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Magister Scientiae - MSc / G1 and G2 dendrimeric salicylaldimine ligands containing both substituted and unsubstituted aryl rings were synthesized via a Schiff base condensation of the appropriate salicylaldehyde and the peripheral amino groups of the corresponding G1 and G2 polypropyleneimine dendrimers. The new ligands were characterized using FTIR, 1H NMR and 13C NMR spectroscopy, elemental analysis and ESI mass spectrometry. The dendrimeric ligands were converted to multinuclear nickel complexes by reaction with nickelacetate. The metal complexes were characterized by FTIR spectroscopy, elemental analysis and ESI mass spectrometry.Some of the dendritic complexes were evaluated as catalyst precursors in the oligomerization of α-olefins such as ethylene and 1-pentene, using aluminium alkyls such as EtAlCl2 and modified methylaluminoxane (MMAO) as activators. All the dendrimeric catalysts evaluated are active in the oligomerization reactions. From the oligomerization results it was observed that there is a clear dendritic effect, in that both catalyst activity as well as selectivity are impacted by the dendrimer generation. In most cases it was observed that the second generation complexes show higher activity than the corresponding first generation complexes.The dendrimeric complexes were also evaluated as catalyst precursors in the vinyl polymerization of norbornene. In this case methylaluminoxane (MAO) were employed as an activator. Once again it was noted that a dendritic effect is operative, with second generation metallodendrimers having a higher activity than the first generation complexes. / South Africa

The chemistry of co-ordination compounds in general has played an important role in the development of the modern theory of valency, but the properties of complex salts between chromium and organic compounds containing carboxyl and amino- groups are of additional interest because of their bearing on the theory of certain technological processes such as chromium plating and, in particular, chrome-tanning. Owing to the rapid development of valence theory over the last two decades the technological chemist finds himself at a disadvantage vis-a-vis his academic counterpart in attempting to interpret the results of researches relating to these compounds as he must rely on the less powerful "classical" approach to his problems. Hence the need was felt for a brief survey of modern concepts of valency in terms of wave mechanics. For a more extended study the reader may consult the appropriate references and text books.

In this work physical and analytical methods have been used to investigate the potassium salts of certain dioxalato chromium (III) complexes. The solid potassium salts of the trioxalatochromiate and the cis and trans dioxalatodiaquochromiates together with a salt corresponding to potassium dioxalatosulphatoaquochromiate were prepared. The mono- and dihydroxo derivatives of the cis and trans dioxalatochromiates were also obtained in aqueous solution. The methods of preparation and analysis used are described. Spectrophotometric absorption curves obtained on solutions of these salts using a Beckman Spectrophotometer are in agreement with results of previous workers, and the new absorption curve obtained from a solution of the solid cis dioxalatodiaquochromia salt shows that it is pure and gives additional proof of the completeness of the trans - cis isomerisation. Summary, p. i.

(1) The ammonium, potassium and sodium salts of three complex thorium oxalates were prepared and studied. (2) Their solubilities and conditions of stability were studied. (3) The reaction between thorium and excess oxalate, and vice versa, was studied by means of conductivity and high frequency conductivity measurements. (4) The formation constant of Th(C₂O₄)₄⁴⁻ and Th(C₂O₄)₃²⁻, and the solubility product of (NH₄)₂Th₂(C₂O₄)₅, were determined by a solubility method.

