Application of chemotherapeutic agents in current cancer treatment has been limited by adverse effects as poor selectivity results in systemic toxicity; most chemotherapy approaches also experience inherited or acquired drug resistance which lead to reduced treatment outcome. Research efforts have focused on the discovery of novel chemotherapies that overcome the limitations mentioned above. Ru(II) polypyridyl complexes with anti-cancer properties have been extensively studied as traditional cytotoxic agents and photodynamic therapy agents due to their photophysical and photochemical characteristics. Most research has focused on the design of Ru(II) polypyridyl complexes that have affinities to nucleic acids as inspired by the classic small molecule metal complex cisplatin. Though modifying the structures of ligands on the ruthenium metal center, the hydrophilicity, charge state and photochemical properties can be tuned, resulting to Ru(II) polypyridyl complexes that act through cellular targets other than DNA. Understanding the mechanism of action and identifying functional targets remain the challenging and complex research topic in the design and study of novel medication or candidates. With the development of semi-high throughput cytological profiling in a bacterial system, rapid investigation of the mechanism of action can be achieved to distinguish anti-cancer agents which possess different mechanisms of actions. Ru(II) polypyridyl complexes with different scaffolds have been studied and suggested to have anti-cancer properties through DNA damage response, and/or translational inhibition.

Thesis (Ph.D. (Physics)) --University of Limpopo, 2011 / Planewave pseudopotential calculations were conducted to predict the energetics and phase stability of Pt-Cr and Ru-Cr binary alloys. Validation of appropriate number of k-points and planewave energy cut-off was carried out for all studied systems. At the composition of A3B and AB3 (where A = Cr and B = Pt or Ru) phases, the heats of formation determined for five different structures, L12, A15, tP16, DOC and DO′ C are almost of the same magnitude and the relaxed structures show no rotation. We observed that the cubic L12 Pt3Cr is the most stable structure in agreement with the experiments. The results for PtCr3 indicate the negative heat of formation for the A15 phase whereas all the remaining studied phases have positive heats of formation. It is clear that the PtCr3 (A15) is the most stable structure. PtCr (L10) was found to be more stable compared with PtCr (B2) phase. The L12 Pt3Cr, A15 PtCr3 and L10 PtCr phases could be considered as possible coatings to cover the engines which are exposed to aggresive environments. The heats of formation of all studied compositions and phases of Ru-Cr systems are positive, these results suggest that, generally, studied Ru-Cr phases are not stable. The effect of pressure and doping were investigated on A15 RuCr3 structure which was reported to exist at a higher temperature. Elastic constants and moduli were investigated to determine the strength of the PtCr systems. The strength of PtCr L10 is greater than that of B2 phase. The ratio of shear to bulk modulus (G/B) has been used to predict the ductility or the brittleness of the material. It was found that Pt3Cr L12 is the most ductile phase among those considered in this study. The density of states were calculated to further analyze the stability of systems. The magnetic properties of Cr were studied using VASP which predicted an anti-ferromagnetic and a non-magnetic ground state for pure Cr. We have investigated the thermal stability at 0 GPa for different phases of Pt3Cr, PtCr3, PtCr and RuCr3 A15 phase, where we detected the soft modes at X, G, M and R points of the Brillouin zone from the phonon spectra of Pt3Cr A15 phase. Pt3Cr L12 and PtCr3 A15 are predicted as dynamically stable structures. RuCr3 A15 phase was found to be dynamically stable but thermodynamically unstable. Phonon DOS were studied to observe the modes of vibration and atoms that contribute to soft modes. Lastly we investigated the thermal expansion of Pt3Cr L12 and A15 phases. / The National Research Foundation,and the South African Gas Turbine Research Program

Nous avons développé la synthèse de pyridoacridines, analogues d'alcaloïdes naturels et évalué leurs propriétés (physico-chimiques et biologiques). D'une part, nous avons préparé des conjugués entre le motif pyridoacridone et des amines par addition de Michael sur une fonction quinone, ainsi que des conjugués entre le chromophore pyridoacridine et des sucres par lien oxime. Dans un deuxième temps, nous avons élaboré deux voies de synthèse pour accéder à une structure octacyclique. L'étape clé est la condensation d'ortho-diamines sur un bis-électrophile, la phendione. Cette même condensation a été utilisée pour élaborer une nouvelles famille de composés polycycliques fonctionnalisés par des amines (heptacycles). Les propriétés des produits ont été étudiées : D'abord la cytotoxicité des pyridoacridines (ones) avec une IC50 de l'ordre du micromolaire pour les plus actifs. Ensuite, l'électroactivité de certaines pyridoacridones a servi à élaborer un biocateur (détection de l'hybridation de l'ADN). Finalement, deux complexes de ruthénium (II) ont été préparés et caractérisés. Les ligands heptacycliques introduits dans ces complexes modifient fortement l'émission de fluorescence des complexes. De plus, ils interagissent fortement avec le double brin d'ADN et produisent des photocoupures sous illumination.

