Thesis (M. A. Sc.)--University of Toronto, 2003. / Includes bibliographical references (p. 76-80 of photocopy). Abstract and 24 page preview available online.

No abstract / Applied Science, Faculty of / Chemical and Biological Engineering, Department of / Graduate

Understanding of molecular events involved in food safety and human health has become a major concern of contemporary life. Mass spectrometry (MS) is a powerful tool for characterization of complex food ingredients and biological molecules. Advances in MS-based techniques have offered new opportunities to understand the chemical changes occurring during food storage and processing as well as the molecular events perturbed by either endogenous or exogenous stimulus. In this thesis, we developed novel MS-based approaches for authentication of edible oil (i.e., edible vegetable oil, deep frying oil and gutter oil), assessment of genotoxicity of fatty acid hydroperoxides, and investigation of metabolic deregulation in pleural effusion and tissue of human lung cancer, aiming to gain a better understanding of food safety and human health. MS-based methods were developed for authentication of edible vegetable oil adulterated with used cooking oil. Gas chromatography-mass spectrometry (GC-MS) analysis revealed that six monoglycerides could be used as the markers to discriminate the used cooking oil (e.g., deep frying oil and gutter oil) and qualified edible oil. Accumulation behavior of these six monoglycerides was detected in the repeatedly heated edible oils. Quantitation of the monoglycerides enabled authentication of commercial olive oil adulterated with a small amount of used cooking oil (approximately 1%). In addition, a matrix-assisted laser desorption/ionization imaging mass spectrometry (MALDI-IMS) method was developed for visual authentication of edible oil samples, including commercial vegetable oil, used cooking oil and adulterated edible oil. The method provided the capability for quantifying major chemical composition of edible oil, such as triglycerides, diglycerides and monoglycerides. The present method required minimal sample preparation and allowed screening of oil samples with high throughput (approximately 360 samples per day), providing a simple way to authenticate different types of oil samples. Liquid chromatography-electrospray ionization mass spectrometry (LC-ESI-MS) was applied to investigate the genotoxicity of two fatty acid hydroperoxides, i.e., 13-hydroperoxyoctadeca-cis-9,trans-11-dienoic acid (13-HPODE) and 13-hydroperoxy-9,11E,15Z-octadecatrienoic acid (13-HPOTE), which are important inducers of oxidative deterioration in oils and fats generated from the oxidation of linolenic acid and linoleic acid. The results demonstrated that the α,β-unsaturated aldehydes, such as 4-oxo-2-nonenal, dioxo-10-dodecenoic acid, 4-hydroperoxy-2-nonenal and 4-hydroxy-2-nonenal are the main degradation compounds of 13-HPODE and 13-HPOTE, which can covalently bound to deoxyribose-nucleosides and ribose-nucleosides to form adducts. This study provided evidences regarding the genotoxicity of fatty acid hydroperoxides at the molecular level. MS-based metabolomics methods were developed and applied for the investigation of metabolic signatures of pleural effusion and tissue of human lung cancer. A database-assisted global metabolomics method was established with utility of LC-Orbitrap MS, followed by automated mass spectral searching. The method enabled unbiased identification of 194 endogenous metabolites in pleural effusions caused by tuberculosis and malignancy. Among which, 33 differential metabolites involved in tryptophan catabolism, bile acid biosynthesis, and β-oxidation of fatty acids were found between tuberculous and malignant pleural effusions, which provided non-invasive biomarkers for diagnosis of pleural effusion samples with high sensitivity and specificity. In addition, a large-scale targeted metabolomics method was developed, which enabled reliable detection of over 400 biological metabolites, covering 92 metabolic pathways in human samples. The method was applied to characterize the metabolic profiles of non-small cell lung cancer (NSCLC) tissues. A number of distant metabolic pathways were found to be differentiated between tumor and normal tissues of lung squamous cell carcinoma and adenocarcinoma, including purine metabolism, citric acid cycle, amino acid metabolism, urea cycle, and ammonia recycling. In addition, several metabolites, such as adenosine, glutamate, glucose 1,6-bisphosphate, betaine, creatine and methionine sulfoxide were found to be associated with prognosis of NSCLC patients, which might provide potential biomarkers to monitor metabolic characteristics of NSCLC patients and treatment outcomes of the cancer.

