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Novel oxylipins formed from docosahexaenoic acid by potato lipoxygenase—10(S)-hydroxydocosahexaenoic acid and 10,20-dihydroxydocosahexaenoic acid

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Lipids

Abstract

Potato tuber lipoxygenase (ptLOX) has been shown to catalyze the aerobic formation of at least four major oxygenated derivatives of DHA. Two of the products—7,17(S)- and 10,17(S)-dihydro(pero)xy-DHA [7,17- and 10,17-diH(P)DHA]— were formed from soybean 15-LOX-derived 17(S)-hydro(pero)xy-DHA [17(S)-H(P)DHA], whereas two novel oxylipin compounds— 10(S)-hydro(pero)xy-DHA and 10,20-dihydro(pero)xy-DHA [10(S)-H(P)DHA and 10,20-diH(P)DHA, respectively]—were the major direct products of DHA oxidation by ptLOX. The reactions proceeded relatively slowly but could be stimulated by catalytic amounts of SDS. Micromolar concentrations of 10(S)-HPDHA effectively abolished the kinetic lag period of ptLOX activation. Enzymatic activity with DHA or 17(S)-HPDHA as substrate was about 8% of that with linoleic acid—a standard natural ptLOX substrate—whereas 17(S)-HDHA was converted at a rate of ∼1%. The enzyme was relatively unstable and quickly inactivated during the reaction with DHA on with 17(S)-HPDHA (first-order kinetic constant of inactivation k in=1.5±0.3 min−1), but not with 17(S)-HDHA. Both 7,17- and 10,20-diH(P)DHA were clearly products of double oxygenation catalyzed by soybean 15-LOX and/or ptLOX. Our observation that ptLOX could convert 17-HDHA to 10,17-diH(P)DHA indicates that this dihydroxylated derivative of DHA also can be formed via a double lipoxygenation mechanism.

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Abbreviations

C12E10 :

monododecyl ether of decaethylene glycol

ASA:

acetylsalicylic acid

DHA:

cis-4,7,10,13,16,19-docosahexaenoic acid

7,17-, 10,17-, and 10,20-diHDHA, 7,17-, 10,17-, and 10,20-dihydroxy-DHA:

7,17-, 10,17-, and 10,20-diHPDHA, 7,17-, 10,17-, and 10,20-dihydroperoxy-DHA

EI GC-MS:

GC-MS with electron impact ionization

10-HDHA:

10-hydroxy-DHA

10-HPDHA:

10-hydroperoxy-DHA

LA:

linoleic acid

LOX:

lipoxygenase

MC:

menthoxycarbonyl

ptLOX:

potato tuber lipoxygenase

RT:

retention time of a chromatographic peak

SP-HPLC:

straight (or normal)-phase HPLC

TEMPO:

2,2,6,6-tetramethyl-1-piperidinyloxy

TMS:

trimethylsilyl

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Authors and Affiliations

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

    Igor A. Butovich, Mats Hamberg & Olof Rådmark

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  1. Igor A. Butovich
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  2. Mats Hamberg
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  3. Olof Rådmark
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Correspondence to Igor A. Butovich.

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Butovich, I.A., Hamberg, M. & Rådmark, O. Novel oxylipins formed from docosahexaenoic acid by potato lipoxygenase—10(S)-hydroxydocosahexaenoic acid and 10,20-dihydroxydocosahexaenoic acid. Lipids 40, 249–257 (2005). https://doi.org/10.1007/s11745-005-1379-z

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  • DOI: https://doi.org/10.1007/s11745-005-1379-z

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