A região amazônica apresenta grande quantidade de plantas perenes, com particular relevância para as espécies frutíferas. Os frutos amazônicos são conhecidos pelo seu grande potencial energético e são usados como fonte de alimento nas grandes regiões do país. Dentre esses frutos, destaca-se o açaí, fruto do açaizeiro (Euterpe oleracea Martius), a copaíba (Copaifera officinalis L.) e a castanha do Pará (Bertholletia excelsa). Esses frutos são importantes para o desenvolvimento agroindustrial da região amazônica. Os mesmos contêm na sua composição proteínas, fibras e ácidos graxos. Os frutos possuem ácidos graxos são usados na área farmacêutica, com finalidade clínica e dermatológica. O projeto tem como objetivo apresentar técnicas analíticas de caracterização e quantificação dos ácidos graxos presente na composição oleosa dos frutos e descrever a ação farmacológica. Esses ácidos são o oléico, linoleico e palmítico. As técnicas analíticas com características de quantificação deverão gerar informações confiáveis e interpretáveis sobre a amostra, sendo o critério de avaliação denominado validação. A validação foi estudada neste trabalho, visando ter confiabilidade e reprodutibilidade nos resultados. Os processos analíticos com características de identificação e quantificação aplicados nesse projeto são: a cromatografia a gás acoplada a espectrometria de massas (CG/MS), a espectrometria de massas Tanden (MS/MS) e cromatografia líquida de alta eficiência com detector ultra violeta (HPLC/UV). Os resultados demonstram que os três frutos amazônicos comtem ácidos oléico, linoleico e palmítico em proporções diferentes potencializando seu uso em aplicações farmacêuticas, específicamente em tratamentos dermatológicos. / The Amazon region presents a great amount of perennial plants, with particular relevance to the fruit species. The Amazonian fruits are known for their high energy potential and are used as a food source in large regions of the country. Among these fruits, there is acai, the fruit of the açai palm (Euterpe oleracea Martius), copaiba (Copaifera officinalis L.) and Brazil nut (Bertholletia excelsa). These fruits are important for agro-industrial development in the Amazon region. They contain in their composition of protein, fiber and fatty acids. The fruits are fatty acids are used in the pharmaceutical field, with clinical and dermatological purposes. The project aims to provide analytical techniques for characterization and quantification of fatty acids present in the composition of the oily fruits and describe the pharmacological action. These acids are oleic, linoleic and palmitic acids. Analytical techniques for quantifying characteristics should generate reliable and interpretable information about the sample, and the evaluation criteria called validation. The validation was studied in this work, aiming to have reliability and reproducibility of the results. The analytical procedures to identify and quantify features implemented in this project are: a gas chromatography-mass spectrometry (GC / MS), Tanden mass spectrometry (MS / MS) and high performance liquid chromatography with UV detector (HPLC / UV). The results show that the three Amazon fruits did contain oleic, linoleic and palmitic acids at different increasing its use in pharmaceutical applications, specifically in dermatological treatments.

There is a growing interest in documenting the effect of diet on the ability to convert saturated fatty acids (SFA) to monounsaturated fatty acids (MUFA) by modulating expression of the SCD gene. We propose that if cattle were raised to a constant body weight, their MUFA:SFA ratio will be the same regardless of being calf-fed (CF) or yearling-fed (YF). Twenty-four Angus cattle were acquired for this study. Cattle were slaughtered at weaning at 8 mo of age (SFCF, n=4), eight steers were assigned to the CF group and slaughtered at 12 mo of age (MFCF, n=4) and 16 mo of age (LFCF, n=4). Twelve cattle were assigned to the YF group and slaughtered at 12 mo of age (SFYF, n=4) 16 mo of age (MFYF, n=4) and market weight of 525 kg (LFYF, n=4). Cattle were then statistically analyzed based on time on high energy diet. Fatty acids from digesta, plasma, liver, L. dorsi, and s.c. and i.m. adipose tissue were all analyzed by FAME. In s.c. 18:1 and 16:1 were greatest in LFCF (41.27% and 5.58%, respectively, P = 0.05), and 18:0 and 16:0 did not differ between groups (P > 0.10). MUFA:SFA ratios of s.c. tended to be higher in LFCF animals (1.26) vs. LFYF (1.06, P = 0.10). However, there was no difference seen when comparing CF to YF animals (P = 0.26). MUFA:SFA ratio was higher in i.m. (P = 0.03) and also increased with age (P < .01). A trained sensory panel saw no significant differences between palatability of flavor characteristics of cooked steaks from LFCF, MFYF, or LFYF (P > 0.05). We showed increased SCD gene expression in the LFYF (248.41 to 1528.69 SCD/GAPDH, P = 0.01). Expression was higher in YF (P = 0.04), but their initial deposits of SFA, combined with the lack of SCD expression while on pastures, prevented the MUFA:SFA ratio from increasing at a rate fast enough to change the final ratios in the animal.

