Orientador: Antonio Jose Ramirez Londono / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecânica / Made available in DSpace on 2018-08-19T15:09:29Z (GMT). No. of bitstreams: 1 GrandoStroppa_Daniel_D.pdf: 7882693 bytes, checksum: 21824c021c6088d93bb5e17e9b0386ff (MD5) Previous issue date: 2011 / Resumo: O desenvolvimento de tecnologias baseadas em nanoestruturas é dependente da criação de modelos confiáveis que possam suportar a obtenção de materiais com características controladas. Neste contexto, o aprimoramento de técnicas de caracterização quantitativa e com alta resolução espacial é fundamental para o melhor entendimento das correlações entre a configuração de síntese, a morfologia e as propriedades resultantes de materiais nanoestruturados. Esta tese apresenta a avaliação e a aplicação de diferentes técnicas de Microscopia Eletrônica de Transmissão de Alta Resolução Quantitativa (QHRTEM) visando a extração de informações relacionadas à estrutura tridimensional e à segregação de espécies dopantes em nanocristais individuais de óxidos semicondutores dopados (Sb:SnO2 e Gd:CeO2). Os resultados experimentais combinados a cálculos teóricos proporcionaram a obtenção de informações referentes à distribuição de energia superficial e aos mecanismos de crescimento de cristais envolvidos na evolução temporal dos sistemas estudados. A descrição de tais aspectos de sistemas nanocristalinos explicita a importância das técnicas QHRTEM, tanto no contexto do desenvolvimento e aplicação do modelamento de nanocristais, quanto para o avanço das teorias fundamentais que descrevem o comportamento dos materiais em escala nanométrica. Neste sentido, os resultados presentes nesta tese constituem significativos avanços para o entendimento das características dos materiais em escala atômica e para a posterior manipulação destas segundo o preceito da engenharia de materiais no desenvolvimento de novas tecnologias / Abstract: Technologies based on nanostructured materials depend on the development of reliable models which can support the fabrication of nanocrystals with highly controlled features. In this scenario, advances on high resolution quantitative techniques are required in order to improve the description of the nanostructured systems, especially the correlations among the nanocrystals synthesis parameters, the resultant morphology and the system properties. This PhD thesis presents the evaluation and use of different Quantitative High Resolution Transmission Electron Microscopy (QHRTEM) techniques aiming the three-dimensional morphology and the dopant species segregation characterization of individual oxide nanocristals (Sb:SnO2 e Gd:CeO2). In addition, the combined use of such techniques and theoretical calculations provided valuable insights on the surface energy distribution and growth mechanisms present on the analyzed nanocrystalline systems. The obtained high resolution quantitative characterization results indicate that QHRTEM techniques are priceless tools for both the nanocrystal modeling procedures development and application, and for the improvement of fundamental theories that describe the materials features at nanoscale. In this scenario, this thesis presents significant advances on the nanomaterials characteristics description and, consequently, on their further manipulation aiming novel technologies development according to the materials engineering approach / Doutorado / Materiais e Processos de Fabricação / Doutor em Engenharia Mecânica

Orientador: Marcos Nogueira Eberlin / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-21T13:56:59Z (GMT). No. of bitstreams: 1 Klitzke_ClecioFernando_D.pdf: 5751557 bytes, checksum: 0cd80e6f5c01aa04c7fdd89f600b374c (MD5) Previous issue date: 2012 / Resumo: O petróleo é uma mistura complexa, constituída de milhares de compostos e sua caracterização é fundamental em diversos processos da indústria petrolífera. A abordagem moderna para a caracterização total dos compostos polares (N, O, S) do petróleo é através da petroleômica, utilizando a espectrometria de massas de altíssima resolução e exatidão obtida em espectrômetros de ressonância ciclotrônica de íons com análise por transformada de Fourier (FT-ICR MS). FT-ICR MS é o equipamento ideal para estas análises, no entanto a literatura carece de informações quanto a otimização do número de scans e do efeito da resolução na análise petroleômica. Determinamos como condições ideais para a análise destas amostras de altíssima complexidade a obtenção de espectros de MS com poder de resolução de 400.000 em m/z 400 e acúmulo de 100 mscans. Foram analisados também os compostos polares presentes em outras fontes de combustíveis fósseis, como carvão mineral e folhelho. Os resultados mostraram padrões distintos em relação à origem do material e possivelmente ao grau de evolução térmica. Comparamos a análise por FT-ICR MS dos ácidos carboxílicos de amostras de petróleo com os resultados das análise de frações ácidas por FAB MS obtidas no CENPES . PETROBRAS, mostrando que as análises por FT-ICR MS apresentam resultados superiores na identificação da distribuição de DBE sendo que por FAB MS não temos informações relativas a DBE superior a 7. A análise abrangente da composição de ácidos do petróleo é de extrema importância com conta da corrosão e formação de depósitos e emulsões, dependentes da composição destes ácidos. Comparamos alguns resultados da análise por FT-ICR MS com TOF MS (UHRT) de altíssima resolução, 100.000. Os