Detection Of Tetracycline In Milk Research Articles

A metal-organic framework-based sensor for specific detection of tetracycline in milk

Molecularly imprinted fluorescent sensors are of interest to researchers due to their specificity, high sensitivity, and stability. In this study, the fluorescence-imprinted sensor (NH2-MIL-53/MIP) for the detection of tetracycline (TC) in animal-derived foods was developed based on the characteristics of luminescent metal-organic frameworks (MOFs) and molecularly imprinted polymers (MIPs). The MOFs provide fluorescence sensing signals and large specific surface areas, while the MIPs provide the specific recognition sites for TC. As a result, the sensor exhibits a wide detection range (0.05–50 μg/mL), high sensitivity (LOD of 0.006 μg/mL), fast detection speed and good selectivity. The sensing principle can be attributed to photoinduced electron transfer. Furthermore, the sensor can determine TC in milk with good recovery rates (95.05–104.71 %). This work addresses the limitation of current molecularly imprinted sensors such as slow corresponding speed and limited detection capability, providing valuable insights for target determination in complex systems.

Eu3+-based InP/ZnS quantum dot fluorescence platform for multi-color and sensitive visualization of tetracycline

A turn-on type ratiometric fluorescence sensing system of blue quantum dot Eu-MPA-InP/ZnS was established for multi-color visualization determination of tetracycline (TC). Mercaptopropionic acid (MPA)-capped InP/ZnS quantum dots (MPA-InP/ZnS QDs) both modify the hydrophilicity of InP/ZnS QDs and serve as a scaffold for coordinating of Eu3+ ions. The blue fluorescence of Eu-MPA-InP/ZnS at 478 nm is reduced by the TC through the inner filter effect (IFE) under a single excitation wavelength of 365 nm. Rich colour gradients and a highly discriminative colour change were features of this multicolour response to TC, which allowed visual quantification of TC in a dose-dependent manner. Furthermore, by cross-linking Eu-MPA-InP/ZnS with agarose (Aga.), a mouldable Eu-MPA-InP/ZnS@Aga 96-well gel sensing device was designed to serve as a handheld sensor for on-site detection of TC. This probe expands the use of InP QDs in analytical sensing and has been effectively applied to the visual detection of tetracycline in milk and the environment.

Highly Stable Fluorescent-Traffic-Light Sensor for Point-of-Care Detection of Tetracycline.

Fluorescent point-of-care (POC) sensors have found great utility in fields like clinical diagnosis, food testing, and environmental monitoring. Herein, we developed a highly stable POC sensor that enabled the visual detection of tetracycline (TC) in a distinct fluorescent-traffic-light manner. In the sensor, a composite material of copper nanoclusters and metal-organic framework (CuNCs@MOF-5) prepared with a facile one-pot synthetic strategy was employed as the core element for target recognition and signal transduction. As evidenced by experiments, the as-prepared CuNCs@MOF-5 exhibited significantly improved fluorescence properties in terms of emission enhancement (about 28-fold) and stability improvement (over 110 days) compared to the CuNCs without confining and protection by MOF-5. More importantly, it was found that TC could uniquely interact with Zn(II) to trigger the disassembly of CuNCs@MOF-5, resulting in green fluorescence emission from the TC-Zn(II) complex and red fluorescence weakening of CuNCs. On the basis of this finding, a simple and stable sensor was proposed for POC detection of TC, which demonstrated high sensitivity, selectivity, and reproducibility. In addition to homogeneous visual detection in a 96-well plate, a CuNCs@MOF-5-contained agarose gel array was easily fabricated to achieve direct detection of TC in milk without any pretreatment, thanks to the size-sieving effect of the gel. Moreover, a test paper array was also put forward for low-cost TC detection, which indicates the extensibility and practicability of this sensing strategy.

Development and validation of reverse - phase HPLC method for detection of tetracycline residue in fresh milk samples

Dairy products are highly required by humans for growth, development and repairs as they are good sources of essential nutrients. Indiscriminate administration of veterinary drugs for prophylactic and therapeutic purposes could lead to the presence of their residues in dairy products such as milk. Reversed-phase high performance liquid chromatographic method with UV detection was developed and validated for detection of tetracycline in milk from five different samples. Mobile phase consisting of a mixture of deionized water, acetonitrile, monobasic potassium and acetic acid was delivered at a flow rate of 1.0 mL/min. The column used was Agilent ZORBAX ODS 4.6 X 150 mm 5μm.. The eluent was monitored by UV detection at 220 nm. Analysis was performed at 35oC and the total run time was 20 minutes. Analytical parameters such as linearity, accuracy, precision and limit of detection were determined by validation procedure and found to be satisfactory. Calibration curve was linear over the concentration range of 0.01- 0.5 mg/mL with an R2 of 0.9978. The limits of detection and limit of quantification were found to be 0.00023 mg/mL and 0.00110 mg/mL, respectively. The % RSD is found to be 3.62, 0.23 and 0.44 for 0.01, 0.1 and 0.5 mg/mL concentration with percentage recovery of 78.7 – 98.6 %. Generally, the developed method was found to be simple, rapid, precise and accurate for quality control of tetracycline in fresh milk samples.

