Information on EC 4.2.1.92 - hydroperoxide dehydratase

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The expected taxonomic range for this enzyme is: Bacteria, Eukaryota

EC NUMBER
COMMENTARY
4.2.1.92
-
RECOMMENDED NAME
GeneOntology No.
hydroperoxide dehydratase
-
REACTION
REACTION DIAGRAM
COMMENTARY
ORGANISM
UNIPROT
LITERATURE
(9Z,11E,15Z)-(13S)-hydroperoxyoctadeca-9,11,15-trienoate = (9Z,15Z)-(13S)-12,13-epoxyoctadeca-9,11,15-trienoate + H2O
show the reaction diagram
acts on a number of unsaturated fatty-acid hydroperoxides, forming the corresponding allene oxides
-
-
-
(9Z,11E,15Z)-(13S)-hydroperoxyoctadeca-9,11,15-trienoate = (9Z,15Z)-(13S)-12,13-epoxyoctadeca-9,11,15-trienoate + H2O
show the reaction diagram
mechanism
-
(9Z,11E,15Z)-(13S)-hydroperoxyoctadeca-9,11,15-trienoate = (9Z,15Z)-(13S)-12,13-epoxyoctadeca-9,11,15-trienoate + H2O
show the reaction diagram
mechanism
-
(9Z,11E,15Z)-(13S)-hydroperoxyoctadeca-9,11,15-trienoate = (9Z,15Z)-(13S)-12,13-epoxyoctadeca-9,11,15-trienoate + H2O
show the reaction diagram
mechanism
-
(9Z,11E,15Z)-(13S)-hydroperoxyoctadeca-9,11,15-trienoate = (9Z,15Z)-(13S)-12,13-epoxyoctadeca-9,11,15-trienoate + H2O
show the reaction diagram
reaction mechanisms of wild-type AOS and mutant F137L, QM/MM calculations, overview
-
REACTION TYPE
ORGANISM
UNIPROT
COMMENTARY
LITERATURE
C-O bond cleavage by elimination of water
-
-
-
-
PATHWAY
BRENDA Link
KEGG Link
MetaCyc Link
jasmonic acid biosynthesis
-
-
alpha-Linolenic acid metabolism
-
-
Metabolic pathways
-
-
Biosynthesis of secondary metabolites
-
-
SYSTEMATIC NAME
IUBMB Comments
(9Z,11E,15Z)-(13S)-hydroperoxyoctadeca-9,11,15-trienoate 12,13-hydro-lyase [(9Z,15Z)-(13S)-12,13-epoxyoctadeca-9,11,15-trienoate-forming]
Acts on a number of unsaturated fatty-acid hydroperoxides, forming the corresponding allene oxides. The product of the above reaction is unstable and is acted upon by EC 5.3.99.6, allene-oxide cyclase, to form the cyclopentenone derivative (15Z)-12-oxophyto-10,15-dienoate (OPDA), which is the first cyclic and biologically active metabolite in the jasmonate biosynthesis pathway [3]. The enzyme from many plants belongs to the CYP-74 family of P-450 monooxygenases [4].
SYNONYMS
ORGANISM
UNIPROT
COMMENTARY
LITERATURE
10S-hydroperoxide lyase
-
13-HPL
-
-
13-HPL
-
-
13-HPL
-
-
13-hydroperoxide lyase
-
-
13-hydroperoxide lyase
-
-
5,8-hydroperoxide isomerase
-
-
8,11-hydroperoxide isomerase
-
-
9-HPL
-
-
9R-DOX-AOS
Aspergillus terreus A1156
-
-
allene oxide synthase
-
-
allene oxide synthase
-
-
allene oxide synthase
-
allene oxide synthase
-
allene oxide synthase
Aspergillus terreus A1156
-
-
allene oxide synthase
-
-
allene oxide synthase
-
-
allene oxide synthase
Lasiodiplodia theobromae 2334, Lasiodiplodia theobromae CBS 117454, Lasiodiplodia theobromae CBS 122127
-
-
-
allene oxide synthase
-
-
allene oxide synthase
-
allene oxide synthase
-
-
allene oxide synthase
-
-
allene oxide synthase
-
allene oxide synthase
-
allene oxide synthase
-
-
allene oxide synthase-1
-
-
AOS
belongs to the CYP74 family
AOS
Aspergillus terreus A1156
-
-
AOS
Lasiodiplodia theobromae 2334, Lasiodiplodia theobromae CBS 117454, Lasiodiplodia theobromae CBS 122127
-
-
-
catalase-related allene oxide synthase
-
-
CmHPL
-
gene name
CYP74
-
-
CYP74A
-
-
CYP74B
-
-
cytochrome P450 74A
-
-
-
-
EC 5.3.99.1
-
-
formerly
-
eLOX3
-
-
-
-
fatty acid hydroperoxide lyase
-
-
HPI
-
-
-
-
HPO-lyase
-
-
hydroperoxide dehydrase
-
-
-
-
hydroperoxide isomerase
-
-
-
-
hydroperoxide isomerase
-
-
hydroperoxide isomerase
-
-
hydroperoxide lyase
-
-
hydroperoxide lyase
-
-
hydroperoxide lyase
-
-
hydroperoxide lyase
-
-
hydroperoxide lyase
-
-
hydroperoxidehydrase
-
-
-
-
isomerase, hydroperoxide
-
-
-
-
KC525886
Aspergillus terreus A1156
-
-
linoleate hydroperoxide isomerase
-
-
-
-
linoleic acid hydroperoxide isomerase
-
-
-
-
Npun_R5469
gene name
OsAOS1
-
-
OsHPL3
-
-
OsHPL3/CYP74B2
-
-
RPP
-
-
-
-
rubber particle protein
-
-
-
-
additional information
-
AOS belongs to the CYP74 family
CAS REGISTRY NUMBER
COMMENTARY
118390-60-6
-
37318-50-6
-
ORGANISM
COMMENTARY
LITERATURE
UNIPROT
SEQUENCE DB
SOURCE
garlic
-
-
Manually annotated by BRENDA team
gene ATEG_02036; gene ATEG_02036
UniProt
Manually annotated by BRENDA team
Aspergillus terreus A1156
gene ATEG_02036; gene ATEG_02036
UniProt
Manually annotated by BRENDA team
green bell pepper variety
-
-
Manually annotated by BRENDA team
susceptible and resistant pearl millet cultivars to Sclerospora graminicola infection, IP18292, ICMP451-P6, ICMR-01004, IP18293, H77/833-2, 700651, P310-17, 7042S, 843B and 852B, gene PgAOS1
-
-
Manually annotated by BRENDA team
var. lanatus, gene HPLCl
-
-
Manually annotated by BRENDA team
gene CmHPL
-
-
Manually annotated by BRENDA team
gene FOXB_01332
UniProt
Manually annotated by BRENDA team
gene FOXB_01332
UniProt
Manually annotated by BRENDA team
enzyme additionally has dioxygenase activity
-
-
Manually annotated by BRENDA team
i.e. Botryodiplodia theobromae, no activity in strain CBS 122127
-
-
Manually annotated by BRENDA team
Lasiodiplodia theobromae 2334
i.e. Botryodiplodia theobromae, no activity in strain CBS 122127
-
-
Manually annotated by BRENDA team
Japanese Honeysuckle
UniProt
Manually annotated by BRENDA team
gene Npun_R5468
UniProt
Manually annotated by BRENDA team
Picual and Arbequina cultivars
-
-
Manually annotated by BRENDA team
gene HPL3
-
-
Manually annotated by BRENDA team
Passiflora f. edulis flavicarpa
UniProt
Manually annotated by BRENDA team
french bean
-
-
Manually annotated by BRENDA team
gene 13-hpl
-
-
Manually annotated by BRENDA team
eggplant
-
-
Manually annotated by BRENDA team
GENERAL INFORMATION
ORGANISM
UNIPROT
COMMENTARY
LITERATURE
evolution
-
phylogenetic analysis and sequence comparisons of 5,8-linoleate diol synthase, overview
evolution
-
