Samples of oils of different degrees of unsaturation, namely palm olein, olive oil, highlinoleic sunflower oil, high-oleic sunflower oil, rapeseed oil and soybean oil, were heated at 180°C for 2, 4, 6, 8 and 10 h in the presence or absence of their natural antioxidants. Also, tocopherol-stripped oils were supplemented with a-tocopherol (500 mg kg À1 ), d-tocopherol (500 mg kg À1 ) or a mixture of a-, b-, g-and d-tocopherols (250 mg kg À1 each) and heated under the same conditions. Losses of tocopherols and formation of polymeric triacylglycerols were followed. Total polar compounds were also evaluated after 10 h of heating. Results demonstrated that tocopherols were lost very rapidly, in the expected order, with a-tocopherol being the least stable. Polymeric and polar compound formation during heating was inhibited to a variable extent, being more dependent on the natural content and type of tocopherols than on the degree of unsaturation of the oil. For example, polymeric and polar compound contents in soybean oil were significantly lower than those found in high-linoleic sunflower oil. However, the expected influence of the degree of unsaturation was evident when oils were unprotected or possessed identical initial antioxidant contents. Finally, levels of degradation compounds after 10 h of heating were not dependent on the remaining content of antioxidants. INTRODUCTIONIn a previous study we stressed the interest in defining the action of natural antioxidants, particularly concerning the relationships between loss of antioxidants and formation of new compounds at the high temperature of processes such as frying. 1 With this aim we initiated a series of experiments to determine the influence of tocopherols on the alteration of the lipid substrate without the influence of minor uncontrolled compounds normally present in the oils, which might exert an antioxidant or pro-oxidant effect. We selected three model systems constituted by monoacid triacylglycerols, ie triolein, trilinolein and a 50:50 mixture of the two, of clearly differentiated degrees of unsaturation, and both loss of tocopherols and triacylglycerol degradation were analysed after heating at frying temperature for different periods of time. The results obtained indicated that, under the conditions used, addition of tocopherols had a protective action at high temperature, particularly when a mixture of the four

In deep‐fat frying the food is completely surrounded by the frying fat or oil and different events occur within a few minutes: dehydration of food surface, absorption of fat, formation of flavour compounds, development of surface colour, etc. Due to the drastic conditions applied during deep‐frying, the frying fat also undergoes degradation. Although much work has been done on modifications of used frying fats and oils under different conditions, changes in the fried substrate have been much less studied. Particularly, there is minimal information on some physical and chemical aspects of the interactions between frying fats and fried foods. In this paper the main changes in the frying fat due to the nature of the food fried in it as well as modifications in the food as a consequence of the fat or oil used as heat transfer medium are reviewed. Fat absorption and lipid exchanges are the main physical changes involved. Chemical reactions include interaction between food constituents and oxidised lipids as well as hydrolysis of frying fats due to food moisture.

This work was aimed at studying lipid oxidation in dried microencapsulated oils (DMOs) during long-term storage. Samples were prepared by freeze-drying of emulsions containing sodium caseinate and lactose as encapsulating components. Evaluation of lipid oxidation was approached by quantitative analysis of nonvolatile lipid oxidation products and tocopherol. Lipid oxidation products were analyzed by separation of polar compounds by adsorption chromatography followed by HPSEC with refraction index detection for quantitation of oxidized triglyceride monomers, dimers, and oligomers. The analytical method applied enabled the detection of different oxidative patterns between the free and encapsulated oil fractions. The free oil fraction of DMOs showed a typical oxidative pattern for oils in continuous phase, which consisted of a clear induction period, in which hydroperoxides (oxidized triglyceride monomers) accumulated, before oxidation accelerated. The end of the induction period was marked by the total loss of tocopherol and the initiation of polymerization. On the contrary, the encapsulated oil showed a pattern characteristic of a mixture of oils with different oxidation status. Thus, high contents of advanced oxidation compounds (polymerization compounds) were detected when the antioxidant (tocopherol) was still present in high amounts. It is concluded that the encapsulated oil was comprised of oil globules with very different oxidation status. The results obtained in this study gave evidence of heterogeneous aspects of lipid oxidation in a dispersed-lipid food system.

