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On the specificity of allene oxide cyclase

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Lipids

Abstract

Jasmonic acid is a carbocyclic fatty acid that is biosynthesized from α-linolenic acid in several steps. The formation of the ring structure of jasmonic acid is catalyzed by the enzyme allene oxide cyclase (EC 5.3.99.6) and involves the cyclization of an unstable allene oxide into the cyclopentenone 12-oxo-10,15(Z)-phytodienoic acid. In this study, a number of allene oxides were generated, and their enzymatic and nonenzymatic cyclization into cyclopentenones was investigated. Nonenzymatic cyclization was observed with allene oxides having one pair of conjugated double bonds and an additional isolated double bond in the β,γ position relative to the epoxide group, i.e., the partial structure 4,5-epoxy-1,3,7-octatriene. Enzymatic cyclization took place provided that this structural element was inserted in the fatty acid chain with its epoxide group in the n−6,7 position and the isolated double bond in the n−3 position. A number of oxygenated fatty acids having structural features in common with the natural allene oxides were tested as inhibitors of allene oxide cyclase. Fatty acids having an allene oxide structure in the n−6,7 position but lacking the double bond in the n−3 position, as well as fatty acids having a saturated epoxide group in the n−6,7 position, served as competitive inhibitors of the enzyme. Data on the substrate specificity of allene oxide synthase (EC 4.2.1.92) from corn seeds indicated that fatty acid hydroperoxides with a double bond at n−3 and with the hydroperoxide function at n−6 exhibit the highest affinity but the slowest reaction velocity.

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Abbreviations

9(S),10-EOD:

9(S),10-epoxy-10,12(Z)-octadecadienoic acid

9(S),10-EOT:

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

10,11(S)-EHT:

10,11(S)-epoxy-7(Z),9,13(Z)-hexadecatrienoic acid

12,13(S)-EOD:

12,13(S)-epoxy-9(Z),11-octadecadienoic acid

12,13(S)-EOT:

12,13(S)-epoxy-9(Z),11,15(Z)-octadecatrienoic acid

14,15(S)-EETE:

14,15(S)-epoxy-5(Z),8(Z),11(Z),13-eicosatetraenoic acid

9(S)-HPOD:

9(S)-hydroperoxy-10(E),12(Z)-octadecadienoic acid

9(S)-HPOT:

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

11(S)-HPHT:

11(S)-hydroperoxy-7(Z),9(E),13(Z)-hexadecatrienoic acid

13(S)-HPOD:

13(S)-hydroperoxy-9(Z),11(E)-octadecadienoic acid

13(S)-HPOT:

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

15(S)-HPEP:

15(S)-hydroperoxy-5(Z),8(Z),11(Z),13(E),17(Z)eicosapentaenoic acid

15(S)-HPET:

15(S)-hydroperoxy-11(Z),13(E),17(Z)-eicosatrienoic acid

15(S)-HPETE:

15(S)-hydroperoxy-5(Z),8(Z),11(Z),13(E)-eicosatetraenoic acid

17(S)-HPDP:

17(S)-hydroperoxy-7(Z),10(Z),13(Z),15(E),19(Z)-docosapentaenoic acid

γ-9(S):

10-EOT, 9(S),10-epoxy-6(Z),10,12(Z)-octadecatrienoic acid

γ-9(S)-HPOT:

9(S)-hydroperoxy-6(Z),10(E),12(Z)-octadecatrienoic acid

12-oxo-PDA:

12-oxo-10,15(Z)-phytodienoic acid

AOC:

allene oxide cyclase

AOS:

allene oxide synthase

GC-MS:

gas-liquid chromatography-mass spectrometry

GLC:

gas-liquid chromatography

JA:

jasmonic acid [used as a collective name for (−)-jasmonic acid and (+)-7-iso-jasmonic acid]

α-ketol:

12-oxo-13-hydroxy-9(Z),15(Z)-octadecadienoic acid

γ-ketol:

12-oxo-9-hydroxy-10(E),15(Z)-octadecadienoic acid

MC:

(−)-menthoxycarbonyl

RP-HPLC:

reversed-phase high-performance chromatography

TLC:

thin-layer chromatography

UV:

ultraviolet

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Authors and Affiliations

  1. Department of Medical Biochemistry and Biophysics, Division of Physiological Chemistry II, Karolinska Institutet, S-171 77, Stockholm, Sweden

    Jörg Ziegler & Mats Hamberg

  2. Abteilung Hormonfonrschung, Institut für Pflanzenbiochemie, Weinberg 3, D-06120, Halle, Germany

    Claus Wasternack

Authors
  1. Jörg Ziegler
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  2. Claus Wasternack
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  3. Mats Hamberg
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Correspondence to Jörg Ziegler.

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Ziegler, J., Wasternack, C. & Hamberg, M. On the specificity of allene oxide cyclase. Lipids 34, 1005–1015 (1999). https://doi.org/10.1007/s11745-999-0451-z

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  • DOI: https://doi.org/10.1007/s11745-999-0451-z

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