BRENDA - Enzyme Database

Discovery of a linoleate 9S-dioxygenase and an allene oxide synthase in a fusion protein of Fusarium oxysporum

Hoffmann, I.; Oliw, E.H.; J. Lipid Res. 54, 3471-3480 (2013)

Data extracted from this reference:

Cloned(Commentary)
EC Number
Cloned (Commentary)
Organism
4.2.1.92
gene FOXB_01332, phylogenetic tree, expression of wild-type and mutant enzymes
Fusarium oxysporum
Engineering
EC Number
Protein Variants
Commentary
Organism
4.2.1.92
E946V
site-directed mutagenesis, mutant Glu946Val oxidized 18:2n-6 as the native enzyme with formation of the alpha-ketol as the main product after 30 min
Fusarium oxysporum
4.2.1.92
F416W
site-directed mutagenesis, the catalytic residue mutant shows an unaltered product profile compared to the wild-type enzyme
Fusarium oxysporum
4.2.1.92
N921V
site-directed mutagenesis, the mutant shows activity similar to the wild-type enzyme
Fusarium oxysporum
4.2.1.92
S949A
site-directed mutagenesis, the mutant also forms alpha-ketol like the native enzyme
Fusarium oxysporum
Natural Substrates/ Products (Substrates)
EC Number
Natural Substrates
Organism
Commentary (Nat. Sub.)
Natural Products
Commentary (Nat. Pro.)
Organism (Nat. Pro.)
Reversibility
ID
4.2.1.92
(9S)-hydroperoxy-(10E,12Z)-octadecadienoic acid
Fusarium oxysporum
recombinant FOXB_01332 oxidizes 18:2n-6 to (9S)-hydroperoxy-(10E,12Z)-octadecadienoic acid by hydrogen abstraction and antarafacial insertion of molecular oxygen and sequentially to an allene oxide, (9S,10)-epoxy-(10Z,12Z)-octadecadienoic acid, which gives nonenzymatic hydrolysis products alpha- and gamma-ketols
(9S,10)-epoxy-(10Z,12Z)-octadecadienoic acid + H2O
-
-
?
4.2.1.92
(9S)-hydroperoxy-(10E,12Z)-octadecadienoic acid
Fusarium oxysporum Fo5176
recombinant FOXB_01332 oxidizes 18:2n-6 to (9S)-hydroperoxy-(10E,12Z)-octadecadienoic acid by hydrogen abstraction and antarafacial insertion of molecular oxygen and sequentially to an allene oxide, (9S,10)-epoxy-(10Z,12Z)-octadecadienoic acid, which gives nonenzymatic hydrolysis products alpha- and gamma-ketols
(9S,10)-epoxy-(10Z,12Z)-octadecadienoic acid + H2O
-
-
?
4.2.1.92
additional information
Fusarium oxysporum
FOXB_01332 is a linoleate 9-dioxygenase with homology to animal heme peroxidases and a 9-dioxygenase-allene oxide synthase fusion protein
?
-
-
?
4.2.1.92
additional information
Fusarium oxysporum Fo5176
FOXB_01332 is a linoleate 9-dioxygenase with homology to animal heme peroxidases and a 9-dioxygenase-allene oxide synthase fusion protein
?
-
-
?
Organism
EC Number
Organism
UniProt
Commentary
Textmining
4.2.1.92
Fusarium oxysporum
F9F4K7
gene FOXB_01332
-
4.2.1.92
Fusarium oxysporum Fo5176
F9F4K7
gene FOXB_01332
-
Substrates and Products (Substrate)
EC Number
Substrates
Commentary Substrates
Literature (Substrates)
Organism
Products
Commentary (Products)
Literature (Products)
Organism (Products)
Reversibility
Substrate Product ID
4.2.1.92
(9S)-hydroperoxy-(10E,12Z)-octadecadienoic acid
recombinant FOXB_01332 oxidizes 18:2n-6 to (9S)-hydroperoxy-(10E,12Z)-octadecadienoic acid by hydrogen abstraction and antarafacial insertion of molecular oxygen and sequentially to an allene oxide, (9S,10)-epoxy-(10Z,12Z)-octadecadienoic acid, which gives nonenzymatic hydrolysis products alpha- and gamma-ketols
730154
Fusarium oxysporum
(9S,10)-epoxy-(10Z,12Z)-octadecadienoic acid + H2O
-
-
-
?
