Side chain cleavage of some cholesterol esters

For some time it has been known that the side chain of cholesterol sulfate is cleaved by the cleavage enzyme system present in bovine adrenal mitochondria without prior hydrolysis of the sulfate moiety. In this work, other inorganic esters as well as some organic esters of cholesterol were tested as substrates for this enzyme system. The results revealed that cholesterol nitrate, cholesterol phosphate, and a series of acyl esters of cholesterol can also be cleaved by the enzyme system to their respective pregnenolone derivatives without first being hydrolyzed to cholesterol. The rate of oxidation of the carboxylic acid esters decreased as the size of the acyl groups increased. Cholesterol stearate and cholesterol phosphate were demonstrated to be inhibitors of the side chain cleavage of cholesterol. While digitonin, as might be expected, inhibits the cleavage of cholesterol, it accelerates the oxidation of both cholesterol sulfate and cholesterol nitrate. The results reported in this paper add support to the previously proposed hypothesis that more than one cholesterol side chain cleavage enzyme system exists in adrenal mitochondria.