Thesis (PH. D.)--University of Chicago, 1933. / "Private edition, distributed by the University of Chicago libraries, Chicago, Illinois." eContent provider-neutral record in process. Description based on print version record.

Thesis (PH. D.)--University of Chicago, 1933. / "Private edition, distributed by the University of Chicago libraries, Chicago, Illinois." eContent provider-neutral record in process. Description based on print version record.

A study of the n.m.r. absorption of oleic acid has been carried out between 77°K. and 287°K. A sharp increase in line width and second moment is observed below 100°K. indicative of an increase in the intramolecular interactions. A narrow line, indicative of liquid-like motion, is observed at temperatures above 208°K. The second moment and line width decrease rapidly as the melting point is approached, dropping to liquid-like values at 287°K. The experimental data are compared with the theoretical data obtained from the known crystal structure. From this comparison, a crystal transition is proposed to take place below 100°K., and heteronuclear premelting is proposed to take place above 208°K. It is likely that end methyl group rotation takes place at all temperatures but there is no extensive torsional oscillation or vibration below 26o°K. and there is little apparent change in the cell dimensions between 260°K. and 100°K. Elaidic acid has been studied between 77°K. and 315°K. The line width and second moment increase slightly below 170GK. and a narrow component is observed above 225°K. The line width and second moment fall sharply only at the melting point, decreasing to a liquid-like line. As no crystal structure is available for elaidic acid, the experimental data are compared with experimental and theoretical data for oleic acid and stearic acid. Some form of molecular vibration or hindered rotation is proposed to account for the transition at 170°K., and heteronuclear premelting is proposed to take place above 225°K. The difference in the behaviour of oleic acid and elaidic acid near the melting point is explained in terms of the molecular shape. / Science, Faculty of / Chemistry, Department of / Graduate

The objective of the study was to examine the effects of trans-9-octadecenoic acid (elaidic) and trans-II-octadecenoic acid (trans-vaccenic) on uptake and alteration of exogenous fatty acids by mouse mammary epithelial cells. Cells from a subclone of the COMMA-D cell line were plated on uncoated plastic petri dishes and grown to confluence. Supplemental fatty acids bound to bovine serum albumin were added to the medium applied to the confluent cell cultures. Treatments included 200 JlM octadecanoic acid (CI8:0) as a control and 100 JlM CI8:0 with one of the following JlM ratios of cis-octadecenoic acid (cis-CI8:I) to elaidic or trans-vaccenic: 100:0, 75:25, 50:50, 0:100. In addition, all treatments were conducted with or without lactogenic hormone supplementation. The cellular protein to DNA ratio and total amount of fatty acids per mg protein were decreased (P < .05) by addition of lactogenic hormones. In treatments without hormone supplementation, however, the total amount of cellular fatty acids per mg protein was decreased (P < .05) by addition of either trans-CI8:I isomer. Results indicated a significant (P < .05) relationship between the concentration oftrans-C18:1 in the media and uptake of trans-C 18: 1 isomers, and retroconversion of trans-C 18: 1 to trans-C 16: 1. The slopes of the lines for cellular C16:0, cis-C16:1, and cis-CI8:1 were less (P < .05) than zero as concentration oftrans-CI8:1 in the media increased. However, trans-CI8:1 isomers did not influence the proportion of polar and nonpolar lipids synthesized by the cells. It appears that trans fatty acids may depress milk fat output by decreasing de novo fatty acid synthesis and cis-C 18: I content. / Master of Science