4.2.1.92
(9S)-hydroperoxy-(10E,12Z)-octadecadienoic acid
recombinant FOXB_01332 oxidizes 18:2n-6 to (9S)-hydroperoxy-(10E,12Z)-octadecadienoic acid by hydrogen abstraction and antarafacial insertion of molecular oxygen and sequentially to an allene oxide, (9S,10)-epoxy-(10Z,12Z)-octadecadienoic acid, which gives nonenzymatic hydrolysis products alpha- and gamma-ketols
730154
Fusarium oxysporum Fo5176
(9S,10)-epoxy-(10Z,12Z)-octadecadienoic acid + H2O
-
-
-
?
4.2.1.92
(9S)-hydroperoxy-(10E,12Z)-octadecadienoic acid
recombinant FOXB_01332 oxidizes 18:2n-6 to (9S)-hydroperoxy-10(E),12(Z)-octadecadienoic acid by hydrogen abstraction and antarafacial insertion of molecular oxygen and sequentially to an allene oxide, (90S)-(10)-epoxy-10,12(Z)-octadecadienoic acid, which gives nonenzymatic hydrolysis products alpha- and gamma-ketols
730154
Fusarium oxysporum
(9S,10)-10-epoxy-(10Z,12Z)-octadecadienoic acid + H2O
-
-
-
?
4.2.1.92
(9S)-hydroperoxy-(10E,12Z,15Z)-octadecatrienoic acid
-
730154
Fusarium oxysporum
(9S,10)-epoxy-(10Z,12Z,15Z)-octadecatrienoic acid + H2O
-
-
-
?
4.2.1.92
(9Z,11E,13R)-13-hydroperoxyoctadeca-9,11-dienoic acid
-
730154
Fusarium oxysporum
11-hydroxy-12(13)-epoxy-octadecadienoic acid + 9-hydroxy-12(13)-epoxy-octadecadienoic acid + H2O
-
-
-
?
4.2.1.92
(9Z,11E,13R)-13-hydroperoxyoctadeca-9,11-dienoic acid
-
730154
Fusarium oxysporum Fo5176
11-hydroxy-12(13)-epoxy-octadecadienoic acid + 9-hydroxy-12(13)-epoxy-octadecadienoic acid + H2O
-
-
-
?
4.2.1.92
13-hydroperoxy-(10E,12Z)-octadecadienoic acid
-
730154
Fusarium oxysporum
11-hydroxy-12(13)-epoxy-octadecadienoic acid + 9-hydroxy-12(13)-epoxy-octadecadienoic acid + H2O
-
-
-
?
4.2.1.92
13-hydroperoxy-(10E,12Z)-octadecadienoic acid
-
730154
Fusarium oxysporum Fo5176
11-hydroxy-12(13)-epoxy-octadecadienoic acid + 9-hydroxy-12(13)-epoxy-octadecadienoic acid + H2O
-
-
-
?
4.2.1.92
additional information
FOXB_01332 is a linoleate 9-dioxygenase with homology to animal heme peroxidases and a 9-dioxygenase-allene oxide synthase fusion protein
730154
Fusarium oxysporum
?
-
-
-
?
4.2.1.92
additional information
(9S)-dioxygenase-allene oxide synthase converts 9S-hydroperoxyoctadecadienoic acid to alpha- and gamma-ketols, likely formed by hydrolysis of (9S,10)-(10)-epoxy-(10Z,12Z)-octadecadienoic acid, along with small amounts of epoxy alcohols. The (9R)-hydroperoxyoctadecadienoic acid preparation contains a few percent (9S)-hydroperoxyoctadecadienoic acid, and only the latter is apparently transformed to an alpha-ketol by (9S)-dioxygenase-allene oxide synthase. (13S)-hydroperoxyoctadecadienoic acid, (13S)-hydroxy-(10E,12Z,15Z)-octadecatrienoicacid, (13R)-hydroperoxyoctadecadienoic acid, and (13R)-hydroxy-(10E,12Z,15Z)-octadecatrienoicacid are not transformed to detectable amounts of allene oxides/alpha-ketols, but variable amounts of epoxy alcohols accumulate, mass spectrometric analysis of products, substrate specificity, overview
730154
Fusarium oxysporum
?
