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Due to the development of multidrug resistance in Streptococcus pneumoniae, research has begun to define new drug targets for pneumonia therapy. Different research groups have identified a lipoprotein, PsaA that is important for pneumonia virulence. PsaA is a manganese transporter that is required for bacterial virulence and growth. We have employed computer modeling to virtually screen a small-molecule database for inhibition of PsaA function by targeting the metal binding pocket, performing receptor-based virtual screening and molecular docking and scoring to identify potential inhibitors of PsaA function. We have developed an assay for screening compounds, including the use of a PsaA mutant, testing of multiple compounds, and identification of compounds that inhibit Streptococcus pneumoniae growth at concentrations less than 20 μM. We experimentally tested the effect on Mn uptake and their PsaA dependence for 42 compounds, but these experiments suggested that these compounds were affecting bacterial growth by a different mechanism.

M.Sc. / It is the focus of the study to qualitatively describe and then quantify the mineralogical and geochemical changes associated with the supergene alteration of carbonate-rich braunite lutite (Mamatwan-type ore) immediately below the Kalahari unconformity along the southeastern suboutcrop perimeter of the Hotazel Formation in the Kalahari deposit. It was also the objective of this study to determine the timing and duration of supergene alteration. Samples for polished thin sections were carefully selected from eight representative boreholes to be representative of all the lithostratigraphic zones and ore types. The thin sections were used to study mineralogy by means of reflected light microscopy and scanning electron microscopy. X-ray powder diffractometry on representative powder samples were used to study the mineralogy and geochemistry of the samples. Microprobe analyses were also performed on the representative samples. Finally the samples were submitted for 40Ar/39Ar geochronology. In this supergene enrichment zone carbonates are leached (associated with an increase in porosity) and Mn2+/Mn3+ -bearing minerals (kutnahorite, Mn-calcite an braunite) are altered to supergene Mn4+-bearing mineral phases (todorokite and manganomelane) and minor quartz. This process upgrades ore from 38 wt% Mn to ore with more than 40 wt% Mn. Element fluxes, enrichment and depletion of major and trace elements were quantified by mass balance calculations. Na2O, K2O, Sr, Ba, Zn and H2O were enriched, while Mn3O4, Fe2O3, CaO, MgO, P, B and CO2 were leached from the ore during supergene alteration. Results of this study suggest that the development of Post African I erosional surface may have taken place 45 Ma ago. The bottom of the weathering profile gives a well-defined peak at ca. 5 Ma that may possible coincide with the development of Post African II erosional surface. The major characteristics of the alteration process of the unaltered Mamatwan-type ore to supergene altered braunite lutite can be summarized as follow: • Leaching of Mn carbonates and Mn2+/Mn3+-oxides. • Formation of Mn4+-oxyhydroxides and quartz. • Decrease in relative density of the ore. • Increase in porosity of the ore. • Leaching of Mn3O4, Fe2O3, CaO, MgO, P, B, CO2. • Enrichment of Na2O, K2O, Sr, Ba, Zn, H2O. Chemical weathering processes along the Cenozoic Kalahari unconformity appear to have affected the manganiferous lithologies of the Hotazel Formation from 45 Ma onwards to 5 Ma. The weathering front processes very slowly through the Mn-rich braunite lutite (<10m in 40 Ma; <0.25m/Ma); producing a very uniform and microcrystalline supergene mineral assemblage with distinct characteristics.

