Made available in DSpace on 2014-10-09T12:26:48Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:00:22Z (GMT). No. of bitstreams: 0 / Dissertacao (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Made available in DSpace on 2014-10-09T12:26:48Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:00:22Z (GMT). No. of bitstreams: 0 / Tendo em vista um mercado cada vez mais exigente na qualidade dos alimentos, faz-se necessário o desenvolvimento de processos que atendam às expectativas do consumidor. Dentre os processos existentes, destacam-se a cadeia do frio e a irradiação. A cadeia do frio compreende todas as etapas de conservação do alimento, desde a produção, resfriamento, congelamento, armazenamento, e transporte até o consumidor final. A irradiação, como processo de conservação de alimentos, estende a vida de prateleira, inibe o brotamento e reduz a contaminação por patógenos, entre outros benefícios. É importante a identificação da degradação dos alimentos em função de falhas nos processos a que foram submetidos. O teste do cometa (DNA Comet Assay) é um método de varredura largamente estudado, considerado rápido e de baixo custo, pelo fato de identificar quebras no DNA, é possível considerar sua utilização como mais uma ferramenta no controle de falhas na cadeia do frio que podem degradar e prejudicar os alimentos. Algumas etiquetas e selos usados no controle dos processos do frio não consideram a situação anterior do alimento, indicando falhas a partir do momento em que forem colocadas em contato com o mesmo, já o teste do cometa verifica a degradação ocorrida no alimento até o momento de sua realização podendo ainda, acompanhar o aumento da degradação. / Dissertacao (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

No description available.

Functionalization of hydrocarbons via a free-radical based allyl transfer reaction using various allyl bromide substrates has been previously studied. The work described in this dissertation focuses on the replacement of Br by phthalimido-N-oxyl (PINO ) which helps make this chemistry environmentally friendly. To replace Br with PINO , replacement of previously used allyl-bromide substrates with new allyl-PINO substrates were necessary. Various allyl- PINO compounds were synthesized and the use of these allyl-phthalimido-N-oxyl (allyl-PINO) compounds for the functionalization of various alkyl aromatic hydrocarbons is demonstrated. Kinetic studies were performed to observe the efficiency of the new chain reaction compared to the previously reported studies with allyl-bromides. We recently discovered that these allyl substrates are useful for the functionalization of ethers and acetals. The functionalization of various cyclic and acyclic ethers was performed using these allyl transfer reactions. This reaction was also performed in-solution, which allowed us to perform these reactions at low reagent concentrations. Kinetic chain lengths were measured for these reactions. High chain lengths were observed for all used ethers. Kinetic studies to investigate the rate of radical addition-elimination processes were performed using laser flash photolysis and competition kinetics. These experiments helped us to measure the reactivity and selectivity of PINO as a chain carrier in comparison with Br. Additionally, a new competition experiment was designed to study the relative rate constant for the 􀈕-fragmentation process. For this experiment a novel substrate that contains two leaving groups, Br and PINO, was synthesized, and the relative rates of elimination of Br vs PINO were compared. / Ph. D.