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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
171

Especiação de antimônio em amostras de água mineral e especiação de cromo em águas naturais empregando métodos de microextração e espectrometria de absorção atômica

Andrade, Jucimara Kulek 22 February 2018 (has links)
Submitted by Eunice Novais (enovais@uepg.br) on 2018-04-24T17:27:14Z No. of bitstreams: 2 license_rdf: 811 bytes, checksum: e39d27027a6cc9cb039ad269a5db8e34 (MD5) Jucimara Kulek de Andrade.pdf: 4583083 bytes, checksum: 9a03d4f30fb1122bb87feac6d618d7a1 (MD5) / Made available in DSpace on 2018-04-24T17:27:14Z (GMT). No. of bitstreams: 2 license_rdf: 811 bytes, checksum: e39d27027a6cc9cb039ad269a5db8e34 (MD5) Jucimara Kulek de Andrade.pdf: 4583083 bytes, checksum: 9a03d4f30fb1122bb87feac6d618d7a1 (MD5) Previous issue date: 2018-02-22 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / O antimônio e o cromo são elementos presentes no ambiente de forma natural ou decorrente de atividades antrópicas. O comportamento, biodisponibilidade, toxicidade e transporte desses elementos são dependente das suas formas específicas, ou seja, sua especiação. Assim, é importante conhecer as diferentes espécies do elemento em um meio específico. O presente trabalho teve por objetivo implantar e validar em laboratório protocolos analíticos para o estudo da especiação de Sb e Cr em amostras de água mineral e natural, empregando técnicas de extração com detecção por espectrometria atômica. A especiação de Sb por extração por ponto nuvem envolveu a extração seletiva de Sb(III) em pH 2, com pirrolidina ditiocarbamato de amônio – APDC (complexante) em meio de surfactante (Triton X-114). A determinação do teor total de Sb foi realizada pelo mesmo procedimento, após redução do Sb(V) para Sb(III) usando L-cisteína. Um amplo estudo da presença de Sb(III) e Sb(V) em amostras brasileiras de água mineral envasadas em PET foi realizado. A concentração média de Sb(total) para 39 amostras recentemente envasadas foi de 4 ± 1,4 μg L-1, sendo que 70% das amostras estão dentro dos limites aceitáveis pela ANVISA (5,0 μg L-1). A espécie majoritária nas amostras foi o Sb(III) com 53 a 79% do teor total de Sb, sugerindo a migração do Sb2O3 do PET para a bebida. Um estudo foi conduzido com cinco marcas de água mineral envasada e analisadas durante seis meses. O teor de Sb(total) na água mineral aumentou de 2 a 27% após 6 meses de estocagem. Esses resultados indicam que ocorre a migração do Sb presente no PET para a bebida engarrafada. A migração do Sb do PET para água mineral foi avaliada sob diferentes condições de armazenamento (tempo, temperatura, exposição solar) usando a própria bebida como simulante e com simulantes alimentícios (água ultrapura e solução ácida). Nesses ensaios, observou-se um aumento de até 214% do teor de Sb quando a temperatura de armazenamento aumentou até 80ºC. Um aumento de 323% foi observado quando as amostras foram expostas por 7 dias à radiação solar e de até 600% com simulante ácido acético por 10 dias. Com relação à distribuição das espécies, a espécie que apresentou aumento mais significativo foi de Sb(III). A especiação de Cr por emulsificação assistida por ultrassom envolveu a extração seletiva do Cr(VI) e pré-concentração com tributilfosfato (TBP) (solvente extrator orgânico), em meio de HCl e NaCl. A dispersão da solução extratora foi realizada com banho ultrassônico em substituição a um solvente dispersor. A determinação do teor total de Cr(III) foi realizada pelo mesmo procedimento, após oxidação do Cr(III) para Cr(VI) usando KMnO4. Um estudo de especiação de Cr em amostras de água natural do Oeste, Centro-Oeste e Campos Gerais do Estado do Paraná, Brasil foi realizado. As concentrações totais de Cr foram inferiores a 1,0 μg L-1, portanto, compatíveis com águas não contaminadas. O Cr dissolvido foi a maior fração para as amostras, indicando que o Cr pode ter uma maior capacidade de mobilidade e possível biodisponibilidade nessas águas. Com relação a