Total synthesis of the pyrrolizidine alkaloid NP25302: (+)-NP25302 is an unusual vinylogous urea containing pyrrolizidine alkaloid shown to exhibit cell adhesion inhibition. It was envisaged that this natural product could be accessed by a novel 5-endo-dig cyclisation to construct the pyrrolizidine core, and a Curtius rearrangement to install the vinylogous urea motif. This methodology was first tested on a model system, furnishing nor-NP25302 from L-proline in 12 steps and 9% overall yield. The total synthesis of (±)-NP25302 was completed in 9 steps and 26% overall yield from ethyl 2-nitropropionate using similar methodology. Studies into the stereospecificity of the Au(I)-catalysed cyclisation of monoallylic diols: During the synthesis of (+)-isoaltholactone in the Robertson group, the key Au(I)-catalysed cyclisation was observed to occur with some stereospecificity. Further investigations were therefore conducted into the stereochemical outcome of this reaction using stereodefined allylic alcohols, and from the combined results a mnemonic was proposed to predict the stereochemistry of the products of this reaction. Studies into the total synthesis of ascospiroketals A and B: Investigations were conducted into the total synthesis of the recently isolated natural products ascospiroketals A and B. A second generation synthesis was used to construct advanced intermediates 1 and 2.

Submitted by Cleide Dantas (cleidedantas@ufpa.br) on 2014-02-14T14:28:37Z No. of bitstreams: 2 license_rdf: 23898 bytes, checksum: e363e809996cf46ada20da1accfcd9c7 (MD5) Dissertacao_AvaliacaoResistenciaFratura.pdf: 953152 bytes, checksum: b5b9de92a57b7fc1e1520c39fa23823f (MD5) / Approved for entry into archive by Ana Rosa Silva (arosa@ufpa.br) on 2014-04-29T15:43:22Z (GMT) No. of bitstreams: 2 Dissertacao_AvaliacaoResistenciaFratura.pdf: 953152 bytes, checksum: b5b9de92a57b7fc1e1520c39fa23823f (MD5) license_rdf: 23898 bytes, checksum: e363e809996cf46ada20da1accfcd9c7 (MD5) / Made available in DSpace on 2014-04-29T15:43:22Z (GMT). No. of bitstreams: 2 Dissertacao_AvaliacaoResistenciaFratura.pdf: 953152 bytes, checksum: b5b9de92a57b7fc1e1520c39fa23823f (MD5) license_rdf: 23898 bytes, checksum: e363e809996cf46ada20da1accfcd9c7 (MD5) Previous issue date: 2008 / O sucesso dos implantes osseointegrados é comprovado cientificamente e com isso, veio outras preocupações como a de se solucionar esteticamente e funcionalmente o tratamento restaurador, tendo como escolha na maioria das vezes a confecção de coroas metalocerâmicas ou metaloplásticas. Este trabalho teve como objetivo comparar a resistência à fratura por compressão axial e avaliar o tipo de fratura de 30 coroas unitárias sobre implante do primeiro pré-molar superior, confeccionadas com diferentes infraestruturas metálicas (infra-estruturas enceradas e fundidas em níquel-cromo sobre pilares UCLA calcináveis e infra-estruturas representadas por pilares UCLA provisórios pré-fabricados em titânio), ambos restaurados com resina composta laboratorial, sendo que, as restaurações totais em resina compostas laboratoriais confeccionadas sobre o pilar UCLA pré-fabricado em titânio foram reforçadas internamente com fibras de vidro. Não foram encontradas diferenças estatisticamente significantes entre as médias tanto de resistência à fratura quanto da deformação máxima de rompimento entre os grupos (p= 0.5812 e p= 0.1743 respectivamente). As fraturas apresentadas pelos espécimes com infra-estruturas fundidas em níquel-cromo com e sem retenção apresentaram em sua totalidade fraturas parciais adesivas enquanto que no grupo com infra-estruturas com fibras-de-vidro o tipo de fratura foi a parcial coesiva. A resina composta laboratorial suporta forças acima das encontradas na mastigação indiferente do tipo de reforço utilizado, podendo ser indicada para confecção de próteses unitárias sobre implante. / The success of the osseointegrated implants is proved scientifically and with these, other preoccupations came such as to solve the aesthetically and functionally restoring treatment, having like chosen most times the production of metaloceramic or metaloplastic crowns. This work has the objective to compare the fracture resistance for axial compression of 30 single crowns on implant of the first superior pre-molar, made with different metal infrastructures (infrastructures waxed and fused in nickel-chrome on calcinable UCLA pillars and infrastructures represented by titanium prefabricated provisional UCLA pillars), both restored with laboratory compound resin, being that, the total restorations in laboratory compound resin made on the titanium prefabricated provisional UCLA pillars were reinforced internally with fiberglass. They were not found differences statistically significant between the averages so much of fracture resistance as the deformation (p= 0.5812 and p= 0.1743 respectively). The fractures presented by the specimens with infrastructures fused in nickel-chrome with and without retention presented partial adhesive fractures in its entirety whereas in the group with infrastructures with fiberglass the type of fracture was the partial cohesive one. The compound resin laboratorial supports strength above the considered ones in the mastication, indifferent of the type of the used reinforcement, being able to be indicated for production of implants single prosthesis.