Glucagon-like peptide-1 (GLP-1) is an anti-diabetic intestinal L cell hormone. The monounsaturated fatty acid, oleic acid (OA), is an effective GLP-1 secretagogue that crosses the cell membrane by an unknown mechanism. Immunoblotting demonstrated the presence of fatty acid transport proteins (CD36 and FATP1, 3 and 4) in the murine GLUTag L cell model. The cells demonstrated specific 3H-OA uptake, which was dose-dependently inhibited by unlabeled-OA. Phloretin and SSO, inhibitors of carrier-mediated transport and CD36, respectively, also significantly decreased 3H-OA uptake, as did knocking down FATP4 by transfection of siRNA. OA dose-dependently increased GLP-1 secretion in GLUTag cells, while phloretin and FATP4 knockdown, but not SSO, decreased this response. OA injected directly into the ileum of wild-type mice increased plasma GLP-1 levels; in contrast, preliminary findings suggest decreased GLP-1 levels in FATP4 null mice at 60 min. Collectively, these findings indicate a role for FATP4 in OA-induced GLP-1 secretion.

Glucagon-like peptide-1 (GLP-1) is an anti-diabetic intestinal L cell hormone. The monounsaturated fatty acid, oleic acid (OA), is an effective GLP-1 secretagogue that crosses the cell membrane by an unknown mechanism. Immunoblotting demonstrated the presence of fatty acid transport proteins (CD36 and FATP1, 3 and 4) in the murine GLUTag L cell model. The cells demonstrated specific 3H-OA uptake, which was dose-dependently inhibited by unlabeled-OA. Phloretin and SSO, inhibitors of carrier-mediated transport and CD36, respectively, also significantly decreased 3H-OA uptake, as did knocking down FATP4 by transfection of siRNA. OA dose-dependently increased GLP-1 secretion in GLUTag cells, while phloretin and FATP4 knockdown, but not SSO, decreased this response. OA injected directly into the ileum of wild-type mice increased plasma GLP-1 levels; in contrast, preliminary findings suggest decreased GLP-1 levels in FATP4 null mice at 60 min. Collectively, these findings indicate a role for FATP4 in OA-induced GLP-1 secretion.

