Spelling suggestions: "subject:"bopolar"" "subject:"bronchiolar""
71 |
Right Ventricle Segmentation Using Cardiac Magnetic Resonance ImagesRosado-Toro, Jose A. January 2016 (has links)
The world health organization has identified cardiovascular disease as the leading cause of non-accidental deaths in the world. The heart is identified as diseased when it is not operating at peak efficiency. Early diagnosis of heart disease can impact treatment and improve a patient's outcome. An early sign of a diseased heart is a reduction in its pumping ability, which can be measured by performing functional evaluations. These are typically focused on the ability of the ventricles to pump blood to the lungs (right ventricle) or to the rest of the body (left ventricle). Non-invasive imaging modalities such as cardiac magnetic resonance have allowed the use of quantitative methods for ventricular functional evaluation. The evaluation still requires the tracing of the ventricles in the end-diastolic and end-systolic phases. Even though manual tracing is still considered the gold standard, it is prone to intra- and inter-observer variability and is time consuming. Therefore, substantial research work has been focused on the development of semi- and fully automated ventricle segmentation algorithms. In 2009 a medical imaging conference issued a challenge for short-axis left ventricle segmentation. A semi-automated technique using polar dynamic programming generated results that were within human variability. This is because a path in a polar coordinate system yields a circular object in the Cartesian grid and the left ventricle can be approximated as a circular object. In 2012 there was a right ventricle segmentation challenge, but no polar dynamic programming algorithms were proposed. One reason may be that polar dynamic programming can only segment circular shapes. To use polar dynamic programming for the segmentation of the right ventricle we first expanded the capability of the technique to segment non-circular shapes. We apply this new polar dynamic programming in a framework that uses user-selected landmarks to segment the right ventricle in the four chamber view. We also explore the use of four chamber right ventricular segmentation to segment short-axis views of the right ventricle.
|
72 |
Paleomagnetism and petrogenesis of Paleoproterozoic units from the Uatumã event in the northern Amazonian Craton / Paleomagnetismo e petrogênese de unidades Paleoproterozóicas do evento Uatumã no norte do Craton AmazônicoAntonio, Paul Yves Jean 16 February 2017 (has links)
An anorogenic magmatism covered a large part (1.500.000 km2) of the Amazonian craton at ca. 1880 Ma and defined a Silicic Large Igneous Province (SLIP) called the Uatumã event. The aim of this work is to study the paleomagnetism and petrology of these rocks to define the space-time framework of the Uatumã event and to try to elucidate the Amazonian craton evolution during the Columbia supercontinent amalgamation. Two regions were selected in the southwestern Amazonian craton (Pará) for sampling: (1) The Tucumã area where 16 felsic dikes, 7 mafic dikes, a gabbroic dike and 3 sites of the Archean basement were collected, and (2) the São Felix do Xingu area where, 7 sites of rhyolitic lava flows, 2 sites of ignimbrites, a felsic dike and a volcanic breccia belonging to the Santa Rosa Formation were sampled, and also 6 sites of the Sobreiro Formation (volcanoclastic rocks, andesitic) and one felsic dike of the Velho Guilherme Suite were collected. Petrology of the felsic dikes of Tucumã (1880.9 ± 6.7 Ma U-Pb zrn) showed that they represent the dike swarm associated with the Santa Rosa volcanic Formation. The remanent magnetization of the felsic dikes is carried by PSD magnetite and hematite. This hematite is syn- to post magmatic derived from hydrothermal fluids. Magnetic mineralogy can be used as a proxy to quantify the hydrothermal alteration. AF, thermal, LTD + AF and LTD + thermal demagnetizations show a northwest direction with a positive inclination (component A), whose site mean directions gives a paleomagnetic pole located at 52.9°S, 76.4°E, A95= 10.4 °, K= 13.52). However, this component seems to represent a remagnetization, probabily occurred at Neoproterozoic times. Another magnetic component (named component B) was also isolated for these rocks, and it was associated to a Mesozoic regional remagnetization related to the Central Atlantic Magmatic Province (CAMP). Yet, a third southwestern direction with low positive inclination (component C) was also isolated for some sites. This component was interpreted to be related with the ca. 1760 Ma Velho Guilherme magmatic intrusion. The best paleomagnetic results were obtained in the São Felix do Xingu area. Two new primary paleomagnetic poles have been determined: (i) SF1 pole (319.7°E, 24.7°S, N= 10; A95= 16.9 °) was obtained for andesites and rhyolites dated to 1877.4 ± 4.3 Ma (U-Pb zrn, LA-ICPMS), and its primary origin is confirmed by an inverse baked contact test (> 1853 Ma). Petrography shows that the magnetic mineralogy of this component is hematite formed by hydrothermal fluids syn- to post magmatic. (Ii) SF2 pole (220.1°E, 31.1°N, N= 15 ° A95= 9.7 °) was determined by the remanent magnetization of the felsic dike of the Velho Guilherme Suite but also as secondary magnetizations in samples of the Santa Rosa and Sobreiro Formations. An age of 1853.7 ± 6.2 Ma (U-Pb zrn, LA-ICPMS) is calculated for the felsic dike carrying