Currently, the CubeSat spacecraft is predominantly used for missions at Low- Earth Orbit (LEO). There are various limitations to expanding past that range, one of the major ones being the lack of sufficient radiation shielding on the Poly-Picosatellite Orbital Deployer (P-POD). The P-POD attaches to a launch vehicle transporting a primary spacecraft and takes the CubeSats out into their orbit. As the demand for interplanetary exploration grows, there is an equal increase in interest in sending CubeSats further out past their current regime. In a collaboration with NASA’s Jet Propulsion Laboratory (JPL), students from the Cal Poly CubeSat program worked on a preliminary design of an interplanetary CubeSat deployer, the Poly-Picosatellite Deep Space Deployer (PDSD). Radiation concerns were mitigated in a very basic manner, by simply increasing the thickness of the deployer wall panels. While this provided a preliminary idea for improved radiation shielding, full analysis was not conducted to determine what changes to the current P-POD are necessary to make it sufficiently radiation hardened for interplanetary travel. This thesis develops a tool that can be used to further analyze the radiation environment concerns that come up with interplanetary travel. This tool is the connection between any geometry modeled in CAD software and the radiation tool OLTARIS (On- Page iv Line Tool for the Assessment of Radiation In Space). It reads in the CAD file and converts it into MATLAB, at which point it can then perform ray-tracing analysis to get a thickness distribution at any user-defined target points. This thickness distribution file is uploaded to OLTARIS for radiation analysis of the user geometry. To demonstrate the effectiveness of the tool, the radiation environment that a CubeSat sees inside of the current P-POD is characterized to create a radiation map that CubeSat developers can use to better design their satellites. Cases were run to determine the radiation in a low altitude orbit compared to a high altitude orbit, as well as a Europa mission. For the LEO trajectory, doses were seen at levels of 102 mGy, while the GEO trajectory showed results at one order of magnitude lower. Electronics inside the P-POD can survive these doses with the current design, confirming that Earth orbits are safe for CubeSats. The Europa- Jovian Tour mission showed results on a higher scale of 107 mGy, which is too high for electronics in the P-POD. Additional cases at double the original thickness and 100 times the original thickness resulted in dose levels at orders of about 107 and 104 mGy respectively. This gives a scale to work off for a “worst case” scenario and provides a path forward to modifying the shielding on deployers for interplanetary missions. Further analysis is required since increasing the existing P-POD thickness by 100 times is unfeasible from both size and mass perspectives. Ultimately, the end result is that the current P-POD standard does not work too far outside of Earth orbits. Radiation-based changes in the design, materials, and overall shielding of the P- POD need to be made before CubeSats can feasibly perform interplanetary missions.

The purpose of this study is to improve spacecraft shielding from radiation in space. It focuses on the evaluation of shielding efficiency of different materials. The efficiency of a shield is evaluated by the dose profile within the shield and the amount of dose absorbed by a target using the Monte Carlo transport code called FLUKA. The output of this code is validated by recreating the experiments from published papers and comparing the results. Once the FLUKA’s output is validated, the efficiency of sixteen materials, subject to SPE and GCR sources, are evaluated. The efficiency comparison is made by fixing the area density of a shield. It was found that polyethylene, water, carbon and silicon outperform aluminum – the primary metal used in spacecraft. In case of composite shield, made of layers of different materials, the 3Carb-9Al combination has better performance than the shield made just of aluminum. This holds true for both Solar Particle Events (SPEs) and Galactic Cosmic Ray (GCR). However, the choice of material is more efficient at shielding from SPE particles rather than from GCR. In case of GCR, the choice of materials is found to have rather small effect on the efficiency of a shield. The percent difference between the rate of dose absorption by a target, shielded by different materials, is within about 9%. Secondary particles make a significant contribution to the target’s dose. For SPEs, the secondary particles are primarily electrons and neutrons. For GCRs, the secondary particles are primarily pions, α-particles and electrons. Protons contribute more than 50% to the target’s dose in both cases.

