Determination of Sulfonamides in Chicken Meat by Magnetic Molecularly Imprinted Polymer Coupled to HPLC-UV

In this work, Fe₃O₄ magnetic nanoparticles were synthesized and modified by a molecularly imprinted polymer for easy and selective extraction and determination of sulfonamides in chicken meat samples. Imprinted polymer magnetic nanoparticles were characterized by Fourier transform infrared spectroscopy, X-ray diffraction pattern, thermal analysis, and scanning electron microscope micrograph. The template was removed by methanol elution. The effective parameters on extraction and determination of sulfonamides on the sorbent such as eluent type, extraction solvent, and adsorption and desorption times were optimized. Sulfonamide separation and determination were performed by high-performance liquid chromatography–UV. The linear ranges for sulfonamides were 0.5–150 μg/L and the limits of detection were 0.1–0.5 μg/L. Relative standard deviations were within 4.3–5.4 %. The method showed good selectivity for extraction of sulfonamides in real samples.     

Molecularly Imprinted Polymer as Sorbent for Solid-Phase Extraction Coupling to Gas Chromatography for the Simultaneous Determination of Trichlorfon and Monocrotophos Residues in Vegetables

In this study, a molecularly imprinted polymer (MIP) was prepared using the mixture of trichlorfon and monocrotophos as the mixed template. The imprinted polymer was characterized and exhibited good recognition ability and fast adsorption–desorption dynamic toward the trichlorfon and monocrotophos. Using this imprinted polymer as sorbent, a new method of molecularly imprinted solid-phase extraction coupled to gas chromatography for the simultaneous determination of two organophosphate pesticides residues was developed. Under optimal condition, the linear range was 0.005–10.0 mg/l. At a loading flow rate of 2.0 ml/min for loading 100 ml, the detection limits were 0.28 μg/l for trichlorfon and 0.090 μg/l for monocrotophos, the peak area precision (RSD) for five replicates was 4.23–4.50 %. The blank rape samples spiked with two organophosphate pesticides at 0.05 and 0.1 mg/l levels were determined by this method with recoveries ranging from 89.41 % to 95.12 %. Moreover, this method was successfully applied to the quantitative detection of the trichlorfon and monocrotophos residues in leek samples.     

Study on a Molecularly Imprinted Solid-Phase Extraction Coupled to Capillary Electrophoresis Method for the Determination of Trace Trichlorfon in Vegetables

How to determine the pesticide residues in vegetable is an urgent problem. In this study, we reported a new method of solid-phase extraction coupled to capillary electrophoresis (SPE–CE) based on a molecularly imprinted polymer (MIP) for determination of trace trichlorfon. The electrophoretic conditions and factors which affected the molecularly imprinted solid-phase extraction were optimized. Under optimal conditions, the linear ranges of the calibration graph were 0.1 μg/L to 10 mg/L. The limit of detection (LOD) and method quantitation limit (MQL) were 4.9 and 16.2 μg/kg, respectively. With a flow rate of 2.5 mL/min for 50 mL loading, an enrichment factor of 160 was obtained. The relative standard deviation (RSD) for five replicate extractions of 0.01 mg/L trichlorfon standard solution was 4.5 %. The blank cucumber, lettuce, and radish samples spiked with trichlorfon at three levels were extracted and determined by this presented method with recoveries ranging from 77.6 to 93.2 %. Moreover, this proposed methodology was successfully applied to the quantitative detection of the trichlorfon residues in the leek samples, and the results were in good agreement with that obtained by the gas chromatography method.     

