Modified magnetic-based solvent-assisted dispersive solid-phase extraction: application to the determination of cortisol and cortisone in human saliva

Abstract

A modification of magnetic-based solvent-assisted dispersive solid-phase extraction (M-SA-DSPE) has been employed for the determination of the biomarkers cortisol and cortisone in saliva samples. M-SA-DSPE is based on the dispersion of the sorbent material by using a disperser solvent like in dispersive solid phase extraction (SA-DSPE) but a magnetic sorbent is used like in magnetic dispersive solid-phase extraction (M-DSPE). Thus, the magnetic sorbent containing the target analytes is retrieved using an external magnet like in M-DSPE. Finally, the analytes are desorbed into a small volume of organic solvent for the subsequent chromatographic analysis. To this regard, a M-SA-DSPE-based method was developed using a magnetic composite as sorbent, made of CoFe₂O₄ magnetic nanoparticles embedded into a reversed phase polymer (Strata-X^TM-RP), which exhibits affinity to the target analytes. Then, liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) was used to measure both analytes in the M-SA-DSPE extract. Under the optimized conditions, good analytical features were obtained: limits of detection of 0.029 ng mL^-1 for cortisol and 0.018 ng mL^-1 for cortisone, repeatability (as RSD) ≤ 10 %, and relative recoveries between 86 and 111 %, showing no significant matrix effects. Finally, the proposed method was applied to the analysis of saliva from different volunteers. This new methodology allows a fast and non-invasive determination of cortisol and cortisone, and it employs small amounts of sample, organic solvent and sorbent. Likewise, the sample treatment is minimum, since any supporting equipment (vortex, centrifuge, ultrasounds, etc.) is required.

Keywords: Biomarkers; Dispersive-based microextraction; Liquid chromatography-tandem mass spectrometry; Magnetic sorbent; Saliva samples.