Combining GC-MS/MS with a LLE-SPE sample pretreatment step to simultaneously analyse enrofloxacin and ofloxacin residues in chicken tissues and pork.

A widely applicable original gas chromatography-tandem mass spectrometry (GC-MS/MS) method was explored to qualitatively and quantitatively measure enrofloxacin and ofloxacin residues in chicken tissues and pork. The experimental samples were processed based on liquid-liquid extraction (LLE) and solid-phase extraction (SPE). Trimethylsilyl diazomethane (TMSD) was chosen to react derivatively with enrofloxacin and ofloxacin. In total, 78.25% âˆ¼ 90.56% enrofloxacin and 78.43% âˆ¼ 91.86% ofloxacin was recovered from the blank fortified samples. The limits of detection (LODs) were 0.7-1.0 µg/kg and 0.1-0.2 µg/kg, respectively. The limits of quantitation (LOQs) were 1.6-1.9 µg/kg and 0.3-0.4 µg/kg, respectively. It was verified that various experimental data met the requirements of the FAO & WHO (2014) for the detection of veterinary drug residues. Real samples obtained from local markets were analysed using the established method, and no residues of enrofloxacin or ofloxacin were detected in the samples.

A ratiometric fluorescent dark box and smartphone integrated portable sensing platform based on hydrogen bonding induction for on-site determination of enrofloxacin.

Enrofloxacin (ENR) residues in animal-derived food and water threaten human health. Simple, low-cost and on-site detection methods are urgently needed. Blue emitting carbon quantum dots (CQDs) and orange rhodamine B (RhB) were used as recognition and reference signals, respectively, to construct a ratiometric fluorescence sensor. After the addition of ENR, the color of the sensor changed from orange to blue because hydrogen bonding induced a considerable increase in CQDs fluorescence. Based on this mechanism, a simple and low cost on-site portable sensing platform was constructed, which integrated a stable UV light strip and a smartphone with voice-controlled phototaking function and an RGB app. The t-test results of spiked ENR recoveries for diluted milk, honey and drinking water revealed no significant differences between the ratiometric fluorescent sensor and portable sensing platform. Thus, this portable sensing platform provides a novel strategy for on-site quantification of quinolone antibiotics in foodstuffs and environmental water.

Pentacenequinone-Modulated 2D GdSn-PQ Nanosheets as a Fluorescent Probe for the Detection of Enrofloxacin in Biological and Environmental Samples.

The fate and effects of fluoroquinolone antibacterial (FQ) on the environment are important since there appears to be a surge in FQ resistance like enrofloxacin (ENR) in both environmental and clinical organisms. Numerous reports indicate that the sensing capabilities of these antibiotics need to be improved. Here, we have investigated the interaction of ENR with our synthesized pentacenequinone-modulated gadolinium-tin (GdSn-PQ) nanosheets and the formation of intermolecular interactions that caused the occurrence of aggregation-induced emission enhancement. The concept for designing hybrid metallic nanosheets comes from the unique features inherited from the parent organic precursor. Due to the distinct interaction between ENR and GdSn-PQ, the interstate conversion (ISC) between GdSn-PQ and ENR induces a significant wavelength shift in photoluminescence (PL), improving reliability, selectivity, and visibility compared to quenching- or AIEE-based methods without peak shifts, allowing for highly sensitive and visually detectable analyses. The fluorescence signal of GdSn-PQ exhibited a linear relationship (R2 = 0.9911), with the added ENR concentrations ranging from 5 to 90 nM, with a detection limit of 0.10 nM. We have demonstrated its potential and wide use in the detection of ENR in biological samples (human urine and blood serum) and environmental samples (tap water and seawater) with a recovery rate of 98- 108%. The current approach has demonstrated that the 2D GdSn-PQ nanosheet is a novel and powerful platform for future biological and environmental studies.

Citizen science in action: Time-resolved immunofluorescence-based field detection of antibiotics with portable analytical kit.

