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Rapid isolation and identification of spores from various environmental samples is necessitated because anthrax spores can be used as biological weapons. The hydrophobic nature of spores may allow for their rapid concentration and partial purification from contaminating materials. In this study, spores from four taxonomic groups of Bacillaceae were isolated, purified and characterized for hydrophobicity by hexadecane partitioning, surface morphology by scanning electron microscopy, and steady-state fluorescence by spectroscopy. The morphology of spores was similar within taxonomic groups and dissimilar between groups. Spore hydrophobicity ranged from 0.3% to 65% and all spores had fluorescence emission peaks at 335 nm and 450 nm. The excitation maxima for the peak at 450 nm were shifted to higher wavelengths for the least hydrophobic spores. Regression analysis demonstrated a correlation between the taxonomic identity, as established by fatty acid analyses, and hydrophobicity. Hydrophobicity can be used to help isolate spores from complex environmental samples and intrinsic fluorescence is helpful in discriminating the taxonomic groups.

Thesis (Ph. D.)--University of Wisconsin--Madison, 1965. / Vita. Typescript. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references.

Bifunctional catalysts consisting of palladium or platinum and supported on amorphous silica-alumina were prepared and tested in the hydrocracking of n-hexadecane, which is considered to be representative of n-paraffins in hydrocracker feeds. In addition to the evaluation of the  physicochemical properties, a comprehensive study on catalyst activity and selectivity has been conducted, in the full range of conversions. A theoretical model was proposed to fit the experimental conversion-selectivity data. The n-hexadecane reactivity pattern was expressed in terms of a reaction network involving lumps consisting of monobranched and multibranched n-hexadecane isomers, and cracking products. Pseudo first order kinetics and irreversible reaction steps were assumed in order to obtain the kinetic constants of each step. For the same metallic molar loading, a platinum-based catalyst proved more active than a palladium one. The reaction network model showed that cracking products were produced by means of a bifunctional mechanism on palladium catalysts, with n-hexadecane isomers as intermediates. However, on platinum catalysts, an additional monofunctional mechanism was observed. The noble metal catalyzes the hydrogenolysis of n-hexadecane without requiring any acid function. An increase in the platinum loading leads to an increase in the importance of this direct cracking route. The deactivation in the platinum-based catalysts is only due to coke formation, which deactivates the metal sites. The regeneration by means of a Temperature-Programmed Oxidation does not lead to a complete recovery of the metal function, according to the volumetric chemisorption measurements and the experimental selectivity  data. Further work is required to determine the real causes.

Fischer-Tropsch synthesis enables the production of high quality diesel fuel from biomass derived synthesis gas. In order to increase the overall diesel yield, it is necessary to perform a subsequent hydrocracking of the long-chain linear paraffins. This work is focused on characterization and testing of catalysts for the hydrocracking reaction of Fischer-Tropsch waxes. In particular, noble metal catalyst based on Pt and Pd on amorphous silica-alumina support were tested. Palladium based catalysts performed nearly an ideal bifunctional mechanism, while platinum based catalysts performed another way of cracking: hydrogenolysis. Platinum based catalysts are more active than palladium ones, with the same metal loading. This is a consequence of the nature of the metal sites. The product distribution is similar for both platinum and palladium catalysts. However, due to the hydrogenolysis cracking mechanism performed by platinum based catalysts, the amount of light gases produced on platinum based catalysts is higher. Furthermore, the deactivation behavior of the Platinum and Palladium catalysts has been studied, and the results showed that the dispersion of the active phase decreased with deactivation and the average crystallite diameter increased. This means a decrease in activity. A regeneration program, temperature programmed oxidation (TPO), has been carried out demonstrating that the activity was not completely recovered.

