Minor peroxide components as catalysts and precursors to monocarbonyls in the autoxidation of methyl linoleate

Morita, Makio; Fujimaki, Masao

doi:10.1021/jf60189a035

Cited by 20 publications

(13 citation statements)

References 10 publications

(13 reference statements)

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“…Experimental evidence supports not only the lack of autocatalytic activity of hydroperoxides in the absence of added transition metals (Morita & Fujimaki 1973;Morita & Tokita 1990, 1993 but also the formation of peroxide-linked dimers as significant products even at the early stages of lipid autoxidation (Miyashita et al 1982). …”

Section: Autoxidationmentioning

confidence: 87%

Autoxidation of Conjugated Linoleic Acid Methyl Ester in the Presence of α‐Tocopherol: The Hydroperoxide Pathway

Pajunen

Johansson

Hase

et al. 2008

Lipids

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The autoxidation of conjugated linoleic acid (CLA) is poorly understood in spite of increasing interest in the beneficial biological properties of CLA and growing consumption of CLA-rich foods. In this thesis, the autoxidation reactions of the two major CLA isomers, 9-cis,11-transoctadecadienoic acid and 10-trans,12-cis-octadecadienoic acid, are investigated. The results contribute to an understanding of the early stages of the autoxidation of CLA methyl ester, and provide for the first time a means of producing and separating intact CLA methyl ester hydroperoxides as well as basic knowledge on lipid hydroperoxides and their hydroxy derivatives.Conjugated diene allylic monohydroperoxides were discovered as primary autoxidation products formed during autoxidation of CLA methyl esters in the presence and absence oftocopherol. This established that one of the autoxidation pathways of CLA methyl ester is the hydroperoxide pathway.Hydroperoxides were produced from the two major CLA methyl esters by taking advantage of the effect of -tocopherol to promote hydroperoxide formation. The hydroperoxides were analysed and separated first as methyl hydroxyoctadecadienoates and then as intact hydroperoxides by HPLC. The isolated products were characterized by UV, GC-MS, and NMR techniques. In the presence of a high amount of -tocopherol, the autoxidation of CLA methyl ester yields six kinetically-controlled conjugated diene monohydroperoxides and is diastereoselective in favour of one particular geometric isomer as a pair of enantiomers. The primary autoxidation products produced from the two major CLA isomers include new positional isomers of conjugated diene monohydroperoxides, the 8-, 10-, 12-, and 14-hydroperoxyoctadecadienoates. Furthermore, two of these new positional isomers have an unusual structure for a cis,trans lipid hydroperoxide where the allylic methine carbon is adjacent to the cis instead of the usual trans double bond.The 1 H and 13 C NMR spectra of nine isomeric methyl hydroxyoctadecadienoates and of ten isomeric methyl hydroperoxyoctadecadienoates including the unusual cis,trans hydroperoxides, i.e. Me 8-OOH-9c,11t and Me 14-OOH-10t,12c, were fully assigned with the aid of 2D NMR spectroscopy. The assigned NMR data enabled determination of the effects of the hydroxyl and hydroperoxyl groups on the carbon chemical shifts of CLA isomers, identification of diagnostic signals, and determination of chemical shift differences of the olefinic resonances that may help with the assignment of structure to as yet unknown lipid hydroperoxides either as hydroxy derivatives or as intact hydroperoxides.A mechanism for the hydroperoxide pathway of CLA autoxidation in the presence of a high amount of -tocopherol was proposed based on the characterized primary products, their relative distribution, and theoretical calculations. This is an important step forward in CLA research, where exact mechanisms for the autoxidation of CLA have not been presented before. Knowledge of these hydroperoxide formation steps is of cr...

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Section: Autoxidationmentioning

confidence: 87%

Autoxidation of Conjugated Linoleic Acid Methyl Ester in the Presence of α‐Tocopherol: The Hydroperoxide Pathway

Pajunen

Johansson

Hase

et al. 2008

Lipids

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“…Instead, the major active component extracted from partially autoxidized linoleate was identified as a class of peroxide distinct from hydroperoxides; these C-O-O-C-linked products, subsequently identified as fatty acid dimers, were potent inducers of lipid peroxidation. The titles of the articles give the gist of the findings: "Non-hydroperoxide Peroxides as Autocatalysts of Lipid Peroxidation" (33) and "Minor Peroxide Components as Catalysts and Precursors to Monocarbonyls in the Autoxidation of Methyl Linoleate" (34). As indicated in the latter title, in the course of the work, the role of these peroxides in the production of aldehydes was recognized.…”

Section: Involvement In the Initiation Of Lipidmentioning

confidence: 99%

“…Peroxidation-Beginning with studies in the 1970s, Makio Morita and co-workers (33,34) sought to identify the components in autoxidizing methyl linoleate that would initiate further peroxidation of lipids. Strikingly, they found that in the absence of added transition metals, fatty acid hydroperoxides showed little activity.…”

Section: Involvement In the Initiation Of Lipidmentioning

confidence: 99%

Routes to 4-Hydroxynonenal: Fundamental Issues in the Mechanisms of Lipid Peroxidation