Purpose: Evidence suggests that olive oil consumption is associated with a decreased prevalence of cardiovascular disease and certain cancers. The purpose of this study was to assess the intake and knowledge of olive oil and other lipids in a collegiate population. Methods: Using an IRB-approved protocol, volunteered college students (N=56) from the college of Health and Human Sciences at Georgia State University completed a questionnaire on lipid and knowledge and eating behavior. Results were assessed to determine if students were able to accurately answer questions on the contents of different lipids, and also to determine the consumption behaviors of different lipids. Statistical comparisons were made between undergraduate and graduate students, and between students in different academic majors (nutrition, nursing, respiratory therapy, social work, criminal justice, and other). Results: It was hypothesized that eating behaviors would overemphasize unhealthy lipids. Lipids assessed included: olive oil, butter, canola oil, peanut oil, corn oil, margarine, sunflower oil, and soybean oil. There were no statistically significant differences between the ratios of consumed lipids labeled as ‘good’, and lipids labeled as ‘bad’. There were also no statistically significant differences in the presence of ‘good’ to ‘bad’ lipids in the subjects’ kitchens. Therefore, the results of this study were not able to disprove the null hypothesis. Nevertheless, using a Likert scale response scheme, there was a difference (p=0.041) between academic majors in the consumption of canola oil (an oil high in monounsaturated fatty acid), with Nursing majors reporting the highest consumption (X=3.73; SD=1.61) and Respiratory Therapy majors reporting the lowest consumption (X=1.89; SD=1.53). There was no statistically significant difference between graduate and undergraduate students in the presence of lipids in the kitchen. It was hypothesized that subject knowledge of lipid constituents would be poor. The majority of subjects either failed to respond correctly to the constituents of different lipids or reported that they did not know. Based on this result, the study is able to reject the lipid knowledge null hypothesis. There were clear differences in subgroup knowledge of commonly consumed lipids. Most notably, 100% of nutrition students responded correctly to the constituents of olive oil. Conclusions: This study focused on a group of college students in the College of Health and Human Sciences. One might assume that such a population would be sensitive and knowledgeable about key dietary factors that may influence disease risk. Nevertheless, these findings indicate that, except for isolated exceptions, the eating behaviors and lipid knowledge of these students in not at a level that could be considered health promoting. This suggests that, even with students in the health sciences, personal health classes are likely to be beneficial in reducing disease prevalence.

There is a growing interest in documenting the effect of diet on the ability to convert saturated fatty acids (SFA) to monounsaturated fatty acids (MUFA) by modulating expression of the SCD gene. We propose that if cattle were raised to a constant body weight, their MUFA:SFA ratio will be the same regardless of being calf-fed (CF) or yearling-fed (YF). Twenty-four Angus cattle were acquired for this study. Cattle were slaughtered at weaning at 8 mo of age (SFCF, n=4), eight steers were assigned to the CF group and slaughtered at 12 mo of age (MFCF, n=4) and 16 mo of age (LFCF, n=4). Twelve cattle were assigned to the YF group and slaughtered at 12 mo of age (SFYF, n=4) 16 mo of age (MFYF, n=4) and market weight of 525 kg (LFYF, n=4). Cattle were then statistically analyzed based on time on high energy diet. Fatty acids from digesta, plasma, liver, L. dorsi, and s.c. and i.m. adipose tissue were all analyzed by FAME. In s.c. 18:1 and 16:1 were greatest in LFCF (41.27% and 5.58%, respectively, P = 0.05), and 18:0 and 16:0 did not differ between groups (P > 0.10). MUFA:SFA ratios of s.c. tended to be higher in LFCF animals (1.26) vs. LFYF (1.06, P = 0.10). However, there was no difference seen when comparing CF to YF animals (P = 0.26). MUFA:SFA ratio was higher in i.m. (P = 0.03) and also increased with age (P < .01). A trained sensory panel saw no significant differences between palatability of flavor characteristics of cooked steaks from LFCF, MFYF, or LFYF (P > 0.05). We showed increased SCD gene expression in the LFYF (248.41 to 1528.69 SCD/GAPDH, P = 0.01). Expression was higher in YF (P = 0.04), but their initial deposits of SFA, combined with the lack of SCD expression while on pastures, prevented the MUFA:SFA ratio from increasing at a rate fast enough to change the final ratios in the animal.