AOS is a non-classical cytochrome P450, which, like other CYP74 enzymes, does not require molecular oxygen and NADPH-dependent P450 reductase
evolution
the fungal allene oxide synthases belongs to the CYP74 family
evolution
-
allene oxide synthases, like hydroperoxide lyases and divinyl ether synthases belong to the CYP74 family of cytochrome P450 enzymes. These enzymes rearrange fatty acid hydroperoxides differently, sharing an epoxyallylic radical as a common intermediate
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
evolution
-
phylogenetic relationship of pearl millet PgAOS1 and other known allene oxide synthases, overview
evolution
Aspergillus terreus A1156
-
the fungal allene oxide synthases belongs to the CYP74 family
-
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
-
malfunction
-
loss-of-function mutant hpl3-1 produces disease-resembling lesions spreading through the whole leaves. Mutant hpl3-1 plants exhibit enhanced induction of jasmonic acid, trypsin proteinase inhibitors and other volatiles, but decreased levels of green leaf volatiles including (Z)-3-hexen-1-ol. Mutant hpl3-1 plants are more attractive to a BPH egg parasitoid, Anagrus nilaparvatae, than the wild-type, most likely as a result of increased release of BPH-induced volatiles. Mutant hpl3-1 plants also show increased resistance to bacterial blight (Xanthomonas oryzae pv. oryzae)
metabolism
AOS is involved in jasmonic acid biosynthesis. AOS1 operates acid biosynthesis predominantly
metabolism
-
role for Phe137 in catalysis, mutation to Leu switches the product outcome from AOS to hydroperoxide lyase
metabolism
-
the enzymes are involved in the biosynthesis of (8R,11S)-dihydroxylinoleic acid via isomerization of (8R)-hydroperoxylinoleic acid to (5S,8R)-dihydroxylinoleic acid and to (8R,11S)-dihydroxylinoleic acid by abstraction of the pro-S hydrogens at C-5 and C-11 of (8R)-hydroperoxylinoleic acid, respectively, followed by suprafacial oxygenation
metabolism
-
AOS is involved in the jasmonate biochemical pathway, detailed overview
metabolism
-
jasmonic acid is synthesized from linolenic acid (18:3n-3) by sequential action of 13-lipoxygenase, allene oxide synthase, and allene oxide cyclase
metabolism
-
allene oxide synthase and its relationship to the catalytic cycle of cytochrome P450s, overview
metabolism
-
allene oxide synthase is an intermediary enzyme in the octadecanoid pathway involved in conversion of (13S,9Z,11E,15Z)-13-hydroperoxy-9,11,15-octadecatrienoic acid to allene oxid
metabolism
-
allene oxide synthase is involved in jasmonic acid biosynthesis
physiological function
expressed AOS2 protein is not obtained in soluble form
physiological function
-
is a cytochrome P450
physiological function
-
is a potential rubber transferase, the enzyme polymerizes thousands of isoprenes into molecules of rubber. Plays no role in jasmonate biosynthesis
physiological function
-
plays a role in jasmonate biosynthesis
physiological function
-
the lipoxygenase-catalyzed addition of molecular oxygen to alpha-linolenic acid initiates jasmonate synthesis by providing a 13-hydroperoxide substrate for formation of an unstable allene oxide by allene oxide synthase. This allene oxide then undergoes enzyme-guided cyclization to produce 12-oxophytodienoic acid. Phe137 stabilizes the carbon-centered radical intermediate, which is essential for AOS activity
physiological function
-
the enzyme is involved in synthesis of green note substances from linoleic acid and alpha-linolenic acid in the plant
physiological function
-
the enzyme plays an important role in regulation of allene oxide synthase level and activity in pearl millet upon Sclerospora graminicola infection
physiological function
-
role for the rice enzyme in mediating plant-specific defense responses. OsHPL3 possesses intrinsic hydroperoxide lyase activity hydrolyzing hydroperoxylinolenic acid to produce green leaf volatiles, that play diverse roles in plant defense responses against insect pests and pathogens. OsHPL3 positively modulates resistance to the rice brown planthopper, Nilaparvata lugens, but negatively modulates resistance to the rice striped stem borer, Chilo suppressalis (Walker)
metabolism
Lasiodiplodia theobromae 2334, Lasiodiplodia theobromae CBS 117454, Lasiodiplodia theobromae CBS 122127
-
jasmonic acid is synthesized from linolenic acid (18:3n-3) by sequential action of 13-lipoxygenase, allene oxide synthase, and allene oxide cyclase
-
additional information
-
putative type II ligand-induced spin state transition in OsAOS1
additional information
the acid-alcohol pair Glu946-Ser949 lacks catalytic importance for the allene oxide synthase activity
additional information
-
the acid-alcohol pair Glu946-Ser949 lacks catalytic importance for the allene oxide synthase activity
-
SUBSTRATE
PRODUCT                      
REACTION DIAGRAM
ORGANISM
UNIPROT
COMMENTARY
(Substrate)
LITERATURE
(Substrate)
COMMENTARY
(Product)
LITERATURE
(Product)
Reversibility
r=reversible
ir=irreversible
?=not specified
(12R)-hydroperoxy-(5Z,8Z,10E,14Z)-eicosatetraenoic acid
(8R)-hydroxy-(11R,12R)-epoxyeicosa-(5Z,9E,14Z)-trienoic acid + H2O
show the reaction diagram
-
poor substrate
-
?
(12R)-hydroperoxy-(5Z,8Z,10E,14Z)-eicosatetraenoic acid
(8R)-hydroxy-(11R,12R)-epoxyeicosa-(5Z,9E,14Z)-trienoic acid + H2O
show the reaction diagram
-
intramolecular oxygenation with retention of the configuration of the carbon atom hydroxylated
-
?
(12S)-hydroperoxy-(5Z,8Z,10E,14Z)-eicosatetraenoic acid
(10R)-hydroxy-(11S,12S)-epoxyeicosa-(5Z,8Z,14Z)-trienoic acid + (8R)-hydroxy-(11S,12S)-epoxyeicosa-(5Z,9E,14Z)-trienoic acid + H2O
show the reaction diagram
-
-
the former being a isomer of hepoxilin A3, ration of products is 2:1
?
(13R)-hydroperoxy-(10E,12Z)-octadecadienoic
11-hydroxy-12(13)-epoxy-octadecadienoic acid + 9-hydroxy-12(13)-epoxy-octadecadienoic acid + H2O
show the reaction diagram
-
-
?