SF2, whose primary origin is confirmed by a positive baked contact test. The SF1 and SF2 poles have a significant difference in angular distance, for a time interval of only ~25 Ma. Similar coeval paleomagnetic discrepancies were observed for other cratons (India, Superior (Laurentia), Slave (Laurentia), Kalahari, Baltica and Siberia), which can be explained by a True Polar Wander (TPW) event at ca. 1880 1860 Ma. This period is marked by a high mantle activity, which results in the amalgamation of the Columbia supercontinent, formed at ca. 1850 1800 Ma. Amalgamation of supercontinent may cause the formation of superplume and thermal insulation which can disturb mass distribution in mantle and alter the inertial gravity tensor of the Earth. A True Polar Wander (TPW) event may thus have taken place, which will move the cratons and the superplumes towards the equator. These conditions may be related to a reorganization of the whole mantle following a global magmatic quiescence between 2400 and 2200 Ma. / Um grande magmatismo intraplaca cobriu várias áreas (1.500.000 km2) do Cráton Amazônico há 1880 Ma, o qual define uma grande província ígnea (SLIP) chamada coletivamente de \"evento Uatumã\". O objetivo deste trabalho é estudar o paleomagnetismo e a petrologia dessas rochas para definir o contexto espaço-temporal do evento Uatumã e a posição do cráton Amazônico dentro do Supercontinente Columbia. Duas áreas de estudo foram escolhidas para a amostragem, localizadas no sudoeste do cráton Amazônico (Pará): (1) A região de Tucumã, onde 16 diques félsicos, 7 diques máficos, um dique de gabro e 3 sítios da granodioritos do embasamento Arqueano foram coletadas. (2) A região de São Felix do Xingu, onde 7 sitios de lavas riolíticas, 2 sitios de ignimbritos, um dique felsico e um de brechas vulcânicas da Formação Santa Rosa foram amostrados. Seis sitios da Formação Sobreiro (rochas vulcanoclásticas andesíticas) e um dique felsico da Suite Velho Guilherme foram também coletados. O estudo petrológico em amostras dos diques felsicos de Tucumã (1880.9 ± 6.7 Ma U-Pb zrn) mostra que eles representam um sistema de siques associado à Formação vulcânica Santa Rosa. A magnetização remanente dos diques felsicos é portada por magnetita PSD e hematita. A hematita é sin- a pós-magmática e a mineralogia magnética pode ser usada para quantificar esta alteração hidrothermal. Desmagnetizações AF, térmica, LTD + AF e LTD + térmica mostram uma componente característica com direção noroeste e inclinação positiva (Componente A) para amostras de 16 sítios, cuja direção média é Dm= 330.5, Im= 27.9 (N= 16, 95= 11.4, R= 14.7, k= 11.47). O pólo paleomagnético calculado com a média dos PGVs está localizado em 52.9°S, 76.4°E (A95= 10.4°, K= 13.52). Entretanto, esta componente parece ser decorrente de uma remagnetização, provavelmente ocorrida durante o final do Neoproterozoico. Outra componente (chamada de Componente B) foi também isolada para estas rochas, a qual foi associada a uma remagnetização regional ocorrida durante a formação da Província Magmática do Atlântico Central (PMAC). Ainda, uma Terceira componente (C), representada por direções sudoeste e inclinações positivas baixas foi isolada para amostras de alguns sítios. Esta componente foi interpretada como sendo relacionada ao evento magmático da Suíte Intrusiva Velho Guilherme com idade de ~1860 Ma. Os melhores resultados, entretanto, foram obtidos para a região de São Felix do Xingu. Dois novos polos paleomagnéticos, considerados de origem primária, foram encontrados para o Craton Amazônico: O polo SF1 (319.7°E; 24.7°S; N= 10; A95= 16.9°) foi obtido para rochas félsicas e andesíticas, as quais foram datadas em 1877.4 ± 4.3 Ma (U-Pb zrn, LA-ICP-MS), sendo que sua origem primária é embasada em um teste de contato cozido inverso. A investigação petrográfica mostra que o portador magnético desta componente é atribuído à hematita, formada por processos hidrotermais tardi- a pós-magmáticos. O polo SF2 (220.1°E; 31.1°S; N= 15; A95= 9.7°) foi determinado para a componente de magnetização revelada para o dique da Suíte Velho Guilherme, Esta componente é também encontrada como componente secundária em amostras das formações Santa Rosa e Sobreiro, além de algumas amostras de sítios coletados na região de Tucumã (Componente C). Uma idade de 1853.7 ± 6.2 Ma (U-Pb zrn, LA-ICP-MS) foi atribuída à componente SF2 e sua origem primária é confirmada pelo teste de contato cozido positivo realizado para este dique. Os polos SF1 e SF2 são bem discrepantes, embora a diferença de idade destes polos seja de apenas 25 Ma. Resultados similares têm sido obtidos para polos de mesma idade de outros blocos cratônicos (India, Superior (Laurentia), Slave (Laurentia), Kalahari, Baltica e Sibéria), os quais podem ser explicados por um evento de deriva polar verdadeira (DPV) ocorrido nesta época, em decorrência de uma reorganização do Manto. Esta época (1880 Ma) é marcada por uma alta atividade do Manto, a qual culminou com a formação do Supercontinente Columbia, por volta de 1850 1800 Ma. A formação de superplumas e o isolamento térmico causado pela consequente formação do Columbia podem ter sido causas de perturbações de densidades que alteraram o tensor inercial da Terra e, consequentemente, um evento de DPV pode ter deslocado os continente e as superplumas para a região do equador. Estas condições podem estar ligadas a uma inteira reorganização mantélica que seguiu um período de pouca atividade magmática, ocorrido entre 2400 e 2200 Ma.
