Abstract
Soybean phosphatidylcholine (PC) and dilinoleoyl PC (di-18∶2 PC) were oxidized with singlet molecular oxygen using methylene blue as the photosensitizer. The oxidation products, PC monohydroperoxides (PC-MHP) and PC dihydroperoxides (PC-DHP), were isolated by reverse phase liquid chromatography, and their structures were analyzed by nuclear magnetic resonance (NMR) and gas chromatography-mass spectrometry (GC-MS). Signals for the hydroperoxy proton appeared downfield in NMR spectra of PC-MHP and PC-DHP. Soybean PC-MHP and di-18∶2 PC-MHP were converted to trimethylsilyl (TMS) derivatives of hydrogenated diglycerides when treated with phospholipase C and hydrogenated. Thetert-butyldimethylsilyl (TBDMS) derivatives of hydrogenated diglycerides were also prepared from di-18∶2 PC-MHP. Fragmentation of the TMS and TBDMS derivatives was obtained in electron impact mass spectra. The isomeric composition of hydroperoxylinoleate component in di-18∶2 PC-MHP was determined by methanolysis of the hydrogenated diglyceride and mass chromatographic analysis of the resulting isomeric hydroxy octadecanoates.
Similar content being viewed by others
References
Tabbel, A.L., Fed. Proc. 32:1870 (1973).
Mead, J.F., in “Free Radicals in Biology,” Vol. 1, edited by W.A. Pryor, Academic Press, New York, 1976, pp. 51–68.
Lundberg, W.O., and P. Jarvi, in “Progress in the Chemistry of Fats and Other Lipids,” Vol. 9, edited by R.T. Holman, Pergamon Press, Oxford, 1971, pp. 377–406.
Chan, H.W.-S., and G. Levett, Lipids 12:99 (1977).
Chan, H.W.-S., and G. Levett, Lipids 12:1055 (1977).
Porter, N.A., R.A. Wolf, E.M. Yarbro and H. Weenen, Biochem. Biophys. Res. Commun. 89:1058 (1979).
Terao, J., and S. Matsushita, Agric. Biol. Chem. 39:2027 (1975).
Frankel, E.N., W.E. Neff, W.K. Rohwedder, B.P.S. Khambay, R.F. Garwood and G.C.L. Weedon, Lipids 12:901 (1977).
Frankel, E.N., W.E. Neff, W.K. Rohwedder, B.P.S. Khambay, R.F. Garwood and B.C.L. Weedon, Lipids 12:908 (1977).
Frankel, E.N., W.E. Neff, W.K. Rohwedder, B.P.S. Khambay, R.F. Garwood and B.C.L. Weedon, Lipids 12:1055 (1977).
Crawford, C.G., R.D. Plattner, D.J. Sessa and J.J. Rackis, Lipids 15:91 (1980).
Porter, N.A., R.A. Wolf and H. Weenen, Lipids 15:163 (1980).
Nakano, M., T. Noguchi, K. Sugiota, H. Fukuyama and M. Sato, J. Biol. Chem. 250:2404 (1975).
Nakano, M., K. Takayama, Y. Shimizu, Y. Tsuji, H. Inaba and T. Migita, J. Am. Chem. Soc. 98:1974 (1976).
King, M.M., E.F. Lai and P.B. McCay, J. Biol. Chem. 250:6496 (1975).
Smith, L.L., and J.I. Teng, J. Am. Chem. Soc. 96:2040 (1974).
Pederson, T., and S.D. Aust, Biochim. Biophys. Acta 397:232 (1975).
Rawls, H.R., and P.A. Van Santen, J. Am. Oil Chem. Soc. 47:121 (1970).
Clements, A.H., R.H. Van Den Engh, J. Frost, K. Hogenhout and J.R. Nool, J. Am. Oil Chem. Soc. 50:325 (1973).
Terao, J., and S. Matsushita, J. Am. Oil Chem. Soc. 54:234 (1977).
Porter, N.A., J. Logan and V. Kontoyiannidou, J. Org. Chem. 44:3177 (1979).
Frankel, E.N., W.E. Neff and T.R. Bessler, Lipids 14:961 (1979).
Terao, J., and S. Matsushita, J. Food Process. Pres. 3:329 (1980).
Terao, J., and S. Matsushita, Agric. Biol. Chem. 45:587 (1981).
Lea, C.H., D.H. Rhodes and R.D. Stoll, Biochem. J. 60:353 (1955).
Selingen, Z., and Y. Lapidot, J. Lipid Res. 7:174 (1966).
Chadha, J.S., Chem. Phys. Lipids 4:105 (1970).
Patel, K.M., J.D. Morriset and J.T. Sparrow, J. Lipid Res. 20:674 (1979).
Bartlett, G.R., J. Biol. Chem. 234:466 (1959).
Nishihara, M., and M. Kito, Biochim. Biophys. Acta 531:25 (1978).
Casparrini, G., M.G. Horning and E.C. Horning, Anal. Lett. 1:481 (1968).
Horning, M.G., G. Casparrini and E.C. Horning, J. Chromatogr. Sci. 7:267 (1969).
Satouchi, K., and K. Saito, J. Biomed. Mass Spectrom. 6:396 (1979).
Gollnick, K., in “Singlet Oxygen,” edited by B. Ranby and J.F. Rabeck, Wiley (Interscience), New York, 1978, pp. 111–134.
Terao, J., and S. Matsushita, Agric. Biol. Chem. 42:667 (1978).
Author information
Authors and Affiliations
About this article
Cite this article
Terao, J., Hirota, Y., Kawakatsu, M. et al. Structural analysis of hydroperoxides formed by oxidation of phosphatidylcholine with singlet oxygen. Lipids 16, 427–432 (1981). https://doi.org/10.1007/BF02535010
Received:
Issue Date:
DOI: https://doi.org/10.1007/BF02535010