BRENDA - Enzyme Database show

Factors influencing the rearrangement of bis-allylic hydroperoxides by manganese lipoxygenase

Oliw, E.H.; J. Lipid Res. 49, 420-428 (2008)

Data extracted from this reference:

Cloned(Commentary)
EC Number
Commentary
Organism
1.13.11.45
expression in Pichia pastoris
Gaeumannomyces graminis
Engineering
EC Number
Amino acid exchange
Commentary
Organism
1.13.11.45
G316A
site-directed mutagenesis, the mutant changes the the position of lipoxygenation toward the carboxyl group of 20:2n-6 and 20:3n-3 and prevents the bis-allylic hydroperoxide of 20:3n-3 but not of 20:2n-6to interact with the catalytic metall
Gaeumannomyces graminis
1.13.11.45
N466L
site-directed mutagenesis, the mutation hardly affects the bis-allylic hydroperoxide rearrangement
Gaeumannomyces graminis
1.13.11.45
S469A
site-directed mutagenesis, the mutation hardly affects the bis-allylic hydroperoxide rearrangement, the mutant shows the same substrate profile as the wild-type enzyme
Gaeumannomyces graminis
KM Value [mM]
EC Number
KM Value [mM]
KM Value Maximum [mM]
Substrate
Commentary
Organism
Structure
1.13.11.45
0.0024
-
linoleate
pH 7.5, 18:3n-3 substrate
Gaeumannomyces graminis
Localization
EC Number
Localization
Commentary
Organism
GeneOntology No.
Textmining
1.13.11.45
extracellular
secretion
Gaeumannomyces graminis
-
-
Metals/Ions
EC Number
Metals/Ions
Commentary
Organism
Structure
1.13.11.45
Mn2+
required for activity
Gaeumannomyces graminis
1.13.11.45
additional information
no activity with Fe3+
Gaeumannomyces graminis
Organism
EC Number
Organism
Primary Accession No. (UniProt)
Commentary
Textmining
1.13.11.45
Gaeumannomyces graminis
-
take-all fungus
-
Reaction
EC Number
Reaction
Commentary
Organism
1.13.11.45
linoleate + O2 = (9Z,12Z)-(11S)-11-hydroperoxyoctadeca-9,12-dienoate
reaction mechanism, tail-first model with rearrangement at C13 at the end of lipoxygenation, influenced by double bond configuration and the chain length of fatty acids, overview
Gaeumannomyces graminis
Substrates and Products (Substrate)
EC Number
Substrates
Commentary Substrates
Literature (Substrates)
Organism
Products
Commentary (Products)
Literature (Products)
Organism (Products)
Reversibility
1.13.11.45
(11Z,14Z)-eicosadienoic acid + O2
-
688235
Gaeumannomyces graminis
15-hydroxyperoxy-(9Z,11E)-eicosadienoic acid
-
-
-
?
1.13.11.45
(11Z,14Z,17Z)-eicosa-11,14,17-trienoic acid + O2
via 11-hydroperoxyoctadecadienoic acid, 13-hydroperoxyoctadecadienoic acid and 15-hydroperoxyoctadecadienoic acid
688235
Gaeumannomyces graminis
15-hydroxyperoxy-11Z,13E,17Z-eicosatrienoic acid
-
-
-
?
1.13.11.45
(9Z,12Z,15Z)-octadeca-9,12,15-trienoic acid + O2
oxidation at the n-3 position
688235
Gaeumannomyces graminis
?
-
-
-
?
1.13.11.45
1-linoleyl-lyso-glycerophosphatidylcholine + O2
via formation of the 13-hydroxyperoxy metabolite
688235
Gaeumannomyces graminis
11-hydroxyoctadecanoic acid + 13-hydroxyoctadecanoic acid
-
-
-
?
1.13.11.45
11-hydroperoxyoctadecadienoic acid + O2
-
688235
Gaeumannomyces graminis
11,18-dihydroxy-12E,14Z,16E-eicosatrienoic acid
two diastereoisomers
-
-
?
1.13.11.45
alpha-linolenic acid + O2
-
688235
Gaeumannomyces graminis
(13R)-hydroperoxy octadecadienoic acid + 9-hydroperoxyoctadecadienoic acid
-
-
-
?
1.13.11.45
linoleate + O2
-
688235
Gaeumannomyces graminis
(9Z,12Z)-(11S)-11-hydroperoxyoctadeca-9,12-dienoate
-
-
-
?
1.13.11.45
linoleic acid + O2
-
688235
Gaeumannomyces graminis
?
-
-
-
?
1.13.11.45
additional information
the enzyme catalyzes the rearrangement of bis-allylic S-hydroxyperoxides to allylic R-hydroperoxides, and the oxygenation of 18:2n-6 by suprafacial hydrogen abstraction at C11 and O2 insertion at the bis-allylic position C11 and, with double bond migation, at the allylic position C13, overview, 20:4n-6 is a poor substrate, substrate specificities of wild-type and mutant enzymes, overview
688235
Gaeumannomyces graminis
?
-
-
-
-
Turnover Number [1/s]
EC Number
Turnover Number Minimum [1/s]
