Tetracycline Antibiotics In Water Research Articles

Dye-encapsulated metal–organic frameworks as highly sensitive fluorescent sensors for tetracycline antibiotics in water

As a type of porous material with highly controllable pore structure and surface functionalization, metal–organic frameworks (MOFs) have unique advantages in antibiotic content detection in the environment. Herein, we successfully regulated the luminescent properties of MOF-808 through the in-situ loading of fluorescent dye molecules, and achieved excellent luminescent sensing detection performance for tetracycline antibiotics in water environments (LOD = 79.9 ppb). Additionally, the construction of a convenient luminescent detection test paper sensor provides a new approach and method for the rapid, recyclable detection and monitoring of antibiotics.

A ratiometric dual-fluorescent paper-based synthetic biosensor for visual detection of tetracycline on-site

The excessive use of tetracycline poses a threat to human health, making it essential to monitor and regulate its usage. While whole-cell biosensors offer a simple and cost-effective method, their utility is constrained by limitations in sensitivity, portability, and robustness, hindering real-time measurements within complex environmental contexts. In this study, a ratiometric i/cTetR synthetic biosensing test strip with an engineered modified dual-fluorescence reporting was developed for detecting Tet antibiotics in water and food. First, the standardized unidirectional promoter PtetR by tailoring and screening TetR transcription factor binding sites and verified by molecular docking, shortening the detection time. Secondly, decoupling the sensing and reporting modules enhances the biosensor's performance, eliminating genetic background leakage and tripling the output signal. Thirdly, a ratiometric dual fluorescence signal i/cTetR biosensing test strip was designed. Under the light box LED/UV light source, the dual signal output method significantly reduced false negative results and enhanced the anti-interference capability of the biosensor. The i/cTetR strips can detect Tet in tap water (5–1280 μg/mL) and milk (50–3200 μg/kg) within 45 min in high volume on-site without separation and purification. This study provides a standardized and universal sensing method for the field detection of antibiotic contaminants.

Preparation and characterization of chitosan-curdlan composite magnetized by zinc ferrite for efficient adsorption of tetracycline antibiotics in water

Tetracycline (TC) antibiotic-related water pollution directly threatens human health and ecosystems. Here, a zinc ferrite/chitosan-curdlan (ZNF/CHT-CRD) magnetic composite was prepared via a co-precipitation method to be used as a novel, green adsorbent for TC removal from water. Benefiting from a multitude of functional groups, CRD was first crosslinked with CHT and then magnetized with ZNF to provide an easy separation from the solution with an external magnetic force. The successful synthesis and magnetization of the composite were verified with different characterization techniques. The effect of solution pH and composite dosage was carefully evaluated. The optimum solution pH and composite dosage were 6 and 0.65 g/L, respectively, with complete TC removal. The adsorption process by the magnetic composite followed the pseudo-first-order kinetics and Langmuir isotherm models. The maximum adsorption capacity determined from the Langmuir model was 371.42 mg/g at 328 K. Thermodynamic parameters indicated endothermic and spontaneous adsorption. Meanwhile, the composite could be readily separated from the aqueous solution thanks to its magnetic property. Then, it was regenerated with acetone and ethanol to be reused for five more successive cycles. Interestingly, the prepared adsorbent was highly stable and performant in removing TC, maintaining approximately 90 % of its first-cycle adsorption capacity. The adsorption mechanism was primarily attributed to electrostatic and hydrogen bonding attractions. Overall, the currently developed adsorbent could be a more favorable, efficient, and cost-effective candidate than other magnetic chitosan-based composites. These features make it applicable for treating water contaminated with various pharmaceutical pollutants with high separation efficiency and easy recovery under successive adsorption-desorption cycles.

Optimization and Validation of Europium-Sensitized Fluorescence Method for Determination of Tetracycline Antibiotics in Water from Fish Farms

Sensitized europium fluorescence was used for simple, fast and efficient determination of tetracycline residues in water from fish farms. Tetracycline antibiotics: oxytetracycline (OTC), tetracycline (TC) and chlortetracycline (CTC) were extracted from water samples using polymeric hydrophilic–lipophilic balanced cartridges. After evaporation and pre-concentration, tetracyclines form a complex with europium and citric acid as coligand at pH 8.5. The complex formed has a wide absorption spectrum at 388 nm and a narrow emission maximum at 619 nm resulting from the 5D0 - 7F2 transition within the europium ion. The complex is stable with intensive fluorescence and linear in the concentration range of 5-2500 µg/L for tetracycline and oxytetracycline and 5-1000 µg/L for chlortetracycline. The detection limit was 0.68 µg/L for OTC, 1.29 µg/L for TC and 0.65 µg/L for CTC, respectively.The proposed method is very sensitive and particularly applicable to samples where low concentrations of tetracycline antibiotics are expected.