This study investigates the synthesis of rhenium(III)-isocyanide complexes with potentially bidentate ligands, as well as the reactivity of isocyanide ligands toward rhenium(I) and (V). The crystal structures of all the complexes have been determined by X-ray diffraction methods. The coordination behaviour of trans-[ReIIICl3(t-BuNC)(PPh3)2] with aniline and its derivatives were investigated. The isocyanide-containing rhenium(V) complexes [ReCl3(t-BuNC)(L)(PPh3)] were isolated, with the ligands H2L (aniline, o-phenylenediamine and anthranilic acid). In all these complexes the dianionic ligands L are coordinated monodentately as the imide. However, with 2-aminophenol the complexes [ReVCl2(t-BuNC)(L)(PPh3)2](ReO4) and [ReIIICl2(t-BuNC)(ibq)(PPh3)2] (ibq- = 2-iminobenzoquinonate) were identified as the products. [ReCl2(t-BuNC)(L)(PPh3)2](ReO4) is the product of a disproportionation reaction from Re(III) to Re(VII) and Re(V). All the above complexes show a distorted octahedral geometry around the rhenium. The products of the reaction of the Re(I) complex [Re(CO)5Cl] with isocyanides (tert-butyl- and cyclohexylisocyanide) are reported. Rhenium(I) tricarbonyl complexes of the form [Re(CO)3(CNR)2Cl] were isolated and they were characterized structurally and spectroscopically. The tricarbonyls are coordinated in the typical facial-fashion, whereas the isocyanides are coordinated cis to each other. The reaction of [Re(CO)3(t-BuNC)2Cl] with H2O led to the formation of the rhenium(I) complex [Re(CO)3(t-BuNC)2(OH2)] in which the aquo ligand can readily be substituted by a more complex ligand. The reaction of the rhenium(V) complexes cis-[ReO2I(PPh3)2] and mer-[ReOCl3(SMe2)(OPPh3)] with isocyanides were studied. The seven-coordinate trigonal prismatic, square faced monocapped rhenium(III) complex [ReI3(t-BuNC)3(PPh3)] was surprisingly isolated upon reacting cis-[ReO2I(PPh3)2] with tert-butyl isocyanide. The dimeric complex (μ-O)[ReOCl2(CNC6H11)2]2 was obtained from the reaction of mer-[ReOCl3(SMe2)(OPPh3)] with cyclohexyl isocyanide.

The present thesis is based on a paper by Bencivenga. In this paper the author develops a theory of function for the dual and bireal variables. He constructs the "retto" and "hyperbolic" planes for the geometric representation of the dual and bireal variables, respectively, and establishes a type of conformal mapping of these planes into themselves by means of differentiable functions of the variable. Further, in each of these planes he proves the analogue for the Cauchy integral theorem of the complex plane. Finally he shows that functions of the dual and bireal variable which possess all derivatives at a given point of the plane may be expanded in a Taylor series about that point. In the first chapter we give a summary of this paper. Bencivenga’s dual and bireal number systems, and also the complex number system, are two-dimensional cases of the ɳ - dimensional associative, commutative linear algebra with unit element. In chapter II we generalize Bencivenga's function theory to functions over the above mentioned linear. An important class of results from the theory of functions of a complex variable are not generalizable, since they depend on the field properties peculiar to the complex algebra. In chapter III we undertake a detailed study of the hyperbolic plane with particular reference to the conformal properties of differentiable functions of the bireal variable, as a special case of conformal transformation of the hyperbolic plane, we study the bilinear transformation. We find that the rectangular hyperbola is the geometrical form which is invariant under this transformation of the hyperbolic plane. Singularities play a larger role in this theory than in the case of the analgous transformation theory of the complex plane. / Science, Faculty of / Mathematics, Department of / Graduate

Motifs are over-represented subgraphs in a complex network, and represent the building blocks of the network. There is a lack of studies that apply complex network theory in a supply chain context. In this dissertation 3-node motifs were identified and analysed in a complex network representing direct freight trips between firms in the Nelson Mandela Bay Metropolitan, South Africa. The G-Tries and ISMAGS algorithms were tested on small complex networks, and were compared according to quantitative and qualitative properties. It was found that ISMAGS is the most suitable for this dissertation. Freight activities were identified from raw GPS traces of freight vehicles, and the activities were clustered into firms using a density-based clustering algorithm. Multi-objective optimisation indicated that the clustering parameter configuration γ = (20, 20) can be used to increase the visual accuracy of the firms, while maximising the completeness of the complex network. The freight complex network was built by identifying direct trips between firms. Using ISMAGS, it was found that three firms with two (X0X) or three (XXX) reciprocal freight trips between them are statistically overrepresented in the network. A brewery, shopping centres, distribution centres, and truck stops frequently appeared in the motifs. Motifs that contain the brewery and one of the truck stops were identified as the most central motifs based on the number of direct freight trips that occur in the motifs. Some freight trips in XXX motifs occur frequently over long distances, increasing total transport costs of the firms. Supply chain improvements can be applied to these identified firms. It was also found that there is a relationship between ranking firms according to the number of motifs they appear in and their degree centrality scores. This relationship can be studied more rigorously in future work. Another avenue for future research is to study the supply chain structures of firms in motifs, as well as the commodity flows between firms in motifs. / Dissertation (MEng)--University of Pretoria, 2016. / Industrial and Systems Engineering / Unrestricted