Citizen scientist-based environmental monitoring and public education are becoming increasingly popular. However, current technologies for antibiotic-based novel contaminant identification are still restricted to laboratory sample collection and analysis due to detection methodologies and apparatus limitations. This study developed a time-resolved immunofluorescence-based simultaneous field-based assay for ciprofloxacin (CIP) and enrofloxacin (ENR) that matches test results to geographic locations. The assay helps the public understand the potential levels of antibiotic exposures in their environments and helps them take appropriate action to reduce risk. The assay was developed using smartphones and social software in addition to rapid testing. The method uses a portable, low-cost analytical kit with a smartphone app to build a field-based detection platform for the detection and analysis of ENR and CIP in water and aquatic products. The methodological evaluation was good, with detection limits of 0.4 ng/mL and 0.5 ng/g for ENR in water and fish, and quantification limits of 1.2 ng/mL and 1.4 ng/g, with recoveries of 89.0 %-101.0 % and 78.0 %-97.0 %. For CIP in water and fish, the limits of detection were 0.3 ng/mL and 0.4 ng/g, the limits of quantification were 0.9 ng/mL and 1.2 ng/g, and the recoveries were 75.0 %-91.0 % and 72.0 %-89.0 %, both with coefficients of variation <15 %. These limits were sufficient to prevent the two antibiotics from crossing over during simultaneous detection. The assay was validated using real samples to assess the effectiveness of the assay platform in field deployments, and the results were consistent with those obtained through liquid chromatography-tandem mass spectrometry (LC-MS) and enzyme-linked immunoassay (ELISA) techniques. In addition, the TRFIA assay process requires less time, uses more portable instruments, and is less complex than traditional methods. This study provides a new scientific, accurate, and rapid detection method for antibiotic detection by citizen scientists, helping scientists to obtain a wider range of data and providing more opportunities to solve scientific problems.

A metal-organic framework signaling probe-mediated immunosensor for the economical and rapid determination of enrofloxacin in milk.

Ensuring the safety of animal-derived foods requires the reliable and swift identification of enrofloxacin residues to monitor the presence of antibiotics. In this regard, we synthesized, tuned, and investigated the optical properties of a bimetallic metal-organic framework (Ce/Zr-UiO 66). The investigation was facilitated by employing a polydopamine-coated pipette tip with high adsorption efficiency, serving as an immunoreactive carrier. Subsequently, an immunofunctionalized variant of Ce/Zr-UiO 66, referred to as Ce/Zr-UiO 66@ Bovine serum albumin-enrofloxacin, was developed as an optical probe for the rapid and sensitive identification of enrofloxacin across a variety of samples. The method can accurately detect enrofloxacin at concentrations as low as 0.12 ng/mL, with a determination time of under 15 min; furthermore, it demonstrates exceptional efficacy when applied to food, environmental, and clinical samples. The implementation of this methodology offers a valuable means for cost-effective, rapid, and on-site enrofloxacin determination.

"Two-in-One" PtPdCu Trimetallic Multifunctional Nanoparticles-Mediated Dual-Signal-Integrated Aptasensor for Ultradetection of Enrofloxacin.

Balancing the accuracy and simplicity of aptasensors is a challenge in their construction. This study addresses this issue by leveraging the remarkable loading capacity and peroxidase-like catalytic activity of PtPdCu trimetallic nanoparticles, which reduces the reliance on precious metals. A dual-signal readout aptasensor for enrofloxacin (ENR) detection is designed, incorporating DNA dynamic network cascade reactions to further amplify the output signal. Exploiting the strong loading capacity of PtPdCu nanoparticles, they are self-assembled with thionine (Thi) to form a signal label capable of generating signals in two independent modes. The label exhibits excellent enzyme-like catalytic activity and enhances electron transfer capabilities. Differential pulse voltammetry (DPV) and square-wave voltammetry (SWV) are employed to independently read signals from the oxidation-reduction reaction of Thi and the catalytic oxidation of hydroquinone (HQ) to benzoquinone (BQ) by H2O2. The introduced DNA dynamic network cascade reaction modularizes sample processing and electrode surface signal generation, avoiding electrode contamination and efficiently increasing the output of the catalyzed hairpin assembly (CHA) cycle. Under optimized conditions, the developed aptasensor demonstrates detection limits of 0.112 (DPV mode) and 0.0203 pg/mL (SWV mode). Additionally, the sensor successfully detected enrofloxacin in real samples, expanding avenues for designing dual-mode signal amplification strategies.

High-performance SERS chips for sensitive identification and detection of antibiotic residues with self-assembled hollow Ag octahedra.

High-performance SERS chips via self-assembled hollow Ag octahedra on PDMS were employed to achieve the sensitive identification and detection of antibiotic residues. The developed SERS chips were successfully applied in the detection of ciprofloxacin (CIP), amoxicillin (AMX) and cefazolin (CZL) in wastewater and tap water samples, as well as enrofloxacin (ENR) in milk, demonstrating the sensitive determination of antibiotics in the real environment. From this perspective, these SERS chips are expected to expand the on spot sensitive detection and identification field of antibiotic residues.

