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Thesis (MScEng (Process Engineering))--Stellenbosch University, 2008. / Please refer to full text to view abstract.

Recent progress in magnetic resonance imaging (MRI) has opened the way for micron-scale resolution, and thus for imaging biological cells. In this thesis work, we performed magnetic resonance microscopy (MRM) on the nervous system of Aplysia californica, a model particularly suited due to its simplicity and to its very large neuronal cell bodies, in the aim of studying cellular-scale processes with various MR contrasts. Experiments were performed on a 17.2 Tesla horizontal magnet, at resolutions down to 25 µm isotropic. Initial work consisted in conceiving and building radiofrequency microcoils adapted to the size of single neurons and ganglia. The first major part of the project consisted in using the manganese ion (Mn2+) as neural tract tracer in the buccal ganglia of Aplysia. Manganese is an MR contrast agent that enters neurons via voltage-gated calcium channels. We performed the mapping of axonal projections from motor neurons into the peripheral nerves of the buccal ganglia. We also confirmed the existence of active Mn2+ transport inside the neural network upon activation with the neurotransmitter dopamine. In the second major part of the project, we tested the potential of two diffusion MRI sequences for microscopy. On the one hand, we explored a very original mechanism for diffusion weighting, DESIRE (Diffusion Enhancement of SIgnal and REsolution), particularly suited for small samples. The two-dimensional DESIRE sequence was implemented and successfully tested on phantoms. The measured enhancement was consistent with theoretical predictions. Using this sequence to produce diffusion weighted images with an unprecedented contrast in biological tissue remains a challenge. On the other hand, a more "standard" sequence was implemented to measure the apparent diffusion coefficient (ADC) in nervous tissue with MRM. This sequence was a three-dimensional DP-FISP (Diffusion Prepared Fast Imaging with Steady-state free Precession), which met criteria for high resolution in a short acquisition time, with minimal artifacts. Using this sequence, we studied the changes in water ADC at different scales in the nervous system, triggered by cellular challenges. The challenges were hypotonic shock or exposure to ouabain. ADC measurements were performed on single isolated neuronal bodies and on ganglia tissue, before and after challenge. Both types of stress produced an ADC increase inside the cell and an ADC decrease at tissue level. The results favor the hypothesis that the increase in membrane surface area associated with cell swelling is responsible for the decrease of water ADC in tissue, typically measured in ischemia or other conditions associated with cell swelling.

Made available in DSpace on 2017-05-12T14:46:50Z (GMT). No. of bitstreams: 1 Rafaela.pdf: 1254631 bytes, checksum: 3d834f48484b52c9ceff46d1a42fb49a (MD5) Previous issue date: 2013-03-12 / The cowpea bean, a culture traditionally planted in the Brazilian Northeast, has been expanding to other regions of Brazil, mostly to the Midwest, in the states of Mato Grosso and Mato Grosso do Sul, on account of its wide adaptability to tropical conditions and low production cost. Most of the seeds after harvest do not have appropriate characteristics for the storage, mainly due to high water content at harvest time. Drying is the most widely used process to preserve the quality of the product. The operation consists in removing some water contained in the fresh beans. In this context, the aim of this study was to determine and model the drying curves of cowpea beans at temperatures of 30, 40 and 50 °C, adjusting different mathematical models to experimental data, to select the one that best represents the phenomenon, determine the effective diffusion coefficient, and evaluate the physiological quality of seeds. They were seeds