Deuteration of catecholamines, catecholamine metabolites and tryptophan metabolites

Abstract

The preparation of some deuterium labelled catecholamines, catecholamine metabolites and tryptophan metabolites is described. 4Simple exchange reactions in DCl/D 0 solution or reductions with Li A1 D were used. The deuterium labelled compounds prepared are suitable for use as internal standards for quantitative mass-fragmentographic analysis of their unlabelled analogs in biological material. Mass spectra of trimethylsilyl and trimethylsilyl-N-trifluoroacetyl derivatives of 2,5,6-trideutero vanillactic acid, I,l-dideutero-l-hydroxy-2(2,5,6-trideutero catecho1)ethane, 2,5,6-trideutero epinephrine, 2,5,6-trideutero norrnetanephrine and hexadeutero indole-3-acetic acid are given together with those of their naturaloccurring analogs. 2 The mass-fragmentographic determination of small amounts of biogenic amines and their metabolites in biological material has become of increasing interest in the past few years ( 1 -7 ) . The method combines both specificity and sensitivity and can achieve a high degree of precision with the use of analogs labelled with stable isotopes as internal standards. Howevel; these compounds are not always commercially available, or are unsatisfactory because 0 1970 by John Wiley & Sons L t d .

Analysis of Acidic Metabolites of Biogenic Amines in Bovine Retina and Vitreous and Aqueous Humour by Gas Chromatography‐Negative Ion Chemical Ionisation Mass Spectrometry

“…Deuterated internal standards (with the exception of ['H4]PHMA) were prepared by proton-deuterium exchange in ['HICI. There are various reports in the literature (Lindstrom et al, 1974;Muskiet et al, 1978) concerning conditions for deuteration by exchange in ['HICI and the conditions used for deuteration were as follows:…”

Report on the Workshop Conference

“…After derivatization with bis<trimethylsilyl)trifluoroacetamide at 80 9 C for 10 min or the preparation of methyl-pentafluoropropionyl derivatives, extracts were analyzed by gaschromatography with flame ionization detection using packed columns (13) or capillary columns (14) with propyl gallate as an internal standard, or by gas-chromatography-mass-spectrometry operated in the selected ion monitoring mode utilizing deuterated internal standards (15,16 technique was 0.5-1.0 vg/g of creatinine. After derivatization with bis<trimethylsilyl)trifluoroacetamide at 80 9 C for 10 min or the preparation of methyl-pentafluoropropionyl derivatives, extracts were analyzed by gaschromatography with flame ionization detection using packed columns (13) or capillary columns (14) with propyl gallate as an internal standard, or by gas-chromatography-mass-spectrometry operated in the selected ion monitoring mode utilizing deuterated internal standards (15,16 technique was 0.5-1.0 vg/g of creatinine.…”

“…After derivatization with bis<trimethylsilyl)trifluoroacetamide at 80 9 C for 10 min or the preparation of methyl-pentafluoropropionyl derivatives, extracts were analyzed by gaschromatography with flame ionization detection using packed columns (13) or capillary columns (14) with propyl gallate as an internal standard, or by gas-chromatography-mass-spectrometry operated in the selected ion monitoring mode utilizing deuterated internal standards (15,16 technique was 0.5-1.0 vg/g of creatinine. Iso-homovanillic acid and isovanilmandelic acid (17) and two acidic 3,4-dihydroxyphenylalanine metabolites (vanillacetic acid, vanilpyruvic acid) (18) were determined as well. Gas-chromatography with flame ionization detection and gaschromatography-mass-spectrometry operated in the selected ion monitoring mode for the determinations of urinary homovanillic acid and vanilmandelic acid were found to correlate satisfactorily (17).…”

“…Alcoholic catecholamine metabolites of 3 ml of urine were enzymatically hydrolyzed for about 18 h at 37 °C in acetate buffer, pH 6.2, with z Helix pomatia preparation, extracted, derivatized and analyzed as described for acidic metabolites (13,(16)(17)(18). Extraction recoveries (%) and normal range for urine of 13-71 year-old persons (mg/g of creatinine) were: 3-methoxyr4-hydroxy-phenylethylene glycol 81 and 0.7-2.5; 3,4-dihydroxyphenylethylene glycol 38 and 0.16-0.60; 3-methoxy-4-hydroxyphenylethanol 118 and 0.027-0.037; 3,4-hydroxyphenylethanol 90 and 0.005-0.026.…”