Characterization, quantitation and evolution of monoepoxy compounds formed in model systems of fatty acid methyl esters and monoacid triglycerides heated at high temperature

Berdeaux, Olivier; Márquez‐Ruiz, Gloria; Dobarganes, M. C.

doi:10.3989/gya.1999.v50.i1.636

Cited by 35 publications

(28 citation statements)

References 18 publications

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“…Nonenzymatic oxidation or autoxidation of fats proceeds via typical free radical mechanisms and hydroperoxides are the initial products. They are relatively unstable and enter into numerous complex reactions involving substrate degradation and interaction, resulting in a myriad of compounds of various molecular weights, flavor thresholds, and biological significance (Berdeaux et al, 1999;Frankel, 1998;Gasparoli, 1998;Hidalgo et al, 1991;Kamal-Eldin and Appelqvist, 1996;Nawar, 1996Nawar, , 1998. The enzymatic oxidation of lipids takes place sequentially.…”

Section: The Role Of Lipids In Nonenzymatic Browningmentioning

confidence: 99%

The role of lipids in nonenzymatic browning

Hidalgo¹,

Zamora²

2000

Grasas y Aceites

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RESUMEN El papel de los lípidos en el pardeamiento no enzimáticoEn este trabajo se hace una revisión del papel de los lípidos en el pardeamiento no enzimático de alimentos mediante el estudio de las reacciones proteína/lípido oxidado en comparación con otras reacciones donde ocurre también este oscurecimiento: la reacción de Maillard, el pardeamiento producido por el ácido ascórbico, y las reacciones de las quinonas con los grupos amino. Los mecanismos propuestos para estas reacciones de producción de color y fluorescencia, así como la formación de melanoidinas, lipofuscinas y productos coloreados de bajo peso molecular son discutidos de forma comparada, concluyendo que el papel de los lípidos en estas reacciones no parece ser muy diferente del papel de los carbohidratos en el Maillard o de los fenoles en el pardeamiento enzimático. Estas reacciones carbonil-amino parecen ser un grupo de reacciones secundarias que ocurren de forma gradual, son parcialmente reversibles, son universales e inevitables y ocurren en alimentos y en sistemas biológicos. Sin embargo, la mayoría de estos resultados han sido obtenidos en sistemas modelo y estudios adicionales deberían ser abordados en sistemas más cercanos a los alimentos y a lo seres vivos, lo que debería repercutir en un mejor entendimiento del pardeamiento no enzimático y, en definitiva, nos daría una visión más completa de la bioquímica de los alimentos y de los seres vivos. PALABRAS-CLAVE: Interacciones proteína-lípido oxidado Pardeamiento no enzimático Reacción de MaillardReacciones amino-carbonilo. SUMMARY The role of lipids in nonenzymatic browningThe role of lipids in nonenzymatic browning is studied by reviewing oxidized lipid/protein reactions in comparison with other reactions where the production of browning is known: the Maillard reaction, the ascorbic acid browning, and the quinone/amine reactions. The mechanisms proposed in these reactions for production of color and fluorescence, as well as the formation of melanoidins, lipofuscins, and low molecular weight colored products are discussed comparatively, concluding that the role of lipids in these reactions does not seem to be very different to the role of carbohydrates in the Maillard reaction or the phenols in the enzymatic browning. These carbonyl-amine reactions seem to be a group of gradual, partially reversible, universal, and inevitable side reactions in both food and biological systems. However, most of these results were obtained in model systems and additional studies should be carried out in systems closer to real foods or living beings, which should provide a more complete understanding of nonenzymatic browning, and, therefore, to afford a much more comprehensive knowledge of food and human biochemistry. KEY-WORDS: Amino-carbonyl reactions Maillard reactionNonenzymatic browning Oxidized lipid-protein interactions.