resultados obtidos com UHRT MS estão próximos as análises por FT-ICR MS com 200.000 de resolução em m/z 400. Obtivemos a identificação de boa parte das classes de heteroátomos úteis nas análises petroleômicas. Analisamos por Travelling Wave Ion Mobility Mass Spectrometry (TWIM MS) padrões de ácidos, destilados e amostras de petróleo. Os resultados obtidos mostraram uma tendência da redução do drift time com o aumento da DBE dos analitos. As amostras de petróleo também revelaram perfis distintos para diferentes faixas de drift time, sendo possível diferenciar classes de compostos polares (O2, N e NO). Os resultados obtidos mostraram o grande potencial da análise por FT-ICR MS e UHRT MS, complementados pela análise estrutural fornecida pela mobilidade iônica com o uso da TWIM MS. / Abstract: Crude oil is a complex mixture consisting of thousands of compounds and their characterization is essential in various processes of the petroleum industry. The modern approach to the characterization of total polar compounds (N, O, S) of oil is through petroleomics MS, using the ultra-high resolution mass spectrometry and accuracy obtained in ion cyclotron resonance spectrometers with analysis by Fourier transform (FT-ICR MS). FT-ICR MS is the ideal equipment for these analyses, however the literature lacks information about the optimization of scan number and the effect of resolving power in the petroleomic analysis. We determine the ideal conditions for the analysis of these samples of high complexity getting MS spectra with resolving power of 400,000 in m/z 400 and accumulation of 100 mscans. Polar compounds in crude oil, and other sources of fossil fuels such coal and shale were analyzed. The results showed distinct patterns in relation to the origin of the material and possibly the degree of thermal evolution. We compare the performance of FT-ICR MS with FAB MS in the analysis of carboxylic acids composition of crude oil samples. Analyses by FT-ICR MS feature superior results in identifying the distribution of DBE. FAB MS does not have information on DBE exceeding 7. Comprehensive analysis of the composition of crude oil acids is of extreme importance with account of corrosion and formation of deposits and emulsions, dependent on the composition of these acids. We compare some results of the analysis by FT-ICR MS with ultra-high resolution TOF MS (UHRT) with 100,000 of resolving power. The results obtained with UHRT MS are equivalent to the FT-ICR MS with 200,000 resolving power at m/z 400. We obtained the identification of most of the classes of heteroatoms useful in petroleomic analysis and the results show that UHRT performance is near to FTICR. Traveling Wave Ion Mobility Mass Spectrometry (TWIM MS) show good results to study the patterns of ion mobility of acid samples, distillates cuts and crude oil samples. The results showed a trend of reducing the drift time with increasing DBE of the analytes. The crude oil samples also revealed different drift time profiles for different classes of polar compounds (O2, N, and NO). The results obtained show the great potential of FT-ICR MS and UHRT MS analysis, complemented by structural analysis provided by ion mobility with the use of TWIM MS, of distillate cuts and crude oil samples. / Doutorado / Quimica Organica / Doutor em Ciências

Ce travail de thèse porte sur le développement d'un spectromètre laser à cascade quantique (QCL) dans le moyen infrarouge pour des applications en spectroscopie et en métrologie des fréquences. Les principaux objectifs ont été tout d'abord de lever la forte contrainte que constitue le faible domaine spectral accessible au laser à CO2 mais également d'accroître la faible puissance laser disponible pour nos expériences de spectroscopie. Ce nouvel instrument intéresse directement les expériences développées au sein du groupe Métrologie Molécules et Tests Fondamentaux : la mise en évidence de non conservation de la parité dans les molécules chirales et la détermination de la constante de Boltzmann par spectroscopie laser. Au cours de ce travail de thèse, nous avons caractérisé le bruit d'intensité, le bruit de fréquence ainsi que la largeur de raie de la source QCL libre. Les résultats obtenus comparés à la littérature montrent une grande qualité spectrale de cette source laser. L'asservissement en phase de la source QCL sur un laser à CO2 ultra-stable a permis de démontrer le transfert des propriétés spectrales du laser à CO2 à la source QCL. Le spectromètre a ensuite été utilisé pour des expériences de spectroscopie en absorption linéaire des molécules NH3 et de la molécule de Méthyltrioxorhénium, molécules d'intérêt pour les projets de mesure de la constante de Boltzmann et de recherche d'un et de la non-conservation de la parité. Le potentiel de ce spectromètre a également été démontré dans des expériences de spectroscopie à très haute résolution, en absorption saturée. / This thesis is devoted to the developpement of a laser spectrometer quantum cascade to frequency metrology and high-resolution spectroscopy. The objective of this work is to developp a new tool for projects in our group : Measuring the Boltzman constant and test of non conservation of parity. Thus the new source was characterized by measuring its spectral density noise, amplitude noise and its emission line width. The phase locking of the QCL on the CO2 laser has achived spectroscopy NH and MTO, molecules of interest for the projects of the group mentioned aboive respectively.

