Preferential formation of the hydroperoxide of linoleic acid in choline glycerophospholipids in human erythrocytes membrane during peroxidation with an azo initiator.
The formation of phospholipid hydroperoxides was monitored in human red blood cell (RBC) membranes that had been peroxidized with an azo initiator. Peroxidation of RBC membranes caused a profound decrease in the amount of polyunsaturated fatty acids and concomitantly hydroperoxides, as primary products of peroxidation, appeared in the phospholipids. Hydroperoxides were predominantly generated in choline glycerophospholipid (CGP), while the extent of formation of ethanolamine glycerophospholipid (EGP) hydroperoxides was low and their presence was transient. Hydroxy and hydroperoxy moieties in CGP were identified as 9-hydroxy and 13-hydroxy octadecanoic acid, derived from linoleic acid, by gas chromatography-mass spectrometric analysis. No consistent generation of hydroperoxide from arachidonic acid was evident in CGP. The CGP-hydroperoxide accounted for approximately 76% of linoleic acid consumed during peroxidation of RBC membranes. The prominent generation of phospholipid hydroperoxides was observed in the linoleic acid-rich membranes from rabbit RBC, indicating that the level of linoleic acid in phospholipids determines, in part, the extent of formation of phospholipid hydroperoxides. Aldehydic phospholipids, as secondary products of peroxidation, were detected in oxidized membranes. EGP was the most prominent aldehydic phospholipid, while negligible amounts of aldehydic CGP were formed. This study indicates that the process of oxidation of individual phospholipids clearly differs among phospholipids and depends on the structure of each.
Guo
L
L
School of Pharmaceutical Sciences, Kitasato University, Tokyo, Japan.
Ogamo
A
A
Ou
Z
Z
Shinozuka
T
T
Nakagawa
Y
Y
D000328:Adult; D000578:Amidines / Q000494:pharmacology*; D002851:Chromatography, High Pressure Liquid; D004910:Erythrocyte Membrane / Q000378:metabolism*; D005231:Fatty Acids, Unsaturated / Q000097:blood; D006801:Humans; D006861:Hydrogen Peroxide / Q000097:blood*; D019787:Linoleic Acid; D008041:Linoleic Acids / Q000097:blood*; D044243:Linoleic Acids, Conjugated; D015227:Lipid Peroxidation / Q000187:drug effects*; D010713:Phosphatidylcholines / Q000097:blood*; D010714:Phosphatidylethanolamines / Q000097:blood
D000578:Amidines; D005231:Fatty Acids, Unsaturated; D008041:Linoleic Acids; D044243:Linoleic Acids, Conjugated; D010713:Phosphatidylcholines; D010714:Phosphatidylethanolamines; C024347:9-hydroxy-10,12-octadecadienoic acid; C024348:13-hydroxy-9,11-octadecadienoic acid; C046728:2,2'-azobis(2-amidinopropane); D019787:Linoleic Acid; D006861:Hydrogen Peroxide