Document Detail

Synthesis of dihydroperoxides of linoleic and linolenic acids and studies on their transformation to 4-hydroperoxynonenal.
MedLine Citation:
PMID:  16459928     Owner:  NLM     Status:  MEDLINE    
The cytotoxic aldehydes 4-hydroxynonenal, 4-hydroperoxynonenal (4-HPNE), and 4-oxononenal are formed during lipid peroxidation via oxidative transformation of the hydroxy or hydroperoxy precursor fatty acids, respectively. The mechanism of the carbon chain cleavage reaction leading to the aldehyde fragments is not known, but Hock-cleavage of a suitable dihydroperoxide derivative was implicated to account for the fragmentation [Schneider, C., Tallman, K.A., Porter, N.A., and Brash, A.R. (2001) Two Distinct Pathways of Formation of 4-Hydroxynonenal. Mechanisms of Nonenzymatic Transformation of the 9- and 13-Hydroperoxides of Linoleic Acid to 4-Hydroxyalkenals, J. Biol. Chem. 275, 20831-20838]. Both 8,13- and 10,13-dihydroperoxyoctadecadienoic acids (diHPODE) could serve as precursors in a Hock-cleavage leading to 4-HPNE via two different pathways. Here, we synthesized diastereomeric 9,12-, 10,12-, and 10,13-diHPODE using singlet oxidation of linoleic acid. 8,13-Dihydroperoxyoctadecatrienoic acid was synthesized by vitamin E-controlled autoxidation of gamma-linolenic acid followed by reaction with soybean lipoxygenase. The transformation of these potential precursors to 4-HPNE was studied under conditions of autoxidation, hematin-, and acid-catalysis. In contrast to 9- or 13-HPODE, neither of the dihydroperoxides formed 4-HPNE on autoxidation (lipid film, 37 degrees C), regardless of whether the free acid or the methyl ester derivative was used. Acid treatment of 10,13-diHPODE led to the expected formation of 4-HPNE as a significant product, in accord with a Hock-type cleavage reaction. We conclude that, although the suppression of 4-H(P)NE formation from monohydroperoxides by alpha-tocopherol indicates peroxyl radical reactions in the major route of carbon chain cleavage, the dihydroperoxides previously implicated are not intermediates in the autoxidative transformation of monohydroperoxy fatty acids to 4-HPNE and related aldehydes.
Claus Schneider; William E Boeglin; Huiyong Yin; Donald F Ste; David L Hachey; Ned A Porter; Alan R Brash
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Publication Detail:
Type:  Journal Article; Research Support, N.I.H., Extramural    
Journal Detail:
Title:  Lipids     Volume:  40     ISSN:  0024-4201     ISO Abbreviation:  Lipids     Publication Date:  2005 Nov 
Date Detail:
Created Date:  2006-02-07     Completed Date:  2006-06-06     Revised Date:  2007-11-14    
Medline Journal Info:
Nlm Unique ID:  0060450     Medline TA:  Lipids     Country:  United States    
Other Details:
Languages:  eng     Pagination:  1155-62     Citation Subset:  IM    
Department of Pharmacology, Vanderbilt University Medical School, Nashville, Tennessee 37232, USA.
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MeSH Terms
Aldehydes / metabolism*
Linoleic Acids / chemistry,  metabolism*
Linolenic Acids / chemistry,  metabolism*
Lipid Peroxides / chemical synthesis*,  chemistry
Grant Support
Reg. No./Substance:
0/Aldehydes; 0/Linoleic Acids; 0/Linolenic Acids; 0/Lipid Peroxides; 31823-43-5/3-nonenal

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