Aspiration of gastric content and delayed or failed intubation are the leading causes of anesthesia-related mortality and morbidity. In the recovery period, airway obstruction with subsequent hypoxia is a relatively common cause of morbidity, and is highly associated to the amount of opioids administered, especially in obese patients. The overall aim of this thesis was to study these risk factors for airway complications and postoperative hypoxia in obese patients, and to evaluate possible strategies for their prevention. In Study I, intubation times and incidence of failed intubation in obese patients were compared between direct laryngoscopy and videolaryngoscopy with the Stortz® C-MAC™. In Studies II and III, the effect of esmolol vs. remifentanil on the esophageal junction, and the possible analgesic properties of low-dose esmolol vs. placebo were evaluated using high-resolution manometry and the cold pressor test, respectively. Finally, in Study IV, the possible opioid-sparing effect of esmolol after laparoscopic gastric bypass surgery was evaluated. The use of videlaryngoscopy did not shorten intubation times, however appeared to reduce the incidence of failed intubation. Our results also show that esmolol has a favorable profile, compared to remifentanil, with regard to the protection against passive regurgitation and aspiration of gastric content. No analgesic effect of low-dose esmolol was however demonstrated. The intraoperative administration of esmolol instead of remifentanil also did not reduce the requirement of morphine for treatment of post-operative pain. The use of Stortz® C-MAC™ may be recommended for intubation of obese patients. Further studies are however required to clarify the possible role of esmolol in anesthesia.

Abstract The thesis consists of seven studies dealing with high resolution vibration-rotation spectra of planar asymmetric tops. Six studies deal with D212CO and D213CO species of the formaldehyde molecule and one study is from DCOOH specie of the formic acid molecule. The measurements were carried out at high accuracy and the rotational analyses of the recorded spectra were performed. The observed anharmonic and Coriolis resonances were taking into account in the analyses. The rotational constants of the present and literature studies were used in evaluation of the planarity defects of formaldehyde and formic acid molecules in the summary part of the thesis. Finally, a semi-experimental structure for formaldehyde was obtained by employing experimental and theoretical data.

