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A set of five new C3-symmetric phosphites were synthesized and tested in palladium-catalyzed asymmetric Suzuki coupling. The observed reactivity and selectivity were dependent upon several factors. One of the phosphites was able to achieve some of the highest levels of enantioselectivity in asymmetric Suzuki couplings with specific substrates. Different hypotheses have been made for understanding the ligand effects and reaction selectivities, and those hypotheses were tested via various methods including DOSY NMR experiments, X-ray crystallography, and correlation of catalyst selectivity with Tolman cone angles. Although only modest enantioselectivities were observed in most reactions, the ability to synthesis these phosphites in only three steps on gram scales and to readily tune their properties by simple modification of the binaphthyl 2´-substituents makes them promising candidates for determining structure-selectivity relationships in asymmetric transition metal catalysis, in which phosphites have been previously shown to be successful. A series of novel chiral oxazoline-based carbodicarbene ligands was targeted for synthesis. Unfortunately, the chosen synthetic route could not be completed due to unwanted reactivity of the oxazoline ring. However, a new and efficient route for Pd-catalyzed direct amination of aryl halides with oxazoline amine was developed and optimized during these studies. Chiral binaphthyl based Pd(II) ADC complexes with different substituent groups have been synthesized and tested in asymmetric Suzuki coupling reactions. Although only low enantioselectivities were observed in Suzuki coupling, this represents a new class of chiral metal-ADC catalysts that could be tested in further catalytic.

Throughout stochastic data processing fields, mean and covariance matrices are commonly employed for purposes such as standardizing multivariate data through decorrelation. For practical applications, these matrices are usually estimated, and often, the data used for these estimates are non-Gaussian or may be corrupted by outliers or impulsive noise. To address this, robust estimators should be employed. However, in signal processing, where complex-valued data are common, the robust estimation techniques currently employed, such as M-estimators, provide limited robustness in the multivariate case. For this reason, this dissertation extends, to the complex-valued domain, the high-breakdown-point class of multivariate estimators called S-estimators. This dissertation defines S-estimators in the complex-valued context, and it defines their properties for complex-valued data. One major shortcoming of the leading high-breakdown-point multivariate estimators, such as the Rocke S-estimator and the smoothed hard rejection MM-estimator, is that they lack statistical efficiency at non-Gaussian distributions, which are common with real-world applications. This dissertation proposes a new tunable S-estimator, termed the Sq-estimator, for the general class of elliptically symmetric distributions—a class containing many common families such as the multivariate Gaussian, K-, W-, t-, Cauchy, Laplace, hyperbolic, variance gamma, and normal inverse Gaussian distributions. This dissertation demonstrates the diverse applicability and performance benefits of the Sq-estimator through theoretical analysis, empirical simulation, and the processing of real-world data. Through analytical and empirical means, the Sq-estimator is shown to generally provide higher maximum efficiency than the leading maximum-breakdown estimators, and it is also shown to generally be more stable with respect to initial conditions. To illustrate the theoretical benefits of the Sq for complex-valued applications, the efficiencies and influence functions of adaptive minimum variance distortionless response (MVDR) beamformers based on S- and M-estimators are compared. To illustrate the finite-sample performance benefits of the Sq-estimator, empirical simulation results of multiple signal classification (MUSIC) direction-of-arrival estimation are explored. Additionally, the optimal investment of real-world stock data is used to show the practical performance benefits of the Sq-estimator with respect to robustness to extreme events, estimation efficiency, and prediction performance. / Doctor of Philosophy / Throughout stochastic processing fields, mean and covariance matrices are commonly employed for purposes such as standardizing multivariate data through decorrelation. For practical applications, these matrices are usually estimated, and often, the data used for these estimates are non-normal or may be corrupted by outliers or large sporadic noise. To address this, estimators should be employed that are robust to these conditions. However, in signal processing, where complex-valued data are common, the robust estimation techniques currently employed provide limited robustness in the multivariate case. For this reason, this dissertation extends, to the complex-valued domain, the highly robust class of multivariate estimators called S-estimators. This dissertation defines S-estimators in the complex-valued context, and it defines their properties for complex-valued data. One major shortcoming of the leading highly robust multivariate estimators is that they may require unreasonably large numbers of samples (i.e. they may have low statistical efficiency) in order to provide good estimates at non-normal distributions, which are common with real-world applications. This dissertation proposes a new tunable S-estimator, termed the Sq-estimator, for the general class of elliptically symmetric distributions—a class containing many common families such as the multivariate Gaussian, K-, W-, t-, Cauchy, Laplace, hyperbolic, variance gamma, and normal inverse Gaussian distributions. This dissertation demonstrates the diverse applicability and performance benefits of the Sq-estimator through theoretical analysis, empirical simulation, and the processing of real-world data. Through analytical and empirical means, the Sq-estimator is shown to generally provide higher maximum efficiency than the leading highly robust estimators, and its solutions are also shown to generally be less sensitive to initial conditions. To illustrate the theoretical benefits of the Sq-estimator for complex-valued applications, the statistical efficiencies and robustness of adaptive beamformers based on various estimators are compared. To illustrate the finite-sample performance benefits of the Sq-estimator, empirical simulation results of signal direction-of-arrival estimation are explored. Additionally, the optimal investment of real-world stock data is used to show the practical performance benefits of the Sq-estimator with respect to robustness to extreme events, estimation efficiency, and prediction performance.