M.A. / Hematized iron formation known as the Manganore iron formation is slumped into sinkhole structures in the Campbellrand Subgroup, Transvaal Supergroup, on the Maremane dome. These iron deposits are underlain by manganiferous breccias known as the Wolhaarkop Breccia. Known iron and manganese deposits of this type occur in an arc from Sishen in the north to Postmasburg in the south. The area is not being mined for manganese at the moment due to the relatively high grade of the Kalahari manganese field situated to the north of this area. The iron deposits, though, are some of the richest in the world. The aim is to establish the mode of origin for the Wolhaarkop Breccia. The Wolhaarkop Breccia is interpreted as being a residual ancient manganese wad from a karst environment in manganese rich dolostones of the Campbellrand Subgroup. This siliceous breccia contains authigenic megaquartz and angular poorly sorted clasts of chalcedony and quartz, set in a braunite-hematite matrix. Fluid inclusions in the authigenic quartz of the Wolhaarkop Breccia have been studied to establish the source of the fluid responsible for quartz precipitation in the Wolhaarkop Breccia, and indirectly, for the formation of the Wolhaarkop Breccia. Thermometric data was used to determine the maximum possible pT and depth conditions under which the quartz might have been precipitated. Fluid chemistry was determined using the bulk crush-leach method to shed some light on the fluid origin. It was established that the fluid responsible for chert recrystallization and precipitation of authigenic quartz and chalcedony had a meteoric source. Considering the results of the above-mentioned analysis, it was concluded that the iron and manganese deposits were formed during a cycle of uplift followed by subsidence. During the period of uplift, erosion in a karst environment and enrichment of iron formation in a supergene environment concentrated manganese as a manganese wad, and iron as a residual iron-oxide laterite. Meteoric water was the main fluid present during this period. Later, during a stage of subsidence, the Wolhaarkop Breccia underwent diagenesis and later lower greenschist-facies metamorphism. During a final stage of uplift the deposit was exposed to the atmosphere again, the dolostones were weathered away and the residual Manganore iron formation and Wolhaarkop Breccia were exposed to supergene alteration.

O manganês é um elemento traço essencial, porém existe uma preocupação com seus potenciais efeitos neurotóxicos associados à exposição a níveis excessivos, podendo provocar uma síndrome conhecida como manganismo, cujos sintomas são semelhantes aos da doença de Parkinson. A maioria dos trabalhos envolvendo manganês usa espécies de Mn(II), mas sabe-se que Mn(III) é acumulado em maior quantidade no cérebro. Nesse sentido, foi feito um estudo dos danos oxidativos e de toxicidade provocados por três complexos de Mn(III): citrato, pirofosfato e salicilenodiamina (respectivamente MnCit, MnPPi e EUK8). Para tanto, as três espécies foram sintetizadas e caracterizadas por métodos espectroscópicos. Em seguida foram determinadas suas capacidades pró-oxidantes sobre os seguintes marcadores: dihidrorodamina (DHR), tirosina (Tyr), albumina (BSA) e dopamina (DA). Finalmente, seu efeito sobre células cerebelares e da cepa HeLa estressada por meio de irradiação UV também foi avaliado, e foi usado ascorbato na tentativa de tratar o dano sobre células HeLa. O teste com a DHR também foi feito em presença de H2O2 e ascorbato. A capacidade pró-oxidante testada por fluorescência da DHR sugere que o ascorbato atua como anti-oxidante. Além disso, MnCit e MnPPi (mas não EUK8), quando na presença de H2O2, são menos oxidantes. O mesmo comportamento foi percebido nas medidas de fluorescência de Tyr. A carbonilação da BSA, verificada pela absorbância do seu marcador (DNPH), seria indício de capacidade oxidante dos complexos, mas não percebeu-se variação significativa de grupos C=O na proteína após tratamento com espécies de Mn(III), mesmo em amostras com H2O2, embora notem-se as mesmas tendências apresentadas pelos complexos com DHR e Tyr. Estudos de oxidação de DA por luminescência tiveram resultados inconclusivos, mas dados mais concretos em testes com medidas de absorbância de soluções de DA e fluorescência de misturas de DA com DHR indicaram que DA é preferencialmente oxidada por todos os compostos. A viabilidade celular de culturas de células neuronais granulares (CGC) mostrou pouca diferença entre as toxicidades dos compostos, mas verifica-se uma relação inversamente proporcional entre as toxicidades e lipofilicidades dos complexos. O mesmo não ocorre nos experimentos com HeLa, cuja