In the technologically driven information age, the consumption of power is as vital to daily life as food and shelter. The generation of that power comes from a variety of sources of which coal is the predominant provider of electrical energy. Coal combustion is a well-known technology and the United States possesses the most abundant coal deposits on Earth, however, the drawback accompanying this process is the significant emissions which are released during combustion. Over the years, much effort has gone into reducing the emissions of majority constituent elements CO2, CO, NOx, SOx, etc. but it is only in the last decade or so that much attention has been given to the trace metals present within coal. Most of the work into examining these trace metals has been upon Hg and how it speciates within the flue gas in order to determine the most effective means of removal. In this study, the trace metals arsenic (As) and selenium (Se) will be investigated in a similar manner to evaluate the speciation of these elements. While previous experimental work has been performed in this area, it has been limited to thermodynamic studies which determine the speciation after equilibrium has been reached, this ignores the fact the residence times within the flue are often only several minutes during which time rapid quenching is taking place. This study takes a different approach by examining the speciation using computational chemistry which affords the advantage of being able to perform a kinetic study which is more useful in creating a flue gas model. Using ab initio the properties of various As and Se species can be evaluated compared to existing experimental data for validation. After which, a number of reactions may be selected and the structure of the transition state for each identified. Once the properties of the transition structure are known, the appropriate kinetic model, be it Transition State Theory, RRKM Theory, etc. can be applied and the rate constant determined. It is by the determination of these rate constants that the kinetic model of the flue gas can be improved and a more accurate depiction of the speciation of these race metals created.

Wong, Wing Yin. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2010. / Includes bibliographical references (leaves 90-105). / Abstracts in English and Chinese. / Acknowledgements --- p.i / Abstract --- p.iii / Abstract (Chinese Version) --- p.v / Table of Contents --- p.vi / List of Figures --- p.ix / List of Abbreviations --- p.xi / Chapter Chapter 1 --- General Introduction / Chapter 1.1 --- Overview of cancer --- p.1 / Chapter 1.2 --- Acute lymphoblastic leukemia --- p.3 / Chapter 1.2.1 --- T-cell acute lymphoblastic leukemia --- p.5 / Chapter 1.2.1.1 --- Chemotherapy / Chapter 1.2.1.2 --- Induction therapy / Chapter 1.2.1.3 --- Intensification therapy / Chapter 1.2.1.4 --- Maintenance therapy --- p.6 / Chapter 1.2.2 --- Chemoresistance in T-ALL / Chapter 1.3 --- Apoptosis and cancer --- p.7 / Chapter 1.3.1 --- Chemoresistance --- p.9 / Chapter 1.4 --- Caspase-dependent apoptosis --- p.10 / Chapter 1.4.1 --- Regulation of caspase-dependent apoptosis / Chapter 1.4.2 --- Initiation of apoptosis --- p.11 / Chapter 1.4.3 --- Exrtinsic pathway / Chapter 1.4.4 --- Intrinsic mitochondrial pathway --- p.15 / Chapter 1.4.4.1 --- Regulation of apoptosis by Bcl-2 family proteins --- p.16 / Chapter 1.4.4.2 --- Reactive Oxygen Species --- p.19 / Chapter 1.5 --- Selenium --- p.23 / Chapter 1.5.1 --- Importance of Se to human health --- p.25 / Chapter 1.5.2 --- Cancer chemoprevention by Se --- p.27 / Chapter 1.5.3 --- Preclinical studies --- p.28 / Chapter 1.5.4 --- Clinical investigations / Chapter 1.5.5 --- Mechanisms of action by selenocompounds --- p.29 / Chapter 1.6 --- Aims of current study --- p.31 / Chapter Chapter 2 --- Materials and Methods / Chapter 2.1 --- Cell culture --- p.32 / Chapter 2.2 --- Measurement of growth and survival of T-ALL cell lines / Chapter 2.3 --- Induction and quantification of apoptosis --- p.34 / Chapter 2.4 --- Western blotting / Chapter 2.4.1 --- Protein extraction and determination of protein concentration / Chapter 2.4.2 --- SDS-PAGE and immunodetection --- p.35 / Chapter 2.5 --- Analysis of mitochondrial membrane potential --- p.36 / Chapter 2.6 --- Measurement of ROS generation --- p.37 / Chapter 2.7 --- Verification of ROS generation via the addition of N-Acetyl-L-cysteine and glutathione / Chapter 2.8 --- Statistical analysis --- p.38 / Chapter Chapter 3 --- Results / Chapter 3.1 --- SeC induces prominent growth inhibition on Sup-T1 --- p.39 / Chapter 3.2 --- SeC induces S-phase arrest in cell cycle and triggers apoptosis in Sup-T1 --- p.44 / Chapter 3.3 --- SeC triggers DNA fragmentation in Sup-T1 --- p.48 / Chapter 3.4 --- SeC induces PARP cleavage in Sup-T1 --- p.52 / Chapter 3.5 --- SeC activates caspases in Sup-T1 --- p.53 / Chapter 3.6 --- SeC abrogates mitochondrial membrane potential in Sup-T1 cells --- p.56 / Chapter 3.7 --- SeC modulates expressions of Bcl-2 members and activates Bim and Bid in Sup-T1 --- p.61 / Chapter 3.8 --- SeC induces ROS production in Sup-T1 --- p.64 / Chapter 3.9 --- Antioxidants protect Sup-T1 cells from SeC-induced growth inhibition --- p.66 / Chapter 3.10 --- Antioxidants protect Sup-T1 cells from SeC-induced apoptosis --- p.69 / Chapter 3.11 --- Antioxidants effectively block SeC-induced ROS generation in Sup-T1 cells --- p.72 / Chapter 3.12 --- SeC induces mitochondrial membrane permeabilization via ROS-mediated mechanisms Sup-T1 cells --- p.75 / Chapter Chapter 4 --- Discussion --- p.79 / Conclusion --- p.87 / References --- p.90