distribuição do Cr na fração dissolvida, a fração majoritária foi de Cr(VI). Esta é a espécie mais tóxica e forma mais esperada em águas naturais oxigenadas. A variabilidade nos resultados mostra a necessidade de monitoramento das concentrações totais desses elementos e sua especiação, nos ambientes aquáticos e águas engarrafadas, como forma avaliar sua toxicidade e garantir a segurança social e ambiental. / Antimony and chromium are elements present in the environment naturally or due to anthropic activities. The behavior, bioavailability, toxicity and transport of these elements are dependent on their specific forms, i.e., their speciation. Thus, it is important to know the different species of this element in a specific medium. Thereby, this work proposes to implement and validate in laboratory analytical protocols for the study of Sb and Cr speciation in mineral and natural water, employing extraction technique with detection by atomic absorption. The Sb speciation by cloud point extraction involved the selective extraction of Sb(III) at pH 2, with ammonium pyrrolidinedithiocarbamate - APDC (complexing agent) in surfactant medium (Triton X-114). By the same procedure was performed the determination of the total Sb content, however after reduction of Sb (V) to Sb (III) using L-cysteine. This protocol made possible an extensive study of the presence of Sb(III) and Sb(V) in Brazilian samples of bottled mineral water with PET. The mean concentration of Sb (total) for 39 freshly packaged samples was 4 ± 1.4 μg L-1, and 70% of the samples were within the limits acceptable by ANVISA (5.0 μg L-1). The majority species in the samples was Sb(III) with 53 to 79% of the total Sb content, suggesting the migration of Sb2O3 from PET to the beverage. With five brands of bottled mineral water was conducted a study, with samples analyzed for six months. Sb(total) content in mineral water increased from 2 to 27% after 6 months of storage. These results indicate that migration of the Sb present in the PET to the bottled beverage occurs. The migration of Sb from PET to mineral water was evaluated under different storage conditions (time, temperature, sun exposure) using the beverage as simulant and with food simulants (ultrapure water and acid solution). In these tests, when storage temperature increased to 80 °C was observed an increase of up to 214% in Sb content. When samples were exposed for 7 days to solar radiation was observed an increase of up to 323% in Sb content and when packaging were maintained for 10 days with acetic acid simulant was observed an increase of up to 600%. Regarding the distribution of species, the species that presented the most significant increase was Sb(III). The Cr speciation by ultrasound emulsification microextraction involved the selective extraction of Cr (VI) and preconcentration with organic extractor solvent, tributylphosphate (TBP), in HCl and NaCl medium. . It was performed the dispersion of the extractive solution with an ultrasonic bath in place of a dispersing solvent. By the same procedure, the determination of the total Cr(III) content was performed, but after oxidation of Cr(III) to Cr(VI) using KMnO4. A Cr speciation study in samples of natural water from the West, Center-West and Campos Gerais from the State of Paraná, Brazil was carried out. The total concentrations of Cr were less than 1.0 μg L-1,therefore, these levels are compatible with uncontaminated water. Cr dissolved was the largest fraction for the samples, indicating that Cr may have a greater mobility capacity and possible bioavailability in these waters. Regarding the distribution of Cr in the dissolved fraction, the majority fraction was Cr(VI). This is the more toxic specie and more expected form in oxygenated natural waters. The variability in the results shows the need for monitoring of the total concentrations of theses elements and their speciation in aquatic environments and bottled waters, as a way to evaluate their toxicity and guarantee social and environmental security.
172