Understanding of molecular events involved in food safety and human health has become a major concern of contemporary life. Mass spectrometry (MS) is a powerful tool for characterization of complex food ingredients and biological molecules. Advances in MS-based techniques have offered new opportunities to understand the chemical changes occurring during food storage and processing as well as the molecular events perturbed by either endogenous or exogenous stimulus. In this thesis, we developed novel MS-based approaches for authentication of edible oil (i.e., edible vegetable oil, deep frying oil and gutter oil), assessment of genotoxicity of fatty acid hydroperoxides, and investigation of metabolic deregulation in pleural effusion and tissue of human lung cancer, aiming to gain a better understanding of food safety and human health. MS-based methods were developed for authentication of edible vegetable oil adulterated with used cooking oil. Gas chromatography-mass spectrometry (GC-MS) analysis revealed that six monoglycerides could be used as the markers to discriminate the used cooking oil (e.g., deep frying oil and gutter oil) and qualified edible oil. Accumulation behavior of these six monoglycerides was detected in the repeatedly heated edible oils. Quantitation of the monoglycerides enabled authentication of commercial olive oil adulterated with a small amount of used cooking oil (approximately 1%). In addition, a matrix-assisted laser desorption/ionization imaging mass spectrometry (MALDI-IMS) method was developed for visual authentication of edible oil samples, including commercial vegetable oil, used cooking oil and adulterated edible oil. The method provided the capability for quantifying major chemical composition of edible oil, such as triglycerides, diglycerides and monoglycerides. The present method required minimal sample preparation and allowed screening of oil samples with high throughput (approximately 360 samples per day), providing a simple way to authenticate different types of oil samples. Liquid chromatography-electrospray ionization mass spectrometry (LC-ESI-MS) was applied to investigate the genotoxicity of two fatty acid hydroperoxides, i.e., 13-hydroperoxyoctadeca-cis-9,trans-11-dienoic acid (13-HPODE) and 13-hydroperoxy-9,11E,15Z-octadecatrienoic acid (13-HPOTE), which are important inducers of oxidative deterioration in oils and fats generated from the oxidation of linolenic acid and linoleic acid. The results demonstrated that the α,β-unsaturated aldehydes, such as 4-oxo-2-nonenal, dioxo-10-dodecenoic acid, 4-hydroperoxy-2-nonenal and 4-hydroxy-2-nonenal are the main degradation compounds of 13-HPODE and 13-HPOTE, which can covalently bound to deoxyribose-nucleosides and ribose-nucleosides to form adducts. This study provided evidences regarding the genotoxicity of fatty acid hydroperoxides at the molecular level. MS-based metabolomics methods were developed and applied for the investigation of metabolic signatures of pleural effusion and tissue of human lung cancer. A database-assisted global metabolomics method was established with utility of LC-Orbitrap MS, followed by automated mass spectral searching. The method enabled unbiased identification of 194 endogenous metabolites in pleural effusions caused by tuberculosis and malignancy. Among which, 33 differential metabolites involved in tryptophan catabolism, bile acid biosynthesis, and β-oxidation of fatty acids were found between tuberculous and malignant pleural effusions, which provided non-invasive biomarkers for diagnosis of pleural effusion samples with high sensitivity and specificity. In addition, a large-scale targeted metabolomics method was developed, which enabled reliable detection of over 400 biological metabolites, covering 92 metabolic pathways in human samples. The method was applied to characterize the metabolic profiles of non-small cell lung cancer (NSCLC) tissues. A number of distant metabolic pathways were found to be differentiated between tumor and normal tissues of lung squamous cell carcinoma and adenocarcinoma, including purine metabolism, citric acid cycle, amino acid metabolism, urea cycle, and ammonia recycling. In addition, several metabolites, such as adenosine, glutamate, glucose 1,6-bisphosphate, betaine, creatine and methionine sulfoxide were found to be associated with prognosis of NSCLC patients, which might provide potential biomarkers to monitor metabolic characteristics of NSCLC patients and treatment outcomes of the cancer.

