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HOCl-Mediated Glycerophosphocholine and Glycerophosphoethanolamine Generation from Plasmalogens in Phospholipid Mixtures

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Lipids

Abstract

Many mammalian tissues and cells contain, in addition to (diacyl) phospholipids, considerable amounts of plasmalogens, which may function as important antioxidants. Apart from the “scavenger” function mediated by the high sensitivity of the vinyl-ether bond, the functional role of plasmalogens is so far widely unknown. Furthermore, there is increasing evidence that plasmalogen degradation products have harmful effects in inflammatory processes. In a previous investigation glycerophosphocholine (GPC) formation was verified as a novel plasmalogen degradation pathway upon oxidation with hypochlorous acid (HOCl), however these investigations were performed in simple model systems. Herein, we examine plasmalogen degradation in a more complex system in order to evaluate if GPC generation is also a major pathway in the presence of other highly unsaturated glycerophospholipids (GPL) representing an additional reaction site of HOCl targets. Using MALDI–TOF mass spectrometry and 31P NMR spectroscopy, we confirmed that the first step of the HOCl-induced degradation of GPL mixtures containing plasmalogens is the attack of the vinyl-ether bond resulting in the generation of 1-lysophosphatidylcholine (lysoPtdCho) or 1-lysophosphatidylethanolamine. In the second step HOCl reacts with the fatty acyl residue in the sn-2 position of 1-lysoPtdCho. This reaction is about three times faster in comparison to comparable diacyl-GPL. Thus, the generation of GPC and glycerophosphoethanolamine (GPE) from plasmalogens are relevant products formed from HOCl attack on the vinyl-ether bond of plasmalogens under pathological conditions.

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Abbreviations

amu:

Atomic mass unit

DHA:

Docosahexaenoic acid

DPA:

Docosapentaenoic acid

2-DH-1-LPC:

1-Lyso-2-docosahexaenoyl-sn-glycero-3-phosphocholine

2-DH-1-LPE:

1-Lyso-2-docosahexaenoyl-sn-glycero-3-phosphoethanolamine

CerPCho:

Sphingomyelin

DPPA:

1,2-Dipalmitoyl-sn-glycero-3-phosphate

DPPC:

1,2-Dipalmitoyl-sn-glycero-3-phosphocholine

GPC:

Glycerophosphocholine

GPE:

Glycerophosphoethanolamine

ChoGpl:

Choline glycerophospholipids

EtnGpl:

Ethanolamine glycerophospholipids

GPL:

Glycerophospholipid

PDHPCether :

1-O-1′-Palmityl-2-docosahexaenoyl-sn-glycero-3-phosphocholine

PDHPCplasm :

1-O-1′-Palmitenyl-2-docosahexaenoyl-sn-glycero-3-phosphocholine

PDHPEplasm :

1-O-1′-Palmitenyl-2-docosahexaenoyl-sn-glycero-3-phosphoethanolamine

PDPPEether :

1-O-1′-Palmityl-2-docosapentaenoyl-sn-glycero-3-phosphoethanolamine

PDPPCether :

1-O-1′-Palmityl-2-docosapentaenoyl-sn-glycero-3-phosphocholine

PDPPCplasm :

1-O-1′-Palmitenyl-2-docosapentaenoyl-sn-glycero-3-phosphocholine

HOCl:

Hypochlorous acid

lysoPtdCho:

Lysophosphatidylcholine

lysoPtdEtn:

Lysophosphatidylethanolamine

LPL:

Lysophospholipid

MALDI-TOF MS:

Matrix-assisted laser desorption & ionization time-of-flight mass spectrometry

1-M-2-LPC:

1-Myristoyl-2-lyso-sn-glycero-3-phosphocholine

MPO:

Myeloperoxidase

MPO–H2O2–Cl− :

Myeloperoxidase-hydrogen peroxide-chloride

SAPCplasm :

1-O-1′-Stearenyl-2-arachidonoyl-sn-glycero-3-phosphocholine

SDHPCplasm :

1-O-1′-Stearenyl-2-docosahexaenoyl-sn-glycero-3-phosphocholine

SDHPEplasm :

1-O-1′-Stearenyl-2-docosahexaenoyl-sn-glycero-3-phosphoethanolamine

PakCho:

Plasmanyl choline

PakEtn:

Plasmanyl ethanolamine

PlsCho:

Plasmenyl choline

PlsEtn:

Plasmenyl ethanolamine

PtdCho:

Phosphatidylcholine

PtdEtn:

Phosphatidylethanolamine

PMNL:

Polymorphonuclear leukocytes

PNA:

para-nitroaniline

31P NMR:

31P nuclear magnetic resonance spectroscopy

POPC:

1-Palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine

ROS:

Reactive oxygen species

SDHPC:

1-Stearoyl-2-docosahexaenoyl-sn-glycero-3-phosphocholine

1-S-2-LPC:

1-Stearoyl-2-lyso-sn-glycero-3-phosphocholine

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Acknowledgment

This work was supported by the German Research Council (DFG Schi 476/5-1, FU 771/1-1 and Gl 199/4-3) and the Federal Ministry of Education and Research (Grant BMBF 0313836). The kind gift of boar spermatozoa samples by Dr. Karin Müller and Ulrike Jakop is gratefully acknowledged. We would also like to thank the Translational Centre for Regenerative Medicine (TRM) Leipzig for the possibility to use the selective 31P dual NMR probe. Finally, we are greatly indebted to Dr. Jürgen Schiller for careful proof-reading of the final manuscript version.

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  1. Medical Faculty, Institute of Medical Physics and Biophysics, University of Leipzig, Härtelstraße 16-18, 04107, Leipzig, Germany

    Jacqueline Leßig & Beate Fuchs

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  1. Jacqueline Leßig
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Correspondence to Beate Fuchs.

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Leßig, J., Fuchs, B. HOCl-Mediated Glycerophosphocholine and Glycerophosphoethanolamine Generation from Plasmalogens in Phospholipid Mixtures. Lipids 45, 37–51 (2010). https://doi.org/10.1007/s11745-009-3365-8

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