HOME HELP FEEDBACK SUBSCRIPTIONS ARCHIVE SEARCH TABLE OF CONTENTS		QUICK SEARCH:   [advanced] Author: Keyword(s): Year:  Vol:  Page:

This Article Full Text (PDF) Alert me when this article is cited Alert me if a correction is posted Services Similar articles in this journal Similar articles in PubMed Alert me to new issues of the journal Download to citation manager Request Permissions Citing Articles Citing Articles via HighWire Citing Articles via Google Scholar Google Scholar Articles by St. Pyrek, J. Articles by Schoepfer, G. J. Search for Related Content PubMed PubMed Citation Articles by St. Pyrek, J. Articles by Schoepfer, G. J., Jr Social Bookmarking                      What's this?

Journal of Lipid Research, Vol 32, 1371-1380, Copyright © 1991 by Lipid Research, Inc.

ARTICLES

Inhibitors of sterol synthesis. Characterization of trimethylsilyl dienol ethers of 3 beta-hydroxy-5 alpha-cholest-8(14)-en-15-one. Applications in the analysis of mitochondrial metabolites of the 15- ketosterol by gas chromatography-mass spectrometry

J St. Pyrek, WK Wilson, S Numazawa and GJ Schoepfer Jr
Department of Biochemistry, Rice University, Houston, TX 77251-1892.

Derivatization of delta 8(14)-15-ketosterols as bis-TMS dienol ethers facilitates their analysis by gas chromatography-mass spectrometry (GC- MS). Conditions are presented for the preparation of each of the three possible bis-TMS dienol ethers of 3 beta-hydroxy-5 alpha-cholest-8(14)- en-15-one (1), a potent regulator of cholesterol metabolism. Treatment of 1 with N,O-bis(tri-methylsilyl)-trifluoroacetamide (BSTFA) and pyridine for 20 h at 100 degrees C produced primarily 3 beta,15- bis(trimethylsilyloxy)-5 alpha-cholesta-7,14-diene. Treatment of 1 with BSTFA-pyridine in the presence of 0.1% perchloric acid for 20 h at 22 degrees C gave mainly the delta 8(14)15, dienol ether. Heating this reaction mixture at 100 degrees C for 4 days gave mainly the delta 8,14 ether. The structures of the three dienol ethers were established by GC- MS and 1H and 13C nuclear magnetic resonance spectroscopy. The three TMS dienol ethers of 1 were resolved by capillary GC and gave very simple mass spectra upon electron impact with fragmentation limited almost exclusively to the elimination of trimethylsilanol, methyl, and the side chain. The TMS dienol ethers showed reduced artefact formation, improved chromatographic resolution, and increased sensitivity relative to the delta 8(14)-15-ketosterols, properties that improve the detection and identification of minor components in analyses of complex biological mixtures. The utility of this derivatization is illustrated for the delta 7,14 TMS dienol ethers of the 3-deoxy, 3-keto, 3 alpha-hydroxy, and 3 beta-methoxy analogs of 1 and for delta 8(14)-15-ketosterols in mixtures obtained from incubations of 1 with rat liver mitochondria in the presence of NADPH.
CiteULike    Complore    Connotea    Del.icio.us    Digg    Reddit    Technorati    What's this?

This article has been cited by other articles:

				G. J. Schroepfer Jr. Oxysterols: Modulators of Cholesterol Metabolism and Other Processes Physiol Rev, January 1, 2000; 80(1): 361 - 554. [Abstract] [Full Text] [PDF]