of cowpea bean cultivars BRS Guariba and BRS Novaera, harvested by hand, with water content of 0.21 (bs) and 0.16 (bs) respectively, dried to the level 0.11 (bs). The drying process was carried out in an experimental dryer under controlled temperatures of 30, 40 and 50 ° C and relative humidity of the drying air between 14% and 59%. The drying time for the cowpea bean seeds (BRS Guariba cultivar) was 10.4, 5.6 and 2.1 hours at temperatures of 30, 40 and 50 ° C respectively. For BRS Novaera, the drying lasted 8.7, 4.7 and 2.0 hours at temperatures of 30, 40 and 50 °C respectively. The mathematical model of Midilli was the one that best adapted to the experimental data for both cultivars. The diffusion coefficient increases with the temperature, with values from 5.047 to 12.011 x 10-11 x 10-11 m² s-1, for BRS Guariba, and from 2.482 x 10-11 to 5.187 x 10-11 m² s-1 for BRS Novaera in the temperature range from 30 to 50 °C. The relation between the effective diffusion coefficient and the drying temperature can be described by the Arrhenius equation, which has activation energy of 35.04 kJ.mol-1 and 29.76 kJ.mol-1 for liquid diffusion in the drying process of cowpea bean seeds. After the drying process, the seeds percentage of normal seedlings were more than 87%, and under the different conditions of study they presented low force, since the drying under a temperature of 40 °C was the one which produced the most satisfactory results. / O feijão-caupi, cultura tradicionalmente cultivada no Nordeste brasileiro, vem se expandindo para diversas regiões do Brasil, principalmente para o Centro-Oeste, nos estados do Mato Grosso e Mato Grosso do Sul, em razão da sua ampla adaptabilidade às condições tropicais e ao baixo custo de produção. Após a colheita, a maior parte das sementes possui características inadequadas para o armazenamento, devido principalmente ao alto conteúdo de água na época da colheita. A secagem é o processo mais utilizado para a preservação da qualidade desse produto. A operação consiste na remoção de parte da água contida no feijão recém colhido. Neste contexto, o objetivo deste trabalho foi determinar e modelar as curvas de secagem do feijão-caupi, nas temperaturas de 30, 40 e 50 °C, ajustando-se diferentes modelos matemáticos aos dados experimentais e selecionar aquele que melhor representa o fenômeno, bem como determinar o coeficiente de difusão efetivo e avaliar a qualidade fisiológica das sementes. Foram utilizadas sementes de feijão-caupi das cultivares BRS Guariba e BRS Novaera, colhidas manualmente, com teor de água de 0,21 (b.s) e 0,16 (b.s), respectivamente, secas até o teor 0,11 (b.s.). O processo de secagem foi realizado em secador experimental sob as temperaturas controladas de 30, 40 e 50 °C, e umidade relativa do ar de secagem entre 14 e 59%. O tempo de secagem para as sementes de feijão-caupi (cultivar BRS guariba) foi de 10,4, 5,6 e 2,1 horas para as temperaturas de 30, 40 e 50 °C, respectivamente; para a cultivar BRS Novaera a secagem foi de 8,7, 4,7 e 2,0 horas para as temperaturas de 30, 40 e 50 °C, respectivamente. O modelo matemático de Midilli foi o que melhor se ajustou aos dados experimentais de ambas as cultivares, apontando que o coeficiente de difusão aumenta com a elevação da temperatura, apresentando valores entre 5,047 x 10-11 a 12,011 x 10-11 m² s-1, para a cultivar BRS Guariba e 2,482 x 10-11 a 5,187 x 10-11 m² s-1, na cultivar BRS Novaera, para a faixa de temperatura de 30 a 50 °C. A relação entre o coeficiente de difusão efetivo e a temperatura de secagem pode ser descrita pela equação de Arrhenius, que apresenta uma energia de ativação de 35,04 kJ.mol-1 e de 29,76 kJ.mol-1 para a difusão líquida no processo de secagem das sementes de feijão-caupi. Após o processo de secagem, as sementes apresentaram percentuais de plântulas normais superiores a 87%; nas diferentes condições de estudo apresentaram baixo vigor, sendo a secagem sob a temperatura de 40 °C a que produziu os resultados mais satisfatórios.

