Determination of Six Pyrazole Fungicides in Grape Wine by Solid-Phase Extraction and Gas Chromatography-Tandem Mass Spectrometry.

A gas chromatography-tandem mass spectrometry (GC-MS/MS) method was developed for the first simultaneous identification and quantification of six pyrazole fungicides (furametpyr, rabenzazole, fluxapyroxad, penflufen, bixafen, and isopyrazam) in grape wine samples. The grape wine samples were first diluted with water, then purified by solid-phase extraction, and finally examined by GC-MS/MS in multiple reaction monitoring (MRM) mode. Matrix-matched calibration curves were used to correct the matrix effects. The limits of quantification (LOQs), calculated as 10 times the standard deviation, were 0.2-0.8 µg kg(-1) for the six pyrazole fungicides. The average recoveries were in the range of 74.3-94.5%, with relative standard deviations (RSDs) below 5.8%, measured at three concentration levels. The proposed method is suitable for the simultaneous determination of six pyrazole fungicides in grape wine samples.

Determination of four paraben-type preservatives and three benzophenone-type ultraviolet light filters in seafoods by LC-QqLIT-MS/MS.

For the first time, an efficient and sensitive analytical method based on liquid chromatography-quadrupole linear ion trap-tandem mass spectrometry (LC-QqLIT-MS/MS) was developed for the simultaneous determination of four paraben-type preservatives and three benzophenone-type ultraviolet light filters in both plant (Sargassum fusiforme, porphyra, kelp) and animal (hairtail, yellow croaker, shrimp) seafood. The samples were extracted in methanol by pressurized liquid extraction (PLE), and the extracts were then cleaned up by mixed-mode cationic exchange (MCX) solid-phase extraction cartridges. Both isotope-labeled internal standards and matrix-matched calibration standards were used to alleviate and correct for the matrix effects, and the limits of quantification (LOQs) were 10.0µg kg(-1) for all target compounds. The average recoveries were in the range of 80.6-107.8% at three spiked concentration levels (10, 50 and 100µgkg(-1)) with relative standard deviations (RSDs) below 8.5%. The results suggest that very limited contamination of these seven emerging contaminants, mainly associated with PCPs, occurred in these common seafoods.

Rapid Quantification of Four Anthocyanins in Red Grape Wine by Hydrophilic Interaction Liquid Chromatography/Triple Quadrupole Linear Ion Trap Mass Spectrometry.

The identification and quantification of four anthocyanins (cyanidin-3-O-glucoside, peonidin-3-O-glucoside, delphinidin-3-O-glucoside, and malvidin-3-O-glucoside) in red grape wine were carried out by hydrophilic interaction liquid chromatography/triple quadrupole linear ion trap MS (HILIC/QTrap-MS/MS). Samples were diluted directly and separated on a Merck ZIC HILIC column with 20 mM ammonium acetate solution-acetonitrile mobile phase. Quantitative data acquisition was carried out in the multiple reaction monitoring mode. Additional identification and confirmation of target compounds were performed using the enhanced product ion mode of the linear ion trap. The LOQs were in the range 0.05-1.0 ng/mL. The average recoveries were in the range 94.6 to 104.5%. The HILIC/QTrap-MS/MS platform offers the best sensitivity and specificity for characterization and quantitative determination of the four anthocyanins in red grape wines and fulfills the quality criteria for routine laboratory application.

Determination of four flavorings in infant formula by solid-phase extraction and gas chromatography-tandem mass spectrometry.