(13R)-hydroperoxylinolenic acid
13-ketolinolenic acid + threo-11-hydroxy-(12R,13R)-epoxy-(9Z,15Z)-octadecadienoic acid + erythro-11-hydroxy-(12R,13R)-epoxy-(9Z,15Z)-octadecadienoic acid
show the reaction diagram
the G316A mutant converts (13R)-hydroperoxylinolenic acid to 13-ketolinolenic acid (with an apparent Km of 0.01 mM) and to epoxyalcohols viz. erythro- and threo-11-hydroxy-(12R,13R)-epoxy-(9Z,15Z)-octadecadienoic acids and one of the corresponding cis-epoxides as major products
-
?
(13S)-hydroperoxy-(10E,12Z)-octadecadienoic
11-hydroxy-12(13)-epoxy-octadecadienoic acid + 9-hydroxy-12(13)-epoxy-octadecadienoic acid + H2O
show the reaction diagram
-
-
?
(13S)-hydroperoxy-(9Z,11E)-octadecadienoic acid
(12S,13S)-oxido-(9Z,11)-octadecadienoic acid + H2O
show the reaction diagram
-
-
-
?
(13S)-hydroperoxy-(9Z,11E)-octadecadienoic acid
(12S,13S)-oxido-(9Z,11)-octadecadienoic acid + H2O
show the reaction diagram
-
-
-
-
(13S)-hydroperoxy-(9Z,11E)-octadecadienoic acid
(12S,13S)-oxido-(9Z,11)-octadecadienoic acid + H2O
show the reaction diagram
-
-
?
(13S)-hydroperoxy-(9Z,11E)-octadecadienoic acid
(12S,13S)-oxido-(9Z,11)-octadecadienoic acid + H2O
show the reaction diagram
-
-
?
(13S)-hydroperoxy-(9Z,11E)-octadecadienoic acid
(12S,13S)-oxido-(9Z,11)-octadecadienoic acid + H2O
show the reaction diagram
-
-
products are: 13-hydroxy-12-oxo-cis-9-octadecenoic acid + small amounts of the gamma ketol
?
(13S)-hydroperoxy-(9Z,11E)-octadecadienoic acid
(12S,13S)-oxido-(9Z,11)-octadecadienoic acid + H2O
show the reaction diagram
-
-
spontaneous hydrolysis to 12-keto-13-hydroxy-(9Z)-octadecenoic acid (72% 13(R) and 28% 13(S))
?
(13S)-hydroperoxy-(9Z,11E)-octadecadienoic acid
(12S,13S)-oxido-(9Z,11)-octadecadienoic acid + H2O
show the reaction diagram
-
S)-hydroperoxy-(9Z,11E)-octadecadienoic acid is a poor substrate
products are: (11R,12R)-epoxy-(13S)-hydroxy-(9Z)-octadecenoic acid + (9S,10R)-epoxy-(13S)-hydroxy-(11E)-octadecenoic acid
?
(13S)-hydroperoxy-(9Z,11E)-octadecadienoic acid
(12S,13S)-oxido-(9Z,11)-octadecadienoic acid + H2O
show the reaction diagram
-
substrate listed without specification of steroisomer used
products are 10,13-dihydroxyoctadec-11-enoic acid + 12,13-dihydroxyoctadec-9-enoic acid + trace amounts of 9,12-dihydroxyoctadec-10-enoic acid
?
(13S)-hydroperoxy-(9Z,11E)-octadecadienoic acid
(12,13S)-oxido-(9Z,11)-octadecadienoic acid + H2O
show the reaction diagram
-
-
-
?
(13S)-hydroperoxy-(9Z,11E)-octadecadienoic acid
(12,13S)-oxido-(9Z,11)-octadecadienoic acid + H2O
show the reaction diagram
-
-
-
?
(13S)-hydroperoxy-(9Z,11E)-octadecadienoic acid
(12,13S)-oxido-(9Z,11)-octadecadienoic acid + H2O
show the reaction diagram
-
-
-
?
(13S)-hydroperoxy-(9Z,11E)-octadecatrienoic acid
(12,13S)-epoxy-(9Z,11,15Z)-octadecatrienoic acid + H2O
show the reaction diagram
-
-
12-oxo-13-hydroxy-(9Z,15Z)-octadecadienoic acid + 12-oxo-(10,15Z)-phytodienoic acid, formed by spontaneous chemical or enzyme-catalyzed cyclization
?
(13S)-hydroperoxy-(9Z,11Z,15Z)-octadecatrienoic acid
(12,13S)-epoxy-(9Z,11Z,15Z)-octadecatrienoic acid + H2O
show the reaction diagram
by AOS1
-
?
(13S)-hydroperoxyoctadecadienoic acid
13-hydroxy-12-oxo-9(Z)-octadecenoic acid + 12-oxo-10-phytoenoic acid
show the reaction diagram
-
-
13-hydroxy-12-oxo-(9Z)-octadecenoic acid is the major product
?
(13S)-hydroperoxyoctadecatrienoic acid
13-hydroxy-12-oxo-(9Z,15Z)-octadecadienoic acid + 12-oxo-(10Z,15Z)-phytodienoic acid
show the reaction diagram
-
-
OsAOS1 produces a 1:1 racemic mixture of cis-(+)/cis-(-)-12-oxo-(10Z,15Z)-phytodienoic acid via non-enzymatic cyclization of 12,13-epoxy-9,11,15-octadecatrienoic acid, an unstable allene oxide
?
(13S,9Z,11E,15Z)-13-hydroperoxy-9,11,15-octadecatrienoic acid
?
show the reaction diagram
-
is converted to an allene oxide
-
-
?
(15S)-hydroperoxyeicosatetraenoic acid
(15S)-hydroxy-11,12-epoxyeicosatrienoic acid + H2O
show the reaction diagram
-
-
-
?
(5Z,8Z,11E,13Z,15S)-15-hydroperoxyicosa-5,8,11,13-tetraenoic acid
14,15-hepoxilin A3 + 14,15-hepoxilin B3 + H2O
show the reaction diagram
-
poor substrate
-
?
(5Z,8Z,11E,13Z,15S)-15-hydroperoxyicosa-5,8,11,13-tetraenoic acid
14,15-hepoxilin A3 + 14,15-hepoxilin B3 + H2O
show the reaction diagram
-
high stereoselectivity, not with 15(R)-substrate
mixture of both products
?
(8R)-hydroperoxy-(9Z,12Z)-octadecadienoic acid
(7S,8S)-dihydroxy-(9Z,12Z)-octadecadienoic acid + H2O
show the reaction diagram
-
-
-
?
(8R)-hydroperoxy-(9Z,12Z)-octadecadienoic acid
(7S,8S)-dihydroxy-(9Z,12Z)-octadecadienoic acid + H2O
show the reaction diagram
-
-
-
?
(8R)-hydroperoxy-(9Z,12Z)-octadecadienoic acid
(7S,8S)-dihydroxy-(9Z,12Z)-octadecadienoic acid + H2O
show the reaction diagram
-
-
-
?
(8R)-hydroperoxy-(9Z,12Z)-octadecadienoic acid
(7S,8S)-dihydroxy-(9Z,12Z)-octadecadienoic acid + H2O
show the reaction diagram
-
poor substrate
-
?
(8R)-hydroperoxy-(9Z,12Z)-octadecadienoic acid
(7S,8S)-dihydroxy-(9Z,12Z)-octadecadienoic acid + H2O
show the reaction diagram
Gaeumannomyces graminis, Gaeumannomyces graminis var.graminis
-
stereospecific elimination of the pro-S hydrogen from C-7 and intramolecular suprafacial insertion of oxygen at C-7 with retention of the absolute configuration at C-7
-
?