Orientador: Francisco de Assis Mollo Junior / Banca: João Neudenir Arioli Filho / Banca: Marcelo Ferrarezi de Andrade / Resumo: Dentre as inúmeras fases clínicas e laboratoriais de um tratamento protético, as técnicas de moldagem e vazamento para próteses implantossuportadas são ainda responsáveis por grande preocupação e controvérsia entre os pesquisadores. Este estudo in vitro teve como objetivo avaliar a precisão de uma técnica de registro (Index) e de três técnicas de moldagem (transferentes Cônicos, Quadrados e Quadrados unidos) associadas a três técnicas de vazamento (Convencional, com tubos de Látex e com análogos unidos com Duralay) para próteses implantossuportadas. Todos os componentes protéticos utilizados foram da empresa Conexão (Conexão Sistemas de Prótese). Foi construído um modelo mestre de latão simulando um arco inferior desdentado onde foram fixados provisoriamente quatro análogos de pilares Micro-Unit perpendicularmente à superfície e paralelos entre si, sendo denominados análogos A, B, C e D. Uma estrutura metálica foi confeccionada e parafusada a quatro novos análogos. Este conjunto foi cimentado passivamente no modelo mestre com resina epóxica. Foram confeccionadas (com 2 mm de alívio) uma moldeira individual de alumínio para a técnica com os transferentes quadrados unidos e outra para as técnicas com os transferentes cônicos e quadrados. O material de moldagem utilizado foi um poliéter (Impregum Soft Média Viscosidade - 3M ESPE) e o gesso empregado foi um gesso tipo IV (Vel-Mix, Kerr), espatulado à vácuo. Foi obtido um total de cinquenta modelos, sendo cinco por técnica. A estrutura metálica foi parafusada com um torque de 10 Ncm em todos os modelos no análogo A, enquanto as medições das fendas formadas foram feitas nos análogos C e D. Este processo foi repetido no análogo D, anotando-se as medidas dos análogos A e B. Estas medições foram feitas por um programa (Leica QWin) que recebia as imagens de uma câmara de vídeo ...(Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Among the countless clinical and laboratories procedures of a prosthetic treatment, the implant impression and pouring techniques for implant-supported restorations are still responsible for great concern and controversy among the researches. This study in vitro investigated the accuracy of a stone Index and of three impression techniques (tapered impression copings, squared impression copings and squared impression copings splinted with Duralay resin) associated to three pouring techniques (Conventional, with tubes of Latex and joining the analogs with Duralay resin) for an osseointegrated implant-supported prostheses. Conexão (Conexão Systems of Prosthesis) prosthetic components were used. A mandibular brass cast was constructed with four stainless steel implant abutments analogs 90° to the surface and parallel among themselves, being denominated analog A, B, C and D. A master framework was made and screwed to four new analogs, which were cemented passively into the model master with epoxy resin. This formed a metal implant cast with a passive implant framework fitted to it. An aluminum custom tray was fabricated for the technique copings splinted with Duralay and other for the techniques tapered and squared copings. Polyether impression material (Impregum Soft medium consistency - 3M ESPE) was used for all impressions. A total of fifty stone casts were formed by carefully vibrating improved dental stone (Vel-Mix, Kerr), mixed under vacuum, being five for technique. The standard framework was seated on each cast and guide pin was tightened in the analog A to 10 Ncm using a torque driver, while the measurements of abutment / framework interface gaps were made in analogs C and D. This process was repeated in analog D, being written down the measures of the analogs ones A and B. These measurements were analyzed using software (Leica QWin) that received the images of a video ...(Complete abstract, click electronic access below) / Mestre

