Submitted by Ricardo Cedraz Duque Moliterno (ricardo.moliterno@uefs.br) on 2016-07-19T23:28:56Z No. of bitstreams: 1 DISSERTA??O ANDRESSA PRISCILA PIANC? S. LIMA.pdf: 1903052 bytes, checksum: 3d8a27256e27d81bbdd1cf3ad9eee48f (MD5) / Made available in DSpace on 2016-07-19T23:28:56Z (GMT). No. of bitstreams: 1 DISSERTA??O ANDRESSA PRISCILA PIANC? S. LIMA.pdf: 1903052 bytes, checksum: 3d8a27256e27d81bbdd1cf3ad9eee48f (MD5) Previous issue date: 2016-03-23 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior - CAPES / Chapada Diamantina ? BA presents endemic especies with ornamental potential among which is Orthophytum mucugense, which occurs in the municipality Mucug?. This species is a target of extractivism and it is considered vulnerable, rendering studies of propagation and conservation of the species necessary. Therefore, the objective of this study was to establish protocols of micropropagation and in vitro conservation of O. mucugense. To that end, morphogenetic responses were evaluated in three types of explants, stem, root and leaf under the effect of different concentrations of the plant growth regulators NAA, 2,4-D and BAP. Sprouts formation in stem explants by direct organogenesis, in basal leaf explants by indirect organogenesis and callus formation in basal root and leaf explants were obtained. The rooting of the shoots was carried out with 1 coal g.L-1 activated for 30 days, and microplants acclimatized in a greenhouse with direct exposure to the environment. These results evince that tissue culture is a viable tool for in vitro propagation of O. mucugense. In in vitro conservation the effect of the medium salts reduction, of osmotic agents and of the retardant ancymidol in the minimum growth of the plants were tested; after 300 days of cultivation, analysis of the plant growth, of the chlorophyll content and of the regenerative capacity were carried out. On the basis of these assessments, the ancymidol, in the concentrations used, is not efficient in minimal growth induction, and the reduction of MS salts to ?3, with the combination of 45 g.L-1 of sucrose with 7.8 g.L-1 of mannitol is indicated for in vitro conservation of O. mucugense. / A Chapada Diamantina ? BA apresenta esp?cies end?micas com potencial ornamental dentre as quais est? a Orthophytum mucugense, que ocorre no munic?pio de Mucug?. Esta esp?cie ? alvo de extrativismo e considerada como vulner?vel, sendo necess?rios estudos de propaga??o e conserva??o da mesma. Portanto, objetivou-se neste trabalho estabelecer protocolos de micropropaga??o e conserva??o in vitro de O. mucugense. Para isto foram avaliadas as respostas morfog?nicas em tr?s tipos de explantes, caulinar, radicular e foliar, sob efeito de diferentes concentra??es dos reguladores vegetais ANA, 2,4-D e BAP. Foram obtidas forma??o de brotos em explante caulinar por organog?nese direta, em explante foliar basal por organog?nese indireta e forma??o de calo em explante foliar basal e radicular. O enraizamento dos brotos foi realizado com 1 g.L-1 de carv?o ativado por 30 dias, e as microplantas aclimatizadas em casa de vegeta??o com exposi??o direta ao ambiente. Estes dados demonstram que a cultura de tecidos ? uma ferramenta vi?vel para a propaga??o in vitro de O. mucugense. Na conserva??o in vitro foram testados o efeito da redu??o de sais do meio, de agentes osm?ticos e do retardante ancymidol no crescimento m?nimo das plantas; ap?s 300 dias de cultivo foram realizadas an?lises de crescimento das mesmas, do teor de clorofila e da capacidade regenerativa. Com base nestas avalia??es o ancymidol, nas concentra??es utilizadas, n?o ? eficiente na indu??o do crescimento m?nimo, e a redu??o de sais MS para ?3 com a combina??o de 45 g.L-1 de sacarose com 7,8 g.L-1 de manitol ? indicada para conserva??o in vitro de O. mucugense.

