Chronic exposure to manganese (Mn) causes the neurodegenerative movement disorder, manganism. A mouse model was developed to elucidate mechanisms involved in the etiology and progression of injury. Twelve-week old female C57Bl/6J mice were exposed to MnCl2 (100 mg/kg/day) by oral gavage daily for 8 weeks. After the experiment striatal dopamine (DA) content was decreased with the manifestation of hypoactivity. A distinct population of neurons was vulnerable to the effects of Mn, including enkephalin (ENK)-positive projection neurons, interneurons expressing neuronal nitric oxide synthetase (nNOS/NOS1), and choline acetyltransferase (ChAT)-expressing interneurons. Activation of surrounding astrocytes occurred with expression of inducible nitric oxide synthase (iNOS/NOS2) and production of nitric oxide (NO)/peroxynitrite (ONOO-). Activated astrocytes were detected primarily near the microvasculature in both the striatum and globus pallidus (GP). It is suggested that Mn exposure may damage the blood-brain barrier (BBB) and induce astrocytosis and NOS2 expression, subsequent NO production may cause the death of adjacent neurons. This hypothesis was also tested in an in vitro co-culture model. Differentiated pheochromocytoma cells (PC12 cells) were co-cultured with primary astrocytes and exposed to Mn and inflammatory cytokines. Mn and cytokines induced NOS2 expression and NO production in astrocytes, which correlated with apoptosis of PC12 cells. Apoptosis of PC12 cells was prevented by overexpression of a phosphorylation-deficient mutant of IκBα that inhibited NOS2 expression in astrocytes. It is concluded that Mn-and cytokine-dependent apoptosis in PC12 cells requires astrocyte-derived NO and nuclear factor κB (NF-κB)-dependent expression of NOS2. To explore possible means of interdicting this inflammatory process in astrocytes, a noval pharmacologic ligands of the peroxisome proliferator-activated receptor gamma (PPARγ) agonist, 1,1-Bis(3'-indolyl)-1-(p-trifluoromethylphenyl) methane (DIM-C-pPhCF3) were used in the same co-culture system. DIM-C-pPhCF3 protected PC12 cells from apoptosis through inhibition of NOS2 expression in astrocytes after Mn and cytokines exposure. By contrast, the PPARγ antagonist, 2-chloro-5-nitrobenzanilide (GW9622), had the opposite effect, increasing both NO production in astrocytes and neuronal injury. It is concluded that PPARγ is involved in the regulation of NOS2 expression in astrocytes and that agonists of PPARγ may represent a potential treatment method for Mn neurotoxicity.

Chronic exposure to manganese (Mn) causes the neurodegenerative movement disorder, manganism. A mouse model was developed to elucidate mechanisms involved in the etiology and progression of injury. Twelve-week old female C57Bl/6J mice were exposed to MnCl2 (100 mg/kg/day) by oral gavage daily for 8 weeks. After the experiment striatal dopamine (DA) content was decreased with the manifestation of hypoactivity. A distinct population of neurons was vulnerable to the effects of Mn, including enkephalin (ENK)-positive projection neurons, interneurons expressing neuronal nitric oxide synthetase (nNOS/NOS1), and choline acetyltransferase (ChAT)-expressing interneurons. Activation of surrounding astrocytes occurred with expression of inducible nitric oxide synthase (iNOS/NOS2) and production of nitric oxide (NO)/peroxynitrite (ONOO-). Activated astrocytes were detected primarily near the microvasculature in both the striatum and globus pallidus (GP). It is suggested that Mn exposure may damage the blood-brain barrier (BBB) and induce astrocytosis and NOS2 expression, subsequent NO production may cause the death of adjacent neurons. This hypothesis was also tested in an in vitro co-culture model. Differentiated pheochromocytoma cells (PC12 cells) were co-cultured with primary astrocytes and exposed to Mn and inflammatory cytokines. Mn and cytokines induced NOS2 expression and NO production in astrocytes, which correlated with apoptosis of PC12 cells. Apoptosis of PC12 cells was prevented by overexpression of a phosphorylation-deficient mutant of IκBα that inhibited NOS2 expression in astrocytes. It is concluded that Mn-and cytokine-dependent apoptosis in PC12 cells requires astrocyte-derived NO and nuclear factor κB (NF-κB)-dependent expression of NOS2. To explore possible means of interdicting this inflammatory process in astrocytes, a noval pharmacologic ligands of the peroxisome proliferator-activated receptor gamma (PPARγ) agonist, 1,1-Bis(3'-indolyl)-1-(p-trifluoromethylphenyl) methane (DIM-C-pPhCF3) were used in the same co-culture system. DIM-C-pPhCF3 protected PC12 cells from apoptosis through inhibition of NOS2 expression in astrocytes after Mn and cytokines exposure. By contrast, the PPARγ antagonist, 2-chloro-5-nitrobenzanilide (GW9622), had the opposite effect, increasing both NO production in astrocytes and neuronal injury. It is concluded that PPARγ is involved in the regulation of NOS2 expression in astrocytes and that agonists of PPARγ may represent a potential treatment method for Mn neurotoxicity.

