Soybean Lipoxygenase-Mediated Oxygenation of Monounsaturated Fatty Acids to Enones

Clapp, Charles H.; Senchak, Susan E.; Stover, Theodore J.; Potter, Thomas C.; Findeis, Peter M.; Novak, Mark J.

doi:10.1021/ja0032071

Cited by 26 publications

(29 citation statements)

References 16 publications

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“…Lipoxygenases are nonheme iron-containing dioxygenases that catalyze the addition of molecular oxygen to PUFA with a (cis,cis)-1,4-pentadiene system to give an unsaturated FA hydroperoxide (43). Lipoxygenases may also catalyze the oxygenation of monounsaturated FA such as oleic (44)(45)(46)(47), octadec-cis-12-enoic (47), or cis-vaccenic (42) acid. These processes afford mainly hydroxy-, hydroperoxy-, or oxoacids.…”

Section: Resultsmentioning

confidence: 99%

GC‐MS structural characterization of fatty acids from marine aerobic anoxygenic phototrophic bacteria

Rontani

Christodoulou

Koblížek

2005

Lipids

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The FA composition of 12 strains of marine aerobic anoxygenic phototrophic bacteria belonging to the genera Erythrobacter, Roseobacter, and Citromicrobium was investigated. GC-MS analyses of different types of derivatives were performed to determine the structures of the main FA present in these organisms. All the analyzed strains contained the relatively rare 11-methyloctadec-12-enoic acid, and three contained 12-methyl-octadec-11-enoic acid, which has apparently never been reported before. High amounts of the very unusual octadeca-5,11-dienoic acid were present in 9 of the 12 strains analyzed. A FA containing a furan ring was detected in three strains. Analytical data indicated that this FA was 10,13-epoxy-11-methyloctadeca-10,12-dienoic acid. A very interesting enzymatic peroxidation of the allylic carbon 10 of cis-vaccenic acid was observed in three strains. Deuterium labeling and GC-MS analyses enabled us to demonstrate that this enzymatic process involves the initial dioxygenase-mediated formation of 10-hydroperoxyoctadec-11(cis)-enoic acid, which is then isomerized to 10-hydroperoxyoctadec-11(trans)-enoic acid and converted to the corresponding hydroxyacids and oxoacids. Different biosynthetic pathways were proposed for these different compounds.

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Section: Resultsmentioning

confidence: 99%

GC‐MS structural characterization of fatty acids from marine aerobic anoxygenic phototrophic bacteria

Rontani

Christodoulou

Koblížek

2005

Lipids

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“…The breakdown of hydroperoxypolyenoic FA via the lipohydroperoxidase reaction affords oxopolyenoic FA (1). It is interesting to note that Clapp et al (9) reported the soybean lipoxygenase-mediated oxygenation of monounsaturated FA to allylic oxoacids. These authors assume that the formation of such products may involve a typical dioxygenation reaction to form an allylic hydroperoxide and its subsequent conversion to a ketone by loss of water.…”

Section: Resultsmentioning

confidence: 99%

“…The dioxygenation of PUFA by a lipoxygenase formally consists of three steps: (i) removal of one hydrogen atom from the double allylic methylene carbon atom forming a FA radical, (ii) conjugation of the double bonds with a trans-isomerization of the shifted double bond (the conjugation being accompanied by a rearrangement of the radical electron), and (iii) insertion of dioxygen (5). Lipoxygenases may also catalyze the oxygenation of monounsaturated FA such as oleic (6)(7)(8)(9) and octadec-cis-12-enoic (9) acids, these processes mainly affording hydroxy-, hydroperoxy-, or oxoacids.…”

mentioning

confidence: 99%

Regiospecific enzymatic oxygenation of cis‐vaccenic acid during aerobic senescence of the halophilic purple sulfur bacterium Thiohalocapsa halophila

Marchand¹,

Grossi²,

Hirschler-Réa

et al. 2002

Lipids

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A regiospecific oxygenation of the allylic carbon 10 of cis-vaccenic acid has been observed in senescent cells of the halophilic purple sulfur bacterium Thiohalocapsa halophila incubated under aerobic conditions in darkness. The results obtained strongly suggest that these enzymatic processes involve the initial dioxygenase-mediated formation of 1 O-hydroperoxyoctadec-cis-11-enoic acid, which is not accumulated in the cells of T. halophila owing to its high cytotoxic properties. Deuterium labeling and GC-MS analyses enabled us to demonstrate that subsequent enzymatic conversions of this allylic hydroperoxide involved reduction, cleavage, isomerization, and saturation reactions. Some of the specific oxidation products thus formed could constitute potential T. halophila biomarkers.