Demosponges possess a skeleton made of a composite material with various organic constituents and/or siliceous spicules. Chitin is an integral part of the skeleton of different sponges of the order Verongida. Moreover, sponges of the order Verongida, such as Aplysina cavernicola or Ianthella basta, are well-known for the biosynthesis of brominated tyrosine derivates, characteristic bioactive natural products. It has been unknown so far whether these compounds are exclusively present in the cellular matrix or whether they may also be incorporated into the chitin-based skeletons. In the present study, we therefore examined the skeletons of A. cavernicola and I. basta with respect to the presence of bromotyrosine metabolites. The chitin-based-skeletons isolated from these sponges indeed contain significant amounts of brominated compounds, which are not easily extractable from the skeletons by common solvents, such as MeOH, as shown by HPLC analyses in combination with NMR and IR spectroscopic measurements. Quantitative potentiometric analyses confirm that the skeleton-associated bromine mainly withstands the MeOH-based extraction. This observation suggests that the respective, but yet unidentified, brominated compounds are strongly bound to the sponge skeletons, possibly by covalent bonding. Moreover, gene fragments of halogenases suggested to be responsible for the incorporation of bromine into organic molecules could be amplified from DNA isolated from sponge samples enriched for sponge-associated bacteria.

’Netto-noll utsläpp’ i EU vid 2050 är ett av målen för att påskynda övergången från fossila bränslen till mer förnyelsebara och hållbara alternativ. Detta har däremot introducerat mer turbulens på elnäten. Ett av verktygen för att reglera och förbättra eldistributionen är stor-skaliga batterier, där litium-jon är den mest förekommande kemin. Men på grund av oro kring resursutbud och hopp om teknologidiversifiering har det påbörjat en sökning efter alternativ som kan användas i stället eller tillsammans med litium-jon batterier. Från en lång lista så har tre alternativ med hög potential identifierats. Dessa är nickel-vätgasbatteri, zink-brom flödesbatteri och järn-luftbatteri. Deras lämplighet undersöktes och diskuterades för flertalet användningsområden och för ett speciellt användarfall av Vattenfall. Slutsatsen var att utav de tre, så är det endast nickel-vätgas som kan förväntas vara ett bra alternativ för specifika fall, att zink-brom har få möjligheter att konkurrera och att järn-luft har väldigt hög potential men också många oklarheter som gör det svårt att förutspå dess utveckling. / With net-zero emissions set to be achieved in the EU by 2050, the transition from fossil-based energy sources to more renewable and green options are ever expanding. This puts a strain on the electricity grids because of the intermittent nature from these energy sources. To mitigate this battery systems are used, of which the lithium-ion battery is the most prevalent, and expected to only increase in use. However, material resource concerns and possible danger of over-reliance on one technology has opened for a search to find other alternatives that could be used instead or in conjunction with the battery. Out of a long list of batteries, the nickel-hydrogen battery, zinc-bromide flow battery and iron-air battery are three alternatives that have been identified to have potential. Their suitability was researched and discussed for various grid-applications. The result show that out of the three, it is only believed that the nickel-hydrogen battery have a definitive competitiveness, that the zinc bromide flow battery has few things going for it, and that the iron-air battery has large potential but just as large uncertainty surrounding its future. Lastly, a specific off-shore wind park case was investigated to see the practicality and competitiveness of the nickel-hydrogen battery compared to a specific lithium-ion chemistry.

