Abstract
A high-performance liquid chromatographic method, using post-column detection with diphenyl-1-pyrenyl-phosphine (DPPP), was developed for the quantitative and qualitative determination of isomeric lipid hydroperoxides (OOH). The OOH eluted from a normal-phase column were passed through a photodiode array detector and then mixed with DPPP solution in a reaction coil heated at 80°C. DPPP oxide formed by the reaction with OOH was determined by monitoring the fluorescence intensity at 380 nm and excitation at 352 nm. The conjugated diene OOH (13-cis, trans- and 9-cis, trans-OOH) and nonconjugated OOH (12-cis-trans- and 10-cis, trans-OOH) from photosensitized oxidation of methyl linoleate were determined in a molar ratio of 31∶29∶19∶21, respectively. However, only the two conjugated hydroperoxides were detected by ultraviolet absorption at 234 nm. Further applications were carried out for the determination of OOH of methyl oleate and methyl linolenate. This method proved to be useful for the determination of the OOH containing both conjugated and nonconjugated diene structures.
Article PDF
Similar content being viewed by others
Avoid common mistakes on your manuscript.
Abbreviations
- DPPP:
-
diphenyl-1-pyrenylphosphine
- FAME:
-
fatty acid methyl ester
- GC/MS:
-
gas chromatography/mass spectrometry
- HPLC:
-
high-performance liquid chromatography
- OOH:
-
hydroperoxide
- TMS:
-
trimethylsilyl
- UV:
-
ultraviolet
References
Chan, H.W.S., and Levett, G. (1977) Autoxidation of Methyl Linoleate. Separation and Analysis of Isomeric Mixtures of Methyl Linoleate Hydroperoxides and Methyl Hydroxylinoleates,Lipids 12, 99–104.
Neff, W.E., Frankel, E.N., and Weisleder, D. (1981) High Pressure Liquid Chromatography of Autoxidized Lipids: II. Hydroperoxy-Cyclic Peroxides and Other Secondary Products from Methyl Linolenate,Lipids 16, 439–448.
Coxon, D.T., Price, K.R., and Chan, H.W.S. (1981) Formation, Isolation and Structure Determination of Methyl Linolenate Diperoxides,Chem. Phys. Lipids 28, 365–378.
Yamamoto, Y., Brodsky, M.H., Baker, J.C., and Ames, B.N. (1987) Detection and Characterization of Lipid Hydroperoxides at Picomole Levels by High-Performance Liquid Chromatography,Anal. Chem. 160, 7–13.
Miyazawa, T., Yasuda, K., and Fujimoto, K. (1987) Chemiluminescence High Performance Liquid Chromatography of Phosphatidylcholine Hydroperoxide,Anal. Lett. 20, 915–925.
Yamamoto, Y., and Niki, E. (1989) Presence of Cholesteryl Ester Hydroperoxide in Human Blood Plasma,Biochem. Biophys. Res. Commun. 165, 989–993.
Miyazawa, T. (1989) Determination of Phospholipid Hydroperoxides in Human Blood Plasma by a Chemiluminescence-HPLC Assay,Free Rad. Biol. Med. 7, 209–217.
Miyazawa, T., Suzuki, T., Fujimoto, K., and Yasuda, K. (1992) Chemiluminescent Simultaneous Determination of Phosphatidylcholine Hydroperoxide and Phosphatidylethanolamine Hydroperoxide in the Liver and Brain of the Rat,J. Lipid Res. 33, 1051–1059.
Akaska, K., Suzuki, T., Ohrui, H., and Meguro, H. (1987) Study on Aromatic Phosphines for Novel Fluorometry of Hydroperoxides (II)—The Determination of Lipid Hydroperoxides with Diphenyl-1-Pyrenylphosphine,Anal. Lett. 20, 797–907.
Akasaka, K., Ohrui, H., and Meguro, H. (1993) Determination of Triacylglycerol and Cholesterol Ester Hydroperoxides in Human Plasma by High-Performance Liquid Chromatography with Fluorometric Postcolumn Detection,J. Chromatogr. 617, 205–211.
Akasaka, K., Ohrui, H., and Meguro, H. (1994) Measurement of Cholesterol Hydroperoxides of High and Combined Low and Very Low Lipoprotein in Human Plasma,Biosci. Biotech. Biochem. 58, 396–399.
Akasaka, K., Ohata, A., Ohrui, H., and Meguro, H. (1995) Automatic Determination of Hydroperoxides of Phosphatidylcholine and Phosphatidylethanolamine in Human Plasma,J. Chromatogr. 665B, 37–43.
Neff, W.E., and Frankel, E.N. (1980) Quantitative Analyses of Hydroxystearate Isomers from Hydroperoxides by High Pressure Liquid Chromatography of Autoxidized and Photosensitized-Oxidized Fatty Esters,Lipids 15, 587–590.
Frnakel, E.N., Neff, W.E., and Bessler, T.R. (1979) Analysis of Autoxidized Fats by Gas Chromatography-Mass Spectrometry: V. Photosensitized Oxidation,Lipids 14, 961–967.
Chan, H.W.S. and Levett, G. (1977) Oxidation of Methyl Oleate: Separation of Isomeric Hydroperoxyoctadecenoates and Methyl Hydroxystearates by High performance Liquid Chromatography,Chem. Ind. (London), 692–693.
Frankel, E.N. (1985) Chemistry of Free Radical and Singlet Oxidation of Lipids,Prog. Lipid Res. 23, 197–221.
Terao, J., and Matsushita, S. (1977) Geometric Isomers of Monohydroperoxides Formed by Autoxidation of Methyl Linoleate,Agric. Biol. Chem. 41, 2401–2405.
Kondo, Y., Kawai, Y., Miyazawa, T., and Mizutani, J. (1993) Chemiluminescence-HPLC Analysis of Fatty Acid Hydroperoxide Isomers,Biosci. Biotech. Biochem. 57, 1575–1576.
Toyoda, I., Terao, J., and Matsushita, S. (1982) Hydroperoxides Formed by Ferrous Ion-Catalyzed Oxidation of Methyl Linolenate,Lipids 17, 84–90.
Yamauchi, R., Yamada, T., Kato, K., and Ueno, Y. (1983) Monohydroperoxides Formed by Autoxidation and Photosensitized Oxidation of Methyl Eicosapentaenoate,Agric. Biol. Chem. 47, 2897–2902.
VanRollins, M., and Murphy, R.C. (1984) Autoxidation of Docosahexaenoic Acid: Analysis of Ten Isomers of Hydroxydocosahexaenoate,J. Lipid Res. 25, 507–517.
Author information
Authors and Affiliations
About this article
Cite this article
Ohshima, T., Hopia, A., German, J.B. et al. Determination of hydroperoxides and structures by high-performance liquid chromatography with post-column detection with diphenyl-1-pyrenylphosphine. Lipids 31, 1091–1096 (1996). https://doi.org/10.1007/BF02522467
Received:
Revised:
Accepted:
Issue Date:
DOI: https://doi.org/10.1007/BF02522467