Two {CuI[P4Mo6]2}-Based Coordination Polymers Incorporating In Situ Converted Tetrapyridyl Ligands for Trace Analysis of Nitrofuran Antibiotics.

Nitrofurans are important synthetic broad-spectrum antibacterial drugs with the basic structure of 5-nitrofuran. Due to their toxicity, it is essential to develop a sensitive sensor with strong anti-interference capabilities for their detection. In this work, two {P4Mo6O31}12--based compounds, [H4(HPTTP)]2{CuI[Mo12O24(OH)6(PO4)3(HPO4)(H2PO4)4]}·xH2O (x = 13 for (1), 7 for (2); HPTTP = 4,4',4″,4‴-(1H-pyrrole-2,3,4,5-tetrayl)tetrapyridine), exhibiting similar coordination but distinct stacking modes. Both compounds were synthesized and used for the electrochemical detection of nitrofuran antibiotics. The tetrapyridine-based ligand was generated in situ during assembly, and its potential mechanism was discussed. Composite electrode materials, formed by mixing graphite powder with compounds 1-2 and physically grinding them, proved to be highly effective in the electrochemical trace detection of furazolidone (FZD) and furaltadone hydrochloride (FTD·HCl) under optimal conditions. Besides, the possible electrochemical detection mechanisms of two nitro-antibiotics were studied.

Stable Europium(III) Metal-Organic Framework Fluorescence Probe for Intelligent Visualization Detection of Gossypol and Nitrofuran Antibiotics in Real Samples.

Gossypol (Gsp) and antibiotics present in water bodies become organic pollutants that are harmful to human health and the ecological environment. Accurate and effective detection of these pollutants has far-reaching significance in many fields. A new three-dimensional metal-organic framework (MOF), {[Eu3(L)2(HCOO-)(H2O)3]·2H2O·2DMF}n (Eu-MOF), was synthesized from 3,5-bis(2,4-dicarboxylphenyl)nitrobenzene (H4L) ligand and Eu3+ via the solvothermal method in this paper. The Eu-MOF demonstrates strong red fluorescence and can remain stable in different pH solutions. The MOF fluorescence probe could detect organic pollutants through the "shut-off" effect, with a fast response speed and a low detection limit [Gsp, nitrofurantoin (NFT), and nitrofurazone (NFZ) for 0.43, 0.38, and 0.41 µM, respectively]. During the testing process, Eu-MOF exhibited good selectivity and recoverability. Furthermore, the mechanism of fluorescence quenching was investigated, and the recoveries were also good in real samples. This paper introduced a deep learning model to recognize the fluorescence images, a portable intelligent logic detector designed for real-time detection of Gsp by logic gate strategy, and an anticounterfeiting mark prepared based on inkjet printing. Importantly, this work provides a new way of thinking for the detection of organic pollutants in water with high sensitivity and practicality by combining the fluorescence probe with machine learning and logical judgment.

Rapid Apta-Chromogenic Detection Method for Nitrofuran Metabolite Determination.

Nitrofuran (NF) contamination in food products is a global problem resulting in the banned utilization and importation of nitrofuran contaminated products. A novel chromogenic detection method using a specific DNA aptamer with high affinity and specificity to nitrofurans was developed. Single-stranded DNA aptamers specific to nitrofuran metabolites, including 3-amino-2-oxazolidinone (AOZ), 3-amino-5-methylmorpholino-2-oxazolidinone (AMOZ), and 1-aminohydantoin (AHD), were isolated using magnetic bead-SELEX. The colorimetric detection of nitrofurans using gold nanoparticles (AuNPs) exhibited an AOZ detection range of 0.01-0.06 ppb with a limit of detection (LOD) of 0.03 ppb. At the same time, this system could detect AMOZ and AHD at a range of 0.06 ppb and 10 ppb, respectively. The fast nitrofuran extraction method was optimized for food, such as fish tissues and honey, adjusted to be completed within 3-6 h. This novel apta-chromogenic detection method could detect NF metabolites with a sensitivity below the minimum required performance limit (MPRL). This analysis will be valuable for screening, with a shortened time of detection for aquaculture products such as shrimp and fish muscle tissues.