viabilidade foi avaliada por contagem de colônias após fixação e coloração das células, pois nesse caso o EUK8 se mostrou o mais tóxico dos três. Além disso, ao contrário do observado com a DHR, o ascorbato teve ação pró-oxidante, e, aparentemente, houve um efeito sinérgico negativo entre os complexos e a radiação UV. Tratamento com o quelante p-aminossalicilato só foi eficaz na recuperação das culturas para amostras não irradiadas. / Manganese is an essential trace element, however there is considerable concern regarding its neurological effects when in excess, giving rise to a condition termed manganism which is characterized by Parkinson disease-like symptoms. Most evaluations of manganese toxicity use poorly defined Mn(II) species, although Mn(III) is known to accumulate preferentially in the brain. Therefore, in this work we proposed a study of oxidative damage and citotoxicity of Mn(III) derivatives of citrate, pyrophosphate and salycilenediamine (respectively, MnCit, MnPPi and EUK8). The species were synthesized and characterized by spectroscopic methods. Their pro-oxidant abilities were assessed over markers of oxidant activity dihydrorhodamine (DHR), tyrosine (Tyr), albumin (BSA) and dopamine (DA). In addition, their effect over granular cerebral cells (CGC) and HeLa cells stressed by ultraviolet irradiation was studied, and treated with ascorbate. Tests with DHR were repeated treating the samples with H2O2 and ascorbate. Pro-oxidant ability tested by both DHR and Tyr fluorescence suggest that ascorbate is antioxidant towards Mn(III)-induced oxidative damage. MnCit and MnPPi (but not EUK8), when in presence of peroxide, are less oxidants. An analogous trend was observed for BSA, although without statistical significance. Evaluation of DA formation by luminescence was inconclusive, but competition studies of DA+DHR mixtures indicated that DA is preferentially oxidized by all the complexes. To CGC, little difference was observed for the toxicities of the complexes. An inverse relationship of toxicity and lipophilicity has been observed. However this was not observed for HeLa cells, to which EUK8 was more toxic. In addition, and in opposition to the DHR solution study, ascorbate was found to be pro-oxidant. A negative synergic effect was observed between complex doses and irradiation. Treatment of the cells with paraaminosalicylate was beneficial only for non-irradiated cells.

O objetivo deste trabalho foi determinar a influência do ferro e do manganês em uma liga de alumínio com 9% de silício (% em peso). Para isto, foram elaboradas duas famílias de liga Al-9%Si: uma com os teores de 0,1%, 0,4%, 0,8% e 1,2% de Fe e uma segunda liga de Al-9%Si-0,8%Fe com teores de 0,1%, 0,4% e 0,7% de Mn. Para a realização deste estudo, foram produzidos corpos de prova de tração fundidos em coquilha, segundo a norma ASTM B108. Os corpos de prova obtidos foram tracionados para avaliação das propriedades mecânicas, em seguida, foram submetidos a uma análise microestrutural por microscopia óptica (MO) e eletrônica de varredura (MEV). As superfícies de fratura dos corpos de prova tracionados foram também observadas por MEV com a finalidade de comparar o efeito das adições de Fe e Mn. O efeito da adição crescente de Fe na liga Al-9%Si foi observado no ensaio de tração que mostrou queda tanto nos limites de resistência e de escoamento como no alongamento, decorrentes da formação da fase &beta;-Al5FeSi que apresentou morfologia em plaquetas, interrompendo a continuidade da matriz de alumínio. Para teores abaixo de 0,4% de Fe, ocorreu um ligeiro aumento da resistência mecânica que pode ser atribuído à formação da fase &alpha;-Al8Fe2Si, que apresentou morfologia tipo escrita chinesa, que não interrompe a continuidade da matriz. Com adição de teores crescentes de Mn na liga Al-9%Si-0,8%Fe ocorreu uma elevação do limite de resistência e do alongamento, mas uma queda do limite de escoamento, quando comparados com a mesma liga sem adição de Mn. Conclui-se que esse comportamento pode ser atribuído a mudança de morfologia do intermetálico de plaquetas para escrita chinesa que intercala a matriz dúctil com a fase frágil, devido a adição do Mn. / This study aims to determine the influence of iron and manganese in an aluminum alloy with 9% silicon (% by weight). Were prepared two families of alloy Al-9%Si: one with the content of 0.1%, 0.4%, 0.8% and 1.2% Fe and a second alloy of Al-9% Si-0,8%Fe content of 0.1%, 0.4% and 0.7% Mn. For this study, tensile specimens were produced in permanent mold casting according to ASTM B108. The specimens obtained were pulled for quantitative evaluation of the mechanical properties and were subjected to a qualitative metallographic