-
-
-
?
4.2.1.92
additional information
FOXB_01332 is a linoleate 9-dioxygenase with homology to animal heme peroxidases and a 9-dioxygenase-allene oxide synthase fusion protein
730154
Fusarium oxysporum Fo5176
?
-
-
-
?
4.2.1.92
additional information
(9S)-dioxygenase-allene oxide synthase converts 9S-hydroperoxyoctadecadienoic acid to alpha- and gamma-ketols, likely formed by hydrolysis of (9S,10)-(10)-epoxy-(10Z,12Z)-octadecadienoic acid, along with small amounts of epoxy alcohols. The (9R)-hydroperoxyoctadecadienoic acid preparation contains a few percent (9S)-hydroperoxyoctadecadienoic acid, and only the latter is apparently transformed to an alpha-ketol by (9S)-dioxygenase-allene oxide synthase. (13S)-hydroperoxyoctadecadienoic acid, (13S)-hydroxy-(10E,12Z,15Z)-octadecatrienoicacid, (13R)-hydroperoxyoctadecadienoic acid, and (13R)-hydroxy-(10E,12Z,15Z)-octadecatrienoicacid are not transformed to detectable amounts of allene oxides/alpha-ketols, but variable amounts of epoxy alcohols accumulate, mass spectrometric analysis of products, substrate specificity, overview
730154
Fusarium oxysporum Fo5176
?
-
-
-
?
Synonyms
EC Number
Synonyms
Commentary
Organism
4.2.1.92
9S-DOX-AOS
-
Fusarium oxysporum
4.2.1.92
FOXB_01332
-
Fusarium oxysporum
Cloned(Commentary) (protein specific)
EC Number
Commentary
Organism
4.2.1.92
gene FOXB_01332, phylogenetic tree, expression of wild-type and mutant enzymes
Fusarium oxysporum
Engineering (protein specific)
EC Number
Protein Variants
Commentary
Organism
4.2.1.92
E946V
site-directed mutagenesis, mutant Glu946Val oxidized 18:2n-6 as the native enzyme with formation of the alpha-ketol as the main product after 30 min
Fusarium oxysporum
4.2.1.92
F416W
site-directed mutagenesis, the catalytic residue mutant shows an unaltered product profile compared to the wild-type enzyme
Fusarium oxysporum
4.2.1.92
N921V
site-directed mutagenesis, the mutant shows activity similar to the wild-type enzyme
Fusarium oxysporum
4.2.1.92
S949A
site-directed mutagenesis, the mutant also forms alpha-ketol like the native enzyme
Fusarium oxysporum
Natural Substrates/ Products (Substrates) (protein specific)
EC Number
Natural Substrates
Organism
Commentary (Nat. Sub.)
Natural Products
Commentary (Nat. Pro.)
Organism (Nat. Pro.)
Reversibility
ID
4.2.1.92
(9S)-hydroperoxy-(10E,12Z)-octadecadienoic acid
Fusarium oxysporum
recombinant FOXB_01332 oxidizes 18:2n-6 to (9S)-hydroperoxy-(10E,12Z)-octadecadienoic acid by hydrogen abstraction and antarafacial insertion of molecular oxygen and sequentially to an allene oxide, (9S,10)-epoxy-(10Z,12Z)-octadecadienoic acid, which gives nonenzymatic hydrolysis products alpha- and gamma-ketols
(9S,10)-epoxy-(10Z,12Z)-octadecadienoic acid + H2O
-
-
?
4.2.1.92
(9S)-hydroperoxy-(10E,12Z)-octadecadienoic acid
Fusarium oxysporum Fo5176
recombinant FOXB_01332 oxidizes 18:2n-6 to (9S)-hydroperoxy-(10E,12Z)-octadecadienoic acid by hydrogen abstraction and antarafacial insertion of molecular oxygen and sequentially to an allene oxide, (9S,10)-epoxy-(10Z,12Z)-octadecadienoic acid, which gives nonenzymatic hydrolysis products alpha- and gamma-ketols
(9S,10)-epoxy-(10Z,12Z)-octadecadienoic acid + H2O
-
-
?
