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MetaCyc Pathway: vernolate biosynthesis I

Enzyme View:

Pathway diagram: vernolate biosynthesis I

This view shows enzymes only for those organisms listed below, in the list of taxa known to possess the pathway. If an enzyme name is shown in bold, there is experimental evidence for this enzymatic activity.

Synonyms: vernolic acid biosynthesis I

Superclasses: Biosynthesis Fatty Acid and Lipid Biosynthesis Fatty Acid Biosynthesis Epoxylated Fatty Acids Biosynthesis Vernolate Biosynthesis
Biosynthesis Fatty Acid and Lipid Biosynthesis Fatty Acid Biosynthesis Unsaturated Fatty Acid Biosynthesis

Some taxa known to possess this pathway include ? : Crepis palaestina , Vernonia galamensis

Expected Taxonomic Range: Viridiplantae

Summary:
About This Pathway

Vernolate (vernolic acid) is an unusual fatty acid with an 18-carbon chain that contains a cis double bond at position 9 and an epoxy group at positions 12-13. This unusual fatty acid is found in high concentration (from 60 up to 75%) in seed oils of several Asteraceae genera, including Stokesia, Vernonia, and Crepis [Gunstone54, Badami80], as well as certain Euphorbiaceae species such as Euphorbia lagascae [Kleiman65] and Bernardia pulchella [Spitzer96]. Small amount of vernolate and related epoxy fatty acids are also found in Avena sativa (white oat) [Leonova08, Doehlert10].

Epoxy fatty acids are valuable products and are widely used as plastisizers. The ability of the epoxy group to crosslink makes vernolate-containing oils useful in adhesives and coating materials such as paint [Perdue86]. It can also be used as a precursor of monomeric components of nylon-11 and nylon-12 [Ayorinde89, Ayorinde97].

Epoxy fatty acids are valuable products and are widely used as plastisizers. The ability of the epoxy group to crosslink makes vernolate-containing oils useful in adhesives and coating materials such as paint [Perdue86]. It can also be used as a precursor of monomeric components of nylon-11 and nylon-12 [Ayorinde89, Ayorinde97].

Several types of enzymes have been reported to catalyze the synthesis of vernolate from linoleate. A cytochrome P450 that acts on linoleate bound to phosphatidylcholine [Bafor93] as well as on free linoleate [Blee93] has been described from developing seeds of Euphorbia lagascae (see vernolate biosynthesis II). The same plant was also reported to have a peroxygenase that can epoxidize free linoleate to generate vernolate [Blee93, Meesapyodsuk11] (see vernolate biosynthesis III). In Crepis palaestina a fatty acid desaturase-like enzyme is responsible for the epoxidation (this pathway) [Lee98b].

General Background

In Crepis palaestina a fatty acid desaturase-like enzyme is responsible for the epoxidation [Lee98b]. When the enzyme was expressed in Arabidopsis thaliana, the seed oil from the recombinant plants was found to contain 15% vernolate [Lee98b].

Study of the enzyme from Vernonia galamensis showed that the enzyme acts of vernolate incorporated into phosphatidylcholine. After the synthesis the vernolate groups are transferred to the triacylglycerol pool, where they accumulate [Liu98d]. The enzyme from Vernonia galamensis was shown to be a desaturase-type enzyme [Hitz98].

Variants: (5Z)-dodec-5-enoate biosynthesis , (5Z)-icosenoate biosynthesis , cis-vaccenate biosynthesis , gondoate biosynthesis (anaerobic) , petroselinate biosynthesis , ricinoleate biosynthesis , sapienate biosynthesis , superpathway of unsaturated fatty acids biosynthesis (E. coli) , vernolate biosynthesis II , vernolate biosynthesis III

Credits:
Created 15-Aug-2008 by Zhang P , TAIR
Revised 10-Feb-2015 by Caspi R , SRI International


References

Ayorinde89: Ayorinde FO, Powers FT, Streete LD, Shepard RL, Tabi DN (1989). "Synthesis of dodecanedioic acid from vernonia galamensis oil." Journal of the American Oil Chemists' Society 66(5);690-692.

Ayorinde97: Ayorinde FO, Nana EY, Nicely PD, Woods AS, Price EO, Nwaonicha CP (1997). "Syntheses of 12-aminododecanoic and 11-aminoundecanoic acids from vernolic acid." Journal of the American Oil Chemists' Society 74(5);531-538.