(8R)-hydroperoxyeicosatetraenoic acid
?
show the reaction diagram
-
the substrate is converted to an unstable allene oxide product via the FeIV-OH intermediate, Compound II, the native enzyme shows a strong preference for its natural substrate, the substrate is converted to an unstable allene oxide product via the FeIV-OH intermediate, Compound II
-
-
?
(8R)-hydroperoxylinoleic acid + H2O
(5S,8R)-dihydroxylinoleic acid
show the reaction diagram
-
-
-
?
(8R)-hydroperoxylinoleic acid + H2O
(8R,11S)-dihydroxylinoleic acid
show the reaction diagram
-
-
-
?
(8R)-hydroxyeicosatetraenoic acid
(8R)-hydroxy-(9R,10R)-trans-epoxy-eicosa-(5Z,11Z,14Z)-trienoic acid
show the reaction diagram
-
the native, unmodified enzyme shows no activity with (8R)-hydroxyeicosatetraenoic acid, but the oxidized enzyme epoxidizes the substrate analogue stereospecifically on the 9,10-double bond to form (8R)-hydroxy-(9R,10R)-trans-epoxy-eicosa-(5Z,11Z,14Z)-trienoic acid as the predominant product, via Compound I (FeV=O) intermediate
erythro and threo diastereomers of (8R)-hydroxy-9,10-trans-epoxy-eicosa-5Z,11Z,14Z-trienoate
?
(9R)-hydroperoxy-(10E,12Z,15Z)-octadecatrienoic acid
9-hydroxy-10-oxo-(12Z,15Z)-octadecadienoic acid
show the reaction diagram
Lasiodiplodia theobromae, Lasiodiplodia theobromae 2334, Lasiodiplodia theobromae CBS 122127, Lasiodiplodia theobromae CBS 117454
-
-
-
?
(9S)-hydroperoxy-(10E,12Z)-octadecadienoic acid
10-oxo-(9R)-hydroxy-cis-12-octadecadienoic acid + H2O
show the reaction diagram
-
-
-
?
(9S)-hydroperoxy-(10E,12Z)-octadecadienoic acid
10-oxo-(9R)-hydroxy-cis-12-octadecadienoic acid + H2O
show the reaction diagram
-
-
in presence of linoleate the product is (9R)-linoleoyloxy-10-oxo-cis-12-octadecenoic acid
?
(9S)-hydroperoxy-(10E,12Z)-octadecadienoic acid
10-oxo-(9R)-hydroxy-cis-12-octadecadienoic acid + H2O
show the reaction diagram
-
-
9-hydroxy-10-oxo,cis-12-octadecenoic acid and 13-hydroxy-10-oxo-trans-11-octadecenoic acid in the ratio 2:1
?
(9S)-hydroperoxy-(10E,12Z)-octadecadienoic acid
10-oxo-(9R)-hydroxy-cis-12-octadecadienoic acid + H2O
show the reaction diagram
-
S)-hydroperoxy-(10E,12Z)-octadecadienoic acid is a poor substrate
products: (10R,11R)-epoxy-(9S)-hydroxy-(12Z)-octadecenoic acid + (12R,13S)-epoxy-(9S)-hydroxy-(10E)-octadecenoic acid
?
(9S)-hydroperoxy-(10E,12Z)-octadecadienoic acid
(9S,10)-epoxy-(10Z,12Z)-octadecadienoic acid + H2O
show the reaction diagram
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)-hydroperoxy-(10E,12Z)-octadecadienoic acid
(9S,10)-10-epoxy-(10Z,12Z)-octadecadienoic acid + H2O
show the reaction diagram
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
-
?
(9S)-hydroperoxy-(10E,12Z)-octadecadienoic acid
9-oxononanoic acid + (3Z)-nonenal
show the reaction diagram
-
-
-
?
(9S)-hydroperoxy-(10E,12Z,15Z)-octadecatrienoic acid
(9S,10)-epoxy-(10Z,12Z,15Z)-octadecatrienoic acid + H2O
show the reaction diagram
-
-
?
(9S)-hydroperoxyoctadecadienoic acid
?
show the reaction diagram
-
-
-
-
?
(9S)-hydroperoxyoctadecatrienoic acid
?
show the reaction diagram
-
-
-
-
?
(9S,10E,12Z)-9-hydroperoxy-10,12-octadecadienoic acid
?
show the reaction diagram
-
the divinyl ether synthase enzyme mutant E292G shows allene oxide synthase activity, producing the typical allene oxide synthase product alpha-ketol and 12-oxo-10,15-phytodienoic acid, and lacks divinyl ether synthase activity in contrast to the wild-type divinyl ether synthase CYP74B16
-
-
?
(9S,10E,12Z)-9-hydroperoxy-10,12-octadecadienoic acid
?
show the reaction diagram
-
the divinyl ether synthase enzyme mutant V379F shows allene oxide synthase activity, producing the typical allene oxide synthase product alpha-ketol, and lacks divinyl ether synthase activity in contrast to the wild-type divinyl ether synthase CYP74D3
-
-
?
(9Z,11E)-(9R)-hydroperoxyoctadeca-9,11-dienoate
(9R,10)-10-epoxy-(10Z,12Z)-octadecadienoic acid
show the reaction diagram
Aspergillus terreus, Aspergillus terreus A1156
-
an unstable allene oxide
?
(9Z,11E,13S,15Z)-13-hydroperoxy-9,11,15-octadecatrienoic acid
?
show the reaction diagram
-
the divinyl ether synthase enzyme mutant E292G shows allene oxide synthase activity, producing the typical allene oxide synthase product alpha-ketol and 12-oxo-10,15-phytodienoic acid, and lacks divinyl ether synthase activity in contrast to the wild-type divinyl ether synthase CYP74B16
-
-
?
(9Z,11E,13S,15Z)-13-hydroperoxy-9,11,15-octadecatrienoic acid
?
show the reaction diagram
-
the divinyl ether synthase enzyme mutant V379F shows allene oxide synthase activity, producing the typical allene oxide synthase product alpha-ketol, and lacks divinyl ether synthase activity in contrast to the wild-type divinyl ether synthase CYP74D3
-
-
?
13-hydroperoxy-9,11,15-octadecatrienoic acid
?
show the reaction diagram
-
-
-
-
?
13-hydroperoxy-9,11-octadecadienoic acid
(10E,12Z)-12-[(3S)-3-methyl-3-propyloxiran-2-ylidene]dodec-10-enoic acid + H2O
show the reaction diagram
-
wild-type AOS activity
-
?
13-hydroperoxy-9,11-octadecadienoic acid
(10E,12Z)-13-[(2-hydroxypentan-2-yl)oxy]trideca-10,12-dienoic acid + H2O
show the reaction diagram
-
activity of AOS mutant F137L
-
?
13-hydroperoxy-9,11-octadecadienoic acid
?
show the reaction diagram
-
-
-
-
?
13-hydroperoxylinoleic acid
(Z)-3-hexanal + 12-oxododecenoic acid
show the reaction diagram
-
-
-
?
13-hydroperoxylinoleic acid
?
show the reaction diagram
-
-
-
-
?
13-hydroperoxylinolenic acid
12-oxo-cis-10,15-phytodienoic acid + 9-hydroxy-12-oxo-cis-15-trans-11-octadecadienoic acid + H2O
show the reaction diagram
-
-
the latter is a minor product of approximately 5%
?