evaluation. Qualitative analysis of the bodies of tensile fracture test was conducted in order to compare the effect of additions of Fe and Mn. The effect of incremental addition of Fe in the alloy Al-9% Si was observed in the tensile test that showed a decrease in both the tensile and elongation flow as resulting from the formation of &beta;-Al5FeSi phase platelet morphology showed that interrupting the continuity of aluminum matrix. To levels below 0.4% Fe, there was a slight increase in strength can be attributed to the formation of &alpha;-Al8Fe2Si phase morphology presented in chinese script that does not interrupt the continuity of the matrix. With addition of increasing concentrations of Mn in the alloy Al-9% Si-0, 8% Fe was an increase in the tensile strength and elongation but fall of yield stress when compared to the same alloy without Mn addition. We conclude that this behavior can be attributed to a change in morphology of the intermetallic platelets to chinese writing interspersing the ductile matrix with brittle phase due to the addition of Mn.

Neste trabalho, buscou-se verificar a possibilidade de, com a utilização do processo eletrolítico, se obter dióxido de manganês a partir da reciclagem de pilhas e baterias exauridas, visto a grande demanda por produtos que utilizam esse mineral. Utilizou-se, para tanto, uma solução eletrolítica que continha os íons metálicos: Ca (270mg/L), Ni (3000 mg/L), Co (630 mg/L), Mn(115300 mg/L), Ti (400 mg/L) e Pb (20 mg/L) em meio de ácido sulfúrico, sintetizada, seguindo-se dados de pesquisa anterior. A produção do dióxido de manganês eletrolítico (DME) foi realizada galvanostaticamente, com a utilização de uma fonte estabilizada que monitorava o potencial do eletrodo de trabalho. Utilizaram-se, preliminarmente, um eletrodo de trabalho de chumbo e dois contra-eletrodos de grafite, à temperatura de 98 ºC (±2ºC) e densidade de corrente de 1,69 A.dm-2. Após a verificação preliminar da possibilidade de obtenção do DME, repetiu-se sistematicamente o processo, aplicando-se variações de densidade de corrente (0,61 A.dm-2 a 1,93 A.dm-2) e de pH (0,00 a 1,20). O material obtido com essas variações foi analisado através dos processos de espectrometria de fluorescência de raios-X, difração de raios-X, área superficial específica pelo método BET e microscopia eletrônica de varredura (MEV). Os melhores resultados quanto a eficiência de corrente, pureza e área superficial se obtiveram com densidade de corrente entre 1,02 A.dm-2 e 1,39 A.dm-2 e com pH 0,50. Em todos os experimentos, como comprova a análise de difração de raios-X, foi constatada a obtenção da variedade alotrópica -MnO2, uma das formas viáveis para utilização na fabricação de pilhas. Os resultados apontam para a viabilidade desse processo de reciclagem como alternativa diante da escassez de fontes naturais de MnO2 com características compatíveis com a aplicação em questão e como forma de diminuição da poluição ambiental causada pelo descarte de pilhas e baterias. / Considering the growing demand for products containing manganese in its composition, this work seeks to verify the possibility of using depleted batteries as a source of manganese applying the electrolytic process. It was used an electrolyte solution containing the metal ions: Ca (270mg / L), Ni (3000 mg / L), Co (630 mg / L), Mn (115300 mg / L), Ti (400 mg / L) and Pb (20 mg / L) in concentrated sulfuric acid, following data from previous research. The production of electrolytic manganese dioxide (EMD) was performed through galvanization using a stabilized source that monitored the potential of the working electrode. It was preliminary used an electrode of lead and two counter electrodes of graphite at a temperature of 98ºC (± 2ºC) and current density of 1.69A.dm-2. After preliminary verifying the possibility of obtaining electrolytic manganese dioxide (EMD), the process was systematically repeated, applying different current density (0.61A.dm-2 to 2.51A.dm-2) and pH (0.00 to 1.20). The material obtained at these variations was analyzed through the process of X-ray fluorescence spectrometry, X-ray diffraction, specific surface area (BET) and scanning electron microscopy (SEM). The best values referring to current efficiency, level of purity and specific surface area were obtained with the current density ranging between 1.02 A.dm-2 and 1.39 A.dm-2, and pH 0.50. In any of the tested electrolysis conditions the -MnO2 structure was obtained as evidenced by the diffraction of X-rays analysis. The results indicate the feasibility of this recycling process as an alternative before shortage of natural sources of MnO2 and as a means of reducing environmental pollution caused by the disposal of batteries.