Mémoire numérisé par la Direction des bibliothèques de l'Université de Montréal.

The research of Fe-Mn-Al-C K phase

Metal-RNA interactions are important to neutralize the negative charge and aid in correctly folding the RNA. Spectroscopically active metal ions, especially Mn2+, have been used to probe the type of interaction the metal has with RNA. In previous studies, the hammerhead ribozyme, an RNA motif that catalyzes a site-specific phosphodiester bond cleavage reaction, was determined by room temperature EPR (electron paramagnetic resonance) studies to have a set of tightly and weakly bound metal ions. Under high salt concentrations, the hammerhead was found to bind a single Mn2+ ion with high affinity and with a characteristic low temperature EPR signal. Using site specific 15N labeling of a guanine residue in conjunction with ESEEM (electron spin echo envelope modulation) spectroscopy, the high affinity Mn2+ ion was conclusively determined coordinated to G10.1 of the proposed A9/G10.1 site with four water molecules coordinated to the Mn2+ ion. EPR power saturation studies determined that under low salt conditions the hammerhead coordinates up to four Mn2+ ions in relatively close proximity compared to an RNA duplex. EXAFS (extended X-ray absorption fine structure) spectroscopy was used to determine that a Cd2+ ion coordinates to both the Rp and Sp sulfur atoms of a phosphorothioate modification at the A9 phosphate of the hammerhead. Previous EXAFS results for the Mn2+ substituted A9 phosphorothioate suggested that the Mn2+ ion coordinates to the oxygen atom for both isomers. Molecular modeling suggested that the A9/G10.1 metal site will twist the phosphate group in order to accommodate this coordination. A Mn-GMP and Mn-phosphate model complexes were prepared and characterized by EXAFS to assign the origin of the features observed for the hammerhead sample. A series of RNA sequences with internal loops containing the sheared G-A metal ion binding motif showed greater thermal stabilization of the RNA structure in the presence of Mn2+ ions compared to sequences without the motif. The EPR binding isotherms also showed a set of moderately tight metal ion interaction while circular dichroism spectroscopy was used to investigate structural differences between the sequences. These results suggest a mostly electrostatic, not structural role, for the Mn2+ ion interactions with these sequences.

No description available.

