Composition analysis of normal plant triacylglycerols and hydroperoxidized rac-l-stearoyl-2-oleoyl-3-linoleoyl-sn-glycerols by liquid chromatography-atmospheric pressure chemical ionization mass spectrometry

Kusaka, Takashi; Ishihara, Sachiko; Sakaida, Masako; Mifune, Akiko; Nakano, Yukiko; Tsuda, Kazumi; Ikeda, Mitsunori; Nakano, Hiroyuki

doi:10.1016/0021-9673(95)00996-5

Cited by 34 publications

(12 citation statements)

References 10 publications

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“…On the basis of previous work with standard oxotriacylglycerols (22,42), the earlier eluted peak was attributed to an aldehyde in the secondary position and the later eluted peak to an aldehyde in the primary position of the oxidized triacylglycerol molecule. A functional group in the sn-2 position is known to exert higher polarity than a similar group in the sn-1 or sn-3 position of the triacylglycerol molecule (22,43,44). Furthermore, each regioisomer possessed a double peak, which was attributed to a partial resolution of the syn/anti isomers of the DNPH derivatives.…”

Section: Discussionmentioning

confidence: 97%

Formation of triacylglycerol core aldehydes during rapid oxidation of corn and sunflower oils with tert‐butyl hydroperoxide/Fe²⁺

Sjövall

Kuksis

Kallio

2002

Lipids

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The lipid ester core aldehydes formed during a rapid oxidation (7.8 M tert-butyl hydroperoxide, 90 min at 37 degrees C) of the triacylglycerols of purified corn and sunflower oils were isolated as dinitrophenylhydrazones by preparative thin-layer chromatography and identified by reversed-phase high-performance liquid chromatography with on-line electrospray ionization mass spectrometry and by reference to standards. A total of 113 species of triacylglycerol core aldehydes were specifically identified, accounting for 32-53% of the 2,4-dinitrophenylhydrazine (DNPH)-reactive material of high molecular weight representing 25-33% of the total oxidation products. The major core aldehyde species (50-60% of total triacylglycerol core aldehydes) were the mono(9-oxo)nonanoyl- and mono(12-oxo)-9,10-epoxy dodecenoyl- or (12-oxo)-9-hydroxy-10,11-dodecenoyl-diacylglycerols. A significant proportion of the total (9-oxo)nonanoyl and epoxidized (12-oxo)-9,10-dodecenoyl core aldehydes was found in complex combinations with hydroperoxy or hydroxy fatty acyl groups (6-10% of total triacylglycerol core aldehydes). Identified were also di(9-oxo)nonanoylmonoacylglycerols (0.5% of total) and tri(9-oxo)nonanoylglycerols (trace). The identification of the oxoacylglycerols was consistent with the products anticipated from tert-butyl hydroperoxide oxidation of the major species of corn and sunflower oil triacylglycerols (mainly linoleoyl esters). However, the anticipated (13-oxo)-9,11-tridecadienoyl aldehyde-containing acylglycerols were absent because of further oxidation of the dienoic core aldehyde. A significant proportion of the unsaturated triacylglycerol core aldehydes contained tert-butyl groups linked to the unsaturated fatty chains via peroxide bridges (2-9%). The study demonstrates that rapid peroxidation with tert-butyl hydroperoxide constitutes an effective method for enriching natural oils and fats in triacylglycerol core aldehydes for biochemical and metabolic testing.

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Section: Discussionmentioning

confidence: 97%

Formation of triacylglycerol core aldehydes during rapid oxidation of corn and sunflower oils with tert‐butyl hydroperoxide/Fe²⁺

Sjövall

Kuksis

Kallio

2002

Lipids

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“…Reverse-phase analyses were performed on 10-mL injections using a program of 10 min of isocratic methanol followed by a 20-min gradient of 0 to 25% methylene chloride in methanol, at a flow rate of 0.3 mL/min. In addition to the MH þ value found for each TAG species in the APCI-MS spectra, fragmentation peaks corresponding to the loss of the sn-1 and sn-3 fatty acids were also observed (Kusaka et al, 1996). The fragmentation was increased with in-source collision-induced dissociation, causing the 2-monoacylglycerol fragment to become more prominent.…”

Section: Yeast Strains Cell Culturing and Extraction Of Lipidsmentioning

confidence: 96%

Tung Tree DGAT1 and DGAT2 Have Nonredundant Functions in Triacylglycerol Biosynthesis and Are Localized to Different Subdomains of the Endoplasmic Reticulum

et al. 2006

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Seeds of the tung tree (Vernicia fordii) produce large quantities of triacylglycerols (TAGs) containing ;80% eleostearic acid, an unusual conjugated fatty acid. We present a comparative analysis of the genetic, functional, and cellular properties of tung type 1 and type 2 diacylglycerol acyltransferases (DGAT1 and DGAT2), two unrelated enzymes that catalyze the committed step in TAG biosynthesis. We show that both enzymes are encoded by single genes and that DGAT1 is expressed at similar levels in various organs, whereas DGAT2 is strongly induced in developing seeds at the onset of oil biosynthesis. Expression of DGAT1 and DGAT2 in yeast produced different types and proportions of TAGs containing eleostearic acid, with DGAT2 possessing an enhanced propensity for the synthesis of trieleostearin, the main component of tung oil. Both DGAT1 and DGAT2 are located in distinct, dynamic regions of the endoplasmic reticulum (ER), and surprisingly, these regions do not overlap. Furthermore, although both DGAT1 and DGAT2 contain a similar C-terminal pentapeptide ER retrieval motif, this motif alone is not sufficient for their localization to specific regions of the ER. These data suggest that DGAT1 and DGAT2 have nonredundant functions in plants and that the production of storage oils, including those containing unusual fatty acids, occurs in distinct ER subdomains.