Ru/C type ammonia synthesis catalysts are known to be poisoned by hydrogen. In order to elucidate a mechanism for hydrogen poisoning, H2 adsorption and spillover on Ru based ammonia synthesis catalysts were investigated. Supported Ru catalysts and Na promoted Ru catalyst were prepared by incipient wetness impregnation of Ru(NO)(NO3)3 on SiO2, SBA-15, CNT and Vulcan supports. Dispersion value of the catalysts was determined via H2 chemisorption and Transmission Electron Microscopy (TEM) characterization techniques. Over SBA-15 support, the dispersion of the catalyst determined by two different characterization techniques were in agreement. On the other hand, over CNT and SiO2 supports dispersion measured by TEM characterization method was higher than H2 chemisorption method. H2 chemisorption measurements performed over extended periods of time were used to determine the spilled over hydrogen amounts over Ru/Vulcan and Na-Ru/Vulcan catalysts at 375 torr and 10 torr H2 pressure at room temperature. By using H2 uptake data measured for extended periods of 6 &ndash / 24 hours, diffusion coefficient of hydrogen species over Vulcan support was calculated assuming a point source diffusion mechanism. Coefficient of diffusion for Ru/Vulcan and Na-Ru/Vulcan was found as 1.39 x 10-14 cm2/sec and 1.23 x 10-14 cm2/sec, respectively at 375 torr. Similarly, at 10 torr, diffusion coefficients of Ru/Vulcan and Na-Ru/Vulcan catalysts were determined as 1.51 x 10-15 cm2/sec and 1.81 x 10-15 cm2/sec, respectively.

El trabajo de tesis doctoral ha consistido en el desarrollo de nuevos complejos dinucleares de rutenio, manganeso y cobalto contenientes ligandos descritos tetradetandos de tipo N2O2y un nuevo ligando decadentado de tipo N10. Estos complejos han sido sintetizados y caracterizados a través de técnicas estructurales, espectroscópicas y electroquímicas. Las actividades catalíticas han sido investigadas en las oxidaciones químicas, electroquimica y fotoquímicas de agua y de substratos orgánicos y en la reducción electroquímica de protones. Por último se ha diseñado y desarrollado el montaje de una celda simultánea oxidación de substratos orgánicos y la generación de H2. / The experimental work of this thesis consisted of the development of new ruthenium, manganese and cobalt dinuclear complexes containing described tetradentate ligands of N2O2type and a new decadentate ligand of N10 type. These complexes have been synthesized and characterized by the usual structural, spectroscopic and electrochemical techniques. The catalytic activities have been investigated in the chemical, electrochemical and photochemical oxidation of water and organic substrates and in the electrochemical proton reduction. Lastly an assembly of a cell for simultaneous oxidation of organic substrates and generation of H2 has been designed and developed.

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The Canadian Penning Trap mass spectrometer located at Argonne National Laboratory has been built for the purpose of studying the masses of both stable and unstable nuclides. For this thesis 18 proton-rich unstable nuclides of elements Nb, Mo, Tc, Ru and Rh have been measured with this apparatus to an average precision of 7.8 x10^−8. The masses of 6 of these nuclides had not been measured when this thesis was undertaken, and 4 more were not known to the precisions required for use in astrophysical nucleosynthesis models. The masses of these nuclides were of particular interest as the reaction paths of two proposed nucleosynthetic processes, the rp and νp processes, pass through this region. The rp process is thought to occur in X-ray bursts and directly affects the X-ray luminosity which is emitted from these objects. The νp process is thought to occur in the inner regions of the material ejected during a core-collapse supernova explosion and is of particular interest as it may answer some outstanding questions about the origins of the chemical elements in the Universe. The Canadian Penning Trap and associated apparatus were used to determine the masses of 18 nuclides, some for the first time ever. Our measurements improve the precision on all of the masses, by a factor of 70 in some cases. Our results are necessary to determine the proton-separation energies for these nuclides which are critical for determining the paths and reaction rates of the rp and νp processes. In particular, the effect of our measurements of 92Ru and 93Rh on the expected production ratio of 92Mo to 94Mo in the νp process, and the effect of our measurement of 87Mo on the path of this process will be discussed.

