•A multi-class multi-residue analytical method for veterinary drugs was developed.•A total of 132 veterinary drugs from almost 15 classes were investigated.•A magnetic hypercrosslinked ...polystyrene-based MSPE was developed.•The methodology was applied to the trace drug analysis of milk.
A quantitative multi-class multi-residue analytical method was developed for the determination of veterinary drugs in milk by high-performance liquid chromatography – tandem mass spectrometry (HPLC-MS/MS). A total of 132 veterinary drugs investigated belonged to almost 15 classes including sulfonamides, β-lactams, tetracyclines, quinolones, macrolides, nitrofurans, nitroimidazoles, phenicols, lincosamides, pleuromutilins, macrocyclic lactones, quinoxaline antibiotics, benzimidazoles, anthelmintics, coccidiostats and some others. A magnetic solid-phase extraction procedure was developed using magnetic hypercrosslinked polystyrene (HCP/Fe3O4) for the sample preparation prior to HPLC-MS/MS without deproteinization step. The results indicated recoveries of 85–107% for 14 sulfonamides, 85–120% for 13 β-lactams, 89–115% for 4 tetracyclines, 82–119% for 14 quinolones, 82–115% for 8 macrolides, 97–109% for 4 nitrofurans, 84–115% for 10 nitroimidazoles, 89–114% for 3 phenicols, 86–111% for 3 lincosamides, 97–102% for 2 pleuromutilins, 72–88% for 4 macrocyclic lactones, 87–104% for 4 quinoxaline antibiotics, 76–119% for 21 benzimidazoles, 79–115% for 12 anthelmintics, 81–118% for 12 coccidiostats and 75–119 % for 5 unclassified drugs, with relative standard deviations (RSDs) of less than 20%, and the LOQs ranged from 0.05 to 1 μg kg−1. This methodology was then applied to field-collected real milk samples and trace levels of some veterinary drugs were detected.
A rapid multi-residue LC-MS/MS method for the identification and determination of banned veterinary drugs in honey was developed. A total of 31 investigated veterinary drugs belonging to 4 classes ...including nitrofurans metabolites, nitroimidazoles, amphenicols, and quinolones were quantified by LC-MS/MS with ESI using one single injection. The sample preparation included treatment with 5-nitro-2-furaldehyde (5-NFA) in a thermostated ultrasonic bath (80 °C, 0.5М НСl, 20 min) to liberate matrix-bound residues of nitrofurans. Magnetic hypercrosslinked polystyrene (HCP/Fe3O4) was proposed for the solid-phase extraction and clean-up of target analytes prior to LC-MS/MS analysis. To evaluate and validate the performance of method, the criteria of the Decision (EC) no 2002/657 were applied. The LOQs of the examined analytes range from 0.3 to 1 μg kg-1, which indicates good sensitivity to quantify the target compounds in honey. The recoveries of veterinary drugs from 1 g of honey with 50 mg of the sorbent are 97-109% for nitrofuran metabolites, 84-115% for nitroimidazoles, 86-103% for amphenicols, and 97-118% for quinolones. The relative standard deviations of intra-day and inter-day precision analyses (RSD) are less than 16%. This methodology was applied to real honey samples and trace levels of some veterinary drugs were detected.
Effect of amines on formation of gold nanoparticles (AuNPs)/polymer nanocomposites has been observed and studied. Nanocomposites based on polyurethane foam and AuNPs were synthesized by interaction ...between the polymer modified with sodium borohydride and aqueous solution of tetrachloroauric acid. It has been shown that some amines cause a remarkable decrease of the surface plasmon resonance band of AuNPs in the nanocomposite material. Both aliphatic and aromatic amines as well as amines containing several amino groups were studied. A possible mechanism of the effect is discussed. It is probably based on stabilization of AuNPs with an amine that entails a decrease in the degree of their adsorption on PUF and appearance of the stabilized AuNPs in solution. The decrease of the nanocomposite surface plasmon resonance band is proportional to the concentration of amine in the solution. Based on this effect, a method for the determination of cetylamine, β-naphthylamine and neomycin in water and medical formulations using a monitor calibrator as a portable household tool is proposed. Under the selected conditions, the detection limits for amines were in the range of 0.7–1.5 μM, the determination ranges were approximately an order of magnitude. The observed color change of the nanocomposite samples also provides a good basis for semiquantitative determinations.
