The essential questions of the dissertation research described here address concepts in homogeneous catalysis and organometallic chemistry, with a focus on method development for catalytic reaction applications in organic synthesis. The unifying theme throughout the research is the development of rational design principles for cooperative catalysis through both mechanistic and empirical study. Cooperative catalysis – in which multiple catalysts enable increased activity or selectivity versus a single catalyst system – can involve some combination of a transition metal, Lewis acid, and Brønsted acid. Chapter 1 reviews the literature regarding the cooperativity of transition metal and Lewis acid catalysis, and discusses four main areas in organic synthesis and the facilitation of these trnasformations by Lewis acids: (a) C-C bond and C-H activation, (b) hydrogenolysis of carboxylic acid derivates and ethers, (c) Au catalyzed alkyne activation and cyclization reactions, and related reactions, and (d) Pd catalyzed C-C and C-N bond forming reactions. These different topics are selected based on the mechanistic insight provided into the nature of transition metal-Lewis acid cooperativity. Chapter 2 describes the observation of Lewis acid acceleration of a Pd catalyzed C-N bond coupling. The synthetic methodology is elaborated using metal triflates as cocatalysts, and Lewis acid acceleration is observed for a variety of different N-nucleophiles. Qualitative mechanistic study implicates the role of halide anions in inhibiting this catalytic reaction, and it is proposed that metal triflates are competent to accelerate catalysis by binding halide anions, and therefore attenuating halide inhibition. This hypothesis is supported by initial rate measurements and 31P NMR experiments. Rationalizing trends observed in the reactivity of Lewis acids in the cooperative reactions described in Chapters 1 and 2 is challenging. Therefore, our goal was to provide further insight into the behavior or Lewis acids in complex reaction settings. Inspired by 31P NMR experiments from Chapter 2, a next generation NMR probe to observe anion exchange reactions of metal triflate Lewis acids is developed. Metal-ligand titrations are performed for a variety of metal triflates with complexes of the type (POCOP)Pd(X) (X = Cl, Br, I, OAc) to observe a variety of different X anion affinities for metal triflates. The determined parameters are discussed within the context of Lewis acid catalyzed reactions, along with other Lewis acidity parameters, such as hydrolysis constants and effective charge density. The data suggest that the chloride and iodide anion affinities of a Lewis acid represent a continuum of π-acidity (high anion affinity) and propensity to dissociate into cationic Mz+ species (low anion affinity). The anion affinities do not correlate with the tendency of a metal salt to release Brønsted acids or their respective effective charge densities. Based on the insight into Lewis acidity from Chapters 1 and 3, the parallel between Brønsted and Lewis acids is realized, and the role of both Brønsted and Lewis acids in mediating organic reactions is often related. In Chapter 4, further questions into the cooperativity of π-acids and Brønsted acids is explored. It is demonstrated that selectivity of alkene isomerization can be controlled through a cooperative system. A series of Mo(0) complexes are prepared and explored in their ability to mediate the conversion of terminal alkenes to internal alkenes, and the reaction is found to be promoted by Brønsted acid (TsOH) cocatalyst. Rational design principles are developed to maximize selectivity for (Z)-2-alkenes in this catalyst system. It is proposed that TsOH acts to generate a catalytic MoH species which mediates catalysis, and the role of phosphine ligands is critical in inhibiting the formation of less selective isomerization catalysts. Chapter 5 and 6 entail further method development for catalytic reactions based on the mechanistic wisdom described in previous chapters. High throughput experimentation is employed to rapidly assess conceptual aspects of Pd catalysis, such as ligand and additive effects, and facilitate catalyst discovery and optimization. Based on the substrate scope performed in Chapter 2, it was realized there is a knowledge gap in the ability to synthesize tertiary sulfonamides, both in terms of conventional methods, or modern Pd-catalyzed methods. A significant advance in organic reaction methodology is described: a new Pd catalyst featuring the AdBippyPhos ligand is discovered to be apt for the coupling of secondary sulfonamides with heteroaryl halides to yield tertiary N-heteroarylhalides. Using high throughput experimentation, 24 diverse heterocycles are screened with 12 sulfonamide variants to prepare >100 new products on microscale. Computational modelling reveals the unique steric parameters of the AdBippyPhos ligand, and a mechanistic rationale for its success in catalysis is provided. Lastly, Chapter 6 describes the use of a LiOTf additive to control the selectivity of Pd-catalyzed C-C bond forming reactions. In the presence of LiOTf, a Mizoroki-Heck type reaction, the alkenylation of an aryl halide with a vinyl ether, proceeds with regioselectivity. In the absence of LiOTf, a solvent (CH3CN) activation pathway proceeds to give benzyl nitrile products. High throughput microscale reactions discovered that the Pd/xantphos catalyst is uniquely selective to provide branched styrenes when using the Cs2CO3/CH3CN base/solvent combination. However, reaction performance differed on large scale reactions, where LiOTf was necessary to observe the Mizoroki-Heck reaction pathway. Mechanistic study, in the form of kinetic experiments and 31P NMR experiments, focused on the role of LiOTf in affecting chemoselectivity. It is proposed that xantphos oxidation is responsible for mediating the Mizoroki-Heck reaction pathway, whereas in the absence of xantphos oxidation, CH3CN α-arylation ensues. Due to the insoluble nature of the catalyst materials, xantphos oxidation is ordinarily slow under anaerobic conditions due to mass transfer limitation. LiOTf generates a soluble [(xantphos)Pd(NCCH3)2][OTf]2 and potentially mediates the formation of xantphos-monoxide catalyst which is competent for alkenylation. / Chemistry