Development and validation of a rapid LC-MS/MS method for the confirmatory analysis of the bound residues of eight nitrofuran drugs in meat using microwave reaction.

A rapid analytical method was developed and validated for the analysis of eight bound nitrofurans in animal tissue, shortening laboratory turnaround times from 4 to 2 days. The majority of methodologies for nitrofuran analysis focus on the detection of only four drugs (nitrofurantoin, furazolidone, furaltadone and nitrofurazone), and is time-consuming given the 16-h overnight derivatisation step and a double liquid-liquid extraction. In this study, the narrow scope of analysis was addressed by including further four important nitrofuran drugs (nifursol, nitrofuroxazide, nifuraldezone and nitrovin). Full chromatographic separation was achieved for the metabolites of all eight nitrofurans, using phenyl-hexyl column chemistry and a rigorous optimisation of the mobile phase additives and gradient profile. The conventional, lengthy sample preparation was substantially shortened by replacing the traditional overnight water bath derivatisation with a rapid 2-h microwave-assisted reaction, followed by a modified-QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) extraction. This confirmatory method was fully validated in accordance with the new 2021/808/EC legislation, and was shown to perform satisfactorily when applied to incurred tissues. The decision limit (CCα) for the eight analytes ranged between 0.013 and 0.200 µg kg-1, showing abundant sensitivity given that the current RPA for nitrofurans is 0.5 µg kg-1. This innovative method can play a major role in the surveillance of the illegal use of nitrofuran drugs.

One High-Nuclearity Cd(II)-Yb(III) Nanoring with Near-IR Luminescent Sensing to Antibiotics.

One 12-metal Cd(II)-Yb(III) nanoring, [Cd8Yb4L8(OAc)8]·4OH (1), with a size of 1.2 × 2.8 × 2.8 nm was obtained from a designed flexible salen-type ligand that has eight coordination sites (O and N atoms). The near-IR emission of Yb(III) at 983 nm was detected upon the excitation of ligand-central absorption at 386 nm. This Cd(II)-Yb(III) nanoring exhibits high sensitivity to nitrofuran antibiotics (NFAs) even in the presence of other antibiotics. The quenching constants and limits of detection of NFAs are 2.5 × 104-4.5 × 104 M-1 and 1.5-2.8 µM, respectively.

Construction of a 18-Metal Neodymium(III) Nanoring with NIR Luminescent Sensing to Antibiotics.

One 18-metal Nd(III) nanoring, [Nd18(L1)8(HL2)2(OAc)20(MeOH)8(EtOH)6(H2O)4]·2(MeOH)·6(H2O) (1), was constructed by the use of a hexadentate Schiff base ligand. For 1, the near-infrared (NIR) luminescence of Nd(III) was detected under the excitation of absorption band at 371 nm. The study of luminescent sensing properties exhibits that, even with the existence of other antibiotics, this Nd(III) nanoring displays high sensitivity and selectivity to nitrofuran antibiotics (NFAs). The luminescence quenching constants and limits of detection of 1 to NFAs are found to be 1.4 × 104 to 3.5 × 104 M-1 and 0.9-2.2 µM, respectively.

A multiplex immunochromatographic test using gold nanoparticles for the rapid and simultaneous detection of four nitrofuran metabolites in fish samples.

There is an urgent need for the rapid and simultaneous detection of multiple analytes present in a sample matrix. Here, a multiplex immunochromatographic test (multi-ICT) was developed that successfully allowed for the rapid and simultaneous detection of four major nitrofuran metabolites, i.e., 3-amino-2-oxazolidinone (AOZ), semicarbazide (SEM), 3-amino-5-methylmorpholino-2-oxazolidinone (AMOZ), and 1-aminohydantoin (AHD), in fish samples. Four different antigens were separately immobilized in four test lines on a nitrocellulose membrane. Goat anti-mouse immunoglobulin (IgG) was used as a control. Sensitive and specific monoclonal antibodies (mAbs) that recognize the corresponding antigens were selected for the assay, and no cross-reactivity between the antibodies in the detection assay was observed. The free analytes in samples or standards were pre-incubated with freeze-dried mAb-gold conjugates to improve the sensitivity of the detection assay. The multi-ICT detection was accomplished in less than 15 min by the naked eye. The cutoff values for the strip test were 0.5 ng/mL for AOZ and 0.75 ng/mL for AHD, SEM, and AMOZ, which were all below the maximum residue levels set by the European Union and China. A high degree of consistency was observed between the multi-ICT method and commercially available enzyme-linked immunosorbent assay (ELISA) kits using spiked, incurred, and "blind" fish samples, indicating the accuracy, reproducibility, and reliability of the novel test strip. This newly developed multi-ICT strip assay is suitable for the rapid and high-throughput screening of four nitrofuran metabolites in fish samples on-site, with no treatment or devices required. Graphical abstract A multiplex immunochromatographic test (multi-ICT) was developed that successfully allowed for the rapid and simultaneous detection of four major nitrofuran metabolites (AOZ, SEM, AMOZ, and AHD) in fish samples.