Octahedral Cu2O nanomaterials as electrochemical aptasensor for sensitive detection of tetracycline in milk

In this work, A novel label-free electrochemical biosensor based on octahedral Cu2O @ Au nanocomposites was developed for the detection of tetracycline. The gold nanoparticles (AuNPs) on the surface of Cu2O nanomaterials not only improve the electrochemical performance, but also can be used as a binding site for thiol-modified tetracycline aptamers, which can specifically bind to tetracycline. Cu2O @ Au nanocomposites provide a synergistic effect of electrochemical signal amplification and tetracycline recognition strategy. Under the optimal conditions, the proposed biosensor exhibited different electrochemical reactions for different concentrations of tetracycline, with a linear range of 1 nM-1000 μM and a detection limit of 0.16 nM. This work provides a new idea for rapid and sensitive detection of tetracycline by using a simple and economical tetracycline aptamer combined with Cu2O @ Au biosensor platform.

Development of europium(III) complex functionalized silica nanoprobe for luminescence detection of tetracycline.

Increasing awareness of the health and environment impacts of the antibiotics misuse or overuse, such as tetracycline (TC) in treatment or prevention of infections and diseases, has driven the development of robust methods for their detection in biological, environmental and food systems. In this work, we report the development of a new europium(III) complex functionalized silica nanoprobe (SiNPs-Eu3+) for highly sensitive and selective detection of TC residue in aqueous solution and food samples (milk and meat). The nanoprobe is developed by immobilization of Eu3+ ion onto the surface of silica nanoparticles (SiNPs) as the emitter and TC recognition unit. The β-diketone configuration of TC can further coordinate with Eu3+ steadily on the surface of nanoprobe, facilitating the absorption of light excitation for Eu3+ emitter activation and luminescence "off-on" response. The dose-dependent luminescence enhancement of SiNPs-Eu3+ nanoprobe exhibits good linearities, allowing the quantitative detection of TC. The SiNPs-Eu3+ nanoprobe shows high sensitivity and selectivity for TC detection in buffer solution. Time resolved luminescence analysis enables the elimination of autofluorescence and light scattering for highly sensitive detection of TC in milk and pork mince with high accuracy and precision. The successful development of SiNPs-Eu3+ nanoprobe is anticipated to provide a rapid, economic, and robust approach for TC detection in real world samples.

Fluorescence quenching determination of tetracyclines based on the synergistic oxidation effect between Fe3O4 nanoparticles and tetracyclines

In recent years, tetracyclines (TCs) is a hot research topic. Herein, we report an interesting discovery using the complexation of oxytetracycline and metal ions. In this study, according to the properties of Fe3O4 nanoparticles (Fe3O4 NPs) as a nanoenzyme, it can be used to catalyze the oxidation of KI by H2O2 to produce while at the same time binds to rhodamine 6G (Rh6G) to form a conjoined particle (Rh6G ∼ I3)n, leading to a decrease in the fluorescence intensity of Rh6G. However, in the presence of TCs, Fe3O4 NPs have a synergistic effect with TCs, leading to enhanced catalytic activity, as well as better selectivity compared to the activity of other reducing enzymes. Consequently,the fluorescent signal based on a resonance scattering effect between Rh6G and is dependent on the concentration of TCs, thus achieving highly facile and robust detection of TCs. The limits of detection (LOD) of the method were 20 nM, 10 nM and 40 nM for oxytetracycline(OTC), tetracycline(TC) and chlortetracycline(CTC), respectively. Most importantly, the method can be successfully applied to the detection of TCs in milk, eggs, and honey. The recoveries of spiked samples ranged from 83.11 to 118.95%. Thus, a stable, hands-on strategy for the detection of TCs is proposed, which has potential applications in the field of food safety and environmental protection.

