Strategies for the analysis of chlorinated lipids in biological systems

Free Radic Biol Med. 2013 Jun;59:92-9. doi: 10.1016/j.freeradbiomed.2012.06.013. Epub 2012 Jun 17.

Abstract

Myeloperoxidase-derived HOCl reacts with the vinyl ether bond of plasmalogens yielding α-chlorofatty aldehydes. These chlorinated aldehydes can be purified using thin-layer chromatography, which is essential for subsequent analysis of extracts from some tissues such as myocardium. The α-chlorofatty aldehyde 2-chlorohexadecanal (2-ClHDA) is quantified after conversion to its pentafluorobenzyl oxime derivative using gas chromatography-mass spectrometry and negative-ion chemical ionization detection. 2-ClHDA accumulates in activated human neutrophils and monocytes, as well as in atherosclerotic lesions and infarcted myocardium. Metabolites of 2-ClHDA have also been identified, including the oxidation product, 2-chlorohexadecanoic acid (2-ClHA), and the reduction product, 2-chlorohexadecanol. 2-ClHA can be quantified using LC-MS with selected reaction monitoring (SRM) detection. 2-ClHA can be ω-oxidized by hepatocytes and subsequently β-oxidized from the ω-end, leading to the production of the dicarboxylic acid, 2-chloroadipic acid. This dicarboxylic acid is excreted in the urine and can also be quantified using LC-MS methods with SRM detection. Quantitative analyses of these novel chlorinated lipids are essential to identify the role of these lipids in leukocyte-mediated injury and disease.

Publication types

  • Research Support, N.I.H., Extramural
  • Research Support, Non-U.S. Gov't

MeSH terms

  • Aldehydes / analysis*
  • Aldehydes / chemistry
  • Gas Chromatography-Mass Spectrometry
  • Humans
  • Lipids / analysis*
  • Lipids / chemistry*
  • Oxidation-Reduction
  • Palmitic Acids / analysis*
  • Palmitic Acids / chemistry

Substances

  • 2-chlorohexadecanal
  • 2-chlorohexadecanoic acid
  • Aldehydes
  • Lipids
  • Palmitic Acids