Myeloperoxidase-derived 2-chlorohexadecanal forms Schiff bases with primary amines of ethanolamine glycerophospholipids and lysine

Kristin R. Wildsmith, Carolyn J. Albert, Fong Fu Hsu, Jeff L.F. Kao, David A. Ford

Research output: Contribution to journalArticlepeer-review

30 Scopus citations

Abstract

Numerous studies have suggested relationships between myeloperoxidase, inflammation, and atherosclerosis. MPO-derived reactive chlorinating species (RCS) attack membrane plasmalogens releasing α-chloro-fatty aldehydes (α-Cl-FALDs) including 2-chlorohexadecanal (2-ClHDA). The molecular targets of α-Cl-FALDs are not known. The current study demonstrates 2-ClHDA adducts with ethanolamine glycerophospholipids and Fmoc-lysine. Utilizing electrospray ionization mass spectrometry, chlorinated adducts were observed that are apparent Schiff base adducts. Reduction of these Schiff base adducts with sodium cyanoborohydride resulted in a novel, stable adduct produced by the elimination of HCl. NMR further confirmed this structure. 2-ClHDA adducts with ethanolamine glycerophospholipids were also substrates for phospholipase D (PLD). The hydrolysis products were derivatized to pentafluorobenzoyl esters, and further structurally confirmed by GC-MS. Multiple molecular species of 2-ClHDA-N-modified ethanolamine glycerophospholipids were observed in endothelial cells treated with 2-ClHDA. These results show novel Schiff base adducts of α-Cl-FALDs with primary amines, which may represent an important fate of α-Cl-FALDs.

Original languageEnglish
Pages (from-to)157-170
Number of pages14
JournalChemistry and Physics of Lipids
Volume139
Issue number2
DOIs
StatePublished - Feb 2006

Keywords

  • Electrospray ionization mass spectrometry
  • Endothelial cells
  • Fatty aldehyde
  • Phosphatidylethanolamine
  • Plasmenylcholine
  • Reactive chlorinating species

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