1.13.11.60 (11Z)-icos-11-enoic acid + O2 - Aspergillus nidulans 10-hydroperoxyeicosenoic acid - ? 415814 1.13.11.60 (11Z)-icosa-11-enoate + O2 - Aspergillus fumigatus ? - ? 415815 1.13.11.60 (11Z,14Z)-icosa-11,14-dienoic acid + O2 - Aspergillus nidulans (11Z,14Z)-10-hydroperoxyeicosa-11,14-dienoic acid - ? 415816 1.13.11.60 (11Z,14Z)-icosa-11,14-dienoic acid + O2 - Aspergillus fumigatus ? - ? 415817 1.13.11.60 (11Z,14Z,17Z)-icosa-11,14,17-trienoic acid + O2 - Aspergillus nidulans (11Z,14Z,17Z)-10-hydroperoxyeicosa-11,14,17-trienoic acid - ? 415818 1.13.11.60 (R)-8-hydroperoxy-(9Z,12Z)-octadecadienoate + O2 - Colletotrichum graminicola (8R,11R)-8,11-dihydroperoxy-(9Z,12Z)-octadecadienoate + (7R,8R)-7,8-dihydroperoxy-(9Z,12Z)-octadecadienoate - ? 440447 1.13.11.60 (R)-8-hydroperoxy-(9Z,12Z)-octadecadienoate + O2 - Colletotrichum graminicola M1.001 (8R,11R)-8,11-dihydroperoxy-(9Z,12Z)-octadecadienoate + (7R,8R)-7,8-dihydroperoxy-(9Z,12Z)-octadecadienoate - ? 440447 1.13.11.60 (R)-8-hydroperoxy-(9Z,12Z)-octadecadienoate + O2 - Colletotrichum graminicola M1.001 / M2 / FGSC 10212 (8R,11R)-8,11-dihydroperoxy-(9Z,12Z)-octadecadienoate + (7R,8R)-7,8-dihydroperoxy-(9Z,12Z)-octadecadienoate - ? 440447 1.13.11.60 alpha-linolenate + O2 - Aspergillus fumigatus ? - ? 408373 1.13.11.60 alpha-linolenate + O2 - Colletotrichum gloeosporioides (8R,9Z,12Z)-8-hydroperoxy-9,12,15-octadecatrienoate - ? 441035 1.13.11.60 alpha-linolenate + O2 via (9Z,12Z,15Z)-8-hydroperoxyoctadeca-9,12,15-trienoate, whole enzyme reaction Colletotrichum gloeosporioides (9Z,12Z,15Z)-7,8-dihydroperoxyoctadeca-9,12,15-trienoate - ? 444897 1.13.11.60 alpha-linolenate + O2 via (9Z,12Z,15Z)-8-hydroperoxyoctadeca-9,12,15-trienoic acid, best substrate with respect to whole enzyme activity Colletotrichum gloeosporioides (9Z,12Z,15Z)-7,8-dihydroxyoctadeca-9,12,15-trienoic acid - ? 444899 1.13.11.60 alpha-linolenate + O2 dioxygenase reaction of the N-terminal domain Colletotrichum gloeosporioides (9Z,12Z,15Z)-8-hydroperoxyoctadeca-9,12,15-trienoate - ? 444900 1.13.11.60 alpha-linolenic acid + O2 - Colletotrichum graminicola ? - ? 186655 1.13.11.60 alpha-linolenic acid + O2 - Colletotrichum graminicola M1.001 ? - ? 186655 1.13.11.60 alpha-linolenic acid + O2 - Colletotrichum graminicola M1.001 / M2 / FGSC 10212 ? - ? 186655 1.13.11.60 alpha-linolenic acid + O2 - Penicillium oxalicum (6S,8R,9Z,12Z,15Z)-dihydroxy-9,12,15-octadecatrienoic acid - ? 462240 1.13.11.60 alpha-linolenic acid + O2 - Penicillium oxalicum KCTC 6440 (6S,8R,9Z,12Z,15Z)-dihydroxy-9,12,15-octadecatrienoic acid - ? 462240 1.13.11.60 alpha-linolenic acid + O2 - Blastomyces dermatitidis (6Z,8E,12Z)-10-hydroperoxyoctadecatrienoic acid - ? 462241 1.13.11.60 alpha-linolenic acid + O2 - Gaeumannomyces graminis 8(9)epoxy-10-hydroxy-(12Z,15Z)-octadecadienoate - ? 462244 1.13.11.60 arachidonate + O2 - Colletotrichum gloeosporioides (5Z,8Z,11Z,14Z)-8-hydroxyeicosa-5,8,11,14-tetraenoic acid - ? 444917 1.13.11.60 arachidonic acid + O2 - Fusarium oxysporum (R)-10-hydroxyarachidonic acid - ? 