4.2.1.92
additional information
Fusarium oxysporum
FOXB_01332 is a linoleate 9-dioxygenase with homology to animal heme peroxidases and a 9-dioxygenase-allene oxide synthase fusion protein
?
-
-
?
4.2.1.92
additional information
Fusarium oxysporum Fo5176
FOXB_01332 is a linoleate 9-dioxygenase with homology to animal heme peroxidases and a 9-dioxygenase-allene oxide synthase fusion protein
?
-
-
?
Substrates and Products (Substrate) (protein specific)
EC Number
Substrates
Commentary Substrates
Literature (Substrates)
Organism
Products
Commentary (Products)
Literature (Products)
Organism (Products)
Reversibility
ID
4.2.1.92
(9S)-hydroperoxy-(10E,12Z)-octadecadienoic acid
recombinant FOXB_01332 oxidizes 18:2n-6 to (9S)-hydroperoxy-(10E,12Z)-octadecadienoic acid by hydrogen abstraction and antarafacial insertion of molecular oxygen and sequentially to an allene oxide, (9S,10)-epoxy-(10Z,12Z)-octadecadienoic acid, which gives nonenzymatic hydrolysis products alpha- and gamma-ketols
730154
Fusarium oxysporum
(9S,10)-epoxy-(10Z,12Z)-octadecadienoic acid + H2O
-
-
-
?
4.2.1.92
(9S)-hydroperoxy-(10E,12Z)-octadecadienoic acid
recombinant FOXB_01332 oxidizes 18:2n-6 to (9S)-hydroperoxy-(10E,12Z)-octadecadienoic acid by hydrogen abstraction and antarafacial insertion of molecular oxygen and sequentially to an allene oxide, (9S,10)-epoxy-(10Z,12Z)-octadecadienoic acid, which gives nonenzymatic hydrolysis products alpha- and gamma-ketols
730154
Fusarium oxysporum Fo5176
(9S,10)-epoxy-(10Z,12Z)-octadecadienoic acid + H2O
-
-
-
?
4.2.1.92
(9S)-hydroperoxy-(10E,12Z)-octadecadienoic acid
recombinant FOXB_01332 oxidizes 18:2n-6 to (9S)-hydroperoxy-10(E),12(Z)-octadecadienoic acid by hydrogen abstraction and antarafacial insertion of molecular oxygen and sequentially to an allene oxide, (90S)-(10)-epoxy-10,12(Z)-octadecadienoic acid, which gives nonenzymatic hydrolysis products alpha- and gamma-ketols
730154
Fusarium oxysporum
(9S,10)-10-epoxy-(10Z,12Z)-octadecadienoic acid + H2O
-
-
-
?
4.2.1.92
(9S)-hydroperoxy-(10E,12Z,15Z)-octadecatrienoic acid
-
730154
Fusarium oxysporum
(9S,10)-epoxy-(10Z,12Z,15Z)-octadecatrienoic acid + H2O
-
-
-
?
4.2.1.92
(9Z,11E,13R)-13-hydroperoxyoctadeca-9,11-dienoic acid
-
730154
Fusarium oxysporum
11-hydroxy-12(13)-epoxy-octadecadienoic acid + 9-hydroxy-12(13)-epoxy-octadecadienoic acid + H2O
-
-
-
?
4.2.1.92
(9Z,11E,13R)-13-hydroperoxyoctadeca-9,11-dienoic acid
-
730154
Fusarium oxysporum Fo5176
11-hydroxy-12(13)-epoxy-octadecadienoic acid + 9-hydroxy-12(13)-epoxy-octadecadienoic acid + H2O
-
-
-
?
4.2.1.92
13-hydroperoxy-(10E,12Z)-octadecadienoic acid
-
730154
Fusarium oxysporum
11-hydroxy-12(13)-epoxy-octadecadienoic acid + 9-hydroxy-12(13)-epoxy-octadecadienoic acid + H2O
-
-
-
?
4.2.1.92
13-hydroperoxy-(10E,12Z)-octadecadienoic acid
-
730154
Fusarium oxysporum Fo5176
11-hydroxy-12(13)-epoxy-octadecadienoic acid + 9-hydroxy-12(13)-epoxy-octadecadienoic acid + H2O
-
-
-
?
