High Liquid Chromatography-tandem Mass Spectrometry Research Articles

Simultaneous quantification of donafenib, sorafenib, and their N-oxide metabolites in rat plasma using a HPLC-MS/MS method

Donafenib and sorafenib are small molecule chemotherapy drugs for the management of hepatocellular carcinoma, with donafenib being a deuterated derivative of sorafenib. To date, a high liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) method that quantify donafenib, sorafenib, and their main metabolites has not yet been developed. The objective of this study was to establish a HPLC-MS/MS method for the simultaneous detection of donafenib, donafenib-N-oxide, sorafenib, and sorafenib-N-oxide and for the pharmacokinetic studies in rat. The extraction of all analytes was achieved by simple protein precipitation utilizing acetonitrile. The Waters XBridge C18 column (2.1 × 100 mm, 3.5 µm) was selected, and the analytes could be efficiently separated and quantitated during a 2.8 min gradient elution procedure. The method was linear within the predefined quantification ranges and provided acceptable precision (%CV < 9.4%), reproducible extraction recovery (99.4%–111.5%), and low matrix effect (88.1%–98.6%). The hemolysis effect did not interfere with the quantification of all analytes, and similar results were obtained by changing the anticoagulant K2-EDTA to heparin or sodium citrate. Plasma pharmacokinetics revealed that the values of t1/2, Cmax, and AUC0-t of donafenib were 1.4-, 6.2-, and 3.1-fold higher than those of sorafenib, respectively. In conclusion, the proposed bioassay was successfully applied to pharmacokinetic studies in rat after administration of donafenib and sorafenib. Our work not only improves the bioanalytical method for determining the plasma concentrations of donafenib, sorafenib, and their N-oxide metabolites, but also provides a scientific reference for clinical pharmacokinetic studies.

Synthesis of metal-organic framework @molecularly imprinted polymer adsorbents for solid phase extraction of organophosphorus pesticides from agricultural products

The novel core-shell structural zeolitic imidazolate framework-8 @molecularly imprinted polymers were successfully synthesized by surface imprinting technique and used as adsorbents for solid-phase extraction of organophosphorus pesticides. The obtained hybrid composites were characterized by scanning electron microscopy, transmission electron microscopy and Fourier-transform infrared, and their adsorbing and recognition performance were evaluated by binding experiments. The results showed that zeolitic imidazolate framework-8 @molecularly imprinted polymers presented a typically core-shell structure with molecularly imprinted shell (about 50 nm) homogeneously polymerized on the surface of zeolitic imidazolate framework-8 core, and exhibited specific recognition towards organophosphorus pesticides with fast adsorption capacity. The adsorption and desorption conditions including sample loading solvent, sample pH, washing and elution solvent were optimized. Under optimum conditions, the solid-phase extraction based on zeolitic imidazolate framework-8 @molecularly imprinted polymers combined with high liquid chromatography-tandem mass spectrometry method for determining organophosphorus pesticides was established and exhibited good linearity (R2 ≥ 0.9927) in the range of 1–200 µg/L. With spiked at three different concentration levels in agricultural products (cauliflower, radish, pear, muskmelon), the recoveries ranged from 82.5% to 123.0% with relative standard deviations lower than 8.24%. The developed method was sensitive, convenient and efficient. More importantly, this study could provide a promising strategy for designing new adsorbents with extremely fast mass transfer rate for other potential trace contaminants.

Preparation of magnetic flower-like molybdenum disulfide hybrid materials for the extraction of organophosphorus pesticides from environmental water samples