This bachelor thesis aims to give an introduction to various Hopf algebras that arise in combinatorics, with a view towards symmetric functions. We begin by covering the algebraic background needed to define Hopf algebras, including a discussion of the algebra-coalgebra duality. Takeuchi's formula for the antipode is stated and proved. It is then generalised to incidence Hopf algebras. This is followed by a discussion of the Hopf algebra of symmetric functions. It is shown that the Hopf algebra of symmetric functions is self-dual. We also show that the graded dual of the Hopf algebra of quasisymmetric functions is the Hopf algebra of non-commutative symmetric functions. Relations to the Hopf algebra of symmetric functions in non-commuting variables are emphasised. Finally, we state and prove the Aguiar-Bergeron-Sottile universality theorem.

Les objets numériques 3D sont utilisés dans de nombreux domaines, les films d'animations, la visualisation scientifique, l'imagerie médicale, la vision par ordinateur.... Ces objets sont généralement représentés par des maillages à faces triangulaires avec un nombre énorme de triangles. La simplification de ces objets, avec préservation de la géométrie originale, a fait l'objet de nombreux travaux durant ces dernières années. Dans cette thèse, nous proposons un algorithme de simplification qui permet l'obtention d'objets simplifiés de grande précision. Nous utilisons des fusions de couples de sommets avec une relocalisation du sommet résultant qui minimise une métrique d'erreur. Nous utilisons deux types de mesures quadratiques de l'erreur : l'une uniquement entre l'objet simplifié et l'objet original (Accurate Measure of Quadratic Error (AMQE) ) et l'autre prend aussi en compte l'erreur entre l'objet original et l'objet simplifié ((Symmetric Measure of Quadratic Error (SMQE)) . Le coût calculatoire est plus important pour la seconde mesure mais elle permet une préservation des arêtes vives et des régions isolées de l'objet original par l'algorithme de simplification. Les deux mesures conduisent à des objets simplifiés plus fidèles aux originaux que les méthodes actuelles de la littérature. / Complex 3D digital objects are used in many domains such as animation films, scientific visualization, medical imaging and computer vision. These objects are usually represented by triangular meshes with many triangles. The simplification of those objects in order to keep them as close as possible to the original has received a lot of attention in the recent years. In this context, we propose a simplification algorithm which is focused on the accuracy of the simplifications. The mesh simplification uses edges collapses with vertex relocation by minimizing an error metric. Accuracy is obtained with the two error metrics we use: the Accurate Measure of Quadratic Error (AMQE) and the Symmetric Measure of Quadratic Error (SMQE). AMQE is computed as the weighted sum of squared distances between the simplified mesh and the original one. Accuracy of the measure of the geometric deviation introduced in the mesh by an edge collapse is given by the distances between surfaces. The distances are computed in between sample points of the simplified mesh and the faces of the original one. SMQE is similar to the AMQE method but computed in the both, direct and reverse directions, i.e. simplified to original and original to simplified meshes. The SMQE approach is computationnaly more expensive than the AMQE but the advantage of computing the AMQE in a reverse fashion results in the preservation of boundaries, sharp features and isolated regions of the mesh. For both measures we obtain better results than methods proposed in the literature.