Determinação da sensibilidade de isolados de Leishmania a antimoniato de meglumina, anfotericina B e tamoxifeno. / Determination of the sensitivity of Leishmania isolates to meglumine antimoniate, amphotericin B and tamoxifen.

Nascimento, Rogéria Cristina Zauli 24 June 2009 (has links)
Nesse trabalho avaliamos a sensibilidade a drogas in vitro de alguns isolados obtidos de pacientes brasileiros com leishmaniose cutânea. O microteste de MTT modificado mostrou-se eficaz para avaliação da sensibilidade in vitro de promastigotas de Leishmania e macrófagos de medula como modelo de infecção por L. (V.) braziliensis. A atividade de tamoxifeno e anfotericina B foi similar entre os isolados de Leishmania avaliados. Foi observada uma variação maior da sensibilidade ao Glucantime®, sendo que os isolados de L. (V.) braziliensis apresentaram maior sensibilidade a essa droga. Não foi observada correlação da resposta clínica dos pacientes ao tratamento com a atividade in vitro. Avaliamos também a eficácia de tamoxifeno no tratamento de camundongos BALB/c infectados com L. (V.) braziliensis. Observamos que 20 ou 30 mg/kg/dia de tamoxifeno por 15 dias resultou em redução no tamanho das lesões e carga parasitária em comparação com animais controle.Um isolado apresentou morfologia flagelar distinta daquela observada em promastigotas típicos de Leishmania. / In this work we evaluated the in vitro sensitivity to drugs of some isolates from Brazilian patients with cutaneous leishmaniasis. The modified MTT microtest was effective for evaluation of in vitro sensitivity of Leishmania promastigotes and macrophages from bone marrow as a model of infection by L. (V.) braziliensis. The activity of tamoxifen and amphotericin B was similar among isolates of Leishmania evaluated. Sensitivity to Glucantime®, was more variable with isolates of L. (V.) braziliensis presenting higher sensitivity to the drug. There was no correlation between clinical response to treatment with in vitro activity. We have also evaluated the effectiveness of tamoxifen in the treatment of BALB/c mice infected with L. (V.) braziliensis and observed that 20 or 30 mg/kg/day of tamoxifen for 15 days resulted in reduction in the size of lesions and parasite load when compared with control animals. One of the isolates presented atypical flagellar morphology.
173

Studies of dynamically and statically compressed antimony

Coleman, Amy Louise January 2018 (has links)
Physics at extreme conditions is not a young field; there have been decades of developments that have allowed us to generate high-pressure and high-temperature conditions in a vast array of materials. Conventionally, these extreme conditions were generated using static compression techniques; compressing a material in a diamond anvil cell which could then be heated or cooled, with structural information deduced using synchrotron radiation. These techniques are still invaluable for extreme conditions research although the pressures and temperatures that are accessible to them are limited by the strength of the diamond anvil cells and their ability to withstand extreme temperatures. The necessity for access to pressure-temperature states that are beyond the scope of the conventional diamond anvil cell is driven by the need to characterise extreme environments such as planetary interiors. It was long believed that materials in high pressure-temperature states would exhibit relatively simple, high-symmetry crystal structures, but recent research has proven that, conversely, there is an abundance of complex structural behaviour at these extreme conditions. One means of attaining pressure-temperature states beyond those accessible using static compression techniques is to impart a large amount of energy into a material in a comparatively short period of time (milliseconds to nanoseconds); this is known as dynamic compression. Dynamic compression can be generated using impact techniques or, alternatively, via laser ablation. Access to the most extreme conditions is commonly achieved by generating a shockwave which compresses the sample with the fastest achievable compression wave. Not only does this type of compression facilitate access to the most extreme states, it also allows us to explore the physics of impact phenomena and other such situations involving rapid energy transfer. Dynamic compression occurs on short timescales and, as such, there is a considerable challenge in implementing diagnostics to study the behaviour of compressed materials. Furthermore, because complexity is commonplace in extreme conditions, it is vital that any diagnostics should be able to provide data of high enough quality that this complexity may be resolved. The advent of 4th generation light sources (x-ray free electron lasers) has afforded us the opportunity to obtain extraordinarily high quality data on dynamic compression timescales. In the interest of refining analytical techniques when utilising this novel technology, materials exhibiting complex crystal structures should be investigated. Antimony is an element which is known, under static compression, to transform from a Peierls-distorted rhombohedral phase (R-3m) to an incommensurately modulated host-guest structure (I'4=mcm(00γ)000s), a structure with an incredibly high level of complexity. The complexity of this host-guest phase, and the relatively low pressure at which it forms, makes antimony an ideal candidate for testing the resolution achievable using these 4th generation light sources. Furthermore, it is interesting to observe whether such a complex phase can form on the short timescales of dynamic compression. In this work antimony is both statically and dynamically compressed and the results of both experiments are compared. A static phase diagram is constructed for antimony up to 31 GPa and 835 K, confirming the location of a previously theorised triple point and suggesting the location of an additional triple point. Three solid phases are characterised and data are found to agree with the pre-existing static compression studies. The nature of the host-guest phase is investigated and the guest 'chains' are found to remain intact even at the highest temperatures and pressures, a result which has not previously been observed in high pressure-temperature host-guest structures. Dynamic data from shock-compression experiments at pressures up to 59.3 GPa are plotted alongside the static data and contrasting phase behaviour is discussed. Four solid phases are identified along with one liquid phase. Observation of the host-guest phase in shock-compressed antimony confirms that highly complex crystal structures are able to form on the nanosecond timescale.
174

