Tetracyclines In Honey Research Articles

Integrated assessment of the spatial distribution, sources, degradation, and human risk of tetracyclines in honey in China

Tetracyclines are widely used in Chinese apiculture. However, limited information is available on the presence of tetracycline residues in honey and the sources, degradation patterns, and associated health risks of these compounds. In this study, the presence of tetracyclines in honey samples across China was investigated over a four-year period. Additionally, the risks of dietary intake, as well as the sources and degradation patterns of tetracyclines in honey, were assessed. The three-dimensional spatial distributions (floral region, geographical region and entomological origin) of tetracyclines contamination varied significantly. Tetracycline residues in honey posed a moderate risk to children aged 3–10 years in Northwest China. Source analysis indicated that colony migration serves as the primary source of tetracyclines in honey. Based on the degradation patterns of tetracyclines in honey within colonies and during storage, oxytetracycline is more readily degraded than other tetracyclines. The main degradation products of tetracyclines are epimers and dehydration products, and the effects of these products on human health and the environment should be further evaluated in future studies. This comprehensive investigation provides valuable insights into the safe use and regulation of tetracyclines in Chinese apiculture.

Determination of tetracycline in honey by flow-injection amperometry on an electrode modified with gold and palladium particles, and reduced graphene oxide

A method of immobilizing Au–Pd binary system on a glassy carbon (GC) electrode surface covered by reduced graphene oxide (GOred) was developed. Using GOred as a matrix for inclusion of Au–Pd binary system resulted in significant increase of its catalytic activity in tetracycline (TC) electro-oxidation process due to increased dispersion of the deposit and formation of nano-sized metal particles (average diameter of particles was around 50 nm). Optimal conditions of immobilizing Au–Pd binary system for achieving maximum electrocatalytic effect were determined. A possibility of amperometric detection of TC on GC modified with Au–Pd and GOred composite (Au–Pd–GOred–GC) by flow injection analysis (FIA) was demonstrated. The method demonstrated high sensitivity (the lowest detection limit of 5 nM), rapidity and efficiency (about 60 samples per hour). The flow injection amperometric method for TC determination hereby developed was tested in analyzing flower honey samples from different Volga Region districts.

Determination of quinolones, macrolides, sulfonamides and tetracyclines in honey using QuEChERS sample preparation and UHPLC-MS/MS analysis

Monitoring beehive health and timely prevention of possible infections by bacteria, mould, viruses or parasites is exceptionally important in beekeeping. Antibiotics originating from the environment can be found in honey and due to improper beekeeping practices. Enabling the detection of antibiotic residues in honey and suppressing the development of antibiotic resistance require the development of a sensitive multi-class method for the determination of antibiotics. For the purpose of analysing honey, a screening and confirmatory method for the determination of 36 antibiotics was developed. The QuEChERS procedure and ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) was selected to achieve high sensitivity and selectivity. Validation according to the new Commission Implementing Regulation (EU) 2021/808 included the following performance characteristics: selectivity, trueness, precision, decision limit (CCα), detection capability (CCβ) and relative matrix effect. The method was validated in the measurement range from 1 to 10 μg/kg, where maximum trueness and acceptable coefficients of variation were achieved. The detection capability (CCβ) equals the lowest concentration level for all analytes, ranging from 0.1 μg/kg to 2.5 μg/kg, as the false compliant rate less than 5% was confirmed at this level of interest. For unauthorised pharmacologically active substances, the CCα was determined and ranged from 0.16 μg/kg for sulfaquinoxaline to 3.67 μg/kg for difloxacin. The high matrix influence of floral and chestnut honey indicated the need for quantitative analysis using the matrix calibration curve.