O manganês é um elemento traço essencial, porém existe uma preocupação com seus potenciais efeitos neurotóxicos associados à exposição a níveis excessivos, podendo provocar uma síndrome conhecida como manganismo, cujos sintomas são semelhantes aos da doença de Parkinson. A maioria dos trabalhos envolvendo manganês usa espécies de Mn(II), mas sabe-se que Mn(III) é acumulado em maior quantidade no cérebro. Nesse sentido, foi feito um estudo dos danos oxidativos e de toxicidade provocados por três complexos de Mn(III): citrato, pirofosfato e salicilenodiamina (respectivamente MnCit, MnPPi e EUK8). Para tanto, as três espécies foram sintetizadas e caracterizadas por métodos espectroscópicos. Em seguida foram determinadas suas capacidades pró-oxidantes sobre os seguintes marcadores: dihidrorodamina (DHR), tirosina (Tyr), albumina (BSA) e dopamina (DA). Finalmente, seu efeito sobre células cerebelares e da cepa HeLa estressada por meio de irradiação UV também foi avaliado, e foi usado ascorbato na tentativa de tratar o dano sobre células HeLa. O teste com a DHR também foi feito em presença de H2O2 e ascorbato. A capacidade pró-oxidante testada por fluorescência da DHR sugere que o ascorbato atua como anti-oxidante. Além disso, MnCit e MnPPi (mas não EUK8), quando na presença de H2O2, são menos oxidantes. O mesmo comportamento foi percebido nas medidas de fluorescência de Tyr. A carbonilação da BSA, verificada pela absorbância do seu marcador (DNPH), seria indício de capacidade oxidante dos complexos, mas não percebeu-se variação significativa de grupos C=O na proteína após tratamento com espécies de Mn(III), mesmo em amostras com H2O2, embora notem-se as mesmas tendências apresentadas pelos complexos com DHR e Tyr. Estudos de oxidação de DA por luminescência tiveram resultados inconclusivos, mas dados mais concretos em testes com medidas de absorbância de soluções de DA e fluorescência de misturas de DA com DHR indicaram que DA é preferencialmente oxidada por todos os compostos. A viabilidade celular de culturas de células neuronais granulares (CGC) mostrou pouca diferença entre as toxicidades dos compostos, mas verifica-se uma relação inversamente proporcional entre as toxicidades e lipofilicidades dos complexos. O mesmo não ocorre nos experimentos com HeLa, cuja viabilidade foi avaliada por contagem de colônias após fixação e coloração das células, pois nesse caso o EUK8 se mostrou o mais tóxico dos três. Além disso, ao contrário do observado com a DHR, o ascorbato teve ação pró-oxidante, e, aparentemente, houve um efeito sinérgico negativo entre os complexos e a radiação UV. Tratamento com o quelante p-aminossalicilato só foi eficaz na recuperação das culturas para amostras não irradiadas. / Manganese is an essential trace element, however there is considerable concern regarding its neurological effects when in excess, giving rise to a condition termed manganism which is characterized by Parkinson disease-like symptoms. Most evaluations of manganese toxicity use poorly defined Mn(II) species, although Mn(III) is known to accumulate preferentially in the brain. Therefore, in this work we proposed a study of oxidative damage and citotoxicity of Mn(III) derivatives of citrate, pyrophosphate and salycilenediamine (respectively, MnCit, MnPPi and EUK8). The species were synthesized and characterized by spectroscopic methods. Their pro-oxidant abilities were assessed over markers of oxidant activity dihydrorhodamine (DHR), tyrosine (Tyr), albumin (BSA) and dopamine (DA). In addition, their effect over granular cerebral cells (CGC) and HeLa cells stressed by ultraviolet irradiation was studied, and treated with ascorbate. Tests with DHR were repeated treating the samples with H2O2 and ascorbate. Pro-oxidant ability tested by both DHR and Tyr fluorescence suggest that ascorbate is antioxidant towards Mn(III)-induced oxidative damage. MnCit and MnPPi (but not EUK8), when in presence of peroxide, are less oxidants. An analogous trend was observed for BSA, although without statistical significance. Evaluation of DA formation by luminescence was inconclusive, but competition studies of DA+DHR mixtures indicated that DA is preferentially oxidized by all the complexes. To CGC, little difference was observed for the toxicities of the complexes. An inverse relationship of toxicity and lipophilicity has been observed. However this was not observed for HeLa cells, to which EUK8 was more toxic. In addition, and in opposition to the DHR solution study, ascorbate was found to be pro-oxidant. A negative synergic effect was observed between complex doses and irradiation. Treatment of the cells with paraaminosalicylate was beneficial only for non-irradiated cells.

This thesis describes the synthesis, characterisation and reactivity of new manganese and rhenium(I) NHC complexes, which have been investigated both thermally and photochemically and the results contrasted with existing phosphine analogues in the literature. Cp’Mn(CO)2(NHC) (NHC = IEt2Me2 1, IMes 2, IiPr2Me2 3 and IPr 4) were synthesised and investigated by TRIR spectroscopy. Loss of CO was observed after 355 nm irradiation to form agostically stabilised intermediates, which reformed the parent species by recombination with CO on the nanosecond timescale. Loss of NHC was not observed, in contrast to Cp’Mn(CO)2(PPh3) which lost both CO and PPh3 upon photolysis. [Re(NHC)(Bpy)(CO)3]BAr4F (NHC = IEt2Me2 5, IMes 6) were synthesised and investigated by TRIR spectroscopy and UV/Vis absorption and emission spectrometry. Inclusion of an NHC altered the excited state manifold of the complexes, favouring population of the 3MLCT over the 3IL excited state. The lowest energy excited state for both 5 and 6 proved to be a 3MLCT excited state at 298 and 77 K. In contrast, [Re(PPh3)(Bpy)(CO)3]BAr4F exhibited 3MLCT at 298 K, but 3IL at 77 K. A series of complexes, M(NHC)(CO)4X and M(NHC)2(CO)3X (M = Re, X = Cl; M = Mn, X = Br) formed upon reaction of the corresponding M(CO)5X species and free NHC. The substitution pattern was dictated by the steric bulk of the NHC. Generation of the corresponding cations by halide abstraction was investigated. M(NHC)2(CO)3X was found to form agostic stabilised species upon halide abstraction by NaBAr4F in CH2Cl2. Under the same conditions, Re(IPr)(CO)4Cl was found to form the dichloromethane complex, [Re(IPr)(CO)4(η1-CH2Cl2)]BAr4F. In C6H5F solution under an atmosphere of dihydrogen, the CH2Cl2 ligand could be displaced by H2 to form the dihydrogen species, [Re(IPr)(CO)4(H2)]BAr4F.