9-hydroperoxylinolenic acid
13-hydroxy-10-oxo-cis-15-trans-11-octadecadienoic acid + H2O
show the reaction diagram
-
-
-
?
alpha-linolenic acid
(E,Z)-3,6-nonadienal + 9-oxononanoic acid
show the reaction diagram
-
cleavage of 9-hydroperoxy fatty acid
-
?
heptadecatrienoic acid
12-hydroperoxyheptadecatrienoic acid + (8Z,10S,11Z,14Z)-10-hydroperoxyheptadeca-8,11,14-trienoic acid
show the reaction diagram
the G316A mutant transforms 17:3n-3 to both 12-hydroperoxyheptadecatrienoic acid (about 93%) and 10-hydroperoxyheptadecatrienoic acid (7%)
-
?
linoleate (10S)-10-hydroperoxide
(8E)-10-oxodecenoic acid + 1-octen-3-ol and 2Z-octen-1-ol
show the reaction diagram
the catalase-related hemoprotein reacts rapidly and specifically with linoleate 10S-hydroperoxide with a hydroperoxide lyase activity specific for the 10S-hydroperoxy enantiomer
in a 3:1 ratio, strict enzymatic control in formation of the 3R alcohol configuration with 99% enantiomeric excess
?
linoleic acid
?
show the reaction diagram
Mn-LO G316A metabolizeS 18:2n-6 to (11S)-hydroperoxyoctadecadienoic acid and (13R)-hydroperoxyoctadecadienoic acid in approximately the same relative amounts as the native enzyme, and (13R)-hydroperoxyoctadecadienoic acid accumulates as the end product
-
-
?
linoleic acid
(Z)-3-nonenal + 9-oxononanoic acid
show the reaction diagram
-
cleavage of 9-hydroperoxy fatty acid
-
?
linolenic acid
(13R)-hydroperoxyoctadecatrienoic acid + (11S)-hydroperoxyoctadecatrienoic acid
show the reaction diagram
Mn-LO G316A metabolizes 18:3n-3 to (13R)-hydroperoxyoctadecatrienoic acid and (11S)-hydroperoxyoctadecatrienoic acid
-
?
linolic acid hydroperoxide + H2O
9,12,13-trihydroxy-trans-10-octadecenoic acid + 9,10,13-trihydroxy-trans-11-octadecenoic acid
show the reaction diagram
-
-
-
?
additional information
?
-
-
overview on substrates, configurations and mechanism
-
-
-
additional information
?
-
catalytic properties of Mn-LO and the G316A mutant with heptadecatrienic acid, 18:2n-6, octadecatrienoic acid, and nonadecatrienoic acid as substrates: increasing the fatty acid chain length from C17 to C19 shifts the oxygenation by Mn-LO from the n-6 toward the n-8 carbon. The G316A mutant increases the oxygenation at the n-8 carbon of 17:3n-3 and at the n-10 carbon of the C17 and C18 fatty acids (from 12% to 711%). The most striking effect of the G316A mutant is a 2fold, 7fold, and 15fold increase in transformation of the n-6 hydroperoxides of 19:3n-3, 18:3n-3, and 17:3n-3, respectively, to keto fatty acids and epoxyalcohols. The n-3 double bond is essential. Both oxygen atoms are retained in the epoxyalcohols. (R)-Hydroperoxides at n-6 of C17:3, 18:3, and 19:3 are transformed 5times faster than (S)-stereoisomers
-
-
-
additional information
?
-
allene oxide synthase is a key cytochrome P450 enzyme in the oxylipin pathway leading to allene oxide synthase-derived jasmonates
-
-
-
additional information
?
-
-
CYP74 enzymes use their fatty acid hydroperoxide substrate to activate the enzyme and substrate in one and the same step
-
-
-
additional information
?
-
-
13-HPL and 9-HPL activities on oxylipins, traumatin derivatives, in different plant organs, overview
-
-
-
additional information
?
-
-
two hydroperoxide isomerases in Aspergillus clavatus acting on hydroperoxylinoleic acid: the 5,8-linoleate diol synthase exhibiting 5,8-hydroperoxide isomerase activity, and the 8, 11-linoleate diol synthase exhibiting 8,11-hydroperoxide isomerase activity, overview
-
-
-
additional information
?
-
-
cleavage of 9-hydroperoxy fatty acids in vivo, AOS enzymes also convert hydroperoxy fatty acids to aldehydes via an HPL-like activity
-
-
-
additional information
?
-
-
cleavage of 9-hydroperoxy fatty acids or 13-hydroperoxy fatty acids by a hydroperoxide lyase results in formation of aldehydes (Z)-3-nonenal/(E,Z)-3,6-nonadienal or (Z)-3-hexanal, and omega-oxo fatty acid 9-oxo-nonanoic acid or 12-oxo-dodecenoic acid, respectively
-
-
-
additional information
?
-
FOXB_01332 is a linoleate 9-dioxygenase with homology to animal heme peroxidases and a 9-dioxygenase-allene oxide synthase fusion protein
-
-
-
additional information
?
-
-
OsHPL3 possesses intrinsic hydroperoxide lyase activity hydrolyzing hydroperoxylinolenic acid to produce green leaf volatiles, it catabolizes 9/13-hydroperoxylinoleic acid to form (Z)-3-hexenal
-
-
-
additional information
?
-
-
the enzyme catalyzes the first specific reaction in the formation of 12-oxophytodienoic acid, a signaling compound with multiple functions that is also the immediate precursor of jasmonic acid
-
-
-
additional information
?
-
-
in case of hydroperoxide lyases the homolytic isomerization of fatty acid hydroperoxides leads to a short-lived hemiacetal, which spontaneously disintegrates into (Z)-3-hexenal and (9Z)-12-oxo-9-dodecenoic acid
-
-
-
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
-
-
-
additional information
?
-
-
allene oxide synthase converts fatty acid hydroperoxides into unstable fatty acid epoxides (allene oxides). OsAOS1 exhibits dual positional substrate specificity and prefers 13-positional isomeric to 9-positional isomeric substrates in vitro. OsAOS1 converts (9S)-hydroperoxyoctadecadienoic acid or (9S)-hydroperoxyoctadecatrienoic acid into the corresponding unstable allene oxides, which are non-enzymatically transformed into a 9alpha-ketol as the major product, and 13gamma-ketols and cyclopentenone derivatives as minor products
-
-
-
additional information
?
-
Asn964 may facilitate homolytic cleavage of the dioxygen bond of (9R)-hydroperoxy-10(E),12(Z)-octadecadienoic acid with formation of compound II. No activity with 18:2n-6
-
-
-
additional information
?
-
the enzyme mainly acts as an oleate or linoleate dioxygenase, albeit with alpha-linolenic acid very competitive at low substrate concentrations, substrate specificity and kinetics, overview
-
-
-
additional information
?
-
-
the native enzyme is completely unreactive with polyunsaturated fatty acids or their hydroxylated analogues. Mass spectrometric product analysis, overview
-
-
-
additional information
?
-
FOXB_01332 is a linoleate 9-dioxygenase with homology to animal heme peroxidases and a 9-dioxygenase-allene oxide synthase fusion protein, (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
-
-
-
additional information
?
