Magnetic Solid-Phase Microextraction Protocol Based on Didodecyldimethylammonium Bromide-Functionalized Nanoparticles for the Quantification of Epirubicin in Biological Matrices

Due to epirubicin's (EPI) narrow therapeutic index and risk of cardiotoxicity, it is critical to monitor concentrations of this drug when being used to treat cancer patients. In this study, a simple and fast magnetic solid-phase microextraction (MSPME) protocol for the determination of EPI in plasma and urine samples is developed and tested. Experiments were performed using prepared Fe3O4-based nanoparticles coated with silica and a double-chain surfactant-namely, didodecyldimethylammonium bromide (DDAB)-as a magnetic sorbent. All the prepared samples were analyzed via liquid chromatography coupled with fluorescence detection (LC-FL). The validation parameters indicated good linearity in the range of 0.001-1 mu g/mL with a correlation coefficient > 0.9996 for plasma samples, and in the range of 0.001-10 mu g/mL with a correlation coefficient > 0.9997 for urine samples. The limit of detection (LOD) and limit of quantification (LOQ) for both matrices were estimated at 0.0005 mu g/mL and 0.001 mu g/mL, respectively. The analyte recovery after sample pretreatment was 80 +/- 5% for the plasma samples and 90 +/- 3% for the urine samples. The developed method's applicability for monitoring EPI concentrations was evaluated by employing it to analyze real plasma and urine samples collected from a pediatric cancer patient. The obtained results confirmed the proposed MSPME-based method's usefulness, and enabled the determination of the EPI concentration-time profile in the studied patient. The miniaturization of the sampling procedure, along with the significant reduction in pre-treatment steps, make the proposed protocol a promising alternative to routine approaches to monitoring EPI levels in clinical laboratories.

Automated summary

A simple and fast magnetic solid-phase microextraction protocol using Fe3O4-based nanoparticles coated with silica and didodecyldimethylammonium bromide (DDAB) as a magnetic sorbent was developed to determine epirubicin (EPI) in plasma and urine samples. The developed method showed good linearity, with a detection range of 0.001-1 μg/mL for plasma samples and 0.001-10 μg/mL for urine samples. The applicability of the method was confirmed by analyzing real samples from a pediatric cancer patient, enabling the determination of the EPI concentration-time profile. The proposed protocol offers a promising alternative to routine approaches for monitoring EPI levels in clinical laboratories, due to its miniaturization and reduced pre-treatment steps.