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To explore potential factors contributing to high fluoroquinolone resistance levels, it is essential to develop analytical methods capable of detecting residues and trace amounts of antibiotic use in broilers. The aim of the present study was to develop and in-house validate a sensitive UHPLC-MS/MS method capable of determining enrofloxacin (ENR) and flumequine (FLU) residues at slaughter age (day 45) when the animals were treated with these antimicrobials one day after hatching. Residue depletion of ENR and FLU in feathers was also assessed. Two experimental trials were performed, both consisting of 5 different treatment groups. In the first trial animals were treated with ENR and in the second one with FLU. The developed method was successfully validated and was found to be sensitive enough to detect residues of fluoroquinolones in the feathers up until slaughter age in all treatment groups. Average ENR concentration on day 45 was 10 ng g -1 feather after drinking water treatment, with all concentrations above the limit of quantification (LOQ) of 5 ng g -1 feather. For FLU average concentration on day 45 after drinking water administration was 4 ng g -1 feather, with an LOQ of 1 ng g -1 feather. Therefore, the method is suited for application to monitor fluoroquinolone use in broilers.

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., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

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., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: ShunLong Meng, Chao Song reports financial support was provided by the Central Public Interest Scientific Institution Basal Research Fund, the Freshwater Fisheries Research Center. Chao Song reports financial support was provided by Wuxi City Science and Technology Information Research Institute. Chao Song reports a relationship with 2. Freshwater Fisheries Research Center, Chinese Academy of Fishery Sciences that includes: employment., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Overuse of enrofloxacin (ENR) has posed a potential threat to ecosystems and public health, so it is critical to sensitive and accurate determination of ENR residues. In this work, a novel ultra-sensitive and specific electrochemical aptasensor was fabricated based on the cobalt diselenide loaded gold and platinum nanoflowers (Au@Pt NFs/ CoSe 2 ) and Exonuclease III (Exo III)-assisted cycle amplification strategy for the detection of ENR. Au@Pt NFs/ CoSe 2 nanosheets as the substrate material, with large surface area, accelerate electron transfer and attach more DNA probes on the electrode substrate, have effectively enhanced the electrochemical performance of the electrode. With the existence of Enrofloxacin (ENR), the aptamer recognizes and binds to ENR, thus the signal probe cDNA was released and immobilized onto the electrode surface to hybridized with methylene blue (MB) labelled DNA (MB-DNA), thereby triggering the Exo III-assisted cycle for further signal amplification. As expected, the prepared aptasensor demonstrated excellent sensitivity and selectivity, with a wide linear range from 5.0 × 10 -6  ng/mL to 1.0 × 10 -2  ng/mL for ENR, a low detection limit of 1.59 × 10 -6  ng/mL. Consequently, this strategy provided a promising avenue for ultrasensitive and accurate detection of ENR in milk samples., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

In this work, coacervation in primary amines solutions with hydrophobic natural deep eutectic solvents based on terpenoids and carboxylic acids was demonstrated for the first time. A liquid-phase microextraction approach was developed based on supramolecular solvent formation with primary amine acting as amphiphile and hydrophobic deep eutectic solvent making up mixed vesicles and serving as coacervation agent. Such supramolecular solvents could be used to separate wide range of substances from different aqueous media, such as food products, biological liquids and wastewaters. It is important that both hydrophobic and ionic interactions with supramolecular aggregates take place ensuring synergetic effect and better extraction ability, which is significant in separating relatively polar analytes. Different primary amines and deep eutectic solvents were investigated for liquid-phase microextraction of proof-of-concept amphoteric analyte (enrofloxacin, widely used veterinary fluoroquinolone antibiotic) and its determination by high-performance liquid chromatography with fluorescence detection using Shimadzu LC-20 Prominence chromatograph and RF-20A fluorescence detector. It was found that the supramolecular solvent based on 1-nonylamine, formed after addition of a deep eutectic solvent based on menthol and hexanoic acid (molar ratio of 1:1), provided maximum extraction recovery (85 %) and maximum enrichment factor (34). To characterize the extraction system, the composition of the phases was investigated, and cryo-transmission electron microscopy images were obtained. Vesicular aggregates were observed in the supramolecular solvent. The extraction mechanism was proposed in terms of formation of mixed aggregates to capture the analyte. Limit of detection was found to be 7 μg kg -1 , while linear range of 20-250 μg kg -1 was established. Relative standard deviation values were lower than 7 %. Relative bias did not exceed 12 %., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

