title: An iron 13S-lipoxygenase with an α-linolenic acid specific hydroperoxidase activity from Fusarium oxysporum.
abstract: Jasmonates constitute a family of lipid-derived signaling molecules that are abundant in higher plants. The biosynthetic pathway leading to plant jasmonates is initiated by 13-lipoxygenase-catalyzed oxygenation of α-linolenic acid into its 13-hydroperoxide derivative. A number of plant pathogenic fungi (e.g. Fusarium oxysporum) are also capable of producing jasmonates, however, by a yet unknown biosynthetic pathway. In a search for lipoxygenase in F. oxysporum, a reverse genetic approach was used and one of two from the genome predicted lipoxygenases (FoxLOX) was cloned. The enzyme was heterologously expressed in E. coli, purified via affinity chromatography, and its reaction mechanism characterized. FoxLOX was found to be a non-heme iron lipoxygenase, which oxidizes C18-polyunsaturated fatty acids to 13S-hydroperoxy derivatives by an antarafacial reaction mechanism where the bis-allylic hydrogen abstraction is the rate-limiting step. With α-linolenic acid as substrate FoxLOX was found to exhibit a multifunctional activity, because the hydroperoxy derivatives formed are further converted to dihydroxy-, keto-, and epoxy alcohol derivatives.
authors.affiliation: Georg-August-University, Albrecht-von-Haller-Institute for Plant Sciences, Department of Plant Biochemistry, Goettingen, Germany.
authors.forename: Florian
authors.initials: F
authors.lastname: Brodhun
authors.forename: Alvaro
authors.initials: A
authors.lastname: Cristobal-Sarramian
authors.forename: Sebastian
authors.initials: S
authors.lastname: Zabel
authors.forename: Julia
authors.initials: J
authors.lastname: Newie
authors.forename: Mats
authors.initials: M
authors.lastname: Hamberg
authors.forename: Ivo
authors.initials: I
authors.lastname: Feussner
mesh_terms: D000595:Amino Acid Sequence; D005227:Fatty Acids / Q000737:chemistry / Q000378:metabolism; D005670:Fusarium / Q000145:classification / Q000235:genetics / Q000378:metabolism*; D006863:Hydrogen-Ion Concentration; D007501:Iron / Q000378:metabolism*; D007700:Kinetics; D008084:Lipoxygenase / Q000737:chemistry / Q000235:genetics / Q000378:metabolism*; D013058:Mass Spectrometry; D008969:Molecular Sequence Data; D010084:Oxidation-Reduction; D010802:Phylogeny; D011993:Recombinant Fusion Proteins / Q000737:chemistry / Q000235:genetics / Q000378:metabolism; D016415:Sequence Alignment
chemical_list: D005227:Fatty Acids; D011993:Recombinant Fusion Proteins; D007501:Iron; C117433:13-lipoxygenase; D008084:Lipoxygenase