|
73 |
Além da Antártica: os limites da vida ao frio e à dessecação no âmbito da astrobiologia. / Beyond Antarctica: the limits of life to cold and desiccation in the context of astrobiology.Pereira, Felipe Nóbrega 05 February 2016 (has links)
Na Antártica e no Ártico, a vida microbiana é presente e diversificada, tendo se adaptado a condições similares às encontradas em mundos que despertam interesse à astrobiologia. Este estudo investigou as alterações fisiológicas e fenotípicas do extremófilo psicrotrófico Exiguobacterium antarcticum B7 sob diferentes temperaturas. Foram utilizadas técnicas de eletroforese de proteínas em duas dimensões associada a espectrometria de massa, juntamente com técnicas de microscopia. E. antarcticum foi também submetida a condições físicas encontradas em Marte e no ambiente interplanetário. Seguindo evidências de que micro-organismos psicrotróficos podem também ser resistentes a períodos prolongados de dessecação, foi investigada a presença de linhagens microbianas resistentes a anidrobiose em solos da Antártica e permafrost do Ártico. Por fim, voltando-se à ecologia microbiana de solos polares permanentemente congelados, foi estudada a diversidade microbiana de três estratos de permafrost do ártico canadense com o uso de sequenciamento de DNA de nova geração. / In Antarctica and the Arctic, microbial life is present and diverse, having adapted to low temperature and low humidity conditions, similar to the worlds that arouse more interest to astrobiology. This study investigated the physiological changes of the psychrotrophic extremophile Exiguobacterium antarcticum B7 at different temperatures. Two dimensional protein electrophoresis techniques was used for proteome analysis in conjunction with mass spectrometry, as well as microscopy techniques. E. antarcticum was also subjected to physical parameters found on Mars and in the interplanetary environment. Following evidence that psychrotrophic microorganisms may also be resistant to prolonged periods of desiccation, it was investigated the presence of microbial strains resistant to anhydrobiosis on Antarctic soils and Arctic permafrost. At last, turning the attention to the microbial ecology of permanently frozen polar soils, it was studied the bacterial diversity of three Arctic permafrost strata with next-generation high throughput DNA sequencing.
|
74 |
Bestimmung von Ozonabbauraten über der Arktis und Antarktis mittels Ozonsonden- und Satellitendaten / Determination of ozone loss rates over the Arctic and Antarctic using ozone sonde and satellite dataStreibel, Martin Albert Gerhard January 2005 (has links)
Diese Arbeit beschäftigt sich mit der chemischen Ozonzerstörung im arktischen und antarktischen stratosphärischen Polarwirbel. Diese wird durch Abbauprodukte von anthropogen emittierten Fluorchlorkohlenwasserstoffen und Halonen, Chlor- und Bromradikale, verursacht. Studien in denen der gemessene und modellierte Ozonabbau verglichen wird zeigen, dass die Prozeße bekannt sind, der quantitative Verlauf allerdings nicht vollständig verstanden ist.
<br><br>
Die Prozesse, die zur Ozonzerstörung führen sind in beiden Polarwirbeln ähnlich. Allerdings fällt als Konsequenz unterschiedlicher meteorologischer Bedingungen der chemische Ozonabbau im arktischen Polarwirbel weniger drastisch aus als über der Antarktis. Der arktische Polarwirbel ist im Mittel stärker dynamisch gestört als der antarktische und weist eine stärkere Jahr-zu-Jahr Variabilität auf. Das erschwert die Messung des chemischen Ozonabbaus. Zur Trennung des chemischen Ozonabbaus von der dynamischen Umverteilung des Ozons im arktischen Polarwirbel wurde die Matchmethode entwickelt. Bei dieser Methode werden Luftpakete innerhalb des Polarwirbels mehrfach beprobt, um den chemischen Anteil der Ozonänderung zu quantifizieren. Zur Identifizierung von doppelt beprobten Luftpaketen werden Trajektorien aus Windfeldern berechnet. Können zwei Messungen im Rahmen bestimmter Qualitätskriterien durch eine Trajektorie verbunden werden, kann die Ozondifferenz zwischen beiden Sondierungen berechnet und als chemischer Ozonabbau interpretiert werden. Eine solche Koinzidenz wird Match genannt. Der Matchmethode liegt ein statistischer Ansatz zugrunde, so dass eine Vielzahl solcher doppelt beprobter Luftmassen vorliegen muss, um gesicherte Aussagen über die Ozonzerstörung gewinnen zu können. So erhält man die Ozonzerstörung in einem bestimmten Zeitintervall, also Ozonabbauraten. Um die Anzahl an doppelt beprobten Luftpackten zu erhöhen wurde eine aktive Koordinierung der Ozonsondenaufstiege entwickelt.
<br><br>
Im Rahmen dieser Arbeit wurden Matchkampagnen während des arktischen Winters 2002/2003 und zum ersten Mal während eines antarktischen Winter (2003) durchgeführt. Aus den gewonnenen Daten wurden Ozonabbauraten in beiden Polarwirbeln bestimmt. Diese Abbauraten dienen zum einen der Evaluierung von Modellen, ermöglichen aber auch den direkten Vergleich von Ozonabbauraten in beiden Polarwirbeln.