In this thesis, we present some new results in distribution theory for both discrete and continuous random variables, together with their motivating applications. We start with some results about the Multivariate Gaussian Distribution and its characterization as a maximizer of the Strichartz Estimates. Then, we present some characterizations of discrete and continuous distributions through ideas coming from optimal transportation. After this, we pass to the Simpson's Paradox and see that it is ubiquitous and it appears in Quantum Mechanics as well. We conclude with a group of results about discrete and continuous distributions invariant under symmetries, in particular invariant under the groups $A_1$, an elliptical version of $O(n)$ and $\mathbb{T}^n$. As mentioned, all the results proved in this thesis are motivated by their applications in different research areas. The applications will be thoroughly discussed. We have tried to keep each chapter self-contained and recalled results from other chapters when needed. The following is a more precise summary of the results discussed in each chapter. In chapter \ref{chapter 2}, we discuss a variational characterization of the Multivariate Normal distribution (MVN) as a maximizer of the Strichartz Estimates. Strichartz Estimates appear as a fundamental tool in the proof of wellposedness results for dispersive PDEs. With respect to the characterization of the MVN distribution as a maximizer of the entropy functional, the characterization as a maximizer of the Strichartz Estimate does not require the constraint of fixed variance. In this chapter, we compute the precise optimal constant for the whole range of Strichartz admissible exponents, discuss the connection of this problem to Restriction Theorems in Fourier analysis and give some statistical properties of the family of Gaussian Distributions which maximize the Strichartz estimates, such as Fisher Information, Index of Dispersion and Stochastic Ordering. We conclude this chapter presenting an optimization algorithm to compute numerically the maximizers. Chapter \ref{chapter 3} is devoted to the characterization of distributions by means of techniques from Optimal Transportation and the Monge-Amp\`{e}re equation. We give emphasis to methods to do statistical inference for distributions that do not possess good regularity, decay or integrability properties. For example, distributions which do not admit a finite expected value, such as the Cauchy distribution. The main tool used here is a modified version of the characteristic function (a particular case of the Fourier Transform). An important motivation to develop these tools come from Big Data analysis and in particular the Consensus Monte Carlo Algorithm. In chapter \ref{chapter 4}, we study the \emph{Simpson's Paradox}. The \emph{Simpson's Paradox} is the phenomenon that appears in some datasets, where subgroups with a common trend (say, all negative trend) show the reverse trend when they are aggregated (say, positive trend). Even if this issue has an elementary mathematical explanation, the statistical implications are deep. Basic examples appear in arithmetic, geometry, linear algebra, statistics, game theory, sociology (e.g. gender bias in the graduate school admission process) and so on and so forth. In our new results, we prove the occurrence of the \emph{Simpson's Paradox} in Quantum Mechanics. In particular, we prove that the \emph{Simpson's Paradox} occurs for solutions of the \emph{Quantum Harmonic Oscillator} both in the stationary case and in the non-stationary case. We prove that the phenomenon is not isolated and that it appears (asymptotically) in the context of the \emph{Nonlinear Schr\"{o}dinger Equation} as well. The likelihood of the \emph{Simpson's Paradox} in Quantum Mechanics and the physical implications are also discussed. Chapter \ref{chapter 5} contains some new results about distributions with symmetries. We first discuss a result on symmetric order statistics. We prove that the symmetry of any of the order statistics is equivalent to the symmetry of the underlying distribution. Then, we characterize elliptical distributions through group invariance and give some properties. Finally, we study geometric probability distributions on the torus with applications to molecular biology. In particular, we introduce a new family of distributions generated through stereographic projection, give several properties of them and compare them with the Von-Mises distribution and its multivariate extensions. / Thesis / Doctor of Philosophy (PhD)

Chapter 1 reviews better-known factorization theorems of a square matrix. For example, a square matrix over a field can be expressed as a product of two symmetric matrices; thus square matrices over real numbers can be factorized into two diagonalizable matrices. Factorizing matrices over complex num hers into Hermitian matrices is discussed. The chapter concludes with theorems that enable one to prescribe the eigenvalues of the factors of a square matrix, with some degree of freedom. Chapter 2 proves that a square matrix over arbitrary fields (with one exception) can be expressed as a product of two diagona lizab le matrices. The next two chapters consider decomposition of singular matrices into Idempotent matrices, and of nonsingutar matrices into Involutions. Chapter 5 studies factorization of a comp 1 ex matrix into Positive-( semi )definite matrices, emphasizing the least number of such factors required / Mathematical Sciences / M.Sc. (MATHEMATICS)

Chapter 1 reviews better-known factorization theorems of a square matrix. For example, a square matrix over a field can be expressed as a product of two symmetric matrices; thus square matrices over real numbers can be factorized into two diagonalizable matrices. Factorizing matrices over complex numbers into Hermitian matrices is discussed. The chapter concludes with theorems that enable one to prescribe the eigenvalues of the factors of a square matrix, with some degree of freedom. Chapter 2 proves that a square matrix over arbitrary fields (with one exception) can be expressed as a product of two diagonalizable matrices. The next two chapters consider decomposition of singular matrices into Idempotent matrices, and of nonsingular matrices into Involutions. Chapter 5 studies factorization of a complex matrix into Positive-(semi)definite matrices, emphasizing the least number of such factors required. / Mathematical Sciences / M. Sc. (Mathematics)