-
Aspergillus terreus A1156
Asn964 may facilitate homolytic cleavage of the dioxygen bond of (9R)-hydroperoxy-10(E),12(Z)-octadecadienoic acid with formation of compound II. No activity with 18:2n-6
-
-
-
NATURAL SUBSTRATES
NATURAL PRODUCTS
REACTION DIAGRAM
ORGANISM
UNIPROT
COMMENTARY
(Substrate)
LITERATURE
(Substrate)
COMMENTARY
(Product)
LITERATURE
(Product)
REVERSIBILITY
r=reversible
ir=irreversible
?=not specified
(13S)-hydroperoxy-(9Z,11E)-octadecadienoic acid
(12,13S)-oxido-(9Z,11)-octadecadienoic acid + H2O
show the reaction diagram
-
-
-
?
(13S)-hydroperoxy-(9Z,11E)-octadecadienoic acid
(12,13S)-oxido-(9Z,11)-octadecadienoic acid + H2O
show the reaction diagram
-
-
-
?
(13S)-hydroperoxy-(9Z,11E)-octadecadienoic acid
(12,13S)-oxido-(9Z,11)-octadecadienoic acid + H2O
show the reaction diagram
-
-
-
?
(8R)-hydroperoxyeicosatetraenoic acid
?
show the reaction diagram
-
the substrate is converted to an unstable allene oxide product via the FeIV-OH intermediate, Compound II, the native enzyme shows a strong preference for its natural substrate
-
-
?
(8R)-hydroperoxylinoleic acid + H2O
(5S,8R)-dihydroxylinoleic acid
show the reaction diagram
-
-
-
?
(8R)-hydroperoxylinoleic acid + H2O
(8R,11S)-dihydroxylinoleic acid
show the reaction diagram
-
-
-
?
(9R)-hydroperoxy-(10E,12Z,15Z)-octadecatrienoic acid
9-hydroxy-10-oxo-(12Z,15Z)-octadecadienoic acid
show the reaction diagram
Lasiodiplodia theobromae, Lasiodiplodia theobromae 2334, Lasiodiplodia theobromae CBS 122127, Lasiodiplodia theobromae CBS 117454
-
-
-
?
(9S)-hydroperoxy-(10E,12Z)-octadecadienoic acid
(9S,10)-epoxy-(10Z,12Z)-octadecadienoic acid + H2O
show the reaction diagram
F9F4K7
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
-
?
(9Z,11E)-(9R)-hydroperoxyoctadeca-9,11-dienoate
(9R,10)-10-epoxy-(10Z,12Z)-octadecadienoic acid
show the reaction diagram
Aspergillus terreus, Aspergillus terreus A1156
Q0CW98
-
an unstable allene oxide
?
13-hydroperoxy-9,11-octadecadienoic acid
(10E,12Z)-12-[(3S)-3-methyl-3-propyloxiran-2-ylidene]dodec-10-enoic acid + H2O
show the reaction diagram
-
wild-type AOS activity
-
?
13-hydroperoxy-9,11-octadecadienoic acid
(10E,12Z)-13-[(2-hydroxypentan-2-yl)oxy]trideca-10,12-dienoic acid + H2O
show the reaction diagram
-
activity of AOS mutant F137L
-
?
13-hydroperoxylinoleic acid
(Z)-3-hexanal + 12-oxododecenoic acid
show the reaction diagram
-
-
-
?
alpha-linolenic acid
(E,Z)-3,6-nonadienal + 9-oxononanoic acid
show the reaction diagram
-
cleavage of 9-hydroperoxy fatty acid
-
?
linoleic acid
(Z)-3-nonenal + 9-oxononanoic acid
show the reaction diagram
-
cleavage of 9-hydroperoxy fatty acid
-
?
additional information
?
-
A7XY79
allene oxide synthase is a key cytochrome P450 enzyme in the oxylipin pathway leading to allene oxide synthase-derived jasmonates
-
-
-
additional information
?
-
-
13-HPL and 9-HPL activities on oxylipins, traumatin derivatives, in different plant organs, overview
-
-
-
additional information
?
-
-
two hydroperoxide isomerases in Aspergillus clavatus acting on hydroperoxylinoleic acid: the 5,8-linoleate diol synthase exhibiting 5,8-hydroperoxide isomerase activity, and the 8, 11-linoleate diol synthase exhibiting 8,11-hydroperoxide isomerase activity, overview
-
-
-
additional information
?
-
-
cleavage of 9-hydroperoxy fatty acids in vivo, AOS enzymes also convert hydroperoxy fatty acids to aldehydes via an HPL-like activity
-
-
-
additional information
?
-
-
cleavage of 9-hydroperoxy fatty acids or 13-hydroperoxy fatty acids by a hydroperoxide lyase results in formation of aldehydes (Z)-3-nonenal/(E,Z)-3,6-nonadienal or (Z)-3-hexanal, and omega-oxo fatty acid 9-oxo-nonanoic acid or 12-oxo-dodecenoic acid, respectively
-
-
-
additional information
?
-
F9F4K7
FOXB_01332 is a linoleate 9-dioxygenase with homology to animal heme peroxidases and a 9-dioxygenase-allene oxide synthase fusion protein
-
-
-
additional information
?
-
-
OsHPL3 possesses intrinsic hydroperoxide lyase activity hydrolyzing hydroperoxylinolenic acid to produce green leaf volatiles, it catabolizes 9/13-hydroperoxylinoleic acid to form (Z)-3-hexenal
-
-
-
additional information
?
-
-
the enzyme catalyzes the first specific reaction in the formation of 12-oxophytodienoic acid, a signaling compound with multiple functions that is also the immediate precursor of jasmonic acid
-
-
-
additional information
?