Introducing direct probe electrospray ionization tandem mass spectrometry in apiculture: Comparison with other mass spectrometric methods for the determination of antibiotics in bees and honey

Amphenicols and tetracyclines (TCs) antibiotics use in apiculture is mainly focused on the treatment of bee brood diseases. Despite their efficiency, the serious genotoxic effects that some elicit led to their banning for use in apiculture and for chloramphenicol (CAP) in all food-producing animals. In this work, three tandem mass spectrometric methods were developed and validated for the analysis and quantification of CAP, thiamphenicol (TF), florfenicol (FF), tetracycline (TC), oxytetracycline (OTC) and chlortetracycline (CTC) in honey and honeybees. With the first, we have demonstrated the first use of probe electrospray ionization (PESI) in conjunction with tandem mass spectrometry (MS/MS) for antibiotics determination in honey and bees entailing a minimum sample preparation for bees, resulting in rapid chemical analysis for both commodities. The second was a reversed-phase HPLC-ESI-MS/MS method sharing the same scope. With the third chiral HPLC-ESI-MS/MS method, it was attempted to separate CAP stereoisomers in both commodities since reports have shown that only the D-threo isomer displays antimicrobial properties. The analytical methods fulfilled validation criteria demonstrating recoveries in the range of 74–92%, managing to address the minimum required performance limit (MRPL) for CAP, with the exception of PESI-MS/MS. The latter displayed a detection capability (CCβ) for all compounds in proximity to 1 ng/g, and an overall runtime of 1.5 min. In total, 68 samples of honeybees and honey were evaluated for amphenicols and TCs residues. CAP was detected only in two honeybee samples, while one honey sample was positive to TC and OTC was detected in traces in another sample. PESI-MS/MS managed to quantify both TC in honey and CAP in bees in proximity to the values assigned by the conventional HPLC-ESI-MS/MS methods. With regard to the separation of CAP's isomers, the chiral method managed to resolute all isomers and quantify CAP in one bee sample in the form of its L-threo stereoisomer. Overall, ABCs detection in honey and related matrices still constitutes a challenge, considering their prevalence and potential applications in major honey-producing countries.

Preparation of fatty acid-based ternary deep eutectic solvents: Application for determination of tetracycline residue in water, honey and milk samples by using vortex-assisted microextraction

Simple, rapid, low cost, selective, and sensitive analytical method was developed using fatty acid-based ternary deep eutectic solvents (TDESs) for extraction and determination of tetracycline in honey, milk and water samples by vortex assisted (VA) microextraction and UV–vis spectrophotometer. Four different TDES were prepared by combination of nonanoic acid, dodecanoic acid, decanoic, hexanoic acid, octanoic acid. Analytical parameters such as pH, TDES types and its molar ratio, dispersive solvent types and solvent volume and salt effect were optimized. VA-TDES method was good recovery of tetracycline in the samples from 94 to 99%. The LOD and LOQ values were found 1.0 and 3.3 µg L-1, respectively. The linear range of calibration graph was 3.3 -450 µg L-1. Intra-day and inter-day precision was found 2.8–4.1% and 3.6–5.2%. Enhancement factor was found 109. The factorial design was drawn to evaluate the significant level of factors and effects of variables on the recovery of tetracycline. Standard addition method was used for the validation and accuracy of the method. Present VA-TDES method was successfully applied to real samples.

Lanthanide coordination polymer nanoparticles as a ratiometric fluorescence sensor for real-time and visual detection of tetracycline by a smartphone and test paper based on the analyte-triggered antenna effect and inner filter effect

Lanthanide coordination polymer nanoparticles (LML-Eu3+-GMP CPNPs) were fabricated as a ratiometric fluorescence sensor for real-time and visual assays of tetracycline (TC). The LML-Eu3+-GMP CPNPs were prepared by spontaneous self-assembly of Eu3+, luminol (LML) and guanosine 5′-monophosphate (GMP) at room temperature, which only emitted blue fluorescence dominated by LML, and no red characteristic fluorescence of Eu3+ was observed. In the presence of TC, TC can trigger the antenna effect (AE) and inner filter effect (IFE), the blue fluorescence of LML-Eu3+-GMP CPNPs is quenched by TC via IFE, and the red characteristic fluorescence of Eu3+ can be turned on through AE. When sodium citrate (Cit) is added to the sensing system, it can further enhance the red fluorescence of Eu3+. The dual-ligand CPNP sensor has a rapid fluorescence response, noticeable fluorescence color change, good selectivity, and high sensitivity with a detection limit of 3.4 nM. It was successfully applied to detect TC in honey, milk, lake water and tap water. Meanwhile, the portable smartphone and test paper were applied to develop POCT devices for real-time and visual detection of TC, which could offer a promising application for real-time and semiquantitative assays of TC.

