Document Detail


Steric analysis of epoxyalcohol and trihydroxy derivatives of 9-hydroperoxy-linoleic acid from hematin and enzymatic synthesis.
MedLine Citation:
PMID:  23352713     Owner:  NLM     Status:  MEDLINE    
Abstract/OtherAbstract:
We characterize the allylic epoxyalcohols and their trihydroxy hydrolysis products generated from 9R- and 9S-hydroperoxy-octadecenoic acid (HPODE) under non-enzymatic conditions, reaction with hematin and subsequent acid hydrolysis, and enzymatic conditions, incubation with Beta vulgaris containing a hydroperoxide isomerase and epoxide hydrolase. The products were resolved by HPLC and the regio and stereo-chemistry of the transformations were determined through a combination of (1)H NMR and GC-MS analysis of dimethoxypropane derivatives. Four trihydroxy isomers were identified upon mild acid hydrolysis of 9S,10S-trans-epoxy-11E-13S-hydroxyoctadecenoate: 9S,10R,13S, 9S,12R,13S, 9S,10S,13S and 9S,12S,13S-trihydroxy-octadecenoic acids, in the ratio 40:26:22:12. We also identified a prominent δ-ketol rearrangement product from the hydrolysis as mainly the 9-hydroxy-10E-13-oxo isomer. Short incubation (5 min) of 9R- and 9S-HPODE with B. vulgaris extract yielded the 9R- and 9S-hydroxy-10E-12R,13S-cis-epoxy products respectively. Longer incubation (60 min) gave one specific hydrolysis product via epoxide hydrolase, the 9R/S,12S,13S-trihydroxyoctadecenoate. These studies provide a practical approach for the isolation and characterization of allylic epoxy alcohol and trihydroxy products using a combination of HPLC, GC-MS and (1)H NMR.
Authors:
Christopher P Thomas; William E Boeglin; Yoel Garcia-Diaz; Valerie B O'Donnell; Alan R Brash
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Publication Detail:
Type:  Journal Article; Research Support, N.I.H., Extramural; Research Support, Non-U.S. Gov't     Date:  2013-01-23
Journal Detail:
Title:  Chemistry and physics of lipids     Volume:  167-168     ISSN:  1873-2941     ISO Abbreviation:  Chem. Phys. Lipids     Publication Date:    2013 Feb-Mar
Date Detail:
Created Date:  2013-04-02     Completed Date:  2013-09-09     Revised Date:  2014-02-04    
Medline Journal Info:
Nlm Unique ID:  0067206     Medline TA:  Chem Phys Lipids     Country:  Ireland    
Other Details:
Languages:  eng     Pagination:  21-32     Citation Subset:  IM    
Copyright Information:
Copyright © 2013 Elsevier Ireland Ltd. All rights reserved.
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MeSH Terms
Descriptor/Qualifier:
Beta vulgaris / chemistry,  enzymology*,  metabolism
Chromatography, High Pressure Liquid
Epoxide Hydrolases / metabolism
Epoxy Compounds / chemistry*,  metabolism
Gas Chromatography-Mass Spectrometry
Hemin / analogs & derivatives*,  metabolism
Hydrolysis
Intramolecular Oxidoreductases / metabolism
Isomerism
Linoleic Acid / chemistry*,  metabolism
Magnetic Resonance Spectroscopy
Oleic Acids / chemistry*,  metabolism
Propanols / chemistry*,  metabolism
Stereoisomerism
Grant Support
ID/Acronym/Agency:
P30 CA068485/CA/NCI NIH HHS; P30 CA068485/CA/NCI NIH HHS; R01 AR051968/AR/NIAMS NIH HHS
Chemical
Reg. No./Substance:
0/10-hydroperoxy-8-octadecenoic acid; 0/Epoxy Compounds; 0/Oleic Acids; 0/Propanols; 3W678R12M0/allyl alcohol; 743LRP9S7N/Hemin; 9KJL21T0QJ/Linoleic Acid; EC 3.3.2.-/Epoxide Hydrolases; EC 5.3.-/Intramolecular Oxidoreductases; EC 5.3.99.6/hydroperoxide isomerase
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