Rapid Multi-Residue Detection Methods for Pesticides and Veterinary Drugs.

The excessive use or abuse of pesticides and veterinary drugs leads to residues in food, which can threaten human health. Therefore, there is an extremely urgent need for multi-analyte analysis techniques for the detection of pesticide and veterinary drug residues, which can be applied as screening techniques for food safety monitoring and detection. Recent developments related to rapid multi-residue detection methods for pesticide and veterinary drug residues are reviewed herein. Methods based on different recognition elements or the inherent characteristics of pesticides and veterinary drugs are described in detail. The preparation and application of three broadly specific recognition elements-antibodies, aptamers, and molecular imprinted polymers-are summarized. Furthermore, enzymatic inhibition-based sensors, near-infrared spectroscopy, and SERS spectroscopy based on the inherent characteristics are also discussed. The aim of this review is to provide a useful reference for the further development of rapid multi-analyte analysis of pesticide and veterinary drug residues.

Multiresidue method for the simultaneous determination of 16 acaricides by modified quick, easy, cheap, effective, rugged, and safe extraction and ultra-high performance liquid chromatography coupled with tandem mass spectrometry in citrus.

An ultra-high performance liquid chromatography coupled with tandem mass spectrometry analytical method was developed for simultaneously determining 16 acaricides in citrus based on an optimized quick, easy, cheap, effective, rugged, safe strategy. Good linearities of the standard curve of 5-1000 µg/kg was obtained with regression coefficients higher than 0.9967. Recoveries for all compounds ranged from 72 to 111% with relative standard deviations lower than 14.4% at spiked levels of 5, 50, and 500 µg/kg. Low limits of detection and quantification were readily achieved ranging from 0.05 to 2.7 and 0.10 to 4.3 µg/kg, respectively. Matrix effects were also evaluated for 16 targets with most compounds achieved signal enhancement. Citrus peel gave the highest extent matrix effects, followed by whole citrus and pulp. Finally, this method was successfully applied to detect acaricides residues in real citrus samples. The results showed that pyridaben and quinalphos were the two most frequent and high-concentration compounds with concentrations exceeding the maximum residue limits in five samples, suggesting that the use of these acaricides should be regulated in China in the future.

Simultaneous determination of antiviral drugs in chicken tissues by ultra high performance liquid chromatography with tandem mass spectrometry.

An ultra high performance liquid chromatography with tandem mass spectrometry method was established for the rapid and simultaneous analysis of seven antiviral drugs, amantadine, rimantadine, memantine, moroxydine, imiquimod, oseltamivir, and acyclovir, in chicken liver, muscle, and egg. Homogenized samples were extracted with trichloroacetic acid and acetonitrile solutions and then purified by cation-exchange solid-phase extraction. The target drugs were analyzed by liquid chromatography with a UPLC BEH Amide column (2.1 mm × 100 mm, 1.7 µm) coupled with a tandem mass spectrometer operating in the positive multiple-reaction mode. A perfectly linear relationship was obtained within the concentration ranges of 0.5-20 µg/L for acyclovir and 0.1-10 µg/L for the other six antiviral drugs. The average recoveries of the seven antiviral drugs using four addition levels in chicken liver, muscle, and eggs were 82.67-90.10, 82.30-92.27, and 81.98-93.77%, respectively, and the acceptable coefficients of variation were 5.18-9.88, 4.84-11.2, and 42.8-9.95%, respectively. The detection limits and detection capabilities of the analysis method for the seven antiviral drugs were in the ranges of 0.04-0.64 and 0.11-0.78 µg/kg, respectively. Additionally, an inter-laboratory study among five laboratories further validated the method.

Development of a detection method for 10 non-steroidal anti-inflammatory drugs residues in four swine tissues by ultra-performance liquid chromatography with tandem mass spectrometry.