Adsorption av Sb på zeolit / Sb adsorption by zeolite

Lundstedt, Evert January 2007 (has links)
Detta examensarbete är en förundersökning till Glafos undersökning angående rening av glasbrukens processvatten från antimon med zeolit. Förundersökningen gick ut på att via experiment ta reda på hur mycket antimon som adsorberas av behandlad (för optimering: dels med NaNO3 och dels med NaCl) och obehandlad zeolit (porstorlek 0.4 nm). pH mättes och ställdes eftersom det har betydelse för adsorptionen, åtminstone vid väldigt lågt pH. När lösningarna hade filtrerats mättes den kvarvarande antimonhalten med atomabsorptionsspektrofotometri. Mätningarna visade att i genomsnitt 53 % av Sb-halten i lösningarna hade adsorberats av zeoliten. Förundersökningen visade att det inte blir någon adsorption då pH är väldigt lågt (under 1). Den visade också att när pH är över 4 verkar det inte ha någon betydelse om zeoliten är behandlad eller inte. Zeoliten bör behandlas med NaCl först i en tank med omrörning, sedan blandas i processvattnet (vars pH justerats till pH 4) i en tank eller bassäng och därefter filtreras. Tidsfaktorn för hur lång tid det tar för zeoliten att nå jämvikt och temperaturens inverkan bör även undersökas. / The aim of this diploma work is to study the removal of antimony from glassworks process water using zeolites. The experimental part of the studies were carried out to find the quantity of antimony adsorbed by the zeolite. The studies included treated (for optimization: partly with NaNO3 and partly with NaCl) and untreated zeolite. The pore size is 0.4 nm. pH was measured and adjusted because it is important for the antimony adsorption. When the solutions were filtrated the content of antimony left was measured with atomic absorption spectrophotometry. The measurements showed an average uptake of antimony by the zeolite of 53 %.The preinvestigation indicates that with a very low pH (below 1) there is no antimony adsorption. It also indicates that with pH above 4 it does not matter if the zeolite are treated or not. In further investigations the zeolite should be treated with NaCl in a stirred tank, then be mixed in the process water (pH is set to 4) in a tank or basin and then be filtrated. The time to reach equilibrium and the influence of temperature should also be investigated.
175