Bifenilas policloradas (PCBs) são componentes de óleo ascarel, usado extensamente (no Brasil até os anos 80) como isolante em transformadores de energia devido às suas propriedades físico-químicas como estabilidade térmica e alta constante dielétrica. Apesar de ter sido proibido em todo o mundo devido à alta toxicidade dos PCBs presentes em sua composição, ainda resta grande quantidade de ascarel em circulação como resíduo \"passivo\" e resultante de contaminação em trocas dos fluidos dos transformadores, além de vazamentos. A principal forma de eliminação é por incineração, que, além de ser um processo caro, pode provocar a formação de compostos mais tóxicos, as dioxinas. Por isso é importante o monitoramento da concentração dessas substâncias, a fim de evitar maiores impactos ambientais na sua disposição, bem como em estudos de biodegradação. Esta matriz é extremamente complexa, o que torna a extração e determinação desses analitos um processo trabalhoso e difícil. Neste trabalho avaliaram-se métodos de extração e determinação de PCBs presentes na solução padrão comercial PCB Congener MIX 1, SUPELCO (PCBs 10, 28, 52, 138, 153 e 180). O desenvolvimento de métodos de extração (cromatografia em coluna, extração líquido-líquido (L-L), extração em fase sólida (SPE) e micro-extração em fase sólida - SPME) dos PCBs foi seguido da determinação, por cromatografia gasosa com detector por captura de elétrons (CG/DCE), em três matrizes diferentes: óleo ascarel, amostras provenientes de reatores anaeróbios em batelada e solo. Os métodos cuja purificação e extração diminuíram o efeito dos interferentes da matriz, como SPE - Sulfoxide, cromatografia em coluna de sílica e extração L-L com n-hexano foram validados pela avaliação dos seguintes parâmetros: linearidade e faixa de aplicação; precisão instrumental; limite de detecção, limite de quantificação e recuperação absoluta. O critério de escolha entre os métodos para extração dos PCBs do óleo que forneceram maior eficiência (cartucho SPE Sulfoxide e coluna de sílica gel, após lavagem ácida; método da adição de padrão, entre 1,0 e 4,0 mg L-1) deve considerar a disponibilidade de recursos, pois a sílica gel é mais viável economicamente do que o cartucho SPE. Os valores de R2 > 0,99 para o método de extração com sílica, mesmo tendo sido considerados apenas três pontos para a curva de calibração, atestam maior linearidade do que o método com SPE Sulfoxide (R2 entre 0,97 e 0,99). A extração L-L e determinação por CG/DCE dos PCBs (padronização interna) de amostras provenientes de reatores anaeróbios em batelada (aquosas, em matriz extremamente complexa com biomassa e espuma de poliuretano para imobilização de microrganismos) foram eficientes na faixa de concentração entre 0,05 e 0,5 mg L-1. Esse método foi adequado para monitorar PCBs em estudo de degradação anaeróbia e teste de adsorção dos PCBs em espuma; forneceu linearidade com R2 entre 0,93 e 0,96 e limites de detecção de 0,048 a 0,298 mg L-1, além de recuperação absoluta entre 14,1% e 110,7%. As condições testadas por SPME não permitiram a extração dos PCBs de óleo e de solo, principalmente devido à dessorção incompleta dos PCBs da fibra de polidimetil-siloxano, de 100 μm. / Polychlorinated biphenyls (PCBs) are components of ascarel, oil widely used as insulation (until the \'80s in Brazil) due to its physicochemical properties such as thermal stability and high dielectric constant. Despite having been banned worldwide due to the high toxicity of PCBs present in its composition, there are still lots of outstanding ascarel as \"passive\" residue and resulting contamination of fluids in transformers exchanges, plus leaks. The main form of disposal is incineration, which, besides being costly, can cause the formation of more toxic compounds, that is, dioxins. It is therefore important to monitor the concentration of these substances in order to prevent further environmental impacts in their disposal, as well as in studies of biodegradation. This is an extremely complex matrix, which makes the extraction and determination of this analytes very difficult and