Thesis (Ph. D.)--University of Missouri-Columbia, 2000. / Typescript. Vita. Includes bibliographical references (leaves 156-168). Also available on the Internet.

Thesis (Ph. D.)--University of Missouri-Columbia, 2000. / Typescript. Vita. Includes bibliographical references (leaves 156-168). Also available on the Internet.

To examine the effects of fat composition and supplemental vitamin E (Vit E) and selenium (Se) on in vivo lipid peroxidation, diet-induced hypercholesterolemia, and glutathione (GSH) metabolism, male Syrian hamsters were fed for three weeks butter fat (BF-) or fish oil- (FO-)based diets supplemented with Vit E and/or Se. The effect of supplemental Vit E and Se on tissue lipid peroxidation (LPO), glutathione peroxidase (GSH-Px) activity and GSH concentrations differed between heart and liver and also was affected by dietary fat. The reduced glutathione/oxidized glutathione (GSH/GSSG) ratio was more consistently associated with tissue lipid peroxidation than was tissue Vit E content. Plasma lipids were lowered with supplemental Se and Vit E. Se supplementation, however, exerted a more potent hypolipidemic effect than Vit E. A pro-oxidative action of Se in hearts of FO-fed hamsters was noted, which was inhibited by supplemental Vit E. Hence, the combination of Vit E and Se may offer the most benefit against diet-induced oxidative stress and hyperlipidemia.

