An enzymatic formation of 13-oxo-trideca-9,11-dienoic acid from 13-hydroperoxylinolenic acid by a homolytic hydroperoxide lyase in elicitor-treated soybean cotyledons

Kondo, Yasuo; Hashidoko, Yasuyuki; Mizutani, Junya

doi:10.1016/0005-2760(94)00204-c

Cited by 20 publications

(21 citation statements)

References 26 publications

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“…The only other short-chain compound detected by GC in any significant amount was 2(E)-hexenal, arising from a C-6,12-cleaving hydroperoxide lyase. 1-Penten-3-01 has been identified as a product of a C-5,13-fragmenting hydroperoxide lyase in Agropyron repens (Berger et al, 1986), and 2(Z)-penten-1-01 recently was reported as a fragmentation product of 13s-HPOT in soybeans (Kondo et al, 1995). Five other, more minor metabolites gave longer retention times by GC-MS, and the MS was consistent with isomeric pentene dimers.…”

Section: Resultsmentioning

confidence: 88%

“…Earlier, one of us reported the formation of 13-OTA from 13s-HPOT by a soybean (Gycine max L.) preparation and postulated that an anaerobic reaction of LOX was responsible . After submission of this paper, Kondo et al (1995) "homolytic hydroperoxide lyase" in soybeans that catalyzes formation of 13-OTA and 2-penten-1-01 from 13S-HPOT, but these workers did not attempt to characterize the enzyme(s) involved. They found that 13-OTA possessed antifungal activity, possibly explaining a physiological function for the cleavage reaction.…”

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confidence: 99%

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Characterization of a C-5,13-Cleaving Enzyme of 13(S)-Hydroperoxide of Linolenic Acid by Soybean Seed

et al. 1995

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~An activity was found in mature soybean seeds (Glycine max 1. cv Century) that cleaved 13(S)-hydroperoxy-9(2),11 (E),15(Z)-octadecatrienoic acid (1 3s-HPOT) into 13-0~0-9(Z),11(E)-tridecadienoic acid and two isomeric pentenols, Z(Z)-penten-l-ol and 1 -penten-3-ol. lsomeric pentene dimers were also produced and were presumably derived from the combination of two pentene radicals. 13(S)-Hydroperoxy-9(Z),ll(E)-octadecadienoic acid (1 3s-HPOD) was, by contrast, a poor substrate. Activity with 13s-HPOT increased 24-fold under anaerobic conditions reminiscent of a similar anaerobic promoted reaction of 13s-HPOD catalyzed by lipoxygenase (LOX) in the presence of linoleic acid. However, prior to ion-exchange chromatography, cleavage activity did not require linoleic acid. After separation by gel filtration followed by ionexchange chromatography, cleavage activity was lost but reappeared in the presence of either linoleic acid or dithiothreitol. Under these conditions cleavage activity was coincident with the activity of types 1 and 2 LOX. LOX inhibitors suppressed the cleavage reaction in a manner similar to inhibition of LOX activity. Heat-generated alkoxyl radicals derived from either 13s-HPOT or 13s-HPOD afforded similar products and yields of 13-0x0-9(Z),11 (.€)-tridecadienoic acid compared t o the enzymic reaction.The product 1-penten-3-01 may be the precursor of the "raw-bean" volatile ethylvinylketone.A hydroperoxide lyase, which cleaves between the hydroperoxide-bearing carbon and a vicinal methylene, was first described in mushroom (Wurzenberger and Grosch, 1984), and subsequently a similar enzyme was found in algae and one species of grass (see review by Gardner, 1991). This type of enzyme cleaves 13s-HPOT into 13-OTA and either pentene or pentenol, giving products similar to those from homolytic cleavage of 13s-HPOT. However, LOX, the enzyme catalyzing the oxidation of polyunsaturated fatty acids to hydroperoxides, can catalyze such a homolytic chain cleavage under anaerobic conditions (Garssen et al., 1971). Earlier, one of us reported the formation of 13-OTA from 13s-HPOT by a soybean (Gycine max L.) preparation and postulated that an anaerobic reaction of LOX was responsible . After submission of this paper, Kondo et al. (1995) "homolytic hydroperoxide lyase" in soybeans that catalyzes formation of 13-OTA and 2-penten-1-01 from 13S-HPOT, but these workers did not attempt to characterize the enzyme(s) involved. They found that 13-OTA possessed antifungal activity, possibly explaining a physiological function for the cleavage reaction.In this communication we characterize an activity in soybeans that cleaves 13s-HPOT into 13-OTA and two isomeric pentenols in a much higher yield than cleavage of 13s-HPOD. Although the reaction did not appear to require a LOX substrate (polyunsaturated fatty acid), it was stimulated by anaerobic conditions. After enzyme purification by ion-exchange chromatography, activity was lost, but it could be restimulated by either linoleic acid or DTT. Enzyme characterization of purif...

