This research work includes three parts, with the first section describing the synthesis and applications of neutral 3-coordinate aluminum complexes. As demonstrated in this part, aluminum complexes in a 3-coordinate geometry can be formed only with a ring size greater than or equal to a 6-member ring when supported by diamido ligands. It is found that 1,2-diamido ligands designed for 5-member ring formations can accommodate the formation of only 4-coordinate dinuclear species, which show no activity when used as a single component catalyst in the ring-opening polymerization (ROP) of cyclic esters under specified reaction conditions. Three-coordinate neutral (1,4-diamido)AlMe complexes are successfully synthesized, revealing a higher activity in the ROP of cyclic esters than the existing 6-member analogues under the same reaction conditions. A detailed discussion of the structure-reactivity relationship of Al catalysts in the ROP of cyclic esters is presented. The second part of this thesis project consists of investigations into the applications of 1,4-diamido ligands for the formation of 3-coordinate NHP (N-heterocyclic phosphine) and 2-coordinate NHP+ cations (phosphenium cations). These novel NHP species are the first to be shown in a 7-member ring supported by 1,4-diamido ligands. Various N-substituents in the 1,4-diamido ligands are examined for the formation of a cyclic structure based on their steric hindrance. It is found that a Dipp (2,6-diisopropylphenyl) group is unable to allow for the formation of a 7-member NHP due to its excessive steric bulk. The less bulky mesityl (2,4,6-trimethylphenyl) group at the N-positions in the ligands leads to successful formation of these novel NHPs and NHP+ species. Furthermore, an investigation is carried out to explore their π-accepting property by means of 31P NMR studies. The NHP and NHP+ species synthesized in this project show chemical shifts downfield relative to the existing 5- and 6-member analogues in 31P NMR experiments, suggesting a high potential of 7-member NHPs to be used as π-acceptor ligands. The second section also examined the resulting NHPs and NHP+ species for coordinating to various metals. The last part of this research work is dedicated to presenting the first example of chelating 3–triNHC (tri-N-heterocyclic carbene) ligands that allow for the formation of (triNHC)Pd(II) complexes in a meridional fashion, wherein the triNHC ligand coordinates to the metal center in a pseudo-meridional fashion. Novel [(triNHC)MePdX]X (X = Cl or acetate) complexes are successfully synthesized, and they display extraordinary stability against air and heat. Low activities of the resulting complexes are found in promoting C-C coupling reactions, possibly due to the low solubility of the resulting complexes in organic solvents. Various attempts to change the N-substituents to groups other than methyls are conducted to improve the solubility of the complexes in organic solvents for higher activities in C-C coupling reactions. The results from these attempted modifications to these complexes are discussed in detail. All complexes are characterized by standard spectral methods such as mass spectrometry, X-ray crystallography, elemental analysis, 1H NMR, 13C NMR and 31P NMR spectroscopy.

A computational fluid dynamics model has been developed to examine the separation of an oil film from a spherical oil-coated particle falling through quiescent water due to gravity. Using this model, the separation process was studied as a function of the viscosity ratio of oil to water, R, and the ratio of viscous forces to surface tension, represented by the Capillary number Ca. The governing equations of this flow-induced motion are derived in a non-inertial spherical coordinate system, and discretized using a finite volume approach. The Volume-of-Fluid method is used to capture the oil/water interface. The model predicts two mechanisms for oil separation: at R less than 1, the shear difference between the particle/oil interface and the oil/water interface is not significant and Ca determines whether separation occurs or not; at R larger than 1, the shear difference is considerable, and the Ca effect becomes less dominant.

A computational fluid dynamics model has been developed to examine the separation of an oil film from a spherical oil-coated particle falling through quiescent water due to gravity. Using this model, the separation process was studied as a function of the viscosity ratio of oil to water, R, and the ratio of viscous forces to surface tension, represented by the Capillary number Ca. The governing equations of this flow-induced motion are derived in a non-inertial spherical coordinate system, and discretized using a finite volume approach. The Volume-of-Fluid method is used to capture the oil/water interface. The model predicts two mechanisms for oil separation: at R less than 1, the shear difference between the particle/oil interface and the oil/water interface is not significant and Ca determines whether separation occurs or not; at R larger than 1, the shear difference is considerable, and the Ca effect becomes less dominant.