<br><br>
Der Winter 2002/2003 war zu Beginn durch sehr tiefe Temperaturen in der mittleren und unteren Stratosphäre charakterisiert, so dass die Matchkampagne Ende November gestartet wurde. Ab Januar war der Polarwirbel zeitweise stark dynamisch gestört. Die Kampagne ging bis Mitte März. Für den Höhenbereich von 400 bis 550 K potentieller Temperatur (15-23 km) konnten Ozonabbauraten und der Verlust in der Gesamtsäule berechnet werden. Die Ozonabbauraten wurden in verschiedenen Tests auf ihre Stabilität überprüft.
<br>
Der antarktische Polarwirbel war vom Beginn des Winters bis Mitte Oktober 2003 sehr kalt und stellte Ende September kurzzeitig den Rekord für die größte bisher aufgetretene Ozonloch-Fläche ein. Es konnten für den Kampagnenzeitraum, Anfang Juni bis Anfang Oktober, Ozonabbauraten im Höhenbereich von 400 bis 550 K potentieller Temperatur ermittelt werden. Der zeitliche Verlauf des Ozonabbaus war dabei auf fast allen Höhenniveaus identisch. Die Zunahme des Sonnenlichtes im Polarwirbel mit der Zeit führt zu einem starken Anwachsen der Ozonabbauraten. Ab Mitte September gingen die Ozonabbauraten auf Null zurück, da bis zu diesem Zeitpunkt das gesamte Ozon zwischen ca. 14 und 21 km zerstört wurde.
<br><br>
Im letzten Teil der Arbeit wird ein neuer Algorithmus auf Basis der multivariaten Regression vorgestellt, mit dem Ozonabbauraten aus Ozonprofilen verschiedener Sensoren gleichzeitig berechnet werden können. Dabei können neben der Ozonabbaurate die systematischen Fehler zwischen den einzelnen Sensoren bestimmt werden. Dies wurde exemplarisch am antarktischen Winter 2003 für das 475 K potentielle Temperatur Niveau gezeigt. Neben den Ozonprofilen der Sonden wurden Daten von zwei Satellitenexperimenten verwendet. Die mit der multivariaten Matchtechnik berechneten Ozonabbauraten stimmen gut mit den Ozonabbauraten der Einzelsensor-Matchansätze überein. / <br>The subject of this thesis is the destruction of ozone in the stratospheric polar vortex of the Arctic and Antarctic. It is caused by decomposition products of anthropogenic emitted Chlorofluorocarbons and Halons, radicals of chlorine and bromine. Studies which are dealing with the comparison of measured and modelled ozone loss show that the processes are known but that the quantitative development is not fully understood yet.
<br><br>
The processes that lead to ozone destruction are similar in both polar vortices. But as a consequence of different meteorological conditions the chemical ozone loss in the arctic polar vortex is less dramatic than over the Antarctic. On average the Arctic polar vortex is stronger perturbed and exhibit a stronger annual variability. In order to distinguish between chemical ozone loss and the dynamical redistribution of ozone in the Arctic vortex the Match method was developed. Air parcels in the polar vortex are probed several times in order to quantify the chemical change in ozone. To identify those air parcels trajectories are calculated using wind fields. When it is possible to
connect two measurements by a trajectory within certain quality criteria the difference in ozone can be calculated and is interpreted as chemical ozone loss. Such a coincidence is called a Match. The Match method is a statistical approach which needs many of those doubly probed air parcels in order to draw significant conclusions about the destruction of ozone. So the ozone destruction can be calculated for a certain period in time which gives ozone loss rates. In order to enhance the number of doubly probed air masses an active coordination was established.
<br><br>
Within the scope of the thesis Match campaigns were performed during the Arctic
winter 2002/2003 and for the first time during the Antarctic winter 2003. The
achieved data was used in order to determine ozone loss rates in both polar vortices. The loss rates serve for the evaluation of numerical models but allow as well the direct comparison of ozone loss rates of both polar vortices.
<br><br>
The beginning of the winter 2002/2003 is characterized by very low temperatures in the middle and lower stratosphere. Hence, the Match campaign started at the end of November. From January on the polar vortex was strongly dynamically disturbed at certain times. For the height region of 400 to 500 K potential temperature (15-23 km) ozone loss rates and the column loss were determined. The robustness of the ozone loss rates was checked with a variety of different tests.
<br><br>
From beginning of the winter until October 2003 the Antarctic polar vortex was very cold and the expansion of the ozone hole area reached record values in late September. From the beginning of June until the beginning of October ozone loss has been calculated in a height region from 400 to 550 K potential temperature. The development of the ozone loss was almost identical on the different height levels. The increase in sunlight led to an increase in ozone loss rates. From mid September the ozone loss rates decreased rapidly and the ozone was completely destroyed between approx. 14 and 21 km.
<br><br>
In the last part of the thesis a new algorithm is presented which is based on a multivariate regression in order to calculate ozone loss rates from ozone profiles made by different sensors. At the same time the systematic error between different sensors has to be considered. As an example the approach is shown for the Antarctic Winter 2003 on the 475 K potential temperature level. Beside the ozone profiles from the sondes, data from two satellites experiments have been used. The agreement between the ozone loss rates calculated by the multivariate regression method and those calculated by the single match approach is very good.