Nickel-manganese-cobalt oxide (NMC) cathode materials have been applied in most Li-ion batteries, but there are nevertheless some concerns regarding the stability of this material. High voltage and high temperature during charging have been shown to accelerate the dissolution of NMC due to the release of more acidic components because of rapid electrolyte decomposition. Mn-contaminants (Mn2+) are hypothesized to diminish the diffusion coefficient of Li+ in the electrolyte attributed to the competitive interaction between Mn2+ ions and Li+ ions. With characterizations including 7Li and 1H pulsed field-gradient nuclear magnetic resonance (PFG-NMR) spectroscopy, we demonstrated the Mn (II)-contaminants effect on diffusion coefficient on Li+ dynamics. Under the influence of deliberate manganese salt-additive to the electrolyte, the coin cell shows a capacity fading and unstable charging behavior. The PFG-NMR measurements also validated our hypotheses, as the results showing that Mn-containment causes decrease ~15% in the diffusion coefficient on Li-self diffusion. The activation energy for lithium-ion transport over the temperature range of (273 K - 303 K), was not changed by the presence of the Mn-contaminant electrolyte, which indicates the Mn (II) does not affect the Li-ion transport mechanism. The relative test also includes comparisons with other contamination, such as iron contamination from stain-less steels spacers and copper contamination from the current collector. Additionally, the lithium self-diffusion coefficient was tested before and after charging using a full battery configuration. In electrolytes containing manganese contaminants, a more significant decrease in the diffusion coefficient was observed after charging. Ideally, operando experiments can be used to observe the impact of manganese ions on the SEI. By combining both types of experiments, a closer approximation to the actual application conditions of market-used batteries can be achieved. / Thesis / Master of Science (MSc) / The increasing maturity of lithium battery technology has also promoted the advancement of the electric vehicle manufacturing industry. As an excellent new energy material, the application and development of lithium batteries will be the main trend in the future. However, while improving battery capacity and energy density, lithium batteries also face many challenges. The entire thesis work discusses how electrolyte degradation at high temperatures and high voltages accelerates the dissolution of transition metal manganese ions in NMC materials. The dissolution of manganese ions into the electrolyte creates a competitive effect with lithium ions, thereby reducing the performance of lithium batteries. Here, NMR technology was used to measure the negative effect of manganese ions on the self-diffusion coefficient of lithium ions in the electrolyte. Additionally, a set of operando experiments conducted at different discharge rates demonstrated the changes in mossy lithium and the solid electrolyte interface during the charge and discharge phases caused by pulse discharge. This also proved that such experimental designs can track the impact of manganese ions on the solid electrolyte interface and test the dissolution behavior and impact of manganese ions under different charge and discharge rates.

A castable alloy, i.e., one that flows easily to fill the entire mold cavity and also has resistance to hot tearing during solidification, must invariably contain a sufficient amount of a eutectic structure. For this reason, most traditional aluminum casting alloys contain silicon because the aluminum-silicon eutectic imparts to the alloy excellent casting characteristics. However, the solidus temperature in the Al-Si system does not exceed 577°C, and the major alloying elements (i.e., zinc, magnesium, and copper) used with silicon in these alloys further lower the solidus temperature. Also, these elements have high diffusivity in aluminum and so, while they enhance the room temperature strength of the alloy, they are not useful at elevated temperatures. Considering nickel-base super alloys, whose mechanical properties are retained up to temperatures that approach 75% of their melting point, it is conceivable that castable aluminum alloys can be developed on the same basis so that they are useful at temperatures approaching 350C. A castable aluminum alloy intended for high temperature applications must contain a eutectic structure that is stable at temperatures higher than 600°C, and must contain second phase precipitate particles that are thermodynamically stable at the service temperature. Transition metal trialuminides with the general chemical formula AlxTMy in which TM is a transition metal, are excellent candidates for both the eutectic structure and the precipitate particles. In this research, the use of transition metals in the constitution of aluminum casting alloys is investigated with emphasis on the morphology, crystallography, and mechanisms of formation of the various phases.

