title: Unexpected products of the hypochlorous acid-induced oxidation of oleic acid: A study using high performance thin-layer chromatography-electrospray ionization mass spectrometry.
abstract: Reactive oxygen species (ROS) play important physiological roles and are of particular relevance in the pathogenesis of inflammatory diseases. At inflammatory conditions, the enzyme myeloperoxidase generates hypochlorous acid (HOCl) which adds to the double bonds of fatty acyl residues of (phospho)lipids under the formation of chlorohydrins. This may lead to the development of many inflammatory diseases, such as atherosclerosis or arthritis, if the ROS generation exceeds a certain extent. Using oleic acid as the simplest unsaturated fatty acid which contains just a single double bond, as a model system, we investigated all products - including the chlorohydrin - after its reaction with HOCl by a combination of thin-layer chromatography and electrospray ionization mass spectrometry. Unlike the general acceptance, the reaction of oleic acid and HOCl leads not exclusively to the formation of chlorohydrin (isomers) but is much more complex: there are also considerable amounts of dimeric and (to a minor extent) trimeric products which can be assigned to isomeric ethers and esters. The obtained products after oleic acid chlorination were also compared with the reaction products of 1-palmitoyl-2-oleoyl-sn-phosphatidylcholine (POPC) and HOCl. The reasons why different products are obtained will be discussed and the involvement of the carboxylic acid emphasized.
authors.affiliation: University of Leipzig, Medical Faculty, Institute of Medical Physics and Biophysics, Härtelstr. 16⿿18, Leipzig D-04107, Germany. Electronic address: jenny.schroeter@medizin.uni-leipzig.de.
authors.forename: Jenny
authors.initials: J
authors.lastname: Schröter
authors.affiliation: Merck KGaA, Frankfurter Strasse 250, Darmstadt D-64293, Germany. Electronic address: hans.griesinger@merckgroup.com.
authors.forename: Hans
authors.initials: H
authors.lastname: Griesinger
authors.affiliation: Merck KGaA, Frankfurter Strasse 250, Darmstadt D-64293, Germany. Electronic address: eyla.reuss@merckgroup.com.
authors.forename: Eyla
authors.initials: E
authors.lastname: Reuÿ
authors.affiliation: Merck KGaA, Frankfurter Strasse 250, Darmstadt D-64293, Germany. Electronic address: michael.schulz@merckgroup.com.
authors.forename: Michael
authors.initials: M
authors.lastname: Schulz
authors.affiliation: University of Leipzig, Medical Faculty, Institute of Medical Physics and Biophysics, Härtelstr. 16⿿18, Leipzig D-04107, Germany. Electronic address: thomas.riemer@medizin.uni-leipzig.de.
authors.forename: Thomas
authors.initials: T
authors.lastname: Riemer
authors.affiliation: University of Leipzig, Medical Faculty, Institute of Medical Physics and Biophysics, Härtelstr. 16⿿18, Leipzig D-04107, Germany. Electronic address: rosmarie.suess@medizin.uni-leipzig.de.
authors.forename: Rosmarie
authors.initials: R
authors.lastname: Süÿ
authors.affiliation: University of Leipzig, Medical Faculty, Institute of Medical Physics and Biophysics, Härtelstr. 16⿿18, Leipzig D-04107, Germany. Electronic address: juergen.schiller@medizin.uni-leipzig.de.
authors.forename: Jürgen
authors.initials: J
authors.lastname: Schiller
authors.affiliation: University of Leipzig, Medical Faculty, Institute of Medical Physics and Biophysics, Härtelstr. 16⿿18, Leipzig D-04107, Germany. Electronic address: beate.fuchs@medizin.uni-leipzig.de.
authors.forename: Beate
authors.initials: B
authors.lastname: Fuchs
mesh_terms: D002728:Chlorohydrins / Q000737:chemistry; D002855:Chromatography, Thin Layer; D019281:Dimerization; D004952:Esters; D054879:Halogenation; D006997:Hypochlorous Acid / Q000737:chemistry*; D007536:Isomerism; D019301:Oleic Acid / Q000737:chemistry*; D010084:Oxidation-Reduction; D010713:Phosphatidylcholines / Q000737:chemistry; D021241:Spectrometry, Mass, Electrospray Ionization
chemical_list: D002728:Chlorohydrins; D004952:Esters; D010713:Phosphatidylcholines; D019301:Oleic Acid; D006997:Hypochlorous Acid; C028694:1-palmitoyl-2-oleoylphosphatidylcholine
keywords: ESI MS; Fatty acid chlorohydrin; Hypochlorous acid; TLC–MS