Dehydroepiandrosterone sulfate isolation

Formation of sulfates [328] is relatively reversible. This may be due to the fact that the metabolic clearance rate [318] of sulfates is relatively low [389] and their renal excretion inefficient [4]. The conversion of dehydroepiandrosterone sulfate in vivo to androsterone and etiocholanolone glucuronide was demonstrated by Lieberman and co-workers, who administered isotopically labeled dehydroepiandrosterone sulfate and isolated labeled androsterone and etiocholanolone from glucuronicase-hydrolyzed urine [303]. Since in another study by Lieberman [174], the transconjugation from dehydroepiandrosterone sulfate to dehydroepiandrosterone glucuronide without free dehydroepiandrosterone intermediate was declared to be improbable, in vivo equilibrium between dehydroepiandrosterone sulfate and dehydroepiandrosterone seems probable [303]. 

According to the classical view of metabolism the hormones are synthesized as free steroids in endocrine tissues and prepared for excretion in urine by peripheral metabolism and conjugation. This view had to be modified upon the isolation of dehydroepiandrosterone sulfate from adrenal tumor [307]. Thus dehydroepiandrosterone sulfate, a steroid conjugate, was shown to be secreted by the adrenal tissue. Isotopic methods also pointed in the same direction. Lieberman et al. [304], using... 

Roberts et ah (1964) answered part of the question by injecting doubly labeled cholesterol sulfate into the splenic artery (supplying 90% of the blood to an adrenal carcinoma) of a female patient and isolating various steroid sulfates in the urine of the first 24 hours. Of the recovered radioactivity 0.46% was dehydroepiandrosterone sulfate, bearing the same H/ S ratio as the injected compound. Urinary androstenediol-3-monosulfate and 5-pregnene-3/3,17a,20a-triol-3-monosulfate as well as 16a-hydroxydehydroepiandrosterone-3-monosulfate also had the same ratio as the injected cholesterol sulfate, demonstrating that all these compounds have a common sulfated precursor, which could possibly be cholesterol sulfate. 

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