Yes / We report results of atomistic molecular dynamics simulations of an industrially-relevant, exemplar triacylglycerol (TAG), namely tristearin (TS), under aqueous conditions, at different temperatures and in the presence of an anionic surfactant, sodium dodecylbenzene sulphonate (SDBS). We predict the TS bilayers to be stable and in a gel phase at temperatures of 350 K and below. At 370 K the lipid bilayer was able to melt, but does not feature a stable liquid–crystalline phase bilayer at this elevated temperature. We also predict the structural characteristics of TS bilayers in the presence of SDBS molecules under aqueous conditions, where surfactant molecules are found to spontaneously insert into the TS bilayers. We model TS bilayers containing different amounts of SDBS, with the presence of SDBS imparting only a moderate effect on the structure of the system. Our study represents the first step in applying atomistic molecular dynamics simulations to the investigation of TAG-aqueous interfaces. Our results suggest that the CHARMM36 force-field appears suitable for the simulation of such systems, although the phase behaviour of the system may be shifted to lower temperatures than is the case for the actual system. Our findings provide a foundation for further simulation studies of the TS-aqueous interface. / veski

Call number: LD2668 .T4 1948 J3 / Master of Science

LD2668 .T4 1954 R87 / Master of Science

published_or_final_version / Environmental Management / Master / Master of Science in Environmental Management

No description available.

Increased interest has focused on associations between dietary fatty acids and cardiovascular disease (CVD). Current findings delineating effects of consuming saturated fatty acids (SFA) from dairy on CVD risk remain controversial. The objective of this thesis was to investigate the effects of consuming two types of dairy fat, namely those from cheese and butter on, human plasma and RBC fatty acid profiles, compared with monounsaturated fatty acids (MUFA), polyunsaturated fatty acids (PUFA) and carbohydrate (CHO). A secondary objective was to investigate the association between consuming these dietary fatty acids and endogenous de novo fatty acid synthesis. A randomized, full-feeding, crossover, single-blinded clinical trial was conducted at the Institute of Nutrition and Functional Foods (INAF), Laval University and Richardson Centre for Functional Foods and Nutraceuticals (RCFFN), the University of Manitoba. A total of 92 women and men with abdominal obesity and relative low high density lipoprotein cholesterol (HDL-C) levels were randomized into a series of 5 treatments. The duration of each treatment was 4 weeks and separated by at least 4 weeks washout period. For plasma fatty acid profile, total plasma SFA after cheese treatment was found to be higher (P<0.05) than after MUFA, PUFA and CHO treatments, whereas total plasma SFA after butter treatment was only found to be higher (P<0.05) than after MUFA and PUFA treatments. Total plasma MUFA after MUFA treatment was higher (P<0.05) than after all other treatments, and total plasma PUFA after PUFA treatment was higher (P<0.05) than after all other treatments. Unlike plasma fatty acid profile, RBC total SFA after two dairy treatments were not higher than after CHO and PUFA treatments. Consistent with the plasma fatty acid profile, RBC total MUFA after MUFA treatment were found to be higher (P<0.05) than after all other treatments. Similarly, RBC total PUFA after PUFA treatment were higher (P<0.05) than after all other treatments. We did not detect any differences in de novo palmitic acid synthesis across all treatments in the present study. However, we did see a positive correlation between de novo palmitic acid synthesis and body fat mass. In summary, present results suggest that consuming dairy fats, from cheese or butter, can significantly modulate plasma fatty acids in a manner that increases plasma total SFA, including myristic acid (C14:0), pentadecanoic acid (C15:0), palmitic acid (C16:0) and heptadecanoic acid (C17:0). However, the effect of consuming dairy fats on RBC fatty acid profile is relatively minor. Additionally, the de novo fatty acid synthesis data suggests that the quality of dietary fatty acids does not associate with human endogenous fatty acid synthesis; unlike body fat mass. / May 2017