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•Au/polyurethane nanocomposites were prepared using the polymer modified with borohydride.•Amines cause a decrease of a surface plasmon resonance band of an Au nanocomposite.•Both aliphatic and aromatic amines/polyamines prevent formation of gold nanoparticles.•A method for the determination of amines using a household monitor calibrator was proposed.•The observed nanocomposite color change also suggests naked-eye detection.
We proposed a procedure for the rapid sample preparation of food samples for the determination of nitrofuran metabolites in them by HPLC–MS/MS, using 5-nitro-2-furaldehyde as a new derivatizing ...agent. Meat samples from broiler chickens treated with nitrofurans for 10 days were used to demonstrate that the time of hydrolysis–derivatization in a thermostated ultrasonic bath could be significantly shortened by raising temperature to 80°C and increasing the concentration of hydrochloric acid to 0.5 M. Metabolites of Furaltadone, Furazolidone, Nitrofurantoin, and Nitrofurazone in chicken meat, liver, stomach, and heart are determined using the developed procedure and an official method. The proposed method ensures the quantitative isolation of metabolites.
Hypercrosslinked polystyrene is proposed for the multicomponent solid-phase extraction of residues of 63 veterinary preparations from various classes (sulfonamides, tetracyclines, quinolones, ...amphenicols, nitroimidazoles, β-lactams, macrolides, lincosamides, and pleuromutilins) in their determination in chicken meat by HPLC–tandem mass spectrometry. Sample preparation includes the extraction of analytes with a McIlvaine buffer solution, fat removal by extraction with hexane, and the further purification of the extracts on cartridges with hypercrosslinked polystyrene. The method ensures the quantitative extraction of analytes (recovery rates are from 83 to 117%) and good reproducibility (RSD ≤ 12%). Veterinary preparations were identified by the exact masses of analyte ions formed in electrospray ionization on switching positive and negative polarity. The matrix effect for all veterinary drugs was below 20%. The determination was carried out by the method of matrix calibration; the limits of detection and determination were 0.01–0.3 and 0.02–1 ng/g, respectively. An analysis of contaminated chicken meat samples showed that the results are in satisfactory agreement with the data obtained by the methods adopted in the Russian Federation for the determination of various groups of antibiotics.
5-Nitro-2-furaldehyde is proposed as a new derivatizing agent for determining four nitrofuran metabolites: 3-amino-2-oxazolidinone, 3-amino-5-methylmorpholino-2-oxazolidinone, 1-aminohydantoin, and ...semicarbazide in chicken eggs by HPLC with tandem mass spectrometric detection. The derivatization products were identified; they are the initial nitrofurans: furazolidone, furaltadone, nitrofurantoin, and nitrofurazone, respectively. Sample preparation includes acid hydrolysis, derivatization, fat removal by hexane extraction, and the further purification of the extracts on cartridges packed with Diapak P-3 hypercrosslinked polystyrene. The method ensures the quantitative isolation of metabolites (recovery rates are 95 to 106%) and good reproducibility (RSD ≤ 13%).