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% ∼ 90.56% enrofloxacin and 78.43% ∼ 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., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

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., Competing Interests: Declaration of competing interest The authors declared that we have no conflicts of interest to this work. We declare that we do not have any commercial or associative interest that represents a conflict of interest in connection with the work submitted., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

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 ( R 2 = 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.

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 H 2 O 2 . 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.

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., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

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.

Water-soluble AgInS 2 (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/F 0 ) of AgInS 2 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., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

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 (K ow ) 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., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

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.

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., Competing Interests: Declaration of competing interest None declared., (Copyright © 2022 Elsevier B.V. All rights reserved.)

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., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

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., (Copyright © 2022 Elsevier Inc. All rights reserved.)

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 C 3 symmetric COF BTT-TAGH only had one emission peak at 540 nm, while C 6 symmetric COF BTT-DMGH and COF BTT-H had two emission peaks. COF BTT-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., (Copyright © 2022 Elsevier B.V. All rights reserved.)

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 SO 4 - · 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 O 3 and the H 2 O 2 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 1 O 2 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., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

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.

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.

Enrofloxacin, a veterinary antibiotic that persists in food, poses a risk to human health. Here, a monoclonal antibody against enrofloxacin, 1H12, was prepared based on the hapten ENR-1, and showed excellent sensitivity with a 50% inhibitory concentration (IC 50 ) of 0.03 ng/mL. Using this antibody, 2 lateral-flow immunochromatographic assays were developed for determination of enrofloxacin in egg, milk, honey, and chicken meat samples. The detection ranges (IC 20 -IC 80 ) were 0.16-0.82 ng/g, 0.24-1.8 ng/g, 0.25-3.6 ng/g, and 0.61-3.9 ng/g by colloidal gold-immunochromatographic sensor (CG-ICS) analysis, and 0.022-0.42 ng/g, 0.054-0.42 ng/g, 0.069-1.4 ng/g, and 0.19-2.2 ng/g by Eu-fluorescence-immunochromatographic sensor (EF-ICS) analysis. The intraassay and interassay recovery rates were 88.9 to 108.5% with coefficients of variation of 1.3 to 7.0% by CG-ICS analysis, and 88.6 to 113.6% with coefficients of variation of 1.3 to 8.1% by EF-ICS analysis. Thus, our newly developed ICS are sensitive and reliable, providing an option for rapid quantitative detection of enrofloxacin in food samples., (The Authors. Published by Elsevier Inc. and Fass Inc. on behalf of the American Dairy Science Association®. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).)

A novel fluorescence platform was fabricated for enrofloxacin determination by using cDNA-modified dipeptide fluorescence nanoparticles (FDNP-cDNA) and aptamer-modified magnetic Fe 3 O 4 nanoparticles (Fe 3 O 4 -Apt). The FDNP were prepared via tryptophan-phenylalanine self-assembling. When magnetic Fe 3 O 4 -Apt incubated with standard solution or sample extracts, the target enrofloxacin was selectively captured by the aptamer on the surface of the Fe 3 O 4 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 Fe 3 O 4 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 Fe 3 O 4 nanoparticles, and the more the FDNP-cDNA can be observed in the supernatant. Fluorescence intensity (E x /E m  = 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)., (© 2022. The Author(s), under exclusive licence to Springer-Verlag GmbH Austria, part of Springer Nature.)

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., (© 2022. The Author(s), under exclusive licence to Springer-Verlag GmbH Austria, part of Springer Nature.)

