Trace-level monitoring of anti-cancer drug residues in wastewater and biological samples by thin-film solid-phase micro-extraction using electrospun polyfam/Co-MOF-74 composite nanofibers prior to liquid chromatography analysis.

Sample preparation methods with high accuracy and matrix resistance will benefit the quick analysis of desired analytes in an intricate matrix, such as the monitoring of drug samples in biofluids. Herein, an electrospun composite, consisting of polyfam and a Co-metal organic framework- 74, was developed as a novel sorbent for the high-throughput solid-phase micro-extraction of certain anti-cancer drugs (sorafenib, dasatinib, and erlotinib hydrochloride) from wastewater and biological samples before high-performance liquid chromatography- ultraviolet analysis (HPLC-UV). The synthesis of the resulting composite nanofibers was confirmed using the techniques of Fourier transform-infrared spectroscopy, field emission scanning electron microscopy (FESEM), energy-dispersive X-ray spectroscopy (EDX), and powder X-ray diffraction (XRD). FESEM images illustrated irregular and bead-free nanofibers with a diameter range of 126.9-269.6 nm. Thanks to the incorporation of Co-MOF-74 into the polyfam network, the electrospun nanofibers displayed a large surface area, high porosity, and significant extraction efficiency toward target analytes. Under optimal experimental conditions, the linearity was achieved in the range of 0.1-1500.0 µg L for sorafenib and 0.5-1500.0 µg L for dasatinib and erlotinib hydrochloride, with a coefficient of determination of ≥0.9996. The detection limits (LODs) were calculated within the range of 0.03-0.20 µg L. The relative standard deviation values (RSDs %) were in the range of 3.1%-8.6% (intra-day, n = 6) and 7.0%-10.3% (inter-day, n=3) in the span of three days. Ultimately, the application of the developed method was appraised for the quantification of trace amounts of the intended analytes in various spiked samples.