Application of ionic liquid-based air-assisted dispersive liquid–liquid microextraction combined with high-performance liquid chromatography for the determination of six tetracyclines in honey

Application of ionic liquid-based air-assisted dispersive liquid–liquid microextraction combined with high-performance liquid chromatography for the determination of six tetracyclines in honey

Collaborative compounding of metal–organic frameworks for dispersive solid-phase extraction HPLC–MS/MS determination of tetracyclines in honey

Metal-organic frameworks (MOFs), a sort of dispersive solid-phase extraction (d-SPE) material, has shown considerable prospects in the pretreatment of food, biological and other complex samples. Herein, we developed a method for compounding MOFs for d-SPE and trace determination of tetracyclines (TCs) in honey. When the compounding ratio of MIL-101 (Cr), MIL-100 (Fe) and MIL-53 (Al) was 7:1:2, adsorption–extraction was effective. Followed by high-performance liquid chromatography–tandem mass spectrometry (HPLC–MS/MS), the limits of detection were 0.073–0.435 ng/g and the limits of quantitation ranged from 0.239 to 1.449 ng/g for oxytetracycline, tetracycline, chlortetracycline and doxycycline. The method was applied to four kinds of honey samples with recoveries from 88.1% to 126.2%. The compounding of MOFs provides a strategy for purification and multi-target extraction from complex food matrices by d-SPE.

A CsPbBr3 quantum dots/ultra-thin BN fluorescence sensor for stability and highly sensitive detection of tetracycline

The abuse of tetracycline (TC) antibiotics would seriously affect human health and hence the detection had become essential. Here, we had constructed a hydrophobicity of fluorescence sensor based on the excellent photoluminescence emission of CsPbBr3 QDs and the hydrophobic ability of Boron Nitride (BN). This design effectively solved the instability of CsPbBr3 QDs and realized the sensitive detection of TC. Under optimum conditions, the linear range of TC was 0–0.44 mg L−1 with the 6.5 μg L−1. Furthermore, the sensor was successfully used for the recognition of TC in honey and milk samples. This work also provided an ideal for designing CsPbBr3 QDs-based on fluorescence sensor.

Development of an impedimetric biosensor based on nanomaterial for determination of tetracycline in honey

Development of an impedimetric biosensor based on nanomaterial for determination of tetracycline in honey

Detection of tetracycline antibiotics in honey using high-performance liquid chromatography

It is hard to overestimate the value of honey since the constituent substances in it are of great importance in the food industry and medicine. The quality of honey is established by the legislation of the Russian Federation (GOST). But the levels of these standards are regulated by outdated methods of analysis, which can not give reliable results. The detection of antibiotic residues in honey is a central issue in the quality and safety control of this product. Accumulation of drugs in honey used to treat bee colonies can cause allergies and dysbiosis in people who have eaten such honey, as well as develop antibiotic resistance in microorganisms. At present, one of the promising directions in the field of detecting medicines in honey is the use of high-performance liquid chromatography (HPLC). It helps selectively and accurately detect antibiotic substances in honey bee products. In Russia, the HPLC method is used with mass spectrometry to detect tetracycline residues in honey. A significant drawback with this method that limits the widespread use of it is the application of expensive, technically sophisticated equipment that needs high-quality reagents and consumables. The purpose of this work was to develop the simultaneous identification of tetracycline antibiotics in honey and carry out their quantitative analysis by a reversed-phase HPLC method. A sample preparation algorithm was developed, and the conditions for chromatographing combined indication of tetracyclines in honey at an acceptable concentration according to the MRL (0.01 mg/kg) with Agilent 1260 Infiniti liquid chromatograph equipped with a column thermostat, a gradient pump, and a UV detector were selected. According to the results of the research, the most optimal condition for the simultaneous analysis of oxytetracycline, tetracycline hydrochloride, chlortetracycline in honey by HPLC method with ultraviolet detection was a wavelength of 254 nm, a flow rate of 0.5 ml/min and a column temperature of 25° C. Under these conditions, the antibiotic retention time was determined: 4.069 minutes for oxytetracycline, 4.331 minutes for tetracycline hydrochloride, 4.642 minutes for chlortetracycline. The developed HPLC method for the simultaneous determination of tetracycline antibiotics in honey was tested on honey bee products from the regions of the Republics of Tatarstan and Bashkortostan.

