Anticancer Drug Extraction from Plasma Samples Using Three-Dimensional Polyoxometalate-Based Supramolecular Frameworks as Sorbents

Abstract

Four self-assembled inorganic−organic hybrid materials, namely, H{Na- 4) (pydc−OH = 4-hydroxy-2,6-pyridinedicarboxylate), were hydrothermally synthesized and structurally characterized. Hybrids 1−3 are isostructural and contain a Keggin unit, which is linked to lanthanoids to produce distinct trinuclear lanthanoid building blocks. The fragments are connected by anion−π and hydrogen bonding interactions to create 3D networks. In hybrid 4, a trimeric Pr-organic species bearing a Keggin unit forms a 2D coordination polymer, and then hydrogen bonding interactions between 2D layers lead to the formation of a 3D structure. These polyoxometalate-based frameworks were used as sorbents for the dispersive microsolidphase extraction (D-μSPE) of two anticancer drugs (doxorubicin and epirubicin) in human plasma samples. Analytes were quantified and separated using high-performance liquid chromatography with fluorescence detection (HPLC-FLD). The method's linearity was between 0.8−500 ng mL −1 and 1.0− 500 ng mL −1 for the antineoplastic drugs doxorubicin and epirubicin, respectively. The limits of detection (S/N = 3) were in the range of 0.2−0.3 ng mL −1 , while the precision was in the range of 3.5−4.3%. Finally, human plasma samples from patients treated with doxorubicin or epirubicin were analyzed by using the D-μSPE-HPLC-FLD method.