Lai Chun Hei Gary = 錳氧化物-鈮摻雜之鈦酸鍶異構結的輸運特性 / 黎鎮禧. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2005. / Includes bibliographical references. / Text in English; abstracts in English and Chinese. / Lai Chun Hei Gary = Meng yang hua wu-ni shan za zhi tai suan si yi gou jie de shu yun te xing / Li Zhenxi. / Acknowledgement --- p.i / Abstract --- p.ii / 論文摘要 --- p.iv / Table of contents --- p.vi / List of Figures --- p.x / List of Tables --- p.xv / Chapter Chapter 1 --- Introduction / Chapter 1.1 --- Introduction to perovskite manganites and niobium doped strontium titanate --- p.1-1 / Chapter 1.1.1 --- Structure and properties of perovskite manganites --- p.1-1 / Chapter 1.1.2 --- Structure and properties of niobium doped strontium titanate --- p.1-4 / Chapter 1.1.3 --- Phase transition in perovskite manganites --- p.1-9 / Chapter 1.1.4 --- Charge ordering and small polaron theory in PCMO --- p.1-15 / Chapter 1.1.5 --- Colossal Magnetoresistance (CMR) in perovskite manganites --- p.1-19 / Chapter 1.16 --- Review of semiconducting junction between perovskite manganites and niobium doped strontium titanate --- p.1-23 / Chapter 1.2 --- Research motivation --- p.1-28 / Chapter 1.3 --- Scope of this thesis --- p.1-29 / References --- p.1-31 / Chapter Chapter 2 --- Experimental details / Chapter 2.1 --- Thin film deposition --- p.2-1 / Chapter 2.1.1 --- Facing-target sputtering --- p.2-1 / Chapter 2.1.2 --- Vacuum system --- p.2-3 / Chapter 2.1.3 --- Fabrication and characterization of manganites targets --- p.2-4 / Chapter 2.1.4 --- Substrate --- p.2-7 / Chapter 2.1.5 --- Deposition procedure --- p.2-8 / Chapter 2.1.6 --- Silver electrode coating apparatus --- p.2-10 / Chapter 2.2 --- Annealing systems --- p.2-12 / Chapter 2.2.1 --- Vacuum annealing system --- p.2-12 / Chapter 2.2.2 --- Oxygen annealing system --- p.2-14 / Chapter 2.3 --- Characterization --- p.2-16 / Chapter 2.3.1 --- Profilometer --- p.2-16 / Chapter 2.3.2 --- X-ray diffractometer --- p.2-16 / Chapter 2.3.3 --- Resistance measurement system --- p.2-18 / Chapter 2.3.4 --- Current-voltage characteristics measurement system --- p.2-20 / References --- p.2-23 / Chapter Chapter 3 --- Epitaxial LCMO/STON heterojunction / Chapter 3.1 --- Four point and two point I-V measurement --- p.3-1 / Chapter 3.2 --- Magnetic phase transition of LCMO revealed by four point I-V measurement of LCMO/STON heteroj unction --- p.3-8 / Chapter 3.3 --- Oxygen annealing effect on LCMO/STON heteroj unction --- p.3-14 / Chapter 3.4 --- Positive colossal Magnetoresistance in LCMO/STON heteroj unction --- p.3-16 / References --- p.3-23 / Chapter Chapter 4 --- Epitaxial PCMO/STON heterojunction / Chapter 4.1 --- Ohmic contact for PCMO thin films --- p.4-1 / Chapter 4.2 --- PCMO charge ordering and magnetic phase transition --- p.4-9 / Chapter 4.3 --- Four point I-V measurement of PCMO/STON heterojunction --- p.4-14 / References --- p.4-16 / Chapter Chapter 5 --- Epitaxial LCMO/PCMO/STON junction / Chapter 5.1 --- Tunneling junction fabrication --- p.5-1 / Chapter 5.2 --- Structural characterizations --- p.5-2 / Chapter 5.3 --- PCMO magnetic phase transition revealed by I-V measurement of LCMO/PCMO/STON tunneling junction --- p.5-3 / Chapter 5.4 --- Energy band structure of perovskite manganites --- p.5-11 / Chapter 5.4.1 --- Introduction to energy band of perovskite manganites and STON --- p.5-11 / Chapter 5.4.2 --- Temperature dependent band structure of LCMO explained by diffusion voltage of LCMO/STON heterojunction --- p.5-18 / References --- p.5-22 / Chapter Chapter 6 --- Conclusions / Chapter 6.1 --- Conclusion --- p.6-1 / Chapter 6.2 --- Future outlook --- p.6-3