Therapeutic Monitoring of Palbociclib, Ribociclib, Abemaciclib, M2, M20, and Letrozole in Human Plasma: A Novel LC-MS/MS Method

Ther Drug Monit. 2024 Aug 1;46(4):485-493. doi: 10.1097/FTD.0000000000001174. Epub 2024 Feb 6.

Abstract

Background: Therapeutic drug monitoring (TDM) using cyclin-dependent kinase inhibitors (CDK4/6is) is a novel approach for optimizing treatment outcomes. Currently, palbociclib, ribociclib, and abemaciclib are the available CDK4/6is and are primarily coadministered with letrozole. This study aimed to develop and validate an LC-MS/MS method for the simultaneous analysis of CDK4/6is, 2 active metabolites of abemaciclib (M2 and M20), and letrozole in human plasma for use in TDM studies.

Methods: Sample pretreatment comprised protein precipitation with methanol and dilution of the supernatant with an aqueous mobile phase. Chromatographic separation was achieved using a reversed-phase XBridge BEH C18 column (2.5 μm, 3.0 × 75 mm XP), with methanol serving as the organic mobile phase and pyrrolidine-pyrrolidinium formate (0.005:0.005 mol/L) buffer (pH 11.3) as the aqueous mobile phase. A triple quadrupole mass spectrometer was used for the detection, with the ESI source switched from negative to positive ionization mode and the acquisition performed in multiple reaction monitoring mode.

Results: The complete validation procedure was successfully performed in accordance with the latest regulatory guidelines. The following analytical ranges (ng/mL) were established for the tested compounds: 6-300, palbociclib and letrozole; 120-6000, ribociclib; 40-800, abemaciclib; and 20-400, M2 and M20. All results met the acceptance criteria for linearity, accuracy, precision, selectivity, sensitivity, matrix effects, and carryover. A total of 85 patient samples were analyzed, and all measured concentrations were within the validated ranges. The percent difference for the reanalyzed samples ranged from -11.2% to 7.0%.

Conclusions: A simple and robust LC-MS/MS method was successfully validated for the simultaneous quantification of CDK4/6is, M2, M20, and letrozole in human plasma. The assay was found to be suitable for measuring steady-state trough concentrations of the analytes in patient samples.

MeSH terms

  • Aminopyridines* / blood
  • Aminopyridines* / pharmacokinetics
  • Benzimidazoles* / blood
  • Benzimidazoles* / pharmacokinetics
  • Chromatography, Liquid / methods
  • Cyclin-Dependent Kinase 4 / antagonists & inhibitors
  • Cyclin-Dependent Kinase 6 / antagonists & inhibitors
  • Drug Monitoring* / methods
  • Humans
  • Letrozole* / blood
  • Letrozole* / therapeutic use
  • Liquid Chromatography-Mass Spectrometry
  • Piperazines* / blood
  • Piperazines* / pharmacokinetics
  • Piperazines* / therapeutic use
  • Protein Kinase Inhibitors / blood
  • Protein Kinase Inhibitors / pharmacokinetics
  • Protein Kinase Inhibitors / therapeutic use
  • Purines* / blood
  • Purines* / pharmacokinetics
  • Purines* / therapeutic use
  • Pyridines* / blood
  • Pyridines* / pharmacokinetics
  • Reproducibility of Results
  • Tandem Mass Spectrometry* / methods

Substances

  • ribociclib
  • abemaciclib
  • palbociclib
  • Purines
  • Letrozole
  • Aminopyridines
  • Piperazines
  • Pyridines
  • Benzimidazoles
  • Cyclin-Dependent Kinase 6
  • Protein Kinase Inhibitors
  • Cyclin-Dependent Kinase 4