Total polyamines and their non-alpha-amino acid metabolites simultaneously determined in urine by capillary gas chromatography, with nitrogen-phosphorus detector; and some clinical applications.

A capillary gas-chromatographic method with nitrogen-phosphorus detection is used here to simultaneously determine 1,3-diaminopropane, putrescine, cadaverine, spermidine, spermine, isoputreanine , putreanine , and N-(3-aminopropyl)-N'-(2-carboxyethyl)-1,4- diaminobutane in urine. After acid hydrolysis the compounds are isolated by adsorption onto silica gel and converted into their methyl-heptafluorobutyryl derivatives. We give quality-control data and age-dependent values for urinary excretion of these analytes by 76 apparently healthy controls. Circadian rhythmicity in the excretion of spermidine and (especially) isoputreanine was established and is discussed in the light of its implications for monitoring therapy of cancer. Investigation of menstrual-cycle-dependent diurnal variation in one normal woman showed no distinct, consistent fluctuations. We applied the method to monitor (by use of 24-h urine specimens) an uncomplicated, normally progressing pregnancy, a patient with metastatic melanoma being treated with cytostatic drugs, and (in more detail) the treatment of a patient with high-grade non-Hodgkin lymphoma.

Determination of 4-O-methylated catecholamine metabolites in urine by mass fragmentography.

We describe the determination of the 4-O-methylated catecholamine metabolites 4-methoxy-3-hydroxyphenylacetic acid (iso-HVA), 4-methoxy-3-hydroxyphenylmandelic acid (iso-VMA) and 4-methoxy-3-hydroxyphenylethylene glycol (iso-MOPEG) in urine with use of mass fragmentography and deuterated internal standards. Normal values, expressed in terms of creatinine, are given as a function of age. Urinary excretion values during neuroblastoma, pheochromocytoma, and parkinsonism treated with L-DOPA, and during the intravenous administration of dopamine are discussed. For normal persons, the mean percentages (+/- SD) of 4-O-methylated metabolites relative to their 3-O-methylated analogs were 6.29 +/- 2.79% (iso-HVA/HVA), 0.70 +/- 0.57% (iso-VMA/VMA), and 0.77 +/- 0.53% (iso-MOPEG/MOPEG). We observed no significant changes in these parameters for the patients studied and conclude that the determination of 4-O-methylated catecholamine metabolites for these patients does not add information to the results obtained from their quantitatively more important 3-O-methylated analogs.

Determination of catecholamines and their 3-O-methylated metabolites in urine by mass fragmentography with use of deuterated internal standards.

We report the determination of catecholamines (dopamine, norepinephrine, and epinephrine) and their 3-O-methylated metabolites (3-methoxytyramine, normetanephrine, and metanephrine) in urine by gas chromatography/mass spectrometry, with use of stable isotopically labeled internal standards. Normal excretion values in terms of creatinine, expressed as a function of age, are given, together with results obtained for patients with neuroblastoma, ganglioneuroblastoma, pheochromocytoma, parkinsonism treated with L-DOPA plus peripheral decarboxylase inhibitor, and a patient with cardiogenic shock treated with dopamine. The results obtained for normal adults are discussed in relation to other catecholamine metabolites and mean overall catecholamine turnover.

Determination of 3-methoxy-4-hydroxyphenylpyruvic acid, 3,4-dihydroxyphenylethylene glycol, and 3,4-dihydroxyphenylmandelic acid in urine by mass fragmentography, with use of deuterium-labeled internal standards.

We report the determination of 3-methoxy-4-hydroxyphenylpyruvic acid, 3,4-dihydroxyphenylmandelic acid, and 3,4-dihydroxyphenylethylene glycol in urine, by use of gas chromatography/mass spectrometry in combination with a simple purification method and deuterium-labeled internal standards. Normal excretion values in terms of creatinine, expressed as a function of age, are given, together with results obtained for patients with neuroblastoma, pheochromocytoma, or parkinsonism treated with L-DOPA + peripheral decarboxylase inhibitor, and for a patient receiving dopamine. We were unable to identify 3, 4-dihydroxyphenyllactic acid in urine. The results obtained and their relation to other catecholamine metabolites and catecholamine-precursor metabolites in urine are discussed.

Determination of some L-3,4-dihydroxyphenylalanine and dopamine metabolites in urine by means of mass fragmentography.

We describe a mass-fragmentographic method for determination in urine of the following metabolites of L-3,4-dihydroxyphenylalanine and dopamine: vanillactic acid, 3,4-dihydroxyphenylacetic acid, 3-methoxy-4-hydroxyphenylethanol, and 3,4-dihydroxyphenylethanol. Deuterated analogs were used as internal standards. The method is fast, reproducible, sensitive, and selective, and does not require the use of time-consuming clean-up procedures. Normal excretion values in terms of creatinine, expressed as a function of age, as well as values obtained for patients with neurogenic tumors, a patient during therapy with L-3,4-dihydroxyphenylalanine, and a patient receiving dopamine are presented and discussed.

Gas-chromatographic profiling of urinary acidic and alcoholic catecholamine metabolites.

Urinary acidic and alcoholic catecholamine metabolites were isolated separately from 24-h urines by simple extraction procedures. After derivatization, extracts were analyzed by means of simultaneous gas chromatography on two different stationary phases. The quality of the assay was checked by running "normal" and enriched commercial (Hyland) control urines in each series. Normal values are given for vanilmandelic acid, homovanillic acid, and 3-methoxy-4-hydroxyphenylethylene glycol, expressed as a function of age. We present excretion patterns showing these metabolites and also 3,4-dihydroxyphenylacetic acid, vanillacetic acid, 3,4-dihydroxyphenylethylene glycol, and vanilethanol for 12 patients with neurogenic tumors. Values obtained for vanilmandelic acid by this method correlate well with those obtained by the electrophoretic/colorimetric method of Hermann [Am. J. Clin. Pathol. 41, 373 (1964)].