The ultra-performance liquid chromatography with tandem mass spectrometry (UPLC-MS/MS) detection method was developed for the residues of 10 NSAIDs (salicylic acid, acetylsalicylic acid, acetaminophen, diclofenac, tolfenamic acid, antipyrine, flunixin meglumine, aminophenazone, meloxicam, metamizole sodium) in swine muscle, liver, kidney, and fat. Swine tissue samples were extracted by phosphorylated acetonitrile with the addition of an appropriate amount of internal standard working solution, defatted with acetonitrile-saturated n-hexane, and purified by Hydrophile-Lipophile Balance (HLB) solid-phase extraction column, then separated by UPLC BEH shield RP18 column with 0.1% formic acid in water/0.1% formic acid in acetonitrile with gradient elution, which was detected in the multiple reaction monitoring (MRM) modes. The correlation coefficient of the standard curve equation is greater than 0.99, and the coefficient of variation within and between batches is less than 14.4%. We evaluated the analytical method using two green assessment tools. The method established in this study met the requirements of NSAID residue analysis and provides analytical tools for determining and confirming NSAIDs in swine tissue samples. This is the first report on the simultaneous determination of 10 NSAIDs in four swine tissues by the UPLC-MS/MS method and accurate quantification using deuterated internal standards.

A fluorescence immunoassay based on GSH destroying MnO2@QDs for the simultaneous ultrasensitive detection of four mycotoxins in cereals.

A novel fluorescence immunoassay based on MnO2 nanoflowers loading multicolor quantum dots and glutathione destroying MnO2 nanoflowers to release quantum dots combined with magnetic separation is developed for rapid, ultra-sensitive, and simultaneous quantitative detection of ochratoxin A, aflatoxin B1, fumonisin B1, and zearalenone in cereal samples. The test linear range of assay is from 0.001 to 200 µg L-1. The limit of detection for ochratoxin A, aflatoxin B1, fumonisin B1, and zearalenone is 0.0001 µg L-1, 0.0001 µg L-1, 0.0003 µg L-1, and 0.0001 µg L-1, respectively. The simultaneous detection of four mycotoxins can be achieve within 30 min. The test results of four mycotoxins in the incurred corn, rice, and oat samples have been confirmed by ultra-performance liquid chromatography tandem mass spectrometry, the differences between results are considered no significantly different (p > 0.05). This multiplexed test scheme has provided a potential analysis strategy for multiple food risk factors.

Europium Fluorescent Nanoparticles-Based Multiplex Lateral Flow Immunoassay for Simultaneous Detection of Three Antibiotic Families Residue.

A fluorescent immunoassay based on europium nanoparticles (EuNPs-FIA) was developed for the simultaneous detection of antibiotic residues, solving the problems of single target detection and low sensitivity of traditional immunoassay methods. In the EuNPs-FIA, EuNPs were used as indictive probes by binding to anti-tetracyclines monoclonal antibodies (anti-TCs mAb), anti-sulphonamides monoclonal antibodies (anti-SAs mAb) and anti-fluoroquinolones monoclonal antibodies (anti-FQs mAb), respectively. Different artificial antigens were assigned to different regions of the nitrocellulose membrane as capture reagents. The EuNPs-FIA allowed for the simultaneous detection of three classes of antibiotics (tetracyclines, fluoroquinolones and sulphonamides) within 15 min. It enabled both the qualitative determination with the naked eye under UV light and the quantitative detection of target antibiotics by scanning the fluorescence intensity of the detection probes on the corresponding detection lines. For qualitative analysis, the cut-off values for tetracyclines (TCs), fluoroquinolones (FQs) and sulphonamides (SAs) were 3.2 ng/ml, 2.4 ng/ml and 4.0 ng/ml, respectively, which were much lower than the maximum residue limit in food. For quantitative analysis, these ranged from 0.06 to 6.85 ng/ml for TCs, 0.03-5.14 ng/ml for FQs, and 0.04-4.40 ng/ml for SAs. The linear correlation coefficients were higher than 0.97. The mean spiked recoveries ranged from 92.1 to 106.2% with relative standard deviations less than 8.75%. Among them, the three monoclonal antibodies could recognize four types of TCs, seven types of FQs and 13 types of SAs, respectively, and the detection range could cover 24 antibiotic residues with different structural formulations. The results of the detection of antibiotic residues in real samples using this method were highly correlated with those of high performance liquid chromatography (R 2 > 0.98). The accuracy and precision of the EuNPs-FIA also met the requirements for quantitative analysis. These results suggested that this multiplex immunoassay method was a promising method for rapid screening of three families of antibiotic residues.

Functional Up-Conversion Nanoparticle-Based Immunochromatography Assay for Simultaneous and Sensitive Detection of Residues of Four Tetracycline Antibiotics in Milk.