Ratiometric Fluorescence Detection of Tetracycline in Milk Based on Inner Filter Effect and Antenna Effect for Non-Conjugated Polymer Point and Eu3+

Ratiometric Fluorescence Detection of Tetracycline in Milk Based on Inner Filter Effect and Antenna Effect for Non-Conjugated Polymer Point and Eu3+

A photoelectrochemical aptasensor for tetracycline based on the self-assembly of 2D MoS2 on a 3D ZnO/Au/ITO electrode.

Two-dimensional (2D) layered MoS2 has good dispersion and adsorption properties, but being a narrow bandgap semiconductor limits its application in photoelectric sensing. In this study, a homogeneous photoelectrochemical sensor based on three-dimensional (3D) ZnO/Au/2D MoS2 is proposed for the ultrasensitive detection of tetracycline (TET). MoS2 is uniformly embedded on the 3D ZnO/Au surface by ordered self-assembly. The physical method of π-π interaction of MoS2 replaces the conventional use of chemically modifying aptamers on the electrode material surface. Under optimal conditions, this method has been successfully applied to the detection of TET in milk, honey, pig kidney and pork samples with reliable results. We believe that this study presents a method for the preparation of sensing carriers and target detection with great potential for application.

Portable electrochemiluminescence detection system based on silicon photomultiplier single photon detector and aptasensor for the detection of tetracycline in milk

In this work, a portable electrochemiluminescence (ECL) detection system based on silicon photomultiplier (SiPM) single photon detector was proposed for the detection of ECL signals on a screen-printed electrode (SPE). This instrument innovatively used SiPM single photon detector to detect the ECL signal, which solved friability and bloat caused by the high operating voltage and the limitation of detection components in the traditional ECL detection instrument. This detection instrument showed excellent electrochemical and ECL detection performance. On this basis, an aptasensor based on silver (core)-gold (shell) bimetallic nanoparticles (Ag@AuNPs) was constructed for the detection of tetracycline (TET) in milk on SPE. Here, Ag@AuNPs had a significant effect in enhancing luminol ECL signal and immobilizing aptamer. The concentration of TET was detected according to the changes of the ECL signal intensity of the detection instrument. This instrument exhibited an excellent linearity ranging from 0.01 ng/mL to 1,000 ng/mL for the detection of TET, and a limit of detection (LOD) was 0.0053 ng/mL. The developed portable ECL detection instrument provides a new platform for the detection of small molecule contaminants.

Use of Deep Ultraviolet Emissive Carbon Dots as a Novel Optical Sensor for the Detection of Tetracyclines in Milk

Stable deep ultraviolet emissive carbon dots (DUV-CDs) were produced as a novel optical sensor to detect the concentration of tetracyclines (TCs) in milk. The 2,4-dihydroxybenzoic acid and lysine were used as the precursor for DUV-CDs synthesis. Experiments show that the optimal excitation wavelength and the fluorescence peak wavelength of the carbon dots are 273 and 298 nm, respectively. With the addition of TCs, the fluorescence intensity of DUV-CDs would be significantly quenched. It is inferred by experiments that the fluorescence of DUV-CDs is quenched by TCs due to the combined effect of inner filter effect (IFE) and hydrogen bonding. The results showed that the method has high sensitivity and a large measurement range. The linear range can be fit in the range of 0.25–30 mg/L in water where <inline-formula xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink"> <tex-math notation="LaTeX">${R}^{{2}}$ </tex-math></inline-formula> is 0.996 and the limit of detection (LOD) is <inline-formula xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink"> <tex-math notation="LaTeX">$49.94~\mu \text{g}$ </tex-math></inline-formula> /L. Meanwhile, the linear range is 0.5–40 mg/L in milk, <inline-formula xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink"> <tex-math notation="LaTeX">${R}^{{2}}$ </tex-math></inline-formula> is 0.991, and the LOD is <inline-formula xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink"> <tex-math notation="LaTeX">$70.61~\mu \text{g}$ </tex-math></inline-formula> /L. In this article, the DUV-CDs were applied to foodstuffs for the first time. Compared with the traditional detection method, the DUV-CDs method has the advantages of high sensitivity, simple operation, safety, high energy utilization, and low cost. A new method was established for detecting TCs in milk, which may aid in the detection of food safety.