Thesis / Master of Science (MS)

no / In this paper, a performance analysis of adaptive routing is presented for packet-switched inter-satellite link (ISL)networks, based on shortest path routing and two alternate link routing forwarding policies. The selected routing algorithm and link-cost function are evaluated for a low earth orbit satellite system, using a demographically weighted traffic flow model. Two distinct traffic flow patterns are modelled: hot spot and regional. Performance analysis, in terms of quality of service and quantity of service, is derived using specifically developed simulation software to model the ISL network, taking into account topology adaptive routing only, or topology and traffic adaptive routing.

The applicability and adequacy of three modeling approaches to describe and predict breakthough curves (BTCs) for non-reactive solutes in statistically homogeneous porous media were numerically and experimentally investigated. Modeling approaches were: the convection-dispersion equation (CDE) with scale-dependent dispersivity, mobile-immobile model (MIM), and the fractional convection-dispersion equation (FCDE). In order to test these modeling approaches, a prototype laboratory column system was designed for conducting miscible displacement experiments with a free-inlet boundary. Its performance and operating conditions were rigorously evaluated. When the CDE with scale-dependent dispersivity is solved numerically for generating a BTC at a given location, the scale-dependent dispersivity can be specified in several ways namely, local time-dependent dispersivity, average time-dependent dispersivity, apparent time-dependent dispersivity, apparent distance-dependent dispersivity, and local distance-dependent dispersivity. Theoretical analysis showed that, when dispersion was assumed to be a diffusion-like process, the scale-dependent dispersivity was locally time-dependent. In this case, definitions of the other dispersivities and relationships between them were directly or indirectly derived from local time-dependent dispersivity. Making choice between these dispersivities and relationships depended on the solute transport problem, solute transport conditions, level of accuracy of the calculated BTC, and computational efficiency The distribution of these scale-dependent dispersivities over scales could be described as either as a power-law function, hyperbolic function, log-power function, or as a new scale-dependent dispersivity function (termed as the LIC). The hyperbolic function and the LIC were two potentially applicable functions to adequately describe the scale dependent dispersivity distribution in statistically homogeneous porous media. All of the three modeling approaches described observed BTCs very well. The MIM was the only model that could explain the tailing phenomenon in the experimental BTCs. However, all of them could not accurately predict BTCs at other scales using parameters determined at one observed scale. For the MIM and the FCDE, the predictions might be acceptable only when the scale for prediction was very close to the observed scale. When the distribution of the dispersivity over a range of scales could be reasonably well-defined by observations, the CDE might be the best choice for predicting non-reactive solute transport in statistically homogeneous porous media. / Ph. D.