Turnover Number Maximum [1/s]
Substrate
Commentary
Organism
Structure
1.13.11.45
40
-
linoleate
pH 7.5, 18:3n-3 substrate
Gaeumannomyces graminis
pH Optimum
EC Number
pH Optimum Minimum
pH Optimum Maximum
Commentary
Organism
1.13.11.45
7.5
-
assay at
Gaeumannomyces graminis
Cloned(Commentary) (protein specific)
EC Number
Commentary
Organism
1.13.11.45
expression in Pichia pastoris
Gaeumannomyces graminis
Engineering (protein specific)
EC Number
Amino acid exchange
Commentary
Organism
1.13.11.45
G316A
site-directed mutagenesis, the mutant changes the the position of lipoxygenation toward the carboxyl group of 20:2n-6 and 20:3n-3 and prevents the bis-allylic hydroperoxide of 20:3n-3 but not of 20:2n-6to interact with the catalytic metall
Gaeumannomyces graminis
1.13.11.45
N466L
site-directed mutagenesis, the mutation hardly affects the bis-allylic hydroperoxide rearrangement
Gaeumannomyces graminis
1.13.11.45
S469A
site-directed mutagenesis, the mutation hardly affects the bis-allylic hydroperoxide rearrangement, the mutant shows the same substrate profile as the wild-type enzyme
Gaeumannomyces graminis
KM Value [mM] (protein specific)
EC Number
KM Value [mM]
KM Value Maximum [mM]
Substrate
Commentary
Organism
Structure
1.13.11.45
0.0024
-
linoleate
pH 7.5, 18:3n-3 substrate
Gaeumannomyces graminis
Localization (protein specific)
EC Number
Localization
Commentary
Organism
GeneOntology No.
Textmining
1.13.11.45
extracellular
secretion
Gaeumannomyces graminis
-
-
Metals/Ions (protein specific)
EC Number
Metals/Ions
Commentary
Organism
Structure
1.13.11.45
Mn2+
required for activity
Gaeumannomyces graminis
1.13.11.45
additional information
no activity with Fe3+
Gaeumannomyces graminis
Substrates and Products (Substrate) (protein specific)
EC Number
Substrates
Commentary Substrates
Literature (Substrates)
Organism
Products
Commentary (Products)
Literature (Products)
Organism (Products)
Reversibility
1.13.11.45
(11Z,14Z)-eicosadienoic acid + O2
-
688235
Gaeumannomyces graminis
15-hydroxyperoxy-(9Z,11E)-eicosadienoic acid
-
-
-
?
1.13.11.45
(11Z,14Z,17Z)-eicosa-11,14,17-trienoic acid + O2
via 11-hydroperoxyoctadecadienoic acid, 13-hydroperoxyoctadecadienoic acid and 15-hydroperoxyoctadecadienoic acid
688235
Gaeumannomyces graminis
15-hydroxyperoxy-11Z,13E,17Z-eicosatrienoic acid
-
-
-
?
1.13.11.45
(9Z,12Z,15Z)-octadeca-9,12,15-trienoic acid + O2
oxidation at the n-3 position
688235
Gaeumannomyces graminis
?
-
-
-
?
1.13.11.45
1-linoleyl-lyso-glycerophosphatidylcholine + O2
via formation of the 13-hydroxyperoxy metabolite
688235
Gaeumannomyces graminis
11-hydroxyoctadecanoic acid + 13-hydroxyoctadecanoic acid
-
-
-
?
1.13.11.45
11-hydroperoxyoctadecadienoic acid + O2
-
688235
Gaeumannomyces graminis
11,18-dihydroxy-12E,14Z,16E-eicosatrienoic acid
two diastereoisomers
-
-
?
1.13.11.45
alpha-linolenic acid + O2
-
688235
Gaeumannomyces graminis
(13R)-hydroperoxy octadecadienoic acid + 9-hydroperoxyoctadecadienoic acid
-
-
-
?
1.13.11.45
linoleate + O2
-
688235
Gaeumannomyces graminis
(9Z,12Z)-(11S)-11-hydroperoxyoctadeca-9,12-dienoate
-
-
-
?
1.13.11.45
linoleic acid + O2
-
688235
Gaeumannomyces graminis
?
-
-
-
?
1.13.11.45
additional information
the enzyme catalyzes the rearrangement of bis-allylic S-hydroxyperoxides to allylic R-hydroperoxides, and the oxygenation of 18:2n-6 by suprafacial hydrogen abstraction at C11 and O2 insertion at the bis-allylic position C11 and, with double bond migation, at the allylic position C13, overview, 20:4n-6 is a poor substrate, substrate specificities of wild-type and mutant enzymes, overview
688235
Gaeumannomyces graminis
?
-
-
-
-
Turnover Number [1/s] (protein specific)
EC Number
Turnover Number Minimum [1/s]
Turnover Number Maximum [1/s]
Substrate
Commentary
Organism
Structure
1.13.11.45
40
-
linoleate
pH 7.5, 18:3n-3 substrate
Gaeumannomyces graminis
pH Optimum (protein specific)
EC Number
pH Optimum Minimum
pH Optimum Maximum
Commentary
Organism
1.13.11.45
7.5
-
assay at
Gaeumannomyces graminis