|
75 |
The shift in United States foreign policy in the Middle East since 1989Ward, Brandon M 01 June 2006 (has links)
A bi-polar world emerged at the end of World War II. The United States and the Soviet Union were the world's superpowers and tensions between them spiraled consequently bringing about the Cold War. United States foreign policy during the Cold War revolved around containment policy. The Middle East during the Cold War was a region that the bi-polar world's superpowers wanted to influence, and protect. The United States during the Cold War warned the Soviet Union through presidential doctrines that it would fight to keep the Middle East from communism, and the Soviet Union's influence. The bi-polar international power structure did not allow the United States the ability to pick its battles. The power structure that constrained the Cold War forced the United States to react to the Soviet Union, and it forced foreign policy makers to always consider the Soviet Union's response to its policies. United States foreign policy in the Middle East during the Cold War threatened wit
h military methods to solve local and regional instabilities. However, the United States was constrained by the bi-polar world thus, it was cautious of committing military troops in the region permanently and upsetting the region's delicate balance of power. United States foreign policy toward the Middle East has changed between 1981 and 2006. This change is in the direction of greater use of military methods to resolve what various administrations have perceived to be local and regional instability. This change in policy is partly attributable to changes in the United States power position in the world. A United States foreign policy shift in the Middle East occurred due to a change in the distribution of political power within the interstate system. This change has had the following result: the United States is no longer constrained by the bi-polar international power structure that characterized the Cold War period. The collapse of the Soviet Union created the uni-polar internationa
l power structure. United States foreign policy is now capable of deploying the military to resolve local and regional instabilities in the Middle East, and that deployment has tended to become increasingly permanent in nature.
|
76 |
Metallocen-katalysierte Synthese von polaren Olefin-basierten MakromonomerenJohannsen, Matthias 05 March 2012 (has links) (PDF)
1 Ziel und Gegenstand der Untersuchungen
Gegenstand der vorliegenden Arbeit war die Synthese und Charakterisierung von polaren Olefin-basierten Makromonomeren mit Hilfe von Metallocen-Katalysatoren.
Polyolefine stellen eine Gruppe von Polymeren dar, die durch Additive oder chemische Veränderungen modifiziert, eine große Vielfalt von Einsatzmöglichkeiten auf der Basis einfach aufgebauter Monomere bieten. Sie stellen deshalb heutzutage die wichtigste Kunststoffgruppe dar. Ein Nachteil ist jedoch die unpolare Struktur dieser Polymere.
Ziel dieser Arbeit war die Homopolymerisation polarer Olefine, um ein funktionalisiertes Polyolefin zu erzeugen, dass zudem auch als Makromonomer einsetzbar ist.
Als Katalysatoren wurden im Wesentlichen die klassischen Metallocene auf Zr-Basis eingesetzt, aktiviert mit MAO. Die Makromonomere wurden im Anschluss an die Synthese umfassend charakterisiert.
2 Ergebnisse
Zur Synthese wurde das bekannte 10-Undecen-1-ol (Undecenol) eingesetzt. Für eine erfolgreiche Homopolymerisation dieses Monomers ist eine effektive Abschirmung des Katalysators gegenüber der polaren Gruppe zur Minimierung der Deaktivierung des Katalysators zu gewährleisten. Für die Einführung von Schutzgruppen fand Triisobutylaluminium (TIBA) Verwendung. Auf diese Weise konnte erstmalig erfolgreich die Synthese von Polyundecenol mit Metallocen-Katalysatoren durchgeführt werden.
Es zeigte sich, dass Undecenol als polares und zugleich sterisch anspruchsvolles Monomer mit der überwiegenden Anzahl der eingesetzten Metallocene schwierig zu polymerisieren ist, was im Vergleich zur Polymerisation von kurzkettigen 1 Olefinen, wie zum Beispiel Propen, anhand von geringen Molmassen (< 2000 g/mol) aber auch geringen Ausbeuten zum Ausdruck kommt. Die erzielten Molmassen der Polyundecenole sind jedoch für die Verwendung als Makromonomer vorteilhaft.
Die höchsten Polymerausbeuten ermöglichte der Einsatz von ansa-Metallocenen. Mit dem Katalysator Et[Ind]2ZrCl2 konnten hierbei relative Ausbeuten im Bereich von 50 % bis 60 % bei gleichzeitig geeigneten Molmassen von < 10^4 g/mol erzielt werden. Bei der Verwendung von unverbrückten Metallocenen (bis-Cyclopentadienylkomplexe) sind die Ausbeuten und Molmassen im Vergleich zu den ansa-Metallocenen deutlich reduziert.
Die synthetisierten Polyundecenole wurden hinsichtlich ihres Schmelz- und Kristallisationsverhaltens sowie der kristallinen Struktur untersucht und der Zusammenhang mit der Taktizität und der Molmasse der Polymere hergestellt. Die Ergebnisse der DSC und WAXS Untersuchungen lassen darauf schließen, dass für ataktische und isotaktische Polyundecenole eine Seitenkettenkristallisation als primäre Form der Kristallisation vorliegt. Aufgrund des hohen Gehalts von Hydroxylgruppen, die durch Wasserstoffbrückenbindungen wechselwirken, weist Polyundecenol hohe Schmelztemperaturen auf, im Vergleich mit dem unpolaren Poly(1-Undecen). So besitzt isotaktisches und auch ataktisches Polyundecenol bei vergleichbaren Molmassen eine um rund 80 K höhere Schmelztemperatur als Poly(1-Undecen). Die Wechselwirkung der Hydroxylgruppen wurde mittels FTIR-Spektroskopie nachgewiesen und liegt auch im geschmolzenen Zustand der Polymere vor.