La plupart des voies de signalisation qui régule la croissance cellulaire et le métabolisme sont sous le contrôle du mécanisme du complexe I de la rapamycine (mTORC1). L'un des régulateurs en amont de mTORC1, impliqués dans la détection des acides aminés et l'autophagie, est complexe SEA, chez la levure, et le complexe GATOR, chez les mammifères. Plusieurs composants de GATOR sont dérégulés dans de nombreux cancers et maladies neurodégénératives. Malgré l'intérêt scientifique vis à vis du complexe SEA / GATOR, de nombreux détails concernant sa fonction et son implication dans différents troubles humains sont encore inconnus et restent à investiguer.L'objectif principal de ma thèse était d’élargir notre connaissance sur le complexe SEA / GATOR, et plus particulièrement en ce qui concerne son rôle dans la modulation des voies de signalisation cellulaire. Étant donné que le SEA / GATOR est très conservé, j'ai effectué les expériences en utilisant deux modèles cellulaires : levure S. cerevisiae et lignées cellulaires humaines. Les résultats obtenus ont permis de démontrer un nouveau rôle pour le NPRL2, composant de GATOR, distinct de sa fonction dans la régulation de la voie mTORC1. Nous avons constaté que l'expression ectopique de la NPRL2 induit un stress oxydant et conduit aux dommages de l'ADN et à l'apoptose. Les études sur la levure ont révélé que le complexe SEA relie la voie mTORC1 et la régulation du contrôle de la qualité des mitochondries. Par conséquent, le complexe SEA / GATOR émerge en tant que régulateur multifonctionnel de plusieurs processus cellulaires. / The major signaling pathway that regulates cell growth and metabolism is under the control of the mechanistic target of rapamycin complex 1 (mTORC1). One of the mTORC1 upstream regulators involved in amino acid sensing and autophagy is called the SEA complex in yeast and GATOR in mammalian cells. Several GATOR components are deregulated in many cancers and neurodegenerative diseases. Despite of the growing interest to the SEA/GATOR, many details concerning its function and implication in different human disorders are still unknown.The main objective of my thesis was to extend our knowledge about the SEA/GATOR, especially what concerns its role in the modulating cellular signaling network. Because the SEA/GATOR is highly conserved I performed the experiments using two model systems - budding yeast S. cerevisiae and human cells lines. The results I obtained allowed to demonstrate a new role for the GATOR component NPRL2, distinct from its function in mTORC1 regulation. We found that ectopic expression of NPRL2 induces oxidative stress and leads to the DNA damage and apoptosis. The studies in yeast revealed that the SEA complex connects the TORC1 pathway and the regulation of mitochondria quality control. Therefore, the SEA/GATOR complex is emerging as a multifunctional regulator of several cellular processes.

