Synthetic approaches towards linear fused carbon rings have been developed over the last decades due to their high interest as compounds with potential antibiotic activity and as organic electronics. The application of a novel iterative route towards linear fused carbon ring systems could provide a versatile new mode of access to complex substituted ring systems. Studies have previously demonstrated the use of an allylation-double Claisen-RCM sequence to build fused carbon rings (C). In this thesis we described our work to expand the use of this methodology by developing milder reaction conditions that could be applied to a wider range of compounds. This novel methodology was applied towards the synthesis of benzodifuran compounds (D). Our work was extended by developing, for the first time, a mixed Fries-Claisen rearrangement strategy which furnishes template (F), a key intermediate in the synthesis of pyranonaphthoquinones (G). Our work culminated in a new approach to the pyranonaphthoquinone natural products eleutherin (H) and isoeleutherin (I). [Figures missing from abstract].

The development of novel targeted therapeutics for the treatment of cancer remains difficult due to the complex nature of the disease itself as well as the challenges associated with the synthesis of these therapeutics. Impediments to the discovery of novel drug candidates include lack of available starting materials and access to well-developed syntheses which are both convenient and economically feasible. Semicarbazides, for instance, are a critical synthon for the manufacture of numerous biologically important molecules. Historically, convenient methods for the synthesis of semicarbazides and their derivatives did not exist. Recently, a facile and efficient method for the preparation of semicarbazides via their corresponding phenyl carbamates was developed. These phenyl carbamate intermediates may also be used to prepare a wide variety of other derivatives such as substituted ureas as well as the aryl carbamoyl derivatives of 1,3-diazinane-5-carboxamide. While exploring the preparation of the aryl carbamoyl derivatives of 1,3-diazinane-5-carboxamide, it was found that these compounds possess anti-cancer activity against the glioblastoma LN-229 cell line. Intrigued by these results, additional analogues were designed, leading to the development of a small library of chromenopyrimidinedione and pyrimidinequinolinedione compounds as potential anti-cancer agents. Indeed, these two classes of compounds, with many of the derivatives novel, produced a selection of interesting molecules with potent anti-cancer activity against the glioblastoma cell line LN-229 at biologically relevant concentrations. Taken together, these results provide a unique approach not only to the design but also towards the synthesis of novel therapeutics intended for use as anti-cancer agents.

Master of Science / Department of Mechanical and Nuclear Engineering / Gurpreet Singh / 3D-printing is a popular manufacturing technique for making complex parts or small quantity batches. Currently, the applications of 3D-printing are limited by the material properties of the printed material. The processing parameters of commonly available 3D printing processes constrain the materials used to a small set of primarily plastic materials, which have relatively low strength and electrical conductivity. Adding filler materials has the potential to improve these properties and expand the applications of 3D printed material. Carbon nanomaterials show promise as filler materials due to their extremely high conductivity, strength, and surface area. In this work, Graphite, Carbon Nanotubes, and Carbon Black (CB) were mixed with raw Acrylonitrile Butadiene Styrene (ABS) pellets. The resulting mixture was extruded to form a composite filament. Tensile test specimens and electrical conductivity specimens were manufactured by Fused Deposition Method (FDM) 3D-printing using this composite filament as the feedstock material. Weight percentages of filler materials were varied from 0-20 wt% to see the effect of increasing filler loading on the composite materials. Additional tensile test specimens were fabricated and post-processed with heat and microwave irradiation in attempt to improve adhesion between layers of the 3D-printed materials. Electrical Impedance Spectroscopy tests on 15 wt% Multiwalled Carbon Nanotube (MWCNT) composite specimens showed an increase in DC electrical conductivity of over 6 orders of magnitude compared to neat ABS samples. This 15 wt% specimen had DC electrical conductivity of 8.74x10−6 S/cm, indicating semi-conducting behavior. MWCNT specimens with under 5 wt% filler loading and Graphite specimens with under 1 wt% filler loading showed strong insulating behavior similar to neat ABS. Tensile tests showed increases in tensile strength at 5 wt% CB and 0.5 wt% MWCNT. Placing the specimens in the oven at 135 °C for an hour caused increased the stiffness of the composite specimens.