The Canadian Penning Trap mass spectrometer located at Argonne National Laboratory has been built for the purpose of studying the masses of both stable and unstable nuclides. For this thesis 18 proton-rich unstable nuclides of elements Nb, Mo, Tc, Ru and Rh have been measured with this apparatus to an average precision of 7.8 x10^−8. The masses of 6 of these nuclides had not been measured when this thesis was undertaken, and 4 more were not known to the precisions required for use in astrophysical nucleosynthesis models. The masses of these nuclides were of particular interest as the reaction paths of two proposed nucleosynthetic processes, the rp and νp processes, pass through this region. The rp process is thought to occur in X-ray bursts and directly affects the X-ray luminosity which is emitted from these objects. The νp process is thought to occur in the inner regions of the material ejected during a core-collapse supernova explosion and is of particular interest as it may answer some outstanding questions about the origins of the chemical elements in the Universe. The Canadian Penning Trap and associated apparatus were used to determine the masses of 18 nuclides, some for the first time ever. Our measurements improve the precision on all of the masses, by a factor of 70 in some cases. Our results are necessary to determine the proton-separation energies for these nuclides which are critical for determining the paths and reaction rates of the rp and νp processes. In particular, the effect of our measurements of 92Ru and 93Rh on the expected production ratio of 92Mo to 94Mo in the νp process, and the effect of our measurement of 87Mo on the path of this process will be discussed.

The aim of this essay is to find signs of autofiction in the autobiographical novel Ru written by Kim Thúy. We also examine the functions of autofiction in the novel. What purpose can an autofictional strategy of writing serve?Autofiction is a literary term with many significations and that is why we have formulated our own definition of autofiction in this essay. The practice of autofiction is not new, it is in fact a historical category and we think that this shows the value of autofiction as a very human way of writing, and that this value is related to the human memory and to the wish to relate past events in a more vivid way. For exemple, a comparison can be made between the human memory and autofiction; both of them have pictures of own memories and also pictures of memories that someone else gave them. It is also possible that fiction and reality blend unconsciously when we call to mind events from the past.Ru is the first novel of Kim Thúy and it describes her and her family’s life during the Vietnam War, under the communist regime’s terror, as refugees and as immigrants in Canada. The author hop from present time to past time according to her memory. Ru does not have chapters, instead it is composed of many short stories which are linked togheter by a thought or a word. It is not an enumeration of events, places or numbers, in Ru it is the individual’s perspective that is in focus.We have analysed the autofiction in Ru according to the following points: écriture consonantique, littérarité, rétrospection dialectique, découpage temporal and reconstitution. In our analysis we have shown that there is autofiction in Ru. First of all because the novel is not written in a chronological order but also because it contains the authors search for her-self which is also a search for healing of traumatic experiences. We have also dicussed the functions of autofiction in Ru and we have seen that Kim Thúy insert stories of others which has a function for the collective history of the people of Vietnam. Kim Thúy uses fiction to make the readers imagine the real. In this way, fiction and reality are not opposed, it is just two different manners of talking about the real world.