Problemas reais em áreas como aprendizado de máquina têm chamado atenção pela enorme quantidade de variáveis (> 10^6) e volume de dados. Em problemas dessa escala o custo para se obter e trabalhar com informações de segunda ordem são proibitivos. Tais problemas apresentam características que podem ser aproveitadas por métodos de busca em coordenada. Essa classe de métodos é caracterizada pela alteração de apenas uma ou poucas variáveis a cada iteração. A variante do método comumente descrita na literatura é a minimização cíclica de variáveis. Porém, resultados recentes sugerem que variantes aleatórias do método possuem melhores garantias de convergência. Nessa variante, a cada iteração, a variável a ser alterada é sorteada com uma probabilidade preestabelecida não necessariamente uniforme. Neste trabalho estudamos algumas variações do método de busca em coordenada. São apresentados aspectos teóricos desses métodos, porém focamos nos aspectos práticos de implementação e na comparação experimental entre variações do método de busca em coordenada aplicados a diferentes problemas com aplicações reais. / Real world problemas in areas such as machine learning are known for the huge number of decision variables (> 10^6) and data volume. For such problems working with second order derivatives is prohibitive. These problems have properties that benefits the application of coordinate descent/minimization methods. These kind of methods are defined by the change of a single, or small number of, decision variable at each iteration. In the literature, the commonly found description of this type of method is based on the cyclic change of variables. Recent papers have shown that randomized versions of this method have better convergence properties. This version is based on the change of a single variable chosen randomly at each iteration, based on a fixed, but not necessarily uniform, distribution. In this work we present some theoretical aspects of such methods, but we focus on practical aspects.

Small molecule Zn(II) complexes containing N- and S- donor environments may serve as appropriate models for mimicking Zn protein sites, and thus, their reactions with heavy metal ions such as Pt(II) and W(0) may provide insight into possible adduct formation and zinc displacement. To study such possible interactions between zinc finger proteins and platinum-bound DNA, the ZnN2S2 dimeric complex, N,N?-bis(2- mercaptoethyl)-1,4-diazacycloheptane zinc (II), [Zn-1?]2, has been examined for Znbound thiolate reactivity in the presence of Pt(II) nitrogen ? rich compounds. The reactions yielded Zn/Pt di- and tri- nuclear thiolate-bridged adducts and metalexchanged products, which were initially observed via ESI-mass spectrometry (ESI-MS) analysis of reaction solutions, and ultimately verified by comparison to the ESI-MS analysis, 195Pt NMR spectroscopy, and X-ray crystallography of directly synthesized complexes. The isolation of Zn-(?-SR)-Pt-bridged [(Zn(bme-dach)Cl)(Pt(dien))]Cl adduct from these studies is, to our knowledge, the first Zn-Pt bimetallic thiolatebridged model demonstrating the interaction between Zn-bound thiolates and Pt(II). Additional derivatives involving Pd(II) and Au(III) have been explored to parallel the experiments executed with Pt(II). The [Zn-1?]2 was then modified by cleavage with Na+[ICH2CO2]- to produce (N- (3-Thiabutyl)-N?-(3-thiapentaneoate)-1,4-diazacycloheptane) zinc(II), Zn-1?-Ac or ZnN2SS?O, and 1,4-diazacycloheptane-1,4-diylbis(3-thiapentanoato) zinc(II), Zn-1?-Ac2 or ZnN2S?2O2, monomeric complexes (where S = thiolate, S? = thioether). The [Zn-1?]2 di- and Zn-1?-Ac mono-thiolato complexes demonstrated reactivity towards labile-ligand tungsten carbonyl species, (THF)W(CO)5 and (pip)2W(CO)4, to yield, respectively, the [(Zn-1?-Cl)W(CO)4]- complex and the [(Zn-1?-Ac)W(CO)5]x coordination polymer. With the aid of CO ligands for IR spectral monitoring, the products were isolated and characterized spectroscopically, as well as by X-ray diffraction and elemental analysis. To examine the potential for zinc complexes (or zinc-templated ligands) to possibly serve as a toxic metal remediation agents, Zn-1?-Ac and Zn-1?-Ac2 were reacted with Ni(BF4)2. The formation of Zn/Ni exchanged products confirmed the capability of ?free? Ni(II) to displace Zn(II) within the N-, S-, and O- chelate environment. The Zn/Ni exchanged complexes were analyzed by ESI-MS, UV-visible spectroscopy, IR spectroscopy of the acetate regions, and X-ray crystallography. They serve as foundation molecules for more noxious metal exchange / zinc displacement products.

