Signal Enhancement in the HPLC-ESI-MS/MS analysis of spironolactone and its metabolites using HFIP and NH4F as eluent additives

Anal Bioanal Chem. 2017 May;409(12):3145-3151. doi: 10.1007/s00216-017-0255-4. Epub 2017 Feb 21.

Abstract

This paper describes an LC-MS/MS method to determine the concentration of spironolactone and its metabolites 7-alpha-methylthiospironolactone and canrenone in blood plasma samples. The resulting assay is simple (using protein precipitation for sample preparation) and sensitive (the lower limit of quantification is close to 0.5 ng/ml) while requiring only 50 μl of plasma, making it especially suitable for analyzing samples obtained from pediatric and neonatal patients where sample sizes are limited. The sensitivity is achieved by using ammonium fluoride as an eluent additive, which in our case amplifies the signal from our analytes in the plasma solution on average about 70 times. The method is fully validated according to the European Medicines Agency's guideline and used for the measurement of pediatric patients' samples in clinical trials for evaluating oral spironolactone's and its metabolites' pharmacokinetics in children up to 2 years of age.

Keywords: Ammonium fluoride; Hexafluoroisopropanol; Ionization efficiency; Liquid chromatography-mass spectrometry; Signal enhancement; Spironolactone.

Publication types

  • Validation Study

MeSH terms

  • Canrenone / blood*
  • Canrenone / metabolism
  • Chromatography, High Pressure Liquid / methods*
  • Humans
  • Limit of Detection
  • Mineralocorticoid Receptor Antagonists / blood*
  • Mineralocorticoid Receptor Antagonists / metabolism
  • Spectrometry, Mass, Electrospray Ionization / methods
  • Spironolactone / analogs & derivatives*
  • Spironolactone / blood*
  • Spironolactone / metabolism
  • Tandem Mass Spectrometry / methods*

Substances

  • Mineralocorticoid Receptor Antagonists
  • Spironolactone
  • 7 alpha-thiospironolactone
  • Canrenone