Le compartiment phytoplanctonique joue un rôle prépondérant dans les écosystèmes marins de par sa position comme principal producteur primaire et fixateur de carbone, mais aussi en raison de sa capacité de multiplication élevée, qui lui permet de réagir rapidement aux changements environnementaux et d'en faire un potentiel bio indicateur. La plupart des études antérieures ne se sont basées que sur des observations réalisées à basse fréquence, ou bien ne ciblant qu'une partie des groupes/espèces phytoplanctoniques entraînant une perte importante d'information sur la variabilité d'abondance et composition du phytoplancton. Cette thèse a été réalisée dans le cadre du projet européen transfrontalier DYMAPHY dont l'objectif principal visait à améliorer les connaissances et l'évaluation de la qualité des eaux marines de la Manche et de la Mer du Nord, à travers l'étude de l'ensemble du compartiment phytoplanctonique et ses paramètres complémentaires. Dans ce contexte, une approche à haute fréquence et/ou haute résolution spatiale, via l'utilisation de la cytométrie en flux semi-automatisée, a permis de mieux caractériser la variabilité spatiale et temporelle du phytoplancton en Manche Orientale. Pour cela on a utilisé 3 approches complémentaires dont les résultats principaux obtenus lors de ce travail de thèse sont les suivants : (i) une étude à haute fréquence, avec une analyse cytométrique toutes les 10 minutes, qui a permis de révéler une forte variabilité spatiale du phytoplancton, à une échelle régionale (Manche Orientale), dont l'assemblage communautaire n'était pas déterminé par l'hydrologie ; (ii) un suivi saisonnier de l'ensemble du spectre de taille des cellules phytoplanctoniques le long d'un gradient côte-large proche du détroit du Pas de Calais, qui a révélé, au-delà d'une certaine hétérogénéité spatiale, une forte variabilité temporelle permettant de définir les successions saisonnières et les principaux facteurs les régissant, à savoir la luminosité et la concentration en sels nutritifs ; (iii) un suivi de 3 ans sur un point fixe en eaux côtières, qui a permis de mettre en relation les traits de vie des groupes phytoplanctoniques avec l'environnement, afin de comprendre comment les communautés phytoplanctoniques s'assemblent en réponse à la variabilité environnementale. Les résultats ont montré une différenciation fonctionnelle liée à l'utilisation des ressources et des stratégies de croissance, associées à un gradient de ressources. Cette étude confirme notamment l'importance de "l'hypothèse du ratio de masse", qui prédit que les traits de vie de l'espèce la plus abondante au sein d'une communauté, seraient le moteur des processus les plus importants au sein d'un écosystème. / Phytoplankton micro-organisms play a key role in marine ecosystems as main primary producers, being responsible for most of carbon uptake, but also due to their fast division rates which allow them to effectively react to environmental changes and which make them potentially good bio-indicators. Most previous studies have based their observations on low frequency sampling, only considering one fraction of phytoplankton communities, resulting in a significant loss of information on the dynamics of phytoplankton abundance and diversity. This thesis was carried out in the frame of the European cross-border DYMAPHY project, which main objective was to improve the understanding and the evaluation of the quality of marine waters in the English Channel and the North Sea, through the study of the whole phytoplankton compartment and related environmental parameters. A high frequency and/or high resolution approach, through the use of semi-automated flow cytometry, allowed us to reduce this loss of information and to better characterize the phytoplankton spatial and temporal variability in coastal water of the eastern English Channel.Three approaches were applied, leading to the ollowing results : (i) A high frequency study, performing one analysis every 10 minutes, which revealed a strong phytoplankton variability at the regional scale, with community assemblages that were not governed by hydrology ; (ii) A seasonal monitoring of the whole phytoplankton size-spectrum, which revealed the seasonal successions and the main factors governing them : nutrient concentrations and the daily light level which structured the transition of most phytoplankton groups ; (iii) A three-year follow-up at a coastal station, which made it possible to relate the traits-based characterization of each functional phytoplankton group to the environmental conditions, in order to better understand phytoplankton community assembly in response to environmental variability. The results have revealed a functional differentiation mainly due to the use of resources and the growth strategies, both of them driven by a resource gradient. This study confirms the importance of the "mass ration hypothesis", which predicts that the dominant life traits of the most abundant species, would be the main driver of the key ecosystem processes.