Oleic acid (18:1) is one of the important monounsaturated fatty acids, which is synthesized upon desaturation of stearic acid and this reaction is catalyzed by the SSI2 encoded stearoyl-acyl-carrier-protein-desaturase. A mutation in SSI2 leads to constitutive activation of salicylic acid (SA)-mediated defense responses. Consequently, these plants accumulate high levels of SA and show enhanced resistance to bacterial and oomycete pathogens. Replenishing 18:1 levels in ssi2 plants, via a second site mutation in GLY1 encoded glycerol-3-phosphate (G3P) dehydrogenase, suppresses all the ssi2-triggered phenotypes. Study of mechanism(s) underlying gly1-mediated suppression of ssi2 phenotypes showed that 18:1 levels are regulated via acylation with G3P and a balance between G3P and 18:1 is critical for the regulation of defense signaling pathways. To establish a role for 18:1 and G3P during host defense, interaction between Colletotrichum higginsianum and Arabidopsis was studied. Resistance to C. higginsianum correlated with host G3P levels. The gly1 plants showed increased susceptibility while act1 plants, defective in utilization of G3P, showed enhanced resistance. Plant overexpessing GLY1 showed enhanced resistance in both wild type as well as camalexin deficient backgrounds. Together, these results suggested that G3P conferred resistance acted downstream or independent of camalexin. Exogenous application of glycerol lowered 18:1 levels and produced ssi2-like phenotypes in wild-type plants. Furthermore, glycerol application or the ssi2 mutation produced similar phenotypes in fatty acid desaturation mutants and mutants defective in SA/resistance gene signaling. Expression studies showed that ssi2 phenotypes were likely due to increased expression of resistance genes. Epistatic analysis suggested that certain components of SA pathway had redundant function and were required for 18:1-regulated signaling.

The coalburg seam coal is an example of difficult to float bituminous coal. Laboratory tests conducted on coalburg flotation feed sample revealed recovery values around 28% with 15% product ash when using fuel oil as collector under natural pH conditions. A detailed study showed that increasing pH from natural value of 5.6 to 7.5 provided a significant improvement in recovery of approximately 32 absolute percentage points. The improvement is believed to be result of the release of humic acids from the surface and the dispersion of clay particles thereby leaving a more hydrophobic surface. Based on the tests conducted with various commercially available collectors, oleic acid was selected as a model collector for oxidized coals. Conventional flotation tests found an increase in combustible recovery of 10 absolute percentage points above the pH improvement using 4:1 blend of fuel oil and oleic acid. The problem of higher ash in conventional cell product due to entrainment was minimized by the use of wash water in a flotation column. A flotation concentrate containing less than 7.5% ash was produced while recovering around 75% of the combustible material. Further testing using fatty acids-fuel oil blend also showed evidence of a near 200% increase in flotation rate.

Le faible coût du glycérol sur le marché a conduit à des études approfondies sur la conversion du glycérol en dérivés à valeur ajoutée. Ce travail se concentre sur l'estérification catalytique du glycérol, avec l'acide oléique, réaction d’intérêt industriel en raison de la grande valeur commerciale des produits obtenus. Dans ce travail, un nouveau catalyseur acide hétérogène présentant une surface hydrophobe a été développé sur le support ZrO2-SiO2 car un catalyseur acide solide tolérant à l'eau est essentiel pour les réactions d'estérification en milieu biphasique produisant de l'eau. Le catalyseur synthétisé (ZrO2-SiO2-Me&Et-PhSO3H) a été préparé par silication et modification de surface en utilisant du triméthoxyméthylsilane (TMMS) et du 2-(4- chlorosulfonylphényl) éthyltriméthoxysilane. La morphologie de surface, les propriétés physicochimiques et texturales, l'acidité et l'hydrophobicité ont été caractérisées. Le mécanisme de modification de la surface du catalyseur est proposé en fonction des résultats de caractérisation complets. Une nouvelle technique pour contrôler le niveau d'acidité et d'hydrophobicité du catalyseur conçu est décrite dans ce travail. L'acidité et l'hydrophobicité du catalyseur ont été réglées en contrôlant la quantité d'agents de modification de surface. Il a pu être montré que l'hydrophobicité du catalyseur était diminuée à mesure que son acidité augmentait. Le catalyseur ZrO2-SiO2-Me & Et-PhSO3H_70 avec 70% molaire de TMMS et 0,62 mmol/g d'acidité est le catalyseur optimal pour