This thesis is concerned with studies towards the total synthesis of a class of natural products - the oxazolomycins. Attention was focused on the left-hand side triene fragment and right-hand side lactam heterocyclic system. This thesis describes the synthesis of a racemic terminal phenyl analogue of oxazolomycin A and C, possessing the left-hand side triene geometry as required. A novel truncated pyridine analogue is also described. The molecules represent a racemic total synthesis of analogues of phthoxazolin A and inthomycins B and C. The synthesis is based upon a crucial Stille cross-coupling reaction between stannane and diene iodide fragments. The stannane fragment was synthesised using literature precedented methods and the vinyl halide prepared using a highly stereoselective Wittig, Takai homologation or Stork reaction leading to a variety of ratios of mixtures of Z, E and E, E diene halides. These investigations led to the availability of 1:1, 3:1 and 1:3 mixtures of Z, Z, E : Z, E, E left hand side triene fragments possessing the required stereochemistries for oxazolomycin A and C. Utilising existing methodology developed in the Moloney group, investigations were carried out towards construction of β-keto esters possessing terminal hydroxyl functions, suitable for diastereoselective aldol ring closure. Following extensive protecting group manipulation and N-acylation coupling optimisation, a TIPS protected β-keto acid, existing as predominantly the keto tautomer, was successfully coupled to an oxazolidine heterocycle. This N-acylated oxazolidine upon Dieckmann cyclisation would present an advanced intermediate of opposite configuration (Lserine is used here as a cheaper starting material for the construction of the oxazolidine instead of D-serine) to the oxazolomycin right-hand side.

Thesis (Ph. D.)--Victoria University (Melbourne, Vic.), 2007. / Includes bibliographical references.

Thesis (M.Phil.)--Hong Kong University of Science and Technology, 2009. / Includes bibliographical references (p. 106-121).

published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

No description available.

Orientador: Olga Maria Mascarenhas de Faria Oliveira / Coorientador: Kátia Maria da Silva Cerqueira Leite / Banca: Giuseppina Pace Pereira Lima / Banca: Glaucia Maria Pastore / Resumo: O maracujá amarelo azedo (Passiflora edulis f. flavicarpa Degener) pode ser consumido in natura ou industrializado. Sua importância é dada pelo valor medicinal, popularmente usado no tratamento da ansiedade, insônia e irritabilidade; alimentício, na forma de polpa congelada e suco, doces, geleia e sorvete; e nutracêutico ou alimento funcional, apresentando elevados teores de íons fosfato e potássio, vitamina A, B1 (tiamina), B2 (riboflavina) e C (ácido ascórbico). Algumas alterações podem ocorrer durante o processamento e armazenamento do suco interferindo na cor e sabor do produto final, o que pode implicar em não aceitação por parte dos consumidores. Isso pode ocorrer principalmente devido a reações bioquímicas de escurecimento e alterações bioquímicas moleculares que resultam em flavors indesejáveis e perda de nutrientes. Por esse motivo o controle desses efeitos indesejáveis durante o processamento de frutos é muito importante para a preservação da aparência natural dos mesmos. Deste modo as enzimas Pectinametilesterase (PME; EC: 3.1.1.11), Peroxidase (POD; EC: 1.11.1.7), Polifenoloxidase (PPO; EC: 1.10.3.1) e Ascorbato Oxidase (AO; EC: 1.10.3.3) podem ser responsáveis pelo escurecimento enzimático e outras reações que alteram o produto durante e ao final do processamento. Visto isso, com o objetivo de agregar valores nutricionais e mercadológicos ao maracujá vem sendo desenvolvida e usada a cultura híbrida, que, em síntese, significa o uso de sementes modificadas e com manejo adequado, com vistas à racionalização do uso de defensivos agrícolas e aumento de produtividade. O objetivo desse trabalho é estudar o comportamento cinético das enzimas já citadas e avaliar os teores de compostos bioativos como vitamina C, compostos fenólicos, flavonóides, e atividade antioxidante em cinco... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: The yellow passion fruit (Passiflora edulis f. flavicarpa Degener) can be eaten in natura or industrialized. Its importance is given by medicinal value, commonly used for treating anxiety, insomnia and irritability; food in the form of frozen pulp and juice, candy, jelly and ice cream, and nutraceutical or functional food, with high levels of potassium and phosphate ions, Vitamin A, B1 (thiamine), B2 (riboflavin) and C (ascorbic acid). Some changes may occur during processing and storage of the juice interfere the color and flavor of the final product, which can result in non-acceptance by the consumers. This can occur mainly due to biochemical browning and reactions molecular biochemical changes that result in undesirable flavors and nutrient loss. Therefore the control of these undesirable effects during processing of fruits is very important for preserving the natural appearance. Thus, enzymes pectinmethilesterase (PME, EC: 3.1.1.11), peroxidase (POD, EC: 1.11.1.7), Polyphenoloxidase (PPO, EC: 1.10.3.1) and ascorbate oxidase (AO, EC: 1.10.3.3) can be responsible for enzymatic browning and other reactions that alter the product during and after processing. Seen it, with the goal of adding nutritional value and market the passion fruit has been developed and used a hybrid culture, which, in summary, means the use of modified seeds and with appropriate management, with a view to rationalizing the use of pesticides and increase productivity. The aim of this work is to study the kinetic behavior of the enzymes already mentioned and evaluate the contents of bioactive compounds such as vitamin C, phenolic compounds, flavonoids and antioxidant activity of five hybrid the yellow passion fruit tart cultivar. The main results of this study was to visualize distinct kinetic behaviors of the same enzyme in hybrids studied and higher levels... (Complete abstract click electronic access below) / Mestre

Streptomyces are known to produce a large variety of antibiotics and other bioactive compounds with remarkable industrial importance. Streptomyces sp. COUK1 was found as a contaminant on a plate in which Rhodococcus erythropolis was used as a test strain in a disk diffusion assay and produced a zone of inhibition against the cultured R. erythropolis. The identity of the contaminant was confirmed as Streptomyces through 16S rRNA sequencing. This Streptomyces produces a strong inhibitory compound in different growth media. A culture extract from inorganic salts starch agar was found to be very active; producing a large zone of inhibition against several Gram positive and Gram negative test strains. The active molecules in this extract have been detected via TLC and bioautography. The difference in the antibacterial activity and chromatographic properties of extracts recovered from different growth media suggests that this Streptomyces strain could produce more than one type of inhibitory compound.

Thesis (Ph. D.)--University of Missouri-Columbia, 1996. / Typescript. Vita. Includes bibliographical references (leaves 126-141). Also available on the Internet.

Thesis (Ph. D.)--University of Missouri-Columbia, 1996. / Typescript. Vita. Includes bibliographical references (leaves 126-141). Also available on the Internet.

Thesis (M.S.)--Oregon State University, 2009. / Printout. Includes bibliographical references. Also available on the World Wide Web.