labor intensive. In this work we have evaluated methods of extraction and determination of the PCBs present in the standard solution Congener MIX 1, SUPELCO (PCBs 10, 28, 52, 138, 153 e 180). The extraction and cleanup developed methods which reduced the effects of interfering matrix as solid phase extraction (SPE) - Sulfoxide, column chromatography on silica and liquid-liquid (L-L) extraction with n-hexane, and solid phase microextraction (SPME) after determination of the PCBs by gas chromatography with electron capture detector (GC/ECD) were validated by assessing the following parameters: linearity and range of application; instrumental precision; detection limit; limit of quantification and absolute recovery. The criterion for choosing between the methods for extraction of PCBs from the oil with a higher efficiency (SPE cartridge Sulfoxide and silica gel column, after acid washing; using the standard addition method, between 1.0 and 4.0 mg L-1) must evaluate the availability resources, since the silica gel is more economically viable than the SPE cartridge. The R2 values > 0.99 for silica extraction method, even though it was considered only three points for the calibration curve, attested higher linearity than the method with SPE Sulfoxide (R2 between 0.97 and 0.99). The L-L extraction and determination by GC/ECD of the PCBs (internal standardization) of samples from batch anaerobic reactors (aqueous, in a very complex matrix with biomass and polyurethane foam for the immobilization of microorganisms) were efficient in the concentration range between 0.05 and 0.5 mg L-1. This method was suitable to monitor PCBs in anaerobic degradation studies and its adsorption on foam; provided R2 linearity between 0.93 and 0.96 and detection limits from 0.048 to 0.298 mg L-1, as well as absolute recovery between 14.1% and 110.7%. The conditions tested for SPME technique did not allow the extraction of the PCBs from the oil and soil, mainly due to the \"incomplete dessorption\" of PCBs from the polydimethylsiloxane fiber of 100 micron.

Bifenilas policloradas (PCBs) são componentes de óleo ascarel, usado extensamente (no Brasil até os anos 80) como isolante em transformadores de energia devido às suas propriedades físico-químicas como estabilidade térmica e alta constante dielétrica. Apesar de ter sido proibido em todo o mundo devido à alta toxicidade dos PCBs presentes em sua composição, ainda resta grande quantidade de ascarel em circulação como resíduo \"passivo\" e resultante de contaminação em trocas dos fluidos dos transformadores, além de vazamentos. A principal forma de eliminação é por incineração, que, além de ser um processo caro, pode provocar a formação de compostos mais tóxicos, as dioxinas. Por isso é importante o monitoramento da concentração dessas substâncias, a fim de evitar maiores impactos ambientais na sua disposição, bem como em estudos de biodegradação. Esta matriz é extremamente complexa, o que torna a extração e determinação desses analitos um processo trabalhoso e difícil. Neste trabalho avaliaram-se métodos de extração e determinação de PCBs presentes na solução padrão comercial PCB Congener MIX 1, SUPELCO (PCBs 10, 28, 52, 138, 153 e 180). O desenvolvimento de métodos de extração (cromatografia em coluna, extração líquido-líquido (L-L), extração em fase sólida (SPE) e micro-extração em fase sólida - SPME) dos PCBs foi seguido da determinação, por cromatografia gasosa com detector por captura de elétrons (CG/DCE), em três matrizes diferentes: óleo ascarel, amostras provenientes de reatores anaeróbios em batelada e solo. Os métodos cuja purificação e extração diminuíram o efeito dos interferentes da matriz, como SPE - Sulfoxide, cromatografia em coluna de sílica e extração L-L com n-hexano foram validados pela avaliação dos seguintes parâmetros: linearidade e faixa de aplicação; precisão instrumental; limite de detecção, limite de quantificação e recuperação absoluta. O critério de escolha entre os métodos para extração dos PCBs do óleo que forneceram maior eficiência (cartucho SPE Sulfoxide e coluna de sílica gel, após lavagem