Simple and Fast Determination of Acrylamide and Metabolites in Potato Chips and Grilled Asparagus by Liquid Chromatography Coupled to Mass Spectrometry

The purpose of this study was to evaluate an analytical procedure for the determination of acrylamide in different starchy foods such as potato chips and grilled asparagus. The method is based on high-performance liquid chromatography coupled to triple quadrupole tandem mass spectrometry (HPLC-QqQ-MS/MS). A solid–liquid extraction procedure, using water as extraction solvent, has been developed followed by a cleanup procedure based on solid-phase extraction (SPE) or dispersive solid-phase extraction (d-SPE). Polymeric cartridges (Oasis HLB) and aluminum oxide (Al₂O₃) were used for potato and asparagus matrices, respectively. The optimized procedures were validated, and limits of detection and quantitation were 4 and 12 μg/kg for potato chips and 2 and 5 μg/kg for grilled asparagus, respectively. Recoveries were evaluated, and good values were obtained, ranging from 90 to 117 % for potato chips and from 90 to 116 % for grilled asparagus. The method was applied to real samples, and concentrations ranged from 105 to 860 μg/kg in potato chips, whereas higher values were detected in grilled asparagus (from 292 to 1469 μg/kg). Furthermore, single-stage Orbitrap high-resolution mass spectrometry has been used for the putative identification of acrylamide-N-acetyl-S-(2-carbamoylethyl)-l-cysteine (AAMA) in urine.     

食品中丙烯酰胺吸附功能材料的合成及其选择性能研究

采用分子印迹沉淀聚合法,以丙烯酰胺的结构类似物丙酰胺为模板分子,制备出了对丙烯酰胺具有较好选择性的印迹聚合物。通过振荡吸附实验对聚合物的合成条件进行了优化;吸附动力学和选择性实验结果表明:与本体聚合法相比,印迹聚合物具有较高的吸附容量和吸附速率,对目标分析物丙烯酰胺具有较好的吸附特性,最大吸附量为6.67 mg/g。     

Molecularly Imprinted Solid-Phase Extraction Coupled with High-Performance Liquid Chromatography for the Determination of Trace Trichlorfon and Monocrotophos Residues in Fruits

In this study, a novel molecularly imprinted polymer (MIL@MIP) that could selectively recognize the trichlorfon and monocrotophos was synthesized using metal-organic framework MIL-101 as support material. The prepared MIL@MIP was characterized by Fourier transform infrared, thermogravimetric analysis, scanning electron microscope, static adsorption, kinetic adsorption, and competitive adsorption analyses. Using this material as sorbent, a new method of molecularly imprinted solid-phase extraction coupled with high performance liquid chromatography for simultaneous determination of trichlorfon and monocrotophos was established. Under optimal conditions, the limit of detection (LOD) of this method for trichlorfon and monocrotophos detection was 0.011 and 0.015 mg/kg, respectively. The relative standard deviation (RSD) for five replicates of 0.05 mg/L trichlorfon and monocrotophos mixed solutions was within the range of 1.8 to 3.7 %. Apple and pear samples spiked with the two kinds of organophosphate pesticides were extracted and determined by using this method with good recoveries ranging from 86.5 to 91.7 %. Moreover, this method was successfully applied for the detection of the two organophosphate pesticides in strawberry samples.     

Preparation and Evaluation of Histamine Imprinted Polymer as a Selective Sorbent in Molecularly Imprinted Solid-Phase Extraction Coupled with High Performance Liquid Chromatography Analysis in Canned Fish

A series of molecularly imprinted polymers (MIPs) were prepared against histamine. Different template/monomer ratios were applied to optimize the imprinting condition. Methacrylic acid (MAA) as a functional monomer and Chloroform as a solvent were applied in polymerization process. The binding properties of MIPs were studied in comparison with a blank non-imprinted polymer. The optimized polymer, with a histamine/MAA ratio of 1/4, was selected as a sorbent in molecularly imprinted solid-phase extraction (MISPE) of histamine from canned fish. Scatchard analysis of MIP-histamine interactions revealed two types of binding sites for MIP: high affinity (K_D?=?11.11 μM) and low affinity (K_D?=?333.3 μM). The MISPE procedure was calibrated and a recovery of 76.5–97.6 % was obtained. The intra-and inter-day precision values were less than 5.70 % and 10.1 %, respectively. The selectivity of MISPE for histamine was also studied in comparison with some other structurally similar amines, which could be simultaneously present in canned fish. The performance of the imprinted polymer was examined and the results indicated that its good selectivity and affinity for histamine was very promising. Therefore, the proposed calibrated method could be applied in selective extraction and analysis of histamine in canned fish.     