Schneider

Porter

Brash

2008

Journal of Biological Chemistry

238

205

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Although investigation of the toxicological and physiological actions of ␣/␤-unsaturated 4-hydroxyalkenals has made great progress over the last 2 decades, understanding of the chemical mechanism of formation of 4-hydroxynonenal and related aldehydes has advanced much less. The aim of this review is to discuss mechanistic evidence for these non-enzymatic routes, especially of the underappreciated intermolecular pathways that involve dimerized and oligomerized fatty acid derivatives as key intermediates. These cross-molecular reactions of fatty acid peroxyls have also important implications for understanding of the basic initiation and propagation steps during lipid peroxidation and the nature of the products that arise.

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“…Desde luego se admite que a la temperatura ambiente, propia del proceso de curación de este embutido, se suele obtener una escasa proporción de compuestos volátiles en comparación con la cantidad primaria de monohidroperóxidos que se forman (Grosch, 1987). Pero también se admite la posibilidad de que los volátiles se puedan desarrollar por un mecanismo diferente a la degradación de monohidroperóxidos en los productos cárnicos curados (Shahidi et al, 1987), e incluso se ha hablado de peróxidos polares muy lábiles, aunque no se haya podido aclarar su estructura (Morita et al, 1973) (Morita et al, 1976).…”

Section: Tabla 11unclassified

La oxidación de componentes grasos y formación de hexanal en la curación del salchichón

Chasco¹,

Beriain²,

Bello³

1992

Grasas y Aceites

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RESUMENLa oxidación de componentes grasos y formación de hexanai en la curación del salchichón Se ha estudiado la formación de aicanales de cadena corta (C3-C6) durante el proceso de curación de un salchichón estándar elaborado en planta piloto. Se ha comparado sus contenidos finales con los obtenidos para otros tres lotes de salchichón de fabricación industrial (I, II. III). Con excepción del hexanai, que se encuentra en cantidades importantes, los otros tres aldehidos aparecen en cantidades muy reducidas o incluso no se detectan. No se ha obtenido una correlación estadística entre el contenido en hexanai y los niveles de oxidación de los componentes grasos valorados a través del índice de peróxidos, el número T.B.A. o los compuestos carbonilos totales.Sin embargo, sí existe una cierta correlación entre el contenido en hexanai y las relaciones oleico/linoleico de cada lote de salchichón. La ausencia de hexanai en todos los salchichones del lote II viene correspondida por una mayor proporción de ácido linoleico entre sus AGL. Se propone la determinación de hexanai como un modo útil de comprobar si el mecanismo oxidative de las grasas durante el proceso de curación ha sido correcto. PALABRAS-CLAVE: HexanaiLipidie components oxidation and hexanai formation during the curing of saucisson It has studied formation of alcanals of low weight (03-06) during the curing of standard Saucisson manufactured in pilot plant. Aldehydes content have been compared to others obtained in three batches of industrial process (I, li y III). Except to hexanai, present in important amounts, the rest of aldehydes appear in reduced levels even are not detected. Statistical correlation has not been obtained between hexanai content and oxidation levels of lipidie components titrated by peroxides value, T.B.A. number or total carbonyl compounds. However, certain correlation has been found between hexanai content and ratio of oleic/linoleic of each batch of saucisson. Absence of hexanai in all of saucissons of batch II is corresponded by a greater proportion of linoleic acid between their A.G.L. It is proposed determination of hexanai like an useful method to check whether oxidative mechanism of lipids during the curing has been corrected. KEY-WORDS: Curing process Saucisson.Hexanai -Lipidie oxidationdación en su proceso de maduración-desecación, dando lugar a un núnnero importante de sustancias volátiles entre ellas aldehidos (Bailey et al., 1980). Este conjunto de reacciones en el que toman parte los lípidos desempeña un papel importante en el desarrollo del aroma típico de cada embutido (Shahidi, 1989), a través de mecanismos todavía no bien comprendidos (Gray et al., 1984). Una de las reacciones que se considera más relevante en este proceso es la oxidación del ácido linoleico, que lleva a la formación de hexanai (Ellis et al., 1968) (Henderson et al., 1980) (Frankel et al., 1981. La valoración del contenido en este aldehido se ha propuesto como una fórmula válida para predecir la calidad de algunos aceites vegetales (Dupuy et al., 1976) ...

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Minor peroxide components as catalysts and precursors to monocarbonyls in the autoxidation of methyl linoleate

Cited by 20 publications

References 10 publications

Autoxidation of Conjugated Linoleic Acid Methyl Ester in the Presence of α‐Tocopherol: The Hydroperoxide Pathway

Autoxidation of Conjugated Linoleic Acid Methyl Ester in the Presence of α‐Tocopherol: The Hydroperoxide Pathway

Routes to 4-Hydroxynonenal: Fundamental Issues in the Mechanisms of Lipid Peroxidation

La oxidación de componentes grasos y formación de hexanal en la curación del salchichón

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