RSM-Optimization Approach for Dispersive Micro Solid Phase Extraction of Tetracycline Antibiotics in Water

RSM-Optimization Approach for Dispersive Micro Solid Phase Extraction of Tetracycline Antibiotics in Water

Stable Metal-Organic Frameworks for Fluorescent Detection of Tetracycline Antibiotics.

The rapid detection of antibiotics in agricultural products is of great significance. In this work, two stable fluorescent metal-organic frameworks (MOFs), BUT-178 and BUT-179, are synthesized and used to detect tetracycline antibiotics. Among them, BUT-179 exhibits better performance in the detection of different tetracycline antibiotics in water and eggs. The limits of detection of BUT-179 toward tetracycline, aureomycin, oxytetracycline, and doxycycline all reach the nanomolar level. Furthermore, the cycling tests confirm that BUT-179 can be easily recovered and repeatedly used without an obvious performance loss. This work demonstrates the excellent application potential of MOFs for food safety, especially the fluorescence detection of antibiotics in foods.

Oxidative degradation of tetracycline using peroxymonosulfate activated by cobalt-doped pomelo peel carbon composite.

Tetracycline (TC) is a typical ecotoxic antibiotic, which easily causes bacterial resistance. Therefore, it is necessary to remove TC from the water environment. In recent years, advanced oxidation processes (AOPs) rely on the use of highly reactive oxidizing sulfate radical which is turning into an increasingly popular as a tool of the removal of TC. In this study, cobalt-doped pomelo peel carbon composite (Co-PPCC) was prepared by the impregnation coprecipitation method to activate peroxymonosulfate (PMS) to remove TC. SEM, BET, XRD, FTIR, XPS, TGA, and other analytical techniques indicated that a carbon composite catalyst with excellent performance has been successfully prepared. TC was removed by the synergistic effect of adsorption and catalytic degradation processes. The adsorption capacity was limited (only approximately 20% within 60 min) and tending to saturation, which indicated that the removal of TC in the Co-PPCC/PMS system was mainly due to oxidative degradation. The influence of the Co-PPCC and PMS dosage, initial TC concentration, initial pH values, and coexisting anions on the removal efficiency of TC was investigated. When the Co-PPCC catalyst dosage was 1 g/L, PMS concentration was 2 g/L, and pH value was 11, the removal efficiency of TC with a concentration of 50 mg/L reached 99% within 60 min. Free radical quenching experiment and electron paramagnetic resonance (EPR) analysis indicated that the free radical and non-radical degradation processes exist in the Co-PPCC/PMS/TC system. The main degradation products and the possible transformation pathways of TC were explored by LC-MS. In addition, after four cycles of Co-PPCC tests, the removal efficiency of TC can reach 64%. This study provides a new method to reuse abandoned pomelo peels and synthesize an economical and environmentally friendly catalyst for activating peroxymonosulfate to remove TC antibiotics in water.

Detection of tetracycline antibiotics in water by dispersive micro-solid phase extraction using Fe3O4@[Cu3(btc)2] magnetic composite combined with liquid chromatography-tandem mass spectrometry

Residues of tetracycline antibiotics (TCs) in environments may be harmful to human. Due to their high polarities, it is extremely challenging to efficiently enrich TCs with low concentrations in natural waters for analysis. In this work, a magnetic metal-organic framework Fe3O4@[Cu3(btc)2] was synthesized and applied as a dispersive micro-solid phase extraction adsorbent for TCs enrichment. Effects of dispersive micro-solid phase extraction conditions including extraction time, solution pH, and elution solvent on the extraction efficiencies of TCs were investigated. Results show that TCs could be enriched efficiently by Fe3O4@[Cu3(btc)2], and electrostatic interaction between TCs and Fe3O4@[Cu3(btc)2] dominated this process. Combined with liquid chromatography-tandem mass spectrometry, four TCs residues (oxytetracycline, tetracycline, chlortetracycline, and doxycycline) in natural waters were determined. The detection limits (LOD, S/N = 3) of the four antibiotics were 0.01–0.02 µg/L, and the limits of quantitation (LOQ, S/N = 10) were 0.04–0.07 µg/L. The recoveries obtained from river water and aquaculture water spiked with three TCs concentration levels ranged from 70.3% to 96.5% with relative standard deviations of 3.8%–12.8%. Results indicate that the magnetic metal-organic framework based dispersive micro-solid phase extraction is simple, rapid and high-loading for antibiotics enrichment from water, which further expand the practical application of metal-organic frameworks in sample pretreatment for environmental pollutant analysis.

Tetracycline antibiotics and NH4+ detection by Zn-organic framework fluorescent probe.

