Made available in DSpace on 2014-10-09T12:49:50Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:02:57Z (GMT). No. of bitstreams: 0 / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP

Submitted by Maria Eneide de Souza Araujo (mearaujo@ipen.br) on 2015-02-20T16:32:46Z No. of bitstreams: 0 / Made available in DSpace on 2015-02-20T16:32:46Z (GMT). No. of bitstreams: 0 / Dissertação (Mestrado em Tecnologia Nuclear) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Made available in DSpace on 2014-10-09T12:49:54Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:02:15Z (GMT). No. of bitstreams: 1 10189.pdf: 7945514 bytes, checksum: fc959ff6c97125fc66c813f5c29a3647 (MD5) / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP

Made available in DSpace on 2014-10-09T12:49:50Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:02:57Z (GMT). No. of bitstreams: 0 / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP

Submitted by Maria Eneide de Souza Araujo (mearaujo@ipen.br) on 2015-02-20T16:32:46Z No. of bitstreams: 0 / Made available in DSpace on 2015-02-20T16:32:46Z (GMT). No. of bitstreams: 0 / A Lama Negra de Peruíbe é utilizada em tratamentos terapêuticos, tais como, psoríase, dermatites periféricas, acne e seborreia, além de utilizações em mialgias, artrites e processos reumáticos não articulares. Assim como a demais argilas medicinais ela pode não estar isenta de possíveis efeitos danosos à saúde, sendo os principais, a ocorrência de minerais perigosos ao sistema respiratório e possíveis efeitos devido à presença de elementos tóxicos. Uma vez utilizado com finalidade terapêutica, um material deve ser completamente caracterizado e, desta forma, amostras da lama negra de Peruíbe foram analisadas para determinar suas propriedades físicas e químicas: teor de umidade, matéria orgânica e perda ao fogo; pH, granulometria, capacidade de troca catiônica e grau de inchamento; composição elementar determinada por Análise por Ativação Neutrônica, Absorção Atômica com Forno de Grafite e fluorescência de raios X e composição mineralógica determinada por difração de raios X. Outra ferramenta bastante utilizada para avaliar o comportamento de elementos traço em diversas matrizes ambientais é a extração sequencial. Sendo assim, foi feito um processo de extração sequencial para fracionar a lama em formas geoquímicas específicas e verificar como e em que quantidade os elementos estão contidos nela. Considerando os diversos procedimentos de extração seqüencial, foi utilizado o método BCR-701 (Community Bureau of Reference) por ser o mais reprodutivo entre eles bem como uma extração simples com suor artificial a fim de se avaliar quais elementos estão potencialmente disponíveis para absorção pela pelo do paciente durante um tratamento tópico. Os resultados indicaram que a lama é constituída basicamente por um material silto-argiloso, rico em matéria orgânica e com boa capacidade de troca catiônica. Não foram observadas variações significativas na composição mineralógica e elementar das formas in natura e maturada da lama. As análises por extração sequencial e extração simples indicaram que os elementos que estão eventualmente disponíveis em maior quantidade para serem absorvidos pela pele durante o tratamento são Ca, Mg, Mn e Na. / Dissertação (Mestrado em Tecnologia Nuclear) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

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Hydrocarbon chains are a basic component in a number of systems as diverse as biological membranes, phospholipids and polymers. A better understanding of the physical properties of n-alkane chains should provide a better understanding of these more complex systems. With this aim, vibrational spectroscopy has been extensively used. This technique, sensitive to molecular details, is the only one able to both identify and quantify conformational disorder present in paraffinic systems. To achieve this, methyl deformations have been widely used as "internal standards" for the normalisation of peak areas. However, in the case of n-alkanes with short chain length, such as n-C[44]H[90] for example, the infrared spectra recorded at liquid nitrogen temperature and reported here show the sensitivity of these latter peaks to the various crystal structures formed. Indeed, the main frequencies of the symmetric methyl bending mode were found between 1384 cm[-1] and 1368 cm[-1] as a function of the crystal form. Changes in the frequency of the first order of the L.A.M. present in the Raman spectra were also observed. At higher temperatures, non all-trans conformers, inferred from different infrared bands present in the wagging mode region, were found to be essentially placed at the end of the n-alkane chains. At the monoclinic phase transition, the concentration of end-gauche conformers, proportional to the area of the infrared band at 1342 cm[-1], increases abruptly. On the contrary, in the spectra recorded at liquid nitrogen temperature no such band is observed. We also studied the degree of disorder in two purely monodisperse long chain n-alkanes, namely n-C[198]H[398] and n-C[246]H[494]. The chain conformation as well as the tilt angle of the chains from the crystal surfaces were determined by means of low frequency Raman spectroscopy and S.A.X.S. measurements on solution-crystallised samples. The increase in the number of end-gauche conformers which was expected to occur with the increase of the tilt angle as a function of the temperature was not detected due to a perfecting of the crystals. Indeed, due to successive heating and cooling to -173°C, the concentration of non all-trans conformers was found to decrease within the crystals. Their numbers were found to be up to six times higher in n-C[198]H[398] crystallised in once folded form than when crystallised in extended form. The C-C stretching mode region of the spectra was used to identify the chain conformation and to estimate the length of the all-trans stem passing through the crystal layers at -173°C. The transition between once folded and extended form crystals was indicated by the presence of additional bands in this region at 1089 cm[-1], 1078 cm[-1] and 1064 cm[-1]. Some of those bands may be related to the fold itself. At the same time, a strong decrease of the intensity of the infrared bands present in the wagging mode region was observed. Finally, the triple layered structure proposed on the basis of X-ray measurements obtained from the crystals of a binary mixture of long chain n-alkanes, namely n-C[162]H[326] and n-C[246]H[494], was confirmed from the study of the C-C stretching mode region of the infrared spectra.

Made available in DSpace on 2014-10-09T12:51:15Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:06:06Z (GMT). No. of bitstreams: 1 11260.pdf: 6178223 bytes, checksum: b81ce1592f127211fd426b186d3b8369 (MD5) / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP