Divinylether fatty acids explained

Divinylether fatty acids contain a fatty acid chemically combined with a doubly unsaturated carbon chain linked by an oxygen atom (ether).

Fatty acid hydroperoxides generated by plant lipoxygenases from linoleic and linolenic acids are known to serve as substrates for a divinyl ether synthase which produces divinyl ether fatty acids. Divinyl ethers were detected only within the plant kingdom.

The discovery of that class of compounds dates to 1972, when the structures of two ether C18 fatty acids generated by homogenates of the potato tuber were described.[1] These compounds, named colneleic acid (from linoleic acid) and colnelenicacid (from linolenic acid), could be also produced in potato leaves and tomato roots by rearrangement of 9-hydroperoxides. Isomers of colneleic acid and colnelenic acid were isolated from homogenates of leaves of Clematis vitalba (Ranunculaceae).[2]

Similarly, 13-lipoxygenase-generated hydroperoxides serve as precursor of other divinyl ether fatty acids which are produced in bulbs of garlic[3] or Ranunculus leaves.[4] These compounds were named etheroleic and etherolenic acids. Etheroleic acid has systematic name 12-[1′E-hexenyloxy]-9Z,11Z-dodecadienoic acid. Etherolenic acid has systematic name (9Z,11E,1'E,3'Z)-12-(1',3'-Hexadienyloxy)-9,11-dodecadienoic acid. The physiological significance of divinyl ethers is still not fully studied. As infection of potato leaves leads to increased levels of divinyl ether synthase, it was suggested that this pathway could be of importance in the defense of plants against attacking pathogens.[5] Similar structures have been discovered in the brown alga Laminaria sinclairii, with 18 or 20 carbons and 4, 5 or 6 double bonds,[6] and in the red alga Polyneura latissima, with 20 carbons and 5 double bonds.[7]

Notes and References

  1. Galliard. T.. Phillips. D. R.. The enzymic conversion of linoleic acid into 9-(nona-1′,3′-dienoxy)non-8-enoic acid, a novel unsaturated ether derivative isolated from homogenates of Solanum tuberosum tubers. Biochemical Journal. September 1972. 129. 3. 743–753. 4658996. 1174176. 10.1042/bj1290743.
  2. Hamberg. M.. Isolation and structures of two divinyl ether fatty acids from Clematis vitalba. Lipids. June 2004. 39. 6. 565–569. 15554156. 10.1007/s11745-004-1264-9 .
  3. Grechkin. Alexander N.. Fazliev. F. N.. Mukhtarova. L. S.. The lipoxygenase pathway in garlic (Allium sativum L.) bulbs: detection of the novel divinyl ether oxylipins. FEBS Letters. October 1995. 371. 2. 159–162. 10.1016/0014-5793(95)00895-G. 7672118. free.
  4. Hamberg. M.. A pathway for biosynthesis of divinyl ether fatty acids in green leaves. Lipids. November 1998. 33. 11. 1061–1071. 9870900. 10.1007/s11745-998-0306-7.
  5. Göbel. C. Feussner. I.. Hamberg M. M.. Rosahl. S.. Oxylipin profiling in pathogen-infected potato leaves. Biochim Biophys Acta. 5 September 2002. 1584. 1. 55–64. 12213493. 10.1016/s1388-1981(02)00268-8.
  6. Proteau. P. J.. Gerwick. William H.. Divinyl ethers and hydroxy fatty acids from three species of Laminaria (brown algae). Lipids. 1993. 28. 9. 783–787. 10.1007/bf02536231. 8231653.
  7. Jiang. Z. D.. Gerwick. William H.. Novel oxylipins from the temperate red alga Polyneura latissima. Lipids. 1 March 1997. 32. 3. 231–235. 10.1007/s11745-997-0029-9. 9076659.