In this study, cattail was researched as a natural cellulose source to extract cellulose. Dewaxing, alkali and bleaching treatments were carried out for the cattail fibers (CFs). The FTIR, SEM and XRD results indicated that hemicellulose and lignin were successfully removed from the CFs, and the content of cattail cellulose increased from 41.66 ± 1.11% to 89.72 ± 1.07%. Subsequently, cellulose aerogel was prepared by the extracted cattail cellulose. The Zeolitic imidazolate framework-8 (ZIF-8) was uniformly loaded onto the surface of cellulose aerogel by the in situ growth, and ZIF-8 Cattail Cellulose Aerogel (ZCCA) was finally prepared. The SEM, FTIR, XRD and TGA results further confirmed the successful preparation of ZCCA. Additionally, the results of the adsorption experiment showed that ZCCA had excellent adsorption performance for enrofloxacin, and the maximum adsorption capacity of enrofloxacin reached 172.09 mg·g -1 while showing good reusability. The adsorption process followed the pseudo-second-order kinetic model and the Langmuir isotherm model. Thermodynamic studies showed that the adsorption of enrofloxacin was a spontaneous endothermic reaction and that the adsorption mechanism involves the interaction of hydrogen bonds, electrostatic and π-π stacking., (Copyright © 2021 Elsevier B.V. All rights reserved.)

An innovative, rapid and stable method for simultaneous determination of three tetracycline (oxytetracycline, tetracycline and doxycycline) and two fluoroquinolone (ciprofloxacin and enrofloxacin) residues in poultry eggs by ultra-high performance liquid chromatography-fluorescence detection (UPLC-FLD) was established and optimized. The samples were homogenized and extracted with acetonitrile/ultrapure water (90:10, v/v ) and then purified by solid-phase extraction (SPE). LC separation was achieved on an ACQUITY UPLC BEH C18 column (1.7 µm, 2.1 mm × 100 mm), and the mobile phase was composed of acetonitrile and a 0.1 mol/L malonic acid solution containing 50 mmol/L magnesium chloride (the pH was adjusted to 5.5 with ammonia). When the five target drugs were spiked at the limit of quantification, 0.5 times the maximum residue limit (MRL), 1.0 MRL and 2.0 MRL, the recoveries were above 83.5% and the precision ranged from 1.99% to 6.24%. These figures of merit complied with the parameter validation regulations of the EU and U.S. FDA. The limits of detection and quantifications of the targets were 0.1-13.4 µg/kg and 0.3-40.1 µg/kg, respectively. The proposed method was easily extended to quantitative analyses of target drug residues in 85 egg samples, thus demonstrating its reliability and applicability.

In this work, novel dummy molecularly imprinted membranes (MIMs) were fabricated using the nylon-66 (NY-66) membranes as the subtracts based on an eco-friendly "sandwich" technology with less consumption of organic reagents at mild conditions for recognition and extraction of enrofloxacin (ENR) and ciprofloxacin (CIP) in egg samples. The prepared MIMs were characterized by SEM, ATR-FTIR and TGA, showing the successful construction of uniform and porous polymers on the surface of membranes. A series of adsorption affinity tests were investigated, indicating the prepared materials had specific recognition capacity and excellent stability as novel sorbents. Furthermore, Box-Benhnken design (BBD) and single factor investigations were applied to optimize pretreatment procedures, coupling with Ultra High Performance Liquid Chromatograph (UHPLC) detection. The method showed a good correlation (r 2 >0.9999) within the linear range of 5.0~5000.0 µg kg -1 , and limit of detection (LOD) of ENR and CIP were 0.3 and 0.7 µg kg -1 , respectively. The mean recovery ranged from 84.5% to 97.0% within relative standard deviations (RSDs) of 10.2%. Finally, ENR and CIP were not detected in 3 batches of egg samples. The current study developed the dummy MIMs as sorbents combined with UHPLC analysis for extraction and detection of target analytes in food matrices., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021. Published by Elsevier B.V.)

