64044-08-2Relevant academic research and scientific papers
Oxidation of C18 Hydroxy-Polyunsaturated Fatty Acids to Epoxide or Ketone by Catalase-Related Hemoproteins Activated with Iodosylbenzene
Teder, Tarvi,Boeglin, William E.,Brash, Alan R.
, p. 587 - 597 (2017/06/30)
Small catalase-related hemoproteins with a facility to react with fatty acid hydroperoxides were examined for their potential mono-oxygenase activity when activated using iodosylbenzene. The proteins tested were a Fusarium graminearum 41?kD catalase hemoprotein (Fg-cat, gene FGSG_02217), a Pseudomonas fluorescens Pfl01 catalase (37.5?kD, accession number WP_011333788.1), and a Mycobacterium avium ssp. paratuberculosis 33?kD catalase (gene MAP-2744c). 13-Hydroxy-octadecenoic acids (which are normally unreactive) were selected as substrates because these enzymes react specifically with the corresponding 13S-hydroperoxides (Pakhomova et al. 18:2559–2568, 5; Teder et al. 1862:706–715, 14). In the presence of iodosylbenzene Fg-cat converted 13S-hydroxy-fatty acids to two products: the 15,16-double bond of 13S-hydroxy α-linolenic acid was oxidized stereospecifically to the 15S,16R-cis-epoxide or the 13-hydroxyl was oxidized to the 13-ketone. Products were identified by UV, HPLC, LC–MS, NMR and by comparison with authentic standards prepared for this study. The Pfl01-cat displayed similar activity. MAP-2744c oxidized 13S-hydroxy-linoleic acid to the 13-ketone, and epoxidized the double bonds to form the 9,10-epoxy-13-hydroxy, 11,12-epoxy-13-hydroxy, and 9,10-epoxy-13-keto derivatives; equivalent transformations occurred with 9S-hydroxy-linoleic acid as substrate. In parallel incubations in the presence of iodosylbenzene, human catalase displayed no activity towards 13S-hydroxy-linoleic acid, as expected from the highly restricted access to its active site. The results indicated that with suitable transformation to Compound I, monooxygenase activity can be demonstrated by these catalase-related hemoproteins with tyrosine as the proximal heme ligand.
Lipoxygenase-catalyzed transformation of epoxy fatty acids to hydroxy-endoperoxides: A potential P450 and lipoxygenase interaction
Teder, Tarvi,Boeglin, William E.,Brash, Alan R.
, p. 2587 - 2596 (2015/02/19)
Herein, we characterize a generally applicable transformation of fatty acid epoxides by lipoxygenase (LOX) enzymes that results in the formation of a five-membered endoperoxide ring in the end product. We demonstrated this transformation using soybean LOX-1 in the metabolism of 15,16-epoxy-α-linolenic acid, and murine platelet-type 12-LOX and human 15-LOX-1 in the metabolism of 14,15-epoxyeicosatrienoic acid (14,15-EET). A detailed examination of the transformation of the two enantiomers of 15,16-epoxy-α-linolenic acid by soybean LOX-1 revealed that the expected primary product, a 13 S-hydroperoxy-15,16-epoxide, underwent a nonenzymatic transformation in buffer into a new derivative that was purifi ed by HPLC and identified by UV, LC-MS, and 1H-NMR as a 13,15-endoperoxy-16-hydroxy-octadeca-9,11-dienoic acid. The configuration of the endoperoxide (cis or trans side chains) depended on the steric relationship of the new hydroperoxy moiety to the enantiomeric configuration of the fatty acid epoxide. The reaction mechanism involves intramolecular nucleophilic substitution (SNi) between the hydroperoxy (nucleophile) and epoxy group (electrophile). Equivalent transformations were documented in metabolism of the enantiomers of 14,15-EET by the two mammalian LOX enzymes, 15-LOX-1 and platelet-type 12-LOX. We conclude that this type of transformation could occur naturally with the co-occurrence of LOX and cytochrome P450 or peroxygenase enzymes, and it could also contribute to the complexity of products formed in the autoxidation reactions of polyunsaturated fatty acids.
