EC Number |
Substrates |
Organism |
Products |
Reversibility |
---|
5.4.4.5 | (8R,9Z,12Z)-8-hydroperoxy-10,12-octadecadienoate |
- |
Aspergillus fumigatus |
(7S,8S,9Z,12Z)-7,8-dihydroxyoctadeca-9,12-dienoate |
- |
? |
5.4.4.5 | (8R,9Z,12Z)-8-hydroperoxy-9,12-octadecadienoate |
- |
Aspergillus clavatus |
(5S,8R,9Z,12Z)-5,8-dihydroxy-9,12-octadecadienoate |
- |
? |
5.4.4.5 | (8R,9Z,12Z)-8-hydroperoxy-9,12-octadecadienoate |
the enzyme is involved in the regulation of the life cycle of Aspergillus nidulans. Synthesis of the psi factor (8R,9E,12Z)-8-hydroperoxy-9,12-octadecadienoate, that influences the development of the asexual conidiophores and sexual cleistothecia |
Aspergillus nidulans |
(5S,8R,9Z,12Z)-5,8-dihydroxy-9,12-octadecadienoate |
- |
? |
5.4.4.5 | (8R,9Z,12Z)-8-hydroperoxy-9,12-octadecadienoate |
i.e. (9Z,12Z)-octadeca-9,12-dienoate. Mechanism of biosynthesis: the enzyme oxidizes linoleic acid to (8R)-hydroperoxylinoleic acid and to (5S,8R)-dihydroxylinoleic acids as major products. This occurs by abstraction of the pro-S hydrogen at C-8 and antarafacial dioxygenation at C-8 or at C-10 with double bond migration. (8R,9Z,12Z)-8-Hydroperoxy-9,12-octadecadienoate is then isomerized to (5S,8R,9Z,12Z)-5,8-dihydroperoxy-9,12-octadecadienoate by abstraction of the pro-S hydrogens at C-5 of (8R,9Z,12Z)-8-hydroperoxy-9,12-octadecadienoate, respectively, followed by suprafacial oxygenation |
Aspergillus clavatus |
(5S,8R,9Z,12Z)-5,8-dihydroxy-9,12-octadecadienoate |
- |
? |
5.4.4.5 | (8R,9Z,12Z)-8-hydroperoxy-9,12-octadecadienoate |
the N-terminal heme peroxidase domain is responsible for the dioxygenase reaction as the first step of the PpoA reaction, i.e. oxidation of linoleic acid to (8R,9Z,12Z)-8-hydroperoxy-9,12-octadecadienoate as an intermediate product. The C-terminal P450 domain catalyzes the second reaction step, the isomerization of (8R,9Z,12Z)-8-hydroperoxy-9,12-octadecadienoate to (5S,8R,9Z,12Z)-5,8-dihydroxy-9,12-octadecadienoate, and is therefore termed the 8-hydroperoxide isomerase P450 domain |
Aspergillus nidulans |
(5S,8R,9Z,12Z)-5,8-dihydroxy-9,12-octadecadienoate |
- |
? |
5.4.4.5 | (8R,9Z,12Z)-9-hydroperoxy-10,12-octadecadienoate |
- |
Aspergillus fumigatus |
(5S,8R,9Z,12Z)-5,8-dihydroxyoctadeca-9,12-dienoate |
- |
? |