Document Detail


Interaction between ferric ions, phospholipid hydroperoxides, and the lipid phosphate moiety at physiological pH.
MedLine Citation:
PMID:  15669764     Owner:  NLM     Status:  MEDLINE    
Abstract/OtherAbstract:
Iron-catalyzed lipid peroxidation was examined using 1H NMR in a biphasic aqueous-chloroform system. At physiological pH (7.4), mole ratios of phospholipids/Fe3+ as low as 1300:1 catalyzed the rapid disappearance of endogenous lipid hydroperoxides with a loss of two of the four double bonds in PC containing palmitic (16:0) and arachidonic (20:4) acids in the sn-1 and sn-2 positions, respectively. The predominant phospholipid products after 1 h at 20 degrees C were a 9-carbon mono-unsaturated carbonyl and a phospholipid with an 11-carbon delta5,8 FA in the sn-2 position. PC with linoleic acid (18:2) in the sn-2 position lost one double bond and formed a phospholipid with a 9-carbon FA. Cardiolipin (linoleic acid-rich) also lost about 40% of its double bonds. No detectable loss was seen for PC containing oleic acid (18:1) or neutral lipids with PUFA. At arachidonyl PC/Fe3+ ratios less than 20:1, significant broadening of the choline methyl proton peak was evident, indicating that Fe3+ may form a complex with the adjacent phosphate group and that the complex involves both the phosphate and the hydroperoxide adjacent to the delta11 double bond. The results demonstrate that, at physiological pH, Fe3+-catalyzed peroxidation in polyunsaturated phospholipids occurs selectively adjacent to specific double bonds (delta9 or delta11). These PC-derived products have been shown to activate components of the inflammatory system. This suggests that the episodic release of ferric ions may play a significant role in generating inflammatory mediators.
Authors:
Gene A Morrill; Adele Kostellow; Lawrence M Resnick; Raj K Gupta
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Publication Detail:
Type:  Journal Article; Research Support, N.I.H., Extramural; Research Support, U.S. Gov't, P.H.S.    
Journal Detail:
Title:  Lipids     Volume:  39     ISSN:  0024-4201     ISO Abbreviation:  Lipids     Publication Date:  2004 Sep 
Date Detail:
Created Date:  2005-01-26     Completed Date:  2005-08-05     Revised Date:  2007-11-14    
Medline Journal Info:
Nlm Unique ID:  0060450     Medline TA:  Lipids     Country:  United States    
Other Details:
Languages:  eng     Pagination:  881-9     Citation Subset:  IM    
Affiliation:
Department of Physiology & Biophysics, Albert Einstein College of Medicine, Bronx, New York 10461, USA. morrill@aecom.yu.edu
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MeSH Terms
Descriptor/Qualifier:
Arachidonic Acid / chemistry,  metabolism
Catalysis
Choline / chemistry
Fatty Acids / chemistry,  metabolism
Hydrogen-Ion Concentration
Ions
Iron / chemistry,  metabolism*
Lipid Peroxidation
Lipid Peroxides / chemistry,  metabolism
Magnetic Resonance Spectroscopy / methods
Phosphates / chemistry,  metabolism*
Phospholipids / chemistry,  isolation & purification,  metabolism*
Phosphorylcholine / chemistry,  metabolism
Grant Support
ID/Acronym/Agency:
CA13330/CA/NCI NIH HHS; GM071234/GM/NIGMS NIH HHS; GM57421/GM/NIGMS NIH HHS
Chemical
Reg. No./Substance:
0/Fatty Acids; 0/Ions; 0/Lipid Peroxides; 0/Phosphates; 0/Phospholipids; 107-73-3/Phosphorylcholine; 506-32-1/Arachidonic Acid; 62-49-7/Choline; 7439-89-6/Iron

From MEDLINE®/PubMed®, a database of the U.S. National Library of Medicine


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