Extraction and determination of trace amounts of three anticancer pharmaceuticals in urine by three-phase hollow fiber liquid-phase microextraction based on two immiscible organic solvents followed by high-performance liquid chromatography.

An automated three-phase hollow fiber liquid-phase microextraction based on two immiscible organic solvents followed by high-performance liquid chromatography with UV-Vis detection method was applied for the extraction and determination of exemestane, letrozole, and paclitaxel in water and urine samples. n-Dodecane was selected as the supported liquid membrane and its polarity was justified by trioctylphosphine oxide. Acetonitrile was used as an organic acceptor phase with desirable immiscibility having n-dodecane. All the effective parameters of the microextraction procedure such as type of the organic acceptor phase, the supported liquid membrane composition, extraction time, pH of the donor phase, hollow fiber length, stirring rate, and ionic strength were evaluated and optimized separately by a one variable at-a-time method. Under the optimal conditions, the linear dynamic ranges were 1.8-200 (R2  = 0.9991), 0.9-200 (R2  = 0.9987) and 1.2-200 µg/L (R2  = 0.9983), and the limits of detection were 0.6, 0.3, and 0.4 µg/L for exemestane, letrozole, and paclitaxel, respectively. To evaluate the capability of the proposed method in the analysis of biological samples, three different urinary samples were analyzed under the optimal conditions. The relative recoveries of the three pharmaceuticals were in the range of 91-107.3% for these three analytes.

Novel generation of deep eutectic solvent as an acceptor phase in three-phase hollow fiber liquid phase microextraction for extraction and preconcentration of steroidal hormones from biological fluids.

In this study, a novel generation of deep eutectic solvents (DESs) was used as an acceptor phase in three-phase hollow fiber liquid phase microextraction (HF-LPME) based on two immiscible organic phases. It was compared with other common DESs for extraction and preconcentration of dydrogesterone (DYD) and cyproterone acetate (CPA) from urine and plasma samples. The extracted analytes were analyzed by high performance liquid chromatography with UV-vis detector (HPLC-UV). This phosphonium based DES due to low volatility, low price and multifunctionality introduced itself as worthy next generation of acceptor phase in HF-LPME. The factors affected on extraction efficiency of the analytes were investigated and optimized. The performance of the proposed method was studied in terms of linear ranges (LRs from 1 to 500µgL-1 with R2 ≥ 0.9946), precision (RSD% ≤ 6.3) and limits of detection (LODs in the range of 0.5-2µgL-1). Under the optimized conditions, preconcentration factors in the range of 187-428 were obtained. Finally, the method was applied to the analysis of DYD and CPA in human urine and plasma samples and desirable results were obtained.

Automated hollow-fiber liquid-phase microextraction followed by liquid chromatography with mass spectrometry for the determination of benzodiazepine drugs in biological samples.

In this study, two-phase hollow-fiber liquid-phase microextraction and three-phase hollow-fiber liquid-phase microextraction based on two immiscible organic solvents were compared for extraction of oxazepam and Lorazepam. Separations were performed on a liquid chromatography with mass spectrometry instrument. Under optimal conditions, three-phase hollow-fiber liquid-phase microextraction based on two immiscible organic solvents has a better extraction efficiency. In a urine sample, for three-phase hollow fiber liquid-phase microextraction based on two immiscible organic solvents, the calibration curves were found to be linear in the range of 0.6-200 and 0.9-200 µg L(-1) and the limits of detection were 0.2 and 0.3 µg L(-1) for oxazepam and lorazepam, respectively. For two-phase hollow fiber liquid-phase microextraction, the calibration curves were found to be linear in the range of 1-200 and 1.5-200 µg L(-1) and the limits of detection were 0.3 and 0.5 µg L(-1) for oxazepam and lorazepam, respectively. In a urine sample, for three-phase hollow-fiber-based liquid-phase microextraction based on two immiscible organic solvents, relative standard deviations in the range of 4.2-4.5% and preconcentration factors in the range of 70-180 were obtained for oxazepam and lorazepam, respectively. Also for the two-phase hollow-fiber liquid-phase microextraction, preconcentration factors in the range of 101-257 were obtained for oxazepam and lorazepam, respectively.