Molecularly Imprinted Nanosilica Solid-Phase Extraction for Bisphenol A in Fish Samples

This paper reports a method using molecularly imprinted nanosilica as the solid-phase extraction sorbent to extract bisphenol A (BPA) from fish samples. The selective extraction efficiency of BPA from its structure-analogous by molecularly imprinted solid-phase extraction (MISPE) was compared with commercial C18 SPE column. The reproducibility of MISPE and optimal flow rate of sample were studied. There was a linear correlation in the concentration range of 0.7–114.1 μg l^?1 of BPA (r?=?0.997). The limit of detection (LOD) based on three times ratio of signal to noise was 0.11 μg l^?1. Under optimal conditions, the proposed method was applied to the analysis of BPA in fish samples. The amount of BPA in bream was 4.00 μg kg^?1, and both concentrations of BPA in crucian and weever were below the LOD. The recoveries of BPA standard solution spiked with fish samples were in the range of 92.56–102.3 % with the relative standard deviation less than 10 %.     

Determination of acrylamide in food using a UPLC–MS/MS method: results of the official control and dietary exposure assessment in Cyprus

ABSTRACT

The determination of acrylamide in potato products, bakery products and coffee, and the human dietary exposure is reported. The method reported is based on a single extraction step with water, followed by the clean-up of the extract using solid phase extraction columns and finally, the determination of acrylamide using UPLC–MS/MS. The MS/MS detection was carried out using an ESI interface in positive ion mode. Internal calibration was used for the quantification of acrylamide, because of the suppression/enhancement matrix effects due to the complex nature of the samples. The method performance characteristics were determined after spiking blank samples. The mean recoveries in spiked coffee samples, potato chips, breakfast cereals and crispbread ranged from 93% to 99%, with RSDs lower than 5% for both repeatability and reproducibility conditions. The estimated limits of detection and quantification of the method were 10 and 32 μg kg^?1, respectively. The method was used for monitoring acrylamide in 406 samples. Acrylamide amounts ranged from <32 to 2450 μg kg^?1. A total of 360 samples (89%) were contaminated with acrylamide, but only 14% of the samples exceeded the benchmark levels of the EU legislation. Foods with the highest mean acrylamide amounts were potato crisps (642 μg kg^?1), French fries (383 μg kg^?1) and biscuits (353 μg kg^?1). The mean and 95th percentile acrylamide exposures of adolescents in Cyprus were 0.8 and 1.8 μg kg^?1 body weight per day, respectively. The estimated levels of dietary exposure to acrylamide are not of concern with respect to neurotoxicity. However, the margins of exposure (MOEs) indicate a concern for carcinogenicity. Potato fried products (45%), fine bakery ware (21%) and potato chips (14%) contributed the most to overall acrylamide exposure.     

Upconversion Nanoparticles Capped with Molecularly Imprinted Polymer as Fluorescence Probe for the Determination of Ractopamine in Water and Pork

A novel fluorescence probe was designed and synthesized to quantify ractopamine in foods using molecularly imprinted polymer (MIP) as a specific recognition element and YF₃:Yb³⁺, Er³⁺ upconversion nanoparticles (UCNPs) as a fluorescence signaling component. The developed UCNP@MIP probe was characterized using X-ray powder diffraction, scanning electron microscopy, and thermogravimetric analysis. The fluorescence of UCNP@MIP probe was quenched specifically by ractopamine, and good linear regression ranging from 1.66 × 10^?8 to 3.3 × 10^?7 mol/L was obtained with the limit of detection of 8.6 × 10^?10 mol/L. This method was further applied to determine ractopamine in water and pork samples. Recoveries between 76.61 and 88.97% were obtained with relative standard deviation ranging from 1.15 to 2.67% (n = 3). This UCNP@MIP probe combined high selectivity of MIP and high sensitivity of upconversion fluorophore and showed potential to determine various food chemical hazards.     