441053 1.13.11.60 arachidonic acid + O2 - Fusarium oxysporum Fo5176 (R)-10-hydroxyarachidonic acid - ? 441053 1.13.11.60 arachidonic acid + O2 - Colletotrichum gloeosporioides 8-hydroxyarachidonic acid - ? 441054 1.13.11.60 dihomo-gamma-linolenate + O2 - Colletotrichum gloeosporioides (8Z,11Z,14Z)-8-hydroxyeicosa-8,11,14-trienoic acid - ? 445450 1.13.11.60 dihomo-gamma-linolenic acid + O2 - Colletotrichum gloeosporioides 8-hydroxydihomo-gamma-linolenic acid - ? 441310 1.13.11.60 docosapentaenoic acid + O2 - Fusarium oxysporum (R)-10-hydroperoxy-docosapentaenoic acid - ? 441349 1.13.11.60 docosapentaenoic acid + O2 - Fusarium oxysporum Fo5176 (R)-10-hydroperoxy-docosapentaenoic acid - ? 441349 1.13.11.60 eicosadienoate + O2 - Colletotrichum gloeosporioides (11Z,14Z)-8-hydroxyeicosa-11,14-dienoic acid - ? 445467 1.13.11.60 eicosadienoic acid + O2 - Colletotrichum gloeosporioides 8-hydroxyeicosadienoic acid - ? 441357 1.13.11.60 eicosenoate + O2 - Colletotrichum gloeosporioides (11Z)-8-hydroxyeicosa-11-enoic acid - ? 445469 1.13.11.60 eicosenoic acid + O2 - Colletotrichum gloeosporioides 8-hydroxyeicosenoic acid - ? 441360 1.13.11.60 elaidate + O2 - Aspergillus fumigatus ? - ? 416972 1.13.11.60 gamma-linolenic acid + O2 - Fusarium oxysporum (R)-8-hydroxy-gamma-linolenic acid - ? 441413 1.13.11.60 gamma-linolenic acid + O2 - Fusarium oxysporum Fo5176 (R)-8-hydroxy-gamma-linolenic acid - ? 441413 1.13.11.60 linoleate - Colletotrichum graminicola (7S,8S,9Z,12Z)-7,8-dihydroxyoctadeca-9,12-dienoate - r 444359 1.13.11.60 linoleate via (8R,9Z,12Z)-8-hydroperoxyoctadeca-9,12-dienoate, whole enzyme reaction, best substrate Colletotrichum gloeosporioides (7S,8S,9Z,12Z)-7,8-dihydroxyoctadeca-9,12-dienoate - r 444359 1.13.11.60 linoleate via (8R,9Z,12Z)-8-hydroperoxyoctadeca-9,12-dienoate, whole enzyme reaction, best substrate Colletotrichum gloeosporioides KACC 40961 (7S,8S,9Z,12Z)-7,8-dihydroxyoctadeca-9,12-dienoate - r 444359 1.13.11.60 linoleate + O2 - Gaeumannomyces graminis (8R,10E,12Z)-8-hydroperoxy-10,12-octadecadienoate - ? 415665 1.13.11.60 linoleate + O2 i.e. (9Z,12Z)-octadeca-9,12-dienoate Gaeumannomyces graminis (8R,10E,12Z)-8-hydroperoxy-10,12-octadecadienoate - ? 415665 1.13.11.60 linoleate + O2 - Gaeumannomyces graminis (8R,9Z,12Z)-8-hydroperoxy-9,12-octadecadienoate - ? 415666 1.13.11.60 linoleate + O2 - Colletotrichum gloeosporioides (8R,9Z,12Z)-8-hydroperoxy-9,12-octadecadienoate - ? 415666 1.13.11.60 linoleate + O2 i.e. (9Z,12Z)-octadeca-9,12-dienoate Aspergillus clavatus (8R,9Z,12Z)-8-hydroperoxy-9,12-octadecadienoate - ? 415666 1.13.11.60 linoleate + O2 i.e. (9Z,12Z)-octadeca-9,12-dienoate Gaeumannomyces graminis (8R,9Z,12Z)-8-hydroperoxy-9,12-octadecadienoate - ? 415666 1.13.11.60 linoleate + O2 i.e. (9Z,12Z)-octadeca-9,12-dienoate Aspergillus fumigatus (8R,9Z,12Z)-8-hydroperoxy-9,12-octadecadienoate - ? 