-
F9F4K7
FOXB_01332 is a linoleate 9-dioxygenase with homology to animal heme peroxidases and a 9-dioxygenase-allene oxide synthase fusion protein
-
-
-
COFACTOR
ORGANISM
UNIPROT
COMMENTARY
LITERATURE
IMAGE
cytochrome
P450 6003B
-
cytochrome P450
-
-
-
cytochrome P450
-
-
-
cytochrome P450
-
heme containing
-
cytochrome P450
-
AOS is a cytochrome P450 of the CYP74 family
-
heme
-
ferric heme iron
METALS and IONS
ORGANISM
UNIPROT
COMMENTARY
LITERATURE
Fe2+
-
ferric heme iron
Fe2+
-
heme ligand of the cytochrome P450 enzyme
Fe2+
-
heme enzyme
heme
-
CYP74 heme is strongly hold in place than usual via ionic interactions with its proprionate groups
INHIBITORS
ORGANISM
UNIPROT
COMMENTARY
LITERATURE
IMAGE
CH3HgI
-
-
imidazole
-
imidazole may coordinate to ferric heme iron, triggering a heme-iron transition from high spin state to low spin state
N-bromosuccinimide
-
-
nordihydroguaiaretic acid
-
-
nordihydroguaiaretic acid
-
-
p-chloromercuribenzoate
-
-
iodoacetic acid
-
-
additional information
-
mechanism based suicide inactivation is a common feature of hydroperoxide lyases and many other enzymes of the P450 family
-
ACTIVATING COMPOUND
ORGANISM
UNIPROT
COMMENTARY
LITERATURE
IMAGE
cytochrome P450
-
AOS is a non-classical cytochrome P450, which, like other CYP74 enzymes, does not require molecular oxygen and NADPH-dependent P450 reductase
-
additional information
mechanical wounding and methyl jasmonate treatment induce the accumulation of AOS transcripts
-
additional information
-
exhibits weak activity prior to activation (in vitro), can be massively activated with detergent
-
KM VALUE [mM]
SUBSTRATE
ORGANISM
UNIPROT
COMMENTARY
LITERATURE
IMAGE
0.0593
(13S)-hydroperoxy-(9Z,11Z,15Z)-octadecatrienoic acid
with 0.0001 mg purified AOS1, in 1 mL of buffer containing 50 mM sodium phosphate, pH 6.0
0.0123
(13S)-hydroperoxyoctadecadienoic acid
-
pH 7.5, 22C
0.0125
(13S)-hydroperoxyoctadecatrienoic acid
-
pH 7.5, 22C
-
0.0069
(9S)-hydroperoxyoctadecadienoic acid
-
pH 7.5, 22C
-
0.0086
(9S)-hydroperoxyoctadecatrienoic acid
-
pH 7.5, 22C
-
0.024
linoleate hydroperoxide
-
-
TURNOVER NUMBER [1/s]
SUBSTRATE
ORGANISM
UNIPROT
COMMENTARY
LITERATURE
IMAGE
494.5
(13S)-hydroperoxyoctadecadienoic acid
Oryza sativa
-
pH 7.5, 22C
537.8
(13S)-hydroperoxyoctadecatrienoic acid
Oryza sativa
-
pH 7.5, 22C
-
44.9
(9S)-hydroperoxyoctadecadienoic acid
Oryza sativa
-
pH 7.5, 22C
-
17.5
(9S)-hydroperoxyoctadecatrienoic acid
Oryza sativa
-
pH 7.5, 22C
-
kcat/KM VALUE [1/mMs-1]
SUBSTRATE
ORGANISM
UNIPROT
COMMENTARY
LITERATURE
IMAGE
39600
(13S)-hydroperoxyoctadecadienoic acid
Oryza sativa
-
pH 7.5, 22C
197758
43700
(13S)-hydroperoxyoctadecatrienoic acid
Oryza sativa
-
pH 7.5, 22C
197759
6500
(9S)-hydroperoxyoctadecadienoic acid
Oryza sativa
-
pH 7.5, 22C
197760
2000
(9S)-hydroperoxyoctadecatrienoic acid
Oryza sativa
-
pH 7.5, 22C
197761
SPECIFIC ACTIVITY [µmol/min/mg]
ORGANISM
UNIPROT
COMMENTARY
LITERATURE
2.32
-
purified recombinant His-tagged enzyme, solubilized with Triton X-100, pH 7.0, 22C
5.44
-
purified recombinant His-tagged enzyme, solubilized with dodecyl maltoside, pH 7.0, 22C
pH OPTIMUM
ORGANISM
UNIPROT
COMMENTARY
LITERATURE
7
-
assay at
7.5
-
assay at
7.5
-
assay at
7.6
-
assay at
pH RANGE
ORGANISM
UNIPROT
COMMENTARY
LITERATURE
5 - 7.8
-
about 20% of maximum activity at pH 5 and pH 7.8
5.5 - 9
-
about 50% of maximum activity at pH 5.5 and pH 9.0
TEMPERATURE OPTIMUM
ORGANISM
UNIPROT
COMMENTARY
LITERATURE
20
-
assay at
22
-
assay at room temperature
22
-
assay at room temperature
22
-
assay at room temperature
22
-
assay at room temperature
25
-
assay at
25
-
assay at
pI VALUE
ORGANISM
UNIPROT
COMMENTARY
LITERATURE
8.4
calculated from amino acid sequence
SOURCE TISSUE
ORGANISM
UNIPROT
COMMENTARY
LITERATURE
SOURCE
-
embryos, activity decreases during germination
Manually annotated by BRENDA team
-
quiescent barley
Manually annotated by BRENDA team
-
9-HPL and 13-HPL activity, increasing with leaf age, no AOS activity, overview
Manually annotated by BRENDA team
Aspergillus terreus A1156, Lasiodiplodia theobromae 2334, Lasiodiplodia theobromae CBS 117454, Lasiodiplodia theobromae CBS 122127
-
-
-
Manually annotated by BRENDA team
-
maximum enzyme abundance in vascular as well as in the epidermal regions
Manually annotated by BRENDA team
-
maximum enzyme abundance in vascular as well as in the epidermal regions
Manually annotated by BRENDA team
-
9-HPL and 13-HPL activity, increasing with age, no AOS activity, overview
Manually annotated by BRENDA team
-
of germinating barley
Manually annotated by BRENDA team
-
sprouted, cotyledons
Manually annotated by BRENDA team
additional information
-
enzyme is bound in a catalytically active state to the insoluble barley grist
Manually annotated by BRENDA team
additional information
-
CYP74A2 is most abundant in rubber, accounting for about 50% of the protein content
Manually annotated by BRENDA team
additional information
-
quantitative PCR expression analysis of OsHPL3, overview
Manually annotated by BRENDA team
LOCALIZATION
ORGANISM
UNIPROT
COMMENTARY
GeneOntology No.
LITERATURE
SOURCE
-
rhomboid proteases AtRBL8 and AtRBL9 in the chloroplast envelope affect the level of allene oxide synthase in Arabidopsis thaliana
Manually annotated by BRENDA team
-
rhomboid proteases AtRBL8 and AtRBL9 in the chloroplast envelope affect the level of allene oxide synthase in Arabidopsis thaliana
Manually annotated by BRENDA team
Aspergillus terreus A1156
-
-
-
Manually annotated by BRENDA team
additional information
-
equally distributed between the high speed supernatant and particulate fractions
-
Manually annotated by BRENDA team
MOLECULAR WEIGHT
ORGANISM
UNIPROT
COMMENTARY
LITERATURE
40000 - 45000
-
gel filtration, 2 bands of enzyme activity, MW 220000 and MW 40000-45000
648489
53000
-
-
706127
53500
sequence analysis; sequence analysis
702754
59200
calculated from amino acid sequence
700116
133000
recombinant C-terminally His6-tagged, V5-tagged enzyme
730012
220000
-
gel filtration, 2 bands of enzyme activity, MW 220000 and MW 40000-45000
648489
SUBUNITS
ORGANISM
UNIPROT
COMMENTARY
LITERATURE
?
-
x * 293000, SDS-PAGE
?
