Relative basicities of free base porphyrins : understanding the role of macrocyclic distortion

Porphyrins have been the center of numerous investigations in different areas of chemistry, geochemistry, and the life sciences. In nature the conformation of the porphyrin macrocycle varies, depending on the function of its apoenzyme. It is believed that the conformation of the porphyrin ring is necessary for the enzyme to achieve its function and modify its reactivity. It is important to understand how the conformation of the porphyrin ring will influence its properties. In synthetic porphyrins particular conformations and ring deformations can be achieved by peripheral substitution, metallation, core substitution, and core protonation among other alterations of the macrocycle. The macrocyclic distortions will affect the ring current, the ability of pyrroles to intramolecularly hydrogen bond and the relative basicity of each of the porphyrins. To understand these effects different theoretical models are used. The ground state structure of each of 19 free base porphyrins is determined using molecular mechanics (MM+) and semiempirical methods (PM3). The energetics of deformation of the macrocyclic core is calculated by carrying out single point energy calculations for the conformation achieved by each synthetic compound. Enthalpies of solution and enthalpies of protonation of 10 porphyrins with varying degrees of macrocyclic deformation and varying electron withdrawing groups in the periphery are determined using solution calorimetry. Using Hess's Law, the relative basicity of each of the different free base porphyrins is calculated. NMR results are described, including the determination of free energies of activation of ring tautomerization and hydrogen bonding for several compounds. It was found that in the absence of electronic effects, the greater macrocyclic deformation, the greater the basicity of the porphyrins. This basicity is attenuated by the presence of electron withdrawing groups and ability to of the macrocycle to intramolecularly hydrogen bond.

Estudo da evolução das tensões residuais através da difratometria de raios x em aço rolamento submetido a esforços cíclicos

The micro-deformations caused by cyclic loading origins the variation of the distances between atoms of the crystal lattice producing the irreversible component. In order to study and understand the microstructural behavior of the material this paper investigated the influence suffered by residual stresses in thrust rolling bearing races fabricated in AISI 52100 steel, after tests by cyclic rolling contact in a tribometer at 1m/s under two contact pressures (500 MPa and 1400 MPa) in dry and boundary lubrication conditions. Procedures of tests thermo-acustically isolated were developed for monitoring the contact temperature and sound pressure level signals to establish a comparison between the residual stress measurements, micro-hardness Vickers and micrographic registers searching an indication of wear evolution. The sin²ψ method by X-ray diffraction technique was used to quantify the residual stresses. Three raceway zones were selected for the evaluation of wear and surface morphology after predetermined cycling, comparing with their new condition ("as received"). Micro-hardness and residual stress measurements showed significant changes after the tests and it was possible to observe the relationship between the increase of sound pressure level and the residual stress for dry and lubricated conditions.

Estudo da evolução das tensões residuais através da difratometria de raios x em aço rolamento submetido a esforços cíclicos

The micro-deformations caused by cyclic loading origins the variation of the distances between atoms of the crystal lattice producing the irreversible component. In order to study and understand the microstructural behavior of the material this paper investigated the influence suffered by residual stresses in thrust rolling bearing races fabricated in AISI 52100 steel, after tests by cyclic rolling contact in a tribometer at 1m/s under two contact pressures (500 MPa and 1400 MPa) in dry and boundary lubrication conditions. Procedures of tests thermo-acustically isolated were developed for monitoring the contact temperature and sound pressure level signals to establish a comparison between the residual stress measurements, micro-hardness Vickers and micrographic registers searching an indication of wear evolution. The sin²ψ method by X-ray diffraction technique was used to quantify the residual stresses. Three raceway zones were selected for the evaluation of wear and surface morphology after predetermined cycling, comparing with their new condition ("as received"). Micro-hardness and residual stress measurements showed significant changes after the tests and it was possible to observe the relationship between the increase of sound pressure level and the residual stress for dry and lubricated conditions.