Resumo: A colocação de PPR de extremidade livre no arco inferior é uma das mais complexas dentro da área protética. A associação desta com implantes na região distal tem melhorado biomecanicamente seu funcionamento. Porém, existem poucos estudos a respeito desta associação levando em consideração o nível de inserção óssea do dente suporte. Assim, o objetivo desta pesquisa foi avaliar, por meio do método dos elementos finitos bidimensional, a distribuição de tensão nas estruturas de suporte de uma PPREL, associada a um implante osseointegrado de 10,0 x 3,75 mm (Sistema Branemark), próximo ao dente suporte, com diferentes níveis de inserção óssea (íntegro e 1/2 da raiz) e com diferentes tipos de conexão entre a PPR e o dente suporte (apoio incisal e placa distal). Para o estudo, foram confeccionados 8 modelos mandibulares, de extremo livre, com a presença apenas do dente 33, sendo: MA - PPREL convencional, apoio incisal distal, inserção íntegra; MB - idem ao MA, mas utilizando placa distal; MC - idem ao MA, com implante de 3,75 x 10,0 mm e sistema ERA associado; MD - idem ao MC, mas utilizando placa distal; ME - idem ao MA, mas com perda de inserção de 1/2 da raiz; MF - idem ao MB, mas com perda de inserção de 1/2 da raiz; MG - idem ao MC, mas com perda de inserção de 1/2 da raiz; MH - idem ao MD, mas com perda de inserção de 1/2 da raiz. Com o auxilio do programa ANSYS 9.0, os modelos foram carregados com forças verticais de 50 N em cada ponta de cúspide. Os resultados foram obtidos pelos mapas de deslocamento e de tensão de von Mises e mostraram que o implante favorece a associação da forma descrita, que a placa possibilita um maior alívio e menor deslocamento do dente suporte, e que a perda do periodonto de suporte prejudica o prognóstico da prótese. / Abstract: The rehabilitation with distal extension RPDA is very complex in the prosthetic area and the association with implants had improving its work biomechanical. However, there is little studies about this type of association and no study about the lost of insertion was encountered by FEA. So, the aim of this study was to evaluate, by FEA 2-D, the tension distribution in support structures of a DERPD associated with a osseointegrated implant of 10,0 x 3,75 mm (Branemark System), near to support tooth, with different levels of bone insertion (no lost and 1/2 of root) and with different type of connection between the DERPD and de support tooth (incisal rest and distal plate). For the study, 8 distal extension mandibular models were made, with the presence of tooth 33, presenting: MA - conventional DERPD, incisal rest, no bone lost; MB - like MA, but with distal plate; MC - like MA, but with implanto of 3,75 x 10,0 mm and ERA system associated; MD - like MC, but with distal plate; ME - like MA, but with bone lost of 1/2 of root; MF - like MB, but with bone lost of 1/2 of root; MG - like MC, but with bone lost of 1/2 of root; MH - like MD, but with bone lost of 1/2 of root. By mean of program of FEA ANSYS 9.0, the models were carried with axial forces of 50 N in each cusp tip. The results were obtained by dislodgement maps and von Mises tension maps and shown that the implant was benefit to association by the study, and the plate decreased the tension and the dislodgement of the support tooth, and the bone lost was prejudicial to prognostic of this type of prosthesis. By this methodology, was possible to conclude that: the introduction of an osseointegrated implant with ERA system used like this study decrease the dislodgement of above structures in all models. / Orientador: Eduardo Pizza Pellizzer / Coorientador: João Antônio Pereira / Banca: Marcelo Coelho Goiato / Banca: Mário Alexandre Coelho Sinhoreti / Banca: Humberto Gennari Filho / Banca: Dalva Cruz Laganá / Doutor

<p>The aim of this work was to develop a production process for the enzyme xyloglucan <i>endo</i>-transglycosylase from <i>Populus tremula x tremuloides</i> (<i>Ptt</i>XET16-34). The natural transglycosylating activity of this enzyme has previously been employed in a XET-Technology. This chemo enzymatic method is useful for biomimetic modification of cellulose surfaces and holds great potential for industrial applications. Thus, it requires that the XET-enzyme can be produced in larger scale.</p><p>This work also shows how the wildtype <i>Ptt</i>XET16-34 was modified into a glycosynthase. By mutation of the catalytic nucleophile into an alanine, glycine or serine residue, enzymes capable of synthesising defined xyloglucan fragments were obtained. These defined compounds are very valuable for further detailed studies of xyloglucan active-enzymes, but are also useful in molecular studies of the structurally important xyloglucan-cellulose interaction.</p><p>A heterologous production system for <i>Ptt</i>XET16-34 was previously developed in the methylotrophic yeast Pichia pastoris. A methanol-limited fed-batch process was also previously established, but the yield of active XET was low due to proteolysis problems and low productivity. Therefore, two alternative fed-batch techniques were investigated for the production of <i>Ptt</i>XET16-34: a temperature-limited fed-batch (TLFB) and an oxygen-limited high-pressure fed-batch (OLHPFB).</p><p>For the initial recovery of XET after the fermentation process, two different downstream processes were investigated: expanded bed adsorption (EBA) and cross-flow filtration (CFF).</p>

No description available.

