RESUMEN
The use of an ELS detector in NP-HPLC for quantitative analysis of oxidation products in FAME obtained from oils is evaluated in this study. The results obtained have shown that the ELS detector enables the quantitative determination of the hydroperoxides of oleic and linoleic acid methyl esters as a whole, and connected in series with a UV detector makes it possible to determine both groups of compounds by difference, providing useful complementary information. The limits of detection (LOD) and quantification (LOQ) found for hydroperoxides were respectively 2.5 and 5.7 µg mL⻹ and precision of quantitation expressed as coefficient of variation was lower than 10%. Due to a low sensitivity the ELS detector shows limitations to determine the low contents of secondary oxidation products in the direct analysis of FAME oxidized at low or moderate temperature. Analysis of FAME samples obtained either from high linoleic sunflower oil (HLSO) or high oleic sunflower oil (HOSO) and oxidized at 80 °C showed that only ketodienes formed from methyl linoleate can be determined in samples with relatively high oxidation, being the LOD and LOQ 0.2 and 0.4 mg/g FAME, respectively, at the analytical conditions applied. The ELS detector also enabled the determination of methyl cis-9,10-epoxystearate and methyl trans-9,10-epoxystearate, which were resolved at the chromatographic conditions applied. Results showed that these compounds, which are formed from methyl oleate, were not detected in the high-linoleic sample, but occurred at non-negligible levels in the oxidized FAME obtained from HOSO.
Asunto(s)
Cromatografía Líquida de Alta Presión/métodos , Ácidos Grasos/análisis , Peróxidos Lipídicos/análisis , Cromatografía Líquida de Alta Presión/instrumentación , Ácidos Grasos/metabolismo , Luz , Límite de Detección , Modelos Lineales , Peróxidos Lipídicos/metabolismo , Aceites de Plantas/química , Aceites de Plantas/metabolismo , Presión , Reproducibilidad de los Resultados , Dispersión de Radiación , Aceite de Girasol , TemperaturaRESUMEN
Quantitative analysis of the main oxidation products of linoleic acid - hydroperoxy-, keto- and hydroxy-dienes - in refined oils is proposed in this study. The analytical approach consists of derivatization of TAGs into FAMEs and direct analysis by HPLC-UV. Two transmethylation methods run at room temperature were evaluated. The reactants were KOH in methanol in method 1 and sodium methoxide (NaOMe) in method 2. Method 1 was ruled out because resulted in losses of hydroperoxydienes as high as 90 wt%. Transmethylation with NaOMe resulted to be appropriate as derivatization procedure, although inevitably also gives rise to losses of hydroperoxydienes, which were lower than 10 wt%, and formation of keto- and hydroxy-dienes as a result. An amount of 0.6-2.1 wt% of hydroperoxydienes was transformed into keto- and hydroxy-dienes, being the formation of the former as much as three times higher. The method showed satisfactory sensitivity (quantification limits of 0.3 µg/mL for hydroperoxy- and keto-dienes and 0.6 µg/mL for hydroxydienes), precision (coefficients of variation ≤ 6% for hydroperoxydienes and ≤ 15% for keto- and hydroxy-dienes) and accuracy (recovery values of 85(± 4), 99(± 2) and 97.0(± 0.6) % for hydroperoxy-, keto- and hydroxy-dienes, respectively). The method was applied to samples of high-linoleic (HLSO), high-oleic (HOSO) and high-stearic high-oleic (HSHOSO) sunflower oils oxidized at 40 °C. Results showed that the higher the linoleic-to-oleic ratio, the higher were the levels of hydroperoxy-, keto- and hydroxy-dienes when tocopherols were completely depleted, i.e. at the end of the induction period (IP). Levels of 23.7, 2.7 and 1.1 mg/g oil were found for hydroperoxy-, keto- and hydroxy-dienes, respectively, in the HLSO when tocopherol was practically exhausted. It was estimated that hydroperoxydienes constituted approximately 100, 95 and 60% of total hydroperoxides in the HLSO, HOSO and HSHOSO, respectively, along the IP.
Asunto(s)
Alquenos/análisis , Peróxido de Hidrógeno/análisis , Aceites de Plantas/química , Hidróxidos , Límite de Detección , Modelos Lineales , Ácido Linoleico/química , Metanol , Ácido Oléico/química , Oxidación-Reducción , Compuestos de Potasio , Reproducibilidad de los Resultados , Ácidos Esteáricos/químicaRESUMEN
Discordances exist in epidemiological studies regarding the association between the intake of nutrients and death and disease. We evaluated the social and health profile of persons who consumed olive oil in a prospective population cohort investigation (Pizarra study) with a 6-year follow-up. A food frequency questionnaire and a 7 d quantitative questionnaire were administered to 538 persons. The type of oil used in food preparation was determined by direct measurement of the fatty acids in samples obtained from the kitchens of the participants at baseline and after follow-up for 6 years. The fatty acid composition of the serum phospholipids was used as an endogenous marker of the type of oil consumed. Total fat intake accounted for a mean 40 % of the energy (at baseline and after follow-up). The concordance in intake of MUFA over the study period was high. The fatty acid composition of the serum phospholipids was significantly associated with the type of oil consumed and with fish intake. The concentration of polar compounds and polymers, indicative of degradation, was greater in oils from the kitchens where sunflower oil or refined olive oil was used, in oils used for deep frying and in oils that had been reused for frying five times or more. Consumption of olive oil was directly associated with educational level. Part of the discordance found in epidemiological studies between diet and health may be due to the handling of oils during food preparation. The intake of olive oil is associated with other healthy habits.