Isotope Internal Standard Method for Determination of Four Acrylamide Compounds in Food Contact Paper Products and Food Simulants by Ultra-High Performance Liquid Chromatography Tandem Mass Spectrometry

A new method was developed for the determination of four acrylamide compounds (acrylamide, methacrylamide, N-methylol acrylamide, N-(Methoxymethyl)methacrylamide) in food contact paper products, three kinds of water-based food simulants, and dry food simulant (modified polyphenylene oxide, MPPO) by using ultra-high performance liquid chromatography tandem mass spectrometry (UPLC-MS/MS). Acetonitrile was used as the extraction solvent for different kinds of samples. The extraction solution of paper products was purified with QuEChERS technology. Four analytes were separated by gradient elution in a UPLC HSS T3 column (100 mm?×?2.1 mm, 1.8 μm) with methanol and 0.1 % formic acid water as mobile phases, and then detected in electrospray ionization mode of MS/MS with multiple reaction monitoring (MRM). Under the optimal conditions, the calibration curves for four analytes were linear within the range of 1.0–200 μg/L and the correlation coefficients were higher than 0.998. The quantitation limits of the method (S/N?=?10) of four analytes were in the range of 0.3–20 μg/kg. The mean recoveries for five sample matrixes at three spiked concentration levels of 0.3–200 μg/kg were in the range of 81–108 % with the relative standard deviations (RSDs, n?=?6) values ranging from 2.5 to 7.1 %. The developed method is accurate, simple and rapid, which can be applied to the determination of acrylamide compounds in food contact paper products and food simulants.     

Application of Vacuum Frying as a Furan and Acrylamide Mitigation Technology in Potato Chips

Consumers like fried snacks, and taste, color, and texture are key aspects in their preference. However, during frying of foods some toxic compounds, such as furan and acrylamide, are produced. The objective of this work was to mitigate furan and acrylamide formation in potato chips, without affecting their main quality attributes, by using vacuum frying. To accomplish this purpose, potato slices were fried at atmospheric (P _abs 29.92 inHg) and vacuum conditions (P _abs 3.00 inHg), using equivalent thermal driving forces (T _{water boiling point} ? T _oil = 50, 60, or 70 °C). Furan and acrylamide concentration, oil content, and texture of both atmospheric and vacuum-fried samples were determined. Vacuum-fried potato chips showed reductions of about 81, 58, and 28% of furan, acrylamide, and oil content, respectively, when compared to their atmospheric counterparts. Additionally, the texture was not affected (p > 0.05) by changes in the pressure during frying. Results clearly showed that vacuum frying is an effective technology for furan and acrylamide mitigation in potato chips, since it reduces the content of both contaminants and preserves the quality attributes of fried snacks.     

Highly Selective Determination of Chrysoidine in Foods Through a Surface Molecularly Imprinted Sol–Gel Polymer Solid-Phase Extraction Coupled with HPLC

A highly selective determination method for chrysoidine, an industrial azoic dye banned in foods, was developed through a novel molecularly imprinted polymer (MIP) online solid-phase extraction coupled with high-performance liquid chromatography. The MIP was firstly synthesized by a surface molecular imprinting technique in combination with a sol–gel process and characterized by FT-IR and adsorption experiments. The MIP exhibited high selectivity and high adsorption capacity for chrysoidine and offered a fast kinetics for the adsorption and desorption of chrysoidine. A number of parameters, including the pH of loading solution, the sample loading flow rates, and eluting time of analyte, were carefully optimized to improve the extraction efficiency. Under the optimal experimental conditions, for a 50-mL sample solution, the enrichment factor was 279 and the detection limit (S/N?=?3) was 6 ng L^?1. The linear plots with r ²?>?0.99 were achieved over a range of 0.04–40 μg L^?1, and the peak area precision (relative standard deviation) for nine parallel determinations was below 6.32 %. This method was employed for quantitative determination of chrysoidine in oil bean curd, yellow croaker, and paprika with satisfactory recoveries (89.3–97.6 %).     