The formation and evolution of monoepoxy fatty acids, arising from oleic and linoleic acids, were investigated in olive oil and conventional sunflower oil, representatives of monounsaturated and polyunsaturated oils, respectively, during thermoxidation at 180 degrees C for 5, 10, and 15 h. Six monoepoxy fatty acids, cis-9,10- and trans-9,10-epoxystearate, arising from oleic acid, and cis-9,10-, trans-9,10-, cis-12,13-, and trans-12,13-epoxyoleate, arising from linoleic acid, were analyzed by gas chromatography after oil derivatization to fatty acid methyl esters. Considerable amounts, ranging from 4.29 to 14.24 mg/g of oil in olive oil and from 5.10 to 9.44 mg/g of oil in sunflower oil, were found after the heating periods assayed. Results showed that the monoepoxides quantitated constituted a major group among the oxidized fatty acid monomers formed at high temperature. For similar levels of degradation, higher contents of the monoepoxides were found in olive oil than in sunflower oil. Ten used frying oils from restaurants and fried-food outlets in Spain were analyzed to determine the contents of the monoepoxides in real frying oil samples. Levels ranged from 3.37 to 14.42 mg/g of oil. Results show that, for similar degradation levels, the monoepoxides were more abundant in the monounsaturated oils than in the polyunsaturated oils.

The degradation of alpha-tocopherol and the formation of alpha-tocopherol and triacylglycerol oxidation products at high temperatures (150-250 degrees C) over a heating period (0-4 h) for a model system ranging between triolein and tripalmitin were modeled by use of an experimental design. The oxidation products of alpha-tocopherol formed under these conditions were alpha-tocopherolquinone (1 .4-7.7%) and epoxy-alpha-tocopherolquinones (4.3-34.8%). The results indicate a very high susceptibility of alpha-tocopherol to capture peroxyl radicals upon oxidation, leading to the formation of polar tocopherol oxidation products. Both alpha-tocopherolquinone and epoxy-alpha-tocopherolquinones were not stable upon prolonged heating and were further degraded to other unknown oxidation products. The kinetics of alpha-tocopherol oxidation were significantly influenced by the triolein/tripalmitin ratio. By increasing the level of triacylglycerol unsaturation the rate of alpha-tocopherol recovery after heating increased significantly from 2.2 to 44.2% whereas in the meantime triacylglycerol polymerization increased from 0 to 3.7%.

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In deep‐fat frying the food is completely surrounded by the frying fat or oil and different events occur within a few minutes: dehydration of food surface, absorption of fat, formation of flavour compounds, development of surface colour, etc. Due to the drastic conditions applied during deep‐frying, the frying fat also undergoes degradation. Although much work has been done on modifications of used frying fats and oils under different conditions, changes in the fried substrate have been much less studied. Particularly, there is minimal information on some physical and chemical aspects of the interactions between frying fats and fried foods. In this paper the main changes in the frying fat due to the nature of the food fried in it as well as modifications in the food as a consequence of the fat or oil used as heat transfer medium are reviewed. Fat absorption and lipid exchanges are the main physical changes involved. Chemical reactions include interaction between food constituents and oxidised lipids as well as hydrolysis of frying fats due to food moisture.

RESUMEN Variables que intervienen en la oxidación lipídica de aceites microencapsulados.Los aceites microencapsulados son alimentos o ingredientes en polvo preparados mediante secado de emulsiones naturales o formuladas, donde los glóbulos de aceite se encuentran dispersos en una matriz de hidratos de carbono y/o proteínas. El estudio de la oxidación lipídica en aceites microencapsulados es muy difícil ya que, además de las numerosas variables implicadas normalmente en la oxidación lipídica, principalmente el grado de insaturación, oxígeno, luz, temperatura, prooxidantes y antioxidantes, en estos sistemas lipídicos heterofásicos existen otros factores que ejercen una importante influencia. En este trabajo, se revisa la situación actual del conocimiento sobre oxidación lipídica en aceites microencapsulados en relación con las variables que intervienen específicamente en la oxidación de estos sistemas lipídicos. Concretamente, dichas variables incluyen las implicadas en el proceso de preparación (tipo y concentración de los componentes de la matriz y procedimiento de secado) y las relacionadas con las propiedades físico-químicas de los aceites microencapsulados (tamaño de partícula, tamaño de glóbulo de aceite, distribución lipídica, actividad del agua, pH e interacciones entre los componentes de la matriz). PALABRAS-CLAVE: Aceites microencapsulados --Antioxidantes -Oxidación lipídica -Sistemas lipídicos heterofásicos SUMMARY Variables affecting lipid oxidation in dried microencapsulated oils.Dried microencapsulated oils are powdery foods or ingredients, prepared by drying natural or formulated emulsions, wherein the oil globules are dispersed in a matrix of saccharides and/or proteins. The study of lipid oxidation in microencapsulated oils is a very difficult task since, in addition to the numerous variables normally involved in lipid oxidation, mainly unsaturation degree, oxygen, light, temperature, prooxidants and antioxidants, other factors exert an important influence in these heterophasic lipid systems. In this paper, the present state of the art on lipid oxidation in dried microencapsulated oils is reviewed, focused on the variables specifically involved in oxidation of these lipid systems. Such variables include those pertaining to the preparation process (type and concentration of the matrix components and drying procedure) and those related to the physicochemical properties of microencapsulated oils (particle size, oil globule size, lipid distribution, water activity, pH and interactions between matrix components).