6H-1,2-Oxazines were functionalised at the C-C double bond by 1,3-dipolar cycloadditions and halogenation reactions. The reactions were carried out with 6-ethoxy-3-phenyl-6H-1,2-oxazine, 6-ethoxy-3-ethoxycarbonyl-6H-1,2-oxazine and 6-ethoxy-3-trifluoromethyl-6H-1,2-oxazine. The cycloadditions of 6H-1,2-oxazines were performed with nitrile oxides, nitrile imines, nitrile ylides, diazoalkanes, azomethine ylides and a nitrone. High diastereoselectivity was observed, induced by the steric hindrance of the ethoxy group at the 6H-1,2-oxazines. The cycloadditions occur with high regioselectivity. In addition, the constitutions of the bicycles were predicted by the frontier-orbital model using the semi-empirical PM3-method, and subsequently compared with those of the isolated products. The low strength of the N-O bond of 1,2-oxazines can often be used for mild hydrogenolysis reactions, but the reductions of the biheterocycles obtained here were not selective and led in most cases to decomposition. For the derivatives of 3-ethoxycarbonyl-3a,7a-dihydro-4H-isoxazolo[5,4-d]-1,2-oxazine the conversion of the five-membered ring into cis-configurated α-hydroxynitriles (saponification and decarboxylation) was demonstrated. Finally, the 4-chloro- and 4-bromo-6H-1,2-oxazines were prepared in good yields. Investigations with palladium catalysed coupling reactions were initiated. The halogen of 4-bromo-6H-1,2-oxazines was substituted by the phenyl group of benzolboronic acid using the Suzuki method. / Im Verlauf dieser Arbeit wurden 6H-1,2-Oxazine an der C-C-Doppelbindung durch 1,3-dipolare Cycloadditionen und Halogenierungen funktionalisiert. Als Modellsubstrate für die 6H-1,2-Oxazine wurden 6-Ethoxy-3-phenyl-6H-1,2-oxazin, 6-Ethoxy-3-ethoxycarbonyl-6H-1,2-oxazin und 6-Ethoxy-3-trifluormethyl-6H-1,2-oxazin eingesetzt. Die 6H-1,2-Oxazine konnten bei den Cycloadditionen erfolgreich mit Nitriloxiden, Nitriliminen, Nitrilyliden, Diazoverbindungen, Azomethinyliden und einem Nitron umgesetzt werden, wobei die Ausbeuten stark variieren. Die Reaktionen verliefen mit hoher Regioselektivität. Durch die sterische Abschirmung der Ethoxygruppe an den 6H-1,2-Oxazinen (Briefumschlagskonformation der 6H-1,2-Oxazine und pseudoaxiale Ausrichtung der Ethoxygruppe) wurde ebenfalls eine hohe Diastereoselektivität beobachtet. Ergänzend wurden die Konstitutionen der Cycloaddukte mit der semiempirischen PM3-Methode auf Basis des Grenzorbitalmodells vorhergesagt und mit denen der isolierten Biheterocyclen verglichen. Die dargestellten Cycloaddukte sollten unter Ausnutzung der geringen Bindungsenergie der N-O-Bindung hydrogenolysiert werden. Die Reduktionen waren jedoch im allgemeinen nicht selektiv, so daß die Umsetzungen zu komplexen Produktgemischen führten. Für die 3-Ethoxycarbonyl-3a,7a-dihydro-4H-isoxazolo[5,4-d]-1,2-oxazinderivate wurde ferner der Abbau des Fünfringes (Verseifung und Decarboxylierung) in cis-konfigurierte α-Hydroxynitrile beschrieben. Die 4-Chlor- und 4-Brom-6H-1,2-oxazine konnten in guten Ausbeuten unter milden Reaktionsbedingungen dargestellt werden. Anschließend wurden mit den bromierten Verbindungen verschiedene palladiumkatalysierte Kupplungsreaktionen getestet. Durch die Methode von Suzuki konnte das Halogen der 4-Brom-6H-1,2-oxazine durch den Phenylrest der Benzolboronsäure substituiert werden.