Anhand der Ergebnisse von WAXS-Untersuchungen konnte gezeigt werden, dass Polyundecenol in smektischen Schichten kristallisiert. Der Abstand zwischen den Hauptketten entspricht etwa zwei vollständig gestreckten Seitenketten des Polymers, welche orthogonal zur Hauptkette angeordnet sind. Diese Schicht-Anordnung wurde unabhängig von Molmasse und Taktizität der Polymere nachgewiesen und lässt die Schlussfolgerung zu, dass die Kristallisation isotaktischer Rückgrat-Ketten gegenüber der Seitenketten-Kristallisation unterdrückt ist. Es wurde jedoch beobachtet, dass die Taktizität einen Einfluss auf die Kristallisation hat. Polyundecenole mit isotaktischer Hauptkette weisen bei entsprechend langsamer Kristallisation eine Anordnung der Seitenketten in einer monoklinen Packung auf, was als Hinweis auf eine Kristallisation der Hauptkette interpretiert wird, auch wenn diese im Rahmen der Arbeit nicht eindeutig nachgewiesen werden konnte.
Bei Polyundecenolen mit ataktischer Hauptkette ordnen sich die Seitenketten hingegen in einer hexagonalen Packung an, da die Hauptkette nicht in der Lage ist zu kristallisieren.
Von besonderer Bedeutung für die Synthese der Polyundecenole waren einerseits die erzielbaren Polymerausbeuten, andererseits aber auch die Einführung geeigneter Endgruppen, welche ausschlaggebend sind für eine Nutzung als Makromonomer.
Die Untersuchungen zum Polymerisationsverhalten verschiedener Metallocen-Katalysatoren zeigten, dass im Falle von ansa-Metallocenen sowie einem "CGC"-Komplex Polymere erhalten werden, die vor allem Endgruppen mit internen Doppelbindungen, doppelt- und dreifachsubstituiert, aufweisen. Solche Endgruppen sind jedoch für einen späteren Einsatz der Polymere als Makromonomer ungeeignet. Der Einsatz von unverbrückten Metallocen-Katalysatoren auf Basis der Biscyclopentadienyl-Struktur ermöglicht hingegen die Synthese von Polyundecenol mit einem hohen Anteil endständiger Vinyliden-Endgruppen zu synthetisieren. Die so erreichten Vinyliden-Endgruppenanteile bewegten sich nahezu unabhängig vom Katalysator im Bereich von etwa 85 % bis 90 %.
Ein wesentliches Ergebnis der Arbeit stellt die Synthese von Polyundecenol mit Allyl-Endgruppen dar. Dieses wurde durch gezielte Kettenabbruchreaktionen mit Hilfe von Vinylchlorid erreicht. Bei Einsatz des Katalysator MBI konnten Anteile der favorisierten Allyl-Endgruppe von rund 90 % erreicht werden. Somit wurden auf diesem Wege erstmalig erfolgreich Polyundecenol-Makromonomere synthetisiert. Ein Einsatz dieser Polymere in der Copolymerisation mit Propen wurde aber durch geringe Ausbeuten verhindert. Jedoch konnte gezeigt werden, dass der Einsatz von Vinylchlorid die Synthese von Polyundecenol-Makromonomeren ermöglicht.
|
77 |
Paleomagnetism and petrogenesis of Paleoproterozoic units from the Uatumã event in the northern Amazonian Craton / Paleomagnetismo e petrogênese de unidades Paleoproterozóicas do evento Uatumã no norte do Craton AmazônicoPaul Yves Jean Antonio 16 February 2017 (has links)
An anorogenic magmatism covered a large part (1.500.000 km2) of the Amazonian craton at ca. 1880 Ma and defined a Silicic Large Igneous Province (SLIP) called the Uatumã event. The aim of this work is to study the paleomagnetism and petrology of these rocks to define the space-time framework of the Uatumã event and to try to elucidate the Amazonian craton evolution during the Columbia supercontinent amalgamation. Two regions were selected in the southwestern Amazonian craton (Pará) for sampling: (1) The Tucumã area where 16 felsic dikes, 7 mafic dikes, a gabbroic dike and 3 sites of the Archean basement were collected, and (2) the São Felix do Xingu area where, 7 sites of rhyolitic lava flows, 2 sites of ignimbrites, a felsic dike and a volcanic breccia belonging to the Santa Rosa Formation were sampled, and also 6 sites of the Sobreiro Formation (volcanoclastic rocks, andesitic) and one felsic dike of the Velho Guilherme Suite were collected. Petrology of the felsic dikes of Tucumã (1880.9 ± 6.7 Ma U-Pb zrn) showed that they represent the dike swarm associated with the Santa Rosa volcanic Formation. The remanent magnetization of the felsic dikes is carried by PSD magnetite and hematite. This hematite is syn- to post magmatic derived from hydrothermal fluids. Magnetic mineralogy can be used as a proxy to quantify the hydrothermal alteration. AF, thermal, LTD + AF and LTD + thermal demagnetizations show a northwest direction with a positive inclination (component A), whose site mean directions gives a paleomagnetic pole located at 52.9°S, 76.4°E, A95= 10.4 °, K= 13.52). However, this component seems to represent a remagnetization, probabily occurred at Neoproterozoic times. Another magnetic component (named component B) was also isolated for these rocks, and it was associated to a Mesozoic regional remagnetization related to the Central Atlantic Magmatic Province (CAMP). Yet, a third southwestern direction with low positive inclination (component C) was also isolated for some sites. This component was interpreted to be related with the ca. 1760 Ma Velho Guilherme magmatic intrusion. The best paleomagnetic results were obtained in the São Felix do Xingu area. Two new primary paleomagnetic poles have been determined: (i) SF1 pole (319.7°E, 24.7°S, N= 10; A95= 16.9 °) was obtained for andesites and rhyolites dated to 1877.4 ± 4.3 Ma (U-Pb zrn, LA-ICPMS), and its primary origin is confirmed by an inverse baked contact test (> 1853 Ma). Petrography shows that the magnetic mineralogy of this component is hematite formed by hydrothermal fluids syn- to post magmatic. (Ii) SF2 pole (220.1°E, 31.1°N, N= 15 ° A95= 9.7 °) was determined by the remanent magnetization of the felsic dike of the