The hydroperoxide moiety of aliphatic lipid hydroperoxides is not affected by hypochlorous acid

• Hypochlorous acid reacts with double bonds of unsaturated fatty acid hydroperoxides.
• The hydroperoxide moiety of 15S-hydroperoxy-5Z,8Z,11Z,13E-eicosatetraenoic acid is not affected by hypochlorous acid.
• The myeloperoxidase-H2O2-Cl− system creates chlorohydrin products of unsaturated fatty acid hydroperoxides.

The oxidation of polyunsaturated fatty acids to the corresponding hydroperoxide by plant and animal lipoxygenases is an important step for the generation of bioactive lipid mediators. Thereby fatty acid hydroperoxide represent a common intermediate, also in human innate immune cells, like neutrophil granulocytes. In these cells a further key component is the heme protein myeloperoxidase producing HOCl as a reactive oxidant. On the basis of different investigation a reaction of the fatty acid hydroperoxide and hypochlorous acid (HOCl) could be assumed. Here, chromatographic and spectrometric analysis revealed that the hydroperoxide moiety of 15S-​hydroperoxy-​5Z,​8Z,​11Z,​13E-​eicosatetraenoic acid (15-HpETE) and 13S-​hydroperoxy-​9Z,​11E-​octadecadienoic acid (13-HpODE) is not affected by HOCl. No reduction of the hydroperoxide group due to a reaction with HOCl could be measured. It could be demonstrated that the double bonds of the fatty acid hydroperoxides are the major target of HOCl, present either as reagent or formed by the myeloperoxidase-hydrogen peroxide-chloride system.