Student Number : 0002306V - MSc dissertation - School of Chemistry - Faculty of Science / The first part of the dissertation involves the use of ring closing metathesis (RCM) and ruthenium mediated isomerisation-RCM tandem reactions to form a wide range of nitrogencontaining benzo-fused heterocycles. Those synthesized include the 6-membered isoquinolines, the 7-membered benzazepines and the 8-membered benzazocines. In order to put these compounds into perspective, a review of selected naturally occurring nitrogencontaining benzo-fused heterocycles is included along with some of their synthetic approaches. Of major significance is our utilization of the Wits methodology allowing one to access the 6-, 7- and 8-membered ring systems from a common synthetic intermediate. The 1,2,3,6-tetrahydro-2-benzazocines were all obtained after RCM in excellent yields (82-99%). We were also able to show that some ofthe protecting groups used were easily removed and that the ring could be hydrogenated after RCM to yield the 1,2,3,4,5,6-hexahydro-2- benzazocines. The isoquinolines were synthesized in 78% and 27% yield for the Ac- and Tsprotected compounds respectively, with no product isolated for the Boc- or SO2Bn-protected compounds. These poor results, caused a change to our strategy and we then used a “combinatorial-type” approach for the synthesis of the 2,5-dihydro-1H-2-benzazepines and the 2,3-dihydro-1H-2-benzazepines with yield of 9, 47, 58 and 82% and 8, 26, 39 and 82% obtained respectively for the RCM reaction Futhermore, we attempted the synthesis of the substituted 4-phenyl isoquinolines and 5-phenyl benzazepines, but we found that the systems would not undergo RCM even at high temperatures and with large amounts of Grubbs II metathesis catalyst. A short review is given in the second part of the dissertation concerning the naturally occurring and pharmaceutically useful indenols, indenones and indanones. It further highlights how our methodology was extended to include the synthesis of 4-isopropoxy-5- methoxy-1H-inden-1-ol (X), 4-isopropoxy-5-methoxy-1H-inden-1-one (X) and 4-isopropoxy- 5-methoxy-1H-indanone (X) through the use of ruthenium-mediated isomerisation and RCM from a similar common intermediate. We have shown the synthesis of 3-substituted indenols, indenones and indanones using the same synthetic procedure, but by changing the reaction temperature during RCM. This dissertation also answers many of the questions posed during the post-doctoral work of Coyanis. Namely, we were able to support our proposed mechanism that the conversion of the unsubstituted indenol to the indenone was occurring via a dehydrogenative-oxidation, through the use of 1H NMR studies that were coupled with an ICP-MS analysis. To the best of our knowledge, this is the first reported use of the Grubbs II catalyst (or its degradation products) in a tandem RCM-oxidation procedure by our group recently.

