Analysis of phospholipid molecular species in brain by31P NMR spectroscopy

Pearce, John M.; Komoroski, Richard A.

doi:10.1002/1522-2594(200008)44:2<215::aid-mrm8>3.0.co;2-n

Cited by 48 publications

(49 citation statements)

References 39 publications

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“…The dried organic and aqueous layers of the reaction mixtures were combined and solubilized [55,56] [57] and the GPC resonance can be clearly resolved whereas the GPC and CerPCho resonances overlap in the spectra recorded at 30°C. Other NMR parameters were as follows: experiment time: 2-8 h, data size: 8 k, 60°pulse (6.7 ls), pulse delay 2 s, and a line broadening of 1 Hz.…”

Section: P-nmr Spectroscopic Measurementsmentioning

confidence: 99%

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

Lessig¹,

Fuchs²

2009

Lipids

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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 (31)P 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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Section: P-nmr Spectroscopic Measurementsmentioning

confidence: 99%

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

Lessig¹,

Fuchs²

2009

Lipids

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“…The dried organic and aqueous layers were redissolved as described previously (32,33) in 50 mM Tris (pH 7.65) containing 200 mM sodium cholate and 5 mM EDTA. As a concentration standard, 1,2-dipalmitoyl-sn-glycero-3-phosphate was added.…”

Section: P Nmr Spectroscopic Measurementsmentioning

confidence: 99%

Hypochlorous acid-mediated generation of glycerophosphocholine from unsaturated plasmalogen glycerophosphocholine lipids

Lessig

Schiller

Arnhold

et al. 2007

Journal of Lipid Research

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The myeloperoxidase-derived metabolite hypochlorous acid (HOCl) promotes the selective cleavage of plasmalogens into chloro fatty aldehydes and 1-lysophosphatidylcholine (LPC). The subsequent conversion of the initially generated LPC was investigated in plasmalogen samples in dependence on the fatty acid residue in the sn-2 position by matrix-assisted laser desorption and ionization time-of-flight mass spectrometry and 31 P NMR spectroscopy. Plasmalogens containing an oleic acid residue in the sn-2 position are converted by moderate amounts of HOCl primarily to 1-lyso-2-oleoyl-sn-glycero-3-phosphocholine and at increased HOCl concentrations to the corresponding chlorohydrin species. In contrast, plasmalogens containing highly unsaturated docosahexaenoic acid yield upon HOCl treatment 1-lyso-2-docosahexaenoyl-glycerophosphocholine and glycerophosphocholine. The formation of the latter product denotes a novel pathway for the action of HOCl on plasmalogens. Olefinic residues of fatty acyl residues of phospholipids are an important target for oxidative damage induced by reactive oxygen species (ROS) known to occur under various pathological conditions, including chronic inflammation, atherosclerosis, aging, and cancer. Some mammalian tissues and cells, such as erythrocytes, kidney, lung, testes, skeletal muscle, brain, heart, and particularly selected animal spermatozoa (e.g., from bull), contain considerable levels of plasmalogen glycerophosphocholine lipids (1). Plasmalogens also represent an important target for ROS (2) and are often considered antioxidants. Although the 1-alkenyl residues in plasmalogens (mainly plasmalogen glycerophosphocholine and glycerophosphoethanolamine) of mammalian cells are usually derived from saturated long-chain fatty aldehydes, the acyl residues are highly unsaturated (2). For instance, in spermatozoa from boar or bull, docosahexaenoic and docosapentaenoic acid residues do nearly occur exclusively (3). Accordingly, the oxidative attack of ROS may affect the vinyl-ether function as well as the olefinic residue in the fatty acid moiety (4). The presence of a vinyl-ether bond makes plasmalogens more susceptible to oxidative damages compared with their 1-acyl analogs (2). This has prompted the hypothesis that plasmalogens may act as ROS scavengers, protecting other phospholipids and lipoprotein particles from oxidative damage (2). Thus, plasmalogens seem to have an antioxidative effect toward many ROS (5).Hypochlorous acid (HOCl) is generated by polymorphonuclear leukocytes under the catalysis of the enzyme myeloperoxidase (MPO) (6). HOCl reacts with a variety of molecules, including amino acids, proteins, carbohydrates, nucleic acids, and lipids (7-12). In the latter case, chlorohydrins are generated as the primary products when HOCl reacts with the double bonds in unsaturated phosphatidylcholines (12)(13)(14). HOCl and the MPO-H 2 O 2 -Cl 2 system also induce the formation of 2-lysophosphatidylcholines (LPCs) in polyunsaturated phosphatidylcholines, as shown by matrixassisted...

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Section: )mentioning

confidence: 99%

“…31 P NMR spectra can be recorded and interpreted very easily because no suppression of solvent signals is required and only a limited number of resonances have to be assigned. 31 P NMR spectroscopy enables the diVerentiation of all biologically relevant PL classes even in complex mixtures [10][11][12][13].Surprisingly, there were so far only a very few reports on the 31 P NMR spectroscopic characterization of isolated PPI [14] and no reports at all on the analysis of enzymatically generated PPI.Figs. 1A-D show 31 P NMR spectra of isolated phosphoinositides as measured in aqueous sodium cholate.…”

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Analysis of enzymatically generated phosphoinositides by 31P nuclear magnetic resonance spectroscopy

Müller

Schiller

Petković

et al. 2004

Analytical Biochemistry

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Analysis of phospholipid molecular species in brain by31P NMR spectroscopy

Cited by 48 publications

References 39 publications

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

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

Hypochlorous acid-mediated generation of glycerophosphocholine from unsaturated plasmalogen glycerophosphocholine lipids

Analysis of enzymatically generated phosphoinositides by 31P nuclear magnetic resonance spectroscopy

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