Comparison of oriented and non-oriented antibody conjugation with AIE fluorescence microsphere for the immunochromatographic detection of enrofloxacin.

Antibodies and labels were typically non-oriented conjugated in conventional immunochromatographic assays (ICAs). In this work, a C-terminal cysteine-tagged recombinant protein A (rPA) was conjugated in an oriented manner onto aggregation-induced emission fluorescence microsphere (AIEFM). The Fc fragment of anti-enrofloxacin monoclonal antibody (anti-ENR mAb) was then conjugated onto the rPA. The resulting oriented mAb-AIEFM probe was used in an ENR-ICA for the rapid detection of ENR, a widely abused animal drug. The ENR-ICA with the oriented probe saved 66.7% of anti-ENR mAb and 25% of ENR-bovine serum albumin, and had a limit of detection of 0.035 ng/mL, compared with 0.079 ng/mL for the non-oriented probe. The corresponding linear ranges of the ENR-ICA based on the oriented and non-oriented probes were 0.25-10 ng/mL and 0.1-2.5 ng/mL, respectively. This novel ICA based on the oriented probe has the potential to be used for sensitive and rapid detection in food safety.

Detection of enrofloxacin residues in dairy products based on their fluorescence quenching effect on AgInS2 QDs.

Water-soluble AgInS2 (AIS) quantum dots (QDs) were successfully prepared through the one-pot water phase method with thioglycolic acid (TGA) as the stabilizing agent. Because enrofloxacin (ENR) effectively quenches the fluorescence of AIS QDs, a highly-sensitive fluorescence detection method is proposed to detect ENR residues in milk. Under optimal detection conditions, there was a good linear relationship between the relative fluorescence quenching amount (ΔF/F0) of AgInS2 with ENR and ENR concentration (C). The detection range was 0.3125-20.00 µg/mL, r = 0.9964, and the detection limit (LOD) was 0.024 µg/mL (n = 11). The average recovery of ENR in milk ranged from 95.43 to 114.28%. The method established in this study has advantages including a high sensitivity, a low detection limit, simple operation and a low cost. The fluorescence quenching mechanism of AIS QDs with ENR was discussed and the dynamic quenching mechanism of light-induced electron transfer was proposed.

Inhomogeneous antibiotic distribution in sediment profiles in anthropogenically impacted lakes: Source apportionment, fate drivers, and risk assessment.

Antibiotic residues in lake ecosystems have been widely reported; however, the vertical distribution of antibiotics in lake sediment profiles have rarely been examined. This study systematically revealed the vertical distribution pattern, sources, and risks of antibiotics in sediments of four typical agricultural lakes in central China. Nine of 33 target antibiotics were detected with a total concentration range of 39.3-18,250.6 ng/g (dry weight), and the order of average concentration was erythromycin (1447.4 ng/g) > sulfamethoxazole (443.7 ng/g) > oxytetracycline (62.6 ng/g) > enrofloxacin (40.7 ng/g) > others (0.1-2.1 ng/g). The middle-layer sediments (9-27 cm) had significantly higher antibiotic detected number and concentration than those in the top layer (0-9 cm) and bottom layer (27-45 cm) (p < 0.05). Correlation analysis showed that significant relationships existed between antibiotic concentrations and the octanol-water partition coefficients (Kow) of antibiotics (p < 0.05). Redundancy analysis indicated that Pb, Co, Ni, water content, and organic matter (p < 0.05) jointly affected the distribution of antibiotics in sediment profiles. Risk assessment showed that the highest potential ecological and resistance selection risks of antibiotics occurred in the middle-layer sediments, and oxytetracycline, tetracycline, and enrofloxacin had the most extensive potential risks in the sediment profiles. Additionally, the positive matrix factorization model revealed that human medical wastewater (54.5%) contributed more antibiotic pollution than animal excreta (45.5%) in sediment. This work highlights the inhomogeneous distribution of antibiotics in sediment profiles and provides valuable information for the prevention and control of antibiotic contamination in lakes.

Use of Fluorescence Spectroscopy and Chemometrics to Visualise Fluoroquinolones Photodegradation Major Trends: A Confirmation Study with Mass Spectrometry.