The use of the antibiotic enrofloxacin (ENR) in poultry is controversial. A high-performance liquid chromatography coupled to fast-scanning fluorescence detection (HPLC-FSFD) method for the determination of ENR in egg white, egg yolk, and lyophilized samples was developed. In a first analysis, the long-term administration of ENR (100 days) to laying hens was carried out to determine its presence in egg white, yolk, or both. The predominance of ENR was observed in egg white and variations in the weight of egg white and eggshell was evidenced, showing a potential problem in the industry. Eventually, the presence of ENR was confirmed in commercial lyophilized egg white samples in concentration values around 350 µg kg -1 . The consumer exposure assessment was estimated for children, adolescents, and adults. The result displayed that, in an intake of lyophilized egg white with food-producing animals, the %ADI exceeds 100%, showing toxicological levels., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

In order to ensure the safety of animal food and regulate the application of veterinary drugs, it is necessary to strictly monitor their content, and to constantly improve the methods used to detect non-specific, illegally added substances in veterinary drugs. A study about the screening, analysis, and confirmation of illegal additives in enrofloxacin powder (used for aquaculture) using non-targeted analysis technology was introduced. First, an enrofloxacin powder test solution under acidic conditions was prepared by adding formic acid, and an enrofloxacin powder test solution under alkaline conditions was prepared by adding sodium carbonate. An ultra-performance liquid chromatography with photodiode array detector (UPLC-PDA) was used to assay the test solutions for the presence of unknown additives. Results revealed two high-response unknown peaks in the acidified test solution, with retention times of 1.870 min and 5.122 min respectively. In the alkalized test solution, only one high-response unknown peak was found, with a retention time of 5.122 min. The ultraviolet spectrum characteristic peaks at 5.122 min in acidified and alkalized test solutions were similar, but the peak area in the alkalized test solution was almost ten times that in the acidified solution. Two potential unknown substances were detected. Unknown substance 1 (1.870 min) and unknown substance 2 (5.122 min) may transform under acidic or alkaline conditions. Ultra-performance liquid chromatography-time of flight high resolution mass spectrometry (UPLC-TOF-HRMS) was used to analyze the unknown compounds in more detail. The acidified and alkalized test solutions were detected in the positive and negative ion modes of mass spectrometry, respectively. Accurate mass of the precursor ion, characteristics of secondary ion fragments, and isotopic intensity ratio of the two unknown substances were collected. This information was imported into SCIEX OS software. The molecular formula of the parent ion of unknown substance 2 was found to fit to C 11 H 8 O 2 , and its secondary fragment structure may contain a benzene ring and two carbonyl groups, with a propylene structure connected to them through ring formation. From this, unknown substance 2 was presumed to be a menadione. The molecular ion peak of unknown substance 1 was found to fit to C 11 H 9 O 5 S - , only HSO 3 - was collected in the secondary fragments, and the missing part was consistent with unknown substance 2. Considering the most common derivatives of menadione, unknown substance 1 can be proposed to be menadione sodium bisulfite. Finally, we used menadione and menadione sodium bisulfite as reference substances in a comparative study. The same treatment method was used to prepare menadione, menadione sodium bisulfite reference solution, and enrofloxacin powder test solution. After UPLC-PDA detection, unknown substance 1 and menadione sodium bisulfite, unknown substance 2 and menadione, were found to have similar retention times and UV spectra. When the reference solution was added to the enrofloxacin powder test solution, the peak purity of the unknown substance did not change, and were all single peaks. UPLC-TOF-HRMS analysis revealed that the retention time of unknown substance 1 was consistent with that of sodium menadione bisulfite: compared to its accurate mass number in theory, the mass accuracy error was 1.0×10 -6 , and the matching degree of fragmentation information in the library was 100%. The retention time of unknown substance 2 was same as the menadione: compared to its accurate mass number in theory, the mass accuracy error was 0.6×10 -6 , and the matching degree of fragmentation information in the library was 99.7%. The structures of unknown substances 1 and 2 were confirmed. Menadione sodium bisulfite is known to participate in the synthesis of thrombin in the liver, and also promotes the formation of prothrombin, and accelerates coagulation. The indication of enrofloxacin powder (used for aquaculture) is the treatment of hemorrhage and sepsis in aquaculture animals such as fish and eel. The pharmacological effects of the two drugs correspond to each other, which can cause producers to take risks and add them illegally. With the strict supervision and severe restrictions on the addition of veterinary drugs, illegal additives are becoming more and more subtle. Conventional targeted analysis does not always meet the monitoring requirements. In this paper, the non-targeted analysis of unknown substances using UPLC-PDA combined with UPLC-TOF-HRMS is described in detail. The results may provide a technical reference for screening and identifying illegal additives in drugs, food, health care products, cosmetics, and pesticides.