M dwarfs are abundant and long-lived stellar objects. The formation of planets around stars in stellar systems is believed to be metallicity dependent. To determine the metallicity with synthetic spectrum analysis, the elements producing the absorption lines ofthe spectra first have to be identified. The aim of this thesis is to identify and list the elements or molecules that produce the absorption lines in the spectra of Barnard's star. This thesis was done at the Division for Astronomy and Space Physics at Uppsala University. High resolution infrared spectral data recorded in the J band 1.1–1.4 μm was downloaded from the CRIRES-POP database. The data had to be wavelength corrected due to the effects of Doppler shift. A modified IDL program was used to read the data files,normalize the flux to unity and plot the spectra. This procedure was also done with the telluric spectra using data from a solar flux atlas. The IDL program plotted the normalized spectra together in the same plot. With this procedure the absorption features originating from the earth’s atmosphere could be identified and discarded. The analysis of the spectral lines resulted in wavelength values which were tested against the VALD3 database to determine what elements were possibly responsible for the absorption features. The results are presented in a line list. It can be used with other software programs to determine the metallicity. The identified elements and molecules agrees in part with earlier measurements of stellar spectra from M dwarf stars except for a number of lines where no matching elements were found in the VALD3 database. A line list with possible elements in the photosphere of Barnard’s star can be constructed from the spectra using high-resolution infrared spectroscopy. / M dvärgstjärnor är de mest förekommande stjärnorna i vår galax. De har en mycket långlivslängd, vissa tusen gånger längre än vår sol. Det finns teorier om att planetbildning runt stjärnor styrs av halten av ämnen som inte är väte eller helium. Denna halt kallas metallicitet. För att på konstgjord eller syntetisk väg bestämma metalliciteten i Barnard’s stjärna, en M dvärg, behöver de ämnen som bidrar till absorptionslinjerna i fotosfären först identifieras. Målsättningen med detta arbete var att identifiera de grundämnen och eventuella molekyler som skapar absorptionslinjerna i spektrumet till Barnard’s stjärna. Detta arbete utfördes på institutionen för fysik och astronomi. Metoden använde ett modifierat IDL program för att läsa och plotta data. Högupplöst infraröd spektraldata från Jbandet (1.1–1.4 μm) till Barnard’s stjärna hämtades från CRIRES-POP databasen och data för det telluriska spektrumet från en databas med telluriska linjer. Därefter plottades de samtidigt i ett våglängdsöverlappande normaliserat spektra. I programmet gick absorptionslinjer som inte hade sitt ursprung i jordens atmosfär att urskilja manuellt. Då våglängderna för absorptionlinjerna bestämts, matades värden in i databasen VALD3. Analysen av de returnerade värdena från VALD3 genererade en resultatlista med de mest sannolika elementen för de olika absorptionsvåglängderna. Resultatlistan kan användas som ingångsvärde till program som syntetiskt beräknar metalliciteten. Resultaten överensstämmer till viss del med tidigare mätningar. Slutsatsen är att metoden med högupplöst infraröd spektral data kan användas för att bestämma en lista med element och molekyler från fotosfären i Barnard’s stjärna.

L’intérêt de la télédétection appliquée aux volcans actifs et potentiellement dangereux a été démontré depuis longtemps dans la mesure où cette technique a participé à l’amélioration de la compréhension des processus éruptifs et des aléas volcaniques, amélioration qui permet une réduction des risques volcaniques. Nous avons entrepris plusieurs études volcanologiques reposant sur l’usage d’images de moyenne et haute résolution spatiale, qu’elles soient optiques (IKONOS, Pléiades, GeoEye, Quickbird and SPOT5), radar (ALOS-PALSAR) ou bien thermiques (ASTER et MODIS «hot spot»). Associées à l’analyse de MNTs et de photographies aériennes acquises par un drone, ces études ont consisté à appliquer des techniques de télédétection sur le Semeru et le Merapi, deux des volcans composites les plus actifs et les plus densément peuplés de l’ile de Java en Indonésie. Cette recherche fondée sur la télédétection a permis de mettre en évidence des structures géologiques et tectoniques, d’identifier, de classer et de cartographier des dépôts éruptifs sur les deux volcans et a servi à améliorer l’évaluation des risques à la suite des grandes éruptions de 2002-2003 au Semeru et de 2010 au Merapi. Nous avons également initié une étude afin de comprendre les interactions entre l’activité éruptive et le contexte sismo-tectonique régional en utilisant l’analyse des données MODIS avec la méthode MODVOLC. Nous avons remis à jour la carte géologique du volcan Semeru en y associant des données