In this work, we employed EEM-PARAFAC (fluorescence excitation-emission matrices-parallel factor analysis) as a low-cost tool to study the oxidation pathways of (fluoro)quinolones. Amounts of 12.5 µM of enrofloxacin (ENR), ciprofloxacin (CIP), ofloxacin (OFL), oxolinic acid (OA), and flumequine (FLU), as individual solutions, were irradiated under UVA light. A 5-component PARAFAC model was obtained, four of them related to the parent pollutants, named as ENR-like (including CIP), OFL-like, OA-like, and FLU-like, and an additional one related to photoproducts, called ENRox-like (with an emission red-shift with respect to the ENR-like component). Mass spectrometry was employed to correlate the five PARAFAC components with their plausible molecular structures. Results indicated that photoproducts presenting: (i) hydroxylation or alkyl cleavages exhibited fingerprints analogous to those of the parent pollutants; (ii) defluorination and hydroxylation emitted within the ENRox-like region; (iii) the aforementioned changes plus piperazine ring cleavage emitted within the OA-like region. Afterwards, the five antibiotics were mixed in a single solution (each at a concentration of 0.25 µM) in seawater, PARAFAC being also able to deconvolute the fingerprint of humic-like substances. This approach could be a potential game changer in the analysis of (fluorescent) contaminants of emerging concern removals in complex matrices, giving rapid visual insights into the degradation pathways.

The antibiotic resistance and risk heterogeneity between urban and rural rivers in a pharmaceutical industry dominated city in China: The importance of social-economic factors.

Rivers are important environmental sources of human exposure to antibiotic resistance. Many factors can change antibiotic resistance in rivers, including bacterial communities, human activities, and environmental factors. However, the systematic comparison of the differences in antibiotics resistance and risks between urban rivers (URs) and rural rivers (RRs) in a pharmaceutical industry dominated city is still rare. In this study, Shijiazhuang City (China) was selected as an example to compare the differences in antibiotics resistance and risks between URs and RRs. The results showed higher concentrations of total quinolones (QNs) antibiotics in both water and sediment samples collected from URs than those from RRs. The subtypes and abundances of antibiotic resistance genes (ARGs) in URs were significantly higher than those in RRs, and most emerging ARGs (including OXA-type, GES-type, MCR-type, and tet(X)) were only detected in URs. The ARGs were mainly influenced by QNs in URs and social-economic factors (SEs) in RRs. The composition of the bacterial community was significantly different between URs and RRs. The abundance of antibiotic-resistant pathogenic bacteria (ARPBs) and virulence factors (VFs) were higher in URs than those in RRs. Therein, 371 and 326 pathogen types were detected in URs and RRs, respectively. Most emerging ARGs showed a significantly positive correlation with priority ARPBs. Variance partitioning analysis revealed that SEs were the main driving factors of ARGs (80 %) and microbial communities (92 %) both in URs and RRs. Structural equation models indicated that antibiotics (QNs) and microbial communities were the most direct influence of ARGs in URs and RRs, respectively. The cumulative resistance risk of QNs was high in URs, but relatively low in RRs. Enrofloxacin and flumequine posed the highest risk in water and sediment, respectively. This study could help us to better manage and control the risk of antibiotic resistance in different rivers.

A high-precision prediction for spatiotemporal distribution and risk assessment of antibiotics in an urban watershed using a hydrodynamic model.

A methodology for the high-precision prediction and risk assessment of antibiotics at the watershed scale was established. Antibiotic emission inventory and attenuation processes were integrated into the MIKE 11 model to predict the spatiotemporal distribution of norfloxacin, ofloxacin, enrofloxacin, erythromycin, roxithromycin, and sulfamethoxazole in the Nanfei River watershed, China. Considering the variations in antibiotic removal in sewage treatment plants, manure composting, and lagoon systems, the high, medium, and low removal efficiencies of selected antibiotics across China were obtained and used as the best, expected, and worst scenarios, respectively, to evaluate the uncertainty of antibiotic emissions. The predicted concentrations were comparable to antibiotic measurements after flow calibration. The prediction results showed that the highest concentration exposures were mainly concentrated in urban areas with a dense population. Flow variations controlled the temporal distribution characteristics of antibiotics via the dilution effect, and the concentrations of antibiotics in the dry season were 3.1 times higher than those in the wet season. The median concentrations of norfloxacin and erythromycin ranged from 111.36 ng/L to 592.33 ng/L and 106.63 ng/L to 563.01 ng/L, respectively, which both posed a high risk to cyanobacteria and a medium risk to spreading antibiotic resistance. Scenario analysis further demonstrated that high removal efficiencies of these antibiotics can considerably reduce the potential ecotoxicity risks and bacterial resistance selection. The developed methodology for predicting the distribution and risk of antibiotics was suitable for the risk assessment and control strategy of human- and livestock-sourced pollutants.

