HPLC-electrospray tandem mass spectrometry for rapid determination of dihydropyrimidine dehydrogenase activity

Clin Chem. 2007 Mar;53(3):528-30. doi: 10.1373/clinchem.2006.074096. Epub 2007 Feb 1.

Abstract

Background: Patients with a partial dihydropyrimidine dehydrogenase (DPD) deficiency have an increased risk of developing severe 5-fluorouracil-associated toxicity. We developed a rapid and specific method to measure the DPD activity in peripheral blood mononuclear cells using HPLC tandem-mass spectrometry (HPLC-MS/MS).

Methods: The activity of DPD was measured with thymine as the substrate, followed by reversed-phase HPLC combined with electrospray ionization MS/MS and detection of the product dihydrothymine with multiple-reaction monitoring. Stable-isotope labeled dihydrothymine was used as the internal standard.

Results: Dihydrothymine was measured within an analytical run of 10 min, with a lower limit of quantification of 54 microg/L (0.4 micromol/L). The intraassay and interassay variations of the DPD activity assay were both <7%. A linear correlation (R(2) = 0.980; P <0.001) was observed between the HPLC-MS/MS data and those obtained with a reference method using radiolabeled thymine. There were no systematic differences between the 2 methods, and both methods yielded similar results.

Conclusion: The analysis of the DPD activity with HPLC-MS/MS is rapid, accurate, and sufficiently sensitive to be used as a screening method for patients with a DPD deficiency.

MeSH terms

  • Chromatography, High Pressure Liquid
  • Dihydrouracil Dehydrogenase (NADP) / blood*
  • Humans
  • In Vitro Techniques
  • Leukocytes, Mononuclear / enzymology
  • Spectrometry, Mass, Electrospray Ionization
  • Tandem Mass Spectrometry

Substances

  • Dihydrouracil Dehydrogenase (NADP)