Problemas reais em áreas como aprendizado de máquina têm chamado atenção pela enorme quantidade de variáveis (> 10^6) e volume de dados. Em problemas dessa escala o custo para se obter e trabalhar com informações de segunda ordem são proibitivos. Tais problemas apresentam características que podem ser aproveitadas por métodos de busca em coordenada. Essa classe de métodos é caracterizada pela alteração de apenas uma ou poucas variáveis a cada iteração. A variante do método comumente descrita na literatura é a minimização cíclica de variáveis. Porém, resultados recentes sugerem que variantes aleatórias do método possuem melhores garantias de convergência. Nessa variante, a cada iteração, a variável a ser alterada é sorteada com uma probabilidade preestabelecida não necessariamente uniforme. Neste trabalho estudamos algumas variações do método de busca em coordenada. São apresentados aspectos teóricos desses métodos, porém focamos nos aspectos práticos de implementação e na comparação experimental entre variações do método de busca em coordenada aplicados a diferentes problemas com aplicações reais. / Real world problemas in areas such as machine learning are known for the huge number of decision variables (> 10^6) and data volume. For such problems working with second order derivatives is prohibitive. These problems have properties that benefits the application of coordinate descent/minimization methods. These kind of methods are defined by the change of a single, or small number of, decision variable at each iteration. In the literature, the commonly found description of this type of method is based on the cyclic change of variables. Recent papers have shown that randomized versions of this method have better convergence properties. This version is based on the change of a single variable chosen randomly at each iteration, based on a fixed, but not necessarily uniform, distribution. In this work we present some theoretical aspects of such methods, but we focus on practical aspects.

Thesis (PhD)--Stellenbosch University, 2015. / ENGLISH ABSTRACT: Please refer to full text for abstract. / AFRIKAANSE OPSOMMING: Sien asb volteks vir opsomming.

Redundantly actuated manipulators have only recently aroused significant scientific interest. Their advantages in terms of enlarged workspace, higher payload ratio and better manipulability with respect to non-redundantly actuated systems explain the appearance of numerous applications in various fields: high-precision machining, fault-tolerant manipulators, transport and outer-space applications, surgical operation assistance, etc. The present Ph.D. research proposes a unified approach for modeling and actuation of redundantly actuated parallel manipulators. The approach takes advantage of the actuator redundancy principles and thus allows for following trajectories that contain parallel (force) singularities, and for eliminating the negative effect of the latter. As a first step of the approach, parallel manipulator kinematic and dynamic models are generated and treated in such a way that they do not suffer from kinematic loop closure numeric problems. Using symbolic models based on the multibody formalism and a Newton-Euler recursive computation scheme, faster-than-real-time computer simulations can thus be achieved. Further, an original piecewise actuation strategy is applied to the manipulators in order to eliminate singularity effects during their motion. Depending on the manipulator and the trajectories to be followed, this strategy results in non-redundant or redundant actuation solutions that satisfy actuator performance limits and additional optimality criteria. Finally, a validation of the theoretical results and the redundant actuation benefits is performed on the basis of well-known control algorithms applied on two parallel manipulators of different complexity. This is done both by means of computer simulations and experimental runs on a prototype designed at the Center for Research in Mechatronics of the UCL. The advantages of the actuator redundancy of parallel manipulators with respect to the elimination of singularity effects during motion and the actuator load optimization are thus confirmed (virtually and experimentally) and highlighted thanks to the proposed approach for modeling, simulation and control.

