et une méthode « itérative » basée sur la méthode du gradient conjugué. A ces méthodes sont couplées des techniques de filtrages des données comme la SVD. Les équations sont résolues par différences finies sous leur forme linéaire. Des modifications sont apportées à l’algorithme itératif pour améliorer sa convergence ainsi que les résultats. Les problématiques envisagées font partie des problèmes inverses en thermique. L’objectif de la première partie est de trouver un lien entre l’apparition de macro-fissure et la localisation de termes sources de chaleur au sein d’un matériau composite. La seconde partie consiste à élaborer des méthodes d’estimation des diffusivités thermiques directionnelles. Les méthodes reposent sur une modélisation du transfert de chaleur à l’aide des quadripôles thermiques. Les estimations de paramètres sont réalisées sur des zones ciblées à risque sur un matériau déjà endommagé. Le but est de faire le lien entre un endommagement mécanique connu diffus et une dégradation des propriétés thermiques. Ce manuscrit est présenté en deux parties : une partie de validation des méthodes. Une partie expérimentale où sont analysés les composites. / This work deals with the damage detection of composite materials. These materials are used in the aeronautics industry. The first part concerns the development of methods to estimate the heat sources terms of a stressed material. During this process, a set of mechanical defects leads to heat productions. The sources detection can conduct to the detection of these defects. Two main methods are presented: a "direct" method based on a discretization of the measured temperature field and an "iterative" method based on the conjugate gradient method. These methods are coupled with data filtering techniques such as SVD. In order to optimize computation time, equations are solved by finite differences in their linear form. Modifications are also made for the iterative algorithm to improve its convergence as well as the results of the estimation. These problems are considered as thermal inverse problems. The main objective of the first part is to find an experimental link between the appearance of a macro fissure and the localization of a heat source term within a composite material. The second part consists in the elaboration of methods for estimating thermal directional diffusivities. The methods are based on a modeling of heat transfer using thermal quadrupoles. Parameter estimations are made on targeted "risked" areas on a material, which is already damaged but not under stress. The aim is to link a known mechanical damage, which is called "diffuse" to thermal properties degradation in the main directions. This manuscript is presented in two parts: a validation part of the methods, and an experimental part in which composites are analyzed.