An experimental set-up for studying acrylamide formation in potato crisps

The objective of this work was to set up lab-scale equipment for production of crisps mimicking industrial conditions. Slices of Saturna potatoes were deep-fat fried for 2-4.5 min at 160 °C. A solid phase extraction method for acrylamide from potato crisps was used, and the extraction recovery was calculated to 95%. Acrylamide was analysed using liquid chromatography tandem mass spectrometry. The relative standard deviation was below 3% for analyses performed on the same day and below 5% for inter-day analyses. The limit of quantification was estimated to be 160 μg/kg potato crisps. The colour of potato slices was determined using a digital imaging method and related to the acrylamide content. There were tendencies that L*(lightness) decreased and that that a*(redness) and b*(yellowness) increased with increasing acrylamide content. In another experiment, potatoes with different glucose levels were fried for 4 min but no significant difference in acrylamide content (2200-2800 μg/kg) was observed. The experiment was repeated after three months of storage. The levels of acrylamide increased significantly to 8200-13200 μg/kg. The potatoes had been fertilized with different levels of nitrogen, but no relation was found between the nitrogen supplied and the acrylamide content. The experimental set-up was shown to give realistic and reproducible experimental data, regarding colour, water content and acrylamide levels. It will be used together with the analytical methods as a platform for further research on the formation of acrylamide.     

Preparation and Application of a Molecular Imprinting Matrix Solid Phase Dispersion Extraction for the Determination of Olaquindox in Chicken by High Performance Liquid Chromatography

In this paper, a new method was established to extract olaquindox in chicken by matrix solid phase dispersion extraction using the molecularly imprinted polymers as solid phase materials. The polymers were prepared using olaquindox as the template, methacrylic acid as the functional monomer, and ethylene glycol dimethacrylate as the cross-linking agent. The imprinted material was characterized by static and kinetic adsorption experiments. The results showed that it had good recognition, selective ability, and fast adsorption–desorption dynamics for olaquindox. The prepared material was used as solid phase materials of matrix solid phase dispersion to enrich the olaquindox and then determined by high performance liquid chromatography. Under the optimized conditions, the range of recovery spiked with olaquindox at 1.0 and 2.0 μg?g^?1 levels was between 85.3 and 93.2 %.     

Functionalized β-Cyclodextrin Polymer Solid Phase Extraction Coupled with UV–Visible Spectrophotometry for Analysis of Kaempferol in Food Samples

Functionalized β-cyclodextrin polymer, mono-6-deoxy-6-imidazole-β-cyclodextrin polymer (β-CDIMCP), was synthesized as a new solid phase adsorbent coupled with UV–visible spectroscopy to separate/analyze trace kaempferol. The results showed that kaempferol was adsorbed rapidly by β-CDIMCP (adsorption efficiency, 94.7 %) and then eluted by methanol (elution efficiency, 93.4 %). Under the optimum conditions, the calibration curve was linear in the concentration range from 0.10 to 14.0 μg/mL, with a correlation coefficient (R) of 0.9965. And the limit of detection was 0.028 μg/mL for kaempferol. The preconcentration factor of the method was tenfold. The molecular interaction between β-CDIMCP and kaempferol was studied through inclusion constant and FTIR analysis. The present method had been successfully applied to determine kaempferol in red wine samples.     

Determination of acrylamide in potato chips by a reversed-phase LC–MS method based on a stable isotope dilution assay

Potato-based products represent an important part of the daily intake of food-derived acrylamide, mainly on adolescent population from western countries. A reversed-phase liquid chromatography-mass spectrometry based on a stable isotope dilution assay was used for acrylamide analysis. Aqueous sample extraction, cleaning with Carrez solution and solid phase extraction with methanol was applied. The ratio potato/NaCl solution is critical during extraction where the optimum ratio is 0.125 g/ml NaCl 2 M solution. The use of virgin olive oil, as retaining matrix, during methanol desiccation was critical to achieve high recoveries. The method performance was validated for limit of detection (23.2 μg/kg) and quantitation (91.8 μg/kg), linearity (r > 0.999, 25–1000 μg/kg), recovery (98.8%). The method was applied on commercial potato chips; the intra-day repeatability was set at 3.9% and values were corrected with a labeled internal standard (¹³C₃-acrylamide). No significant differences on the acrylamide content were observed between industrial-scale and local-scale processed potato chips.     