An ultrahigh-sensitivity lateral flow immunochromatography (LFIC) assay based on up-converting nanoparticles (UCNPs) was developed to carry out a multi-residue detection of tetracycline in milk. The sensitivity of the immunoassay was greatly improved by the use of a broad-spectrum monoclonal antibody attached to UCNPs to form a signal probe. Under the optimal conditions, the UCNP-LFIC assay enabled sensitive detection of tetracycline (TC) as well as of oxytetracycline (OTC), chlortetracycline (CTC), and doxycycline (DOX) within 10 min, with IC 50 values of 0.32, 0.32, 0.26, 0.22 ng/mL, respectively. There was no cross-reactivity with ten other antibiotics. Similarly, we evaluated the experimental results for matrix effects. Experiments involving spiking showed the four tetracycline antibiotics displaying mean recoveries ranging from 93.95 to 111.90% with relative standard deviations (RSDs) of < 9.95%. The detection results of actual samples using the developed method showed a good correlation (R 2 ≥ 0.98) with the results using high-performance liquid chromatography (HPLC). Thus, the assay can achieve an ultrahighly sensitive detection of antibiotics in milk, and can hence promote human health and provides promising applications in the bio-detection field.

Simultaneous extraction of four plant growth regulators residues in vegetable samples using solid phase extraction based on thiol-functionalized nanofibers mat.

A simple and environmentally friendly sample pretreatment method was established for extraction of four plant growth regulators (PGRs) residues in vegetable samples. In order to effectively extract targets from complex sample matrices, three types of polar groups (COOH, NH2, or SH) functionalized polyacrylonitrile nanofibers mats (PAN NFsM) were prepared and evaluated, respectively. The superior -SH functionalized PAN NFsM was further selected as a novel adsorbent of solid phase extraction (SPE). Under optimal conditions, the proposed method could achieve high sensitivity (0.2-2 ng g-1) and acceptable recovery (88.94%-106.42%) by consuming lower amount of adsorbent (only 5 mg) and organic reagent (only 1.4 mL), and performing much fewer steps than current methods. In addition, the prepared SH-PAN NFsM possessed excellent reusability which could be reused for 6 times without degradation in adsorption capability. These results presented the great potential of the established method for environmental-friendly and efficiently detecting PGRs residues.

Up-Converting Nanoparticle-Based Immunochromatographic Strip for Multi-Residue Detection of Three Organophosphorus Pesticides in Food.

Organophosphorus (OP) pesticides are widely used to control pests because of their high activity. This study described a rapid and sensitive lateral flow immunochromatographic (LFIC) assay based on up-converting nanoparticles (UCNPs) for multi-residue detection of three OP pesticides. The developed assay integrated novel fluorescent material UCNPs labeled with a broad-specific monoclonal antibody. Based on the competitive platform by immobilized antigen in the test zone, the optimized UCNPs-LFIC assay enabled sensitive detection for parathion, parathion-methyl, and fenitrothion with IC50 of 3.44, 3.98, and 12.49 ng/mL (R 2 ≥ 0.9776) within 40 min. The detectable ability ranged from 0.98 to 250 ng/mL. There was no cross-reactivity with fenthion, phoxim, isocarbophos, chlorpyrifos, or triazophos, even at a high concentration of 500 ng/mL. Matrix interference from various agricultural products was also studied in food sample detection. In the spiked test, recoveries of the three OP pesticides ranged from 67 to 120% and relative standard deviations were below 19.54%. These results indicated that the proposed strip assay can be an alternative screening tool for rapid detection of the three OP pesticides in food samples.

Bio-barcode detection technology and its research applications: A review.

With the rapid development of nanotechnology, the bio-barcode assay (BCA), as a new diagnostic tool, has been gradually applied to the detection of protein and nucleic acid targets and small-molecule compounds. BCA has the advantages of high sensitivity, short detection time, simple operation, low cost, good repeatability and good linear relationship between detection results. However, bio-barcode technology is not yet fully formed as a complete detection system, and the detection process in all aspects and stages is unstable. Therefore, studying the optimal reaction conditions, optimizing the experimental steps, exploring the multi-residue detection of small-molecule substances, and preparing immuno-bio-barcode kits are important research directions for the standardization and commercialization of BCA. The main theme of this review was to describe the principle of BCA, provide a comparison of its application, and introduce the single-residue and multi-residue detection of macromolecules and single-residue detection of small molecules. We also compared it with other detection methods, summarized its feasibility and limitations, expecting that with further improvement and development, the technique can be more widely used in the field of stable small-molecule and multi-residue detection.