A chemical method is proposed for obtaining a nanocomposite based on gold nanoparticles (
AuNP
) and polyurethane foams (
PUF
). It includes the sorption of a reducing agent, sodium borohydride, on ...PUF from a solution containing sodium hydroxide as a stabilizer and cetyltrimethylammonium bromide as an ion-pair reagent, and the subsequent interaction of the modified polymer with chloroauric acid, leading to the formation of a colored nanocomposite. A possibility of using the process of the formation of a nanocomposite based on AuNP and PUF for the determination of melamine in milk powder and milk powder substitute by diffuse reflectance spectroscopy is evaluated. It is found that melamine affects the formation of this nanocomposite, causing a decrease in the intensity of the surface plasmon resonance band of gold nanoparticles in the material. It is proposed to use this effect for the determination of melamine by diffuse reflectance spectroscopy. The influence of the interaction time, the pH of the solution, and the concentration of chloroauric acid on the analytical signal, as well as the interfering effect of amino acids in the determination of melamine, are investigated. Under the chosen conditions, the limit of detection for melamine was 0.2 mg/L.
The present work describes preparation of polyurethane foam modified with borohydride. Adsorption of borohydride from alkaline solutions in presence of a cationic surfactant is discussed. The ...polyurethane foam modified with borohydride possesses reductive ability with respect to Au(III). Possibilities of the new material for synthesis of gold nanoparticles are described. This solid reducting agent is convenient for use in the synthesis of nanoparticles, since it ensures precise dosing of a reductant while desorbed from polymer. Gold nanoparticles can be synthesized both in solution and on the polymer surface by varying reagents concentrations during the preparation of modified polyurethane foam.
•Current trends in LC-MS/MS determination of NF metabolites in food are considered.•Main approaches to sample preparation of food are discussed.•Multi-class, multi-residue methods for NF metabolites ...determination are considered.•Future trends in food analysis during NF metabolites determination are outlined.
Nitrofurans (NFs) are synthetic broad-spectrum antibacterial and antiparasitic drugs, which recently were extensively used in veterinary practice. In the body of animals, NFs are converted into carcinogenic and mutagenic metabolites that can be accumulated in foods of animal origin having an adverse effect on human health. Therefore, NFs are currently banned in animal husbandry and aquaculture of many countries. However, the data from monitoring the quality of food products indicate that, despite the prohibitions established by the law, they still are used not only in the developing countries but also in the European Union, due to their high antibacterial activity, low cost, and accessibility. Thus, it is of great importance for human health to develop reliable and sensitive analytical methods for monitoring NF metabolites in animal-derived foods. The objective of this review is to summarize the pretreatment strategies and chromatographic methods that have been reported during the last decade for the determination of NF metabolites in food samples, and to outline the future trends with an emphasis on the novel solutions in this area.
In this study, 5-nitro-2-furaldehyde (5-NFA) was proposed as a new derivatizing agent for nitrofuran metabolites. It reacts with nitrofuran metabolites producing the parent nitrofurans (furazolidone, ...furaltadone, nitrofurantoin, and nitrofurazone). Magnetic hypercrosslinked polystyrene (HCP/Fe3O4) was first used for magnetic solid phase extraction (MSPE) clean-up before the determination of nitrofuran metabolite derivatives in honey via LC–MS/MS. Main parameters affecting the derivatization and MSPE efficiency were investigated in detail and the optimal conditions were found. The method was validated using honey spiked with the four metabolites at 1, 2 and 200 μg kg−1. Recoveries of >85% were achieved for the all analytes. The matrix calibration curve was fitted with the correlation coefficient (R2) > 0.99 in the range of 1–200 μg kg−1. Precision values expressed as relative standard deviation (RSD) were <12% and <15% for intra-day and inter-day precision, respectively. The limits of detection (LODs) for the nitrofuran metabolites were of 0.1–0.3 μg kg−1 and the limits of quantitation (LOQs) were of 0.3–1.0 μg kg−1. The proposed LC–MS/MS method was applied to the analysis of real honey samples.
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•5-Nitro-2-furaldehyde was proposed as a derivatizing agent for nitrofuran metabolites.•Magnetic hypercrosslinked polystyrene was first used for MSPE of nitrofurans.•The magnetic adsorbent showed good extraction efficiency towards nitrofurans.•With 5-NFA, one can select conditions for MSPE and determination using nitrofurans.•The proposed method speeds up the analysis and reduces its cost.
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