Asunto(s)
Índice de Masa Corporal , Grasas de la Dieta , Ingestión de Energía , Estado de Salud , Estilo de Vida , Aceites de Plantas , Adolescente , Adulto , Anciano , Grasas Insaturadas en la Dieta , Conducta Alimentaria , Femenino , Humanos , Masculino , Islas del Mediterráneo , Persona de Mediana Edad , Aceite de Oliva , Fosfolípidos/sangre , Estudios Prospectivos , España , Encuestas y Cuestionarios , Adulto JovenRESUMEN
BACKGROUND: The family kitchen resembles an uncontrolled laboratory experiment, and some discrepancies in the relation between the risk of hypertension and dietary fat may be partly due to the manipulation to which the fats were subjected. OBJECTIVE: We investigated whether deterioration in the quality of the cooking oils in the family household contributes to the risk of high blood pressure. DESIGN: The study was cross-sectional. Anthropometric measurements were obtained for 1226 persons aged 18-65 y who were selected randomly from the municipal census of Pizarra, Spain. An oral-glucose-tolerance test was given to 1020 of these persons. Samples of the cooking oil being used were taken from the kitchens of a random subset of 538 persons. The concentrations of polar compounds and polymers were used as markers of the deterioration of the oils. The strength of association between variables was measured by calculating the odds ratio from logistic models. RESULTS: Hypertension was strongly associated with obesity and was influenced by sex, diabetes, and age. The presence of excess polar compounds in the cooking oil and the use of sunflower oil were related to the risk of hypertension, whereas the concentration of monounsaturated fatty acids in the serum phospholipids was negatively related to this risk. These associations remained after inclusion in the models of age, sex, obesity, and the presence of carbohydrate metabolism disorder. CONCLUSIONS: The risk of hypertension is positively and independently associated with the intake of cooking oil polar compounds and inversely related to blood concentrations of monounsaturated fatty acids.
Asunto(s)
Culinaria , Grasas de la Dieta/administración & dosificación , Ácidos Grasos Monoinsaturados/sangre , Hipertensión/sangre , Hipertensión/etiología , Adolescente , Adulto , Factores de Edad , Anciano , Culinaria/métodos , Estudios Transversales , Diabetes Mellitus/sangre , Diabetes Mellitus/fisiopatología , Grasas de la Dieta/análisis , Grasas de la Dieta/normas , Grasas Insaturadas en la Dieta/administración & dosificación , Grasas Insaturadas en la Dieta/análisis , Femenino , Humanos , Hipertensión/epidemiología , Modelos Logísticos , Masculino , Persona de Mediana Edad , Obesidad/sangre , Obesidad/fisiopatología , Oportunidad Relativa , Factores Sexuales , España/epidemiologíaRESUMEN
Virgin olive oils were subjected to simulated common domestic processing, including frying, microwave heating, and boiling with water in a pressure cooker. The impact of these processes on polyphenol content and physicochemical characteristics of oils was assessed. Thermal oxidation of oils at 180 degrees C caused a significant decrease in hydroxytyrosol- and tyrosol-like substances. In contrast, oils heated for 25 h still retained a high proportion of the lignans 1-acetoxypinoresinol and pinoresinol. Thermal oxidation also resulted in a rapid degradation of alpha-tocopherol and the glyceridic fraction of oils. Microwave heating of oils for 10 min caused only minor losses in polyphenols, and the oil degradation was lower than that in thermoxidation assays. Again, lignans were the least affected polyphenols and did not change during microwave heating. Boiling a mixture of virgin olive oil and water in a pressure cooker for 30 min provoked the hydrolysis of the secoiridoid aglycons and the diffusion of the free phenolics hydroxytyrosol and tyrosol from the oil to the water phase. Losses of polyphenols were detected only at pH lower than 6. Moreover, alpha-tocopherol and the glyceridic fraction of oils were not modified during this process. It is worth noting that all the heating methods assayed resulted in more severe polyphenols losses and oil degradation for Arbequina than for Picual oil, which could be related to the lower content in polyunsaturated fatty acids of the latter olive cultivar. These findings may be relevant to the choice of cooking method and olive oil cultivar to increase the intake of olive polyphenols.
Asunto(s)
Flavonoides , Manipulación de Alimentos/métodos , Calor , Fenoles/análisis , Alcohol Feniletílico/análogos & derivados , Aceites de Plantas/química , Polímeros/análisis , Fenómenos Químicos , Química Física , Cromatografía Líquida de Alta Presión , Glicéridos/análisis , Lignanos/análisis , Microondas , Aceite de Oliva , Oxidación-Reducción , Alcohol Feniletílico/análisis , Polifenoles , Presión , alfa-Tocoferol/análisisRESUMEN
In this paper, changes in ultrasonic properties during thermoxidation of virgin olive oil were studied. Samples of virgin olive oil were heated over different periods of time from 2 to 16 h at 200 degrees C. Oil degradation was characterized by means of physical and chemical changes, i.e., viscosity, color, polar compounds, polymers, and polar fatty acids. Ultrasonic measurements were carried out while the oil sample was cooled from 35 to 25 degrees C. It was found that velocity and attenuation measurements were related to viscosity measurements through a classical equation for viscous liquids. The ultrasonic measurements were also related to the percentages of polar compounds and polymers, which shows the feasibility of using ultrasonic properties to monitor oil quality. Nevertheless, as long as the ultrasonic measurements are temperature dependent, this variable must be controlled in order to obtain repetitive and reliable measurements.