Synthetic fuels produced using the Fischer-Tropsch technology will play an important role in the future of the transportation sector. The Fischer-Tropsch synthesis (FTS) allows converting synthesis gas (CO + H2) into fuels of outstanding quality. The synthesis gas can be obtained from different carbon sources: natural gas, coal and biomass. In order to maximize the yield of middle distillates, the process is carried out in two main steps: the FT-synthesis that produces long-chain hydrocarbons (waxes) and a hydrocracking step, to selectively convert the waxes into fuels. Diesel produced by this process is characterized by excellent combustion properties and reduced harmful tailpipe emissions compared to conventional diesel. Due to the growing interest in synthetic fuel production, from the industry and the academia, and to the peculiar characteristics of the Fischer-Tropsch products, research in hydrocracking has received renewed attention. Catalysts for the hydrocracking of long-chain paraffins have been the subject of the present work, which is the summary of four scientific publications. Noble metals supported on acid carriers have been compared, especially for what regards the mechanisms through which hydrocracking proceeds. The catalysts were synthesized and characterized by various techniques, including N2 physisorption, H2 chemisorption, TEM, pyridine adsorption FTIR, ammonia TPD, etc. It was shown that catalytic activity is mainly dependent on the acid support used; that selectivity is strongly dependent on conversion, high conversion favoring highly branched cracking products. Two main reaction routes were observed: bifunctional hydrocracking and hydrogenolytic cracking. Platinum-containing catalysts showed high selectivity towards the latter, while palladium/silica-alumina behaved as pure bifunctional catalysts. Catalyst deactivation was investigated and initial sintering of metal particles was observed. Coking was also a cause of deactivation. Formation of coke deposits was highly dependent on the metal loading of the catalysts. Metal loading also influenced catalyst selectivity, especially in the case of platinum/silica-alumina catalysts. Monofunctional hydrogenolysis on the platinum particles, superimposed to the bifunctional mechanism was observed. This route increased selectivity towards linear hydrocarbons and methane, with increasing amounts of platinum. The specific rate of hydrogenolysis was constant for different loadings of platinum on the same acid silica-alumina support. Using a different, less acid, support negatively affected the hydrogenolytic activity of the platinum catalytic sites. It was concluded that metal-support interactions might play an important role in the catalytic properties of platinum surfaces. This work has contributed to increasing the knowledge about hydrocracking of long-chain alkanes and pointed out some features that might have practical interest in the application of this technology to synthetic-fuel production. / Syntetiska drivmedel tillverkade genom Fischer-Tropsch teknologin kommer i framtiden att ha en betydande roll för transportsektorn. Fischer-Tropsch syntesen (FTS) möjliggör omvandling av syntesgas (CO + H2) till högkvalitativa bränslen. Syntesgasen kan erhållas från olika kolkällor: naturgas, kol och biomassa. För att maximera utbytet av medeldestillat, utförs processen i två huvudsteg: FT-syntes som producerar långa kolväten (vaxer) och ett hydrokrackning steg, för att selektivt omvandla vaxerna till bränslen. Diesel som produceras med denna process kännetecknas av utmärkta förbränningsegenskaper och ger upphov till minskade utsläpp av skadliga ämnen jämfört med vanlig diesel. På grund av det växande intresset för syntetiska bränslen, både från industrin och den akademiska världen, och av de speciella egenskaperna hos Fischer-Tropsch-produkter, har forskningen i vätekrackning fått förnyad uppmärksamhet. Ämnet för detta arbete, som är en sammanfattning av fyra vetenskapliga publikationer, är katalysatorer för hydrokrackning av långkedjiga paraffiner. Ädelmetaller uppburna på sura bärare har jämförts, särskilt vad gäller vätekrackningsmekanismer. Katalysatorerna preparerades och karaktäriserades med hjälp av olika tekniker, bland andra N2 fysisorption, H2 kemisorption, TEM, pyridin adsorption FTIR, ammoniak TPD, etc. Det visade sig att den katalytiska aktiviteten är främst beroende av surheten hos bärarmaterialet, att selektivitet är starkt beroende av omsättningen, där hög omsättning gynnar flergrenade krackningsprodukter. Två huvudsakliga reaktionsvägar observerades: bifunktionell vätekrackning och hydrogenolytisk crackning. Platinakatalysatorer visade hög selektivitet mot det senare, medan katalysatorer med palladium på kiseloxid-aluminiumoxid uppträdde som rena bifunktionella katalysatorer. Katalysatordeaktivering undersöktes och sintring av metallpartiklar observerades. Koksning var också en orsak till deaktivering. Koksbildning var starkt beroende av metallhalten i katalysatorerna. Metallhalten påverkade också selektivitet, särskilt för platina-kiseloxid-aluminiumoxidkatalysatorer. Monofunktionellt hydrogenolys på platinapartiklarna, observerades utöver den bifunktionella mekanismen. Med denna reaktionsväg ökade selektivitet mot linjära kolväten och metan, med ökande platinahalter på katalysator. Den specifika reaktionshastigheten för hydrogenolys var konstant för olika platinahalter på en sur kiseloxid-aluminiumoxidbärare. Den hydrogenolytiska aktiviteten hos platina katalytiska säten påverkas negativt när en mindre sur bärare användes. Slutsatsen var att interaktioner mellan metallen och bäraren kan spela en viktig roll för de katalytiska egenskaperna hos platina ytor. Detta arbete har bidragit till att öka kunskapen om vätekrackning av långkedjiga alkaner och påpekade vissa funktioner som kan ha praktiskt intresse vid tillämpningen av denna teknik för produktionen av syntetiska bränslen. / <p>QC 20131007</p>

