Development and validation of an LC-MS/MS method for the bioanalysis of psilocybin's main metabolites, psilocin and 4-hydroxyindole-3-acetic acid, in human plasma

J Chromatogr B Analyt Technol Biomed Life Sci. 2021 Feb 1:1164:122486. doi: 10.1016/j.jchromb.2020.122486. Epub 2020 Dec 7.

Abstract

Psilocin is the active metabolite of psilocybin, a serotonergic psychedelic substance. It is used recreationally and investigated in substance-assisted psychotherapy. The pharmacokinetic properties of psilocin are only partially characterized. Therefore, we developed and validated a rapid LC-MS/MS method to quantify psilocin and its metabolite 4-hydroxyindole-3-acetic acid (4-HIAA) in human plasma. Plasma samples were processed by protein precipitation using methanol. The injected sample was mixed with water in front of a C18 analytical column to increase retention of the analytes. Psilocin and 4-HIAA were detected by multiple reaction monitoring (MRM) in positive and negative electrospray ionisation mode, respectively. An inter-assay accuracy of 100-109% and precision of ≤8.7% was recorded over three validation runs. The recovery was near to complete (≥94.7%) and importantly, consistent over different concentration levels and plasma batches (CV%: ≤4.1%). The plasma matrix caused negligible ion suppression and endogenous interferences could be separated from the analytes. Psilocin and 4-HIAA plasma samples could be thawed and re-frozen for three cycles, kept at room temperature for 8 h or 1 month at -20 °C without showing degradation (≤10%). The linear range (R ≥ 0.998) of the method covered plasma concentrations observed in humans following a common therapeutic oral dose of 25 mg psilocybin and was therefore able to assess the pharmacokinetics of psilocin and 4-HIAA. The LC-MS/MS method was convenient and reliable for measuring psilocin and 4-HIAA in plasma and will facilitate the clinical development of psilocybin.

Keywords: Drug screening; Glucuronidation; Metabolism; Pharmacokinetics; Psychedelic drugs.

MeSH terms

  • Administration, Oral
  • Chromatography, Liquid / methods
  • Hallucinogens / blood*
  • Hallucinogens / chemistry
  • Hallucinogens / pharmacokinetics
  • Humans
  • Hydroxyindoleacetic Acid / analogs & derivatives
  • Hydroxyindoleacetic Acid / blood*
  • Hydroxyindoleacetic Acid / chemistry
  • Hydroxyindoleacetic Acid / pharmacokinetics
  • Linear Models
  • Psilocybin / administration & dosage
  • Psilocybin / analogs & derivatives*
  • Psilocybin / blood
  • Psilocybin / chemistry
  • Psilocybin / pharmacokinetics*
  • Reproducibility of Results
  • Sensitivity and Specificity
  • Tandem Mass Spectrometry / methods

Substances

  • Hallucinogens
  • Psilocybin
  • Hydroxyindoleacetic Acid
  • psilocin