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Formation of oxylipins by CYP74 enzymes

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Abstract

Lipid peroxidation is common to all biological systems, both appearing in developmentally and environmentally regulated processes. Products are hydroperoxy polyunsaturated fatty acids and metabolites derived there from collectively named oxylipins. They may either originate from chemical oxidation or are synthesized by the action of various enzymes, such as lipoxygenases. Cloning of many lipoxygenases and other key enzymes metabolizing oxylipins revealed new insights on oxylipin functions, new reactions and the first hints on enzyme mechanisms. These aspects are reviewed with respect to metabolism of fatty acid hydroperoxides by an atypical P450 subfamily: the CYP74. Up to now this protein family contains three different enzyme activities: (i) allene oxide synthase leading to the formation of unstable allene oxides which react to ketol and cyclopentenone fatty acids, (ii) hydroperoxide lyase producing hemiacetals decomposing to aldehydes and ω-oxo fatty acids and (iii) divinyl ether synthase which forms divinyl ethers. Signalling compounds such as jasmonates, antimicrobial and antifungal compounds such as leaf aldehydes or divinyl ethers, and a plant-specific blend of volatiles including leaf alcohols are among their numerous products.

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Abbreviations

AOC:

Allene oxide cyclase

AOS:

Allene oxide synthase

DES:

Divinyl ether synthase

9-HPOTE:

(9S,10E,12Z,15Z)-9-Hydroperoxy-10,12,15-octadecatrienoic acid

13-HPOTE:

(9Z,11E,13S,15Z)-13-Hydroperoxy-9,11,15-octadecatrienoic acid

HPO(D/T)E:

Hydroperoxy linole(n)ic acid

HPL:

Hydroperoxide lyase

JA:

Jasmonic acid

KO(D/T)E:

Keto linole(n)ic acid

LA:

Linoleic acid

LeA:

Linolenic acid

LOX:

Lipoxygenase

OPDA:

(9S,13S)-12-Oxo phytodienoic acid

PUFA:

Polyunsaturated fatty acids

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Acknowledgements

The authors apologize to scientists whose work we overlooked or were not able to include because of length limitations. We are grateful for the constructive help of two anonymous reviewers. Our work was supported by the Deutsche Forschungsgemeinschaft and the European Community.

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  1. Department of Plant Biochemistry, Albrecht-von-Haller-Institute for Plant Sciences, Georg-August-University Göttingen, Justus-von-Liebig-Weg 11, D-37077, Göttingen, Germany

    Michael Stumpe & Ivo Feussner

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  1. Michael Stumpe
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  2. Ivo Feussner
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Correspondence to Ivo Feussner.

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Stumpe, M., Feussner, I. Formation of oxylipins by CYP74 enzymes. Phytochem Rev 5, 347–357 (2006). https://doi.org/10.1007/s11101-006-9038-9

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