ácida; método da adição de padrão, entre 1,0 e 4,0 mg L-1) deve considerar a disponibilidade de recursos, pois a sílica gel é mais viável economicamente do que o cartucho SPE. Os valores de R2 > 0,99 para o método de extração com sílica, mesmo tendo sido considerados apenas três pontos para a curva de calibração, atestam maior linearidade do que o método com SPE Sulfoxide (R2 entre 0,97 e 0,99). A extração L-L e determinação por CG/DCE dos PCBs (padronização interna) de amostras provenientes de reatores anaeróbios em batelada (aquosas, em matriz extremamente complexa com biomassa e espuma de poliuretano para imobilização de microrganismos) foram eficientes na faixa de concentração entre 0,05 e 0,5 mg L-1. Esse método foi adequado para monitorar PCBs em estudo de degradação anaeróbia e teste de adsorção dos PCBs em espuma; forneceu linearidade com R2 entre 0,93 e 0,96 e limites de detecção de 0,048 a 0,298 mg L-1, além de recuperação absoluta entre 14,1% e 110,7%. As condições testadas por SPME não permitiram a extração dos PCBs de óleo e de solo, principalmente devido à dessorção incompleta dos PCBs da fibra de polidimetil-siloxano, de 100 μm. / Polychlorinated biphenyls (PCBs) are components of ascarel, oil widely used as insulation (until the \'80s in Brazil) due to its physicochemical properties such as thermal stability and high dielectric constant. Despite having been banned worldwide due to the high toxicity of PCBs present in its composition, there are still lots of outstanding ascarel as \"passive\" residue and resulting contamination of fluids in transformers exchanges, plus leaks. The main form of disposal is incineration, which, besides being costly, can cause the formation of more toxic compounds, that is, dioxins. It is therefore important to monitor the concentration of these substances in order to prevent further environmental impacts in their disposal, as well as in studies of biodegradation. This is an extremely complex matrix, which makes the extraction and determination of this analytes very difficult and labor intensive. In this work we have evaluated methods of extraction and determination of the PCBs present in the standard solution Congener MIX 1, SUPELCO (PCBs 10, 28, 52, 138, 153 e 180). The extraction and cleanup developed methods which reduced the effects of interfering matrix as solid phase extraction (SPE) - Sulfoxide, column chromatography on silica and liquid-liquid (L-L) extraction with n-hexane, and solid phase microextraction (SPME) after determination of the PCBs by gas chromatography with electron capture detector (GC/ECD) were validated by assessing the following parameters: linearity and range of application; instrumental precision; detection limit; limit of quantification and absolute recovery. The criterion for choosing between the methods for extraction of PCBs from the oil with a higher efficiency (SPE cartridge Sulfoxide and silica gel column, after acid washing; using the standard addition method, between 1.0 and 4.0 mg L-1) must evaluate the availability resources, since the silica gel is more economically viable than the SPE cartridge. The R2 values > 0.99 for silica extraction method, even though it was considered only three points for the calibration curve, attested higher linearity than the method with SPE Sulfoxide (R2 between 0.97 and 0.99). The L-L extraction and determination by GC/ECD of the PCBs (internal standardization) of samples from batch anaerobic reactors (aqueous, in a very complex matrix with biomass and polyurethane foam for the immobilization of microorganisms) were efficient in the concentration range between 0.05 and 0.5 mg L-1. This method was suitable to monitor PCBs in anaerobic degradation studies and its adsorption on foam; provided R2 linearity between 0.93 and 0.96 and detection limits from 0.048 to 0.298 mg L-1, as well as absolute recovery between 14.1% and 110.7%. The conditions tested for SPME technique did not allow the extraction of the PCBs from the oil and soil, mainly due to the \"incomplete dessorption\" of PCBs from the polydimethylsiloxane fiber of 100 micron.