Chemically identical but topologically different cyclic and linear polymers not only result in marked differences in dynamics, but also lead to unique transport properties of their blends, where cyclic polymers have chances to be threaded onto the linear polymers. This dissertation addresses the effect of ring architecture on dynamics using different time/length scale techniques: self-diffusion coefficients, NMR spin-spin relaxation time (T2) and bulk viscosity. In deuterated water, synthesized cyclic poly(oxyethylene) (CPOE) (400-1500 g/mol) diffused faster than corresponding linear POE (LPOE) and linear POE dimethyl ether (LPOEDE). However, the self-diffusion coefficients in melts were arranged in the following manner: LPOEDE > CPOE > LPOE, in excellent agreement with T2 and viscosity data, showing topological and chain end effects. Compared to LPOEDE, both CPOE and LPOE had higher activation energies for viscosity with less dependence on the molecular weight. In the blends of CPOE and LPOE for 900 and 1500 g/mol, the diffusion coefficient and viscosity in melts were higher and lower than the values predicted by a binary mixing rule, respectively. These deviations were attributed to the threading conformation, and the weight fraction of the threaded chains for 1500 g/mol was estimated by a three-term mixing rule. This threading conformation also appeared to influence such important bulk properties as the glass transition and spherulitic growth rate of the blends.

Document formatted into pages; contains 115 pages. / Title from PDF of title page. / Original thesis was submitted in HTML and can be accessed at http://www.lib.usf.edu/EDT-db/theses/available/etd-10262001-162331/unrestricted/default.htm / Thesis (M.S.)--University of South Florida, 2002. / Includes bibliographical references. / Text (Electronic thesis) in PDF format. / ABSTRACT: The purposes of this research were to determine the efficacy of using the Ogawa]a passive sampling device (PSD) to measure ammonia and to identify significant ammonia sources adjacent to Hillsborough and Tampa Bay. Ninety-four samplers were deployed over a 180-km2 area for two weeks in October 2001. Within the area sampled were located suburbs, an urban center, major highways, port activities, fertilizer manufacturing, wastewater treatment, coal-combustion power plants, warehousing and dairy farming. The sampled locations were arranged in a triangular grid pattern spaced 1.5 km apart. The pattern was designed to locate circular hot spots with a minimum radius of 0.75 km. The minimum, maximum, mean, and median ammonia concentrations were 0.06, 15, 2.0, and 1.5 mg/m3, respectively, and the estimated precision was 16%. Hot spots identified from kriged concentration data coincided with inventoried ammonia sources. / ABSTRACT: The relative bias and precision of the PSD based on collocation with an annular denuder system were (plus or minus) 30 % and 20 %. / System requirements: World Wide Web browser and PDF reader. / Mode of access: World Wide Web.

Οι ζεόλιθοι είναι κρυσταλλικά αργιλοπυριτικά υλικά με πόρους μοριακών διαστάσεων και για το λόγο αυτό συχνά καλούνται και ως μοριακά κόσκινα. Χαρακτηρίζονται από την ικανότητα ρόφησης αερίων και ατμών, ανταλλαγής των κατιόντων της δομής τους, καθώς και κατάλυσης σημαντικού αριθμού χημικών αντιδράσεων. Λόγω των ιδιαίτερων φυσικοχημικών ιδιοτήτων τους, οι ζεόλιθοι αποτελούν ιδανικά υλικά για το διαχωρισμό μορίων με διαφορετικό σχήμα, μέγεθος ή πολικότητα γι’αυτό την τελευταία δεκαετία μέρος του ερευνητικού ενδιαφέροντος έχει επικεντρωθεί στην ανάπτυξη πολυκρυσταλλικών μεμβρανών από ζεόλιθους με σκοπό το διαχωρισμό αερίων και υγρών μιγμάτων. Στην παρούσα Διατριβή μελετήθηκε η κρυστάλλωση μεμβρανών φωγιασίτη πάνω