Mémoire : Sciences : Paris, Faculté des sciences : 1832. / Titre provenant de l'écran-titre.

Thèse : Sciences : Université, Faculté des sciences de Paris : 1855. / Titre provenant de l'écran-titre.

The entire thesis text is included in the research.pdf file; the official abstract appears in the short.pdf file; a non-technical public abstract appears in the public.pdf file. Title from PDF of title page (University of Missouri--Columbia, viewed on February 12, 2010). Thesis advisor: Dr. Galen J. Suppes. Includes bibliographical references.

Thesis (Ph. D.)--University of Washington, 2001. / Vita. Includes bibliographical references (p. 95-103).

published_or_final_version / Botany / Master / Master of Philosophy

No description available.

Fourier transform near-infrared (FT-NIR) spectroscopy was investigated as a means of quantitative analysis of edible fats and oils. Initially, a method of simultaneously determining the cis and trans content, iodine value and saponification number of neat fats and oils using a heated transmission flow cell was developed. Two partial least squares (PLS) calibrations were devised, a process-specific calibration based on hydrogenated soybean oil and a more generalized calibration based on many oil types, the latter able to analyze oils from a variety of sources accurately and reproducibly. Methodology for the quantitative determination of the peroxide value (PV) of edible oils using a novel glass-vial sample handling system was subsequently developed, based on the stoichiometric reaction of triphenylphosphine with hydroperoxides to form triphenylphosphine oxide. The PV calibration was derived using PLS regression, and the results of a validation study demonstrated that PV could be quantitated accurately if a normalization routine was used to compensate for the inherent dimensional variability of the vials. The vial sample handling system was then used in the development of PLS IV calibrations for the process analysis of commercial oil samples, and these samples were also used to evaluate a global IV calibration devised by Bomem Inc. The discriminant features available through PLS were shown to enhance the accuracy of the IV predictions by facilitating the selection of the most appropriate calibrations based on the spectral characteristics of closely related oils. The predictions obtained using the global IV calibration provided clear evidence that a generalized calibration based on a large and varied selection of oils could provide a means of IV determination by FT-NIR spectroscopy. Subsequently, a generalized FT-NIR trans calibration was developed and shown to yield trans values that were in good agreement with those obtained by the AOCS mid-FTIR single-bounce hori

A novel and rapid method was developed to monitor the autoxidation of edible oils by Fourier transform infrared (FTIR) spectroscopy with the use of disposable polymer infrared (PIR) cards having a microporous polytetrafluoroethylene (PTFE) sample substrate. Under conditions of mild heating (~58°C) and aeration, both model triacylglycerols (TAGS) and edible oils applied onto the PIR cards underwent rapidly accelerated oxidation. In order to compare the oxidative stability of samples on the PIR cards in terms of the time required to reach a peroxide value (PV) of 100 mequiv/kg oil, matching the end-point measured in the standard active oxygen method (AOM), an absorbance slope factor (ASF) was determined to relate changes in hydroperoxide (ROOH) absorbance (peak maximum found within the range of 3500--3200 cm-1 ) to PV. Similar ASF values were found for the four edible oils tested (safflower, canola, sunflower, and extra virgin olive oil), permitting determination of a pooled, universally applicable ASF value of 0.0526 mAbs/PV.

Three new quantitative Fourier transform infrared (FTIR) spectroscopic methods were developed for the analysis of edible oils: two procedures to measure free fatty acids (FFA) and one to measure moisture (H2O), the latter two methods ultimately being automated and implemented on an auto-sampler equipped FTIR spectrometer. The methods developed for FFA determination both convert FFAs to their carboxylate salts by means of acid/base reaction without causing oil saponification, one approach using 1-propanol, an oil-miscible solvent, and the other using methanol, an oil-immiscible solvent into which the FFA salts are extracted. The first method involves splitting oil samples into two halves, with one half treated with propanol containing base and the other half with propanol only. The spectra of each half is collected and a differential spectrum obtained, from which quantization is performed. The methanol procedure simply involves extracting FFA into methanol containing a weak base and quantitating the FFA salts produced. Both FFA methods determine the FFA content by measuring the v (COO-) absorbance at ∼1570 cm-1 relative to a reference wavelength of 1820 cm-1 from a differential spectrum relative to the solvent, the extraction procedure being superior in terms of both speed and sensitivity, being able to measure FFA levels down to ∼0.001%. The method developed for moisture determination involves extracting water in edible oils into dry acetonitrile and then quantitating it by measuring the absorbance of the OH stretching band (3629 cm-1) and/or the HOH bending band (1631 cm -1). All three methods were validated by standard addition experiments, evaluated for potential interferences, and, in the case of FFA determination, compared to the performance of AOCS official methods. The results indicated that the extraction-based procedures were superior to conventional wet chemical methods in both sensitivity and reproducibility. The FFA and H2O extraction procedures were subsequently automated by connecting an auto-sampler to the FTIR spectrometer and developing procedures and software algorithms to enable the analysis of up to 100 samples/h. The methods developed and implemented are a substantive improvement over conventional methods for the analysis of FFA and H2O in edible oils and provide a means by which QC and process laboratories can analyze large volumes of edible oils for these two important parameters.

To investigate interactive effects of dietary fatty acid composition and energy restriction on body lipid metabolism and its regulation, rats were fed for 10 weeks diets varying in fat type and energy intake level. Energy deficiency was achieved by removing carbohydrate from the diets while keeping fat and other nutrient intakes constant. Tissue fatty acid deposition was influenced by the interaction between the dietary fat source and body energy balance. Less total fatty acids were deposited in livers of the ad libitum beef tallow-fed animals than the other fat feedings. However, such difference no longer existed when energy intake was restricted. Similarly, less energy supply eliminated the higher docosahexaenoic acid and lower arachidonic acid contents associated with the fish oil feeding in hepatocyte membrane phosphatidylchohne, phosphatidylserine and sphingomyelin. Tissue lipogenesis was also examined as a function of the interaction of dietary fatty acid composition and energy restriction. Comparable absolute cholesterol synthesis rates were observed in livers of the food restricted animals fed different types of dietary fat, although the synthesis rates were different among the dietary fat groups fed ad libitum. Energy restriction increased the triglyceride-fatty acid synthesis rates in the intestine of the fish and safflower oil-fed groups, but not in that of the olive oil- and beef tallow-fed animals. Plasma leptin concentrations were 60% higher in the ad libitum-fed fish and safflower oil groups as compared with those in the beef tallow diet group, despite smaller perirenal fat mass and fat cell size in the fish oil-fed animals. Energy restriction decreased plasma leptin levels of the fish and safflower oil-fed rats, but not those in the beef tallow-fed animals. Taken together, these results demonstrate that the structural, functional and regulating aspects of tissue lipid metabolism were influenced by an interaction between dietary fatty acid composit