O presente estudo teve como objetivo avaliar os compostos carbonílicos na atmosfera da cidade de São Paulo. Para tal medidas de carbonílicos foram feitas empregando metodologia analítica já existente. A influência do ozônio na geração de artefatos durante a amostragem de compostos carbonílicos empregando sorventes sólidos, como C18 e sílica, observada em amostragens diurnas e noturnas ( ausência de O3) permitiu estabelecer um protocolo de amostragem que recomenda a utilização de um coletor de O3 na entrada do cartucho de sílica impregnado com 2,4-dinitro-fenil-hidrazina (DNPH) para evitar possíveis artefatos de amostragem. Os compostos carbonílicos presentes na fase gasosa da atmosfera da cidade de São Paulo foram medidos durante o inverno de 1999, em dois sítios distintos, Cidade Universitária (CID) e Água Funda (AF). Semelhante a outras regiões urbanas do mundo, os carbonílicos majoritários foram formaldeído (0,6-46,7 ppbv) e acetaldeído (1,2-75,3 ppbv). Os carbonílicos de peso molecular maior (>C2) tiveram abundância relativa de 20-40%, sendo acetona (0,3-13,0 ppbv), acroleína (0,1-5,2 ppbv), propionaldeído (0,5-8,5 ppbv), isômeros C4 (0,1-2,4 ppbv), benzaldeído (0,1-5,4 ppbv), valeraldeído (0,1-3,5 ppbv), m-tolualdeído (0,1-2,4 ppbv) e hexaldeído (0,1-4,5 ppbv). As razões de concentração para acetaldeído/formaldeído > l em julho sugerem que a contribuição das emissões diretas é predominante. Já no mês de agosto, foi observada uma diminuição das razões médias, 1,1-1,3 (manhã), 0,7-0,8 (meio-dia) e 0,6 (tarde), indicando que há contribuição de emissões diretas na manhã e nos outros períodos prevalece a formação fotoquímica in situ. Neste trabalho, a influência de parâmetros meteorológicos nos níveis dos compostos carbonílicos foi verificada em alguns eventos. Foram propostas fontes de emissão através de correlações com CO e O3. As correlações no sítio CID em agosto mostraram que a contribuição das emissões veiculares é muito importante pela manhã, mas a influência dos processos fotoquímicos foi observada nos períodos seguintes. Finalmente, considera-se que este trabalho contribuiu para uma compreensão atual sobre o panorama dos carbonílicos na cidade e para o estudo em grande escala que permitirá diagnosticar e prever os episódios de poluição na cidade de São Paulo. / The goals of this study were to evaluate the carbonylic compounds in the atmosphere of São Paulo City. To accomplish this, measures were carried out using the pre-existent analytical methodology. The ozone influence in artifacts generation during carbonyls sampling using solid sorbents such as C18 and silica, observed through day and night samples, allowed to establish a sampling protocol which recommends the utilization of an ozone scrubber at the upstream end of the DNPH-impregnated silica cartridge to avoid eventual sarnpling artifacts. Carbonyl compounds present in the gaseous phase of São Paulo atmosphere were measured during winter, 1999, at two different sites, Cidade Universitária (CID) and Água Funda (AF). As observed in other urban regions of the world, the major carbonyls were formaldehyde (0,6-46, 7 ppbv) e acetaldehyde (1,2-75,3 ppbv). Toe higher molecular weight carbonyls (>C2) showed relative abundances of 20-40%, being acetone (0,3-13,0 ppbv), acrolein (0,1-5,2 ppbv), propionaldehyde (0,5-8,5 ppbv), isomers C4 (0,1-2,4 ppbv), benzaldehyde (0,1-5,4 ppbv), valeraldehyde (0,1-3,5 ppbv), m-tolualdehyde (0,1-2,4 ppbv) and hexaldehyde (0,1-4,5 ppbv). The acetaldehyde/formaldehyde (A/F) ratio >1 in July suggests that direct emissions influence is predominant. In August, a decrease in average concentration was observed, 1,1-1,3 (morning), 0,7-0,8 (midday) and 0,6 (evening), indicating the direct emissions contribution in the morning, while for the other periods the in situ photochemical formation prevails. At the present work, the influence of meteorological parameters in carbonyls levels was also pointed out for some events. The emission sources are proposed by calculating the correlations between carbonyls and CO and O3. The correlations found for the CID site in August showed that the vehicular emissions are very important in the morning, but the influence of photochemical processes was observed in the subsequent periods. Finally, this work contributed to a current comprehension of the carbonyls panorama in the city and for the large scale study that will allow the diagnosis and mimic of the urban chemical environment in São Paulo City.