Geometric inequalities for initial data with symmetries

We consider a class of initial data sets (Σ,h,K) for the Einstein constraint equations which we define to be generalized Brill (GB) data. This class of data is simply connected, U(1)²-invariant, maximal, and four-dimensional with two asymptotic ends. We study the properties of GB data and in particular the topology of Σ. The GB initial data sets have applications in geometric inequalities in general relativity. We construct a mass functional M for GB initial data sets and we show:(i) the mass of any GB data is greater than or equals M, (ii) it is a non-negative functional for a broad subclass of GB data, (iii) it evaluates to the ADM mass of reduced t − φi symmetric data set, (iv) its critical points are stationary U(1)²-invariant vacuum solutions to the Einstein equations. Then we use this mass functional and prove two geometric inequalities: (1) a positive mass theorem for subclass of GB initial data which includes Myers-Perry black holes, (2) a class of local mass-angular momenta inequalities for U(1)²-invariant black holes. Finally, we construct a one-parameter family of initial data sets which we show can be seen as small deformations of the extreme Myers- Perry black hole which preserve the horizon geometry and angular momenta but have strictly greater energy.

Centrifuge modeling of oblique pipe-soil interaction in dense and loose sand

Due to relative ground movement, buried pipelines experience geotechnical loads. The imposed geotechnical loads may initiate pipeline deformations that affect system serviceability and integrity. Engineering guidelines (e.g., ALA, 2005; Honegger and Nyman, 2001) provide the technical framework to develop idealized structural models to analyze pipe‒soil interaction events and assess pipe mechanical response. The soil behavior is modeled using discrete springs that represent the geotechnical loads per unit pipe length developed during the interaction event. Soil forces are defined along three orthogonal directions (i.e., axial, lateral and vertical) to analyze the response of pipelines. Nonlinear load-displacement relationships of soil defined by a spring, is independent of neighboring spring elements. However, recent experimental and numerical studies demonstrate significant coupling effects during oblique (i.e., not along one of the orthogonal axes) pipe‒soil interaction events. In the present study, physical modeling using a geotechnical centrifuge was conducted to improve the current understanding of soil load coupling effects of buried pipes in loose and dense sand. A section of pipeline, at shallow burial depth, was translated through the soil at different oblique angles in the axial-lateral plane. The force exerted by the soil on pipe is critically examined to assess the significance of load coupling effects and establish a yield envelope. The displacements required to soil yield force are also examined to assess potential coupling in mobilization distance. A set of laboratory tests were conducted on the sand used for centrifuge modeling to find the stress-strain behavior of sand, which was used to examine the possible mechanisms of centrifuge model test. The yield envelope, deformation patterns, and interpreted failure mechanisms obtained from centrifuge modeling are compared with other physical modeling and numerical simulations available in the literature.

(Table) Grain size distribution of sediments from core Ak-509, Black Sea continental slope

New results of geomorphological, seismoacoustic, and lithological investigations on the upper continental slope off the Arkhipo-Osipovka Settlement are presented. Here, a large submarine slump was discovered by seismic survey in 1998. The assumed slump body, up to 200 m thick, rises 50-60 m above the valley floor that cuts the slope. Recent semiliquid mud that overlies laminated slope sediments with possible slump deformations flows down in the valley thalweg. Radiocarbon age inversion recorded in a Holocene sediment section of shelf facies recovered from the upper slope points to the gravity dislocation of sediments.

Modeling of a Heat-Induced Buckling of Plates Using the Mesh-free Method

In the process of engineering design of structural shapes, the flat plate analysis results can be generalized to predict behaviors of complete structural shapes. In this case, the purpose of this project is to analyze a thin flat plate under conductive heat transfer and to simulate the temperature distribution, thermal stresses, total displacements, and buckling deformations. The current approach in these cases has been using the Finite Element Method (FEM), whose basis is the construction of a conforming mesh. In contrast, this project uses the mesh-free Scan Solve Method. This method eliminates the meshing limitation using a non-conforming mesh. I implemented this modeling process developing numerical algorithms and software tools to model thermally induced buckling. In addition, convergence analysis was achieved, and the results were compared with FEM. In conclusion, the results demonstrate that the method gives similar solutions to FEM in quality, but it is computationally less time consuming.

