Propagation rate constants for the peroxidation of sterols on the biosynthetic pathway to cholesterol

Propagation rate constants for the peroxidation of sterols on the biosynthetic pathway to cholesterol

The free radical chain autoxidation of cholesterol and the oxidation products formed, i.e. oxysterols, have been the focus of intensive study for decades. The peroxidation of sterol precursors to cholesterol such as 7-dehydrocholesterol (7-DHC) and desmosterol as well as their oxysterols has receive...

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Published in:Chemistry and physics of lipids Vol. 207; no. Pt B; pp. 51 - 58
Main Authors: Lamberson, Connor R., Muchalski, Hubert, McDuffee, Kari B., Tallman, Keri A., Xu, Libin, Porter, Ned A.
Format: Journal Article
Language:English
Published: Ireland Elsevier B.V 01-10-2017
Subjects:
Cholesterol - biosynthesis
Cholesterol - chemistry
Free radicals
Kinetics
Molecular Structure
Oxidation-Reduction
Oxysterols
Peroxidation
Peroxides - chemistry
Peroxides - metabolism
Radical clock
Rate constants
Sterols
Sterols - chemistry
Sterols - metabolism
8-DHC
Free radicals
Rate constants
MS
MeOAMVN
Radical clock
Sterols
7-DHC
Oxysterols
CDPX2
SLOS
DHCR7
HPLC
Peroxidation
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Summary:The free radical chain autoxidation of cholesterol and the oxidation products formed, i.e. oxysterols, have been the focus of intensive study for decades. The peroxidation of sterol precursors to cholesterol such as 7-dehydrocholesterol (7-DHC) and desmosterol as well as their oxysterols has received less attention. The peroxidation of these sterol precursors can become important under circumstances in which genetic conditions or exposures to small molecules leads to an increase of these biosynthetic intermediates in tissues and fluids. 7-DHC, for example, has a propagation rate constant for peroxidation some 200 times that of cholesterol and this sterol is found at elevated levels in a devastating human genetic condition, Smith-Lemli-Opitz syndrome (SLOS). The propagation rate constants for peroxidation of sterol intermediates on the biosynthetic pathway to cholesterol were determined by a competition kinetic method, i.e. a peroxyl radical clock. In this work, propagation rate constants for lathosterol, zymostenol, desmosterol, 7-dehydrodesmosterol and other sterols in the Bloch and Kandutsch–Russell pathways are assigned and these rate constants are related to sterol structural features. Furthermore, potential oxysterols products are proposed for sterols whose oxysterol products have not been determined.
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Current Address: Department of Chemistry, California State University Fresno, Fresno CA 93740
Current Address: Department of Medicinal Chemistry, University of Washington, Seattle, WA 98195.
ISSN:0009-3084
1873-2941
DOI:10.1016/j.chemphyslip.2017.01.006