Ni-Co-Mn-In system is a new type of magnetic shape memory alloys (MSMAs) where the first order structural and magnetic phase transitions overlap. These materials can generate large reversible shape changes due to magnetic-field-induced martensitic transformation, and exhibit magneto-caloric effect and magnetoresistance. Ni-Co-Mn-Sn alloys are inexpensive alternatives of the Ni-Co-Mn-In alloys. In both materials, austenite has higher magnetization levels than martensite. Fe-Mn-Ga is another MSMA system, however, whose magnetization trend is opposite to those of the Ni-Co-Mn-X (In-Sn) systems upon phase transformation. The MSMAs have attracted great interest in recent years, and their magnetic and thermo-mechanical properties need to be further investigated. In the present study, the effects of indium concentration, cooling, and annealing on martensitic transformation and magnetic response of single crystalline Ni-Co-Mn-In alloys were investigated. Increasing indium content reduced the martensitic transformation start (Ms) temperature, while increasing temperature hysteresis and saturation magnetization. Increasing annealing temperature led to an increase in the Ms temperature whereas annealing at 400 degrees C and 500 degrees C led to the kinetic arrest of austenite. Cooling after solution heat treatment also notably affected the transformation temperatures and magnetization response. While the transformation temperatures increased in the oil quenched samples compared to those in the water quenched samples, these temperatures decreased in furnace cooled samples due to the kinetic arrest. The possible reasons for the kinetic arrest are: atomic order changes, or precipitate formation. Shape memory and superelastic response, and magnetic field-induced shape recovery behavior of sintered Ni43Co7Mn39Sn11 polycrystalline alloys were also examined. The microstructural analysis showed the existence of small pores, which seem to increase the damage tolerance of the sintered polycrystalline samples. The recoverable transformation strain, irrecoverable strain and transformation temperature hysteresis increased with stress upon cooling under stress. Moreover, magnetic-field-induced strain due to the field-induced phase transformation was confirmed to be 0.6% at 319K. Almost perfect superelastic response was obtained at 343K. A magnetic entropy change of 22 J kg-1 K-1 were determined at 219K from magneto-caloric effect measurements which were conducted on annealed Ni43Co7Mn39Sn11 ribbons. Magnetic characteristics and martensitic transformation behavior of polycrystalline Fe-Mn-Ga alloys were also examined. Cast alloys at various compositions were undergone homogenization heat treatments. It was verified by magnetization measurements that the alloys heat treated at 1050 degrees C shows martensitic transformation. The heat treatment time was determined to be 1 day or 1 week depending on the compositions.

