Document Detail


{Omega}-oxidation of {alpha}-chlorinated fatty acids: identification of {alpha}-chlorinated dicarboxylic acids.
MedLine Citation:
PMID:  20956542     Owner:  NLM     Status:  MEDLINE    
Abstract/OtherAbstract:
Myeloperoxidase-derived HOCl targets tissue- and lipoprotein-associated plasmalogens to generate α-chlorinated fatty aldehydes, including 2-chlorohexadecanal. Under physiological conditions, 2-chlorohexadecanal is oxidized to 2-chlorohexadecanoic acid (2-ClHA). This study demonstrates the catabolism of 2-ClHA by ω-oxidation and subsequent β-oxidation from the ω-end. Mass spectrometric analyses revealed that 2-ClHA is ω-oxidized in the presence of liver microsomes with initial ω-hydroxylation of 2-ClHA. Subsequent oxidation steps were examined in a human hepatocellular cell line (HepG2). Three different α-chlorinated dicarboxylic acids, 2-chlorohexadecane-(1,16)-dioic acid, 2-chlorotetradecane-(1,14)-dioic acid, and 2-chloroadipic acid (2-ClAdA), were identified. Levels of 2-chlorohexadecane-(1,16)-dioic acid, 2-chlorotetradecane-(1,14)-dioic acid, and 2-ClAdA produced by HepG2 cells were dependent on the concentration of 2-ClHA and the incubation time. Synthetic stable isotope-labeled 2-ClHA was used to demonstrate a precursor-product relationship between 2-ClHA and the α-chlorinated dicarboxylic acids. We also report the identification of endogenous 2-ClAdA in human and rat urine and elevations in stable isotope-labeled urinary 2-ClAdA in rats subjected to intraperitoneal administration of stable isotope-labeled 2-ClHA. Furthermore, urinary 2-ClAdA and plasma 2-ClHA levels are increased in LPS-treated rats. Taken together, these data show that 2-ClHA is ω-oxidized to generate α-chlorinated dicarboxylic acids, which include α-chloroadipic acid that is excreted in the urine.
Authors:
Viral V Brahmbhatt; Carolyn J Albert; Dhanalakshmi S Anbukumar; Bryce A Cunningham; William L Neumann; David A Ford
Publication Detail:
Type:  Journal Article; Research Support, N.I.H., Extramural; Research Support, Non-U.S. Gov't     Date:  2010-10-18
Journal Detail:
Title:  The Journal of biological chemistry     Volume:  285     ISSN:  1083-351X     ISO Abbreviation:  J. Biol. Chem.     Publication Date:  2010 Dec 
Date Detail:
Created Date:  2010-12-27     Completed Date:  2011-02-09     Revised Date:  2012-01-02    
Medline Journal Info:
Nlm Unique ID:  2985121R     Medline TA:  J Biol Chem     Country:  United States    
Other Details:
Languages:  eng     Pagination:  41255-69     Citation Subset:  IM    
Affiliation:
Edward A Doisy Department of Biochemistry and Molecular Biology, Saint Louis University School of Medicine, St Louis, Missouri 63104, USA.
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MeSH Terms
Descriptor/Qualifier:
Animals
Chlorine / chemistry*
Dicarboxylic Acids / chemistry*,  metabolism
Fatty Acids / metabolism*
Hep G2 Cells
Hepatocytes / cytology
Humans
Mass Spectrometry / methods
Microsomes, Liver / metabolism
Oxygen / chemistry
Palmitic Acids / chemistry
Peroxidase / chemistry
Peroxidases / chemistry
Rabbits
Rats
Grant Support
ID/Acronym/Agency:
HL074214/HL/NHLBI NIH HHS; HL088073/HL/NHLBI NIH HHS; HL098907/HL/NHLBI NIH HHS; R01 HL074214-05A2/HL/NHLBI NIH HHS; R21 HL088073-02/HL/NHLBI NIH HHS; R21 HL098907-01A1/HL/NHLBI NIH HHS; R21 HL098907-02/HL/NHLBI NIH HHS; RR019232/RR/NCRR NIH HHS; S10 RR019232-01/RR/NCRR NIH HHS
Chemical
Reg. No./Substance:
0/2-chlorohexadecanoic acid; 0/Dicarboxylic Acids; 0/Fatty Acids; 0/Palmitic Acids; 7782-44-7/Oxygen; 7782-50-5/Chlorine; EC 1.11.1.-/Peroxidases; EC 1.11.1.7/Peroxidase

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