Quantification of fumarate and investigation of endogenous and exogenous fumarate stability in rat plasma by LC-MS/MS

Bioanalysis. 2016 Apr;8(7):661-75. doi: 10.4155/bio-2015-0026. Epub 2016 Mar 15.

Abstract

Background: Fumaric acid is a commonly used excipient in pharmaceutical products. It is not known if its presence may lead to fluctuation of endogenous fumarate levels. An LC-MS/MS method was developed and validated to quantify fumarate in support of a toxicokinetics study.

Results: Stability evaluation showed that endogenous fumarate was stable for 6 h at room temperature, while exogenously added fumaric acid was converted to malate within 1 h due to the presence of fumarase. Citric acid, a fumarase inhibitor, prevented the conversion of added fumaric acid in rat plasma.

Conclusion: The method was validated in citric acid stabilized rat plasma using a surrogate matrix approach. A discrepancy in stability was observed between endogenous fumarate and exogenously added fumaric acid.

Keywords: TCA cycle; biomarker stability; endogenous; exogenous; fumarase; fumarate; fumaric acid; isotope effects; small-molecule biomarker; surrogate matrix.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Animals
  • Carbon Radioisotopes / chemistry
  • Chromatography, High Pressure Liquid* / standards
  • Citric Acid / chemistry
  • Citric Acid / metabolism
  • Drug Stability
  • Fumarate Hydratase / antagonists & inhibitors
  • Fumarate Hydratase / metabolism
  • Fumarates / blood*
  • Fumarates / standards
  • Isotope Labeling
  • Malates / analysis
  • Malates / metabolism
  • Quality Control
  • Rats
  • Tandem Mass Spectrometry* / standards
  • Temperature

Substances

  • Carbon Radioisotopes
  • Fumarates
  • Malates
  • Citric Acid
  • malic acid
  • fumaric acid
  • Fumarate Hydratase