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Os manguezais sÃo ecossistemas entremarÃs produtivos e biologicamente importantes que ocorrem em regiÃes tropicais e subtropicais do mundo. Ãreas de manguezais nÃo perturbados fornecem habitats para uma variedade de plantas, animais e microrganismos. Estes ecossistemas recebem materiais sedimentares do mar e continente, tornando-se uma Ãrea de transiÃÃo com elevada produtividade. Importantes processos, tais como ciclagem de nutrientes, estÃo diretamente conectados à atividade e diversidade das comunidades microbianas dos solos do manguezal. No entanto, devido a sua localizaÃÃo estratÃgica, manguezais tÃm sido amplamente impactados por todo o mundo. A compreensÃo da estrutura e das funÃÃes das comunidades microbianas e suas adaptaÃÃes Ãs alteraÃÃes ambientais resultantes de xenobiÃticos, alteraÃÃes climÃticas e a prÃtica industrial, tais como a exploraÃÃo petrolÃfera, à essencial para manter ou restabelecer funÃÃes desejÃveis do ecossistema. Dessa forma, o presente estudo investigou a estrutura de comunidades bacterianas de amostras de solos do manguezal da Barra Grande, Icapuà (37 20âW, 4 40âS), por mÃtodo independente de cultivo usando Polimorfismo do Tamanho de Fragmentos de RestriÃÃo Terminal (T-RFLP) e tambÃm avaliou o mÃtodo dependente de cultivo (enriquecimento) para isolar cepas de bactÃrias com potencial para degradar petrÃleo e n-Hexadecano. Um total de trÃs pontos foi amostrado ao longo do manguezal, com 150 metros de distÃncia entre cada um deles. Temperatura, pH, salinidade, matÃria orgÃnica e granulometria dos solos foram medidas. AnÃlises de T-RFLP foram feitas apÃs a digestÃo de DNA genÃmico com as enzimas HhaI e MspI e o nÃmero e diversidade de Unidades TaxonÃmicas Operacionais (OTU) de cada amostra foi analisado pelo programa T-Align (Applied Biosystems). A cepa selecionada para testes de diferentes concentraÃÃes de n-Hexadecano foi identificada pelo seqÃenciamento do gene do rRNA 16S. Esta cepa foi tambÃm avaliada em relaÃÃo à susceptibilidade a radiaÃÃo UV e antibiÃticos. Os resultados mostraram que as comunidades bacterianas de solos do manguezal sÃo semelhantes em nÃmero de OTUs, mas diferem em composiÃÃo. Provavelmente a peculiaridade das variÃveis fÃsico-quÃmicas e granulometria do solo sÃo responsÃveis pelas diferenÃas na composiÃÃo e estrutura das comunidades bacterianas. Dezoito cepas de bactÃrias foram isoladas de culturas de enriquecimento com petrÃleo e quatro cepas mostraram potencial particular para degradar n-Hexadecano. Uma cepa identificada como Acinetobacter sp. IC18 foi caracterizada como uma boa degradadora de hidrocarboneto, pois foi capaz de degradar 1% do n-Hexadecano em 48 horas. Esta cepa tambÃm utilizou cerca de 30% de uma concentraÃÃo total de 20% (v/v) de n-Hexadecano durante o mesmo perÃodo de incubaÃÃo. AlÃm disso, IC18 foi susceptÃvel a vÃrios antibiÃticos e resistente à radiaÃÃo UV. Em conclusÃo, a estrutura da comunidade bacteriana de solos do manguezal da Barra Grande parece nÃo ser afetada pela presenÃa da exploraÃÃo petrolÃfera em IcapuÃ. AlÃm disso, os solos deste manguezal sÃo colonizados por vÃrias cepas com potencial para degradar hidrocarbonetos, que à particularmente interessante em virtude do risco de derramamentos de petrÃleo.