issues de l’interprétation d’images HSR récentes, des photographies aériennes, l’analyse de MNTs et des observations de terrain, notamment dans le réseau hydrograhique qui convoie des lahars. Nous avons décrit l’histoire éruptive postérieure à 2001 au Semeru en incluant la grande éruption à l’origine des écoulements pyroclastiques (EPs) en 2002-2003 et les éruptions effusives de 2012-2014, qui constituent un phénomène rarement observé sur ce volcan. Le Semeru a produit un volume de 2.5 ± 0.5 106m3 de coulées de lave provenant du cratère sommital entre 2010 et 2014, ce qui peut annoncer, pour la première fois depuis 1967 ou 1941, une modification profonde du style éruptif de ce volcan. Au moment de terminer cette thèse, le dome-coulée situé dans le cratère Jonggring-Seloko continue à croître et les coulées de lave dépassent 2 km de longueur dans la cicatrice majeure en pente raide sur le flanc SE ; leurs fronts pourraient s’effondrer et produire des EPs dont le volume moyen pourrait excéder les valeurs de 3 à 6.5 million de m3 mesurées sur la période 1967-2007. Les écoulements futurs pourront déborder des parois de la cicatrice vers l’aval et se propager vers les vallées des flancs est et sud-ouest. L’épisode éruptif du 26 octobre au 23 novembre 2010 s’est avéré l’événement majeur de l’activité du Merapi depuis 1872. Notre interprétation des images HSR démontre qu’à l’issue des éruptions explosives, le sommet du Merapi a perdu un volume de 10 x 106m3 et la gorge de Gendol orientée SSE a été élargie jusqu’à mesurer 1.3 x 0.3 x 0.2 km. Le nouveau cratère élargi et profond inclut le dome post-2010, qui a été fracturé en 2013, tandis que ses parois verticales instables peuvent être fragilisées par les explosions mineures de 2013 et 2014. Nous avons identifié et cartographié les dépôts pyroclastiques et de lahar de 2010 en appliquant plusieurs méthodes de classification aux images optiques HSR et aux données polarisées de Radar à Synthèse d’Ouverture (RSO). Les résultats démontrent la capacité de l’imagerie satellitaire HSR à capturer l’extension et les impacts de dépôts immédiatement après une grande éruption et avant tout remaniement. Cette technique met en exergue l’utilité de l’imagerie haute résolution et des données radar pour les volcans en activité persistante dont l’accès est souvent rendu impossible. (...) / Remote sensing has long been recognized as a tool for analysis at active and hazardous volcanoes because it can augment our understanding of the processes that underlie volcanic activity so as enable us to apply this understanding to volcanic risk reduction. This thesis presents a volcanological study using High-Spatial Resolution optical images (IKONOS, Pléiades, GeoEye, Quickbird and SPOT5 satellites), radar data (ALOS-PALSAR sensor) and thermal (ASTER satellite and MODIS hot spot) images. In association with DEMs and low-altitude aerial photographs, remote sensing techniques have been applied for tracing the evolution of activity at Semeru and Merapi, two of the most active and densely populated volcanoes in Java, Indonesia. This remotely sensing-based study has unraveled structures, geological features and erupted deposits of both volcanoes and has improved the existing hazard assessment after their most recent eruptions. The thesis also presents the first advance towards deciphering possible interactions between regional tectonic earthquakes and renewed stages of eruptive activity of Merapi and Semeru volcanoes based on the analysis of volcanic hotspots detected by the MODVOLC technique. The geological map of Semeru is updated, including additional data derived from the interpretation of the most recent satellite images, aerial photographs, DEM analysis and fieldwork. The post-2001 eruptive activity at Semeru, including the large PDC-forming eruption in 2002-2003 and uncommon lava flow eruptions in 2010-2014 are investigated. The fact that Semeru has produced several lava flows from the central summit vent between 2010 and 2014 may herald a profound change in eruption style for the first time since at least 1967. At the time of writing, a dome-fed coulée in the Jonggring-Seloko crater continues to grow and lava flows are extending to distances of >2 km down Semeru's SE-scar; their fronts may collapse and produce large-volume pyroclastic density currents (PDCs), perhaps exceeding the average (1967-2007) volume range of 3 to 6.5 million m3. Future dome-collapse PDCs may travel farther down the main SE scar and can spill over its lowermost rims towards the southwest and eastward radiating drainage network. The 26 October-23 November 2010 eruption was the Merapi’s largest event since 1872 (it attained VEI=4). The interpretation of HSR images shows that due to the explosive eruptions, the summit area lost about 10 x 106m3 and the SSE-trending Gendol Breach enlarged to reach 1.3 x 0.3 x 0.2 km in size. The new, enlarged and deep summit crater including the 2010 lava dome is extremely unstable having been weakened by