Epoxidation, hydroxylation and aromatization is catalyzed by a peroxygenase from Solanum lycopersicum
Fuchs, Christopher,Schwab, Wilfried
, p. 52 - 60 (2013/10/22)
Plant peroxygenase (PXG) oxidizes unsaturated fatty acids by transferring an oxygen atom of a hydroperoxide to the double bond, thereby providing epoxides. In this work we investigated the potential of a PXG from tomato (Solanum lycopersicum, SlPXG) to catalyze the oxidation of a variety of natural products. A SlPXG gene was cloned from tomato, heterologously expressed in yeast and the membrane bound recombinant SlPXG protein was used as enzyme source. Unsaturated fatty acids, fatty acid derivatives, and terpenes were epoxidized by SlPXG in the presence of various hydroperoxides exclusively at their cis-double bonds. Terpenes with p-menthene skeleton were transformed in different ways depending on their molecular structures. R-(+)- and S-(-)-limonene were converted to R-(+)-limonene-trans-1,2-epoxide (97%) and cis-S-(-)-limonene-1,2- epoxide (88%), respectively whereas α-terpinenewas hydroxylated to cis-1,4-dihydroxy-p-menth-2-ene and γ-terpinene was aromatized to p-cymene. In the last reaction the hydroperoxide served as hydrogen acceptor rather than an oxygen donor. PXG appears to be a versatile biocatalyst able to perform different kinds of oxidation reactions. As no cofactors like NAD(P)H are required and H2O2is an environmentally friendly oxidant, PXG enables new applications for the synthesis of fine chemicals from renewable resources.
Enantioselective epoxidation of linolenic acid catalysed by cytochrome P450BM3 from Bacillus megaterium
Celik, Ayhan,Sperandio, Davide,Speight, Robert E.,Turner, Nicholas J.
, p. 2688 - 2690 (2007/10/03)
Cytochrome P450BM3, from Bacillus megaterium, catalyses the epoxidation of linolenic acid 1 yielding 15,16-epoxyoctadeca-9,12-dienoic acid 2 with complete regioand moderate enantio-selectivity (60% ee). The absolute configuration of the product is tentatively assigned as 15(R),16(S)-. The Michaelis-Menten parameters kcat and Km for the reaction were determined to be 3126 ± 226 min-1 and 24 ± 6 μM respectively. The Royal Society of Chemistry 2005.
N-(15,16-Dihydroxylinoleoyl)-glutamine and N-(15,16-epoxylinoleoyl)-glutamine isolated from oral secretions of lepidopteran larvae
Spiteller, Dieter,Boland, Wilhelm
, p. 135 - 139 (2007/10/03)
N-(15,16-Dihydroxylinoleoyl)-glutamine (1) and N-(15,16-epoxylinoleoyl)-glutamine (2) and were identified in the regurgitant of lepidopteran larvae (Spodoptera exigua and Spodoptera frugiperda) by LC-MS. After methanolysis and derivatisation with MSTFA, the positions of the hydroxy groups of 1 were identified by GC-MS. The structures of both conjugates were confirmed by synthesis.
Highly terminal-selective epoxidation of linolenic acid with an amphiphilic iron porphyrin catalyst casted in bilayer membranes
Naruta, Yoshinori,Goto, Masa-oki,Tawara, Toshifumi,Tani, Fumito
, p. 162 - 163 (2007/10/03)
An amphiphilic iron porphyrin having four hexadecanoic acid chains on each face of the porphyrin was prepared and the catalytic epoxidation of linolenic acid with the heme-casted bilayer membranes was achieved in high regioselectivity at the terminal doub
Preparation of the enantiomers of hydroxy-C18 fatty acids and their anti-rice blast fungus activities
Kato, Tadahiro,Nakai, Toshio,Ishikawa, Rumiko,Karasawa, Aya,Namai, Tsuneo
, p. 2695 - 2701 (2007/10/03)
In order to examine the correlation between the anti-rice blast fungus activity and the chirality of allylic alcohols 1-3, which were characterized from the infected rice plants as an enantiomeric mixture with 10% e.e., a procedure for the chemical prepa
Preparation of optically active 15-epoxy-α-linolenic acids and their anti-rice blast fungus activities
Kato, Tadahiro,Nakai, Toshio,Ishimatu, Takayuki,Hoshikawa, Masahiro,Namai, Tsuneo
, p. 1353 - 1358 (2007/10/03)
By the action of NBS in aq. DME, α-linolenic acid was oxidized to 15- bromo-16-hydroxy-α-linolenic acid in 35% conversion yield. The bromohydrin was treated with lipase-PS and vinyl acetate to give the resolved acetate and bromohydrin. (15S,16R)- and (15R
UNSATURATED HYDROXY FATTY ACIDS, THE SELF DEFENSIVE SUBSTANCES IN RICE PLANT AGAINST RICE BLAST DISEASE
Kato, Tadahiro,Yamaguchi, Yoshihiro,Hirano, Takumi,Yokoyama, Toshiro,Uyehara, Tadao,et al.
, p. 409 - 412 (2007/10/02)
In addition to the previously described epoxy fatty acids, five hydroxy fatty acids were characterized as self defensive substances produced in the rice plant against rice blast disease.
