Mechanism of 1,4-dehydrogenation catalyzed by a fatty acid (1,4)-desaturase of Calendula officinalis

European Journal of Biochemistry

Volumn 269, Issue 20, 2002, Pages 5024-5029

  Reed, Darwin W ^a   Savile, Christopher K ^b   Qiu, Xiao ^a   Buist, Peter H ^b   Covello, Patrick S ^a  

^a NATIONAL RESEARCH COUNCIL CANADA   (Canada)

^b CARLETON UNIVERSITY   (Canada)

Author keywords

Calendula; Conjugated fatty acid; Desaturase; Deuterium labelling; Kinetic isotope effect

Indexed keywords

1,4 DESATURASE; FATTY ACID DERIVATIVE; HYDROGEN; ISOTOPE; LINOLEIC ACID; UNCLASSIFIED DRUG;

ARTICLE; CALENDULA; CATALYST; CONTROLLED STUDY; ENZYME DEGRADATION; ENZYME MECHANISM; FATTY ACID ANALYSIS; GAS CHROMATOGRAPHY; HYDROGEN BOND; HYDROGENATION; MASS SPECTROMETRY; NONHUMAN; OXIDATION; PRIORITY JOURNAL; PROTEIN EXPRESSION; SACCHAROMYCES CEREVISIAE;

BIOCHEMISTRY; CALENDULA; CATALYSIS; DEUTERIUM; FATTY ACID DESATURASES; ISOTOPE LABELING; LINOLEIC ACID; LINOLEIC ACIDS; OXIDATION-REDUCTION; SACCHAROMYCES CEREVISIAE;

CALENDULA; CALENDULA OFFICINALIS; SACCHAROMYCES; SACCHAROMYCES CEREVISIAE;

EID: 0036413788     PISSN: 00142956     EISSN: None     Source Type: Journal    
DOI: 10.1046/j.1432-1033.2002.03209.x     Document Type: Article

References (41)