415666 1.13.11.60 linoleate + O2 i.e. (9Z,12Z)-octadeca-9,12-dienoate Gaeumannomyces graminis (8R,9Z,12Z)-8-hydroperoxy-9,12-octadecadienoate the wild-type enzyme forms 98% (8R,9Z,12Z)-8-hydroperoxy-9,12-octadecadienoate and 2% (10R,9Z,12Z)-8-hydroperoxy-9,12-octadecadienoate. The V330L mutation augments the formation of (10R,9Z,12Z)-8-hydroperoxy-9,12-octadecadienoate 3fold ? 415666 1.13.11.60 linoleate + O2 the enzyme is involved in the regulation of the life cycle of Aspergillus nidulans. Synthesis of the psi factor (8R,9Z,12Z)-8-hydroperoxy-9,12-octadecadienoate, that influences the development of the asexual conidiophores and sexual cleistothecia Aspergillus nidulans (8R,9Z,12Z)-8-hydroperoxy-9,12-octadecadienoate - ? 415666 1.13.11.60 linoleate + O2 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 Gaeumannomyces graminis (8R,9Z,12Z)-8-hydroperoxy-9,12-octadecadienoate - ? 415666 1.13.11.60 linoleate + O2 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 Gaeumannomyces graminis (8R,9Z,12Z)-8-hydroperoxy-9,12-octadecadienoate - ? 415666 1.13.11.60 linoleate + O2 expression in Pichia pastoris changes the position and stereospecificity of a hydroperoxide isomerase. The recombinant enzyme forms (5S,8R)-dihydroxylinoleic acid (60% 5S) and 8R,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 Gaeumannomyces graminis (8R,9Z,12Z)-8-hydroperoxy-9,12-octadecadienoate - ? 415666 1.13.11.60 linoleate + O2 H2O2 (up to 9 mM) does not support enzyme activity under anaerobic conditions Gaeumannomyces graminis (8R,9Z,12Z)-8-hydroperoxy-9,12-octadecadienoate - ? 415666 1.13.11.60 linoleate + O2 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 hydrogen at C-5 of (8R,9Z,12Z)-8-hydroperoxy-9,12-octadecadienoate, respectively, followed by suprafacial oxygenation Aspergillus clavatus (8R,9Z,12Z)-8-hydroperoxy-9,12-octadecadienoate - ? 415666 1.13.11.60 linoleate + O2 i.e. (9Z,12Z)-octadeca-9,12-dienoate. The dioxygenase reaction involves stereospecific abstraction of the pro-S hydrogen from C-8 followed by antarafacial insertion of dioxygen to produce (8R)-hydroperoxylinoleic acid Gaeumannomyces graminis (8R,9Z,12Z)-8-hydroperoxy-9,12-octadecadienoate - ? 415666 1.13.11.60 linoleate + O2 i.e. (9Z,12Z)-octadeca-9,12-dienoate. The N-terminal heme peroxidase domain might be 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-dihydroperoxy-9,12-octadecadienoate, and is therefore termed the 8-hydroperoxide isomerase P450 domain Aspergillus nidulans (8R,9Z,12Z)-8-hydroperoxy-9,12-octadecadienoate - ? 415666 1.13.11.60 linoleate + O2 - Gaeumannomyces graminis var. graminis (8R,9Z,12Z)-8-hydroperoxy-9,12-octadecadienoate - ? 415666 1.13.11.60 linoleate + O2 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 Gaeumannomyces graminis var. graminis (8R,9Z,12Z)-8-hydroperoxy-9,12-octadecadienoate - ? 415666 1.13.11.60 linoleate + O2 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 Gaeumannomyces graminis var. graminis (8R,9Z,12Z)-8-hydroperoxy-9,12-octadecadienoate - ? 415666 1.13.11.60 linoleate + O2 - Colletotrichum gloeosporioides KACC 40961 (8R,9Z,12Z)-8-hydroperoxy-9,12-octadecadienoate - ? 