Today's supply chains face increasing volatility on many fronts. From the shop-floor where machines break and suppliers fail to the boardrooms where unanticipated price inflation erodes profi tability. Turbulence is the new normal. To remain competitive and weather these (daily) storms, supply chains need to move away from an effi ciency mindset towards a resilience mindset. For over a little more than a decade industry and academia have awakened to this reality. Academic literature and case studies show that there is no longer a shortage of resilience strategies and designs. Unfortunately, industry still lacks the tools with which to assess and evaluate the effectiveness of such strategies and designs. Without the ability to quantify the benefi t it is impossible to motivate the cost. This thesis adds one piece to the puzzle of quantifying supply chain vulnerability. Speci fically, it focussed on supply chains within urban areas. It addresses the question: "How does a supply chain's network design (internal con figuration) and its dependence on the underlying road network (external circumstances) make it more or less vulnerable to disruptions of the road network?" Multilayered Complex Network Theory (CNT) held promise as a modelling approach that could capture the complexity of the dependence between a logical supply chain network and the physical road network that underpins it. This approach addressed two research gaps in complex network theory applications. In the supply chain arena CNT applications have reaped many benefi ts but the majority of studies regarded single-layer networks that model only supply chain relations. There were no studies found where the dependence of supply chain layers on underlying physical infrastructure was modelled in a multilayered manner. Road network applications offered many more multilayered applications but these primarily focussed on passenger transport, not freight transport. The first artefact developed in the thesis was a multilayered complex network formulation representing a logical (supply chain) layer placed on a physical (road infrastructure) layer. The individual layers had predefi ned network characteristics and on their own could not hint at the inherent vulnerability that the system as a whole might have. From the multilayered formulation, the collection of shortest paths emerged. This is the collection of all shortest path alternatives within a network. The collection of shortest paths is the unique fingerprint of each multilayered network instance. The key to understanding vulnerability lies within the characteristics of the collection of shortest paths. Three standard supply chain network archetypes were de fined namely the Fully Connected (FC), Single Hub (SH) and Double Hub (DH) archetypes. A sample of 500 theoretical multilayered network instances was generated for each archetype. These theoretical instances were subjected to three link-based progressive targeted disruption simulations to study the vulnerability characteristics of the collection of shortest paths. Two of the simulations used relative link betweenness to prioritise the disruptions while the third used the concept of network skeletons as captured by link salience. The results from these simulations showed that the link betweenness strategies were far more effective than the link salience strategy. From these results three aspects of vulnerability were identifi ed. Redundancy quantifi es the number of alternative shortest paths available to an instance. Overlap measures to what degree the shortest path sets of an instance overlap and have road segments in common. Effi ciency step-change is a measure of the magnitude of the "shock" absorbed by the shortest paths of an instance during a disruption. For each of these aspects one or more metrics were defi ned. This suite of vulnerability metrics is the second artefact produced by the thesis. The design of the artefacts itself, although novel, was not considered research. It is the insights derived during analysis of the artefacts' performance that contributes to the body of knowledge. Link-based progressive random disturbance simulations were used to assess the ability of the vulnerability metrics to quantify supply chain vulnerability. It was found that none of the de fined vulnerability aspects are good stand-alone predictors of vulnerability. The multilayered nature and random disturbance protocol result in vulnerability being more multi-faceted than initially imagined. Nonetheless, the formulation of the multilayered network proved useful and intuitive and even though the vulnerability metrics fail as predictors they still succeed in capturing shortest path phenomena that would lead to vulnerability under non-random protocols. To validate the fi ndings from the theoretical instances, link-based random disturbance simulations were executed on 191 case study instances. These instances were extracted from real-life data in three urban areas in South Africa, namely Gauteng Province (GT), City of Cape Town (CoCT) and eThekwini Metropolitan Municipality (ET). The case study instances showed marked deviations from the assumptions underlying the theoretical instances. Despite these differences, the multilayered formulation still enables the quanti fication of the relationship between supply chain structure and road infrastructure. The performance of the vulnerability metrics in the case study corroborates the findings from the theoretical instances. Although the suite of vulnerability metrics was unsuccessful in quantifying or predicting vulnerability in both the theoretical and case study instances, the rationale behind their development is sound. Future work that will result in more effective metrics is outlined in this thesis. On the one hand the development of a more realistic disruption strategy is suggested. Road network disruptions are neither completely random nor specifi cally targeted. Important segments with greater tra ffic loads are more likely to be disrupted, but the reality is that disruptions such as accidents, equipment failure or road maintenance could really occur anywhere on the network. A more realistic disruption strategy would lie somewhere on the continuum between targeted and random disruptions. Other future work suggests the refi nement of both artefacts by incorporating link weights in both the logical and physical layers. An unanticipated fi nding from this thesis is that future research in the fi eld may be expedited if theory-building emanates from real-life empirical networks as opposed to theoretically generated networks. Expanding the scope of the case study, characterising the true network archetypes found in practice and increasing the number of case study samples is a high priority for future work. / Thesis (PhD)--University of Pretoria, 2018. / National Research Foundation of South Africa (Grant UID: 105519). Partial funding of doctoral research. / Industrial and Systems Engineering / PhD / Unrestricted