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“…In order to be satisfactory, an ionisation method should be chosen that produces MS information on both the molecular weight as well as characteristic fragment ions to facilitate the identification of both the location and the nature of functional groups formed upon oxidation. Ionisation techniques such as (low voltage) electron ionisation [41] and (atmospheric pressure) chemical ionisation [31,36,42] are therefore thought to be more suitable than electrospray (ESI) [29, 43 -45] unless MS/MS is performed. More recently, the coupling of matrix assisted laser desorption/ionisation (MALDI) or ESI with Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) has proven suitable for the analysis of oxygenated TAGs without prior chromatographic separation [46,47].…”

Section: Fatty Acid B) C)mentioning

confidence: 99%

Effects of traditional processing methods of linseed oil on the composition of its triacylglycerols

Berg¹,

Vermist

Carlyle

et al. 2004

J of Separation Science

105

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Different oil processing methods were performed, which included washing with water and treatment with lead-based driers, with and without heating to different temperatures, giving a set of 7 oils to be investigated. The effects of the traditional processing methods of linseed oil on its triacylglycerol (TAG) composition were studied, using the following analytical methods: high performance size exclusion chromatography (HPSEC), Fourier transform infrared spectroscopy (FTIR), high-performance liquid chromatography-atmospheric pressure chemical ionisation-mass spectrometry (HPLC-APCI-MS), direct temperature resolved mass spectrometry (DTMS), matrix assisted laser desorption/ionisation time-of-flight mass spectrometry (MALDI-TOF-MS), and electrospray ionisation Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICR-MS). A decrease of the initial cis-double bonds and the formation of trans-double bonds upon heating of the oils was observed. Heating a lead and oil mixture to 150 degrees C, or heating the oil alone to 300 degrees C led to the highest degree of oxidation. A difference was observed for the oxidation patterns for oils with and without the addition of lead. Furthermore, levels of oxygen incorporation were higher when lead was added to the oil. High temperature treatment of the oils resulted in an increased average molecular weight. The changes in the initial conformation of the double bond systems observed with FTIR were supported by HPLC-APCI-MS measurements that showed the formation of a number of new isomeric TAGs in the heated oil compared to freshly pressed, untreated oil. Oligomerisation up to hexamers was observed with HPSEC, and MALDI-TOF-MS. The formation of oligomers up to trimers only, however, was observed with ESI-FTICR-MS. Incorporation of oxygen was mainly observed with MALDI-TOF-MS and ESI-FTICR-MS whereas with DTMS and FTIR hardly any evidence was found for this.

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Composition analysis of normal plant triacylglycerols and hydroperoxidized rac-l-stearoyl-2-oleoyl-3-linoleoyl-sn-glycerols by liquid chromatography-atmospheric pressure chemical ionization mass spectrometry

Cited by 34 publications

References 10 publications

Formation of triacylglycerol core aldehydes during rapid oxidation of corn and sunflower oils with tert‐butyl hydroperoxide/Fe²⁺

Formation of triacylglycerol core aldehydes during rapid oxidation of corn and sunflower oils with tert‐butyl hydroperoxide/Fe²⁺

Tung Tree DGAT1 and DGAT2 Have Nonredundant Functions in Triacylglycerol Biosynthesis and Are Localized to Different Subdomains of the Endoplasmic Reticulum

Effects of traditional processing methods of linseed oil on the composition of its triacylglycerols

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Composition analysis of normal plant triacylglycerols and hydroperoxidized rac-l-stearoyl-2-oleoyl-3-linoleoyl-sn-glycerols by liquid chromatography-atmospheric pressure chemical ionization mass spectrometry

Cited by 34 publications

References 10 publications

Formation of triacylglycerol core aldehydes during rapid oxidation of corn and sunflower oils with tert‐butyl hydroperoxide/Fe2+

Formation of triacylglycerol core aldehydes during rapid oxidation of corn and sunflower oils with tert‐butyl hydroperoxide/Fe2+

Tung Tree DGAT1 and DGAT2 Have Nonredundant Functions in Triacylglycerol Biosynthesis and Are Localized to Different Subdomains of the Endoplasmic Reticulum

Effects of traditional processing methods of linseed oil on the composition of its triacylglycerols

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Formation of triacylglycerol core aldehydes during rapid oxidation of corn and sunflower oils with tert‐butyl hydroperoxide/Fe²⁺

Formation of triacylglycerol core aldehydes during rapid oxidation of corn and sunflower oils with tert‐butyl hydroperoxide/Fe²⁺