A Lanthanide MOF Thin-Film Fixed with Co3 O4 Nano-Anchors as a Highly Efficient Luminescent Sensor for Nitrofuran Antibiotics.

Nitrofurans are a group of widely used veterinary antibiotics, which have been banned due to antibiotics pollution. Development of a rapid and effective method for the detection of nitrofuran antibiotics (NFAs) is an important challenge. Herein, we designed a chemical sensor based on a thin-film composed of the lanthanide metal-organic framework (Ln-MOF) {[Eu2 (BCA)3 (H2 O)(DMF)3 ]⋅0.5DMF⋅H2 O}n (Eu-BCA, in which BCA is 2,2'-biquinoline-4,4'-dicarboxylate) coated on a cost-effective stainless steel wire mesh (SSWM) by Co3 O4 nano-anchor fixation method. The MOF coatings were well adhered to the SSWM, resulting in a three-dimensional porous, flexible, and processable sensor. The structure of the as-prepared MOF thin-film was confirmed by powder X-ray diffraction (PXRD), and the surface morphology was examined by scanning electron microscopy (SEM). Significantly, the Eu-BCA thin-film was highly selective and sensitive to NFAs, and yet remained unaffected by other common antibiotics that may be present. The limits of detection for nitrofurantoin (NFT) and nitrofurazone (NFZ) are 0.21 and 0.16 µm, respectively. NFAs were also successfully detected in water from the Pearl River in Guangzhou, and from bovine serum samples. Hence, the reported Ln-MOF thin-film is a promising sensor for the detection of NFAs, thereby helping to protect human beings from all manner of hazards that arise from the abuse of antibiotics in livestock breeding.

Determination of a metabolite of nifursol in foodstuffs of animal origin by liquid-liquid extraction and liquid chromatography with tandem mass spectrometry.

An analytical method has been developed for the detection of a metabolite of nifursol, 3,5-dinitrosalicylic acid hydrazide, in foodstuffs of animal origin (chicken liver, pork liver, lobster, shrimp, eel, sausage, and honey). The method combines liquid chromatography and tandem mass spectrometry with liquid-liquid extraction. Samples were hydrolyzed with hydrochloric acid and derivatized with 2-nitrobenzaldehyde at 37°C for 16 h. The solutions of derivatives were adjusted to pH 7.0-7.5, and the metabolite was extracted with ethyl acetate. 3,5-Dinitrosalicylic acid hydrazide determination was performed in the negative electrospray ionization method. Both isotope-labeled internal standard and matrix-matched calibration solutions were used to correct the matrix effects. Limits of quantification were 0.5 µg/kg for all samples. The average recoveries, measured at three concentration levels (0.5, 2.0, and 10 µg/kg) were in the range of 75.8-108.4% with relative standard deviations below 9.8%. The developed method exhibits a high sensitivity and selectivity for the routine determination and confirmation of the presence of a metabolite of nifursol in foodstuffs of animal origin.

Lateral flow biosensor for multiplex detection of nitrofuran metabolites based on functionalized magnetic beads.