Position measurements at five permanent GPS stations in the Bavarian Alps as part of the Geodetic Alpine Integrated Network (GAIN) of the ALPS-GPSQUAKENET project

In the frame of the transnational ALPS-GPSQUAKENET project, a component of the Alpine Space Programme of the European Community Initiative Programme (CIP) INTERREG III B, the Deutsches Geodätisches Forschungsinstitut (DGFI) in Munich, Germany, installed in 2005 five continuously operating permanent GPS stations located along the northern Alps boundary in Bavaria. The main objective of the ALPS-GPSQUAKENET project was to build-up a high-performance transnational space geodetic network of Global Positioning System (GPS) receivers in the Alpine region (the so-called Geodetic Alpine Integrated Network, GAIN). Data from this network allows for studying crustal deformations in near real-time to monitor Earthquake hazard and improve natural disaster prevention. The five GPS stations operatied by DGFI are mounted on concrete pillars attached to solid rock. The names of the stations are (from west to east) Hochgrat (HGRA), Breitenberg (BREI), Fahrenberg (FAHR), Hochries (HRIE) and Wartsteinkopf (WART). The provided data series start from October 7, 2005. Data are stored with a temporal spacing of 15 seconds in daily RINEX files.

Stress Inversion Using LiDAR Tunnel Deformation Measurements

Far-field stresses are those present in a volume of rock prior to excavations being created. Estimates of the orientation and magnitude of far-field stresses, often used in mine design, are generally obtained by single-point measurements of stress, or large-scale, regional trends. Point measurements can be a poor representation of far-field stresses as a result of excavation-induced stresses and geological structures. For these reasons, far-field stress estimates can be associated with high levels of uncertainty. The purpose of this thesis is to investigate the practical feasibility, applications, and limitations of calibrating far-field stress estimates through tunnel deformation measurements captured using LiDAR imaging. A method that estimates the orientation and magnitude of excavation-induced principal stress changes through back-analysis of deformation measurements from LiDAR imaged tunnels was developed and tested using synthetic data. If excavation-induced stress change orientations and magnitudes can be accurately estimated, they can be used in the calibration of far-field stress input to numerical models. LiDAR point clouds have been proven to have a number of underground applications, thus it is desired to explore their use in numerical model calibration. The back-analysis method is founded on the superposition of stresses and requires a two-dimensional numerical model of the deforming tunnel. Principal stress changes of known orientation and magnitude are applied to the model to create calibration curves. Estimation can then be performed by minimizing squared differences between the measured tunnel and sets of calibration curve deformations. In addition to the back-analysis estimation method, a procedure consisting of previously existing techniques to measure tunnel deformation using LiDAR imaging was documented. Under ideal conditions, the back-analysis method estimated principal stress change orientations within ±5° and magnitudes within ±2 MPa. Results were comparable for four different tunnel profile shapes. Preliminary testing using plastic deformation, a rough tunnel profile, and profile occlusions suggests that the method can work under more realistic conditions. The results from this thesis set the groundwork for the continued development of a new, inexpensive, and efficient far-field stress estimate calibration method.

