[Determination of 12 prohibited veterinary drug residues in pig urine by ultra high performance liquid chromatography-tandem mass spectrometry].

A method was established for the simultaneous detection of 12 prohibited veterinary drugs, including ß2-receptor agonists, nitrofuran metabolites, nitroimidazoles, chlorpromazine, and chloramphenicol, in pig urine. The sample was pretreated by enzymolysis, acid hydrolysis/derivatization, and liquid-liquid extraction combined with solid-phase extraction. Detection was performed using ultra high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS). Ammonium acetate solution (0.2 mol/L, 4.5 mL) and ß-glucuronidase/aryl sulfatase (40 µL) were added to the sample, which was subsequently enzymolized at 37 ℃ for 2 h. Then, 1.5 mL of 1.0 mol/L hydrochloric acid solution and 100 µL of 0.1 mol/L o-nitrobenzaldehyde solution were added to the sample. The mixture was incubated at 37 ℃ for 16 h, and the analytes were extracted with 8 mL of ethyl acetate by liquid-liquid extraction. The lower aqueous phase obtained after extraction was extracted and purified using a mixed cation-exchange solid-phase extraction column. The extracts were combined, the extraction solution was blow-dried with nitrogen, and the residue was redissolved for determination. The samples were analyzed under multiple-reaction monitoring mode with both positive and negative electrospray ionization, and quantified using an isotope internal standard method. The correlation coefficients (r) of the 12 compounds were >0.99. The limits of detection (LODs) and quantification (LOQs) of chloramphenicol were 0.05 and 0.1 µg/L, respectively, and the LODs and LOQs of the other compounds were 0.25 and 0.5 µg/L, respectively. The mean recoveries and RSDs at 1, 2, and 10 times the LOQ were 83.6%-115.3% and 2.20%-12.34%, respectively. The proposed method has the advantages of high sensitivity, good stability, and accurate quantification; thus, it is suitable for the simultaneous determination of the 12 prohibited veterinary drug residues in pig urine.

Preparation of malathion MIP-SPE and its application in environmental analysis.

Malathion is an organophosphorous insecticide for controlling insects on fruits and vegetables, miscellaneous household insects, and animal parasites. It is important to develop highly efficient and selective pre-treatment method for analyzing malathion residues in environment and samples from agricultural products based on the molecularly imprinted polymers (MIPs). In this study, we developed a tailor-made MIP method with highly specific recognization to the template. The MIPs were prepared using malathion as a template, methacrylic acid (MAA) as a functional monomer, ethylene glycol dimethacrylate (EGDMA) as a crosslinker, azodiisobutyronitrile (AIBN) as an initiator, and the acetonitrile-chloroform (1:1, v/v) as a porogen. The molecular recognization mechanism of malathion and MAA was evaluated by molecular simulation, ultraviolet spectrometry (UV), and (1)H-nuclear magnetic resonance ((1)H-NMR). MAA interacted specifically with malathion by hydrogen bond with a ratio of 2:1. The MIPs exhibit a high affinity, recognition specificity, and efficient adsorption performance for malathion. The Fourier transform infrared spectroscopy (FT-IR), scanning electron microscope (SEM), surface area and porosimeter analyzer, thermogravimetric/differential thermal analyzer (TG/DTA) were used to characterize the properties of MIP. The malathion residues in soil, tap water, and cabbage were cleaned up by MIP-SPE, detected quantitatively using GC-FPD, and confirmed by GC-MS/MS. The limits of tap water, soil, and cabbage were confined to 0.001 mg L(-1), 0.004 and 0.004 mg kg(-1), respectively. The spiked recoveries of malathion were 96.06-111.49% (with RSD being 5.7-9.2%), 98.13-103.83% (RSD, 3.5-8.7%), and 84.94-93.69% (RSD, 4.7-5.8%) for tap water, soil, and cabbage samples, respectively. Thus, the method developed here can be used effectively in assessing malathion residues in multiple environmental samples. The aim of the study was to provide an efficient, selective, and accurate method for analyzing malathion at trace levels in multiple media.

A method developed for determination of heptachlor and its metabolites from pork.

A new method has been developed to determine heptachlor and its metabolites heptachlor-exo-epoxide and heptachlor-endo-epoxide in pork. The pork samples were extracted with acetone-n-hexane (2:8, V:V) and cleaned up by gel permeation chromatography and florisil solid-phase extraction cartridge. The extract was then determined by gas chromatography equipped with electron capture detector (GC-ECD), followed by validation using gas chromatography-mass spectrometry (GC-MS) with negative chemical ionization. Linearity of calibration curves ranged from 0.01 to 0.5 mg L(-1), with correlation coefficients of more than 0.9980 for GC-ECD and GC-MS, respectively. At spiked concentrations of 0.01, 0.05, and 0.1 mg kg(-1), the average recovery and relative standard deviation values were 87.1-102.2 and 4.0-11.3%, respectively. The limit of quantification for each analyte was 0.01 mg kg(-1), which satisfied the current maximum residue limit permitted in pork. Our results showed that the method developed was successfully used to determine heptachlor and heptachlor epoxide residues in real pork samples.