Tendo em vista a natureza finita dos minerais naturais, torna-se evidente a necessidade de utilizarmos este recurso de maneira estratégica. Desta forma, diversas pesquisas vêm sendo desenvolvidas principalmente nas áreas químicas, metalúrgicas e mineralógicas desde as etapas de extração, beneficiamento, aplicação e reutilização dos resíduos de minérios. Portanto, é extremamente importante a intensificação dos estudos para aumentar o conhecimento quanto às características e propriedades físico-químicas destes minerais, visando melhorar o seu aproveitamento e longevidade das jazidas naturais, como as fontes de bauxita, que é a principal matéria-prima para a produção de óxido de alumínio fundido. Na sua forma cristalina mais comum, denominada coríndon, ou óxido de alumínio ?, sua baixa condutividade elétrica, baixo calor específico, alta condutividade térmica, alto ponto de fusão, elevada dureza e resistência mecânica, o torna adequado para uso em produtos refratários, cerâmicos e abrasivos tais como, lixas, rebolos, ferramentas de corte e de polimento. Na síntese deste produto as principais impurezas que afetam a qualidade dos grãos são Fe, Si, Ca, K, Na e Zr, oriundas da matéria prima bauxita e da carta de mistura, composta por ilmenita, limalha de ferro, carvão vegetal e coque de petróleo. Desta forma, o presente trabalho assumiu o objetivo de estudar a dispersão das propriedades físico-químicas em blocos de alumina fundida marrom obtida em fornos Higgins a arco por eletrofusão, produzidos na Saint-Gobain Abrasivos, unidade de Lorena, SP. Por fim, foram utilizadas técnicas de caracterização físico-químicas de difratometria de raios X (DRX), análises químicas de fluorescência de raios X (FRX), ensaio de dureza Knoop e caracterização microestrutural via (MEV/EDS). Desta forma, foi definido o mapeamento composicional nos blocos de alumina eletrofundida marrom, que servirão como referência técnico-científica para subsidiar ações de melhoria deste produto, em decorrência do avanço do estado da arte deste referido assunto. / The mineral ores are not renewable sources and we need to use it in the best way possible. In this way, a large number of researches are being developed around the world aiming the improvement of current methods of production mainly in chemical, metallurgy, mineralogical from the steps of extraction, processing, application and reuse of waste ore. Therefore, it is extremely important to intensify the studies to increase the knowledge about the characteristics and physicochemical properties of these minerals, in order to improve their utilization and longevity of natural deposits, such as sources of bauxite, which is the main raw material to product aluminum oxide fused. In its most common crystalline form, called corundum or ?-aluminum oxide, its low electrical conductivity, low specific heat, high thermal conductivity, high melting point, high hardness and mechanical strength, making it suitable for use as refractories, ceramics and fine or coarse abrasives. The synthesis of this product major impurities that affect quality of grain is Fe, Si, Ca, K, Na and Zr, derived from the raw material bauxite and the mixture chart consisting of ilmenite, iron filings, charcoal and coke oil. Thus, this shows the dispersion of physicochemical properties of brown fused alumina blocks produced by eletrocfusion at Higgins furnace process in the company Saint Gobain Abrasivos, Lorena- SP. Finally, the samples were physicochemical analyzed by X ray diffraction (XRD), chemical analyses by X ray fluorescence (XRF), hardnes using Knoop method, microstructural characterization by (SEM). The results of this work show a compositional gradient map of the fused alumina block; that shows the main physicochemical differences into the block, to support changes in the alumina production process; and it is also important to improve the actual state of art of this particular theme.