In this thesis, the paper is divided into 2 parts, each corresponding to 2 individual projects. We started with looking into the synthesis of 3-coordinate palladium complexes incorporating a nacnac ligated system for academic interest. We utilized [{2,6-iPr2Ph)2nacnac}PdCl]2 as the precursor into synthesizing these 3-coordinate palladium complexes. Through many failed attempts of manipulating different substrates, we were able to synthesize a 4-coordinate [{(2,6-iPr2Ph)2nacnacPdCl}(NH2Ph)]. The second project deals with the application of dibromobis(1,1'-dibenzyl-3,3'-methylenediimidazolin-2,2'-diylidene)dicopper(I) complex to catalysis. We decided to focus our attentions specifically on carbonyl reduction of ketones being that hydrosilations with copper catalysts have only been recently looked at. The dibromobis(1,1'-dibenzyl-3,3'-methylenediimidazolin-2,2'-diylidene)dicopper(I) complex proved to be very effective at hydrosilations of a wide variety of ketones at high temperatures. We further investigated the scope of the dibromobis(1,1'-dibenzyl-3,3'-methylenediimidazolin-2,2'-diylidene)dicopper(I) catalyst by testing it on the arylation and alkylation of imidazole. The arylation of imidazole showed little to no conversion, whereas the alkylation proved to be quite active for both alkyl bromides and chlorides. We also looked at the attempts in synthesizing bulkier analogues of dibromobis(1,1'-dibenzyl-3,3'-methylenediimidazolin-2,2'-diylidene)dicopper(I) by varying the benzyl groups to 2,6-diisopropylphenyl and mesityl groups. However, results show that there were difficulties in coordinating these bulkier ligands onto copper. Optimization of complexing bulkier ligands onto copper needs to be conducted before one can proceed onto further reactions.

Dimensional measurement plays a critical role in product development and quality control. With the continuously increasing demand for tighter tolerances and more complex workpiece shapes in the industry, dimensional metrology often becomes the bottleneck of taking the quality and performance of manufacturing to the next level. As one kind of the most useful and powerful measuring instruments, coordinate measuring machines (CMMs) are widely employed in manufacturing industries. Since the accuracy and efficiency of a CMM have a vital impact on the product quality, productivity and manufacturing cost, the evaluation and improvement of CMM performance have always been important research topics since the invention of CMM. A novel Advanced Virtual Coordinate Measuring Machine (AVCMM) is proposed against such a background. The proposed AVCMM is a software package that provides an integrated virtual environment, in which user can plan inspection strategy for a given task, carry out virtual measurement, and evaluate the uncertainty associated with the measurement result, all without the need of using a physical machine. The obtained estimate of uncertainty can serve as a rapid feedback for user to optimize the inspection plan in the AVCMM before actual measurement, or as an evaluation of the result of a performed measurement. Without involving a physical CMM in the inspection planning or evaluation of uncertainty, the AVCMM can greatly reduce the time and cost needed for such processes. Furthermore, as the package offers vivid 3D visual representation of the virtual environment and supports operations similar to a physical CMM, it does not only allow the user to easily plan and optimise the inspection strategy, but also provide a cost-effective, risk-free solution for training CMM operators. A modular, multitier architecture has been adopted to develop the AVCMM system, which incorporates a number of functional components covering CMM and workpiece modelling, error simulation, inspection simulation, feature calculation, uncertainty evaluation and 3D representation. A new engine for detecting collision/contact has been developed and utilized, which is suitable for the virtual environment of simulated CMM inspections. A novel approach has been established to calculate errors required for the error simulation, where the data are obtained from FEA simulations in addition to conventional experimental method. Monte Carlo method has been adopted for uncertainty evaluation and has been implemented with multiple options available to meet different requirements. A prototype of the proposed AVCMM system has been developed in this research. Its validity, usability and performance have been verified and evaluated through a set of experiments. The principles for utilising the AVCMM in practical use have also been established and demonstrated. The results have indicated that the proposed AVCMM system has great potentials to improve the functionalities and overall performance of CMMs.