Document Detail


A perspective on free radical autoxidation: the physical organic chemistry of polyunsaturated fatty acid and sterol peroxidation.
MedLine Citation:
PMID:  23445181     Owner:  NLM     Status:  MEDLINE    
Abstract/OtherAbstract:
This Perspective describes advances from the author's laboratory on the free radical reactions of organic compounds with molecular oxygen. Polyunsaturated fatty acids (PUFAs) and sterols are particularly prone to undergo radical chain oxidation, and evidence suggests that this process, known as lipid peroxidation, occurs in vivo under a variety of conditions that are the result of an oxidative stress. Cyclic peroxides, hydroperoxides, and epoxy alcohols are major products formed from peroxidation, and the basic mechanisms of product formation are now reasonably well understood. These mechanisms include reversible addition of oxygen to carbon radicals, rearrangement and cyclization of allyl and pentadienyl peroxyl radicals, and homolytic substitution of carbon radicals on the peroxide bond. A physical organic approach to the problem of free radicals in biology and medicine is highlighted in this Perspective with stereochemical, kinetic, and extrathermodynamic probes applied to the study of mechanism. A radical clock permits the determination of free radical propagation rate constants, and 7-dehydrocholesterol, the immediate biosynthetic precursor of cholesterol, is found by this clock to be one of the most oxidizable lipids known. The consequences of the extreme reactivity of 7-dehydrocholesterol on human health is the focus of a current research theme in the author's laboratory.
Authors:
Ned A Porter
Publication Detail:
Type:  Journal Article; Research Support, N.I.H., Extramural; Research Support, U.S. Gov't, Non-P.H.S.     Date:  2013-04-09
Journal Detail:
Title:  The Journal of organic chemistry     Volume:  78     ISSN:  1520-6904     ISO Abbreviation:  J. Org. Chem.     Publication Date:  2013 Apr 
Date Detail:
Created Date:  2013-04-19     Completed Date:  2013-08-12     Revised Date:  2014-04-22    
Medline Journal Info:
Nlm Unique ID:  2985193R     Medline TA:  J Org Chem     Country:  United States    
Other Details:
Languages:  eng     Pagination:  3511-24     Citation Subset:  IM    
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MeSH Terms
Descriptor/Qualifier:
Chemistry, Physical
Dehydrocholesterols
Fatty Acids, Unsaturated / chemistry*
Free Radicals / chemistry*
Heterocyclic Oxides / chemistry*
Humans
Oxidative Stress
Peroxides / chemistry*
Sterols / chemistry*
Grant Support
ID/Acronym/Agency:
P30 ES000267/ES/NIEHS NIH HHS; R01 HD064727/HD/NICHD NIH HHS
Chemical
Reg. No./Substance:
0/Dehydrocholesterols; 0/Fatty Acids, Unsaturated; 0/Free Radicals; 0/Heterocyclic Oxides; 0/Peroxides; 0/Sterols; BK1IU07GKF/7-dehydrocholesterol
Comments/Corrections

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