This research studied the effects of dietary lipids unsaturation or oxidation on growth, body composition, tissue oxidative status, and health of the juvenile cobia. Five isonitrogenous and isoenergetic experimental diets containing 20% crude lipid, among which 9% was fish oil and 11% was various supplemental oils, were evaluated. The supplemental oils included palm oil (FP), soybean oil (FS), fish oil (FO), oxidized fish oil (OF) and fish oil supplemented with 300 mg/kg diet vitamin E (FE). The degree of lipid oxidation in FE, FO and OF was increased progressively, and so was the degree of unsaturation in FP, FS and FO. The results of a 10-week growth trial showed that lipid unsaturation didn¡¦t affect fish groeth significantly, but lipid oxidation significantly reduced growth. Decrease in lipid unsaturation and increase in lipid oxidation significantly reduced the crude lipid level of ventral muscle but not that of dorsal muscle and liver. Decreasing lipid unsaturation significantly affected serum TC and LDL concentration. The tissue fatty acid composition was significantly affected by the dietary fatty acid composition. Degree of dietary lipid Oxidation was negatively correlated with tissue n-3 PUFA and HUFA concentrations. Muscle TBARS concentrations was significantly affected by dietary lipids oxidation, but not was liver TBARS. Muscle TBARS was decreased as dietary lipid unsaturation was decreased, especially in dorsal muscle. The degree of dietary lipid oxidation of was positively correlated with tissue TBARS. The supplement additional of vitamin E reduced muscle TBARS. Liver catalase activity was decreased when dietary lipid unsaturated was decreased. Even though lysozyme activity in serum, SOD activity in erythrocyte, oxidative burst activity and phagocytic activity in neutrophils, and intracellular superoxide anion ratio in head kidney macrophages were not significantly affected by dietary lipids unsaturation or oxidation, these parameters showed the lowest levels in the group of fish fed the OF diet, indicating the adverse effects of oil oxidation on fish immunity. The results of this research show that oxidation of dietary lipids was more prominent than unsaturation in affecting growth, body lipid composition, peroxidative status, and health of cobia.

Unsaturated fatty acids of known degree, position, and configuration of unsturation were esterified, and stereospecifically dihydroxylated at the double bond(s). cis-Hydroxylation was effected using Woodward's reagent (silver acetate/iodine/acetic acid), while trans-hydroxylation was effected using Fenton's reagent (hydrogen peroxide/ferrous sulfate/acetic acid). Diols derived from monounsaturated esters were recovered quantitatively, while tetraols derived from diunsaturates were lost, presumably during extensive washing. The stereospecifically dihydroxylated esters were analyzed by thin-layer chromatography on borate-impregnated silica gel plates, and by gas-liquid chromatography, on a nonpolar capillary column, as the trimethylsilyl, acetyl, n-butylboronyl, isopropylidene, and trifluoroacetyl derivatives. For each derivative, the erythro and threo diols were readily separable, and some resolution of positional isomers was observed. Thus, the cis/trans configuration, and in some instances, the position of unsaturation of the original monounsaturated fatty acid may be deduced. However, gas chromatography-mass spectrometry of appropriately derivatized diol esters is required for unambiguous determination of position of unsaturation in most cases. These reactions are simple, use readily available reagents, and require relatively little operator attention. Further, they do not require specialized apparatus, as do hydrogenation and ozonolysis, or potentially toxic chemicals, such as osmium tetroxide. This series of analyses was applied to the unsaturated non-hydroxylated fatty acids of Legionella species, which were shown to be monounsaturated and of the cis Δ9 family. Position of unsaturation was confirmed by gas chromatography-mass spectrometry.

No description available.

Abstract Phospholipids are the main components of cell membranes, lipoproteins and other membrane structures in living organisms. Properties of lipid molecules are important to the overall behaviour and interactions of membranes. Furthermore, characteristics of the biological membranes act as important regulators of membrane functions. Molecular dynamics (MD) simulations were applied in this thesis to study properties of biological membranes. A certain degree of acyl chain polyunsaturation is essential for the proper functioning of membranes, but earlier MD simulations had not addressed the effects of polyunsaturation. Therefore a solvated all-atom bilayer model consisting of diunsaturated 1-palmitoyl-2-linoleoyl-3-phosphatidylcholine (PLPC) molecules was simulated. The analysis of the simulation data was focused on the effects of double bonds on a membrane structure. Self-organising neural networks were applied to the analysis of the conformational data from the 1-ns simulation of PLPC membrane. Mapping of 1.44 million molecular conformations to a two-dimensional array of neurons revealed, without human intervention or requirement of a priori knowledge, the main conformational features. This method provides a powerful tool for gaining insight into the main molecular conformations of any simulated molecular assembly. Furthermore, an application of MD simulations in the comparative analysis of the effects of lipid hydrolysis products on the membrane structure was introduced. The hydrolysis products of the phospholipase A2 (PLA2) enzyme are known to have a role in a variety of physiological processes and the membrane itself acts as an important regulator of this enzyme. The simulations revealed differences in the bilayer properties between the original and hydrolysed phospholipid membranes. This study provides further evidence that MD simulations on biomembranes are able to provide information on the properties of biologically and biochemically important lipid systems at the molecular level.