Metabolites in Milk after Enrofloxacin Treatment and Their Persistence to Temperature.

In this work, metabolomic profile changes in milk from cows affected by mastitis and treated with enrofloxacin (ENR) have been studied using LC-HRMS techniques. Principal component analysis was applied to the obtained results, and the interest was focused on changes affecting compounds without a structural relationship to ENR. Most of the compounds, whose concentrations were modified as a result of the pharmacological treatment and/or the pathological status, were related to amino acids and peptides. Compounds that may become possible biomarkers for either disease or treatment have been detected. Additionally, the alterations caused by thermal processes, such as those applied to milk before consumption, on the identified metabolites have also been considered.

Uptake of Pharmaceutical Pollutants and Their Metabolites from Soil Fertilized with Manure to Parsley Tissues.

Manure is a major source of soil and plant contamination with veterinary drugs residues. The aim of this study was to evaluate the uptake of 14 veterinary pharmaceuticals by parsley from soil fertilized with manure. Pharmaceutical content was determined in roots and leaves. Liquid chromatography coupled with tandem mass spectrometry was used for targeted analysis. Screening analysis was performed to identify transformation products in the parsley tissues. A solid-liquid extraction procedure was developed combined with solid-phase extraction, providing recoveries of 61.9-97.1% for leaves and 51.7-95.6% for roots. Four analytes were detected in parsley: enrofloxacin, tylosin, sulfamethoxazole, and doxycycline. Enrofloxacin was detected at the highest concentrations (13.4-26.3 ng g-1). Doxycycline accumulated mainly in the roots, tylosin in the leaves, and sulfamethoxazole was found in both tissues. 14 transformation products were identified and their distribution were determined. This study provides important data on the uptake and transformation of pharmaceuticals in plant tissues.

Benzotrithiophene-based covalent organic frameworks for real-time visual onsite assays of enrofloxacin.

Enrofloxacin (ENR) is a fluoroquinolone antibiotic that has been used to treat bacterial diseases in aquaculture extensively. ENR might accumulate in the body and cause severe liver damage. Therefore, it is necessary to develop a method for rapid detection of ENR. Herein, amine monomers with different numbers of amino groups, charge and length (1,3-diaminoguanidine monohydrochloride: DMGH, triaminoguanidine hydrochloride: TAGH, hydrazine: H) were used to regulate the fluorescence of benzotrithiophene tricar-baldehyde (BTT)-based covalent organic frameworks (COFs) for real-time visual onsite assays of ENR for the first time. The C3 symmetric COFBTT-TAGH only had one emission peak at 540 nm, while C6 symmetric COFBTT-DMGH and COFBTT-H had two emission peaks. COFBTT-TAGH could achieve the color transition from green to blue with increasing ENR. Thus test paper and gel were designed as real-time detection tools, combined with a smartphone APP. The detection limits obtained by RGB analysis were 106.2 nM for test paper and 26.00 nM for test gel, respectively. This method was applied to detect ENR in fish and clam metabolite successfully. This work also provides important reference to regulate fluorescence of COFs according to actual application.

Association between fluoroquinolone exposure and children's growth and development: A multisite biomonitoring-based study in northern China.

BACKGROUND: Although animal experiments found that antibiotic exposure during early life increased adiposity, limited human epidemiological evidence is available for the effects of veterinary antibiotic exposure on children's growth and development. OBJECTIVE: This study was conducted to examine the body burden of fluoroquinolones in northern Chinese children and assess its association with growth and development. METHODS: After recruiting 233 children aged 0-15 years from 12 different sites in northern China in 2020, we measured urinary concentrations of 5 respective fluoroquinolones (fleroxacin, ofloxacin, norfloxacin, ciprofloxacin, and enrofloxacin) by high performance liquid chromatography. Categories of children's growth and development were identified based on the Z score of body mass index. The health risks of individual and combined antibiotic exposure were estimated by the hazard quotient (HQ) and hazard index (HI), respectively. The association between children's growth and development with antibiotic concentrations was evaluated via multiple logistic regression analysis. RESULTS: In total, 4 antibiotics, fleroxacin, ofloxacin, ciprofloxacin, and enrofloxacin, were found in urine samples of northern Chinese children at an overall frequency of 57.08%. Due to diet and economic differences, antibiotic concentrations in urine samples differed by study area, and the highest concentrations were found in Tianjin, Henan, and Beijing. The percentage of the participants with HQ > 1 caused by ciprofloxacin exposure was 20.61%, and the HI values in 23.18% of samples exceeded 1, suggesting potential health risks. The odds ratio (95% confidence interval) of overweight or obesity risk of tertile 2 of enrofloxacin was 3.01 (1.12, 8.11), indicating an increase in overweight or obesity risk for children with middle-concentration enrofloxacin exposure. CONCLUSION: This is the first study to show a positive association of enrofloxacin internal exposure with overweight or obesity risk in children, demonstrating that more attention should be given to the usage and disposal of fluoroquinolones to safeguard children's health.

