Cloned (Comment) | Organism |
---|---|
gene FOXB_01332, phylogenetic tree, expression of wild-type and mutant enzymes | Fusarium oxysporum |
Protein Variants | Comment | Organism |
---|---|---|
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 |
F416W | site-directed mutagenesis, the catalytic residue mutant shows an unaltered product profile compared to the wild-type enzyme | Fusarium oxysporum |
N921V | site-directed mutagenesis, the mutant shows activity similar to the wild-type enzyme | Fusarium oxysporum |
S949A | site-directed mutagenesis, the mutant also forms alpha-ketol like the native enzyme | Fusarium oxysporum |
Natural Substrates | Organism | Comment (Nat. Sub.) | Natural Products | Comment (Nat. Pro.) | Rev. | Reac. |
---|---|---|---|---|---|---|
(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 | - |
? | |
(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 | - |
? | |
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 | ? | - |
? | |
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 | UniProt | Comment | Textmining |
---|---|---|---|
Fusarium oxysporum | F9F4K7 | gene FOXB_01332 | - |
Fusarium oxysporum Fo5176 | F9F4K7 | gene FOXB_01332 | - |
Substrates | Comment Substrates | Organism | Products | Comment (Products) | Rev. | Reac. |
---|---|---|---|---|---|---|
(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 | Fusarium oxysporum | (9S,10)-epoxy-(10Z,12Z)-octadecadienoic acid + H2O | - |
? | |
(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 | Fusarium oxysporum Fo5176 | (9S,10)-epoxy-(10Z,12Z)-octadecadienoic acid + H2O | - |
? | |
(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 | Fusarium oxysporum | (9S,10)-10-epoxy-(10Z,12Z)-octadecadienoic acid + H2O | - |
? | |
(9S)-hydroperoxy-(10E,12Z,15Z)-octadecatrienoic acid | - |
Fusarium oxysporum | (9S,10)-epoxy-(10Z,12Z,15Z)-octadecatrienoic acid + H2O | - |
? | |
(9Z,11E,13R)-13-hydroperoxyoctadeca-9,11-dienoic acid | - |
Fusarium oxysporum | 11-hydroxy-12(13)-epoxy-octadecadienoic acid + 9-hydroxy-12(13)-epoxy-octadecadienoic acid + H2O | - |
? | |
(9Z,11E,13R)-13-hydroperoxyoctadeca-9,11-dienoic acid | - |
Fusarium oxysporum Fo5176 | 11-hydroxy-12(13)-epoxy-octadecadienoic acid + 9-hydroxy-12(13)-epoxy-octadecadienoic acid + H2O | - |
? | |
13-hydroperoxy-(10E,12Z)-octadecadienoic acid | - |
Fusarium oxysporum | 11-hydroxy-12(13)-epoxy-octadecadienoic acid + 9-hydroxy-12(13)-epoxy-octadecadienoic acid + H2O | - |
? | |
13-hydroperoxy-(10E,12Z)-octadecadienoic acid | - |
Fusarium oxysporum Fo5176 | 11-hydroxy-12(13)-epoxy-octadecadienoic acid + 9-hydroxy-12(13)-epoxy-octadecadienoic acid + H2O | - |
? | |
additional information | FOXB_01332 is a linoleate 9-dioxygenase with homology to animal heme peroxidases and a 9-dioxygenase-allene oxide synthase fusion protein | Fusarium oxysporum | ? | - |
? | |
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 | Fusarium oxysporum | ? | - |
? | |
additional information | FOXB_01332 is a linoleate 9-dioxygenase with homology to animal heme peroxidases and a 9-dioxygenase-allene oxide synthase fusion protein | Fusarium oxysporum Fo5176 | ? | - |
? | |
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 | Fusarium oxysporum Fo5176 | ? | - |
? |
Synonyms | Comment | Organism |
---|---|---|
9S-DOX-AOS | - |
Fusarium oxysporum |
FOXB_01332 | - |
Fusarium oxysporum |
General Information | Comment | Organism |
---|---|---|
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 |
additional information | the acid-alcohol pair Glu946-Ser949 lacks catalytic importance for the allene oxide synthase activity | Fusarium oxysporum |