l'estérification du glycérol avec l'acide oléique. Enoutre, le rôle de l'hydrophobicité dans la réaction catalytique a été étudié ici. Ce travail a montré qu'à acidité constante du catalyseur, le catalyseur le plus hydrophobe présentait un meilleur rendement. La conversion en utilisant le catalyseur préparé (ZrO2-SiO2-Me et EtPhSO3H_70) est de 88,2% avec une sélectivité en monooléate de glycérol de 53,5% et une sélectivité en dioléate de glycérol de 40,0% (sélectivité combinée de 94% en monooléate et dioléate de glycérol) pour un rapport équimolaire d'acide oléique/glycérol, une température de réaction de 160°C, une concentration massique du catalyseur de 5% par rapport à la masse d’acide oléique introduit, en conditions de réaction sans solvant et avec un temps de réaction de 8 h. Ce travail révèle que l'hydrophobicité et le volume des pores du catalyseur conçu affectent significativement la sélectivité en produit. De plus, les performances du catalyseur hydrophobe ZrO2-SiO2-Me&Et- PhSO3H_70, ont été comparées à celles de la zircone sulfatée (SO42-/ZrO2) et des catalyseurs commerciaux (Amberlyst 15 et Aquivion). Les résultats de corrélation ont montré que le volume moyen des pores (taille des pores) influençait la sélectivité du produit lorsque le catalyseur ZrO2- SiO2-Me&Et-PhSO3H_70 était comparé à trois catalyseurs SO42-/ZrO2 développés à partir de différents précurseurs de zirconium. Ainsi, le catalyseur à volume de pores le plus élevé est favorable à la production de dioléate de glycérol dans des conditions réactionnelles identiques. On peut conclure que le volume et la taille des pores peuvent être utilisés pour contrôler la sélectivité en produit. En outre, cette étude a également révélé que la propriété d'hydrophobicité améliorait la vitesse de réaction initiale. / The low market value of glycerol has led to extensive investigations on glycerol conversion to value-added derivatives. This work focuses on industrially important catalytic esterification of glycerol with oleic acid due to the high commercial value of the resulting products. In this work, a novel heterogeneous acid catalyst featuring hydrophobic surface was developed on ZrO2-SiO2 support as water tolerant solid acid catalyst is vital for biphasic esterification reactions producing water. The synthesized catalyst (ZrO2-SiO2-Me&Et-PhSO3H) was prepared through silication and surface modification using trimethoxymethylsilane (TMMS) and 2-(4-chlorosulfonylphenyl) ethyltrimethoxysilane. The surface morphology, physiochemical and textural properties, acidity and hydrophobicity were characterized. The mechanism of the catalyst surface modification is thereof proposed according to comprehensive characterization results. A novel technique to control acidity and hydrophobicity level of the designed catalyst is disclosed in this work. The acidity and hydrophobicity of the catalyst were tuned by controlling the amount of surface modification agents. It was found that the hydrophobicity of the catalyst decreased as its acidity increased. ZrO2-SiO2-Me&Et-PhSO3H_70 catalyst with 70 mol% of TMMS and 0.62 mmol/g acidity is the optimal catalyst for glycerol esterification with oleic acid. Furthermore, the role of hydrophobicity in catalytic reaction was investigated herein. It was found that at constant catalyst acidity, the more hydrophobic catalyst showed better yield. The conversion using the designed catalyst (ZrO2-SiO2-Me&EtPhSO3H_70) is 88.2% with 53.5% glycerol monooleate selectivity and 40.0% glycerol dioleate selectivity (combined 94% selectivity of glycerol monooleate and dioleate) at equimolar oleic acid-to-glycerol ratio, 160 oC, reaction temperature, 5 wt% catalyst concentration with respect to weight of oleic acid, solvent-less reaction conditions and 8 h reaction time. This work reveals that the hydrophobicity and the pore volume of the designed catalyst significantly affect the product selectivity. In addition, the performance of the hydrophobic designed ZrO2-SiO2-Me&Et-PhSO3H_70 catalyst was used to benchmark with catalytic activity of sulfated zirconia (SO42-/ZrO2) and commercial catalysts (Amberlyst 15 and Aquivion). The correlation results showed that the average pore volume (pore size) influenced the product selectivity when ZrO2-SiO2-Me&Et-PhSO3H_70 catalyst was compared to three SO42-/ZrO2 catalysts that were developed from different zirconium precursors. Whereby, the higher pore volume catalyst is favourable to glycerol dioleate production at identical reaction conditions. It can be concluded that pore volume and size can be used to control the product selectivity. In addition, this study also revealed that hydrophobicity characteristic facilitated initial reaction rate effectively.