A “Signal On” Photoelectrochemical Aptasensor For Tetracycline Detection Based On Semiconductor Polymer Quantum Dots

A tetraphenylporphyrin (TPP) doped PFBT polymer quantum dots (TP-Pdots) were synthesized via the reprecipitation method for photoelectrochemical (PEC) aptasensor detection of tetracycline (TC). The TP-Pdots exhibit a superior cathode photocurrent signal. TP-Pdots increase the separation of photo-generated charges, and improve photocurrent conversion efficiency, resulting in enhanced photocurrent response. The aptamer was used as a recognition element and TP-Pdots as a photoactive material to prepare a PEC aptasensor for sensitivity detection of TC. The PEC aptasensor was constructed by immobilizing TP-Pdots on ITO electrode and combining it with aptamer by EDC coupling. After the TC reacts specifically with the aptamer, causing the aptamer to fall off from the TP-Pdots /ITO electrodes surface and the photocurrent intensity restored. This PEC aptamer sensor possesses a wide linear range from 1.0 nmol.l−1 to 1.0 × 10 4 nmol.l−1 with the detection limit of 0.26 nmol.l−1. Meanwhile, the PEC aptasensor was successfully used for the detection of tetracycline in honey.

Rapid analysis of tetracycline in honey by microwave plasma torch mass spectrometry with ablation samples

A rapid and sensitive mass spectrometric analysis method with minimal or no prior sample pretreatment was developed for the direct detection of trace amounts of tetracycline in honey products using a microwave plasma torch combined with mass spectrometry.

An aptamer cocktail-based electrochemical aptasensor for direct capture and rapid detection of tetracycline in honey

Herein, we immobilized an aptamer cocktail on the surface of gold screen-printed electrodes and developed an electrochemical aptasensor with high sensitivity and specificity for direct capture and rapid detection of tetracycline (TC) in honey. The aptamer cocktail was composed of a comparatively short aptamer (Apt40) and a comparatively long aptamer (Apt76), which had different base composition, different chain lengths, and different folded binding sites. Application of the aptamer cocktail contributed to good spatial arrangement of binding sites of the two aptamers and large contact area of the aptamers-functionalized electrodes with TC-containing honey samples. All of the binding sites of the two aptamers were well exposed to capture TC, and thus, the aptamer cocktail exhibited higher recognition ability towards the TC than the individual aptamer. The aptamer cocktail-based electrochemical aptasensor provided a limit of detection (LOD) of 0.0073 ng/mL and a linear working range of 0.01–1000 ng/mL, when detecting TC in honey. Moreover, the aptasensor provided high specificity and good recovery rates of 96.45–114.6%. This study not only provided a new rapid detection method for highly sensitive and specific detection of TC residues but also served as a reference for developing aptasensors towards other targets.

A Ratiometric Fluorescent Nano-Probe for Rapid and Specific Detection of Tetracycline Residues Based on a Dye-Doped Functionalized Nanoscaled Metal–Organic Framework

Tetracycline (TC) residues are harmful to the environment and human body, so it is necessary to develop a highly sensitive probe for rapid detection of tetracycline residues. In the present paper, a novel dye-doped porous metal–organic framework (UiO-66)-based multi-color fluorescent nano-probe was designed for sensitive ratiometric detection of tetracycline (TC). In this probe, dye-molecules doped UiO-66 was used as a fluorescent internal standard, and the externally grafted lanthanide Eu3+ complex was used as response signals. The fluorescence of the Eu3+ complex was selectively enhanced with increasing concentrations of TC, which was accompanied by a visual blue-to-red color switch. The nano-probe had a linear response between 0.1 and 6 μM with a lowest detection limit of 17.9 nM, which was much lower than the maximum residue limits set by the United States Food and Drug Administration (676 nM) and the European Union (225 nM). The applicability of this method in the analysis of actual samples was evaluated by the determination of TC in honey and milk samples, indicating satisfactory recovery and good reproducibility. In addition, a cost-effective paper-based probe for rapid and visual detection of TC was developed by fixing the nano-probe on filter papers. With the help of a smartphone camera to capture the fluorescence color, and chromaticity analysis software, the calculation and analysis of red (R) and blue (B) values can be realized, which has the potential for real-time visual detection of TC.