Increasing attention has been focused on the artificial flavorings added in foods, especially those for infants and children. For the first time, a sensitive and efficient analytical method based on gas chromatography-tandem mass spectrometry (GC-MS/MS) was developed for the simultaneous identification and quantification of four flavoring agents (vanillin, methylvanillin, ethylvanillin, and coumarin) in infant formula samples. The flavorings in samples were extracted with methanol/water (v/v, 1:1), cleaned up by solid-phase extraction, and determined by GC-MS/MS in selected reaction monitoring (SRM) mode. Both isotope-labeled internal standards and matrix-matched calibration solutions were used to correct the matrix effects. The limit of quantification (LOQ) was calculated as 10 times the standard deviation, and it was 10.0 µg kg (-1) for vanillin, methylvanillin, ethylvanillin, and coumarin. The average recoveries were in the range of 82.8-107.5% with relative standard deviations (RSDs) below 8.9% measured at three concentration levels (10, 50, and 100 µg kg(-1)). The proposed method is suitable for the sensitive and accurate simultaneous determination of four flavoring agents in infant formula samples and also provided potential use for reference in terms of real analysis of other foods.

Microwave-assisted extraction and determination of dicyandiamide residue in infant formula samples by liquid chromatography-tandem mass spectrometry.

A simple, precise, accurate, and validated liquid chromatography-tandem mass spectrometry (LC-MS/MS) method was developed for the determination of dicyandiamide residue in infant formula samples. Following microwave-assisted extraction with 5% formic acid and clean-up on a Sep-Pak AC-2 SPE cartridge, samples were separated on a ZIC-HILIC HPLC column (150 × 2.1mm i.d., 5-µm film thickness; Merck KGaA, Darmstadt, Germany) with 20mM ammonium acetate solution-acetonitrile as mobile phase at a flow rate of 0.25 mL/min. A linear calibration curve was obtained in the concentration range from 1.0 to 50 ng/mL. Infant formula samples were fortified with dicyandiamide at 3 levels, producing average recovery yields of 83.6 to 95.7%. The limits of detection and quantification of dicyandiamide were 3 and 10 µg/kg, respectively. Due to its simplicity and accuracy, the straightforward method is particularly suitable for routine dicyandiamide detection.

Simultaneous determination of three Curcuminoids in Curcuma wenyujin Y.H.chen et C.Ling. by liquid chromatography-tandem mass spectrometry combined with pressurized liquid extraction.

A sensitive and efficient method based on pressurized liquid extraction (PLE) followed by liquid chromatography-tandem mass spectrometry (LC-MS/MS) was developed for simultaneous identification and quantification of three Curcuminoids in Curcuma wenyujin Y.H.chen et C.Ling., a well known traditional Chinese medicinal herb. PLE was performed using methanol as the extractant, and with the temperature set at 100 °C and the pressure at 1500 psi. Shorter extraction time and less solvent consumption were obtained compared to other extraction methods. LC was performed by using a Waters XBridge C18 column (150 mm × 2.1 mm i.d., 3.5 µm) and a mobile phase of acetonitrile containing 0.1% acetic acid. The operating parameters were thoroughly optimized. The recoveries ranged from 92.4% to 104.1% and relative standard deviations were lower than 3.6%. The method was applied to the determination of Curcumin, Demethoxycurcumin and Bisdemethoxycurcumin contained in Curcuma wenyujin Y.H.chen et C.Ling. samples, which provided a new analytical approach for analysis and quality assessment of traditional Chinese medicines.

Microwave-assisted extraction and determination of citrus red 2 dye in oranges and orange juice by liquid chromatography-tandem mass spectrometry.

A fast, simple, low cost, and high-throughput method has been developed for the determination of citrus red 2 dye in orange and orange juice samples. The procedure is based on microwave-assisted extraction followed by liquid chromatography-tandem mass spectrometry (LC-MS/MS) analysis. The method was optimized, and the analyte was efficiently extracted from the samples in 30 min using hexane/acetone (v/v, 3 : 1). The method was validated and showed good linearity and selectivity. The limits of quantification (LOQs) were 5 µg/kg (sample size of 2 g) for both orange and orange juice samples. The average recoveries, measured at 3 concentration levels (5, 10, and 20 µg/kg), were in the range 77.5% to 87.6% for the compound tested with relative standard deviations below 7.3%. The proposed method is rapid, accurate, and could be utilized for the routine analysis of citrus red 2 dye in orange and orange juice samples.