Este trabalho investiga a obtenção de nanopartículas (NP) de óxido de ferro por coprecipitação, sua estabilização com surfactantes e caracterização quanto à morfologia e comportamento magnético. Atualmente, as NP estão sendo amplamente utilizadas para aplicações biomédicas, tais como contraste em imagens médicas e sistema de distribuição de drogas. Na síntese das NP foram investigados, parâmetros como a temperatura da reação, o pH da solução e a velocidade de agitação. O estudo da estabilidade comparou dois diferentes surfactantes: o ácido oleico (AO) e o polietileno glicol (PEG). As NP obtidas foram caracterizadas por difração de raios X (DRX), e quanto à sua morfologia por microscopia eletrônica por varredura (MEV) e microscopia eletrônica de transmissão (MET), a qual também proporcionou uma distribuição de tamanho de partículas, com variação entre 5 nm e 10,23 nm. A interação entre o óxido de ferro e seus revestimentos foi caracterizada por espectrocopia no infravermelho (FTIR) e espectrocopia Raman. O comportamento magnético das NP foi caracterizado por magnetometria de gradiente de força alternada (AGFM) e espectroscopia Mössbauer. Os resultados revelaram que as NP de óxido de ferro são tipicamente constituídas por magnetita ( ) revestida com AO e PEG e com um tamanho médio de cristalito entre 4,6 e 19,2 nm, calculado através da equação de Scherrer. O AGFM mostrou que as propriedades magnéticas das partículas foram mais eficientes para as NP com revestimento, do que com as NP sem revestimento, e o valor de magnetização de saturação (M) para a revestida com PEG foi maior quando comparado com a revestida com AO. A espectroscopia Mössbauer foi utilizada para confirmação do óxido de ferro como , para estimar tamanho de partícula quando os espectros são medidos a baixa temperatura e para análise do comportamento superparamagnético das partículas. / This work investigates the obtained nanoparticles (NP) iron oxide by coprecipitation stabilization with surfactants and characterize the morphology and magnetic behavior. Currently, the NP are being widely used for biomedical applications such as contrast in medical imaging and drug delivery system. In the synthesis of NP were investigated parameters such as the reaction temperature, the pH and stirring speed. The stability study compared two different surfactants: oleic acid (OA) and polyethylene glycol (PEG). The NP were characterized by X-ray diffraction (XRD), and morphologically by scanning electron microscopy (SEM) and transmission electron microscopy (TEM), which also provided a distribution of particle size, ranging from 5 nm and 10.23 nm. The interaction between the iron oxide and their coatings was characterized by infrared spectroscopy (FTIR) and Raman spectroscopy. The magnetic behavior of NP was characterized by magnetometry alternating gradient force (AGFM) and Mössbauer spectroscopy. The results show that the NP iron oxide are typically comprised of magnetite ( ) coated with PEG and AO and a crystallite size between 4.6 and 19.2 nm calculated by the Scherrer equation. The AGFM showed that the magnetic properties of the particles were more efficient for the NP uncoated than to NP coated, and the value of saturation magnetization (M) to coated with PEG was higher when compared to coated AO. Mössbauer spectroscopy was used to confirm the iron oxide as , to estimate the size of particle where the spectra are measured at low temperature and to analyze the behavior of superparamagnetic particles.