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“…The genome of P. aeruginosa contains no obvious homologues to heme-containing fatty acid dioxygenases (cyclooxygenases, linoleate diol synthases, 10-DOX, and ␣-DOX), and monounsaturated fatty acids are poor substrates for lipoxygenases (22). Furthermore, partial purification of the (10S)-DOX and hydroperoxide isomerase activities suggested that they were linked.…”

Section: Discussionmentioning

confidence: 99%

“…Vance et al (21) found that P. aeruginosa secreted an arachidonate 15-lipoxygenase and expressed this protein by aid of the PA1169 sequence. As far as is known, lipoxygenases only oxidize oleic acid slowly (22). On the other hand, heme-containing fatty acid dioxygenases can oxidize oleic acid to hydroperoxy fatty acids, but there are no apparent homologues to cyclooxygenases, (10R)-DOX, linoleate diol synthase, or ␣-DOX in the genome of P. aeruginosa.…”

Section: H]18:2n-6 and [8r-mentioning

confidence: 99%

Biochemical Characterization of the Oxygenation of Unsaturated Fatty Acids by the Dioxygenase and Hydroperoxide Isomerase of Pseudomonas aeruginosa 42A2

Martínez

Hámberg

Busquets

et al. 2010

Journal of Biological Chemistry

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We have studied oxygenation of fatty acids by cell extract of Pseudomonas aeruginosa 42A2. Oleic acid ((9Z)-18:1) was transformed to (10S)-hydroperoxy-(8E)-octadecenoic acid ((10S)-HPOME) and to (7S,10S)-dihydroxy-(8E)-octadecenoic acid (7,10-DiHOME). Experiments under oxygen-18 showed that 7,10-DiHOME contained oxygen from air and was formed sequentially from (10S)-HPOME by isomerization. (10R)-HPOME was not isomerized. The (10S)-dioxygenase and hydroperoxide isomerase activities co-eluted on ion exchange chromatography and on gel filtration with an apparent molecular size of ϳ50 kDa. 16:1n-7, 18:2n-6, and 20:1n-11 were also oxygenated to 7,10-dihydroxy fatty acids, and ( 2 H]18:2n-6 as substrates. The pro-R hydrogen at C-8 was lost in the biosynthesis of (10S)-HPODE, whereas the pro-S hydrogen was lost and the pro-R hydrogen was retained at C-7 during biosynthesis of the 7,10-dihydroxy metabolites. Analysis of the fatty acid composition of P. aeruginosa revealed relatively large amounts of (9E/Z)-16:1 and (11E/Z)-18:1 and only traces of 18:1n-9. We found that (11Z)-18:1 (vaccenic acid) was transformed to (11S,14S)-dihydroxy-(12E)-octadecenoic acid and to a mixture of 11-and 12-HPOME, possibly due to reverse orientation of (11Z)-18:1 at the active site compared with oleic acid. The reaction mechanism of the hydroperoxide isomerase suggests catalytic similarities to cytochrome P450.

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Soybean Lipoxygenase-Mediated Oxygenation of Monounsaturated Fatty Acids to Enones

Cited by 26 publications

References 16 publications

GC‐MS structural characterization of fatty acids from marine aerobic anoxygenic phototrophic bacteria

GC‐MS structural characterization of fatty acids from marine aerobic anoxygenic phototrophic bacteria

Regiospecific enzymatic oxygenation of cis‐vaccenic acid during aerobic senescence of the halophilic purple sulfur bacterium Thiohalocapsa halophila

Biochemical Characterization of the Oxygenation of Unsaturated Fatty Acids by the Dioxygenase and Hydroperoxide Isomerase of Pseudomonas aeruginosa 42A2

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