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Section: The Role Of Lipids In Nonenzymatic Browningmentioning

confidence: 99%

The role of lipids in nonenzymatic browning

Hidalgo¹,

Zamora²

2000

Grasas y Aceites

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“…Estes resultados estão de acordo com Velasco et al (2004a), que em estudo com óleos termoxidados, de oliva, do grupo dos monoinsaturados e de girassol, do grupo dos poliinsaturados, e com óleos e gorduras usados em frituras descontínuas do comércio, concluíram que óleos do grupo de ácidos graxos monoinsaturados apresentam menor tendência à polimerização do que óleos do grupo de ácidos graxos poliinsaturados; e com Berdeaux, Márquez-Ruíz e Dobarganes (1999), que verificaram maior formação de polímeros a partir dos ésteres metílicos do ácido linoléico (poliinsaturado) do que a partir dos ésteres metílicos do ácido oléico (monoinsaturado).…”

Section: Resultsunclassified

“…Os grupos dos ésteres metílicos oxidados (monoepoxiáci-dos, monocetoácidos e monohidroxiácidos) foram identificados mediante cromatografia a gás acoplada à espectrometria de massas com a ajuda dos padrões disponíveis (BERDEAUX et al, 1999;MARMESAT, 2007 no modo de ionização eletrônica (70 eV) acoplado a um cromatógrafo a gás Carlo Erba GC série 8000. Os espectros foram adquiridos em uma faixa de 28-600 a.m.u.. As condições de análises cromatográficas foram as mesmas utilizadas para a determinação da composição de ácidos graxos.…”

Section: Métodos Analíticosunclassified

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Avaliação quantitativa de monoepoxiácidos, monocetoácidos e monohidroxiácidos em óleos e gorduras provenientes de fritura descontínua de batatas

Machado¹,

Marmesat²,

Dobarganes³

et al. 2008

Ciênc. Tecnol. Aliment.

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A fritura é um meio de preparo de alimentos bastante utilizado em todo o mundo. Neste processo o óleo ou gordura é submetido a altas temperaturas na presença de ar e de água. Esta condição propicia a formação de um número considerável de substâncias oriundas de reações térmicas, oxidativas e hidrolíticas (CHANG; PETERSON; HO, 1978;MÁRQUEZ-RUÍZ, 1988; GASPAROLI, 1998;JORGE et al., 1996;MÁRQUEZ-RUIZ;TASIOULA-MARGARI;DOBARGANES, 1995;NAWAR, 1998;SCHWARTZ;RADY;CASTAÑEDA, 1994;VELASCO et al., 2004b). As reações hidrolíticas liberam substâncias como diacilgliceróis e ácidos graxos livres, e as reações térmicas e oxidativas formam um grande número de substâncias como triacilgliceróis dimerizados e polimerizados e monômeros de triacilgliceróis oxidados (VELASCO et al., 2004b).Estes grupos de substâncias constituem os compostos polares (AOAC, 2003). Neste sentido, legislações de muitos países preconizam para óleos e gorduras usados em frituras o valor máximo de 25%, m/m do óleo, em compostos polares (DANA; SAM SAGUY, 2001).A alteração tanto quantitativa quanto qualitativa destes óleos ou gorduras depende de um número elevado de variáveis entre elas, a que está relacionada com a adição de óleo novo AbstractDuring frying, fats and oils undergo degradation with the formation of polar compounds. Among these are polymeric triglycerides, as well as oxidized monomeric triglycerides. The last group has been related to several diseases and contains groups including epoxy, keto and hydroxy groups of importance from a quantitative point of view. In this study, monoepoxyacids, monoketoacids and monohydroxyacids were quantified in partially hydrogenated soybean oil, soybean oil and palm oil, after heating for 25 hours, at 180 °C, in frying experiments. The determination was carried out by gas chromatography after fat derivatization to fatty acid methyl esters at room temperature and concentration of the compounds of interest by solid phase extraction on silica cartridges. Quantitative analyses of polar fatty acids were also obtained by combination of adsorption and size exclusion chromatography. The major content corresponded to polymeric compounds. Amounts ranging from 3.30 to 8.24; from 1.51 to 4.32 and from 3.42 to 8.71 mg.g -1 were found for monoepoxyacids, monoketoacids and monohydroxyacids, respectively, for samples containing polar compounds between 20.8 and 44.1%. The results suggested that monounsaturated oils have a higher tendency to the formation of oxidized monomers while polyunsaturated oils have a higher tendency to the formation of polymers. Keywords: epoxy fatty acids; frying oils; hydroxy fatty acids; keto fatty acids; polar compounds; polymers. ResumoNa fritura, os óleos e gorduras sofrem degradação formando os compostos polares, como os triacilgliceróis polimerizados e os monômeros de triacilgliceróis oxidados, estes últimos têm sido relacionados a patologias e se constituem de grupos como os monoepoxiácidos, monocetoácidos e monohidroxiácidos. Foram determinados os teores destes três grupos de substâncias, atrav...