Studying the effects of free stream turbulence on noise, vibration, and heat transfer on structures is very important in engineering applications. The problem of the interaction of large scale turbulence with a flat-plate cascade is a model of important problems in propulsion systems. Addressing the problem of large scale turbulence interacting with a flat plate cascade requires flow simulation over a large number of plates (6-12 plates) in order to be able to represent numerically integral length scales on the order of blade-to-blade spacing. Having such a large number of solid surfaces in the simulation requires very large computational grid points to resolve the boundary layers on the plates, and that is not possible with the current computing resources. In this thesis we develop a computational technique to predict the distortion of homogeneous isotropic turbulence as it passes through a cascade of thin flat plates. We use Large-Eddy Simulation (LES) to capture the spatial development of the incident turbulence and its interaction with the plates which are assumed to be inviscid walls. The LES is conducted for a linear cascade composed of six plates. Because suppression of the normal component of velocity is the main mechanism of distortion, we neglect the presence of mean shear in the boundary layers and wakes, and allow slip velocity on the plate surfaces. We enforce the zero normal velocity condition on the plates. This boundary condition treatment is motivated by rapid distortion theory (RDT) in which viscous effects are neglected, however, the present LES approach accounts for nonlinear and turbulence diffusion effects by a sub-grid scale model. We refer to this type of turbulence-blade interaction as shear-free interaction. To validate our calculations, we computed the unsteady loading and radiated acoustic pressure field from flat plates interacting with vortical structures. We consider two fundamental problems: (1) A linear cascade of flat plates excited by a vortical wave (gust) given by a 2D Fourier mode, and (2) The parallel interaction of a finite-core vortex with a single plate. We solve the nonlinear Euler equations by a high-order finite-differece method. We use nonreflecting boundary conditions at the inflow and outflow boundaries. For the gust problem, we found that the cascade response depends sensitively on the frequency of the convicted gust. The unsteady surface pressure distribution and radiated pressure field agree very well with predictions of the linear theory for the tested range of reduced frequency. We have also investigated the effects of the incident gust frequency on the undesirable wave reflection at the inflow and outflow boundaries. For the vortex-plate interaction problem, we investigate the effects of the internal structure of the vortex on the strength and directivity of radiated sound. Then we solved the turbulence cascade interaction problem. The normal Reynolds stresses and velocity spectra are analyzed ahead, within, and downstream of the cascade. Good agreement with predictions of rapid distortion theory in the region of its validity is obtained. Also, the normal Reynolds stress profiles are found to be in qualitative agreement with available experimental data. As such, this dissertation presents a viable computational alternative to rapid distortion theory (RDT) for the prediction of noise radiation due to the interaction of free stream turbulence with structures. / Ph. D.

The two projects described in this dissertation demonstrate the wide utility of noble metal N-heterocyclic carbene (NHC) complexes. The first project details the design of iridium NHC amino acid complexes for asymmetric transfer hydrogenation (ATH) of prochiral ketones. Iridium(I) bis-NHC complexes were found to undergo oxidative addition with a variety of alpha-amino acids, generating chiral iridium(III) complexes of the form Ir(NHC)2(aa)(H)(X) (aa = amino acid, X = halide). The complexes were screened for ATH of aryl and alkyl ketones, and optimization studies found enantioselectivity in this system was highly sensitive to the reaction temperature, NHC ligand, and amino acid. Incorporation of secondary amino acids was essential to enantioselectivity. Aryl ketones were reduced in high conversion and enantioselectivity when employing the Ir(IMe)2(L-Pro)(H)(I) catalyst in isopropyl alcohol, in some cases giving over 90% ee of the alcohol products. Density functional theory calculations were conducted in order to gain insight into the active catalytic species, and the results suggest that the high enantioselectivity of this system primarily arises from steric effects. The second project details the design of rhodium and iridium NHC piano-stool complexes featuring derivatized tetramethylcyclopentadienyl ligands (Cp*R, R = alkyl or aryl substituent) for antimicrobial applications. Complexes of the form (Cp*R)M(NHC)Cl2 (M = Rh or Ir) were synthesized by transmetallation of the NHC ligand using silver(I) oxide in the presence of the desired noble metal Cp*R dimer. The complexes were screened for biological activity against various bacteria, yeast, and fungi. Many of these compounds were highly active against Mycobacterium smegmatis, displaying minimum inhibitory concentrations (MICs) as low at 0.25 microgram per mL. Analysis of structure-activity relationships found that incorporation of the NHC ligand greatly enhances the antimicrobial properties of rhodium and iridium piano-stool complexes, more so than previously investigated diamine, amino acid, or beta-diketonato ligands. Cytotoxicity studies on one of the rhodium NHC complexes showed this compound was nontoxic towards mammalian cells at low concentrations, which strengthens the potential of these types of compounds as viable drug candidates. / Doctor of Philosophy / This dissertation describes two practical applications of a series of complexes featuring the noble metals rhodium and iridium. In all of these complexes, the metal center is bonded to one or two groups known as N-heterocyclic carbenes (NHCs). The most common structural variant of NHCs are five-membered rings. The metal is usually bonded to a carbon atom on these rings, which is flanked by two nitrogen atoms. Noble metal complexes containing NHCs are widely investigated in contemporary chemical literature for a variety of reactions, primarily because noble metals form exceptionally strong bonds with NHCs, making these complexes very stable. N-Heterocyclic carbene compounds are also fairly easy to synthesize and structurally modify, which allows fine-tuning for specific applications. The first project in this dissertation employed iridium NHC amino acid complexes for the selective production of alcohols, meaning only one structure of the alcohol product is favorably generated. This is an important transformation in the chemical and pharmaceutical industries, which often require the synthesis of highly pure products. These complexes were found to be quite successful for this application on a range of model substrates, in some cases generating as high as 95% of one alcohol product over the other. Product selectivity was found to depend on the specific structure of the NHC compound. The second project investigated the antimicrobial properties of rhodium and iridium NHC complexes. In recent years, the growing threat of antimicrobial resistance against traditional pharmaceuticals has led to an interest in the development of metal-based drugs, which may allow for metal-specific mechanisms of drug action that are not possible for commonly employed antimicrobial agents. These NHC complexes were screened for biological activity against various bacteria, yeast, and fungi. Many of the complexes displayed high activity against Mycobacterium smegmatis, comparable to those displayed by other clinical drugs such as ampicillin or streptomycin. These results were highly encouraging, as Mycobacterium smegmatis often serves as a model to study other mycobacteria.