L-histidine functionalized ZiF-8 with aggregation-induced emission for detection of tetracycline

In this study, we constructed zinc based metal–organic framework functionalized by L-histidine (His@ZiF-8). The His@ZiF-8 had high porosity, large surface area, abundant carboxyl and amino group, which has been found to greatly enhance the aggregation-induced emission (AIE) of tetracycline (TC). After the His@ZiF-8 enrichment with TC, the TC exhibited strong fluorescence emission peak at 565 nm based on AIE. Under the optimal conditions, the fluorescence intensity of TC exhibited a good linear relationship with TC concentration within 0.1–80 μM with a low limit of detection of 28.6 nM. Antibiotic analogs such as neomycin, chloramphenico, ampicillin, kanamycin, and erythromycin have no obvious interference. In addition, the developed method was successfully used to the detection of TC in milk, river water, and honey.

Synthesis of a Dual Metal–Organic Framework Heterostructure as a Fluorescence Sensing Platform for Rapid and Sensitive Detection of Tetracycline in Milk and Beef Samples

Synthesis of a Dual Metal–Organic Framework Heterostructure as a Fluorescence Sensing Platform for Rapid and Sensitive Detection of Tetracycline in Milk and Beef Samples

Enzyme-free dual-amplification assay for colorimetric detection of tetracycline based on Mg2+-dependent DNAzyme assisted catalytic hairpin assembly.

Detection of ultralow concentration of tetracycline (TC) plays a key role in food safety and human health. Herein, we fabricated an enzyme-free dual-amplification assay for sensitive detection of TC in milk. The sensing system ingeniously combined Mg2+-dependent DNAzyme (MNAzyme) cleavage and catalytic hairpin assembly (CHA). Through the binding of TC and specific aptamer (Apt), DNA1 was released from the Apt-DNA1 complex. Then the separated DNA1 would hybridize with DNA2 to activate the catalytic activity of MNAzyme, which subsequently cleaved the substrate H0 and generated a new unit to trigger the following CHA reaction between H1 and H2, thereby releasing the G-rich sequence of H1 to induce the formation of G-quadruplex-hemin DNAzyme as a colorimetric signal readout. Under optimal conditions, the absorption intensity exhibited a significant linear correlation with the logarithm of the target TC concentration over a range of 4 orders of magnitude dynamic range from 1 pM to 10nM. The limit of detection was calculated to be 0.89 pM and the method showed high selectivity for TC. More impressively, the proposed method was employed for TC determination in the milk sample.

UiO-66-NH2 based fluorescent sensing for detection of tetracyclines in milk.

In this work, a fluorescent sensor based on a zirconium-based metal organic framework was prepared for the detection of tetracyclines (TCs) in milk. The UiO-66-NH2 fluorescent sensor was synthesized by a simple microwave-assisted method with 2-aminoterephthalic acid and zirconium chloride as precursors. In the presence of target TCs, the synergistic effect of the inner filter effect (IFE) and photo-induced electron transfer (PET) was responsible for the fluorescence quenching of UiO-66-NH2, and the fluorescence sensor showed a rapid fluorescence quenching response (5 min) to target TCs. The proposed UiO-66-NH2 sensor had good sensitivity and selectivity, and under the optimal conditions possessed detection limits of 0.449, 0.431, and 0.163 μM for tetracycline (TET), oxytetracycline (OTC), and doxycycline (DOX), respectively. Besides, the UiO-66-NH2 sensor was successfully applied to the quantitative detection of TCs in milk samples with reasonable recoveries of 93.26–115.17%, and the detection results achieved from the as-fabricated fluorescence sensing assay were consistent with those of high-performance liquid chromatography (HPLC), indicating the potential applicability of the UiO-66-NH2 sensor for detecting TCs in actual food samples.

Laser-Induced Graphene Electrodes Modified with a Molecularly Imprinted Polymer for Detection of Tetracycline in Milk and Meat.

Tetracycline (TC) is a widely known antibiotic used worldwide to treat animals. Its residues in animal-origin foods cause adverse health effects to consumers. Low-cost and real-time measuring systems of TC in food samples are, therefore, extremely needed. In this work, a three-electrode sensitive and label-free sensor was developed to detect TC residues from milk and meat extract samples, using CO2 laser-induced graphene (LIG) electrodes modified with gold nanoparticles (AuNPs) and a molecularly imprinted polymer (MIP) used as a synthetic biorecognition element. LIG was patterned on a polyimide (PI) substrate, reaching a minimum sheet resistance (Rsh) of 17.27 ± 1.04 Ω/sq. The o-phenylenediamine (oPD) monomer and TC template were electropolymerized on the surface of the LIG working electrode to form the MIP. Surface morphology and electrochemical techniques were used to characterize the formation of LIG and to confirm each modification step. The sensitivity of the sensor was evaluated by differential pulse voltammetry (DPV), leading to a limit of detection (LOD) of 0.32 nM, 0.85 nM, and 0.80 nM in buffer, milk, and meat extract samples, respectively, with a working range of 5 nM to 500 nM and a linear response range between 10 nM to 300 nM. The sensor showed good LOD (0.32 nM), reproducibility, and stability, and it can be used as an alternative system to detect TC from animal-origin food products.