O experimento foi conduzido no Sistema de Pecuária de Leite (SISPEL), na Embrapa, em Pelotas, Rio Grande do Sul, com 32 vacas em lactação da raça Jersey em lactação, divididas em quatro grupos, de acordo com a produção de leite, peso vivo, escore corporal e tempo de lactação. O estudo teve o objetivo de avaliar o efeito da suplementação de diferentes fontes e níveis de selênio (Se) em vacas em lactação, sobre as características físicoquímicas do leite, produção de leite e concentração desse no sangue e leite, assim como verificar a ocorrência do leite instável não ácido (LINA) e as alterações na composição do leite e sangue decorrentes da instabilidade. Os tratamentos foram determinados como: grupo controle (dieta padrão), Selênio Inorgânico 0,3 (dieta padrão + 0,3mg Selenito de sódio/kg de concentrado), Selênio Orgânico 0,3 (dieta padrão + 0,3 mg Selêniometionina/kg de concentrado) e Selênio Orgânico 0,6 (dieta padrão + 0,6 mg selêniometionina/kg de concentrado). No leite, foram analisadas composição química, características físicas, contagem de células somáticas (CCS) e teores de Se, cálcio iônico e uréia e, no sangue, albumina, uréia, triglicerídeos, colesterol, glicose, proteína total, Ca, Mg, P e Se. A suplementação de selênio aumentou linearmente a concentração do mineral no leite e no sangue, independente da fonte. Porém, não ocorreram alterações expressivas nas características físico-químicas, CCS e produção de leite relacionada com a suplementação. Das 124 amostras de leite analisadas durante o experimento, 101 (81,45%) foram estáveis e 23 (18,55%) precipitaram em concentrações de etanol até 72%. O leite classificado como leite instável não ácido (LINA) apresentou maior concentração de cálcio iônico e menor concentração de lactose que o leite normal. O sangue de animais que produziram LINA apresentou maior concentração de uréia e triglicerídeos. / The trial was lead in the intensive system of milk production - SISPEL, at the Embrapa, in Pelotas, Rio Grande do Sul State, with 32 lactating Jersey cows, distributed in four groups, according to milk production, body weight, body condition score and days in milking. The study had the objective to evaluate the effect of the supplementation with different sources and levels of selenium (Se) for dairy cows, on the physical-chemical characteristics of milk, milk yield and selenium concentration in the blood and milk, as well as, to verify the occurrence of not acid unstable milk (LINA) and the alterations in the composition of milk and blood. The treatments were denominated as follows: control (diet without added selenium), Inorganic Selenium (standard diet + 0,3 mg sodium Selenite /kg concentrate), Organic Selenium 0,3 (standard diet + 0,3 mg Selenomethionine/kg concentrate) and Organic Selenium 0,6 (diet standard diet + 0,6 mg selenomethionine/ kg concentrate). Physical-chemical characteristics, somatic cells count (SCC), concentration of Se, ionic calcium and urea in milk and albumen, urea, triglycerides, cholesterol, glucose, total protein, Ca, Mg, P in blood had been analyzed. Supplementation of selenium increased linearly the concentration of the Se in milk and blood, independently of the source. There were not expressive alterations for physical and chemical characteristics, SCC and milk yield related to supplementation. Of the 124 analyzed milk samples during the experiment, 101 (81,45%) were stable and 23(18,55%) precipitated in alcoholic solutions wirth ethanol concentrations to 72%. Milk samples classified as not acid unstable milk (LINA) presented greater concentration of ionic calcium and lower concentration of lactose that stable milk. The blood of animals that had produced LINA presented greater concentration of lactosis and triglycerides.

O experimento foi conduzido no Sistema de Pecuária de Leite (SISPEL), na Embrapa, em Pelotas, Rio Grande do Sul, com 32 vacas em lactação da raça Jersey em lactação, divididas em quatro grupos, de acordo com a produção de leite, peso vivo, escore corporal e tempo de lactação. O estudo teve o objetivo de avaliar o efeito da suplementação de diferentes fontes e níveis de selênio (Se) em vacas em lactação, sobre as características físicoquímicas do leite, produção de leite e concentração desse no sangue e leite, assim como verificar a ocorrência do leite instável não ácido (LINA) e as alterações na composição do leite e sangue decorrentes da instabilidade. Os tratamentos foram determinados como: grupo controle (dieta padrão), Selênio Inorgânico 0,3 (dieta padrão + 0,3mg Selenito de sódio/kg de concentrado), Selênio Orgânico 0,3 (dieta padrão + 0,3 mg Selêniometionina/kg de concentrado) e Selênio Orgânico 0,6 (dieta padrão + 0,6 mg selêniometionina/kg de concentrado). No leite, foram analisadas composição química, características físicas, contagem de células somáticas (CCS) e teores de Se, cálcio iônico e uréia e, no sangue, albumina, uréia, triglicerídeos, colesterol, glicose, proteína total, Ca, Mg, P e Se. A suplementação de selênio aumentou linearmente a concentração do mineral no leite e no sangue, independente da fonte. Porém, não ocorreram alterações expressivas nas características físico-químicas, CCS e produção de leite relacionada com a suplementação. Das 124 amostras de leite analisadas durante o experimento, 101 (81,45%) foram estáveis e 23 (18,55%) precipitaram em concentrações de etanol até 72%. O leite classificado como leite instável não ácido (LINA) apresentou maior concentração de cálcio iônico e menor concentração de lactose que o leite normal. O sangue de animais que produziram LINA apresentou maior concentração de uréia e triglicerídeos. / The trial was lead in the intensive system of milk production - SISPEL, at the Embrapa, in Pelotas, Rio Grande do Sul State, with 32 lactating Jersey cows, distributed in four groups, according to milk production, body weight, body condition score and days in milking. The study had the objective to evaluate the effect of the supplementation with different sources and levels of selenium (Se) for dairy cows, on the physical-chemical characteristics of milk, milk yield and selenium concentration in the blood and milk, as well as, to verify the occurrence of not acid unstable milk (LINA) and the alterations in the composition of milk and blood. The treatments were denominated as follows: control (diet without added selenium), Inorganic Selenium (standard diet + 0,3 mg sodium Selenite /kg concentrate), Organic Selenium 0,3 (standard diet + 0,3 mg Selenomethionine/kg concentrate) and Organic Selenium 0,6 (diet standard diet + 0,6 mg selenomethionine/ kg concentrate). Physical-chemical characteristics, somatic cells count (SCC), concentration of Se, ionic calcium and urea in milk and albumen, urea, triglycerides, cholesterol, glucose, total protein, Ca, Mg, P in blood had been analyzed. Supplementation of selenium increased linearly the concentration of the Se in milk and blood, independently of the source. There were not expressive alterations for physical and chemical characteristics, SCC and milk yield related to supplementation. Of the 124 analyzed milk samples during the experiment, 101 (81,45%) were stable and 23(18,55%) precipitated in alcoholic solutions wirth ethanol concentrations to 72%. Milk samples classified as not acid unstable milk (LINA) presented greater concentration of ionic calcium and lower concentration of lactose that stable milk. The blood of animals that had produced LINA presented greater concentration of lactosis and triglycerides.