Adsorption av Sb på zeolit / Sb adsorption by zeolite

Lundstedt, Evert January 2007 (has links)
<p>Detta examensarbete är en förundersökning till Glafos undersökning angående rening av glasbrukens processvatten från antimon med zeolit.</p><p>Förundersökningen gick ut på att via experiment ta reda på hur mycket antimon som adsorberas av behandlad (för optimering: dels med NaNO3 och dels med NaCl) och obehandlad zeolit (porstorlek 0.4 nm). pH mättes och ställdes eftersom det har betydelse för adsorptionen, åtminstone vid väldigt lågt pH. När lösningarna hade filtrerats mättes den kvarvarande antimonhalten med atomabsorptionsspektrofotometri. Mätningarna visade att i genomsnitt 53 % av Sb-halten i lösningarna hade adsorberats av zeoliten. Förundersökningen visade att det inte blir någon adsorption då pH är väldigt lågt (under 1). Den visade också att när pH är över 4 verkar det inte ha någon betydelse om zeoliten är behandlad eller inte.</p><p>Zeoliten bör behandlas med NaCl först i en tank med omrörning, sedan blandas i processvattnet (vars pH justerats till pH 4) i en tank eller bassäng och därefter filtreras.</p><p>Tidsfaktorn för hur lång tid det tar för zeoliten att nå jämvikt och temperaturens inverkan bör även undersökas.</p> / <p>The aim of this diploma work is to study the removal of antimony from glassworks process water using zeolites.</p><p>The experimental part of the studies were carried out to find the quantity of antimony adsorbed by the zeolite. The studies included treated (for optimization: partly with NaNO3 and partly with NaCl) and untreated zeolite. The pore size is 0.4 nm. pH was measured and adjusted because it is important for the antimony adsorption. When the solutions were filtrated the content of antimony left was measured with atomic absorption spectrophotometry. The measurements showed an average uptake of antimony by the zeolite of 53 %.The preinvestigation indicates that with a very low pH (below 1) there is no antimony adsorption. It also indicates that with pH above 4 it does not matter if the zeolite are treated or not.</p><p>In further investigations the zeolite should be treated with NaCl in a stirred tank, then be mixed in the process water (pH is set to 4) in a tank or basin and then be filtrated.</p><p>The time to reach equilibrium and the influence of temperature should also be investigated.</p>
176

The properties of nitrogen and oxygen in silicon

Murphy, John Douglas January 2006 (has links)
A novel dislocation locking technique is used to study the behaviour of nitrogen and oxygen in silicon. Specimens containing well-defined arrays of dislocation half-loops are subjected to isothermal anneals of controlled duration, during which nitrogen or oxygen diffuses to the dislocations. The stress required to move the dislocations away from the impurities is then measured. Measurement of this unlocking stress as a function of annealing time and temperature allows information on the transport of nitrogen and oxygen to be deduced. Despite being present in a concentration of just 3E14cm-3 in some specimens, nitrogen is found to provide substantial benefits to the mechanical properties of float-zone silicon (FZ-Si). The segregation of nitrogen at dislocations is stable to at least 1200 degrees centigrade and the unlocking stress measured at 550 degrees centigrade is of similar magnitude to that found previously for oxygen in Czochralski silicon (Cz-Si). The unlocking stress initially rises linearly with annealing time, before it takes a constant value. The rate of the initial rise is dependent on temperature and the 1.5eV activation energy found agrees with that found previously. The rate of the initial rise also depends on nitrogen concentration. In the 500 to 700 degrees centigrade temperature range, the unlocking stress is found to decrease linearly as the temperature at which the unlocking process takes place increases. The results of a pre-annealing experiment confirm that oxygen monomers and dimers in Cz-Si exist in thermodynamic equilibrium at 550 degrees centigrade. Numerical simulation of oxygen diffusion to dislocations allows values of the effective diffusivity of oxygen in Cz-Si with four different oxygen concentrations to be deduced. At 500 degrees centigrade, the effective diffusivity depends upon oxygen concentration in a way which is consistent with oxygen dimers being responsible for transport. The transport of oxygen in Cz-Si at 550 to 600 degrees centigrade is found to be unaffected by nitrogen doping at a level of 2.1E15cm-3. The dislocation locking technique has also been used to study the effect of high concentrations of shallow dopants on oxygen transport in Cz-Si in the 350 to 550 degrees centigrade temperature range. Oxygen transport has been found to be unaffected by a high antimony concentration ~3E18cm-3, but is found to be enhanced by, on average, a factor of approximately 44 in Cz-Si with a high boron concentration ~5E18cm-3. Furthermore, deep-level transient spectroscopy (DLTS) and high-resolution DLTS (HR-DLTS) are used to study the electrical activity of defects in silicon. A deep-level with an enthalpy of 0.50eV and a concentration of order 10E11cm-3 is found in n-type nitrogen-doped FZ-Si and n-type nitrogen-doped neutron transmutation doped FZ-Si. No additional deep-levels are found in either material, for which the detection limit is 6E10cm-3. No deep-levels are found in p-type nitrogen-doped Cz-Si, for which the detection limit is approximately 10E12cm-3. DLTS and HR-DLTS are also used to investigate the electrical activity of oxygen-decorated dislocations in Cz-Si and states associated with oxygen at dislocation cores have been identified.
177