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“…Base-catalized transesterification is also proved to be suitable for the quantitative analysis of the labile monoepoxy fatty acids, in which the oxirane ring remained unaltered (Berdeaux et al 1999b). Thus, after olive and sunflower frying oil transesterification, 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 (Δ9c,12c-18:2)) were separated and quantified by GC under conditions similar to those applied for short-chain compounds .…”

Section: Oxidized Fatty Acidsmentioning

confidence: 98%

Analytical Methods for Quantification of Modified Fatty Acids and Sterols Formed as a Result of Processing

et al. 2008

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Fats and oils are often submitted to technological treatments before being consumed. Some treatments like refining, hydrogenation, and frying often lead to the formation of modified fatty acids such as cyclic fatty acid monomers (CFAM), geometrical fatty acid isomers, and/or oxidized fatty acids and sterols (cholesterol and phytosterols). Both cholesterol oxidation products (COP) and phytosterol oxidation products (POP), may be present in foods. As some of the newly formed components may present some adverse effects upon consumption, methods have been developed to analyze these compounds in food products and biological samples. Gas liquid chromatography (GC) on long polar columns (100m) is a good choice to quantify trans mono-and polyunsaturated fatty acids. In some cases a pre-fractionation step using silver nitrate thin layer chromatography (AgNO 3 -TLC) may be necessary to avoid GC overlapping of cis and trans isomers. Analysis of CFAM usually involves transformation of the sample in fatty acid methyl esters (FAME) which after addition of an internal standard (IS) are further hydrogenated. An enrichment step using reverse phase high performance liquid chromatography (RP-HPLC) permits to obtain a fraction which consists of a mixture of CFAM and the IS. This fraction is further analyzed by GC on a polar column. The analysis of oxidized triacylglycerol monomers (oxTG) as a group was feasible by a combination of adsorption and sizeexclusion chromatography. Quantification in used frying fats and oils around the limit of rejection for human consumption (25% polar compounds) has shown that the amount of oxTG range 5.9-9.4% expressed on fat or oil weight. In foods and biological tissues, the level of oxidized sterols (SOP) is often a very small fraction of their unoxidized forms. Analysis of SOP involved extraction of lipids, saponification or transesterification, enrichment, and subsequent qualitative and quantitative determination by GC and GC-MS, or HPLC and HPLC-MS. In addition, enrichment of SOP requires complete separation from the unoxidized sterols in order to separate these compounds even by high resolution GC capillary columns.

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Characterization, quantitation and evolution of monoepoxy compounds formed in model systems of fatty acid methyl esters and monoacid triglycerides heated at high temperature

Cited by 35 publications

References 18 publications

The role of lipids in nonenzymatic browning

The role of lipids in nonenzymatic browning

Avaliação quantitativa de monoepoxiácidos, monocetoácidos e monohidroxiácidos em óleos e gorduras provenientes de fritura descontínua de batatas

Analytical Methods for Quantification of Modified Fatty Acids and Sterols Formed as a Result of Processing

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