O estudo do eletrorrevestimento de tântalo sobre aço e sobre cobre foi realizado na mistura eutética FLINAK (29,2% LiF - 11,7% NaF - 59,1% KF - % em massa) contendo 15% em massa de K2TaF7. Foram estudadas as influências da densidade de corrente catódica, do tempo de eletrólise, da temperatura e da natureza do substrato sobre as eficiências de correntes catódicas e a morfologia dos revestúnentos. Depósitos de tântalo lisos, brilhantes, aderentes e uniformes foram obtidos com alta eficiência de corrente catódica usando os seguintes parâmetros: densidade de corrente catódica de 23 mA/cm2 a 50 mA/cm2, temperatura de 750°C e tempo de eletrólise de 30 minutos a 120 minutos. Os revestimentos obtidos nestas condições possuem espessuras de 18 µm a 41 µm. Os depósitos de tântalo sobre aço e sobre cobre são constituídos de tântalo puro, sem formação de camada de difusão. Ensaios de eletrodeposição de camadas delgadas de tântalo em catodos de formas e geometrias complexas mostraram o bom poder de cobertura do tântalo. Curvas potencial de circuito aberto x tempo, feitas à temperatura ambiente em soluções de ácido nítrico a 40%, a 50% e a 60% em massa, ácido clorídrico a 3,6% em massa e ácido sulfúrico a 80% em massa, mostraram ótima concordância entre o potencial de circuito aberto estacionário do tântalo maciço comercial e dos revestimentos de tântalo sobre cobre nestes meios. Curvas potencial de circuito aberto x tempo feitas à temperatura ambiente em meio de ácido clorídrico a 3,6% em massa, para revestimentos sobre aço mostraram que a semelhança com o tântalo maciço só é observada em depósitos recentes, o que foi atribuído à difusão do ferro do substrato para a superficie do revestimento. Ensaios gravimétricos mostraram que a velocidade de corrosão dos revestimentos é comparável com a do tântalo comercial, em meios de ácido nítrico a 40% e a 50% em massa, à temperatura de ebulição. / The study of tantalum electroplating on copper and carbon steel has been carried out in FLINAK eutectic (29.2% LiF -11.7% NaF -59.1% KF - wt%) containing 15wt% K2TaF7. The effects of current cathodic density, time of electrolysis, temperature and substrate kind have been studied in relation to the cathodic current efficiencies and the coating morphology. Tantalum deposits, with good smoothness, brightness, adherence and uniformity were obtained with high cathodic efficiency, using the following conditions: 23 mA/cm2 to 50 mA/cm2 cathodic current densities, 30 minutes to 120 minutes electrolysis time interval and 750°C temperature. Under these conditions the coatings are about 18 µm to 41 µm thick. The deposits obtained on carbon steel and copper are both constituted of pure tantalum without formation of interdiffusion layer. The results of tantalum thin coatings electrodeposition on cathodes of complex geometrics and shapes showed the good throwing power of tantalum. Open circuit potential x time curves have been recorded for massive tantalum and for tantalum coatings on copper in 40 wt%, 50 wt% and 60 wt% nitric acid, 3.6 wt% hydrochloric acid and 80 wt% sulfurie acid at room temperature. They showed similar stationary open-circuit poteutial values for both the massive tantalum and the tantalum coatings. Open circuit potential x time curves for tantalum coatings on carbon steel performed in 3.6%wt hydrochloric acid at room temperature showed that the similarity with massive tantalum exists only with recent deposits, because of iron diffusion from substrate to coating surface. Gravimetric tests showed comparable corrosion rate values for massive tantalum and tantalum coatings in boiling 40wt% and 50wt% nitric acid.

<div>Fused deposition modeling (FDM) represents one of the most common techniques for rapid proto-typing in additive manufacturing (AM). This work applies image based thermography to monitor the FDM process in-situ. The nozzle temperature, print speed and print orientation were adjusted during the fabrication process of each specimen.</div><div>Experimental and numerical analysis were performed on the fabricated specimens. The combination of the layer wise temperature profile plot and temporal plot provide insights</div><div>for specimens fabricated in x, y and z-axis orientation. For the x-axis orientation build possessing 35 layers, Specimens B16 and B7 printed with nozzle temperature of 225 ➦C and</div><div>235 ➦C respectively, and at printing speed of 60 mm/s and 100 mm/s respectively with the former possessing the highest modulus, yield strength, and ultimate tensile strength. For the y-axis orientation build possessing 59 layers, Specimens B23, B14 and B8 printed with nozzle temperature of 215°C, 225°C and 235°C respectively, and at printing speed of 80 mm/s, 80 mm/s and 60 mm/s respectively with the former possessing the highest modulus and yield strength, while the latter the highest ultimate tensile strength. For the z-axis orientation build possessing 1256 layers, Specimens B6, B24 and B9 printed with nozzle temperature of 235°C, 235°C and 235°C respectively, and at printing speed of 80 mm/s, 80 mm/s and 60 mm/s respectively with the former possessing the highest modulus and ultimate tensile strength, while B24 had the highest yield strength and B9 the lowest modulus, yield strength and ultimate tensile strength. The results show that the prints oriented in the y-axis orientation perform relatively better than prints in the x-axis and z-axis orientation.</div>