La protéine « Selenium Binding Protein » (SBP1), présente chez la plupart des êtres vivants, a un rôle qui n'est pas encore élucidé. Cette protéine possède dans sa structure primaire de nombreux sites potentiels de liaisons aux métaux. Chez Arabidopsis thaliana, la surexpression de SBP1 augmente la tolérance à deux composés toxiques pour la plante, le cadmium (Cd) et le sélénium (Se) qui sont présents dans les sols pollués. Pour mieux comprendre la fonction de SBP1 dans les mécanismes de détoxication, une démarche intégrée combinant deux approches complémentaires, in vitro et in planta, a été menée. La caractérisation biochimique de SBP1 a mis en évidence ses propriétés chélatrices vis-à-vis de différents ligands dont le Cd et le Se. Le Cd se lie à SBP1 avec un ratio molaire ligand/SBP1 de 3 et un KD de 2,2 × 10-7 M via principalement des acides aminés soufrés et potentiellement à moindre échelle des résidus histidines. Le Se, initialement sous forme SeO32-, se lie à SBP1 de façon covalente, avec un ratio molaire ligand/SBP1 de 1, via les cystéines 21 et 22 pour former une liaison de type R-S-Se-S-R. Les analyses in planta de localisation subcellulaire ont montré que SBP1 était à la fois cytosolique et nucléaire. L'utilisation de lignées bioluminescentes a permis d'analyser la zone promotrice du gène SBP1. Le motif cis ‘GAGAC' connu pour être impliqué dans la régulation de certains gènes à une carence en soufre (S) a été identifié comme élément cis majeur de la régulation de l'expression de SBP1 en réponse à différents stress, dont le Cd et le Se. Ce résultat démontre l'existence d'un lien entre la fonction de SBP1 et une demande en S de la cellule. La surexpression de SBP1 in planta perturbe le niveau d'accumulation du Se dans les parties aériennes, mais pas sa spéciation. L'ensemble de ces résultats semble indiquer que SBP1 soit impliquée dans des mécanismes de détoxication via ses propriétés chélatrices et qu'elle joue également un rôle dans le métabolisme du S et du Se. / The function of the protein “Selenium binding protein 1” (SBPP1), present in almost all organisms, is not yet well established. This protein has numerous potential metal binding sites. In Arabidopsis thaliana, SBP1 overexpression increases tolerance to two toxic compounds for the plant, cadmium (Cd) and selenium (Se), which are often found as soil pollutants. For a better understanding of SBP1 function and its involvement in detoxification mechanisms, an integrated approach combining in vitro and in planta experiments, has been performed. Biochemical characterization of SBP1 has revealed its chelating properties to different ligands including Cd and Se. Cd is bound to SBP1 with a metal ion to protein molar ratio of 3 and a KD of 2.2 × 10-7 M mainly via sulfur-containing amino acids and potentially histidine residues. Se from SeO32- can covalently bound SBP1 with a ligand to protein molar ratio of 1. This binding occurs via cysteines 21 and 22 and forms a R-S-Se-S-R complex. In planta analyses have shown that SBP1 is cytosolic and nuclear. The use of bioluminescent lines allowed the identification of a GAGAC motif in the SBP1 promoter region. This motif is a sulfur starvation responsive element and a major cis element involved in SBP1 expression in response to stress, including Cd and Se. The result directly links SBP1 function to an enhanced sulfur demand of the cell. SBP1 over expression in plants disturbs Se accumulation in shoots but not its speciation. All together these results strongly suggested that SBP1 could act as a detoxifying protein through its chelating properties and plays a role in S/Se metabolisms.

