Advertisement

Biochemistry (Moscow)

, Volume 74, Issue 8, pp 855–861 | Cite as

Specificity of oxidation of linoleic acid homologs by plant lipoxygenases

  • I. R. ChechetkinEmail author
  • E. V. Osipova
  • N. B. Tarasova
  • F. K. Mukhitova
  • M. Hamberg
  • Y. V. Gogolev
  • A. N. Grechkin
Article

Abstract

The lipoxygenase-catalyzed oxidation of linoleic acid homologs was studied. While the linoleic acid oxidation by maize 9-lipoxygenase (9-LO) specifically produced (9S)-hydroperoxide, the dioxygenation of (11Z,14Z)-eicosadienoic (20:2) and (13Z,16Z)-docosadienoic (22:2) acids by the same enzyme lacked regio- and stereospecificity. The oxidation of 20:2 and 22:2 by 9-LO afforded low yields of racemic 11-, 12-, 14-, and 15-hydroperoxides or 13- and 17-hydroperoxides, respectively. Soybean 13-lipoxygenase-1 (13-LO) specifically oxidized 20:2, 22:2, and linoleate into (ω6S)-hydroperoxides. Dioxygenation of (9Z,12Z)-hexadecadienoic acid (16:2) by both 9-LO and 13-LO occurred specifically, affording (9S)- and (13S)-hydroperoxides, respectively. The data are consistent with the “pocket theory of lipoxygenase catalysis” (i.e. with the penetration of a substrate into the active center with the methyl end first). Our findings also demonstrate that the distance between carboxyl group and double bonds substantially determines the positioning of substrates within the active site.

Key words

lipoxygenase enzyme-substrate interaction polyenoic fatty acid oxylipin 

Abbreviations

GC-MS

gas chromatography-mass spectrometry

HPLC

high performance liquid chromatography

9-LO

maize 9-lipoxygenase CSSAP 92

13-LO

soybean lipoxygenase-1

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. 1.
    Liavonchanka, A., and Feussner, I. (2006) J. Plant Physiol., 163, 348–357.PubMedCrossRefGoogle Scholar
  2. 2.
    Grechkin, A. (1998) Prog. Lipid Res., 37, 317–352.PubMedCrossRefGoogle Scholar
  3. 3.
    Egmond, M. R., Vliegenthart, J. F. G., and Boldingh, J. (1972) Biochem. Biophys. Res. Commun., 48, 1055–1060.PubMedCrossRefGoogle Scholar
  4. 4.
    Gardner, H. W. (1989) Biochim. Biophys. Acta, 1001, 274–281.PubMedGoogle Scholar
  5. 5.
    Borngraber, S., Browner, M., Gillmor, S., Gerth, C., Anton, M., Fletterick, R., and Kuhn, H. (1999) J. Biol. Chem., 274, 37345–37350.PubMedCrossRefGoogle Scholar
  6. 6.
    Ruddat, V. C., Mogul, R., Chorny, I., Chen, C., Perrin, N., Whitman, S., Kenyon, V., Jacobson, M. P., Bernasconi, C. F., and Holman, T. R. (2004) Biochemistry, 43, 13063–13071.PubMedCrossRefGoogle Scholar
  7. 7.
    Gillmor, S. A., Villasenor, A., Fletterick, R., Sigal, E., and Browner, M. F. (1997) Nat. Struct. Biol., 4, 1003–1009.PubMedCrossRefGoogle Scholar
  8. 8.
    Hornung, E., Walther, M., Kuhn, H., and Feussner, I. (1999) Proc. Natl. Acad. Sci. USA, 96, 4192–4197.PubMedCrossRefGoogle Scholar
  9. 9.
    Hughes, R. K., Lawson, D. M., Hornostaj, A. R., Fairhurst, S. A., and Casey, R. (2001) Eur. J. Biochem., 268, 1030–1040.PubMedCrossRefGoogle Scholar
  10. 10.
    Schwarz, K., Walther, M., Anton, M., Gerth, C., Feussner, I., and Kuhn, H. (2001) J. Biol. Chem., 276, 773–779.PubMedCrossRefGoogle Scholar
  11. 11.
    Coffa, G., and Brash, A. R. (2004) Proc. Natl. Acad. Sci. USA, 101, 15579–15584.PubMedCrossRefGoogle Scholar
  12. 12.
    Coffa, G., Imber, A. N., Maguire, B. C., Laxmikanthan, G., Schneider, C., Gaffney, B. J., and Brash, A. R. (2005) J. Biol. Chem., 280, 38756–38766.PubMedCrossRefGoogle Scholar
  13. 13.
    Butovich, I. A., and Reddy, C. C. (2001) Biochim. Biophys. Acta, 1546, 379–398.PubMedGoogle Scholar
  14. 14.
    Boeglin, W. E., Itoh, A., Zheng, Yu., Coffa G., Howe, G. A., and Brash, A. R. (2008) Lipids, 43, 979–987.PubMedCrossRefGoogle Scholar
  15. 15.
    Chechetkin, I. R., Mukhitova, F. K., Gogolev, Yu. V., and Grechkin, A. N. (2007) Dokl. Ros. Akad. Nauk, 415, 829–831.Google Scholar
  16. 16.
    Ivanov, I., Schwarz, K., Holzhutter, H. G., Myagkova, G., and Kuhn, H. (1998) Biochem. J., 336, 345–352.PubMedGoogle Scholar
  17. 17.
    Ivanov, I., Rathmann, J., Myagkova, G., and Kuhn, H. (2001) Biochemistry, 40, 10223–10229.PubMedCrossRefGoogle Scholar
  18. 18.
    Hamberg, M., Chechetkin, I. R., Grechkin, A. N., Ponce de Leon, I., Castresana, C., and Bannenberg, G. (2006) Lipids, 41, 499–506.PubMedCrossRefGoogle Scholar
  19. 19.
    Chechetkin, I. R., Blufard, A., Hamberg, M., and Grechkin, A. N. (2008) Phytochemistry, 69, 2008–2015.PubMedCrossRefGoogle Scholar

Copyright information

© Pleiades Publishing, Ltd. 2009

Authors and Affiliations

  • I. R. Chechetkin
    • 1
    Email author
  • E. V. Osipova
    • 1
  • N. B. Tarasova
    • 1
  • F. K. Mukhitova
    • 1
  • M. Hamberg
    • 2
  • Y. V. Gogolev
    • 1
  • A. N. Grechkin
    • 1
  1. 1.Kazan Institute of Biochemistry and Biophysics, Kazan Scientific CenterRussian Academy of SciencesKazanRussia
  2. 2.Department of Medical Biochemistry and Biophysics, Division of Physiological Chemistry IIKarolinska InstitutetStockholmSweden

Personalised recommendations