Supercapacitors, also known as electrochemical capacitors, have shown great potential as energy storage devices; and 3D printing likewise as a manufacturing technique. This research progressively investigates combining these two technologies to fabricate 3D-printed, electrochemical double-layer capacitors (EDLCs). Small EDLCs were designed in a sandwich structure with an FDM-printed plastic frame and carbon electrodes. Inkjet printing was initially combined with FDM printing to produce a pilot sample with a silver ink current collector, however this performed poorly (Cs = 6 mF/g). Henceforth a paste extrusion system was added to the FDM printer to deposit the current collectors and electrodes, fabricating the entire device in a single continuous process. This process was progressively developed and tested, ultimately attaining specific capacitances of 200 mF/g. The fully integrated 3D printing process used to manufacture the EDLCs was a novel approach. Combining the FDM printer with a paste extruder allowed for a high degree of dimensional accuracy, as well as simplifying the production process. This aspect of the design functioned successfully, without significant faults, and proved a reliable fabrication method. The later designs used in this study provided the EDLCs extendable by incorporating connection jacks. This was to create the possibility to increase capacitance simply by connecting multiple EDLCs together. Tests of this feature showed that it worked well, with the extendable EDLCs delivering outputs very close to the theoretical maximum efficiency of the unit. Carbon conductive paint was applied as a current collector and electrode for the 3D printed EDLCs in an exploration of metal-free 3D printed supercapacitors. These metal-free EDLCs were found to provide around 60% of the specific capacitance of the best performing EDLC variant produced (silver paint current collectors with activated carbon and carbon paint mixture electrodes). Although considerable improvement is required to produce EDLC samples with comparable capacitances to existing commercial manufacturing techniques, this study lays important groundwork in this area, and has introduces effective and innovative design ideas for supercapacitors and integrated 3D printing processes.

Tendo em vista a natureza finita dos minerais naturais, torna-se evidente a necessidade de utilizarmos este recurso de maneira estratégica. Desta forma, diversas pesquisas vêm sendo desenvolvidas principalmente nas áreas químicas, metalúrgicas e mineralógicas desde as etapas de extração, beneficiamento, aplicação e reutilização dos resíduos de minérios. Portanto, é extremamente importante a intensificação dos estudos para aumentar o conhecimento quanto às características e propriedades físico-químicas destes minerais, visando melhorar o seu aproveitamento e longevidade das jazidas naturais, como as fontes de bauxita, que é a principal matéria-prima para a produção de óxido de alumínio fundido. Na sua forma cristalina mais comum, denominada coríndon, ou óxido de alumínio ?, sua baixa condutividade elétrica, baixo calor específico, alta condutividade térmica, alto ponto de fusão, elevada dureza e resistência mecânica, o torna adequado para uso em produtos refratários, cerâmicos e abrasivos tais como, lixas, rebolos, ferramentas de corte e de polimento. Na síntese deste produto as principais impurezas que afetam a qualidade dos grãos são Fe, Si, Ca, K, Na e Zr, oriundas da matéria prima bauxita e da carta de mistura, composta por ilmenita, limalha de ferro, carvão vegetal e coque de petróleo. Desta forma, o presente trabalho assumiu o objetivo de estudar a dispersão das propriedades físico-químicas em blocos de alumina fundida marrom obtida em fornos Higgins a arco por eletrofusão, produzidos na Saint-Gobain Abrasivos, unidade de Lorena, SP. Por fim, foram utilizadas técnicas de caracterização físico-químicas de difratometria de raios X (DRX), análises químicas de fluorescência de raios X (FRX), ensaio de dureza