A fluorescent probe based on single metal-organic framework material without additional fluorophores and active sites can significantly improve the stability of the probe for detection, and has very important application value in environmental analysis and detection. In this paper, a simple and rapid fluorescence detection method was established with Zn-MOF, which realized the highly sensitive detection of tetracycline antibiotics and NH4+ in water. The prepared Zn-MOF has abundant pores and can exist stably in water. When tetracycline antibiotics are present in Zn-MOF aqueous solution, based on the unique coordination ability between Zn and N, tetracycline antibiotics rich in N will be adsorbed into the pore canals of MOF, and aggregation-induced luminescence will occur. The original non-fluorescent Zn-MOF will immediately produce yellow fluorescence, realizing the detection of tetracycline antibiotics in water, with the limit of detection reaching 0.017 μM in a linear range of 0.02-13 μM. Zn-MOF is further used for the detection of tetracycline antibiotics in actual samples of milk and honey. Oxytetracycline (OTC) with the best fluorescence response of tetracycline antibiotics was coated on Zn-MOF to synthesize OTC@Zn-MOF fluorescent probe. NH4+ will replace the original ligand of Zn-MOF, which will disintegrate MOF and release OTC, resulting in a fluorescence decrease. Therefore, NH4+ can be detected with low limit of detection (0.038 μM) in a linear range of 0 to 3 mM. The probe is expected to be able to detect ammonia in the environment.

Copper carboxymethyl cellulose nanoparticles for efficient removal of tetracycline antibiotics in water.

Copper carboxymethyl cellulose nanoparticles were prepared and characterized by FT-IR, XRD, SEM, TEM, and EDX techniques. Removal of tetracycline was obtained at 90% with optimized parameters of 500μg/L concentration, 40min contact time, 7.5 pH, 1.5g/L dose, and 298 K temp. The adsorption followed Freundlich model very well in comparison to Langmuir. Tempkin model described good interactions between tetracycline and nanoparticles. Dubinin-Radushkevich isotherm confirmed the chemical nature of adsorption. The adsorption was pseudo-second order with a liquid film diffusion kinetics mechanism. The adsorption was endothermic and spontaneous as suggested by thermodynamics results. The supramolecular mechanism was developed for the process. Interestingly, the process was suitable at 7.5 pH with low contact time. These features of the adsorption made this process applicable at natural water conditions, making the process eco-friendly and feasible. Therefore, it may be an excellent method for the removal of tetracycline in any water system.

3D hierarchical H2-reduced Mn-doped CeO2 microflowers assembled from nanotubes as a high-performance Fenton-like photocatalyst for tetracycline antibiotics degradation

Developing of active and synergistic system is fundamentally important to rapidly and efficiently remove persistent toxic and hazardous pollutants. Herein, we report a coupling system by integrating sulfate radical-based Fenton-like process with visible light-driven photocatalysis for fast removal of three typical tetracycline antibiotics in water, i.e., tetracycline (TC), chlortetracycline (CTC), and oxytetracycline (OTC), where the newly-designed nanotubes-assembled 3D hierarchical H2-reduced Mn-doped CeO2 microflowers (re-Mn-CeO2 NMs) are developed as efficient Fenton-like photocatalyst for peroxymonosulfate (PMS) activation. The obtained re-Mn-CeO2 NMs samples, featuring large surface area, good visible light response, excellent redox properties, and abundant oxygen vacancy, exhibit appreciable adsorption capacity, remarkable catalytic performance, and favorable stability. Especially, in the optimal reaction system (re-7Mn-CeO2 NMs/PMS/Vis), the degradation efficiencies of TC, CTC, and OTC reach up to 98.6%, 97.4%, and 88.1% only in 10 min of irradiation. All residues can be completely eliminated in 60 min, which is ∼1.1 and 2.0-fold higher than those of Fenton-like reaction and photocatalysis alone, confirming the synergistic effect of Fenton-like process and photocatalysis occurred in the coupling system. Moreover, the possible decomposition pathways, main reactive oxygen species, and reasonable enhanced mechanism for the Fenton-like photocatalytic system are systematically investigated. Our findings highlight that the Fenton-photocatalysis synergy holds great promising for environment remediation, and offer a feasible means to tune the performance of CeO2-based materials especially in Fenton-like photocatalytic oxidation of antibiotics.