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Section: Resultsmentioning

confidence: 88%

mentioning

confidence: 99%

Characterization of a C-5,13-Cleaving Enzyme of 13(S)-Hydroperoxide of Linolenic Acid by Soybean Seed

et al. 1995

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“…In algae, the 13-HPODE was cleaved into pentanol or pentane, and a 13-oxodienoic acid by an enzyme preparation obtained from Oscillatoria Sp.18) and Chlorella pyrenoidosa, 20) respectively. In the grass Agropyron repens 461 and soybean cotyledon 47 ) extracts, pentenol was identified as a product of a C5,13-cleaving HPL activity. Another type of HPL, a C8, lO-cleaving enzyme, was also reported in mushrooms, requiring a lO-HPODE as substrate.…”

Section: Carbonyl Compounds Formed By Hydroperoxide-cleaving Activitymentioning

confidence: 99%

Characterization of Hydroperoxides and Carbonyl Compounds Obtained by Lipoxygenase Extracts of Selected Microorganisms

Bisakowski

Perraud

Kermasha

1997

Bioscience, Biotechnology, and Biochemistry

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“…In starfish oocytes, the homolytic cleavage of arachidonic acid hydroperoxide gives a C-7 hydroxyacid and C-13 aldehydes (Brash et al 1991). Here are only a few reports of the occurrence of such enzymatic activities in higher plants, in olive oil (Angerosa et al 1998) and in soybean (Kondo et al 1995, Salch et al 1995, but the enzyme responsible for their synthesis is still unknown. Nevertheless, as reported by Table 3.…”

Section: -Hpotmentioning

confidence: 99%

“…With oxygenation of of reaction medium reaction medium 1-pentan-3-ol 54 ± 10 13 ± 4 2-pentan-1-ol 62 ± 12 14 ± 4 Pentene dimers (total) 22 ± 5 5 ± 2 Kondo et al 1995, a soluble form of HPO lyase could be responsible for such an homolytic activity. Or, as suggested by Salch et al 1995, a secondary activity of Lox could explain the homolytic cleavage of HPO.…”

Section: Without Oxygenationmentioning

confidence: 99%

Fatty acid hydroperoxides biotransformation by potato tuber cell-free extracts

Fauconnier

Delcarte

Jaziri

et al. 2002

Journal of Plant Physiology

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SummaryCleavage of 13-HPOD, 13-HPOT, 9-HPOD and 9-HPOT by potato tuber cell-free extracts was investigated. 13-HPOD and 13-HPOT enzymes were degraded almost completely while 9-HPOD and 9-HPOT were partially transformed. GC-MS analysis of the volatile compounds formed during the reactions revealed that (Z)-3 hexenal, (E)-2-hexenal, pentenols and dimers of pentene were obtained from 13-HPOT while from 13-HPOD hexanal and pentan-1-ol were formed. No volatile was found when 9-HPO isomers were used as substrate, but colneleic acid was produced. When Triton X-100 was omitted in the extraction buffer, only pentenols and dimers of pentene were identified from 13-HPOT and pentan-1-ol from 13-HPOD. Our results reveal that potato tubers that contain Lox, which forms mainly 9-HPO, are able to metabolise the four HPO isomers. Moreover, 13-HPO cleaving activities are due to two distinct enzymatic systems based on, respectively, homolytic and heterolytic mechanisms. The fact that oxygenation of reaction medium dramatically decreases the amount of product resulting from homolytic cleavage strengthens the hypothesis of an anaerobic reaction due to Lox.Key words: aldehyde -fatty acid hydroperoxide -heterolytic and homolytic hydroperoxide cleavage -hydroperoxide lyase -potato tuber -Solanum tuberosum L.Abbreviations: GC-MS = gas-chromatography mass spectrometry. -HPLC = high performance liquid chromatography. -HPO = fatty acid hydroperoxide. -13-HPOT = 13 hydroperoxide of linolenic acid. -13-HPOD = 13 hydroperoxide of linoleic acid. -9-HPOT = 9 hydroperoxide of linolenic acid. -9-HPOD = 9 hydroperoxide of linoleic acid. -Lox = lipoxygenase *

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An enzymatic formation of 13-oxo-trideca-9,11-dienoic acid from 13-hydroperoxylinolenic acid by a homolytic hydroperoxide lyase in elicitor-treated soybean cotyledons

Cited by 20 publications

References 26 publications

Characterization of a C-5,13-Cleaving Enzyme of 13(S)-Hydroperoxide of Linolenic Acid by Soybean Seed

Characterization of a C-5,13-Cleaving Enzyme of 13(S)-Hydroperoxide of Linolenic Acid by Soybean Seed

Characterization of Hydroperoxides and Carbonyl Compounds Obtained by Lipoxygenase Extracts of Selected Microorganisms

Fatty acid hydroperoxides biotransformation by potato tuber cell-free extracts

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