Identification of bile alcohols in human bile.

Human gallbladder bile was examined for bile alcohols. Following isolation and hydrolysis, the bile alcohols were analyzed by capillary gas-liquid chromatography-mass spectrometry. The following bile alcohols were identified with certainty by direct comparison with reference standards: 5/3-cholane-3a, 7a,23,24-tetrol; 5/3-cholane-3a,7a,l2a,24-tetrol; 24-nor-5/3cholestane-3a,7a,l2a,25-tetrol; 27-nor-5/3-cholest-25-ene-3a,7a,12q24-tetrol; 3a,7a,l2a-trihydroxy-27-nor-5/3-cholestan-24-one; 27-nor-5/3-cholestane-3a,7a,12a,24,25-pentol; 27-nor-5fl-cholestane-3a,7a,12a,24,25,26-hexol; 5/3-cholestane-3a,7ar,24-triol; 5/3-cholestane-3a,7a,25-triol; 5@-cholestane-3a,7a,26-triol; 5acholestane-3a,7a,12a,24-tetro~ 5/3-cholestane-3a,7a,l2a,24-tetrol; 5/3-cholestane-3a,7ar,12a,25-tetrol; 5/3-cholestane-3a,7a,12ar,26tetrol; (24R)and (24S)-5/3-cholestane-3a,7a,12a,24,25-pentols; 5/3-cholestane-3a,7a,l2a,24,26-pentol; 5/3-cholestane-3a,7a,12a,25,26-pentol; 5/3-cholestane-3a,7a,l2a,26,27-pentol; 26-methoxy5/3-cholestane-3a,7a,l2a,25-tetrol. There also existed two norcholestanetetrols and three cholestanetetrols with two hydroxyl substituents on the nucleus and two in the side chain. The human biliary bile alcohols occurred mainly as sulfate esters and in lesser amounts as glucuronoconjugated and unconjugated forms. The amount of total bile alcohols was about 0.9 mg (0.7-1.2 mg) in 1 g of bile solid, or 0.16 pmol (0.07-0.24 pmol) in 1 ml of gallbladder bile. -Kumki, S., K. Shimam, M. Kuwabara, M. Une, K. Kihira, T. Kuramoto, and T. Hoshita. Identification of bile alcohols in human bile. J. Lipid RES. 1985. 26: 230-240. Supplementary key words gas-liquid chromatography-mass spectrometry * ion-exchange chromatography * bile alcohol sulfate * bile alcohol glucuronide cholelithiasis Bile alcohols are not only major biliary constituents of evolutionarily primitive vertebrates such as fishes and amphibians but are also considered to be intermediates in the pathway for the formation of bile acids from cholesterol in mammals (1). Until recently, it had been thought that the distribution of bile alcohols is confined to the primitive vertebrates. In 1974, however, Setoguchi et al. (2) reported the accumulation of bile alcohols in the bile and feces of patients with a rare inherited disease, cerebrotendinous xanthomatosis (CTX). Since then, many investigations have been performed to indicate occurrence of bile alcohols in mammals (3-9). Nowadays, bile alcohols are known to be present in urine (6-9) not only of patients with liver diseases, but also of healthy individuals. However, in bile, the major route of bile acid excretion, little is known about the occurrence of bile alcohols. The aim of the present investigation is to identify bile alcohols in the bile of patients whose liver functions are not severely