The use of potential mutagenic nitrofuran antibiotic in food animal production has been banned world-wide. Common methods for nitrofuran detection involve complex extraction procedures. In the present study, magnetic beads functionalized with antibody against nitrofuran derivative were used as both the extraction and color developing media in lateral flow biosensor. Derivatization reagent carboxybenzaldehyde is firstly modified with ractopamine. After reaction with nitrofuran metabolites, the resultant molecule has two functional groups: the metabolite moiety and the ractopamine moiety. Metabolite moiety is captured by the antibody that is coated on magnetic beads. This duplex is then loaded onto biosensor and ractopamine moiety is further captured by the antibody immobilized on the test zone of nitrocellulose membrane. Without tedious organic reagent-based extraction procedure, this biosensor was capable of visually detecting four metabolites simultaneously with a detection limit of 0.1 µg/L. No cross-reactivity was observed in the presence of 50 µg/L interferential components. Graphical abstract Derivatization of nitrofuran metabolites (AHD, AOZ, SEM, or AMOZ) and LFA detection of the derivative products.

Fortified versus incurred residues: extraction of furazolidinone metabolite from prawn.

Most methods reported in the literature for determination of nitrofuran metabolites use the same extraction and derivatisation conditions to hydrolyse and extract the protein-bound residues from animal tissue. While undertaking certification of reference materials for nitrofuran metabolites in freeze-dried prawn, it was found that these conditions are satisfactory for recovery of spiked residues; however, extraction efficiencies of incurred furazolidinone could be substantially increased by further optimisation of the extraction conditions. The availability of a suitable certified reference material allows laboratories to ensure that their method is optimised for incurred residues.

Quantitative Analysis of Nitrofuran Metabolites and Chloramphenicol in Shrimp Using Acetonitrile Extraction and Liquid Chromatograph-Tandem Mass Spectrometric Detection: A Single Laboratory Validation.

A method was developed and validated for the simultaneous analysis of chloramphenicol and nitrofuran metabolites in shrimp according to the guideline established by the U.S. Food and Drug Administration Office of Foods and Veterinary Medicine. The extraction steps following the overnight hydrolysis and derivatization are simpler than the conventional ethyl acetate extraction method. The main steps are neutralization of hydrolysates, addition of acetonitrile for extraction, and salting out of organic phase from the acetonitrile-aqueous mixture. Extracts are analyzed for chloramphenicol and nitrofuran metabolites by LC-MS/MS in a single injection with polarity switching between the positive electrospray ionization (ESI) mode for the nitrofurans and the negative ESI mode for chloramphenicol. Recoveries calculated using an extracted matrix calibration curve and labeled internal standards for chloramphenicol and nitrofurans ranged from 98.6 to 109.2% with RSDs less than 18%. This method that combines the analysis of chloramphenicol with the nitrofurans was shown to generate analytical results similar to those obtained using the individual drug-class analytical methods currently used for the analysis of chloramphenicol or nitrofurans in shrimp.

Simultaneous Determination of Nitrofuran Metabolites and Chloramphenicol in Shrimp with a Single Extraction and LC-MS/MS Analysis.

A method has been developed to quantify the nitrofuran metabolites 3-amino-5-morphorinomethyl-1,3-oxazolidinone, 3-amino-oxazolidinone, 1-aminohydantoin, and semicarbazide, as well as chloramphenicol in shrimp with a single extraction procedure followed by LC-MS/MS analysis. Dynamic selected reaction monitoring with positive and negative ionization mode switching was used. The method LODs were 0.5 ng/g for the nitrofuran metabolites and 0.3 ng/g for chloramphenicol.

Quantitation of Chloramphenicol and Nitrofuran Metabolites in Aquaculture Products Using Microwave-Assisted Derivatization, Automated SPE, and LC-MS/MS.

This paper describes a rapid and robust method utilizing microwave-assisted derivatization, automated SPE, and LC-MS/MS for the quantitation and confirmation of chloramphenicol (CAP) and nitrofuran metabolites in various aquaculture matrixes. The use of equipment presented in this work allowed extractions to be completed on average within 6 h, with quantitation accuracy ranging from 89 to 107% and RSD≤8.3%. The demonstrated detection limits for all the nitrofuran metabolites of interest in three different matrixes were ≤0.06 ng/g, with a quantitation limit of ≤0.2 ng/g. Additionally, the method exhibited a CAP detection limit for all matrixes≤0.01 ng/g and an LOQ of ≤0.03 ng/g.

[Screening of compounds of nitrofuran in imported meat raw materials].