A recycled Tb-MOF fluorescent sensing material for highly sensitive and selective detection of tetracycline in milk

A novel three-dimensional terbium metal–organic framework (Tb-MOF) sensing material has been synthesized by hydrothermal method and applied in fluorescent detection of tetracycline (TC) in milk. The sensing material could emit strong green fluorescence with a long fluorescence lifetime (906.48 ± 1.49 μs), which could be sensitively and selectively quenched by TC aqueous solution. Meanwhile, it had the characteristics of fast response (2 min), low detection limit (184 nmol/L), wide linear range (0–100 and 100–244 μmol/L) and recyclable luminescence sensing during TC detection. The luminescence quenching mechanism was mainly derived from the inner-filter effect and energy transfer from ligand to Tb3+ ion. Furthermore, satisfactory recoveries of 93.5–104.2% were obtained in TC spiked raw milk and pasteurized milk samples, suggesting the potential application of Tb-MOF in the detection of TC in food engineering.

Emerging Electrochemical Sensors for Real-Time Detection of Tetracyclines in Milk.

Antimicrobial drug residues in food are strictly controlled and monitored by national laws in most territories. Tetracyclines are a major broad-spectrum antibiotic class, active against a wide range of Gram-positive and Gram-negative bacteria, and they are the leading choice for the treatment of many conditions in veterinary medicine in recent years. In dairy farms, milk from cows being treated with antibiotic drugs, such as tetracyclines, is considered unfit for human consumption. Contamination of the farm bulk tank with milk containing these residues presents a threat to confidence of supply and results in financial losses to farmers and dairy. Real-time monitoring of milk production for antimicrobial residues could reduce this risk and help to minimise the release of residues into the environment where they can cause reservoirs of antimicrobial resistance. In this article, we review the existing literature for the detection of tetracyclines in cow’s milk. Firstly, the complex nature of the milk matrix is described, and the test strategies in commercial use are outlined. Following this, emerging biosensors in the low-cost biosensors field are contrasted against each other, focusing upon electrochemical biosensors. Existing commercial tests that identify antimicrobial residues within milk are largely limited to beta-lactam detection, or non-specific detection of microbial inhibition, with tests specific to tetracycline residues less prevalent. Herein, we review a number of emerging electrochemical biosensor detection strategies for tetracyclines, which have the potential to close this gap and address the industry challenges associated with existing tests.

Paper-based analytical device for high-throughput monitoring tetracycline residue in milk

A low-cost and portable paper-based analytical device has been developed for high throughput and on-site monitoring TC residue in milk through visualized colorimetric reaction. The filtration and concentration effect induced by the porous nature of paper contribute to strengthen the color intensity, leading to quantitative and sensitive detection of tetracycline reaching 1 ppm detection limit, with the linear range of 1–100 ppm both in water and milk samples. The applicability was demonstrated by detection of TC in 18 different types of real milk samples with good recovery ranging from 88% to 113%. Furthermore, the dynamic degradation behavior of tetracycline was monitored through the device. To the best of our knowledge, this is the first report of colorimetric detection of tetracycline in milk using the paper-based device. This simple, fast, cost-effective (~$0.50 per device) and equipment-free paper-based platform provides a promising tool for future application in food and environmental safety.

A portable test strip based on fluorescent europium-based metal–organic framework for rapid and visual detection of tetracycline in food samples

Residual tetracycline (TC) in animal food caused by abuse of antibiotics leads to many chronic diseases in the human body. The development of a simple and on-site visualization method for TC detection is need of the hour. Herein, a fluorescent europium-based metal–organic framework (Eu-MOF) sensor for visual and rapid detection of TC was developed. Eu-MOF displays a red emission being excited at 260 nm. Upon exposure to TC, significant fluorescence quenching was observed due to the inner filter effect and photoinduced electron transfer. Moreover, the developed sensor was applied for the detection of TC in milk and beef samples with recoveries of 96.1% to 106.3%, respectively. More importantly, a portable test strip based on Eu-MOF was manufactured. It is a highly selective and sensitive portable device for TC detection. The results can be distinguished immediately by naked eyes, making it become an excellent choice to detect TC in real-time application.