A Simple and Efficient Electrochemical Sensor for Nitrite Determination in Food Samples Based on Pt Nanoparticles Distributed Poly(2-aminothiophenol) Modified Electrode

Pt nanoparticles were embedded into an electroactive polymer layer to modify the Au electrode and to fabricate a novel catalyst electrode. Cyclic voltammetry was performed to form the electroactive polymer, poly(2-aminothiophenol) (PATP), and deposit the Pt nanoparticles, separately. Cyclic voltammetry of the 2-aminothiophenol self-assembled monolayer on Au was conducted, and Pt nanoparticles were incorporated into film of PATP by the electrolysis of a solution of PtCl₄. Thus, newer catalyst electrode, Au/PATP-Pt_nano, was fabricated. Various analytical techniques have been used for probing the process of reduction of platinic metal precursors (X-ray diffractometer and field emission transmission electron microscope). The results indicate the presence of uniformly distributed Pt nanoparticles of the sizes d _n?=?23 nm in the Au/PATP-Pt_nano. Electroactivity of Au/PATP-Pt_nano for oxidation of nitrite was evaluated in phosphate buffer (pH 4.0). An oxidation peak at 750 mV with an enhanced peak current was observed for the oxidation nitrite. Differential pulse voltammetry studies reveal that the current response is repeatable and stable and offers a linear dependence over a wide range of nitrite concentrations from 3 μmol/L to 1 mmol/L with a detection limit of 1 μmol/L. The kinetic parameters of these process at Au/PATP-Pt_nano were calculated, i.e., k was 0.75 cm/s and (1???α)n _α was 0.52 for the nitrite oxidation. The proposed method was successfully applied in the detection of nitrite in real samples.     

Rapid determination of Alternaria mycotoxins in tomato samples by pressurised liquid extraction coupled to liquid chromatography with fluorescence detection

ABSTRACT

A sensitive and reliable method using pressurised liquid extraction (PLE) followed by molecularly imprinted solid phase extraction (MISPE) and high performance liquid chromatography with fluorescence detection (HPLC–FLD) has been developed for the analysis of alternariol (AOH) and alternariol monomethyl ether (AME) in tomato samples. Influence of several extraction parameters that affect PLE efficiency were evaluated for the simultaneous extraction of both mycotoxins in the selected samples. AOH and AME were optimally extracted using MeOH/water (25:75, v/v) at 70°C as solvent, a pressure of 1000 psi and a single extraction cycle. The resulting PLE extracts were pre-concentrated by molecularly imprinted solid phase extraction (MISPE) cartridges followed of analysis by HPLC with fluorescence detection (λ_exc = 258, λ_em = 440 nm). The proposed method was applied to the analysis of AOH and AME in fortified tomato samples (20–72 µg· kg–1) with recoveries of 84–97% (RSD < 8%, n = 6) for AOH and 67–91% (RSD < 13%, n = 6) for AME. The detection limit for AOH and AME were 7 and 15 µg· kg^–1, respectively. The ensuing PLE–MISPE–HPLC–FLD method was validated for the analysis of both mycotoxins in tomato samples in accordance with European Commission Decision 2002/657/EC.     

Detection of chloramphenicol in chicken,pork and fish with a molecularly imprinted polymer-based microtiter chemiluminescence method

In this study, 4-nitrotoluene (NT) was used as dummy template to synthesize a molecularly imprinted polymer that was highly specific for chloramphenicol. The polymer was coated in the wells of 96-well microplates as recognition reagent to develop a chemiluminescence method. The analyte solution and an enzyme-labelled hapten were added into the wells to perform competition, and the light signal was induced with a highly efficient luminol-H₂O₂-4-(imidazol-1-yl)phenol system. Then, the optimized method was used to determine chloramphenicol in meat (chicken, pork and fish), and the limit of detection (LOD) was 5.0 pg g^?1. Furthermore, the polymer-coated plate could be reused four times, and one test could be finished within 20 min. The recoveries from the standard fortified blank meat samples were in the range of 71.5–94.4%. Therefore, this method could be used as a useful tool for routine screening the residue of chloramphenicol in meat samples.