Selenium has been a method to test web applications for over a decade, it is interacting directly with the browser and has gained support from both browsers and the community. With the growing amount of browsers, mobile devices and operating systems which a web application is expected to work with, services providing these systems for testing web applications against has gained interest. These services provide testing as a service (TaaS), and runs Selenium-tests in the cloud. This research tried to compare the different services with each other in regard to flexibility, cost, simplicity and reliability. I have also tried to see differences between running the tests locally and using these services. The results showed that there are some differences between the services, and the one best suited might depend on the web application.

O experimento foi conduzido no Sistema de Pecuária de Leite (SISPEL), na Embrapa, em Pelotas, Rio Grande do Sul, com 32 vacas em lactação da raça Jersey em lactação, divididas em quatro grupos, de acordo com a produção de leite, peso vivo, escore corporal e tempo de lactação. O estudo teve o objetivo de avaliar o efeito da suplementação de diferentes fontes e níveis de selênio (Se) em vacas em lactação, sobre as características físicoquímicas do leite, produção de leite e concentração desse no sangue e leite, assim como verificar a ocorrência do leite instável não ácido (LINA) e as alterações na composição do leite e sangue decorrentes da instabilidade. Os tratamentos foram determinados como: grupo controle (dieta padrão), Selênio Inorgânico 0,3 (dieta padrão + 0,3mg Selenito de sódio/kg de concentrado), Selênio Orgânico 0,3 (dieta padrão + 0,3 mg Selêniometionina/kg de concentrado) e Selênio Orgânico 0,6 (dieta padrão + 0,6 mg selêniometionina/kg de concentrado). No leite, foram analisadas composição química, características físicas, contagem de células somáticas (CCS) e teores de Se, cálcio iônico e uréia e, no sangue, albumina, uréia, triglicerídeos, colesterol, glicose, proteína total, Ca, Mg, P e Se. A suplementação de selênio aumentou linearmente a concentração do mineral no leite e no sangue, independente da fonte. Porém, não ocorreram alterações expressivas nas características físico-químicas, CCS e produção de leite relacionada com a suplementação. Das 124 amostras de leite analisadas durante o experimento, 101 (81,45%) foram estáveis e 23 (18,55%) precipitaram em concentrações de etanol até 72%. O leite classificado como leite instável não ácido (LINA) apresentou maior concentração de cálcio iônico e menor concentração de lactose que o leite normal. O sangue de animais que produziram LINA apresentou maior concentração de uréia e triglicerídeos. / The trial was lead in the intensive system of milk production - SISPEL, at the Embrapa, in Pelotas, Rio Grande do Sul State, with 32 lactating Jersey cows, distributed in four groups, according to milk production, body weight, body condition score and days in milking. The study had the objective to evaluate the effect of the supplementation with different sources and levels of selenium (Se) for dairy cows, on the physical-chemical characteristics of milk, milk yield and selenium concentration in the blood and milk, as well as, to verify the occurrence of not acid unstable milk (LINA) and the alterations in the composition of milk and blood. The treatments were denominated as follows: control (diet without added selenium), Inorganic Selenium (standard diet + 0,3 mg sodium Selenite /kg concentrate), Organic Selenium 0,3 (standard diet + 0,3 mg Selenomethionine/kg concentrate) and Organic Selenium 0,6 (diet standard diet + 0,6 mg selenomethionine/ kg concentrate). Physical-chemical characteristics, somatic cells count (SCC), concentration of Se, ionic calcium and urea in milk and albumen, urea, triglycerides, cholesterol, glucose, total protein, Ca, Mg, P in blood had been analyzed. Supplementation of selenium increased linearly the concentration of the Se in milk and blood, independently of the source. There were not expressive alterations for physical and chemical characteristics, SCC and milk yield related to supplementation. Of the 124 analyzed milk samples during the experiment, 101 (81,45%) were stable and 23(18,55%) precipitated in alcoholic solutions wirth ethanol concentrations to 72%. Milk samples classified as not acid unstable milk (LINA) presented greater concentration of ionic calcium and lower concentration of lactose that stable milk. The blood of animals that had produced LINA presented greater concentration of lactosis and triglycerides.