Influence of flame retardant additives on the processing characteristics and physical properties of ABS

Seddon, Richard January 2000 (has links)
Antimony trioxide (Sb203) and halogenated additives are used together in flameretarded formulations due to their synergistic retardant properties. A study has been made to determine the effects of adding different grades of Sb203 (dSD particle sizes 0.11 um, 0.52um and 1.31 um) into ABS polymer either alone or with commercial brominated materials (BTBPE, TBBA, DBDPO) and an experimental bromine grade (sDBDPO). The Sb20 3 was added at 4wt% loadings and the bromines at 20wt% loadings. The results consider the influence of the additives on processing, mechanical, morphological and flame retardant properties. All compounds were produced using a twin-screw co-rotating extruder and then an injection moulder was used to mould notched impact (falling weight testing), flexural, LOI and UL-94 flame test bars. Samples of all the compounded formulations were titrated to determine Sb20 3 and Br contents. Fracture surface, morphology, size and dispersion analysis was carried out using both SEM and TEM equipment. Osmium tetroxide (OS04) staining was used to determine relative locations of filler particles and polybutadiene phase. Additions of the different antimony trioxide grades showed that the 0.52um and 1.31 um grades lowered impact energy absorption (-25 to -30%) when added at 4wt% loading. The use of a sub-micron size grade (0.1 um) did not significantly lower impact properties (-3%) and had similarly small effects on the flexural modulus and flexural strength. Additions of the brominated materials had much greater effects causing large reductions in impact properties (-20 to :70%). The presence of the bromines generally increased flexural modulus and lowered flexural strength with the exception of TB BA, which increased both modulus and strength. Compounds containing both 1.31 um Sb203 and bromines suffered a further reduction in impact energies, with the bromine properties dominating. Using the 0.1 um Sb20 3 grade again improved impact and flexural properties compared to the 1.31 um grade. The 0.1 um grade resulted in improvements in fire resistance as measured by the UL-94 properties when used with all bromine grades.
178

Structural chemistry of lead-antimony and lead-bismuth sulphides.

Skowron, Aniceta. Brown, I.D. Unknown Date (has links)
Thesis (Ph.D.)--McMaster University (Canada), 1991. / Source: Dissertation Abstracts International, Volume: 53-01, Section: B, page: 0503. Supervisor: I. D. Brown.
179

Propriétés photoélectriques de vitrocéramiques et cristaux de chalcogénures / Photoelectric properties of chalcogenide glass-ceramics and crystals