6H-1,2-Oxazines were functionalised at the C-C double bond by 1,3-dipolar cycloadditions and halogenation reactions. The reactions were carried out with 6-ethoxy-3-phenyl-6H-1,2-oxazine, 6-ethoxy-3-ethoxycarbonyl-6H-1,2-oxazine and 6-ethoxy-3-trifluoromethyl-6H-1,2-oxazine. The cycloadditions of 6H-1,2-oxazines were performed with nitrile oxides, nitrile imines, nitrile ylides, diazoalkanes, azomethine ylides and a nitrone. High diastereoselectivity was observed, induced by the steric hindrance of the ethoxy group at the 6H-1,2-oxazines. The cycloadditions occur with high regioselectivity. In addition, the constitutions of the bicycles were predicted by the frontier-orbital model using the semi-empirical PM3-method, and subsequently compared with those of the isolated products. The low strength of the N-O bond of 1,2-oxazines can often be used for mild hydrogenolysis reactions, but the reductions of the biheterocycles obtained here were not selective and led in most cases to decomposition. For the derivatives of 3-ethoxycarbonyl-3a,7a-dihydro-4H-isoxazolo[5,4-d]-1,2-oxazine the conversion of the five-membered ring into cis-configurated α-hydroxynitriles (saponification and decarboxylation) was demonstrated. Finally, the 4-chloro- and 4-bromo-6H-1,2-oxazines were prepared in good yields. Investigations with palladium catalysed coupling reactions were initiated. The halogen of 4-bromo-6H-1,2-oxazines was substituted by the phenyl group of benzolboronic acid using the Suzuki method. / Im Verlauf dieser Arbeit wurden 6H-1,2-Oxazine an der C-C-Doppelbindung durch 1,3-dipolare Cycloadditionen und Halogenierungen funktionalisiert. Als Modellsubstrate für die 6H-1,2-Oxazine wurden 6-Ethoxy-3-phenyl-6H-1,2-oxazin, 6-Ethoxy-3-ethoxycarbonyl-6H-1,2-oxazin und 6-Ethoxy-3-trifluormethyl-6H-1,2-oxazin eingesetzt. Die 6H-1,2-Oxazine konnten bei den Cycloadditionen erfolgreich mit Nitriloxiden, Nitriliminen, Nitrilyliden, Diazoverbindungen, Azomethinyliden und einem Nitron umgesetzt werden, wobei die Ausbeuten stark variieren. Die Reaktionen verliefen mit hoher Regioselektivität. Durch die sterische Abschirmung der Ethoxygruppe an den 6H-1,2-Oxazinen (Briefumschlagskonformation der 6H-1,2-Oxazine und pseudoaxiale Ausrichtung der Ethoxygruppe) wurde ebenfalls eine hohe Diastereoselektivität beobachtet. Ergänzend wurden die Konstitutionen der Cycloaddukte mit der semiempirischen PM3-Methode auf Basis des Grenzorbitalmodells vorhergesagt und mit denen der isolierten Biheterocyclen verglichen. Die dargestellten Cycloaddukte sollten unter Ausnutzung der geringen Bindungsenergie der N-O-Bindung hydrogenolysiert werden. Die Reduktionen waren jedoch im allgemeinen nicht selektiv, so daß die Umsetzungen zu komplexen Produktgemischen führten. Für die 3-Ethoxycarbonyl-3a,7a-dihydro-4H-isoxazolo[5,4-d]-1,2-oxazinderivate wurde ferner der Abbau des Fünfringes (Verseifung und Decarboxylierung) in cis-konfigurierte α-Hydroxynitrile beschrieben. Die 4-Chlor- und 4-Brom-6H-1,2-oxazine konnten in guten Ausbeuten unter milden Reaktionsbedingungen dargestellt werden. Anschließend wurden mit den bromierten Verbindungen verschiedene palladiumkatalysierte Kupplungsreaktionen getestet. Durch die Methode von Suzuki konnte das Halogen der 4-Brom-6H-1,2-oxazine durch den Phenylrest der Benzolboronsäure substituiert werden.