σε πορώδη υποστρώματα από α-Al2O3 με επίπεδη και κυλινδρική γεωμετρία συναρτήσει διαφόρων παραμέτρων σύνθεσης όπως ήταν η σύσταση, η θερμοκρασία, ο χρόνος και η γήρανση των αιωρημάτων σύνθεσης των μεμβρανών Συνολικά εξετάστηκαν πέντε διαφορετικές συστάσεις. Η σύσταση 4.17Na2O : 1.0Al2O3 : 10TEA (τριαιθανολαμίνη) : 1.87SiO2 : 460H2O οδήγησε στην ανάπτυξη μεμβρανών φωγιασίτη με λιγότερες ατέλειες και για αυτό μελετήθηκε περισσότερο. Η ικανότητα των μεμβρανών να διαχωρίζουν μίγματα CO2 / H2, CO2 / N2, CO2 / CH4, CO2 / H2 / N2 / CH4, C3H6 / C3H8, C3H6 / N2, C3H8 / N2 και C3H6 / C3H8 / N2 εξετάστηκε συναρτήσει της θερμοκρασίας, της σύστασης και της πίεσης της τροφοδοσίας καθώς και της παρουσίας ή μη υγρασίας στο ρεύμα της τροφοδοσίας. Τα πειράματα διαπερατότητας απέδειξαν, ότι ευνοείται η εκλεκτική μεταφορά κυρίως του CO2 και του C3H6 μέσα από τις μεμβράνες. Η εκλεκτικότητα μπορεί να αποδοθεί στην ισχυρή αλληλεπίδραση των μορίων αυτών με τα κατιόντα Na+ που περιέχονται στη δομή του φωγιασίτη. Τέλος, μελετήθηκαν οι μηχανισμοί μεταφοράς μάζας των μιγμάτων CO2 / H2 και CO2 / H2 / N2 / CH4 με τη χρήση της θεωρίας Stefan-Maxwell. Επιπρόσθετα εξετάστηκαν διάφορες περιπτώσεις αργού σταδίου (διάχυση και εκρόφηση) καθώς και συνδυασμοί διαφορετικών μηχανισμών διάχυσης (επιφανειακή διάχυση και ενεργοποιημένη διάχυση αερίων). Οι συντελεστές διάχυσης υπολογίστηκαν από το συνδυασμό των πειραματικών δεδομένων ρόφησης και διαπερατότητας των καθαρών συστατικών. Η ανάλυση που πραγματοποιήθηκε οδήγησε στο συμπέρασμα ότι η μεταφορά των μιγμάτων μέσα από τις μεμβράνες μπορεί να προβλεφθεί κυρίως από το μηχανισμό της επιφανειακής διάχυσης. / Zeolites are crystalline aluminosilicate materials. They are frequently called molecular sieves because they have pores of molecular dimensions. They are able to adsorb gases or vapors, to exchange framework cations and to catalyze a large number of chemical reactions. Due to their physicochemical properties they are ideal materials for the discrimination of molecules based on their shape, size or polarity. The last decade part of the research attention has been focused on the synthesis of polycrystalline zeolite membranes for the separation of gas and vapor mixtures. In the present thesis the crystallization of faujasite membranes on porous flat or tubular α-Al2O3 substrates was studied as a function of several synthesis parameters such as composition, temperature, time and aging of sol mixtures. Five different compositions were examined. Membranes synthesized using sols with composition 4.17Na2O : 1.0Al2O3 : 10TEA (triethanolamine) : 1.87SiO2 : 460H2O, had the best separation performance. The ability of the membranes to separate CO2 / H2, CO2 / N2, CO2 / CH4, CO2 / H2 / N2 / CH4, C3H6 / C3H8, C3H6 / N2, C3H8 / N2 and C3H6 / C3H8 / N2 mixtures was examined as a function of temperature, feed mixture composition, total feed pressure and the presence or not of humidity in the feed side. In all cases the membranes were either CO2 or C3H6 selective. The separation ability can be attributed to the strong interaction between those molecules with the Na+ cations of the faujasite framework. The transport of CO2, H2, N2 and CH4 through the membranes was modeled using the Maxwell-Stefan theory. Two different cases of rate limiting step (diffusion and desorption) as well as several combinations of different diffusion mechanisms (surface diffusion and activated gaseous diffusion) were considered. The diffusion coefficients were calculated using the single-component permeation and adsorption data. It has been possible to predict the multicomponent permeation fluxes when surface diffusion was assumed the transport mechanism of all species.

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