5.4.4.6: 9,12-octadecadienoate 8-hydroperoxide 8S-isomerase
This is an abbreviated version!
For detailed information about 9,12-octadecadienoate 8-hydroperoxide 8S-isomerase, go to the full flat file.
Reaction
Synonyms
7,8-diol synthase, 7,8-LDS, 7,8-linoleate diol synthase, EC 1.13.11.44
ECTree
5.4.4.6 9,12-octadecadienoate 8-hydroperoxide 8S-isomeraseAdvanced search results
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results (Substrates Products
Substrates Products on EC 5.4.4.6 - 9,12-octadecadienoate 8-hydroperoxide 8S-isomerase
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SUBSTRATE 
PRODUCT
REACTION DIAGRAM
ORGANISM
UNIPROT
COMMENTARY
(Substrate)
(Substrate)
LITERATURE
(Substrate)
(Substrate)
COMMENTARY
(Product)
(Product)
LITERATURE
(Product)
(Product)
Reversibility
r=reversible
ir=irreversible
?=not specified
r=reversible
ir=irreversible
?=not specified
(8R,9Z,12Z)-8-hydroperoxy-10,12-octadecadienoate
(7S,8S,9Z,12Z)-7,8-dihydroxyoctadeca-9,12-dienoate
(8R,9Z,12Z)-8-hydroperoxy-9,12-octadecadienoate
(7S,8S,9Z,12Z)-7,8-dihydroxy-9,12-octadecadienoate
(8R,9Z,12Z)-8-hydroperoxy-9,12-octadecadienoate
(7S,8S,9Z,12Z)-7,8-dihydroxyoctadeca-9,12-dienoate
-
conversion of (8R)-hydroperoxylinoleic acid into (7S,8S)-dihydroxylinoleic acid by stereospecific elimination of the pro-S hydrogen from C-7 and intramolecular suprafacial insertion of oxygen at C-7
-
-
?
(8R,9Z,12Z)-8-hydroperoxyoctadeca-9,12-dienoate
(7S,8S,9Z,12Z)-7,8-dihydroxyoctadeca-9,12-dienoate
(9Z)-8-hydroperoxyoctadeca-9-enoic acid
(9Z)-7,8-dihydroxyoctadeca-9-enoic acid
isomerase reaction of the C-terminal domain
-
-
r
(9Z,12Z,15Z)-8-hydroperoxyoctadeca-9,12,15-trienoic acid
(9Z,12Z,15Z)-7,8-dihydroxyoctadeca-9,12,15-trienoic acid
isomerase reaction of the C-terminal domain
-
-
r
linoleate
(7S,8S,9Z,12Z)-7,8-dihydroxyoctadeca-9,12-dienoate
via (8R,9Z,12Z)-8-hydroperoxyoctadeca-9,12-dienoate, whole enzyme reaction, best substrate
-
-
r
palmitoleate + O2
(9Z)-5,8-dihydroxyhexadeca-9-enoic acid
via (9Z)-8-dihydroperoxyhexadeca-9-enoate
-
-
?
(8R,9Z,12Z)-8-hydroperoxy-10,12-octadecadienoate
(7S,8S,9Z,12Z)-7,8-dihydroxyoctadeca-9,12-dienoate
-
-
-
-
?
(8R,9Z,12Z)-8-hydroperoxy-10,12-octadecadienoate
(7S,8S,9Z,12Z)-7,8-dihydroxyoctadeca-9,12-dienoate
-
-
-
-
?
(8R,9Z,12Z)-8-hydroperoxy-9,12-octadecadienoate
(7S,8S,9Z,12Z)-7,8-dihydroxy-9,12-octadecadienoate
-
-
-
?
(8R,9Z,12Z)-8-hydroperoxy-9,12-octadecadienoate
(7S,8S,9Z,12Z)-7,8-dihydroxy-9,12-octadecadienoate
-
-
-
-
?
(8R,9Z,12Z)-8-hydroperoxy-9,12-octadecadienoate
(7S,8S,9Z,12Z)-7,8-dihydroxy-9,12-octadecadienoate
-
-
-
?