Time-dependency of Rocks and Implications Associated with Tunnelling

The formulation of a geotechnical model and the associated prediction of the mechanical behaviour is a challenge engineers need to overcome in order to optimize tunnel design and meet project requirements. Special challenges arise in cases where rocks and rockmasses are susceptible to time-effects and time-dependent processes govern. Progressive rockmass deformation and instability, time-dependent overloading of support and delayed failures are commonly the result of time-dependent phenomena. The research work presented in this thesis serves as an attempt to provide more insight into the time-dependent behaviour of rocks. Emphasis is given on investigating and analyzing creep deformation and time-dependent stress relaxation phenomenon at the laboratory scale and in-depth analyses are presented. This thesis further develops the understanding of these phenomena and practical yet scientific tools for estimating and predicting the long-term strength and the maximum stress relaxation of rock materials are proposed. The identification of the existence of three distinct behavioural stages during stress relaxation is presented and discussed. The main observations associated with time-dependent behaviour are employed in numerical analyses and applied at the tunnel scale. A new approach for simulating and capturing the time-dependent behaviour coupled with the tunnel advancement effect is also developed and analyzed. Guidance is provided to increase the understanding of the support-rockmass interaction and the main implications and significance of time-dependent behaviour associated with rock tunnelling are discussed. The work presented in this thesis advances the scientific understanding of time-dependent rock and rockmass behaviour, increases the awareness of how such phenomena are captured numerically, and lays out a framework for dealing with such deformations when predicting tunnel deformations. Practical aspects of this thesis are also presented, which will increase their usage in the associated industries and close the gap between the scientific and industry communities.

Nonlinear soil-structure interaction for buried pressure pipes under differential ground motion

Pipelines extend thousands of kilometers across wide geographic areas as a network to provide essential services for modern life. It is inevitable that pipelines must pass through unfavorable ground conditions, which are susceptible to natural disasters. This thesis investigates the behaviour of buried pressure pipelines experiencing ground distortions induced by normal faulting. A recent large database of physical modelling observations on buried pipes of different stiffness relative to the surrounding soil subjected to normal faults provided a unique opportunity to calibrate numerical tools. Three-dimensional finite element models were developed to enable the complex soil-structure interaction phenomena to be further understood, especially on the subjects of gap formation beneath the pipe and the trench effect associated with the interaction between backfill and native soils. Benchmarked numerical tools were then used to perform parametric analysis regarding project geometry, backfill material, relative pipe-soil stiffness and pipe diameter. Seismic loading produces a soil displacement profile that can be expressed by isoil, the distance between the peak curvature and the point of contraflexure. A simplified design framework based on this length scale (i.e., the Kappa method) was developed, which features estimates of longitudinal bending moments of buried pipes using a characteristic length, ipipe, the distance from peak to zero curvature. Recent studies indicated that empirical soil springs that were calibrated against rigid pipes are not suitable for analyzing flexible pipes, since they lead to excessive conservatism (for design). A large-scale split-box normal fault simulator was therefore assembled to produce experimental data for flexible PVC pipe responses to a normal fault. Digital image correlation (DIC) was employed to analyze the soil displacement field, and both optical fibres and conventional strain gauges were used to measure pipe strains. A refinement to the Kappa method was introduced to enable the calculation of axial strains as a function of pipe elongation induced by flexure and an approximation of the longitudinal ground deformations. A closed-form Winkler solution of flexural response was also derived to account for the distributed normal fault pattern. Finally, these two analytical solutions were evaluated against the pipe responses observed in the large-scale laboratory tests.

Franz Liszt’s Piano Sonata in B Minor: Precedents for an Analytical Evolution

Franz Liszt has all too often been discarded as the virtuosic showman, despite the fact that his several of works have often gained great praise and attracted scholarly engagement. However, one also finds striking development of formal design and tonal harmony in many of the works for his principal composition medium, the piano. This paper seeks to explore the practical application of James A. Hepokoski and Warren Darcy’s 'Sonata Theory' upon Liszt’s magnum opus for the instrument, the Sonata in B Minor.

I shall first consider the historical analyses placed upon the work that deal with structural design, as it pertains to the paradigm of Classical sonata-form. Previous research reveals two main theoretical camps; those in favour of a multi-movement analysis (with conflicting hypotheses therein) and those in favour of a single movement sonata-form. An understanding of these historical conceptions of the piece allows one to then highlight areas of conflict and offer a new solution.