4.2.1.92
additional information
FOXB_01332 is a linoleate 9-dioxygenase with homology to animal heme peroxidases and a 9-dioxygenase-allene oxide synthase fusion protein
730154
Fusarium oxysporum
?
-
-
-
?
4.2.1.92
additional information
(9S)-dioxygenase-allene oxide synthase converts 9S-hydroperoxyoctadecadienoic acid to alpha- and gamma-ketols, likely formed by hydrolysis of (9S,10)-(10)-epoxy-(10Z,12Z)-octadecadienoic acid, along with small amounts of epoxy alcohols. The (9R)-hydroperoxyoctadecadienoic acid preparation contains a few percent (9S)-hydroperoxyoctadecadienoic acid, and only the latter is apparently transformed to an alpha-ketol by (9S)-dioxygenase-allene oxide synthase. (13S)-hydroperoxyoctadecadienoic acid, (13S)-hydroxy-(10E,12Z,15Z)-octadecatrienoicacid, (13R)-hydroperoxyoctadecadienoic acid, and (13R)-hydroxy-(10E,12Z,15Z)-octadecatrienoicacid are not transformed to detectable amounts of allene oxides/alpha-ketols, but variable amounts of epoxy alcohols accumulate, mass spectrometric analysis of products, substrate specificity, overview
730154
Fusarium oxysporum
?
-
-
-
?
4.2.1.92
additional information
FOXB_01332 is a linoleate 9-dioxygenase with homology to animal heme peroxidases and a 9-dioxygenase-allene oxide synthase fusion protein
730154
Fusarium oxysporum Fo5176
?
-
-
-
?
4.2.1.92
additional information
(9S)-dioxygenase-allene oxide synthase converts 9S-hydroperoxyoctadecadienoic acid to alpha- and gamma-ketols, likely formed by hydrolysis of (9S,10)-(10)-epoxy-(10Z,12Z)-octadecadienoic acid, along with small amounts of epoxy alcohols. The (9R)-hydroperoxyoctadecadienoic acid preparation contains a few percent (9S)-hydroperoxyoctadecadienoic acid, and only the latter is apparently transformed to an alpha-ketol by (9S)-dioxygenase-allene oxide synthase. (13S)-hydroperoxyoctadecadienoic acid, (13S)-hydroxy-(10E,12Z,15Z)-octadecatrienoicacid, (13R)-hydroperoxyoctadecadienoic acid, and (13R)-hydroxy-(10E,12Z,15Z)-octadecatrienoicacid are not transformed to detectable amounts of allene oxides/alpha-ketols, but variable amounts of epoxy alcohols accumulate, mass spectrometric analysis of products, substrate specificity, overview
730154
Fusarium oxysporum Fo5176
?
-
-
-
?
General Information
EC Number
General Information
Commentary
Organism
4.2.1.92
evolution
FOXB_01332 is a linoleate 9-DOX with homology to animal heme peroxidases and a 9-dioxygenase-allene oxide synthase fusion protein. The conserved Tyr-(His/Arg)-Trp-His motif contains a Phe instead of the catalytic Tyr residue, which is oxidized by the heme to a radical that performs the hydrogen abstraction of LDS and COX, the replacement of Phe 416 with Trp does not affect the product profile of FOXB_01332
Fusarium oxysporum
4.2.1.92
additional information
the acid-alcohol pair Glu946-Ser949 lacks catalytic importance for the allene oxide synthase activity
Fusarium oxysporum
General Information (protein specific)
EC Number
General Information
Commentary
Organism
4.2.1.92
evolution
FOXB_01332 is a linoleate 9-DOX with homology to animal heme peroxidases and a 9-dioxygenase-allene oxide synthase fusion protein. The conserved Tyr-(His/Arg)-Trp-His motif contains a Phe instead of the catalytic Tyr residue, which is oxidized by the heme to a radical that performs the hydrogen abstraction of LDS and COX, the replacement of Phe 416 with Trp does not affect the product profile of FOXB_01332
Fusarium oxysporum
4.2.1.92
additional information
the acid-alcohol pair Glu946-Ser949 lacks catalytic importance for the allene oxide synthase activity
Fusarium oxysporum