Tese (doutorado)—Universidade de Brasília, Centro de Desenvolvimento Sustentável, 2017. / Submitted by Gabriela Lima (gabrieladaduch@gmail.com) on 2017-11-28T10:36:23Z No. of bitstreams: 1 2017_AlfiadoVictorino.pdf: 2985489 bytes, checksum: 51d8aaaf4d84b5a279f94e0681531ee5 (MD5) / Approved for entry into archive by Raquel Viana (raquelviana@bce.unb.br) on 2018-03-22T21:06:10Z (GMT) No. of bitstreams: 1 2017_AlfiadoVictorino.pdf: 2985489 bytes, checksum: 51d8aaaf4d84b5a279f94e0681531ee5 (MD5) / Made available in DSpace on 2018-03-22T21:06:10Z (GMT). No. of bitstreams: 1 2017_AlfiadoVictorino.pdf: 2985489 bytes, checksum: 51d8aaaf4d84b5a279f94e0681531ee5 (MD5) Previous issue date: 2018-03-22 / O trabalho analisa o aproveitamento energético dos resíduos alimentares gerados no Restaurante Universitário (RU) da Universidade de Brasília (UnB), com a finalidade de avaliar o potencial desses materiais na redução das emissões de gases de efeito, do volume de resíduos aterrados, recuperação de materiais e produção de energia renovável. Com bases em dados primários colhidos no local e, secundários, obtidos na literatura e, recorrendo a métodos de observação/medição direta e revisão bibliográfica, o trabalho analisa o fluxo dos resíduos alimentares gerados no local, suas propriedades físicas/químicas e seu potencial energético. Usa o método de balanço de massa e energia para quantificar os potenciais benefícios econômicos, sociais e ambientais derivados da sua valorização e, alguns elementos do método de decisão multicritério (ADM), para aferir as possibilidades, as limitações e os desafios que a implementação dessa tecnologia coloca para a comunidade universitária local. De acordo com a metodologia adotada, os resultados do estudo sugerem um fluxo considerável de resíduos estimado em 2,184 toneladas por dia, equivalentes a uma produção anual de 797,16 toneladas, com um potencial energético de cerca de 6,6 kl de biogás anuais, correspondente a um potencial de produção de 83,3 m3 por tonelada de resíduos alimentares. Consumido in situ, o biogás (metano) gerado representa uma economia potencial de 64% no consumo de gás de cozinha, além da redução nos custos de coleta, transporte e deposição final, estimados em torno de R$ 21.000 anuais. A recuperação de materiais na ordem de 36% e desvio da matéria orgânica na ordem de 26% são outros potenciais benefícios derivados da aplicação da digestão anaeróbia no tratamento de resíduos gerados no local, acrescidos do desvio de gases de efeito estufa na ordem de 106 kgCO2eq por tonelada de resíduos alimentares gerados, equivalentes a 84,7 tCO2eq por ano. O ensaio de uma planta experimental de biodigestão dos resíduos alimentares do RU resultou numa produção média de biogás na ordem de 0,8 m3/dia, equivalente a 120 dm3 /kg SV, com baixa concentração de metano (1.500 ppm) e, por conseguinte, não inflamável. A análise do desempenho do ensaio experimental revelou que não obstante o potencial energético existente nos resíduos gerados no local, certos aspetos de natureza tecnológico operacional, como o domínio do processo bioquímico, planejamento etc., precisam ser aprimorados para explorar com maior eficácia tal potencial, em benefício do Restaurante da Universidade de Brasília, em particular, e da comunidade acadêmica local, no geral. / This work analyzes the energy utilization of food waste generated at the University Restaurant (RU) of the University of Brasília (UnB), in order to evaluate the potential of these materials in the reduction of greenhouse gas emissions, reduction of landfilled volume and Renewable energy production. Based on the primary and local data obtained in the literature, the work analyzes the flow of food residues generated on the site, its physical/chemical properties and its energy potential, using methods of direct observation/measurement and bibliographic review. It uses the mass and energy balance method to quantify the potential economic, social and environmental benefits derived from its valorization, and some elements of the multicriteria decision method (ADM) to gauge the possibilities, limitations and challenges that the implementation of this technology poses for the local university community According to the methodology adopted, the results of the study suggest a considerable waste stream estimated at 2.184 tons per day, equivalent to an annual production of 797.16 tons, with an estimated energy potential of 6.6 KL of biogas, corresponding to a production of 83.3 m3 per ton of food waste. Consumed in situ, the biogas (methane) generated represents a saving of 64% in the consumption of cooking gas, in addition to saving the costs of collection, transportation and final disposal estimated at around R$21000 per year. The recovery of materials in the order of 36% and organic matter deviation in the order of 26% are other potential benefits derived from the application of anaerobic digestion in the treatment of on-site waste, plus sequestration of greenhouse gases in the order of 106 kgCO2eq per ton of food waste generated, equivalent to 84.7 tCO2eq per year. Testing of an experimental biodigestion plant for RU food waste resulted in a mean biogas production of around 0.8 m3/day, equivalent to 120 dm3/kg SV, with a low methane concentration (1500 ppm). The experimental performance analysis revealed that despite the energetic potential of locally generated waste, to take advantage of this, certain aspects of a technological-operational nature such as the biochemical process domain, planning, etc., need to be improved to explore with greater effectiveness the energy potential of the residues generated in the place, for the benefit of the Restaurant of the University of Brasília in particular and of the local academic community in general.