High-resolution isotope-dilution mass spectrometry using metabolism of isotope-labeled compounds: application to drug metabolites

Rapid Commun Mass Spectrom. 2012 Nov 30;26(22):2569-76. doi: 10.1002/rcm.6376.

Abstract

Rationale: Herein we describe a generic quantitative method using high-resolution, isotope-dilution (HRID) metabolism of isotope-labeled compounds and apply it to the analysis of drug metabolites (DMs) in human plasma. Metabolites (drug) in Safety Testing (MIST) application was one goal.

Methods: Testosterone (T) and diclofenac (D) were chosen for mass defect characteristics. T, [(14)C]T, [(13)C(3)]T, D, [(14)C]D, and [(13)C(6)]D were metabolized separately in vitro to produce test metabolites. Liquid chromatography/radioactivity monitoring (LC/RAM) analysis was used to determine the concentration of the test metabolites in the incubates. The incubates containing 6β-hydroxy-T (6βHT), [(13)C(3)]6βHT, 4'-hydroxy-D (4'HD) and [(13)C(6)]4'HD were used to make standard curves. Plasma samples were prepared by 'dilute-and-shoot' and analyzed by LC/MS using SCIEX 5000 and Thermo Orbitrap instrumentation.

Results: Human hepatic microsomes and the S9 fraction produced between 2-6 μM β-hydroxy-T and 4'-hydroxy-D at 60 min starting with 10 μM parent drug as determined by LC/RAM. It was assumed that the amounts of [(13)C(3)]6βHT and [(13)C(6)]4'HD produced were similar. Dilutions and standard curves were prepared in human plasma. Analysis of the DMs by LC/MS/MS and LC/HRMS exhibited linear responses over a useable range.

Conclusions: HRID with metabolism of an isotope-labeled compound reduces the number of analytical variables considerably. Metabolism of the parent drug to DMs represents a simpler alternative quantitative method compared with traditional approaches. The method will have useful applications for evaluating MIST situations.

MeSH terms

  • Diclofenac / analysis
  • Diclofenac / blood
  • Diclofenac / chemistry
  • Diclofenac / metabolism
  • Humans
  • Isotope Labeling / methods*
  • Isotopes / analysis*
  • Isotopes / chemistry
  • Isotopes / metabolism
  • Mass Spectrometry / methods*
  • Microsomes, Liver / metabolism
  • Models, Chemical
  • Models, Molecular
  • Pharmaceutical Preparations / analysis
  • Pharmaceutical Preparations / blood
  • Pharmaceutical Preparations / chemistry
  • Pharmaceutical Preparations / metabolism*
  • Sensitivity and Specificity
  • Testosterone / analysis
  • Testosterone / blood
  • Testosterone / chemistry
  • Testosterone / metabolism

Substances

  • Isotopes
  • Pharmaceutical Preparations
  • Diclofenac
  • Testosterone