Activation of persulfate by a water falling film DBD process for the enhancement of enrofloxacin degradation.

A synergetic system of water falling film dielectric barrier discharge (DBD) plasma and persulfate (PS) was established and applied to enhance the enrofloxacin (EFA) degradation in this study. The simultaneous existence of electrons, reactive species, heat and UV-visible light in the DBD plasma system were utilized together to activate the PS to form SO4-· and other reactive oxygen species (ROS), and then worked in synergy with the DBD plasma to oxidize the EFA. The obtained results verified that there was a significant increase in the degradation percentages of EFA (20 mg L-1) in the DBD/PS system, and the trend was more obvious under the condition of larger discharge power input. When 0.8 mM PS was added into the DBD system with 0.8 kW discharge power, the degradation percentage of EFA could reach 99.35% after 60 min treatment, the corresponding synergetic factor (SF) was 7.94. Analysis of the O3 and the H2O2 concentrations in the DBD plasma system before and after the PS addition explained the activation of the PS by the HO·. The quenching experiments on reactive species suggested that SO4-·, HO·, and 1O2 were all important reactive species for EFA degradation. The intermediates formed by the EFA degradation were detected and the degradation pathways were speculated. Results of toxicity analysis illustrated that the toxicity of the initial EFA solution decreased after degradation in the synergetic system of DBD/PS.

Dipeptide nanoparticle and aptamer-based hybrid fluorescence platform for enrofloxacin determination.

A novel fluorescence platform was fabricated for enrofloxacin determination by using cDNA-modified dipeptide fluorescence nanoparticles (FDNP-cDNA) and aptamer-modified magnetic Fe3O4 nanoparticles (Fe3O4-Apt). The FDNP were prepared via tryptophan-phenylalanine self-assembling. When magnetic Fe3O4-Apt incubated with standard solution or sample extracts, the target enrofloxacin was selectively captured by the aptamer on the surface of the Fe3O4 nanoparticles. After removing interference by washing with phosphate-buffered saline, the FDNP-cDNA was added, which can bind to the aptamer on the surface of the Fe3O4 nanoparticles not occupied by the analyte. The higher the concentration of the target enrofloxacin in the standard or sample solution is, the less the FDNP-cDNA can be bound with the Fe3O4 nanoparticles, and the more the FDNP-cDNA can be observed in the supernatant. Fluorescence intensity (Ex/Em = 310/380 nm) increased linearly in the enrofloxacin concentration range 0.70 to 10.0 ng/mL with a detection limit of 0.26 ng/mL (S/N = 3). Good recoveries (88.17-99.30%) were obtained in spiked lake water, chicken, and eel samples with relative standard deviation of 2.7-6.2% (n = 3).

Novel electrochemical sensor modified with molecularly imprinted polymers for determination of enrofloxacin in marine environment.

Molecularly imprinted polymers were synthesized by gel-sol method with multi-walled carbon nanotubes as support and enrofloxacin as a template and further modified on the surface of glassy carbon electrode to construct a molecularly imprinted electrochemical sensor. The performance of the imprinted electrochemical sensor was thoroughly investigated by using cyclic voltammetry and differential pulse voltammetry. The influence of imprinted polymers amount, electrolyte pH, and incubation time on the sensor performance was investigated for the detection of enrofloxacin. Under the optimal experimental conditions in a three-electrode system with the modified electrode as the working electrode the differential pulse voltammetry response current of the sensor had a good linear relationship at 0.2 V (vs. saturated calomel reference electrode) with the enrofloxacin concentration within 2.8 pM-28 µM and the limit of detection of the method was 0.9 pM. The competitive interference experiment showed that the imprinted electrochemical sensor could selectively recognize enrofloxacin. The method was applied to analyze spiked natural seawater, fish, and shrimp samples. The recovery was 96.4%-102%, and RSD was less than 4.3% (n = 3), indicating that the proposed imprinted electrochemical sensor was suitable for the determination of trace enrofloxacin in marine environment samples.