Badami80: Badami RC, Patil KB (1980). "Structure and occurrence of unusual fatty acids in minor seed oils." Prog Lipid Res 19(3-4);119-53. PMID: 7033990

Bafor93: Bafor M, Smith MA, Jonsson L, Stobart K, Stymne S (1993). "Biosynthesis of vernoleate (cis-12-epoxyoctadeca-cis-9-enoate) in microsomal preparations from developing endosperm of Euphorbia lagascae." Arch Biochem Biophys 303(1);145-51. PMID: 8489257

Blee93: Blee E, Stahl U, Schuber F, Stymne S (1993). "Regio- and stereoselectivity of cytochrome P-450 and peroxygenase-dependent formation of cis-12,13-epoxy-9(Z)-octadecenoic acid (vernolic acid) in Euphorbia lagascae." Biochem Biophys Res Commun 197(2);778-84. PMID: 8267615

Doehlert10: Doehlert DC, Angelikousis S, Vick B (2010). "Accumulation of Oxygenated Fatty Acids in Oat Lipids During Storage." Cereal Chemistry 87(6);532-537.

Gunstone54: Gunstone F D (1954). "Fatty acids. Part II. The nature of the oxygenated acid present in Vernonia anthelmintica(Willd.) seed oil." Journal of the Chemical Society 1611-1616.

Hitz98: Hitz WD (1998). "Fatty acid modifying enzymes from developing seeds of Vernonia galamensis." U.S. Patent No. 5,846,784.

Kleiman65: Kleiman R, Smith C R, Yates S G, Jones Q (1965). "Search for new industrial oils. XII. Fifty-eight euphorbiaceae oils, including one rich in vernolic acid." Journal of the American Oil Chemists' Society 42(3);169-172.

Lee98b: Lee M, Lenman M, Banas A, Bafor M, Singh S, Schweizer M, Nilsson R, Liljenberg C, Dahlqvist A, Gummeson PO, Sjodahl S, Green A, Stymne S (1998). "Identification of non-heme diiron proteins that catalyze triple bond and epoxy group formation." Science 280(5365);915-8. PMID: 9572738

Leonova08: Leonova S, Shelenga T, Hamberg M, Konarev AV, Loskutov I, Carlsson AS (2008). "Analysis of oil composition in cultivars and wild species of oat (Avena sp.)." J Agric Food Chem 56(17);7983-91. PMID: 18707115

Liu98d: Liu L, Hammond EG, Nikolau BJ (1998). "In vivo studies of the biosynthesis of vernolic acid in the seed of Vernonia galamensis." Lipids 33(12);1217-21. PMID: 9930408

Meesapyodsuk11: Meesapyodsuk D, Qiu X (2011). "A peroxygenase pathway involved in the biosynthesis of epoxy Fatty acids in oat." Plant Physiol 157(1);454-63. PMID: 21784965

Perdue86: Perdue RE, Carlson KD, Gilbert MG (1986). "Vernonia galamensis, Potential new crop source of epoxy acid." Economic Botany 40(1);54-68.

Spitzer96: Spitzer V, Aitzetmuller K, Vosmann K (1996). "The seed oil of Bernardia pulchella (Euphorbiaceae) - A rich source of vernolic acid." Journal of the American Oil Chemists' Society 73(12);1733-1735.

Other References Related to Enzymes, Genes, Subpathways, and Substrates of this Pathway

Latendresse13: Latendresse M. (2013). "Computing Gibbs Free Energy of Compounds and Reactions in MetaCyc."

Lederer94: Lederer F (1994). "The cytochrome b5-fold: an adaptable module." Biochimie 76(7);674-92. PMID: 7893819

Napier03: Napier JA, Michaelson LV, Sayanova O (2003). "The role of cytochrome b5 fusion desaturases in the synthesis of polyunsaturated fatty acids." Prostaglandins Leukot Essent Fatty Acids 68(2);135-43. PMID: 12538077


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Please cite the following article in publications resulting from the use of MetaCyc: Caspi et al, Nucleic Acids Research 42:D459-D471 2014
Page generated by SRI International Pathway Tools version 19.0 on Thu Jul 30, 2015, biocyc11.