the post-2010 explosive events. This instability is a result of the steep Gendol Breach below the mouth of the crater and the steep and unstable crater walls. The 2010 Merapi pyroclastic and lahar deposits have been identified by applying several classification methods to HSR optical images and dual-polarization synthetic aperture radar (SAR) data. The results show the ability of remotely sensed data to capture the extent and impacts of pristine deposits shortly after emplacement and before any reworking, and highlight the purpose of using high-spatial resolution imagery and SAR data on persistently active volcanoes where access for field survey is often impossible. The 2010 tephra and PDC deposits covered ca. 26 km2 in two catchments of Gendol and Opak Rivers on Merapi’s south flank, i.e. 60-75% of the total PDC deposit area and a total bulk volume of 45 x 106m3. The tephra-fall deposit covered an area of ca. 1300 km2 with a volume range of 18-21 x 106m3. Volumes of these deposits were estimated using the areas determined from remote sensing data and deposit thickness measured in the field. (...) / Penginderaan jauh telah lama dikenal sebagai suatu alat untuk analisis di gunungapi aktif dan berbahaya karena dapat meningkatkan pemahaman kita tentang proses yang mendasari aktivitas gunung berapi sehingga memungkinkan kita untuk menerapkan pemahaman ini dalam pengurangan risiko erupsi gunungapi. Disertasi ini menyajikan studi vulkanologi menggunakan citra satelit optik resolusi tinggi (IKONOS, Pléiades, GeoEye, Quickbird dan SPOT5), data radar (ALOS-PALSAR sensor) dan citra termal (satelit ASTER dan hotspot MODIS). Dalam kaitannya dengan DEM dan foto udara, teknik penginderaan jauh telah diterapkan untuk melihat evolusi aktivitas di Semeru dan Merapi, dua gunung berapi yang paling aktif dengan kepadatan penduduk yang tinggi terletak di Pulau Jawa, Indonesia. Studi berbasis penginderaan jauh ini telah mengkaji struktur, fitur geologi dan material erupsi dari kedua gunungapi tersebut dan telah mempertajam penilaian bahaya yang ada setelah erupsi terkini. Disertasi ini juga menyajikan kemajuan awal dalam menafsirkan kemungkinan interaksi antara gempa tektonik regional dan aktivitas gunungapi Merapi dan Semeru berdasarkan analisis hotspot vulkanik yang terdeteksi oleh MODVOLC. Peta geologi Semeru telah diperbaharui dengan memasukkan data tambahan yang berasal dari interpretasi citra satelit terbaru, foto udara, analisis DEM dan data lapangan. Aktivitas erupsi pasca-2001 di Semeru, termasuk erupsi dengan aliran pirokastik (Pyroclastic Density Current/PDC) besar pada tahun 2002-2003 dan erupsi tidak biasa dengan aliran lava pada 2010-2014, telah dikaji. Fakta bahwa Semeru telah menghasilkan beberapa aliran lava dari kawah di puncak antara tahun 2010 dan 2014, mengindikasikan perubahan besar dalam gaya erupsi untuk pertama kalinya setidaknya sejak 1967. Pada saat penulisan disertasi ini, sebuah kubah lava (Coulée) di kawah Jonggring- Seloko terus tumbuj dan aliran lava yang memanjang hingga jarak >2 km arah tenggara Semeru; ujung lava kemungkinan dapat runtuh dan menghasilkan aliran piroklastik yang mungkin melebihi volume rata-rata (tahun 1967 hingga 2007) dalam kisaran 3-6.5 juta m3. Aliran piroklastik yang akan datang mungkin mengalir sepanjang gawir utama ke arah tenggara dan dapat menyebar melampaui lereng paling bawah ke arah barat daya dan ke arah timur menyebar ke jaringan drainase. Erupsi yang terjadi pada 26 Oktober-23 November 2010 adalah erupsi terbesar Merapi (mencapai VEI 4) sejak 1872. Interpretasi citra resolusi tinggi menunjukkan bahwa daerah puncak kehilangan batuannya sekitar 10 juta m3 akibat erupsi eksplosif. Erupsi juga memperbesar “Gendol Breach” dengan orientasi tenggara menjadi berukuran 1.3x0.3x0.2 km. Kawah puncak yang baru, diperbesar dan dalam, termasuk juga kubah lava tahun 2010 sangat tidak stabil dan telah diperlemah oleh beberapa erupsi eksplosif pasca-2010. Ketidakstabilan ini diakibatkan oleh curamnya Gendol Breach di bawah mulut kawah dan kondisi dinding kawah yang curam dan tidak stabil. Deposit piroklastik dan lahar diidentifikasi dengan menerapkan beberapa metode klasifikasi terhadap citra optik resolusi tinggi dan data dual-polarisasi Synthetic Aperture Radar (SAR). Hasilnya menunjukkan kemampuan data penginderaan jauh untuk merekam jangkauan dan dampak dari deposit murni sesaat setelah pengendapan dan sebelum proses erosi, serta menyoroti tujuan penggunaan citra resolusi tinggi dan data SAR di gunungapi sangat aktif dengan akses untuk survei lapangan sering kali tidak memungkinkan. Endapan tephra dan PDC menutupi area sekitar 26 km2 di dua DAS, Kali Gendol dan Opak, di sisi selatan Merapi, atau 60-75% dari total luas endapan PDC, dan total volume 45 juta m3. Deposit tephra jatuh menutupi area seluas sekitar 1.300 km2 dengan volume 18-21 juta m3. Volume endapan vulkanik ini diestimasi menggunakan informasi luas yang ditentukan dari data penginderaan jauh dan ketebalan yang diukur di lapangan. (...)