The article presents the results of screening studies of quantification of the nitrofuran drugs imported in raw meat (turkey, beef pork, veal, lamb, chicken). Identification was carried out by the detection ofsuch nitrofurans metabolites as: 1-aminogidantoin (AGD), 3-amino-2-oxazolidinone (AOZ) and 3-amino-5-morpholinomethyl-2-oxazolidinone (AMOZ). There are analyzed the positive and negative effects of nitrofuran drugs. The data for the establishment of the potential risks to human health when using contaminated raw meat metabolites of nitrofurans are discussed. These drugs are prohibited in livestock in Europe since 1995 due to the adverse effects (carcinogenic, mutagenic, teratogenic and toxic) on animals and the potential risk to humans. In the Russian Federation in accordance with SanPin 2.3.2.1078-01 01.01.2012 for the first time the was introduced rationing for nitrofurans (including furazolidone).

Simultaneous detection of three nitrofuran antibiotics by the lateral flow immunoassay based on europium nanoparticles in aquatic products.

Nitrofuran (NF) antibiotics have been banned worldwide in aquaculture due to their potential carcinogenicity and mutagenicity. Because of the short half-life of NF antibiotics, an easy and sensitive multiple lateral flow immunoassay (mLFIA) based on europium nanoparticles (EuNPs) has been successfully established to simultaneously and quantitatively detect 3-amino-5-morpholinomethyl-2-oxazolidinone (AMOZ), 3-amino-2-oxazolidinone (AOZ) and sodium nifurstylenate (NFS) in aquatic products. The EuNP-mLFIA assay was accomplished within 10 min. The limits of detection (LODs) for AOZ, AMOZ and NFS were 0.013, 0.019 and 0.023 ng/mL, respectively. The average recoveries of AOZ, AMOZ and NFS were 98.0-104.4%, 96.0-102.6% and 98.0-102.8%, respectively. It showed satisfactory consistency, and the feasibility was validated by high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). Briefly, this method will become a powerful tool for monitoring multiple NF antibiotics and provide promising applications in the field of food safety and environmental testing.

Aqueous fate of furaltadone: Kinetics, high-resolution mass spectrometry - based elucidation and toxicity assessment of photoproducts.

Furaltadone (FTD) is an antibiotic belonging to the nitrofurans group. It has been broadly used in livestock and aquaculture for therapeutic purposes, as well as for stimulating promotion. Although the European Union has imposed restrictions on the use of FTD since 1995 due to concerns regarding its toxicity, in many cases FTD has been excessively and/or illegally applied in productive animals in developing countries, because of its high efficacy and low-cost. Unlike other nitrofuran compounds, the hydrolytic and photolytic behavior of FTD in natural aquatic systems has not been thoroughly investigated. To this end, hydrolysis in different pH values and photolysis in aquatic environment, including lake, river and sea water have been both examined. Hydrolysis was found to have an insignificant impact on degradation of FTD in the aquatic environment relevant pH values, whereas indirect photolysis proved to be the main route of its elimination. The identification of tentative photoproducts (PPs) was performed using ultra high performance liquid chromatography coupled to hybrid LTQ/Orbitrap high resolution mass spectrometry. A possible pathway for photolytic transformation of FTD was proposed. Additionally, in silico simulations were used to evaluate the toxicity such as the mutagenicity of FTD and PPs. Complementary to the low-cost and time-limited simulations, an in vitro method (Vibrio Fischeri bioluminescence) was also used to assess ecotoxicity.

Alfalfa biomass as a green source for the synthesis of N,S-CDs via microwave treatment. Application as a nano sensor for nifuroxazide in formulations and gastric juice.