(8R,9Z,12Z)-8-hydroperoxy-9,12-octadecadienoate
(7S,8S,9Z,12Z)-7,8-dihydroxy-9,12-octadecadienoate
bifunctional enzyme with linoleic acid (8R)-dioxygenase and hydroperoxide isomerase activities. The enzyme abstracts the 8-pro-S hydrogen from linoleic acid, which is followed by antarafacial insertion of molecular oxygen at C-8 to generate 8R-hydroperoxylinoleate. The latter is then isomerized to (7S,8S,9Z,12Z)-5,8-dihydroxy-9,12-octadecadienoate by elimination of the 7-pro-S hydrogen and intramolecular suprafacial insertion of an oxygen atom from the hydroperoxide group
-
-
?
(8R,9Z,12Z)-8-hydroperoxy-9,12-octadecadienoate
(7S,8S,9Z,12Z)-7,8-dihydroxy-9,12-octadecadienoate
bifunctional enzyme with linoleic acid 8R-dioxygenase and hydroperoxide isomerase activities. The enzyme abstracts the 8-pro-S hydrogen from linoleic acid, which is followed by antarafacial insertion of molecular oxygen at C-8 to generate 8R-hydroperoxylinoleate. The latter is then isomerized to (7S,8S,9Z,12Z)-5,8-dihydroxy-9,12-octadecadienoate by elimination of the 7-pro-S hydrogen and intramolecular suprafacial insertion of an oxygen atom from the hydroperoxide group
-
-
?
(8R,9Z,12Z)-8-hydroperoxy-9,12-octadecadienoate
(7S,8S,9Z,12Z)-7,8-dihydroxy-9,12-octadecadienoate
expression in Pichia pastoris changes the position and stereospecificity of a hydroperoxide isomerase (the recombinant enzyme forms 5,8(R)-dihydroxylinoleic acid (60% 5S) and 8(R),13-dihydroxyoctadeca-(9E,11E)-dienoic acid) possibly due to N- or O-linked mannosides in the vicinity of the heme group, whereas the (8R)-dioxygenase activity is identical with native 7,8-linoleate diol synthase
-
-
?
(8R,9Z,12Z)-8-hydroperoxy-9,12-octadecadienoate
(7S,8S,9Z,12Z)-7,8-dihydroxy-9,12-octadecadienoate
-
-
-
?
(8R,9Z,12Z)-8-hydroperoxy-9,12-octadecadienoate
(7S,8S,9Z,12Z)-7,8-dihydroxy-9,12-octadecadienoate
expression in Pichia pastoris changes the position and stereospecificity of a hydroperoxide isomerase (the recombinant enzyme forms 5,8(R)-dihydroxylinoleic acid (60% 5S) and 8(R),13-dihydroxyoctadeca-(9E,11E)-dienoic acid) possibly due to N- or O-linked mannosides in the vicinity of the heme group, whereas the (8R)-dioxygenase activity is identical with native 7,8-linoleate diol synthase
-
-
?
(8R,9Z,12Z)-8-hydroperoxy-9,12-octadecadienoate
(7S,8S,9Z,12Z)-7,8-dihydroxy-9,12-octadecadienoate
-
-
-
?
(8R,9Z,12Z)-8-hydroperoxy-9,12-octadecadienoate
(7S,8S,9Z,12Z)-7,8-dihydroxy-9,12-octadecadienoate
bifunctional enzyme with linoleic acid (8R)-dioxygenase and hydroperoxide isomerase activities. The enzyme abstracts the 8-pro-S hydrogen from linoleic acid, which is followed by antarafacial insertion of molecular oxygen at C-8 to generate 8R-hydroperoxylinoleate. The latter is then isomerized to (7S,8S,9Z,12Z)-5,8-dihydroxy-9,12-octadecadienoate by elimination of the 7-pro-S hydrogen and intramolecular suprafacial insertion of an oxygen atom from the hydroperoxide group
-
-
?
(8R,9Z,12Z)-8-hydroperoxy-9,12-octadecadienoate
(7S,8S,9Z,12Z)-7,8-dihydroxy-9,12-octadecadienoate
-
-
-
-
?