Determination of Tetracycline in Water and Honey by Iron(II, III)/Aptamer-Based Magnetic Solid-Phase Extraction with High-Performance Liquid Chromatography Analysis

A novel aptamer-based adsorbent was prepared for the magnetic solid-phase extraction of tetracycline. The Fe3O4/aptamer adsorbent was fabricated by immobilizing an aptamer on the surface of Fe3O4 magnetic nanoparticles by the reaction between avidin and biotin. The parameters affecting the isolation efficiency such as the pH, extraction time, extraction temperature, eluent, and elution time were investigated in detail. Under the optimal conditions, a linear relationship between the peak area and the concentration of tetracycline was observed in the range from 10.0 to 3000.0 µg L−1 with a correlation coefficient of 0.9985 and a limit of detection of 2.5 µg L−1. The developed method was successfully employed for the determination of tetracycline in honey and water samples with recovery values from 82.9 to 107.3% and relative standard deviations less than 7.6%. Compared with previously reported methods for the determination of tetracycline, the proposed protocol provides improvements in the limit of detection and specificity with reduced consumption of adsorbent and organic solvents.

Single-hole hollow molecularly imprinted polymer embedded carbon dot for fast detection of tetracycline in honey

It is difficult to detect tetracycline (TC) in honey sample by using carbon dots (CDs) because the autofluorescence of the matrix of honey sample overlaps with the fluorescence emission spectrum of the large majority of CDs. Herein, single-hole hollow molecularly imprinted polymers embedded carbon dots (HMIP@CD) was prepared via microwave-assisted method. TC in diluted honey sample was adsorbed by the HMIP@CD within 3 min, after which the HMIP@CD absorbed with TC was separated by centrifugation from honey sample and redispersed into phosphate buffer solution. The autofluorescence of honey that interferes with the fluorescence signal of HMIP@CD was avoided. The method exhibited an excellent linearity within 10–200 μg L−1 and a low detection limit of 3.1 μg L−1. At three spiking levels of TC, the recoveries ranged from 93% to 105% with precisions below 1.6%. This method provides an effective strategy for detecting analyte in complex matrix with autofluorescence interference.

The development of a graphene oxide-based aptasensor used for the detection of tetracycline in honey

The absorption properties of graphene oxide and its aggregation ability in saline were used for detecting antibiotic tetracycline.

Determination of Tetracycline in Honey by Voltammetry

The possibility of the voltammetry use for tetracycline determination in probes of honey on a glassy carbon electrode with preliminary electrochemical treatment has been shown for the first time. The algorithm of honey samples treatment using solid phase extraction (SPE) has been developed.

A direct competitive assay-based aptasensor for sensitive determination of tetracycline residue in Honey

Tetracycline (TC) is a common antibacterial agent used for prevention and control of animal diseases. The increasing concern about TC residue in food demands high-performing analytical techniques for food quality assessment. Biosensors represent a promising tool for food safety analysis as they can fulfill some demand that the conventional methods do not attain. In this study, a novel colorimetric aptasensor was developed for sensitive detection of TC in honey. The aptasensor was based on a modified direct competitive enzyme-linked aptamer assay (dc-ELAA) scheme utilizing a 76mer single-stranded DNA (ssDNA) aptamer selected by Systematic Evolution of Ligands by Exponential Enrichment (SELEX). The optimized aptasensor showed a good limit of detection (LOD of 0.0978ng/mL), a wide linear range (0.1–1000ng/mL) toward TC in honey, with good recoveries (92.09–109.7%) in TC-spiked honey, and was compared with an indirect competitive assay-based aptasensor and validated with a standard ELISA. The biosensor based on dc-ELAA with good limit of detection and simplicity can be applied for high-throughput detection of TC in food.