In this thesis manuscript are described our synthetic efforts and the first total synthesis of two natural products isolated from the sponges of the genus Plakortis. In total, two different synthetic approaches were studied to finally accomplish the synthesis of plakortolide I. The first approach is an extension of the method developed by our group which consists in the creation of the 1,2-dioxane cycle by intramolecular opening of vinyl epoxide with β-hydroperoxy group. Firstly, we was interested in the preparation of alkoxymethylhexa-2,5-dien-1-ol. We have also tried to create the 1,2-dioxane cycle by double opening of bis-1,5-epoxide with hydrogen peroxide. Further more we have synthesised trisubstituted β-hydroperoxy vinyl epoxide, precursor of 1,2-dioxan ring, from R-epichlorohydrin. During this synthesis a procedure of chemoselective methylenation of ketone in the presence of epoxide by Nysted reagent and Ti(OiPr)2Cl2 was developed. Finally, (-)-ent-plakortolide I and seco-plakortolide E were synthesised by intramolecular Michael addition of hydroperoxide to double bond of the butenolide moiety

Ce mémoire de thèse est composé de deux parties distinctes ayant comme thématique commune, les réactions de cycloisomérisation. Nous nous sommes intéressés dans un premier temps au développement d'une réaction tandem d'acétalisation / cycloisomérisation catalysée par des sels d'argents. Cette méthodologie nous a permis d'accéder sélectivement aux familles des furoquinoléines et des pyranoquinoléines. Ces composés ont été testés comme agents antipaludiques et ont donné des résultats prometteurs. Une gamme de dérivés de furoquinoléine a également donné des activités cytotoxiques intéressantes. L'étude de leur potentielle activité antitumorale s'inscrit dans le cadre d'un projet financé par la Ligue Nationale contre le Cancer. Une étude approfondie de la réaction tandem, nous a permis de mettre en évidence l'influence de composés azotés sur le comportement du sel d'argent. Cette caractéristique nous a conduits à catalyser nos réactions grâce à un complexe inusité jusqu'alors en catalyse organométallique : l'imidazolate d'argent. Dans un deuxieme temps, nous avons étudié une réaction de benzannélation catalysée par des sels de rhodium ou d'argent. La stratégie de synthèse implique des systèmes de type benzofurane, porteurs d'énynes fonctionnalisées par un éther d'énol silylé, et conduit à des dérivés de dibenzofuranes. Ces hétérocycles, connus pour être biologiquement actifs, présentent un intérêt particulier dans la chimie thérapeutique. Nous avons également travaillé sur des indoles et avons pu synthétiser des dérivés d'oxindole originaux

Soybean [Glycine max (L.) Merr.] is an important crop worldwide. It has been widely consumed for protein, oil and other soy products. To develop soybean cultivars with greater resistance against pests and improved meal quality, it is important to elucidate the molecular bases of these traits. This dissertation aims to investigate the biochemical and biological functions of soybean genes from four gene families, which are hypothesized to be associated with soybean defense against pests and soybean meal quality. There are three specific objectives in this dissertation. The first one is to determine the function of components in the salicylic acid (SA) signaling pathway in soybean resistance against soybean cyst nematode (Heterodera glycines, SCN). The second one is to determine whether insect herbivory induce the emission of volatiles from soybean, and if so, how these volatiles are biosynthesized. The third objective is to identify and characterize soybean mannanase genes that can be used for the improvement of soybean meal quality. The soybean genome has been fully sequenced, which provides opportunities for cross-species comparison of gene families of interest and identification of candidate genes in soybean. The cloned cDNAs of putative genes were expressed in Escherichia coli to produce recombinant enzymes. Through biochemical assays, these proteins were proved to be soybean salicylic acid methyltransferase (GmSAMT1), methyl salicylate esterase (GmSABP2-1), α[alpha]-farnesene synthase (GmTPS1) and E-β[beta]-caryophyllene synthase (GmTPS2), and endo-β[beta]-mannanase (GmMAN1). Through a transgenic hairy root system harboring overexpression of GmSAMT1 and GmSABP2-1, both of these two genes were evaluated for their biological function related to resistance against SCN. The results showed that the over-expression of GmSAMT1 and GmSABP2-1 in the susceptible soybean background lead to enhanced resistance against SCN. Among four putative soybean mannanase genes, one gene was cloned and characterized. GmMAN1 showed the endo-β[beta]-mannanase hydrolyse activity and can hydrolyze cell walls isolated from soybean seeds. In summary, using comparative and functional genomics, a number of genes involved in soybean defense and meal quality were isolated and characterized. This study provides novel knowledge and molecular tools for the genetic improvement of soybean for enhanced resistance and improved meal quality.

Thesis (Ph. D.)--Johann Wolfgang Goethe University, 2003. / Includes bibliographical references.