Earlier designs were driven by the goal of achieving higher performance, but lately, energy efficiency has emerged as an even more important design principle. Strong demand from the consumer electronics drives research in the low power and energy-efficient methodologies. Moreover, with exponential increase in the number of transistors on a chip and with further technology scaling, variability in the design is now of greater concern. Variations can make the design unreliable or the design may suffer from sub-optimal performance. Through the work in this thesis, we present a multi-dimensional investigation into the design of variation aware energy-efficient systems. Our overarching methodology is to use system-level decisions to mitigate undesired effects originating from device-level and circuit-level issues. We first look into the impact of process variation (PV) on energy efficient, scalable throughput many-core DSP systems. In our proposed methodology, we leverage the benefits of aggressive voltage scaling (VS) for obtaining energy efficiency while compensating for the loss in performance by exploiting parallelism present in various DSP designs. We demonstrate this proposed methodology consumes 8% - 77% less power as compared to simple dynamic VS over different workload environments. Later, we show judicious system-level decisions, namely, number of cores, and their operating voltage can greatly mitigate the effects of PV and consequently, improve the energy efficiency of the design. We also present our analysis discussing the impact of aging on the proposed methodology. To validate our proposed system-level approach, design details of a prototype chip fabricated in the 90nm technology node and its findings are also presented. The chip consists of 8 homogeneous FIR cores, which are capable of running from near-threshold to nominal voltages. In the 20-chip population, we observe 7% variation in the speed at nominal voltage (0.9V) and 26% at near threshold voltage (0.55V) among all the cores. We also observe 54% variation in power consumption characteristics of the cores. The chip measurement results show that our proposed methodology of judiciously selecting the cores and their operating voltage can result in 6.27% - 28.15% more energy savings for various workload environments, as compared to globally voltage scaled systems. Furthermore, we present the impact of temperature variations on the energy-efficiency of the above systems. We also study the problem of voltage variations in the integrated circuits. We first present the characteristics of a dynamic voltage noise as measured on a 28nm FPGA. We propose a fully digital on-chip sensor that can detect the fast voltage transients and alert the system of voltage emergency. A traditional approach to mitigate this problem is to use safety guardbands. We demonstrate that our proposed sensor system will be 6% - 27.5% more power efficient than the traditional approach. / Ph. D.

Finite element modeling has become a powerful tool in orthopedic biomechanics, allowing simulations with complex geometries. Current fatigue behavior simulations are unable to accurately predict the cycles to failure, creep, and damage or modulus loss even when applied to a bending model. It is thought that the inhomogeneity of the models may be the source of the problem. It has also been suggested that the volume size of the element will affect the fatigue behavior. This is called a stressed volume effect. In this thesis non-homogeneous finite element models were used to examine the effects of "sizing factors" on damage laws in fatigue simulations. Non-homogeneous finite element models were created from micro computed tomography (CT) images of dumbbell shaped fatigue samples. An automatic voxel meshing technique was used which converted the CT data directly into mesh geometry and material properties. My results showed that including these sizing factors improved the accuracy of the fatigue simulations on the non-homogeneous models. Using the Nelder-Mead optimization routine, I optimized the sizing factors for a group of 5 models. When these optimized sizing factors were applied to other models they improved the accuracy of the simulations but not as much as for the original models, but they improved the results more than with no sizing factors at all. I found that in our fatigue simulations we could account for the effects of stressed volume and inhomogeneity by including sizing factors in the life and damaging laws. / Master of Science

