Determination of primary oxidation products of linoleic acid and triacylglycerols

Gladovič, N.; Zupančič‐Kralj, Lucija; Plavec, Janez

doi:10.1016/s0021-9673(97)00004-6

Cited by 13 publications

(9 citation statements)

References 9 publications

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“…NP-HPLC analysis of fatty acids is usually performed after derivatization to picolinyl or methyl esters, but some work has also been done with underivatized free fatty acids [24,25]. Orellena-Coca analyzed epoxidized free fatty acids with a reversed phase (RP)-HPLC-evaporative light scattering detector (ELSD)-MS and MS/MS with good resolution between individual molecular species [26].…”

Section: Introductionmentioning

confidence: 99%

Liquid Chromatography–Light Scattering Detector–Mass Spectrometric Analysis of Digested Oxidized Rapeseed Oil

Tarvainen

Suomela

Kuksis

et al. 2010

Lipids

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Rapeseed oil was oxidized chemically and thermally to produce two distinct oxidized oils. These oils, along with unoxidized oils, were subjected to an artificial digestion model to simulate the digestive processes in humans. Lipid digestion involves lipases that break down the intact triacylglycerol (TAG) molecules first to diacylglycerols, and eventually to sn-2-monoacylglycerols (MAG) and free fatty acids. A high performance liquid chromatography-evaporative light scattering detector-electrospray ionization-mass spectrometric (HPLC-ELSD-ESI-MS) method was developed to monitor the lipolysis and the presence of oxidized lipids. The HPLC-ELSD-ESI-MS analysis enabled the separation and detection of nearly all the lipid species present in the sample after TAG hydrolysis. The HPLC-MS analyses of digestion products revealed that oxidized triacylglycerols are hydrolyzed by the digestive enzymes in a manner similar to that of native, unoxidized molecules. Significant amounts of sn-1(3)-MAG were found in all the samples after lipolysis, however, more of these were found in unoxidized rapeseed oil samples than in the oxidized oils. Several oxidized molecules were identified with the aid of synthesized oxylipids. This novel method is scalable to small-scale preparative fractionation of oxidized lipid molecules from a complex digestion sample. Also, the fingerprint-like, diagnostic, MS profiles of oxidized oils, reference compounds, and digestion products may be a great aid in comprehensive analysis of lipid oxidation and lipolysis.

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Section: Introductionmentioning

confidence: 99%

Liquid Chromatography–Light Scattering Detector–Mass Spectrometric Analysis of Digested Oxidized Rapeseed Oil

Tarvainen

Suomela

Kuksis

et al. 2010

Lipids

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“…These products play an important role in many pathological processes such as atherosclerosis, cancer, Alzheimer's and Parkinson disease [1][2][3][4]. Hydroperoxides further react forming heterogeneous mixtures of volatile, monomeric and polymeric products [5,6]. Among many analytical methods there is no standard method to detect all oxidative changes in foods.…”

Section: Introductionmentioning

confidence: 99%

“…High-performance liquid chromatography (hplc) is one of the techniques used for the determination of lipid oxidation products [18] and has the advantage of enabling the separation of hydroperoxides without derivatization, with good sensitivity, rapidity and small sample consumption [6,19]. After HPLC separation, the detection schemes including UV absorbance, post-column chemiluminescence and electrochemical reduction [20] are used.…”

Section: Introductionmentioning

confidence: 99%

Influence of native antioxidants on the formation of fatty acid hydroperoxides in model systems