M.Sc. / Donor-acceptor (D-A) systems consist of a donor covalently or non-covalently linked to an acceptor. The simplest D–A system consists of a donor linked to an acceptor and is called a dyad system. Photoactive dyad systems are molecular devices designed to perform through the separation of charge separation states and the conversion of solar energy to chemical energy in analogy to photosynthesis.1 These dyad systems consist of a donor which is usually a chromophore and an acceptor. The design of these systems is guided to mimic photo-induced electron transfer (PET) and charge separation (CS), which are fundamental processes of photosynthesis. In nature, photosynthetic units are often built from dyads consisting of pigments like chlorophyll (donors), non–covalently linked to quinones, (acceptors). The donor harvests light energy and transfers the energy to the nearby pigment molecules until it eventually reaches a special region of the chlorophyll macrocycle called the reaction centre where this light energy is then converted to electrochemical energy. Photoactive dyad systems act as artificial photosynthetic models as they reproduce photo–induced electron transfer and charge separation of natural photosynthesis. In this project, dyad systems were made by covalently linking zinc pheophorbide, a modified chlorophyll derivative to double–walled carbon nanotubes (DWCNTs). Zinc pheophorbide acts as the donor and DWCNTs as the acceptors. Chlorophyll was modified by cutting the phytol chain and inserting zinc as the central metal to yield zinc pheophorbide. This derivative is stable against irradiation, has a good range of acceptor wavelength and is also a good light harvester. DWCNTs are one dimensional nanowires with two concentric tubes. They readily accept electrons because they have an extended π electron system. These electrons are then transported efficiently under ballistic conditions. DWCNTs were synthesised by catalytic chemical vapour deposition (CCVD) of methane over Mg0.99Co0.075Mo0.025O catalyst. In dyad system 1, amidated zinc pheophorbide molecules were covalently attached to oxidised DWCNTs in the presence of N–ethyl–N’–(3-dimethylaminopropyl) carbodiimide hydrochloride (EDC) \ and N–hydroxysuccinnimide (NHS) as a catalysts. Dyad system 2 was synthesized by attaching zinc pheophorbide molecules to amidated DWCNTs using the same catalysts.

The characterization of the normal pulmonary acinus is a necessary first step in understanding the nature of respiratory physiology and in assessing the etiology of pulmonary pathology. Murine models play a vital role in the advancement of current understanding of the dynamics of gas exchange, particle deposition and the manifestations of diseases such as COPD, Cystic Fibrosis and Asthma. With the advent of interior tomography techniques, high-resolution micro computed tomography (μCT) systems provide the ability to nondestructively assess the pulmonary acinus at micron and sub-micron resolutions. With the application of Systematic Uniform Random Sampling (SURS) principles applied to in-situ fixed, intact, ex-vivo lungs, we seek to characterize the structure of pulmonary acini in mice and study the variations across dimensions of age, location within the lung and strain phenotypes. Lungs from mice of three common research strains were perfusion fixed in-situ, and imaged using a multi-resolution μCT system (Micro XCT 400, Zeiss Inc.). Using lower resolution whole lung images, SURS methods were used for identification of region-specific acini for high-resolution imaging. Acinar morphometric metrics included diameters, lengths and branching angles for each alveolar duct and total path lengths from entrance of the acinus to the terminal alveolar sacs. In addition, other metrics such as acinar volume, alveolar surface area and surface area/volume ratios were assessed. A generation-based analysis demonstrated significant differences in acinar morphometry across young and old age groups and across the three strains. The method was successfully adapted to large animals and the data from one porcine specimen has been presented. The registration framework provides a direct technique to assess acinar deformations and provides critical physiological information about the state of alveolar ducts and individual alveoli at different phases of respiration. The techniques presented here allow us to perform direct assessment of the three-dimensional structure of the pulmonary acinus in previously unavailable detail and present a unique technique for comprehensive quantitative analysis. The acinar morphometric parameters will help develop improved mathematical and near-anatomical models that can accurately represent the geometric structure of acini, leading to improved assessment of flow dynamics in the normal lung.