<p> Edible oils consist primarily of triacylglycerols (or TAGs), which are triesters of glycerol and fatty acids. Determination of the TAG compositions of edible oils is becoming more important, given the economic value of these oil products and the increasing incidence of adulterating high quality oils with poorer quality oils. In this study we report the development of an analytical protocol using positive ion infusion electrospray mass spectrometry (ESI/MS) in conjunction with tandem mass spectrometry which affords both identification and quantification of TAGs in edible oils samples.</p> <p> This thesis reports a simple, comprehensive and quantitative method for the analysis of TAGs in edible oils in which the optimized method involves the infusion of an oil sample in chloroform:methanol (1:1) solution (~10-15 μg/mL of oil) in the presence of 0.5 mM LiCl. A sequence of corrections were applied to the raw peak area data of the TAG molecular ions, [M+Li]+, to account for: (1) normalization of peak area data using three internal standards, (2) peak area contributions of M+2 isotopic peaks of TAGs with one more degree of unsaturation and (3) peak area contributions of LiCl adduct ions, [M+Li+LiCl]+, when applicable. The major correction involved multiplication to a given TAG peak area by the appropriate electrospray relative response factor (RRF) for that TAG. The RRFs for all TAGs containing between 48 and 63 carbons in their fatty acyl chains and between 0 and 9 degrees of unsaturation were extrapolated from experimentally determined response factors of a series of standards. The RRFs were found to decrease by 6.7% for each additional acyl chain carbon but increased by 18.6% for each double bond. Comparison of these calculated RRFs to reported RRFs for a series of TAG standards showed an excellent correlation (1.06% ± 10.20% RSD).</p> <p> The use of Li+ in TAG analysis followed from the reports by Hsu and Turk [93] and Han and Gross [18] which showed that Li+ afforded more intense MS, and particularly MS/MS, spectra than either H+ or Na+. The enhanced intensities in MS/MS spectra (determined using a triple quadrupole mass spectrometer) were critical for the identification of TAGs, including the identity of the fatty acyl group located at the sn-2 position. However, this method cannot distinguish unambiguously between isobaric TAGs. This methodology was applied to the profiling of a number of edible oils including canola, olive, sesame, grape seed, walnut and hemp seed oils. The major TAGS in these samples contained 52, 54 and 56 carbons with between 0 and 11 degrees on unsaturation in a given TAG. There were minor amounts of TAGs containing 50, 55 and 57 carbons.</p> <p> The ability of this method to determine quantitatively the number of degrees of unsaturation in an oil sample was tested by examining a series of partially hydrogenated canola oil samples kindly provided by Bunge Canada. Five oil samples derived from a single feedstock with differing numbers of degrees of unsaturation, measured as iodine values, were subjected to our analytical method. The measured iodine values were compared to iodine values calculated from the number of degrees of unsaturation obtained by our MS-based method. The slope of this correlation was 1.10 with an R^2 = 0.995. Overall, this method is much simpler and more accurate than the protocol described by Han and Gross [18]. This methodology will be applied as routine method for the analysis of TAGs in biological samples such as blood samples.</p> / Thesis / Master of Science (MSc)

No description available.

La thèse présente un ensemble de résultats expérimentaux sur des sols fins très plastiques compactés au voisinage de l’optimum Proctor normal (OPN). Elle est réalisée dans le cadre du projet ANR TerreDurable qui traite de la conception des ouvrages en terre en sols fins. Après l’étude de l’effet de compactage sur des chemins de drainage-humidification, la fissuration induite par la dessiccation est mise en évidence et analysée. Par ailleurs, des relations entre différents paramètres mécaniques (module, IPI, Résistance à la compression) et hydriques (succion, perméabilité, ..) en fonction de l’énergie de compactage et du mode de préparation sont présentées. Le comportement mécanique des sols fins compactés est étudié sur des chemins œdométriques et triaxiaux saturés et non saturés, drainés et non drainés. Dans ce dernier cas, l’évolution des paramètres de pression interstitielle de Skempton est analysée sur des chemins isotropes et déviatoires. Ceci a nécessité la mise au point d’une cellule triaxiale équipée de psychromètres à effet Peltier, de tensiomètre et de jauges de déformations. / The thesis presents an experimental study on very high plasticity soils compacted near of the standard Proctor optimum (SPO). It is performed as part of the ANR TerreDurable project which is devoted on the design of earthworks with fine soils. After the study of the effect of compaction on drying-wetting paths, induced cracking of drying is highlighted and analyzed. Furthermore, relationships between different mechanical parameters (modulus, IPI, compressive strength) and water (suction, permeability) according to the energy of compaction and method of preparation are shown. The mechanical behavior of soils compacted fine soils is studied on saturated and unsaturated, drained and undrained oedometer and triaxial. For the unsaturated undrained triaxial, the change in Skempton parameters pore pressure is analyzed on isotropic and deviatoric paths. This required the development of a triaxial cell equipped with psychrometers, tensiometer and strain gauges.