Nogala‐Kałucka

Kupczyk

Polewski³

et al. 2007

Euro J Lipid Sci & Tech

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The effect of alpha-tocopherol (alpha-T) and quercetin on the formation of hydroperoxides of linoleic and linolenic acids during autoxidation at 60 6 1 7C was investigated. Three isomers of hydroperoxides were detected using HPLC. Of isomers of linoleic acid hydroperoxides, 13-hydroperoxy-octadecadienoic acid trans-trans (13-HPODE tt), 9-HPODE cis-trans (9-HPODE c-t) and 9-HPODE trans-trans (9-HPODE t-t) were identified, constituting 64, 19 and 17% of the total amount, respectively. For linolenic acid, the components 13-hydroperoxy-octadecatrienoic acid trans-trans (13-HPO-TE t-t), 9-HPOTE c-t and 9-HPOTE t-t contributed 7, 33 and 60% to the total, respectively. The different dominant hydroperoxide isomers detected in linoleic and linolenic acids during oxidation are related to their chemical structure and the microenvironment of emulsion droplets. The ratios between specific isomers for both fatty acid hydroperoxides did not change during oxidation with or without antioxidants. Alpha-T effectively inhibited the oxidation of fatty acids and reduced the formation of hydroperoxides. The total amount of the hydroperoxides decreased along with the increase in the concentration of alpha-T, 1-40 mM. Quercetin inhibited the oxidation of both fatty acids at similar efficiency only at 40 mM concentration. A synergistic antioxidant effect of quercetin with alpha-T in a binary system on both fatty acids was observed.

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“…Thermal or photochemical oxidation of fatty acid chains contained in oils leads to the formation of ROOH as primary oxidation products (2,3). Their structures are those of secondary ROOH in α-position to a double bond (4,5).…”

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confidence: 99%

Long‐term behavior of oil‐based varnishes and paints. Fate of hydroperoxides in drying oils

Mallégol

Gardette

Lemaire

2000

J Americ Oil Chem Soc

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The thermal stability of linseed oil and poppyseed oil hydroperoxides in a temperature range from ambient to 120°C has been investigated on the basis of iodometric titration. The peroxide value (PV) vs. oxidation time curves show similar developments at the six temperatures chosen for the experiments. These curves are characterized by a fast increase in the PV up to a maximal value, followed by a decrease in the PV at a lower rate. The maximal PV is higher when the curing temperature is lowered. This result indicates thermal decomposition of the hydroperoxides. The peroxy crosslink concentration in the dried oil film varies similarly to the hydroperoxide concentration. This indicates that, for dried films, the network is almost totally constituted of ether and C-C crosslinks. A comparison of the rates of peroxide decomposition under thermolytic and thermooxidative conditions has evidenced that the only homolytic scission of the O-O bonds cannot justify the decrease of the PV in thermooxidation. Another mechanism accounting for hydroperoxide decomposition, based on an induced decomposition of the hydroperoxides, has been proposed. These results have permitted completing the description of the curing mechanisms of drying oils.The oxidation of polyunsaturated fatty acids (PUFA) has been extensively reviewed in the literature. The main interest was the study of oxidation of fatty acids contained in food products because even low levels of oxidation often imply a denaturation of the taste or odor of the product.The aim of our research is to study the oxidation of drying oils in paints where the surface/volume ratio is much higher. In a previous article (1), we reported data that showed that the oxidation levels in the dried films were much more important than in the food industry. Mechanisms accounting for the oxidative polymerization of drying oils have been proposed. However, it is of great interest to investigate the influence of temperature on the fate of the hydroperoxide groups (ROOH) formed in the drying step, because secondary oxidation reactions (formation of oxidized by-products and crosslinking) can probably be influenced by the concentrations of alkoxyl and hydroxyl radicals obtained by decomposition of the hydroperoxides.Thermal or photochemical oxidation of fatty acid chains contained in oils leads to the formation of ROOH as primary oxidation products (2,3). Their structures are those of secondary ROOH in α-position to a double bond (4,5). Although the structures of all these ROOH groups are well determined, only a few articles deal with the stability of these products in dried films. The photochemical degradation of ROOH is a well-known property (6), and their thermal instability at high temperatures up to 150°C has been used to determine their structure (7) and to study the structures of the volatile products formed in autoxidation (4,8-11). However, thermal stability of ROOH at lower temperatures (from ambient to 120°C) has received only little attention in thin layers of drying oils, that is, under ...

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Determination of primary oxidation products of linoleic acid and triacylglycerols

Cited by 13 publications

References 9 publications

Liquid Chromatography–Light Scattering Detector–Mass Spectrometric Analysis of Digested Oxidized Rapeseed Oil

Liquid Chromatography–Light Scattering Detector–Mass Spectrometric Analysis of Digested Oxidized Rapeseed Oil

Influence of native antioxidants on the formation of fatty acid hydroperoxides in model systems

Long‐term behavior of oil‐based varnishes and paints. Fate of hydroperoxides in drying oils

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