415666 1.13.11.60 linoleate + O2 - Gaeumannomyces graminis var. avenae (8R,9Z,12Z)-8-hydroperoxy-9,12-octadecadienoate - ? 415666 1.13.11.60 linoleate + O2 expression in Pichia pastoris changes the position and stereospecificity of a hydroperoxide isomerase. The recombinant enzyme forms (5S,8R)-dihydroxylinoleic acid (60% 5S) and 8R,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 Gaeumannomyces graminis var. avenae (8R,9Z,12Z)-8-hydroperoxy-9,12-octadecadienoate - ? 415666 1.13.11.60 linoleate + O2 i.e. (9Z,12Z)-octadeca-9,12-dienoate Gaeumannomyces graminis var.graminis (8R,9Z,12Z)-8-hydroperoxy-9,12-octadecadienoate - ? 415666 1.13.11.60 linoleate + O2 i.e. (9Z,12Z)-octadeca-9,12-dienoate. The dioxygenase reaction involves stereospecific abstraction of the pro-S hydrogen from C-8 followed by antarafacial insertion of dioxygen to produce (8R)-hydroperoxylinoleic acid Gaeumannomyces graminis var.graminis (8R,9Z,12Z)-8-hydroperoxy-9,12-octadecadienoate - ? 415666 1.13.11.60 linoleate + O2 - Penicillium oxalicum (8R,9Z,12Z)-8-hydroperoxyoctadeca-9,12-dienoate - ? 424887 1.13.11.60 linoleate + O2 - Aspergillus fumigatus (8R,9Z,12Z)-8-hydroperoxyoctadeca-9,12-dienoate - ? 424887 1.13.11.60 linoleate + O2 - Gaeumannomyces graminis (8R,9Z,12Z)-8-hydroperoxyoctadeca-9,12-dienoate - ? 424887 1.13.11.60 linoleate + O2 - Colletotrichum gloeosporioides (8R,9Z,12Z)-8-hydroperoxyoctadeca-9,12-dienoate - ? 424887 1.13.11.60 linoleate + O2 - Paracoccidioides brasiliensis (8R,9Z,12Z)-8-hydroperoxyoctadeca-9,12-dienoate - ? 424887 1.13.11.60 linoleate + O2 all-cis-9,12-octadecadienoic acid Aspergillus fumigatus (8R,9Z,12Z)-8-hydroperoxyoctadeca-9,12-dienoate - ? 424887 1.13.11.60 linoleate + O2 dioxygenase reaction of the N-terminal domain Colletotrichum gloeosporioides (8R,9Z,12Z)-8-hydroperoxyoctadeca-9,12-dienoate - ? 424887 1.13.11.60 linoleate + O2 the enzyme oxidizes linoleate and the Gly conjugate rapidly to hydroperoxides at C-8 but also at C-9 and C-13 (ratio 1:0.1:0.2, respectively) and to 7,8-diol Gaeumannomyces graminis (8R,9Z,12Z)-8-hydroperoxyoctadeca-9,12-dienoate - ? 424887 1.13.11.60 linoleate + O2 - Colletotrichum gloeosporioides KACC 40961 (8R,9Z,12Z)-8-hydroperoxyoctadeca-9,12-dienoate - ? 424887 1.13.11.60 linoleate + O2 dioxygenase reaction of the N-terminal domain Colletotrichum gloeosporioides KACC 40961 (8R,9Z,12Z)-8-hydroperoxyoctadeca-9,12-dienoate - ? 424887 1.13.11.60 linoleate + O2 - Penicillium oxalicum KCTC 6440 (8R,9Z,12Z)-8-hydroperoxyoctadeca-9,12-dienoate - ? 424887 1.13.11.60 linoleate + O2 - Colletotrichum gloeosporioides (7S,8S)-7,8-dihydroxy-(9Z,12Z)-octadecadienoic acid - ? 441573 1.13.11.60 linoleate + O2 - Colletotrichum gloeosporioides KACC 40961 (7S,8S)-7,8-dihydroxy-(9Z,12Z)-octadecadienoic acid - ? 441573 1.13.11.60 linoleate + O2 - Colletotrichum graminicola (R)-8-hydroperoxy-(9Z,12Z)-octadecadienoate + (8R,11R)-8,11-dihydroperoxy-(9Z,12Z)-octadecadienoate + (7R,8R)-7,8-dihydroperoxy-(9Z,12Z)-octadecadienoate - ? 