Reconstructing past sea surface temperature conditions is valuable to observe and evaluate the climate of the past. In the SW Atlantic, so far, few studies have exanimated the applicability of paleotemperature equations, which may reflect in fewer reliable SST estimates. This study aimed to evaluate two marine proxies for SST reconstructions: the alkenones unsaturation index (UK\'37) and the ratio Mg/Ca in different planktonic foraminifera species and size fractions (G. ruber pink; G. ruber white senso stricto and senso lato; between 250 - 300 µm and 300 - 355 &#956;m; G. truncatulinoides (d) crusted and non-crusted forms, between 380 - 620 &#956;m; and G. inflata 300 - 425 &#956;m). The samples were collected in the shelf break of South Brazilian Bight (SBB, 22 °S to 27 °S). The proxies were converted into SSTs and then compared to modern SSTs from the World Ocean Atlas and satellite images. The first chapter describes the UK\'37 signals and the applicability of three different paleotemperature equations, and the second chapter describes the Mg/Ca a proxy for past SSTs and water mass conditions after applying the most used paleotemperature equations for the ratio Mg/Ca. The UK\'37 seems to record mostly autumn conditions at 0m, and the most recent Bayspline equation results into more similar temperature averages when compared to modern annual SSTs (p-value of 0.81, n = 47, &#916;SST of -0.03°C &#177; 0.27), while the most used linear equations result into SSTs similar to autumn conditions. In subtropical regions with low-temperature variations (&#8764;4°C), the function UK\'37 versus SSTs works in an exponential relation, and they are related to seasonal temperatures. For the Mg/Ca in planktonic foraminifera species, the Mg/Ca-inferred temperatures agree well with modern ocean temperatures. Our data suggest that in different size fractions the tested species respond differently to the most used species-specific and general species paleotemperature equations. All the upper water column species agree well with temperatures at 0-meter depth. The G. ruber (p) responds well to the SS equation, where the smallest and the largest size results into annual and autumn estimates, respectively (p-value of 0.81 and 0.71, n = 23); the smallest size of G. ruber (w) s.s. provides summer estimates applying the GE equation (p-value of 0.21, n = 7), while the largest size provides annual estimates (p-value of 0.86, n = 13). The G. ruber (w) s.l. has significant averages when compared the largest size with autumn and summer conditions (p-value of 0.21 for both, n = 16); the deep-dwelling species G. inflata and the G. truncatulinoides (d) crusted form reflect the uplift of the SACW, calcifying at 10 and 20 m depth (p-value of 0.89, n = 10 and p-value of 0.06, n = 14, respectively), while the G. truncatulinoides (d) non-crusted form records annual temperature in deep water layers conditions (p-value of 0.06, n = 16). This is the first study to report Mg/Ca ratios in surface-dwelling and deep-dwelling planktonic foraminifera tests obtained in core-top samples at the SBB. This validation will inform the reconstruction of past environmental conditions of SW Atlantic, especially in the SBB. / As reconstruções das condições da temperatura superficial do mar são importantes para avaliar o clima do passado da Terra. No Atlântico SE, no entanto, poucos estudos avaliaram a aplicabilidade das equações de conversão dos indicadores geoquímicos para temperatura, o que pode resultar em estimativas de paleotemperatura de menor acurácia. Este estudo avaliou dois indicadores marinhos de paleotemperatura: o índice de insaturação de alquenonas (UK\'37), e a razão Mg/Ca em testas de foraminíferos planctônicos de diferentes espécies e frações de tamanho (G. ruber pink; G. ruber white senso stricto e senso lato; entre 250 - 300 &#956;m e 300 - 355 &#956;m; G. truncatulinoides (d) encrustadas e não-encrustadas, entre 380 - 620 &#956;m; e G. inflata 300 - 425 &#956;m). As amostras são provenientes da plataforma externa e quebra da plataforma do Embaiamento de São Paulo (22°S a 27°S). Os indicadores foram transformados em TSM e então comparados com as temperaturas obtidas por meio do World Ocean Atlas e de imagens de satélite. O primeiro capítulo apresenta os dados de UK\'37 e a aplicabilidade de três equações de paleotemperatura. O segundo capítulo apresenta dados da razão Mg/Ca como indicador de TSM e condições de massa d\'água após a aplicação das equações de conversão. O UK\'37 apresenta influência do outono em 0 m de profundidade em seus registros, e a mais recente equação Bayspline resulta em médias de TSM mais similares com as condições atuais, principalmente quando comparado com a média anual de TSM (p-valor de 0.81, n = 47, &#916;SST de -0.03°C &#177; 0.27), já as equações lineares mais conhecidas resultam em TSM mais parecidas com condições de outono. No geral, em regiões com pouca variação de TSM (&#8764;1.5 °C), o UK\'37 responde em uma relação exponencial com a temperatura. A razão Mg/Ca em testas de foraminíferos planctônicos, quando convertidas em TSM, resultam em médias similares com as condições atuais de temperatura. Os nossos dados sugerem que as equações específicas para cada espécie (SS) e as equações gerais (GE) resultam em diferentes médias de TSM para cada espécie/fração de tamanho. Todas as espécies de superfície respondem bem com as temperaturas em 0 metros de profundidade. A G. ruber (p) responde bem à equação SS, onde a menor e a maior fração de tamanho resulta em médias similares às TSM anuais e de outono, respectivamente (p-valor de 0.81 e 0.71, n = 23); a menor fração de tamanho da espécie G. ruber (w) s.s. resulta em médias similares às TSM de verão com a equação GE (p-valor de 0.21, n = 7), enquanto a maior fração de tamanho resulta em TSM anual (p-valor de 0.86, n = 13). A maior fração de tamanho da espécie G. ruber (w) s.l. resulta em médias significativas quando comparadas com TSM de outono e de verão (p-valor de 0.21 para ambas, n = 16). Os registros geoquímicos das espécies de subsuperfície, como a G. inflata e a G. truncatulinoides (d) encrustada registram a subida da ACAS para a superfície na área de estudo, calcificando em 10 e 20 metros de profundidade, respectivamente (p-valor de 0.89, n = 10 e de 0.06, n = 14, respectivamente), enquanto a G. truncatulinoides (d) não-encrustada aparenta registrar as condições anuais de temperatura em profundidades mais próximas da ACAS, com médias um pouco mais elevadas que as duas espécies de subsuperfície (p-valor de 0.06, n = 16). Este é o primeiro estudo que relata as razões Mg/Ca em diferentes espécies de foraminíferos planctônicos no ESP. Esta validação auxiliará a aprimorar futuras estimações de TSM com este indicador.