Finally, I shall use Sonata Theory to survey the Sonata in B Minor’s landscape in a new light. The title ‘Sonata’ has clear generic implications, many of which are met by Liszt; 'Sonata Theory' provides a model with which to outline the compositional deformations employed by the composer and the implications of this practice. In particular, I offer new perspectives on the validity of the double-function form, insight into the rhetorical layout of a rotational discourse, and propose a nuanced analysis befitting of this striking work.

Variationelle Zeitdiskretisierungen höherer Ordnung der Konvektions-Diffusions-Reaktions-Gleichungen in zeitabhängigen Gebieten

Wir betrachten zeitabhängige Konvektions-Diffusions-Reaktions-Gleichungen in zeitabhängi- gen Gebieten, wobei die Bewegung des Gebietsrandes bekannt ist. Die zeitliche Entwicklung des Gebietes wird durch die ALE-Formulierung behandelt, die die Nachteile der klassischen Euler- und Lagrange-Betrachtungsweisen behebt. Die Position des Randes und seine Geschwindigkeit werden dabei so in das Gebietsinnere fortgesetzt, dass starke Gitterdeformationen verhindert werden. Als Zeitdiskretisierungen höherer Ordnung werden stetige Galerkin-Petrov-Verfahren (cGP) und unstetige Galerkin-Verfahren (dG) auf Probleme in zeitabhängigen Gebieten angewendet. Weiterhin werden das C 1 -stetige Galerkin-Petrov-Verfahren und das C 0 -stetige Galerkin- Verfahren vorgestellt. Deren Lösungen lassen sich auch in zeitabhängigen Gebieten durch ein einfaches einheitliches Postprocessing aus der Lösung des cGP-Problems bzw. dG-Problems erhalten. Für Problemstellungen in festen Gebieten und mit zeitlich konstanten Konvektions- und Reaktionstermen werden Stabilitätsresultate sowie optimale Fehlerabschätzungen für die nachbereiteten Lösungen der cGP-Verfahren und der dG-Verfahren angegeben. Für zeitabhängige Konvektions-Diffusions-Reaktions-Gleichungen in zeitabhängigen Gebieten präsentieren wir konservative und nicht-konservative Formulierungen, wobei eine besondere Aufmerksamkeit der Behandlung der Zeitableitung und der Gittergeschwindigkeit gilt. Stabilität und optimale Fehlerschätzungen für die in der Zeit semi-diskretisierten konservativen und nicht-konservativen Formulierungen werden vorgestellt. Abschließend wird das volldiskretisierte Problem betrachtet, wobei eine Finite-Elemente-Methode zur Ortsdiskretisierung der Konvektions-Diffusions-Reaktions-Gleichungen in zeitabhängigen Gebieten im ALE-Rahmen einbezogen wurde. Darüber hinaus wird eine lokale Projektionsstabilisierung (LPS) eingesetzt, um der Konvektionsdominanz Rechnung zu tragen. Weiterhin wird numerisch untersucht, wie sich die Approximation der Gebietsgeschwindigkeit auf die Genauigkeit der Zeitdiskretisierungsverfahren auswirkt.

The relationship between early and intermediate level spatial vision during typical development and in autism spectrum disorder