Luminescent lanthanide metal-organic framework test strip for immediate detection of tetracycline antibiotics in water

Tetracycline antibiotics (TCs) are a kind of commonly used antibiotics for treating infections, however, the overuse of TCs has adversely affected human health and the ecosystem. Thus, detection of TCs in water is important but challenging. In this work, a luminescent lanthanide metal-organic framework (LnMOF) sensor (1) for immediate detection of oxytetracycline (OTC) and tetracycline (TC) is developed. The sensor has high acid-base and water stability. Investigation reveals that among the 27 species of antibiotics, anions and cations under investigation, 1 shows highly selective sensing towards OTC and TC, and the detection is not disturbed by the presence of other species. The limit of detection (LOD) for OTC and TC are ultra-sensitive value of 1.95 and 2.77 nM, respectively. Investigation reveals the sensing mechanism is due to the inner filter effect. Further studies reveal that the sensor can be used in real sample monitoring. More importantly, test strips based on 1 are manufactured. They are an easy-to-use, low-cost, highly selective and sensitive sensing device for detecting OTC and TC. The sensing can be distinguished immediately and easily by the naked eyes, making it an excellent candidate to monitor OTC and TC in real use.

Distribution Characteristics and Ecological Risk Assessment of Tetracyclines Pollution in the Weihe River, China

To examine the residual and distributions of tetracycline antibiotics in the Weihe River, SPE-UPLC (solid phase extraction-ultra performance liquid chromatography with UV-Vis detection) was employed to analyze the oxytetracycline (OTC), chlortetracycline (CTC), and minocycline (MC) of 41 surface water and 35 sediment samples collected from main streams, tributaries, and main sewage outlets. The results showed that: (1) The order of residual levels of tetracycline antibiotics in water and sediment from high to low was the following: OTC > CTC > MC., considering the water solubilities are 313 mg/L, 630 mg/L, and 50200mg/L and octanol water partition coefficients (Kow) are 7.94, 4.16, and 1.12 for OTC, CTC, and MC, respectively. Thus, the distribution of antibiotics was not only related to the basic properties of antibiotics, but also some environmental factors. The concentrations of OTC in water and sediment were in the range of 1.56–87.89 ng/L and 6.13–45.38 ng/g (mean value of 16.13 ng/L and 20.60 ng/g), respectively; while CTC was 1.07–26.78 ng/L and 6.17–32.29 ng/g (mean value of 4.96 ng/L and 14.48 ng/g), respectively; and MC was 0.28–12.35 ng/L and 4.80–29.74 ng/g (mean value of 1.70 ng/L and 12.96 ng/g), respectively. There were maximum concentrations in all sewage outlets. Compared with other areas in China, tetracyclines residual in the Weihe river were at a medium level; (2) in spatial distribution, the levels of tetracyclines in water and sediment from the middle and upper reaches were higher than the lower reaches. Meanwhile, the sewage outfalls and livestock farm waste water discharge appeared to be the main sources of tetracycline antibiotics in the Weihe River; (3) ecological risk assessment revealed that in main streams and tributaries, OTC and CTC may be at a low ecological risk level; while in sewage outfalls, they may represent a medium ecological risk level.

Gold modified microelectrode for direct tetracycline detection

The residues of tetracycline antibiotics in water have attracted many concerns due to their harmful impact to human health. This paper reports an electrochemical sensor for the determination of tetracycline (TC) by the microelectrode, which was fabricated by electrodeposited gold colloids on tungsten tip. Cyclic voltammerty was used to study the electrochemical behavior of TC on the microelectrode. Well anodic wave was obtained at about 1.5 V in acidic solutions. Electrochemical determination of tetracycline was investigated using microelectrode by cyclic voltammetry. Under optimized conditions, the calibration curves for TC were obtained. The oxidation peak currents were linearly related to TC concentrations in the range of 1–10 mg·L−1 and 10–100 mg·L−1, respectively. The detection limit was 0.09 mg·L−1 (S/N = 3).

Separation/enrichment of trace tetracycline antibiotics in water by [Bmim]BF 4–(NH 4) 2SO 4 aqueous two-phase solvent sublation

A new preconcentration/separation method of [Bmim]BF 4–(NH 4) 2SO 4 aqueous two-phase solvent sublation was established and used to analyze tetracycline antibiotics, including tetracycline (TC) and oxytetracycline (OTC). The optimal conditions were investigated and discussed. The real water samples containing TC/OTC were analyzed, and the results were satisfying. The detection limits (LOD) of TC and OTC are 41.7 μg L − 1 and 52.1 μg L − 1 , respectively. The relative standard deviation of 0.04 mg mL − 1 TC/OTC for 10 parallel determinations is less than 2.5%. Molar absorptivities ( ε) of TC and OTC are 1.65 × 10 4 L mol − 1 cm −1 and 1.3 × 10 4 L mol −1 cm −1, respectively. [Bmim]BF 4–(NH 4) 2SO 4 aqueous two-phase solvent sublation is shown to be promising for the separation and enrichment of trace TC/OTC as well as other substances in the environment.