x * 45000, about, sequence calculation
additional information
-
secondary structure analysis by circular dichroism, the enzyme consists of 13.53% alpha-helix, 32.73% beta-sheet, 21.76% turn and 31.13% unordered, overview
POSTTRANSLATIONAL MODIFICATION
ORGANISM
UNIPROT
COMMENTARY
LITERATURE
additional information
-
rhomboid proteases AtRBL8 and AtRBL9 in the chloroplast envelope affect the level of allene oxide synthase in Arabidopsis thaliana
Crystallization/COMMENTARY
ORGANISM
UNIPROT
LITERATURE
AOS free or in complex with 12R,13S-vernolic acid, sitting drop vapour diffusion method, using 100 mM Tris-HCl, pH 7.5, 15-20% polyethylene glycol 3350, and 39 mM nonanoyl-N-hydroxyethylglucamide
-
is a typical P450, the loop forms a compact beta-turn and incorporates the most typical P450 consensus sequence, FXXG, followed by three residues (XRX) followed by CXG encompassing the cysteine. CYP74 heme is strongly hold in place than usual via ionic interactions with its proprionate groups
-
TEMPERATURE STABILITY
ORGANISM
UNIPROT
COMMENTARY
LITERATURE
10 - 80
-
purified enzyme, thermal denaturation at 80C, unfolding starts at about 40C
730885
20
-
pH 7: 10% loss of activity after 20 h, pH 5: 60% loss of activity after 20 h
648493
45
-
pH 6, 60 min, 35% loss of activity
648493
60
-
pH 6, 60 min, complete loss of activity
648493
Purification/COMMENTARY
ORGANISM
UNIPROT
LITERATURE
Ni-NTA column chromatography
-
recombinant His-tagged enzyme from Escherichia coli membranes by solubilization with Triton X-100 or dodecyl maltoside, the latter results in higher enzyme activity, followed by nickel affinity chromatography
-
recombinant N- or C-terminal His6-tagged enzyme from Escherichia coli strain BL21(DE3) by nickel affinity chromatography and dialysis
AOS1 purified on Ni-NTA resin
Cloned/COMMENTARY
ORGANISM
UNIPROT
LITERATURE
expressed in Escherichia coli BL21(DE3) cells
-
gene ATEG_02036, sequence comparisons with other enzymes, cloning and functional expression of the enzyme with V5 epitope and His6-tag from plasmid pIZ/V5-His in Spodoptera frugiperda Sf9 cells and in Escherichia coli
overexpression of His-tagged enzyme in Escherichia coli membranes
-
gene PgAOS1, phylogenetic analysis, quantitative enzyme expression analysis in different cultivars with and without infection by Sclerospora graminicola
-
gene HPLCl, overexpression in Saccharomyces cerevisiae strain BY4743 isogenic
-
gene CmHPL, expression in Nicotiana benthamiana leaves via infiltration method with a aviral vector, real-time PCR expression analysis over 10 days after infiltration with increase of C-9 aldehyde production, overview
-
gene FOXB_01332, phylogenetic tree, expression of wild-type and mutant enzymes
expression in Pichia pastoris
gene Npun_R5468, expression of the enzyme with N- or C-terminal His6 tags in Escherichia coli strain BL21(DE3)
gene OsHPL3, DNA and amino acid sequence determination, analysis, and comparison
-
AOS2 cloned and overexpressed in Escherichia coli; whole ORF of AOS1 amplified and ligated into cloning vector pBluescript SK II(+), sequenced and ligated int vector pET23a and overexpressed in Escherichia coli BL21
gene 13-hpl, sequence comparisons, functional expression in Escherichia coli partly in inculsion bodies, fusion of the maltose binding protein malE to the 5'-truncated 13-hpl gene improves functional expression to some extent
-
EXPRESSION
ORGANISM
UNIPROT
LITERATURE
induction of allene oxide synthase activity in both susceptible and resistant pearl millet cultivars during Sclerospora graminicola infection with higher induction observed in the resistant cultivar
-
high temperature of 35C decreases HPL gene expression in fruit mesocarp
-
temperature, light, wounding and water regime regulate olive the 13-HPL gene at transcriptional level
-
low temperature and wounding upregulates the enzyme and increases HPL enzyme activity, at 15C, a strong and transient increase in OeHPL gene expression level occurs in fruit mesocarp, mechanical damage increases the enzyme activity level
-
expression of AOS1 is higher than that of AOS2; expression of AOS1 is higher than that of AOS2
ENGINEERING
ORGANISM
UNIPROT
COMMENTARY
LITERATURE
F137L
-
the mutant is severely compromised in its ability to generate allene oxide and exhibits robust hydroperoxide lyase activity
F137L
-
site-directed mutagenesis
F137L
-
site-directed mutagenesis, mutation of this residue to Leu results in the enzyme having hydroperoxide lyase activity
F137L/S155A
-
the double mutant exhibits strong hydroperoxide lyase activity
F137L/S155A
-
site-directed mutagenesis
C1073S
site-directed mutagenesis, the substitution in the P450 domain abolishes allene oxide synthase activity
N964D
site-directed mutagenesis, the mutation markedly reduces allene oxide synthase activity
N964V
site-directed mutagenesis, the mutation markedly reduces allene oxide synthase activity
C1073S
Aspergillus terreus A1156
-
site-directed mutagenesis, the substitution in the P450 domain abolishes allene oxide synthase activity
-
N964D
Aspergillus terreus A1156
-
site-directed mutagenesis, the mutation markedly reduces allene oxide synthase activity
-
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
F416W
site-directed mutagenesis, the catalytic residue mutant shows an unaltered product profile compared to the wild-type enzyme
N921V
site-directed mutagenesis, the mutant shows activity similar to the wild-type enzyme
S949A
site-directed mutagenesis, the mutant also forms alpha-ketol like the native enzyme
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
-
F416W
-
site-directed mutagenesis, the catalytic residue mutant shows an unaltered product profile compared to the wild-type enzyme
-
N921V
-
site-directed mutagenesis, the mutant shows activity similar to the wild-type enzyme
-
S949A
-
site-directed mutagenesis, the mutant also forms alpha-ketol like the native enzyme
-
G316A
the G316A mutant increases the oxygenation at the n-8 carbon of 17:3n-3 and at the n-10 carbon of the C17 and C18 fatty acids (from 12% to 711%). The most striking effect of the G316A mutant is a 2-, 7-, and 15-fold increase in transformation of the n-6 hydroperoxides of 19:3n-3, 18:3n-3, and 17:3n-3, respectively, to keto fatty acids and epoxyalcohols. G316A mutant augments the hydroperoxide isomerase activity by positioning the hydroperoxy group at the n-6 carbon of n-3 fatty acids closer to the reduced catalytic metal
G316S
inactive mutant enzyme
G316T
inactive mutant enzyme
G316V
inactivfe mutant enzyme
E292G
-
site-directed mutagenesis, the divinyl ether synthase enzyme mutant E292G shows allene oxide synthase activity, producing the typical allene oxide synthase product alpha-ketol and 12-oxo-10,15-phytodienoic acid, and lacks divinyl ether synthase activity in contrast to the wild-type divinyl ether synthase CYP74B16
N964V
Aspergillus terreus A1156
-
site-directed mutagenesis, the mutation markedly reduces allene oxide synthase activity
-
additional information
-
development of a yeast-based whole cell biocatalyst able to transform polyunsaturated fatty acids into green note aldehydes and alcohols, evaluation, overview
V379F
-
the divinyl ether synthase enzyme mutant V379F shows allene oxide synthase activity, producing the typical allene oxide synthase product alpha-ketol, and lacks divinyl ether synthase activity in contrast to the wild-type divinyl ether synthase CYP74D3
additional information
-
gene 13-hpl is used for random mutagenesis via gene shuffling using template based recombination of restriction fragments and in vitro ligations (L-shuffling) with DNA sequences from melon, Nicotiana attenuata (GenBank accession No. AJ414400), Citrus sinensis (GenBank accession No. AY242385), and Malus domestica and a guava hpl gene containing the 5'DELTA93 bp deletion. Mutant sequence analysis, overview. The mutant variants show highly increased trunover as well as reduced mechanism based suicide inactivation compared to the wild-type
APPLICATION
ORGANISM
UNIPROT
COMMENTARY
LITERATURE
food industry
-
the enzyme produces aldehydes that are used as flavours in foods and beverages
medicine
-
enzyme is involved in skin differentiation and etiology of ichthyosiform diseases