1. Shanklin, J. & Cahoon, E.B. (1998) Desaturation and related modifications of fatty acids. Annu. Rev. Plant Physiol. Plant Mol. Biol. 49, 611-641.
2. Lee, M., Lenman, M., Banas, A., Bafor, M., Singh, S., Schweizer, M., Nilsson, R., Liljenberg, C., Dahlqvist, A., Gummeson, P.-O., Sjödahl, S., Green, A. & Stymne, S. (1998) Identification of non-heme diiron proteins that catalyze triple bond and epoxy group formation. Science 280, 915-918.
3. Okuley, J., Lightner, J., Feldmann, K., Yadav, N., Lark, E. & Browse, J. (1994) Arabidopsis fad2 gene encodes the enzyme that is essential for polyunsaturated lipid synthesis. Plant Cell 6, 147-158.
4. Heinz, E. (1993) Biosynthesis of polyunsaturated fatty acids. In: Lipid Metabolism in Plants (Moore, T.S. Jr, ed.), pp. 33-89. CRC Press, Boca Raton.
5. Van de Loo, F.J., Broun, P., Turner, S. & Somerville, C. (1995) An oleate 12-hydroxylase from Ricinus communis L. is a fatty acyl desaturase homolog. Proc. Natl Acad. Sci. USA 92, 6743-6747.
6. Qiu, X., Reed, D.W., Hong, H., MacKenzie, S.L. & Covello, P.S. (2001) Identification and analysis of a gene from Calendula offcinalis encoding a fatty acid conjugase. Plant Physiol. 125, 847-855.
7. Cahoon, E.B., Carlson, T.J., Ripp, K.G., Schweiger, B.J., Cook, G.A., Hall, S.E. & Kinney, A.J. (1999) Biosynthetic origin of conjugated double bonds: Production of fatty acid components of high-value drying oils in transgenic soybean embryos. Proc. Natl Acad. Sci. USA 96, 12935-12940.
8. 12-oleic- acid desaturase-related enzymes: Biosynthetic origin of calendic acid. J. Biol. Chem. 276, 2637-2643.
9. Pariza, M.W., Park, Y. & Cook, M.E. (2001) The biologically active isomers of conjugated linoleic acid. Prog. Lipid Res. 40, 283-298.
10. Derksen, J.T.P., Cuperus, F.P. & Kolster, P. (1995) Paints and coatings from renewable resources. Ind. Crops Prod. 3, 225-236.
11. Crombie, L. & Holloway, S.J. (1985) The biosynthesis of calendic acid, octadeca-(8E,10E,12IX)-trienoic acid, by developing marigold seeds: Origins of (E,E,Z) and (Z,E,Z) conjugated triene acids in higher plants. J. Chem. Soc. Perkin Trans. I, 2425-2434.
12. 12 desaturase: A kinetic isotope effect study. J. Am. Chem. Soc. 120, 871-876.
13. 9 desaturation. J. Am. Chem. Soc. 118, 6295-6296.
14. 11-myristoyl-CoA desaturase involved in the biosynthesis of Spodoptera littoralis sex pheromone. Biochemistry 38, 15272-15277.
15. 9 desaturase that transforms (E)-11-tetradecenoic acid into Z and E-9,11-tetradecadienoic acid. Angew. Chem. Int. Ed. 39, 3279-3281.
16. Meesapyodsuk, D., Reed, D.W., Savile, C.K., Buist, P.H., Ambrose, S.J. & Covello, P.S. (2000) Characterization of the regiochemistry and cryptoregiochemistry of a Caenorhabditis elegans fatty acid desaturase (FAT-1) expressed in Saccharomyces cerevisiae. Biochemistry 39, 11948-11954.
17. 9 fatty acid desaturase from Spirulina platensis C1 (Arthrospira sp. PCC 9438). Comp Biochem. Physiol. B Biochem. Mol. Biol. 129, 831-835.
18. Savile, C.K., Reed, D.W., Meesapyodsuk, D., Covello, P.S. & Buist, P.H. (2001) Cryptoregiochemistry of a Brassica napus fatty acid desaturase (FAD3): A kinetic isotope effect study. J. Chem. Soc., Perkins Trans. 1, 1116-1121.
19. 4 desaturase initiates substrate oxidation at C- 4. J. Am. Chem. Soc. 123, 4382-4385.
20. 6 desaturation. J. Org. Chem. 66, 1210-1215.
21. Fauconnot, L. & Buist, P.H. (2001) Cryptoregiochemical analysis of an unusual bacterial desaturation. Bioorg. Med. Chem. Lett. 11, 2879-2881.
22. Behrouzian, B., Fauconnot, L., Daligault, F., Nugier-Chauvin, C., Patin, H. & Buist, P.H. (2001) Mechanism of fatty acid desaturation in the green alga Chlorella vulgaris. Eur. J. Biochem. 268, 3545-3549.
23. Cook, G.K. & Mayer, J.M. (1994) C-H bond activation by metaloxo species: Oxidation of cyclohexane by chromyl chloride. J. Am. Chem. Soc. 116, 1855-1868.
24. Buist, P.H. & Marecak, D.M. (1992) Stereochemical analysis of sulfoxides obtained by diverted desaturation. J. Am. Chem. Soc. 114, 5073-5080.
25. Buist, P.H., Alexopoulos, K.A., Behrouzian, B., Dawson, B. & Black, B. (1997) Synthesis and desaturation of monofluorinated fatty acids. J. Chem. Soc. Perkin Trans. 1, 2617-2624.
26. Broun, P., Shanklin, J., Whittle, E. & Somerville, C. (1998) Catalyic plasticity of fatty acid modification enzymes underlying chemical diversity of plant lipids. Science 282, 1315-1317.
27. 2]-non-3-enal. J. Chem. Soc., Perkins Trans. 1929-1937.
28. Toke, D.A. & Martin, C.E. (1996) Isolation and characterization of a gene affecting fatty acid elongation in Saccharomyces cerevisiae. J. Biol. Chem. 271, 18413-18422.
29. Ausubel, F.M., Brent, R., Kingston, R.E., Moore, D.D., Seidman, J.G., Smith, J.A., Struhl, K., Albright, L.M., Coen, D.M. & Varki, A., eds (1995) Current Protocols in Molecular Biology. John Wiley and Sons, New York.
30. Schroepfer, G.J. & Bloch, K. (1965) The stereospecific conversion of stearic acid to oleic acid. J. Biol. Chem. 240, 54-63.
31. Baenziger, J.E., Smith, I.C.P. & Hill, R.J. (1990) Biosynthesis and characterization of a series of deuterated cis, cis-octadeca-6,9-dienoic acids. J. Chem. Phys. Lipids 54, 17-23.
32. Rahier, A. (2001) Deuterated Delta (7)-cholestenol analogues as mechanistic probes for wild-type and mutated delta (7)-sterol-C5 (6)-desaturase. Biochemistry 40, 256-267.
33. Rettie, A.E., Boberg, M., Reetenmeier, A.W. & Baillie, T.A. (1988) Cytochrome P-450-catalyzed desaturation of valproic acid in vitro: species differences, induction effects, and mechanistic studies. J. Biol. Chem. 263, 13733-13738.
34. Enoch, H.G., Catalá, A. & Strittmatter, P. (1976) Mechanism of rat liver microsomal stearyl-CoA desaturase. Studies of the substrate specificity, enzyme-substrate interactions, and the function of lipid. J. Biol. Chem. 251, 5095-5103.
35. Northrop, D.B. (1981) The expression of isotope effects on enzyme-catalyzed reactions. Annu. Rev. Biochem. 50, 103-131.
36. Morris, L.J. & Marshall, M.O. (1966) Occurence of cis, translinoleic acid in seed oils. Chem. Ind., 1493.
37. Fritsche, K., Hornung, E., Peitzsch, N., Renz, A. & Feussner, I. (1999) Isolation and characterization of a calendic acid producing (8,11)-linoleoyl desaturase. FEBS Lett. 462, 249-253.
38. Morris, L.J., Harris, R.V., Kelly, W. & James, A.T. (1968) The stereochemistry of desaturation of long-chain fatty acids in Chlorella vulgaris. Biochem. J. 109, 673-678.
39. Rodriguez, S., Camps, F. & Fabrias, G. (2001) Synthesis of gem-dideuterated tetradecanoic acids and their use in investigating the enzymatic transformation of (Z)-11-tetradecenoic acid into (E,E)-10,12-tetradecadienoic acid. J. Org. Chem. 66, 8052-8058.
40. Jones, J.P. (1987) The separation of the intermolecular isotope effect for the cytochrome P-450 catalyzed hydroxylation of n-octane into its primary and secondary components. J. Am. Chem. Soc. 109, 2171-2173.
41. Broadwater, J.A., Whittle, E. & Shanklin, J. (2002) Desaturation and hydroxylation. Residues 148 and 324 of Arabidopsis FAD2, in addition to substrate chain length, exert a major influence in partitioning of catalytic specificity. J. Biol. Chem. 277, 15613-15620.