TY - JOUR
T1 - Trichloromethyl peroxyl radical (Cl3COO•) mediated oxidation of cholesterol
AU - Kaphalia, Bhupendra S.
AU - Ansari, G. A.S.
N1 - Funding Information:
Cholesterol 7~-hydroperoxide is known to decompose to (II) and (V) in the presence of 02; and (I) 16. Kimura and Muto 17 have shown that t-butyl hydroperoxide and molybdenum complexes oxidize cholesterol acetate to corresponding 7-t-butyl hydroxyl adduct which decomposes to the corresponding alcohols and ketone. These findings further support our proposed trichloromethyl peroxyl adduct (VIII) formation and its decomposition to the observed compounds (II), (IV) and (V) as shown in Figure 5. Compound (III) could be formed through the epoxidation of (II) by CI3COOH. This suggestion is supported by the work of Yamamoto e t a l., l°, where they have shown that 2-cyclohexen-l-one is converted to epoxycyclohexanone by C13CO0" generating system in a aprotic solvent. The in vivo formation of these cholesterol oxidation products and their contribution to the observed toxicity of CC14 is presently unknown, although the cytotoxicity and atherogenicity of cholesterol oxidation products is well establishedlS, 19 ACKNOWLEDGEMENT This research was supported by grant DK27135 awarded by the National Institute of Diabetes, Digestive and Kidney Diseases and Grant ES04815 awarded by the National Institute of Environmental and Health Sciences.
PY - 1990
Y1 - 1990
N2 - Oxidation of cholesterol was studied in situ in a Cl3COO• generating system via a heterogenous reaction of carbon tetrachloride (CCl4), KO2 and 18-crown-6 in aprotic solvent (acetonitrile) at 10°C. The reaction mixture without CCl4 served as a control. Reaction performed with CCl4 showed the formation of products more polar than cholesterol which were separated by preparative thin layer chromatography (TLC) and purified by normal phase high performance liquid chromatography (HPLC). The data obtained collectively from TLC, HPLC and ammonia chemical ionization mass spectrometry confirmed the formation of 3ß-hydroxy-5-cholesten-7-one, 5-cholesten-3ß, 7ß- and 3ß, 7α-diols and possibly 3ß-hydroxy-5, 6ξ-epoxy-5ξ-cholestan-7-one as Cl3COO• mediated oxidation products of cholesterol.
AB - Oxidation of cholesterol was studied in situ in a Cl3COO• generating system via a heterogenous reaction of carbon tetrachloride (CCl4), KO2 and 18-crown-6 in aprotic solvent (acetonitrile) at 10°C. The reaction mixture without CCl4 served as a control. Reaction performed with CCl4 showed the formation of products more polar than cholesterol which were separated by preparative thin layer chromatography (TLC) and purified by normal phase high performance liquid chromatography (HPLC). The data obtained collectively from TLC, HPLC and ammonia chemical ionization mass spectrometry confirmed the formation of 3ß-hydroxy-5-cholesten-7-one, 5-cholesten-3ß, 7ß- and 3ß, 7α-diols and possibly 3ß-hydroxy-5, 6ξ-epoxy-5ξ-cholestan-7-one as Cl3COO• mediated oxidation products of cholesterol.
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U2 - 10.1016/0045-6535(90)90081-4
DO - 10.1016/0045-6535(90)90081-4
M3 - Article
AN - SCOPUS:0025327565
SN - 0045-6535
VL - 20
SP - 5
EP - 11
JO - Chemosphere
JF - Chemosphere
IS - 1-2
ER -