Blutplasma, Urin und Hamofiltrat nierenkranker Patienten ergaben nach enzymatischer Spaltung neben Indigo (la) und Indirubin (2a) in sehr geringer Menge rotviolettes Candidin (5). Das indigoide 5 konnte sich bei der Aufarbeitung aus Indikan (3a) und Tryptanthrin (7), einem moglicherweise uber den Darm resorbierten Metaboliten von Candida lipolytica, gebildet haben.After enzymic cleavage the blood plasma, urine, and haemofiltrate of uraemic patients yield, besides indigotin (la) and indirubin (2a), very small amounts of candidin (5). The indigoid 5 might have been formed from indican (3a) and tryptanthrin (7), a metabolite of Candida lipolytica possibly resorbed through the intestine.
The neutral steroid fractions in the urine of eleven patients suffering from various forms of liver disease with cholestasis and of ten healthy individuals were studied by glass capillary gas chromatography-mass spectrometry. The steroid conjugates in urine were enzymatically solvolysed, the liberated steroids extracted and transformed into the trimethylsilylether for measurements. The excretion rates of androstane and pregnane metabolites of patients with liver disease were far lower than those of healthy persons. The main compounds in the urine of the former were the bile alcohols 27 - nor - 3 alpha, 7 alpha, 12 alpha, 24 xi, 25 xi - pentahydroxy - 5 beta - cholestane and 3 alpha, 7 alpha, 12 alpha, 25 xi, 26 - pentahydroxy - 5 beta - cholestane. Our data suggest a correlation between the excretion rates of these bile alcohols and the serum levels of bilirubin. While the excretion rate of the two bile alcohols in the urine of healthy individuals was approximately 0.24 mg/24 h (0.6 mumol/24 h) a patient with a serum bilirubin of 841 mumol/l excreted 4 mg/24 h (9 mumol/24 h). The accumulation of bile alcohols described in this study possibly indicates alternative pathways of cholic acid formation in liver disease.
Oestrogen metabolites from the urine of males and pregnant and non-pregnant females were enriched by a procedure involving column chromatography on adsorber resins, gels and ion exchangers, enzymatic solvolysis and extraction, thereby separating the oestrogens from most of the interfering material. After derivatization of the oestrogens as their trimethylsilyl ethers profiles were measured with a fused silica column and a flame ionization detector by gas chromatography. Using a combination of capillary gas chromatography and mass spectrometry approximately 50 oestrogen metabolites were detected in the human urine of males and females, of which 19 were unknown urine compounds. Not all could be identified definitely owing to the lack of reference material. Mass spectra of trimethylsilylated oestrogens with functional groups at position 11 (11-dehydroestradiol, 11-dehydroestrone and 11 beta-hydroxyestrone) were discussed in their common and discernible fragmentations.
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