(8R,9Z,12Z)-8-hydroperoxyoctadeca-9,12-dienoate
(7S,8S,9Z,12Z)-7,8-dihydroxyoctadeca-9,12-dienoate
-
-
-
r
(8R,9Z,12Z)-8-hydroperoxyoctadeca-9,12-dienoate
(7S,8S,9Z,12Z)-7,8-dihydroxyoctadeca-9,12-dienoate
isomerase reaction of the C-terminal domain
-
-
r
alpha-linolenate + O2
(9Z,12Z,15Z)-7,8-dihydroperoxyoctadeca-9,12,15-trienoic acid
via (9Z,12Z,15Z)-8-hydroperoxyoctadeca-9,12,15-trienoic acid, best substrate with respect to whole enzyme activity
-
-
?
alpha-linolenate + O2
(9Z,12Z,15Z)-7,8-dihydroperoxyoctadeca-9,12,15-trienoic acid
via (9Z,12Z,15Z)-8-hydroperoxyoctadeca-9,12,15-trienoic acid, whole enzyme reaction
-
-
?
oleate + O2
(9Z)-7,8-dihydroxyoctadeca-9-enoic acid
via (9Z)-8-hydroperoxyoctadeca-9-enoic acid
-
-
?
oleate + O2
(9Z)-7,8-dihydroxyoctadeca-9-enoic acid
via (9Z)-8-hydroperoxyoctadeca-9-enoic acid, whole enzyme reaction
-
-
?
additional information
?
-
the bifunctional enzyme converts linoleic acid to a product, identified as (9Z,12Z)-7,8-dihydroxyoctadeca-9,12-dienoic acid (7,8-DiHODE) by liquid chromatography-mass spectrometry/mass spectrometry (LC-MS/MS) and nuclear magnetic resonance (NMR) spectroscopy. The specific activity and catalytic efficiency (kcat/Km) of 7,8-diol synthase for the conversion of fatty acid to dihydroxy fatty acid follows the descending order linoleic acid, alpha-linolenic acid, and oleic acid, indicating that the enzyme is a 7,8-linoleate diol synthase (7,8-LDS). The reaction via (9Z,12Z)-8-hydroperoxyoctadeca-9,12-dienoic acid (8-HPODE) as an intermediate and the accumulation of 8-HPODE is due to a higher 8-dioxygenase activity in the N-terminal domain than hydroperoxide isomerase activity in the C-terminal domain, EC 5.4.4.6. 8-HPODE is subsequently isomerized to (7S,8S,9Z,12Z)-dihydroxyoctadeca-9,12-dienoic acid (7,8-DiHODE) or (5S,8R,9Z,12Z)-dihydroxyoctadeca-9,12-dienoic acid (5,8-DiHODE) by the C-terminal hydroperoxide isomerase domain of diol synthase
-
-
?
additional information
?
-
the bifunctional enzyme converts linoleic acid to a product, identified as (9Z,12Z)7,8-dihydroxyoctadeca-9,12-dienoic acid (7,8-DiHODE) by liquid chromatography-mass spectrometry/mass spectrometry (LC-MS/MS) and nuclear magnetic resonance (NMR) spectroscopy. The specific activity and catalytic efficiency (kcat/Km) of 7,8-diol synthase for the conversion of fatty acid to dihydroxy fatty acid follows the descending order linoleic acid, alpha-linolenic acid, oleic acid, and palmitoleic acid, indicating that the enzyme is a 7,8-linoleate diol synthase (7,8-LDS). Substrate specificity, overview. The reaction via 8-hydroperoxy-9,12(Z,Z)-octadecadienoic acid (8-HPODE) as an intermediate and the accumulation of 8-HPODE is due to a higher 8-dioxygenase activity in the N-terminal domain than hydroperoxide isomerase activity in the C-terminal domain, EC 5.4.4.6. 8-HPODE is subsequently isomerized to (7S,8S,9Z,12Z)-dihydroxyoctadeca-9,12-dienoic acid (7,8-DiHODE) or (5S,8R,9Z,12Z)-dihydroxyoctadeca-9,12-dienoic acid (5,8-DiHODE) by the C-terminal hydroperoxide isomerase domain of diol synthase. No activity with conjugated linoleic acid, docosapentaenoic acid, and docosahexaenoic acid, and no isomerase activity and no whole enzyme acitivity, but dioxygenase activity with eicosenoic acid, eicosadienoic acid, dihomo-gamma-linolenic acid, and arachidonic acid
-
-
?