441574 1.13.11.60 linoleate + O2 - Colletotrichum gloeosporioides (8R,9Z,12Z)-8-hydroperoxyoctadeca-9,12-dienoic acid - ? 441575 1.13.11.60 linoleate + O2 - Fusarium oxysporum (8R,9Z,12Z)-8-hydroperoxyoctadeca-9,12-dienoic acid - ? 441575 1.13.11.60 linoleate + O2 - Fusarium oxysporum Fo5176 (8R,9Z,12Z)-8-hydroperoxyoctadeca-9,12-dienoic acid - ? 441575 1.13.11.60 linoleate + O2 - Blastomyces dermatitidis (8E,12Z)-10-hydroperoxyoctadeca-8,12-dienoic acid + (8R,9Z,12Z)-8-hydroperoxyoctadeca-9,12-dienoate - ? 462659 1.13.11.60 linoleate + O2 - Rhizoctonia solani (8R)-hydroxy-(9Z,12Z)-octadecadienoic acid - ? 462660 1.13.11.60 linoleate + O2 - Rhizoctonia solani 123E (8R)-hydroxy-(9Z,12Z)-octadecadienoic acid - ? 462660 1.13.11.60 linoleic acid + O2 highest activity Penicillium oxalicum (6R,8R)-dihydroxy-9,12(Z,Z)-octadecadienoic acid - ? 462666 1.13.11.60 linoleic acid + O2 highest activity Penicillium oxalicum KCTC 6440 (6R,8R)-dihydroxy-9,12(Z,Z)-octadecadienoic acid - ? 462666 1.13.11.60 additional information the recombinant enzyme expressed in insect cells, oxygenates 16:1n-7, 18:1n-7, 18:2n-6, 18:3n-3, 20:1n-9, 20:1n-11, and 20:2n-6 at the allylic carbon closest to the carboxyl group Gaeumannomyces graminis ? - ? 89 1.13.11.60 additional information the bifunctional enzyme forms (7S,8S)-7,8-dihydroxylinoleic acid from (8R)-hydroperoxylinoleic acid by intramolecular oxygen transfer. Linoleate diol synthases are fungal dioxygenase-cytochrome P450 fusion enzymes. P450 hydroxylases usually contain an acid-alcohol pair in the I-helices for the heterolytic scission of O2 and formation of compound I, i.e. Por+-Fe(IV)=O, and water. The function of the acid-alcohol pair appears to be replaced by a different amide residue, Asn938 of 7,8-LDS, for heterolysis of (8R,9Z,12Z)-8-hydroperoxyoctadeca-9,12-dienoate to generate compound I Gaeumannomyces graminis ? - ? 89 1.13.11.60 additional information the bifunctional enzyme forms 5S,8S-dihydroxylinoleic acid from (8R)-hydroperoxylinoleic acid by intramolecular oxygen transfer. Linoleate diol synthases are fungal dioxygenase-cytochrome P450 fusion enzymes. P450 hydroxylases usually contain an acid-alcohol pair in the I-helices for the heterolytic scission of O2 and formation of compound I, i.e. Por+-Fe(IV)=O, and water. The function of the acid-alcohol pair appears to be replaced by a different amide residue, Gln890 of 5,8-LDS, for heterolysis of (8R,9Z,12Z)-8-hydroperoxyoctadeca-9,12-dienoate to generate compound I Aspergillus fumigatus ? - ? 89 1.13.11.60 additional information the enzyme forms (5S,8R)-5,8-dihydroxylinoleic acid from (8R)-hydroperoxylinoleic acid by intramolecular oxygen transfer. Linoleate diol synthases are fungal dioxygenase-cytochrome P450 fusion enzymes Aspergillus fumigatus ? - ? 89 1.13.11.60 additional information bifunctional enzyme, the second domain isomerizes the product (8R,9Z,12Z)-8-hydroperoxy-9,12-octadecadienoate to (7S,8S,9Z,12Z)-5,8-dihydroxyoctadeca-9,12-dienoate, cf. EC 5.4.4.6 Colletotrichum gloeosporioides ? - ? 