Massive proliferation of wireless devices throughout world in the past decade comes with a host of tough and demanding design problems. Noise at receivers and wireless interference are the two major issues which severely limits the received signal quality and the quantity of users that can be simultaneously served. Traditional approaches to this problems are known as Power Control (PC), SINR Balancing (SINRB) and User Selection (US) in Wireless Networks respectively. Interestingly, for a large class of wireless system models, both this problems have a generic form. Thus any approach to this generic optimization problem benefits the transceiver design of all the underlying wireless models. In this thesis, we propose an Eigen approach based on the Joint Numerical Range (JNR) of hermitian matrices for PC, SINRB and US problems for a class of wireless models. In the beginning of the thesis, we address the PC and SINRB problems. PC problems can be expressed as Homogeneous Quadratic Constrained Quadratic Optimization Problems (HQCQP) which are known to be NP-Hard in general. Leveraging their connection to JNR, we show that when the constraints are fewer, HQCQP problems admit iterative schemes which are considerably fast compared to the state of the art and have guarantees of global convergence. In the general case for any number of constraints, we show that the true solution can be bounded above and below by two convex optimization problems. Our numerical simulations suggested that the bounds are tight in almost all scenarios suggesting the achievement of true solution. Further, the SINRB problems are shown to be intimately related to PC problems, and thus share the same approach. We then proceed on to comment on the convexity of PC problems and SINRB problems in the general case of any number of constraints. We show that they are intimately related to the convexity of joint numerical range. Based on this connection, we derive results on the attainability of solution and comment on the same about the state-of-the-art technique Semi-De nite Relaxation (SDR). In the subsequent part of the thesis, we address the US problem. We show that the US problem can be formulated as a combinatorial problem of selecting a feasible subset of quadratic constraints. We propose two approaches to the US problem. The first approach is based on the JNR view point which allows us to propose a heuristic approach. The heuristic approach is then shown to be equivalent to a convex optimization problem. In the second approach, we show that the US is equivalent to another non-convex optimization problem. We then propose a convex approximation approach to the latter. Both the approaches are shown to have near optimal performance in simulations. We conclude the thesis with a discussion on applicability and extension to other class of optimization problems and some open problems which has come out of this work.

La integración de tecnologías de ulta-wideband, radio-cognitiva y MIMO representa una herramienta podersoa para mejorar la eficiencia espectral de los sistemas de comunicación inalámbricos. En esta dirección, nuevas estrategias para el modelado de canales MIMO y su caracterización se hacen necesarias si se desea investigar cómo la frecuencia central y el acho de banda afectan el desempeño de los sistemas MIMO. Investigaciones preliminares han enfocado menos atención en cómo estos parámetros afectan las características del canal MIMO. Se presenta una caracterización del canal MIMO en función de la frecuencia, abondándose puntos de vista experimentales y teóricos. Los problemas indicados tratan cinco áreas principales: medidas, post-procesado de datos, generación sintética del canal, estadística multivariable para datos y modelado del canal. Se ha diseñado y validado un sistema de medida basado en un analizador vectorial de redes y se han ejecutado medidas entre 2 y 12 GHz en condiciones estáticas, tanto en línea de vista como no línea de vista. Se ha propuesto y validado un procedimiento confiable para post-procesado, generación sintética de canal y análisis experimental basado en medidas en el dominio de frecuencia. El procedimiento experimental se ha focalizado en matrices de transferencia del canal para casos no selectivos en frecuencia, estimándose además las matrices complejas de covarianza, aplicándose la factorización de Cholesky sobre ls CCM y obteniéndose finalmente matrices de coloreado del sistema. Se presenta un procedimiento de corrección para generación sintética del canal aplicado a casos MIMO de grandes dimensiones y cuando la CCM es indefinida. Este CP permite la factorización de Cholesky y de dichas CCM. Las características multivariables de los datos experimentales han sido investigadas, realizándose un test de normalidad compleja multivariable. / García Ariza, AP. (2009). Modelling and experimental analysis of frequency dependent MIMO channels [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/6563 / Palancia