BACKGROUND: Researchers have investigated different techniques for synthesis of carbon dots. These techniques include Arc discharge, laser ablation, oxidation, water/solvothermal, and chemical vapor deposition. However, these techniques suffer from some limitations like the utilization of gaseous charged particles, high current, high temperature, potent oxidizing agents, non-environmentally friendly carbon sources, and the generation of uneven particle size. Therefore, there was a significant demand for the adoption of a new technology that combines the environmentally friendly aspects of both bio-based carbon sourcing and synthesis technique. RESULTS: Medicago sativa L (alfalfa)-derived N, S-CDs have been successfully synthesized via microwave irradiation. The N,S-CDs exhibit strong fluorescence (λex/em of 320/420 nm) with fluorescence quantum yield of 2.2 % and high-water solubility. The produced N,S-CDs were characterized using TEM, EDX, Zeta potential analysis, IR, UV-Visible, and fluorescence spectroscopy. The average diameter of the produced N, S-CDs was 4.01 ± 1.2 nm, and the Zeta potential was -24.5 ± 6.63 mv. The stability of the produced nano sensors was also confirmed over wide pH range, long time, and in presence of different ions. The synthesized N, S-CDs were employed to quantify the antibacterial drug, nifuroxazide (NFZ), by fluorescence quenching via inner filter effect mechanism. The method was linear with NFZ concentration ranging from 1.0 to 30.0 µM. LOD and LOQ were 0.16 and 0.49 µM, respectively. The method was applied to quantify NFZ in simulated gastric juice (SGJ) with % recovery 99.59 ± 1.4 in addition to pharmaceutical dosage forms with % recovery 98.75 ± 0.61 for Antinal Capsules® and 100.63 ± 1.54 for Antinal suspension®. The Method validation was performed in compliance with the criteria outlined by ICH. SIGNIFICANCE AND NOVELTY: The suggested approach primarily centers on the first-time use of alfalfa, an ecologically sustainable source of dopped-CDs, and a cost-effective synthesis technique via microwave irradiation, which is characterized by low energy consumption, minimized reaction time, and the ability to control the size of the produced CDs. This is in line with the growing global recognition of the implementation of green analytical chemistry principles.

Synthesis of P, N-dopped carbon nanosheets for highly sensitive fluorescence analysis of nitrofuran antibiotics in fish.

The misuse of antibiotics has caused serious impacts on food safety and human health, making it crucial to develop rapidly and highly sensitive methods for detecting trace nitrofuran antibiotics (NFs). In this study, phosphorus, nitride-doped carbon nanosheets (PN/CNs) were synthesized using a simple hydrothermal method based on graphitic carbon nitride. This prepared material showed excellent water solubility and stable optical properties. A new fluorescence sensing platform based on PN/CNs was constructed for the highly sensitive detection of four NFs. This sensitivity was mainly attributed to the fluorescence resonance energy transfer (FRET) mechanism. The limits of detection for nitrofurazone, nitrofurantoin, furazolidone and furaltadone were determined to be 13.41, 15.24, 16.37 and 19.94 nM, respectively. The high sensitivity and selectivity of PN/CNs for these four NFs were thoroughly evaluated by the Stern-Volmer equation and FRET quenching efficiency. This proposed method exhibited high sensitivity and can be successfully applied to detect NFs in fish.

A Recyclable Luminescent MOF Sensor for On-Site Detection of Insecticide Dinotefuran and Anti-Parkinson's Drug Entacapone in Various Environmental and Biological Specimens.

The monitoring and precise determination of pesticides and pharmaceutical drugs and their residues have become increasingly important in the field of food safety and water contamination issues. Herein, a fluorescent aluminium MOF-based sensor (1) was developed for the selective recognition of neonicotinoid insecticide dinotefuran and anti-Parkinson's drug entacapone. Guest-free MOF 1' exhibited ultra-fast response (<5 s) and ultra-low detection limits of 2.3 and 7.6 nM for dinotefuran and entacapone, which are lower than the previously reported MOF-based sensors. In the presence of other competitive analytes, great selectivity was achieved towards both analytes. The probe was recyclable up to five cycles. The sensing ability was explored towards entacapone in human serum, urine and dinotefuran in real soil, rice, honey samples, different fruits, vegetables, real water specimens and a wide range of pH media. A low-cost, handy MOF-based polymer thin-film composite (1'@PVDF-PVP) was developed for the on-site detection of dinotefuran and entacapone. Mechanistic studies involving analytical techniques and theoretical calculations suggested that FRET and PET are the probable reasons for entacapone sensing whereas IFE is responsible for dinotefuran detection. The entire work presents a low cost, multi-use photoluminescent sensor of entacapone and dinotefuran to address the environmental pollution.