Velho Guilherme Suite but also as secondary magnetizations in samples of the Santa Rosa and Sobreiro Formations. An age of 1853.7 ± 6.2 Ma (U-Pb zrn, LA-ICPMS) is calculated for the felsic dike carrying SF2, whose primary origin is confirmed by a positive baked contact test. The SF1 and SF2 poles have a significant difference in angular distance, for a time interval of only ~25 Ma. Similar coeval paleomagnetic discrepancies were observed for other cratons (India, Superior (Laurentia), Slave (Laurentia), Kalahari, Baltica and Siberia), which can be explained by a True Polar Wander (TPW) event at ca. 1880 1860 Ma. This period is marked by a high mantle activity, which results in the amalgamation of the Columbia supercontinent, formed at ca. 1850 1800 Ma. Amalgamation of supercontinent may cause the formation of superplume and thermal insulation which can disturb mass distribution in mantle and alter the inertial gravity tensor of the Earth. A True Polar Wander (TPW) event may thus have taken place, which will move the cratons and the superplumes towards the equator. These conditions may be related to a reorganization of the whole mantle following a global magmatic quiescence between 2400 and 2200 Ma. / Um grande magmatismo intraplaca cobriu várias áreas (1.500.000 km2) do Cráton Amazônico há 1880 Ma, o qual define uma grande província ígnea (SLIP) chamada coletivamente de \"evento Uatumã\". O objetivo deste trabalho é estudar o paleomagnetismo e a petrologia dessas rochas para definir o contexto espaço-temporal do evento Uatumã e a posição do cráton Amazônico dentro do Supercontinente Columbia. Duas áreas de estudo foram escolhidas para a amostragem, localizadas no sudoeste do cráton Amazônico (Pará): (1) A região de Tucumã, onde 16 diques félsicos, 7 diques máficos, um dique de gabro e 3 sítios da granodioritos do embasamento Arqueano foram coletadas. (2) A região de São Felix do Xingu, onde 7 sitios de lavas riolíticas, 2 sitios de ignimbritos, um dique felsico e um de brechas vulcânicas da Formação Santa Rosa foram amostrados. Seis sitios da Formação Sobreiro (rochas vulcanoclásticas andesíticas) e um dique felsico da Suite Velho Guilherme foram também coletados. O estudo petrológico em amostras dos diques felsicos de Tucumã (1880.9 ± 6.7 Ma U-Pb zrn) mostra que eles representam um sistema de siques associado à Formação vulcânica Santa Rosa. A magnetização remanente dos diques felsicos é portada por magnetita PSD e hematita. A hematita é sin- a pós-magmática e a mineralogia magnética pode ser usada para quantificar esta alteração hidrothermal. Desmagnetizações AF, térmica, LTD + AF e LTD + térmica mostram uma componente característica com direção noroeste e inclinação positiva (Componente A) para amostras de 16 sítios, cuja direção média é Dm= 330.5, Im= 27.9 (N= 16, 95= 11.4, R= 14.7, k= 11.47). O pólo paleomagnético calculado com a média dos PGVs está localizado em 52.9°S, 76.4°E (A95= 10.4°, K= 13.52). Entretanto, esta componente parece ser decorrente de uma remagnetização, provavelmente ocorrida durante o final do Neoproterozoico. Outra componente (chamada de Componente B) foi também isolada para estas rochas, a qual foi associada a uma remagnetização regional ocorrida durante a formação da Província Magmática do Atlântico Central (PMAC). Ainda, uma Terceira componente (C), representada por direções sudoeste e inclinações positivas baixas foi isolada para amostras de alguns sítios. Esta componente foi interpretada como sendo relacionada ao evento magmático da Suíte Intrusiva Velho Guilherme com idade de ~1860 Ma. Os melhores resultados, entretanto, foram obtidos para a região de São Felix do Xingu. Dois novos polos paleomagnéticos, considerados de origem primária, foram encontrados para o Craton Amazônico: O polo SF1 (319.7°E; 24.7°S; N= 10; A95= 16.9°) foi obtido para rochas félsicas e andesíticas, as quais foram datadas em 1877.4 ± 4.3 Ma (U-Pb zrn, LA-ICP-MS), sendo que sua origem primária é embasada em um teste de contato cozido inverso. A investigação petrográfica mostra que o portador magnético desta componente é atribuído à hematita, formada por processos hidrotermais tardi- a pós-magmáticos. O polo SF2 (220.1°E; 31.1°S; N= 15; A95= 9.7°) foi determinado para a componente de magnetização revelada para o dique da Suíte Velho Guilherme, Esta componente é também encontrada como componente secundária em amostras das formações Santa Rosa e Sobreiro, além de algumas amostras de sítios coletados na região de Tucumã (Componente C). Uma idade de 1853.7 ± 6.2 Ma (U-Pb zrn, LA-ICP-MS) foi atribuída à componente SF2 e sua origem primária é confirmada pelo teste de contato cozido positivo realizado para este dique. Os polos SF1 e SF2 são bem discrepantes, embora a diferença de idade destes polos seja de apenas 25 Ma. Resultados similares têm sido obtidos para polos de mesma idade de outros blocos cratônicos (India, Superior (Laurentia), Slave (Laurentia), Kalahari, Baltica e Sibéria), os quais podem ser explicados por um evento de deriva polar verdadeira (DPV) ocorrido nesta época, em decorrência de uma reorganização do Manto. Esta época (1880 Ma) é marcada por uma alta atividade do Manto, a qual culminou com a formação do Supercontinente Columbia, por volta de 1850 1800 Ma. A formação de superplumas e o isolamento térmico causado pela consequente formação do Columbia podem ter sido causas de perturbações de densidades que alteraram o tensor inercial da Terra e, consequentemente, um evento de DPV pode ter deslocado os continente e as superplumas para a região do equador. Estas condições podem estar ligadas a uma inteira reorganização mantélica que seguiu um período de pouca atividade magmática, ocorrido entre 2400 e 2200 Ma.