In this study, the magnetic flower-like molybdenum disulfide hybrid materials (Fe3O4/MoS2) were successfully synthesized by in-situ fabrication method and utilized in the magnetic solid-phase extraction of organophosphorus pesticides. Fe3O4 nanoparticles with different loading amounts of MoS2 were evaluated and detail characterized. The results showed that MoS2 played a key role with rapid and high adsorption capacity towards organophosphorus pesticides. The higher extraction efficiency and good magnetic performance were obtained with loading amount of 200 mg MoS2. Fe3O4 was attached on the surface of MoS2 with flower-like shape (500 nm in diameter). The parameters (amounts of adsorbents, adsorption time, solution pH, elution solvents and sample volumes) affecting magnetic solid-phase extraction efficiency were optimized. Under the optimum conditions, magnetic solid-phase extraction coupled with high liquid chromatography-tandem mass spectrometry for analyzing organophosphorus pesticides in environmental water samples was established. All the analytes exhibited good recoveries spiked at three different concentration levels (10, 20, 50 ng/mL) in water samples. The relative standard deviations were between 1.4% and 6.8%. The developed method showed high sensitivity and good potential use of this convenient and high efficient method for determining organophosphorus pesticides. More importantly, this study can provide a new magnetic adsorbent with extremely fast mass transfer rate for other potential trace contaminants.

Determination of Trace Perfluoroalkyl Carboxylic Acids in Edible Crop Matrices: Matrix Effect and Method Development.

A robust method was developed for simultaneous determination of nine trace perfluoroalkyl carboxylic acids (PFCAs) in various edible crop matrices including cereal (grain), root vegetable (carrot), leafy vegetable (lettuce), and melon vegetable (pumpkin) using ultrasonic extraction followed by solid-phase extraction cleanup and high liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). The varieties of extractants and cleanup cartridges, the usage of Supelclean graphitized carbon, and the matrix effect and its potential influencing factors were estimated to gain an optimal extraction procedure. The developed method presented high sensitivity and accuracy with the method detection limits and the recoveries at four fortification levels in various matrices ranging from 0.017 to 0.180 ng/g (dry weight) and from 70% to 114%, respectively. The successful application of the developed method to determine PFCAs in various crops sampled from several farms demonstrated its practicability for regular monitoring of PFCAs in real crops.

Determination of phenolic compounds by ultra high liquid chromatography-tandem mass spectrometry: Applications in nuts

A new method for qualitative and quantitative analysis of fourteen common polyphenolic compounds (gallic acid, 3,4-dihydroxybenzoic or proto-catechuic acid, chlorogenic acid, caffeic acid, syringic acid, 2-hydroxycinnamic or o-coumaric acid, p-coumaric acid, ferulic acid, rutin, rosmarinic acid, catechin, epicatechin, kaempferol and trans-cinnamic acid) was developed using ultra high liquid chromatography (UHPLC) coupled with tandem mass spectrometry (MS/MS). Selected phenolic compounds were detected in multiple reaction monitoring (MRM) mode and determined simultaneously in a 13-min analysis time and a number of validation parameters (calibration range, limit of detection, limit of quantification, repeatability, precision, and recovery) were studied. To show the usefulness of the method, phenolic compounds were studied in nuts such as hazelnut (Corylus avellana L.), pistachio (Pistaciae vera L.) and almond (Prunus amygdaleus L.).

Evaluation of the QuEChERS method for the extraction of pharmaceuticals and personal care products from drinking-water treatment sludge with determination by UPLC-ESI-MS/MS

A modified version of the QuEChERS method has been evaluated for the determination of 21 pharmaceuticals and 6 personal care products (PPCPs) in drinking-water sludge samples by employing ultra high liquid chromatography–tandem mass spectrometry (UPLC-MS/MS). The performance of the method was evaluated through linearity, recovery, precision (intra-day), method detection and quantification limits (MDL and MQL) and matrix effect. The calibration curves prepared in acetonitrile and in the matrix extract showed a correlation coefficient ranging from 0.98 to 0.99. MQLs values were on the ngg−1 order of magnitude for most compounds. Recoveries between 50% and 93% were reached with RSDs lower than 10% for most compounds. Matrix effect was almost absent with values lower than 16% for 93% of the compounds. By coupling a quick and simple extraction called QuEChERS with the UPLC-MS/MS analysis, a method that is both selective and sensitive was obtained. This methodology was successfully applied to real samples and caffeine and benzophenone-3 were detected in ngg−1 levels.