89 1.13.11.60 additional information enzyme metabolizes fatty acids to hydroperoxides with broad substrate specificity. Products show R configuration at the (n-10) positions. Fatty acids of the n-3 series are oxidized less efficiently and often to hydroperoxides with an R configuration at both (n-10) and (n-7) positions Fusarium oxysporum ? - ? 89 1.13.11.60 additional information enzyme oxidizes oleic and linoleic acids in analogy with 7,8-linoleate diol synthases, but with the additional biosynthesis of 8,11-dihydroxylinoleic acid Colletotrichum graminicola ? - ? 89 1.13.11.60 additional information no substrate: gamma-linolenoate Colletotrichum graminicola ? - ? 89 1.13.11.60 additional information the dioxygenase-cytochrome P450 homologue oxidizes oleic and linoleic acids in analogy with 7,8-linoleate diol synthases (LDSs), but with the additional biosynthesis of 8,11-dihydroxylinoleic acid Colletotrichum graminicola ? - ? 89 1.13.11.60 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 Colletotrichum gloeosporioides ? - ? 89 1.13.11.60 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 (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 (9Z,12Z)-7S,8S-dihydroxyoctadeca-9,12-dienoic acid (7,8-DiHODE) or (5R,8R,9Z,12Z)-5,8-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 Colletotrichum gloeosporioides ? - ? 89 1.13.11.60 additional information the Ile and Trp conjugates of linoleate are not oxidized at C-8. The enzyme oxidizes the linoleate-Ile conjugate to 9- and 13-HODE-Ile and to 9(10)- and 12(13)epoxyalcohols. The alpha-linolenic acid-Ile conjugate is transformed to 9-, 13-, and 16-HOTrE-Ile in a ratio of 0.4:0.3:1, respectively Gaeumannomyces graminis ? - - 89 1.13.11.60 additional information enzyme oxidizes oleic and linoleic acids in analogy with 7,8-linoleate diol synthases, but with the additional biosynthesis of 8,11-dihydroxylinoleic acid Colletotrichum graminicola M1.001 ? - ? 89 1.13.11.60 additional information no substrate: gamma-linolenoate Colletotrichum graminicola M1.001 ? - ? 89 1.13.11.60 additional information the dioxygenase-cytochrome P450 homologue oxidizes oleic and linoleic acids in analogy with 7,8-linoleate diol synthases (LDSs), but with the additional biosynthesis of 8,11-dihydroxylinoleic acid Colletotrichum graminicola M1.001 ? - ? 89 1.13.11.60 additional information enzyme oxidizes oleic and linoleic acids in analogy with 7,8-linoleate diol synthases, but with the additional biosynthesis of 8,11-dihydroxylinoleic acid Colletotrichum graminicola M1.001 / M2 / FGSC 10212 ? - ? 89 1.13.11.60 additional information no substrate: gamma-linolenoate Colletotrichum graminicola M1.001 / M2 / FGSC 10212 ? - ? 89 1.13.11.60 additional information the dioxygenase-cytochrome P450 homologue oxidizes oleic and linoleic acids in analogy with 7,8-linoleate diol synthases (LDSs), but with the additional biosynthesis of 8,11-dihydroxylinoleic acid Colletotrichum graminicola M1.001 / M2 / FGSC 10212 ? - ? 