Korolkov, Ilia 10 November 2017 (has links)
La crise de l’énergie ainsi que les problèmes écologiques sont considérés comme les défis les plus importants de demain. Cependant, les sources d’énergies renouvelables et respectueuses de l’environnement ne sont pas suffisamment développées, ce qui entraîne une contribution faible à la production d’énergie. Les cellules solaires font partie des sources d’énergies renouvelables les plus attractives et prometteuses. Cependant, les panneaux solaires existants ont toujours un facteur de qualité négatif, c’est-à-dire que leur production et leur entretien demandent plus d’énergie qu’ils ne sont capables de produire pendant leur cycle de fonctionnement. Malgré la réduction exponentielle du prix des panneaux solaires, leur efficacité de conversion n’est pas suffisante. Les succès récents dans la science des matériaux ont beaucoup contribué à son amélioration, néanmoins des études sur les nouveaux matériaux photovoltaïques sont nécessaires. Les travaux de recherche présentés dans ce manuscrit concernent les vitrocéramiques de chalcogénures dans le système GeSe2-Sb2Se3-CuI. De nombreuses compositions chimiques différentes ont été préparées et analysées du point de vue structural et électrique dans le cadre de ce système. Il a été démontré que la phase Sb2Se3, responsable des propriétés photoélectriques dans les vitrocéramiques, possède un grand potentiel pour les applications photovoltaïques grâce à ses propriétés optiques bien adaptées. L’influence des modifications de la composition des cristaux de Sb2Se3 sur la structure et les propriétés électriques a été étudiée. La flexibilité du type de conductivité et la résistivité des cristaux massifs de Sb2Se3 ont été montrées. Enfin, les couches minces à base de vitrocéramiques et cristaux massifs étudiés ont été préparées par la pulvérisation cathodique RF magnétron. Leur structure et les propriétés électriques sont également décrites dans cette thèse. Une cellule solaire complètement fonctionnelle, basée sur Sb2Se3 dopé iode et sur la vitrocéramique de 40GeSe2-40Sb2Se3-20CuI, a été préparée et caractérisée. / Energy crisis and global ecological problems are considered as important challenges of nearest future. Eco-friendly and renewable sources of energy are still severely undeveloped and contribute weakly to the energy production. One of the most attractive and promising domains of renewable energy is a solar light harvesting. However, existing solar panels still possess negative quality factor, i.e. their fabrication and maintenance require more energy that they are capable to produce during their life cycle. Despite exponential reduction of the price, solar cells are not efficient enough in terms of light to energy conversion. Recent breakthroughs in material science contributed a lot to the increase of efficiency, however further investigation of novel materials are needed. Here, chalcogenide glassceramics of GeSe2-Sb2Se3-CuI system were studied in details. Within this system various chemical compositions were prepared and analyzed for their structure and photoelectric properties. We found that Sb2Se3 phase, responsible for the appearance of photoelectric effect in glass-ceramics, have a great potential for light harvesting due to its suitable optical properties. In the present work we demonstrated the influence of various dopants on photoelectric properties of Sb2Se3 crystals. We showed a possibility of conductivity type and resistivity tuning of bulk Sb2Se3 crystals in a wide range of values. Thin film devices based on studied bulk compositions were prepared by RF sputtering and characterized structurally and electrically as well. We demonstrated a fully functional thin film solar device based on iodine doped Sb2Se3 and 40GeSe2-40Sb2Se3-20CuI glass-ceramic.
180

The Investigation and Characterization of Redox Enzymes Using Protein Film Electrochemistry

January 2014 (has links)
abstract: Redox reactions are crucial to energy transduction in biology. Protein film electrochemistry (PFE) is a technique for studying redox proteins in which the protein is immobilized at an electrode surface so as to allow direct exchange of electrons. Establishing a direct electronic connection eliminates the need for redox­active mediators, thus allowing for interrogation of the redox protein of interest. PFE has proven a versatile tool that has been used to elucidate the properties of many technologically relevant redox proteins including hydrogenases, laccases, and glucose oxidase. This dissertation is comprised of two parts: extension of PFE to a novel electrode material and application of PFE to the investigation of a new type of hydrogenase. In the first part, mesoporous antimony-doped tin oxide (ATO) is employed for the first time as an electrode material for protein film electrochemistry. Taking advantage of the excellent optical transparency of ATO, spectroelectrochemistry of cytochrome c is demonstrated. The electrochemical and spectroscopic properties of the protein are analogous to those measured for the native protein in solution, and the immobilized protein is stable for weeks at high loadings. In the second part, PFE is used to characterize the catalytic properties of the soluble hydrogenase I from <italic>Pyrococcus furiosus</italic> (<italic>Pf</italic>SHI). Since this protein is highly thermostable, the temperature dependence of catalytic properties was investigated. I show that the preference of the enzyme for reduction of protons (as opposed to oxidation of hydrogen) and the reactions with oxygen are highly dependent on temperature, and the enzyme is tolerant to oxygen during both oxidative and reductive catalysis. / Dissertation/Thesis / Doctoral Dissertation Biochemistry 2014

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