Knoop e caracterização microestrutural via (MEV/EDS). Desta forma, foi definido o mapeamento composicional nos blocos de alumina eletrofundida marrom, que servirão como referência técnico-científica para subsidiar ações de melhoria deste produto, em decorrência do avanço do estado da arte deste referido assunto. / The mineral ores are not renewable sources and we need to use it in the best way possible. In this way, a large number of researches are being developed around the world aiming the improvement of current methods of production mainly in chemical, metallurgy, mineralogical from the steps of extraction, processing, application and reuse of waste ore. Therefore, it is extremely important to intensify the studies to increase the knowledge about the characteristics and physicochemical properties of these minerals, in order to improve their utilization and longevity of natural deposits, such as sources of bauxite, which is the main raw material to product aluminum oxide fused. In its most common crystalline form, called corundum or ?-aluminum oxide, its low electrical conductivity, low specific heat, high thermal conductivity, high melting point, high hardness and mechanical strength, making it suitable for use as refractories, ceramics and fine or coarse abrasives. The synthesis of this product major impurities that affect quality of grain is Fe, Si, Ca, K, Na and Zr, derived from the raw material bauxite and the mixture chart consisting of ilmenite, iron filings, charcoal and coke oil. Thus, this shows the dispersion of physicochemical properties of brown fused alumina blocks produced by eletrocfusion at Higgins furnace process in the company Saint Gobain Abrasivos, Lorena- SP. Finally, the samples were physicochemical analyzed by X ray diffraction (XRD), chemical analyses by X ray fluorescence (XRF), hardnes using Knoop method, microstructural characterization by (SEM). The results of this work show a compositional gradient map of the fused alumina block; that shows the main physicochemical differences into the block, to support changes in the alumina production process; and it is also important to improve the actual state of art of this particular theme.

According to the famous axiom known as Moore’s Law the number of transistors that can be etched on a given piece of ultra-pure silicon, and therefore the computing power, will double every 18 to 24 months. However, around 2020 hardware manufacturers will have reached the physical limits of silicon. A proposed solution to this dilemma is molecular electronics. Within this field researchers are attempting to develop individual organic molecules and metal complexes that can act as molecular equivalents of electronic components such as wires, diodes, transistors and capacitors. In this work we have synthesized a number of new bi- and terdentate thiophenyl pyridine and pyridyl thienopyridine ligands and compared the electrochemical, structural and photophysical properties of their corresponding Ru(II) complexes with Ru(II) complexes of a variety of ligands based on 6-thiophen-2-yl-2,2'-bipyridine and 4-thiophen-2-yl-2,2'-bipyridine motifs. While the electrochemistry of the Ru(II) complexes were similar to that of unsubstituted [Ru(bpy)3]2+ and [Ru(tpy)2]2+, substantial differences in luminescence lifetimes were found. Our findings show that, due to steric interactions with the auxiliary bipyridyl ligands, luminescence is quenched in Ru(II) complexes that incorporate the 6-thiophen-2-yl-2,2'-bipyridine motif, while it was comparable with the luminescence of [Ru(bpy)3]2+ in the Ru(II) complexes of bidentate pyridyl thienopyridine ligands. The luminescence of the Ru(II) complexes based on the 4-thiophen-2-yl-2,2'-bipyridine motif was enhanced compared to [Ru(bpy)3]2+ which indicates that complexes of this category may be applicable for energy/electron-transfer systems. At the core of molecular electronics is the search for molecular ON/OFF switches. Based on the ability of the ligand 6-thiophen-2-yl-2,2'-bipyridine to switch reversibly between cyclometallated and non-cyclometallated modes when complexed with Ru(tpy) we have synthesized a number of complexes, among them a bis-cyclometallated switch based on the ligand 3,8-bis-(6-thiophen-2-yl-pyridin-2-yl)-[4,7]phenanthroline, and examined their electrochemical properties. Only very weak electronic coupling could be detected, suggesting only little, if any, interaction between the ruthenium cores.