A green QuEChERS syringe filter based micro-solid phase extraction using hydrophobic natural deep eutectic solvent as immobilized sorbent for simultaneous analysis of five anti-diabetic drugs by HPLC-UV.

BACKGROUND: Here, it has been discussed about creating a specific and sustainable analytical technique for monitoring anti-diabetic drugs in order to accurately determine the dosage in patients and reduce side effects, remove them from wastewater (as emerging contaminants), and ultimately abate pharmaceutical pollutants in the environment. RESULTS: In this research, a green and reproducible Quick Easy Cheap Effective Rugged Safe (QuEChERS) method based on syringe filter based micro-solid phase extraction (SF-µSPE) coupled with HPLC-UV using a green sorbent was developed and optimized for the extraction of five anti-diabetic drugs from wastewater, serum, and plasma real samples. A novel green sorbent composed of a liquid mixture of thymol: menthol ([Thy]:[Men], 1:1) hydrophobic natural deep eutectic solvent (HNADES) and curcumin (Cur) immobilized into the non-toxic and biodegradable polyvinyl alcohol (PVA) electrospun nanofibers' mat was synthesized simply via cheap equipment. Cur was added to enhance the hydrophobicity and functionality of the sorbent. The immobilization process was performed by soaking the mat in the liquid mixture for a specific duration. The correct synthesis and experimental molar ratio of the HNADES components were confirmed by ATR-FTIR and NMR (1H and 13C) spectroscopy. The prepared green sorbent (Cur-HNADES/PVA) was characterized using ATR-FTIR, FE-SEM, EDX/EDX mapping analysis, and water contact angle (WCA) measurement, and it exhibited satisfactory adsorption capacity for the target analytes. SIGNIFICANCE: Under optimal conditions (pH = 6.0, adsorption cycle = 3, sample volume = 5.0 mL, desorption cycle = 1, type and volume of elution = 80:20 %v/v MeOH/ACN and 500.0 µL), the method was validated in terms of specificity, linear dynamic ranges (LDRs = 0.1-2000.0 µg L-1 and 0.1-1800.0 µg L-1), limits of detection (LODs = 0.03-0.09 µg L-1), and precision (within-day RSDs% = 0.32-1.45% and between-day RSDs% = 0.59-2.03%). Evaluation of the greenness aspects of the proposed method was accomplished using the Green Analytical Procedure Index (GAPI) and Analytical GREEnness (AGREE) approaches. It is noteworthy that the conducted research represents the first report of the synthesis and application of this novel and green sorbent for the determination of anti-diabetic drugs in the mentioned real samples.

Electrospun composite nanofibers modified with silver nanoparticles for extraction of trace heavy metals from water and rice samples: An highly efficient and reproducible sorbent.

Herein, a composite of polyacrylonitrile (PAN)/agar/silver nanoparticles (AgNPs) electrospun nanofibers was fabricated and applied as an efficient sorbent for thin-film micro-extraction (TFME) of five metal ions followed by inductively coupled plasma optical emission spectroscopy (ICP-OES). Incorporating agar into the nanofibers followed by in situ photo-reductive reaction under UV-lamp resulted in highly uniform dispersion of AgNPs in the nanofibers. Under the optimized conditions, agreeable linearity was acquired in the range of 0.5-250.0 ng mL-1 (R2 ≥ 0.9985). The LODs (based on S/N = 3) were attained in the range of 0.2 to 0.5 ng mL-1. The relative standard deviations (RSDs) were between 4.5% and 5.6% (intra-day, n = 5) and 5.3%-5.9% (inter-day, n = 3) for three sequential days. The developed method was investigated with water and rice samples, and recoveries (93.9-98.0%) indicated that the PAN/agar/AgNPs could be a promising film for the adsorption of heavy metal ions in varied samples.

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-1 for sorafenib and 0.5-1500.0 µg L-1 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-1. 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.