Certaines recherches ont investigué le traitement visuel de bas et de plus hauts niveaux chez des personnes neurotypiques et chez des personnes ayant un trouble du spectre de l’autisme (TSA). Cependant, l’interaction développementale entre chacun de ces niveaux du traitement visuel n’est toujours pas bien comprise. La présente thèse a donc deux objectifs principaux. Le premier objectif (Étude 1) est d’évaluer l’interaction développementale entre l’analyse visuelle de bas niveaux et de niveaux intermédiaires à travers différentes périodes développementales (âge scolaire, adolescence et âge adulte). Le second objectif (Étude 2) est d’évaluer la relation fonctionnelle entre le traitement visuel de bas niveaux et de niveaux intermédiaires chez des adolescents et des adultes ayant un TSA. Ces deux objectifs ont été évalué en utilisant les mêmes stimuli et procédures. Plus précisément, la sensibilité de formes circulaires complexes (Formes de Fréquences Radiales ou FFR), définies par de la luminance ou par de la texture, a été mesurée avec une procédure à choix forcés à deux alternatives. Les résultats de la première étude ont illustré que l’information locale des FFR sous-jacents aux processus visuels de niveaux intermédiaires, affecte différemment la sensibilité à travers des périodes développementales distinctes. Plus précisément, lorsque le contour est défini par de la luminance, la performance des enfants est plus faible comparativement à celle des adolescents et des adultes pour les FFR sollicitant la perception globale. Lorsque les FFR sont définies par la texture, la sensibilité des enfants est plus faible comparativement à celle des adolescents et des adultes pour les conditions locales et globales. Par conséquent, le type d’information locale, qui définit les éléments locaux de la forme globale, influence la période à laquelle la sensibilité visuelle atteint un niveau développemental similaire à celle identifiée chez les adultes. Il est possible qu’une faible intégration visuelle entre les mécanismes de bas et de niveaux intermédiaires explique la sensibilité réduite des FFR chez les enfants. Ceci peut être attribué à des connexions descendantes et horizontales immatures ainsi qu’au sous-développement de certaines aires cérébrales du système visuel. Les résultats de la deuxième étude ont démontré que la sensibilité visuelle en autisme est influencée par la manipulation de l’information locale. Plus précisément, en présence de luminance, la sensibilité est seulement affectée pour les conditions sollicitant un traitement local chez les personnes avec un TSA. Cependant, en présence de texture, la sensibilité est réduite pour le traitement visuel global et local. Ces résultats suggèrent que la perception de formes en autisme est reliée à l’efficacité à laquelle les éléments locaux (luminance versus texture) sont traités. Les connexions latérales et ascendantes / descendantes des aires visuelles primaires sont possiblement tributaires d’un déséquilibre entre les signaux excitateurs et inhibiteurs, influençant ainsi l’efficacité à laquelle l’information visuelle de luminance et de texture est traitée en autisme. Ces résultats supportent l’hypothèse selon laquelle les altérations de la perception visuelle de bas niveaux (local) sont à l’origine des atypies de plus hauts niveaux chez les personnes avec un TSA.

Modélisation d'éléments finis pour les interactions fluide-structure

Cette thèse concerne la modélisation des interactions fluide-structure et les méthodes numériques qui s’y rattachent. De ce fait, la thèse est divisée en deux parties. La première partie concerne l’étude des interactions fluide-structure par la méthode des domaines fictifs. Dans cette contribution, le fluide est incompressible et laminaire et la structure est considérée rigide, qu’elle soit immobile ou en mouvement. Les outils que nous avons développés comportent la mise en oeuvre d’un algorithme fiable de résolution qui intégrera les deux domaines (fluide et solide) dans une formulation mixte. L’algorithme est basé sur des techniques de raffinement local adaptatif des maillages utilisés permettant de mieux séparer les éléments du milieu fluide de ceux du solide que ce soit en 2D ou en 3D. La seconde partie est l’étude des interactions mécaniques entre une structure flexible et un fluide incompressible. Dans cette contribution, nous proposons et analysons des méthodes numériques partitionnées pour la simulation de phénomènes d’interaction fluide-structure (IFS). Nous avons adopté à cet effet, la méthode dite «arbitrary Lagrangian-Eulerian» (ALE). La résolution fluide est effectuée itérativement à l’aide d’un schéma de type projection et la structure est modélisée par des modèles hyper élastiques en grandes déformations. Nous avons développé de nouvelles méthodes de mouvement de maillages pour aboutir à de grandes déformations de la structure. Enfin, une stratégie de complexification du problème d’IFS a été définie. La modélisation de la turbulence et des écoulements à surfaces libres ont été introduites et couplées à la résolution des équations de Navier-Stokes. Différentes simulations numériques sont présentées pour illustrer l’efficacité et la robustesse de l’algorithme. Les résultats numériques présentés attestent de la validité et l’efficacité des méthodes numériques développées.