Magnetic resonance imaging (MRI) is one of the most important diagnostic tools of modern healthcare. The signal in medical MRI predominantly originates from water and fat molecules. Separation of the two components into water-only and fat-only images can improve diagnosis, and is the premier non-invasive method for measuring the amount and distribution of fatty tissue. Fat-water imaging (FWI) enables fast fat/water separation by model-based estimation from chemical shift encoded data, such as multi-echo acquisitions. Qualitative FWI is sufficient for visual separation of the components, while quantitative FWI also offers reliable estimates of the fat percentage in each pixel. The major problems of current FWI methods are long acquisition times, long reconstruction times, and reconstruction errors that degrade image quality. In this thesis, existing FWI methods were reviewed, and novel fully automatic methods were developed and evaluated, with a focus on fast 3D image reconstruction. All MRI data was acquired on standard clinical scanners. A triple-echo qualitative FWI method was developed for the specific application of 3D whole-body imaging. The method was compared with two reference methods, and demonstrated superior image quality when evaluated in 39 volunteers. The problem of qualitative FWI by dual-echo data with unconstrained echo times was solved, allowing faster and more flexible image acquisition than conventional FWI. Feasibility of the method was demonstrated in three volunteers and the noise performance was evaluated. Further, a quantitative multi-echo FWI method was developed. The signal separation was based on discrete whole-image optimization. Fast 3D image reconstruction with few reconstruction errors was demonstrated by abdominal imaging of ten volunteers. Lastly, a method was proposed for quantitative mapping of average fatty acid chain length and degree of saturation. The method was validated by imaging different oils, using gas-liquid chromatography (GLC) as the reference. The degree of saturation agreed well with GLC, and feasibility of the method was demonstrated in the thigh of a volunteer. The developed methods have applications in clinical settings, and are already being used in several research projects, including studies of obesity, dietary intervention, and the metabolic syndrome.