|
78 |
Além da Antártica: os limites da vida ao frio e à dessecação no âmbito da astrobiologia. / Beyond Antarctica: the limits of life to cold and desiccation in the context of astrobiology.Felipe Nóbrega Pereira 05 February 2016 (has links)
Na Antártica e no Ártico, a vida microbiana é presente e diversificada, tendo se adaptado a condições similares às encontradas em mundos que despertam interesse à astrobiologia. Este estudo investigou as alterações fisiológicas e fenotípicas do extremófilo psicrotrófico Exiguobacterium antarcticum B7 sob diferentes temperaturas. Foram utilizadas técnicas de eletroforese de proteínas em duas dimensões associada a espectrometria de massa, juntamente com técnicas de microscopia. E. antarcticum foi também submetida a condições físicas encontradas em Marte e no ambiente interplanetário. Seguindo evidências de que micro-organismos psicrotróficos podem também ser resistentes a períodos prolongados de dessecação, foi investigada a presença de linhagens microbianas resistentes a anidrobiose em solos da Antártica e permafrost do Ártico. Por fim, voltando-se à ecologia microbiana de solos polares permanentemente congelados, foi estudada a diversidade microbiana de três estratos de permafrost do ártico canadense com o uso de sequenciamento de DNA de nova geração. / In Antarctica and the Arctic, microbial life is present and diverse, having adapted to low temperature and low humidity conditions, similar to the worlds that arouse more interest to astrobiology. This study investigated the physiological changes of the psychrotrophic extremophile Exiguobacterium antarcticum B7 at different temperatures. Two dimensional protein electrophoresis techniques was used for proteome analysis in conjunction with mass spectrometry, as well as microscopy techniques. E. antarcticum was also subjected to physical parameters found on Mars and in the interplanetary environment. Following evidence that psychrotrophic microorganisms may also be resistant to prolonged periods of desiccation, it was investigated the presence of microbial strains resistant to anhydrobiosis on Antarctic soils and Arctic permafrost. At last, turning the attention to the microbial ecology of permanently frozen polar soils, it was studied the bacterial diversity of three Arctic permafrost strata with next-generation high throughput DNA sequencing.
|
79 |
Polar mesoscale cyclones in ERA5 and CARRA / Polära mesoskaliga cykloner i ERA5 och CARRACheng, Zhaohui January 2023 (has links)
Polar mesoscale cyclones (PMCs) are low-pressure systems that form in polar regions. Their small size and short lifespan pose challenges for coarse resolution models in capturing PMCs and their associated air-sea mass and energy transfer. To address the influence of resolution on PMCs, a comparison between a higher resolution dataset (CARRA with 2.5 km resolution) and a lower resolution reanalysis dataset (ERA5 with 30km resolution) over a 10-year period in the North Atlantic is conducted by employing an automatic algorithm. The results revealed that CARRA detected a greater number of PMC activities, highlighting the benefits of higher resolution data in reducing uncertainties during tracking. PMCs identified using CARRA exhibited smaller vortex sizes, but higher relative vorticity and faster movement speeds compared to ERA5 results. Notably, the typical vortex diameters derived from ERA5 and CARRA were 80 km and 120 km, respectively. Furthermore, the climatology of PMCs in the North Atlantic is presented. Monthly variations indicated that the majority of PMCs occurred during winter, with only a few cases developing in summer. The spatial distribution exhibits that the highest density of PMCs was observed in the Irminger Sea and the Norwegian Sea. It also shows that the presence of sea ice can influence the PMC density, as a significant number of cases formed near the sea ice edge. The comparison results indicate that the current coarse climate simulation may underestimate the influence of PMCs in the Arctic due to the misrepresentation of them, thus introducing uncertainties in the climate prediction.
|
80 |
A reconfigurable AGV with omni-directional sensingKotze, B., Jordaan, G.D., Vermaak, H. January 2010 (has links)
Published Article / Automatic guided vehicles are being used increasingly in a manufacturing environment. Developing a platform that could be easily reconfigured is perhaps a desirable option for a user with low capacity outputs. The research described in this article concentrates on such a vehicle and the development of the actuators and sensors for navigation and proper functionality.
|
Page generated in 0.0315 seconds