Devido aos problemas de deficiência de Mn relatados em soja Roundup Ready, à tendência de aumento de cultivo da soja Intacta RR2 PRO® no Brasil e à possibilidade de aumento de rendimentos desta soja relacionado à resposta a adubação foliar com Mn, realizou-se o presente trabalho. Este foi dividido em dois estudos em casa de vegetação (estudos I e II) e um em campo (estudo III). Cada estudo foi realizado em dois solos (um com alto teor de Mn e outro com baixo teor de Mn), avaliando-se os resultados de cada um separadamente. Estudo I: Dois experimentos foram realizados em delineamento em blocos aleatorizados, com quatro repetições e em esquema fatorial 2 × 6 × 4 com parcela subdividida no tempo. Formaram-se 48 tratamentos pela combinação de dois níveis do fator soja (cultivada sem ou com glifosato) e seis do fator fonte do nutriente (sem Mn ou Controle, Cloreto, Sulfato, Carbonato, EDTA e Citrato) alocados nas parcelas principais, e de quatro níveis do fator tempo (4, 24, 48 e 72 h após a aplicação do fertilizante) alocados nas subparcelas. Cada tratamento foi aplicado com uma haste flexível de algodão nas folhas e nos três primeiros trifólios (trifólios tratados) da planta de soja em estádio V4. Avaliou-se a absorção foliar de Mn através da determinação de massa de matéria seca, teor e conteúdo de Mn dos trifólios tratados e da haste de plantas de soja ainda em estádio V4. Estudo II: Dois experimentos foram realizados em delineamento em blocos aleatorizados, com quatro repetições e em esquema fatorial 2 × 6. Formaram-se 12 tratamentos pela combinação de dois níveis do fator soja e seis níveis do fator fonte do nutriente. Cada tratamento foi aplicado nos trifólios tratados da planta de soja em estádio V4. Avaliou-se a distribuição foliar de Mn através da determinação de massa de matéria seca, teor e conteúdo de Mn dos trifólios tratados, hastes, trifólios formados após a aplicação dos tratamentos (trifólios não tratados), vagens e grãos de plantas de soja em estádio R8. Estudo III: Realizaram-se dois experimentos em delineamento similar ao do estudo II, mas com seis blocos. Cada tratamento foi aplicado com pulverizador de pressão constante sobre a parte aérea de plantas de soja em estádio V4. Avaliou-se a massa de matéria seca, teor e conteúdo de Mn das hastes, vagens e grãos de plantas de soja em estádio R8. Foram avaliados também componentes de produção e rendimento de grãos. A quantidade absorvida de Mn é dependente da fonte utilizada e a fonte Cloreto foi a que proporcionou maior absorção de Mn, enquanto a fonte EDTA, apresentou maior eficiência em aumentar o conteúdo de Mn das hastes logo após a aplicação. O Mn aplicado nos trifólios pode ser redistribuído desta parte para outras da planta, embora aparentemente em pequenas quantidades, e até o final do ciclo da soja estará em maior proporção nos trifólios tratados. A soja tratada com Mn não apresentou grãos com maior acúmulo deste, mas na soja cultivada no \"solo -Mn\" e sem glifosato o conteúdo de Mn foi maior do que na soja com glifosato. Em termos de produtividade de grãos, a adubação foliar com Mn em aplicação única na soja no estádio V4 recebendo ou não aplicação de glifosato e cultivada em solo originalmente com alto teor de Mn não proporcionou diferenças. / Due to Mn deficiency problems related to Roundup Ready soybean, the tendency to increase cultivation of Intacta RR2 PROTM soybeans in Brazil and to the possibility of increased yield of this related to the response to Mn foliar fertilization, this work was carried out. It was divided into two greenhouse studies (I and II) and one in the field (study III). Each study was performed in two soils (one with high content of Mn and the other with low content), evaluating the results of each one separately. Study I: the two trials carried out by using factorial split-plot design, with three factors in four replications in randomized complete block design (RCBD). Soybean factor with two levels (without and with glyphosate) and Mn source factor with six levels (Control, Chloride, Sulphate, Carbonate, EDTA and Citrate), both distributed in factorial form into main plots and time factor (4, 24, 48 and 72 h after fertilizer application) distributed in the sub-plots. Each treatment was applied with a swab in the unifoliate leaves and the first three trifoliates (treated trifoliates) of soybean in V4 stage. Mn foliar absorption was determined by dry matter mass, concentration and content of Mn of treated trifoliates and stem of soybean plants in the V4 stage. Study II: The two trials carried out by using 2 × 6 factorial with four replications in RCBD. Soybean factor with two levels and Mn fertilizer source factor with six levels. Each treatment was applied to the treated trifoliates of the V4 soybean plant. the leaf distribution of Mn was determined by the dry matter mass, concentration and Mn content of the treated trifoliates, stems, trifoliates formed after the application of the treatments (untreated trifoliates), pods and grains of soybean plants in the R8 stage. Study III: Two experiments were carried out in a similar design of study II, but with six replications. Each treatment was applied with a constant pressure sprayer on the above ground part of V4 soybean plants. The foliar Mn was evaluated by determining the dry matter mass, content and Mn content of the stems, pods and grains of soybean plants at stage R8. Production components and grain yield were also evaluated. The absorbed amount of Mn is dependent on the source used and the Chloride is the one that provided the highest Mn absorption, but sources such as EDTA showed a higher efficiency in increasing the Mn content of the stems soon after application. The Mn applied in the trifoliates can be redistributed from this part to others of the plant, although apparently in small amounts, and will be in greater proportion in the treated trifoliates until the end of the soybean cycle. Mn-treated soybean did not present grains with higher accumulation, but in soybean cultivated grown in soil with low Mn concentration and without glyphosate the Mn content was higher than in soybean with glyphosate. In terms of grain yield, the foliar fertilization with Mn in single application in the soybean V4 stage without or with glyphosate grown in soil with high Mn content did not present significant differences.