89 1.13.11.60 additional information bifunctional enzyme, the second domain isomerizes the product (8R,9Z,12Z)-8-hydroperoxy-9,12-octadecadienoate to (7S,8S,9Z,12Z)-5,8-dihydroxyoctadeca-9,12-dienoate, cf. EC 5.4.4.6 Colletotrichum gloeosporioides KACC 40961 ? - ? 89 1.13.11.60 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 (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 (9Z,12Z)-7S,8S-dihydroxyoctadeca-9,12-dienoic acid (7,8-DiHODE) or (5R,8R,9Z,12Z)-5,8-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 Colletotrichum gloeosporioides KACC 40961 ? - ? 89 1.13.11.60 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 Colletotrichum gloeosporioides KACC 40961 ? - ? 89 1.13.11.60 additional information enzyme metabolizes fatty acids to hydroperoxides with broad substrate specificity. Products show R configuration at the (n-10) positions. Fatty acids of the n-3 series are oxidized less efficiently and often to hydroperoxides with an R configuration at both (n-10) and (n-7) positions Fusarium oxysporum Fo5176 ? - ? 89 1.13.11.60 oleate + O2 - Aspergillus nidulans (9Z)-8-hydroperoxyoctadec-9-enoate - ? 417437 1.13.11.60 oleate + O2 - Colletotrichum gloeosporioides (9Z)-8-hydroperoxyoctadec-9-enoate - ? 417437 1.13.11.60 oleate + O2 - Colletotrichum gloeosporioides KACC 40961 (9Z)-8-hydroperoxyoctadec-9-enoate - ? 417437 1.13.11.60 oleate + O2 - Colletotrichum graminicola 8-hydroperoxyoctadecamonoenoate + 7,8-dihydroxyoctadecamonoenoate - ? 441802 1.13.11.60 oleate + O2 - Colletotrichum graminicola (9Z)-7,8-dihydroxyoctadeca-9-enoic acid - ? 444384 1.13.11.60 oleate + O2 via (9Z)-8-hydroperoxyoctadeca-9-enoic acid Colletotrichum gloeosporioides (9Z)-7,8-dihydroxyoctadeca-9-enoic acid - ? 444384 1.13.11.60 oleate + O2 via (9Z)-8-hydroperoxyoctadeca-9-enoic acid, whole enzyme reaction Colletotrichum gloeosporioides (9Z)-7,8-dihydroxyoctadeca-9-enoic acid - ? 444384 1.13.11.60 oleate + O2 dioxygenase reaction of the N-terminal domain Colletotrichum gloeosporioides (9Z)-8-hydroperoxyoctadeca-9-enoic acid - ? 445768 1.13.11.60 oleic acid + O2 - Penicillium oxalicum (6R,8R,9Z)-dihydroxy-9-octadecenoic acid - ? 462869 1.13.11.60 oleic acid + O2 - Penicillium oxalicum KCTC 6440 (6R,8R,9Z)-dihydroxy-9-octadecenoic acid - ? 462869 1.13.11.60 palmitoleate + O2 - Aspergillus nidulans (9Z)-8-hydroperoxyhexadec-9-enoate - ? 417457 1.13.11.60 palmitoleate + O2 - Colletotrichum gloeosporioides (9Z)-8-hydroperoxyhexadec-9-enoate - ? 417457 1.13.11.60 palmitoleate + O2 - Colletotrichum gloeosporioides KACC 40961 (9Z)-8-hydroperoxyhexadec-9-enoate - ? 417457 1.13.11.60 palmitoleate + O2 - Aspergillus fumigatus ? - ? 417458 1.13.11.60 palmitoleate + O2 via (9Z)-dihydroperoxyhexadeca-9-enoate Colletotrichum gloeosporioides (9Z)-5,8-dihydroxyhexadeca-9-enoic acid - ? 445778 1.13.11.60 palmitoleic acid + O2 - Penicillium oxalicum (6S,8R,9Z)-dihydroxy-9-hexadecenoic acid - ? 462887 1.13.11.60 palmitoleic acid + O2 - Penicillium oxalicum KCTC 6440 (6S,8R,9Z)-dihydroxy-9-hexadecenoic acid - ? 462887