Submitted by Biblioteca da Faculdade de Farmácia (bff@ndc.uff.br) on 2018-03-05T14:14:06Z No. of bitstreams: 1 JÚLIA GONÇALVES MAYER.pdf: 2883327 bytes, checksum: 6ae955490e1664e27d2c9669ad07a02c (MD5) / Made available in DSpace on 2018-03-05T14:14:06Z (GMT). No. of bitstreams: 1 JÚLIA GONÇALVES MAYER.pdf: 2883327 bytes, checksum: 6ae955490e1664e27d2c9669ad07a02c (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Os métodos analíticos utilizados para medir o percentual de ácido graxo trans (AGT) em alimentos envolvem cromatografia em fase gasosa com detecção de ionização de chama (CG-DIC), espectrometria de massas (CG-EM) e espectroscopia no infravermelho com transformada de Fourier e refletância total atenuada (FT-IR-ATR). O presente estudo teve como objetivo investigar a viabilidade e a aplicabilidade do uso das técnicas de FT-IR-ATR, sem extração, com extração prévia da gordura e após hidrólise e metilação dos ácidos graxos, para avaliar o conteúdo de AGT em biscoitos recheados e comparar os resultados obtidos com os encontrados para a determinação de ácido elaídico pela técnica de CG-EM. Foram escolhidas 9 marcas de biscoitos recheados sabor chocolate e 1 pacote de gordura vegetal hidrogenada, para ser usada como padrão secundário para análise de AGT por FT-IR-ATR. As amostras foram analisadas, inicialmente, quanto aos seus conteúdos de umidade e lipídeos totais. Para todas as amostras não foi observada concentração de umidade superior a 6,03 g/100 g. Os lipídeos totais variaram de 12,51±0,58 a 23,84±0,09 g/100 g. A presença de AGT foi identificada por FT-IR-ATR pela visualização da banda próxima a 966 cm−1 e confirmada com adição de padrão às amostras. Ao analisar as amostras de biscoito homogeneizadas e sem outro preparo, não foi viável a utilização do método de FT-IR-ATR, visto que a absorção de radiação infravermelha de substâncias da amostra se sobrepõe à absorção na região das ligações duplas trans, o que demonstra que a matriz do alimento pode influenciar na análise. Quanto a presença dos AGT, ácido elaídico (C18:1, n-9 trans) foi identificado e confirmado em todas as amostras através de CG-EM. Ao comparar a quantificação pelos métodos CG-EM e FT-IR-ATR em amostras de extratos e na forma de ácidos graxos metilados (FAME), foram observadas concentrações baixas de ácido elaídico/ácidos graxos trans (de 0,03±0,01 a 0,86±0,01 g/100 g de biscoito) obtidas pelos diferentes métodos. Não foram encontradas diferenças significativas entre as concentrações de AGT determinadas pelos três métodos testados para oito das nove amostras analisadas. O presente trabalho mostrou que a técnica de FT-IR-ATR, analisando o extrato lipídico e as amostras em forma de FAME foi adequado para estimar os teores de AGT em biscoito recheado de chocolate, visto que proporciona uma análise mais rápida, com um menor número de etapas e menor consumo de reagentes em relação às análises por CG-EM / The analytical methods used to measure the percentage of trans fatty acids in foods involve gas chromatography with flame ionization detection (GC-FID), mass spectrometry (GC-MS) and attenuated total reflectance fourier transform infrared spectroscopy (ATR-FT-IR). The aim of the present study was to investigate the feasibility and applicability of ATR-FT-IR techniques, without extraction, with previous extraction of fat and after hydrolysis and methylation of fatty acids to evaluate the content of TFA in filled biscuits, and compare the results obtained with those found for the determination of elaidic acid by the CG-MS technique. Were chosen 9 marks of chocolate filled biscuit and 1 packet of hydrogenated vegetable fat to be used as a secondary standard for AGT analysis by ATR-FT-IR. The samples were initially analyzed for their moisture contents and total lipids. For all samples, no moisture content higher than 6.03 g/100 g. Total lipids ranged from 12.51 ± 0.58 to 23.84 ± 0.09 g/100g. The presence of TFA was identified by ATR-FT-IR through the visualization of the band near 966 cm−1 and confirmed with addition of standard to the samples. When analyzing the homogenized cookie samples and without further preparation, the use of the ATR-FT-IR method was not feasible because the absorption of infrared radiation from sample substances overlaps the absorption in the region of the trans double bonds, which demonstrates that the food matrix may influence the analysis. Regarding the presence of TFA, elaidic acid (C18: 1, n-9 trans) was identified and confirmed in all samples by GC-MS. When comparing quantification by GC-MS and ATR-FT-IR in samples of extracts and in the form of fatty acids methly esters (FAME), low concentrations of elaidic acid / trans fatty acids were observed (0.03 ± 0.01 to 0.86 ± 0.01 g / 100 g of biscuit) obtained by the different methods. No significant differences were found between the concentrations of TFA determined by the three methods tested for eight of the nine samples analyzed. The present study showed that the ATR-FT-IR technique, analyzing the lipid extract and the samples in the form of FAME, was adequate to estimate the TFA contents in chocolate filled biscuit, because it provides a faster analysis with a smaller number of steps and lower toxic chemicals in relation to GC-MS analyzes