<p>Etanolni ekstrakti tropa odabranih sorti cvekle (Detroit, Cardeal-F1, Egipatska, Bikor i Kestrel) preči&scaron;ćeni su primenom ekstrakcije na čvrstoj fazi (SPE). Sadržaj ukupnih<br />fenolnih jedinjenja, flavonoida i betalaina u preči&scaron;ćenim ekstraktima određeni su spektrofotometrijskim metodama. HPLC analizom utvrđen je kvalitativni i kvantitativni sastav fenolnih jedinjenja i betalaina ekstrakata tropa odabranih sorti cvekle. ESR spektroskopijom ispitana je antiradikalska aktivnost ekstrakata topa cvekle na stabilne DPPH i reaktivne superoksid anjon i hidroksil radikale.<br />Spektrofotometrijski je određena antioksidativna aktivnost na DPPH radikale i redukciona sposobnost po Oyaizu u ekstraktima odabranih sorti cvekle. Ispitana je in vitro<br />antiproliferativna aktivnost frakcija ekstrakata, njihovim delovanjem na rast tri histolo&scaron;ki različite humane ćelijske linije: MCF-7 (adenokarcinom dojke), HeLa (epitelni karcinom cerviksa)i MRC-5 (fetalni fibroblastni karcinom pluća). U zavr&scaron;noj fazi rada određena je antimikrobna aktivnost ekstrakata tropa odabranih sorti cvekle.</p> / <p> Beetroot (Detroit, Cardeal-F1, Egipatska, Bikor i Kestrel)<br /> pomace ethanol extracts were purified using solid phase<br /> extraction (SPE). Contents of total phenols, flavonoids and<br /> betalains in purified extracts were determined by spectrophotometric<br /> methods. HPLC analysis were used for quantitative<br /> and qualitative characterization of phenolic compounds<br /> and betalains in investigated extracts. ESR spectroscopy<br /> was used for investigation of antiradical activity of<br /> beetroot pomace extracts on stable DPPH and reactive<br /> superoxide anion and hydroxyl radicals. Antioxidant activity<br /> was determined spectrophotometrically on DPPH radicals<br /> and reducing power according to Oyaizu in the beetroot pomace<br /> extracts. Antiproliferative activity of investigated extracts<br /> was determined in vitro, testing their influence on the<br /> growth of three histologically different human cell lines:<br /> MCF-7 (breast adenocarcinoma), HeLa (cervix epithelioid<br /> carcinoma) and MRC-5 (fetal lung). Also, antimicrobial activity<br /> of beetroot pomace extracts was determined.</p>

O presente estudo teve como objetivo avaliar os compostos carbonílicos na atmosfera da cidade de São Paulo. Para tal medidas de carbonílicos foram feitas empregando metodologia analítica já existente. A influência do ozônio na geração de artefatos durante a amostragem de compostos carbonílicos empregando sorventes sólidos, como C18 e sílica, observada em amostragens diurnas e noturnas ( ausência de O3) permitiu estabelecer um protocolo de amostragem que recomenda a utilização de um coletor de O3 na entrada do cartucho de sílica impregnado com 2,4-dinitro-fenil-hidrazina (DNPH) para evitar possíveis artefatos de amostragem. Os compostos carbonílicos presentes na fase gasosa da atmosfera da cidade de São Paulo foram medidos durante o inverno de 1999, em dois sítios distintos, Cidade Universitária (CID) e Água Funda (AF). Semelhante a outras regiões urbanas do mundo, os carbonílicos majoritários foram formaldeído (0,6-46,7 ppbv) e acetaldeído (1,2-75,3 ppbv). Os carbonílicos de peso molecular maior (>C2) tiveram abundância relativa de 20-40%, sendo acetona (0,3-13,0 ppbv), acroleína (0,1-5,2 ppbv), propionaldeído (0,5-8,5 ppbv), isômeros C4 (0,1-2,4 ppbv), benzaldeído (0,1-5,4 ppbv), valeraldeído (0,1-3,5 ppbv), m-tolualdeído (0,1-2,4 ppbv) e hexaldeído (0,1-4,5 ppbv). As razões de concentração para acetaldeído/formaldeído > l em julho sugerem que a contribuição das emissões diretas é predominante. Já no mês de agosto, foi observada uma diminuição das razões médias, 1,1-1,3 (manhã), 0,7-0,8 (meio-dia) e 0,6 (tarde), indicando que há contribuição de emissões diretas na manhã e nos outros períodos prevalece a formação fotoquímica in situ. Neste trabalho, a influência de parâmetros meteorológicos nos níveis dos compostos carbonílicos foi verificada em alguns eventos. Foram propostas fontes de emissão através de correlações com CO e O3. As correlações no sítio CID em agosto mostraram que a contribuição das emissões veiculares é muito importante pela manhã, mas a influência dos processos fotoquímicos foi observada nos períodos seguintes. Finalmente, considera-se que este trabalho contribuiu para uma compreensão atual sobre o panorama dos carbonílicos na cidade e para o estudo em grande escala que permitirá diagnosticar e prever os episódios de poluição na cidade de São Paulo. / The goals of this study were to evaluate the carbonylic compounds in the atmosphere of São Paulo City. To accomplish this, measures were carried out using the pre-existent analytical methodology. The ozone influence in artifacts generation during carbonyls sampling using solid sorbents such as C18 and silica, observed through day and night samples, allowed to establish a sampling protocol which recommends the utilization of an ozone scrubber at the upstream end of the DNPH-impregnated silica cartridge to avoid eventual sarnpling artifacts. Carbonyl compounds present in the gaseous phase of São Paulo atmosphere were measured during winter, 1999, at two different sites, Cidade Universitária (CID) and Água Funda (AF). As observed in other urban regions of the world, the major carbonyls were formaldehyde (0,6-46, 7 ppbv) e acetaldehyde (1,2-75,3 ppbv). Toe higher molecular weight carbonyls (>C2) showed relative abundances of 20-40%, being acetone (0,3-13,0 ppbv), acrolein (0,1-5,2 ppbv), propionaldehyde (0,5-8,5 ppbv), isomers C4 (0,1-2,4 ppbv), benzaldehyde (0,1-5,4 ppbv), valeraldehyde (0,1-3,5 ppbv), m-tolualdehyde (0,1-2,4 ppbv) and hexaldehyde (0,1-4,5 ppbv). The acetaldehyde/formaldehyde (A/F) ratio >1 in July suggests that direct emissions influence is predominant. In August, a decrease in average concentration was observed, 1,1-1,3 (morning), 0,7-0,8 (midday) and 0,6 (evening), indicating the direct emissions contribution in the morning, while for the other periods the in situ photochemical formation prevails. At the present work, the influence of meteorological parameters in carbonyls levels was also pointed out for some events. The emission sources are proposed by calculating the correlations between carbonyls and CO and O3. The correlations found for the CID site in August showed that the vehicular emissions are very important in the morning, but the influence of photochemical processes was observed in the subsequent periods. Finally, this work contributed to a current comprehension of the carbonyls panorama in the city and for the large scale study that will allow the diagnosis and mimic of the urban chemical environment in São Paulo City.

<p>Acetonski ekstrakti bobičastog voća iz familija Ericaceae<br />(borovnica,<em> Vaccinium myrtillus</em> L., i brusnica, <em>Vaccinium<br />macrocarpon</em> L.) i Rosaceae (&scaron;ipak, <em>Rosa canina</em> L., i glog,<br /><em>Crataegus oxyacantha</em> L.) preči&scaron;ćeni su i frakcionisani<br />primenom ekstrakcije na čvrstoj fazi (SPE). Sadržaj ukupnih<br />polifenolnih jedinjenja, flavonoida i antocijana u preči&scaron;ćenim<br />ekstraktima određeni su spektrofotometrijskim metodama.<br />HPLC analizom utvrđen je kvalitativni i kvantitativni<br />sastav frakcija ekstrakata ispitivanih bobica. ESR spektroskopijom<br />ispitana je antiradikalska aktivnost frakcija ekstrakata<br />bobica na stabilne DPPH^● i reaktivne superoksid anjon i<br />hidroksil radikale. ESR spektroskopijom ispitano je i<br />prisustvo slobodnih radikala antioksidanata nastalih tokom<br />reakcije frakcija ekstrakata bobica sa superoksid anjon<br />radikalima. U zavr&scaron;noj fazi rada ispitana je<em> in vitro</em><br />antiproliferativna aktivnost frakcija ekstrakata bobica, njihovim<br />delovanjem na rast tri histolo&scaron;ki različite humane ćelijske<br />linije: HeLa (epitelni karcinom cerviksa), HT-29 (adenokarcinom<br />debelog creva) i MCF-7 (adenokarcinom dojke).</p> / <p>Acetone extracts of berries form Ericaceae (bilberry, <em>Vaccinium<br />myrtillus</em> L., and cranberry, <em>Vaccinium macrocarpon</em><br />L.) and Rosaceae (rose hip, <em>Rosa canina</em> L., and hawthorn,<br /><em>Crataegus oxyacantha </em>L.) families were purified and fractionated<br />using solid phase extraction (SPE). Contents of total<br />polyphenols, flavonoids and anthocyanins in purified extracts<br />were determined by spectrophotometric methods.<br />HPLC analysis were used for quantitative and qualitative<br />characterization of investigated berry extracts fractions. ESR<br />spectroscopy was used for investigation of antiradical activity<br />of berry extracts fractions on stable DPPH^● and<br />reactive superoxide anion and hydroxyl radicals. The<br />presence of antioxidant free radicals formed during reaction<br />of investigated berry extracts fractions with superoxide<br />anion radicals was also investigated by ESR. Antiprolixferative<br />activity of investigated berry extracts fractions was<br />determined<em> in vitro</em>, testing their influence on the growth of<br />three histologically different human cell lines: HeLa (cervix<br />epithelioid carcinoma), HT-29 (colon adenocarcinoma) i<br />MCF-7 (breast adenocarcinoma).</p>

The goal of the QPACE project is to build a novel cost-efficient massive parallel supercomputer optimized for LQCD (Lattice Quantum Chromodynamics) applications. Unlike previous projects which use custom ASICs, this is accomplished by using the general purpose multi-core CPU PowerXCell 8i processor tightly coupled with a custom network processor implemented on a modern FPGA. The heterogeneous architecture of the PowerXCell 8i processor and its core-independent OS-bypassing access to the custom network hardware and application-oriented 3D torus topology pose interesting challenges for the implementation of the applications. This work will describe and evaluate the implementation possibilities of message passing APIs: the more general MPI, and the more QCD-oriented QMP, and their performance in PPE centric or SPE centric scenarios. These results will then be employed to optimize HPL for the QPACE architecture. Finally, the developed approaches and concepts will be briefly discussed regarding their applicability to heterogeneous node/network architectures as is the case in the "High-speed Network Interface with Collective Operation Support for Cell BE (NICOLL)" project.

L’analyse de la composition chimique de deux orchidées de la sous-tribu des Aeridinae, Aerides rosea Lodd. ex. Lindl. & Paxton et Acampe rigida (Buch.-Ham. ex Sm.) P. F. Hunt, a été menée en ayant recours à des techniques de couplages et grâce à une stratégie de déréplication. Dix dérivés phénanthréniques ont ainsi été identifiés dans les tiges d’A. rosea, dont deux nouvellement décrits. Quatre stilbénoïdes, trois dérivés d'acides phénoliques et quatre esters d'acide cinnamique ont été identifiés dans les tiges d’A. rigida. Nous avons également effectué des dosages de traceurs dans différents échantillons de deux représentants de la tribu des Vandeae : Vanda teres (Roxb.) Lindl. et Vanda coerulea Griff. ex. Lindl., afin de mettre en évidence d’éventuelles variations de composition en fonction des facteurs environnementaux et du stade de croissance végétative. Enfin, nous avons mis au point des conditions d’isolement préparatif par chromatographie de partage centrifuge afin de purifier des marqueurs biologiques préalablement identifiés dans les tiges de Vanda teres : trois glucospyranosyloxybenzyl - malates ainsi que leur précurseur biosynthétique. / Phytochemical analyses of the composition of two orchids Aeridinae subtribe, Aerides rosea Lod . ex . Lindl . & Paxton and Acampe rigida (Buch. -Ham . Ex Sm.) P. F. Hunt were conducted using the state-of-the-art hyphenated techniques and a developed dereplication strategy. Ten phenanthrene derivatives have been identified in the stems of A. rosea, including two newly described structures. Four stilbenoids, three phenolic acids derivatives and four cinnamic acid esters were identified in the stems of A. rigida. We also performed quantitative assays of chemical tracers in different samples of two representative species from the Vandeae tribe: Vanda teres (Roxb.) Lindl. and Vanda coerulea Griff. ex. Lindl., in the aim to highlight possible variations in their composition, depending on environmental factors and vegetative growth stage. Finally, we have developed conditions for preparative isolation using centrifugal partition chromatography to purify biomarkers previously identified in the stems of Vanda teres: three glucosyloxybenzyl malates derivatives and their biosynthetic precursor.