The emergence and development of low-cost and high-efficiency nanozymes are promising to replace natural enzymes promoting the application of chemiluminescence immunoassays. Herein, a rapid and highly sensitive flow injection chemiluminescence immunoassay based on cobalt hydroxide (Co(OH) 2 ) nanozyme was established to detect enrofloxacin (ENR) residues in food. In this system, Co(OH) 2 nanosheets act as nanozymes to catalyze and amplify the chemiluminescence signal of the luminol-PIP-H 2 O 2 system, as well as a carrier for immobilizing antibodies to form stable immunoprobes. In addition, carboxyl resin beads with good stability and biocompatibility were used as the base of the immunosensor to carry more coating antigens, based on the principle of competitive immunity and to achieve the rapid detection of ENR. Under optimal conditions, the linear working range is 0.0001 ~ 1000 ng/mL, and the limit of detection (LOD) is 0.041 pg/mL (S/N = 3). The method has been successfully applied to the analysis of aquatic products and poultry food. A non-enzyme immunosensor using Co(OH) 2 nanosheets as antibody-conjugated carriers and peroxidase mimics for catalytic amplification of the chemiluminescence signal of luminol and using carboxyl resin beads as platform was designed to detect ENR residues in food.

In this work, we report on the synthesis of a new-age reusable visible-light photocatalyst using a heterojunction nanocomposite of W 6+ /Yb 3+ on a mixed-phase mesoporous network of monolithic TiO 2 . The structural properties of the monolithic photocatalysts are characterized using p-XRD, SEM-EDAX, TEM-SAED, XPS, PLS, UV-Vis-DRS, FT-IR, micro-Raman, TG-DTA, and N 2 isotherm analysis. The electron microscopic analysis reveals a mesoporous network of ordered worm-like monolithic design, with a polycrystalline mixed-phase (anatase/rutile) TiO 2 composite, as indicated by diffraction studies. The UV-Vis-DRS analysis reveals a redshift in the light absorption characteristics of the mixed-phase TiO 2 monolith as a function of W 6+ /Yb 3+ co-doping. It is observed that the use of (8.0 mol%)W 6+ /0.4 (mole%)Yb 3+ co-doped monolithic TiO 2 photocatalyst, with an energy bandgap of 2.77 eV demonstrates superior visible-light photocatalysis, which corroborates with the PLS studies in terms of voluminous e - /h + pair formation. The practical application of the photocatalyst has been investigated through a time-dependent dissipation of enrofloxacin, a widely employed antimicrobial drug, and its degradation pathway has been monitored by LC-MS-ESI and TOC analysis. The impact of physio-chemical parameters such as solution pH, sensitizers, drug concentration, dopant/codopant stoichiometry, catalyst quantity, and light intensity has been comprehensively studied to monitor the process efficiency.

Copper oxide nanoparticles (CuO-NPs) have been suggested as effective catalysts to degrade many persistent organic contaminants. In parallel, CuO-NPs are considered toxic to soil microorganisms, plants and human cells, possibly because they induce oxidative stress and generation of reactive oxygen species (ROS). However, the mechanism of the catalytic process and the generated ROS are poorly understood. Here we discuss the reaction mechanism of CuO-NPs during the catalytic degradation of enrofloxacin - an antibiotic pharmaceutical used in this study as a representative persistent organic compound. The degradation of an aqueous solution of the enrofloxacin exposed to CuO-NPs and hydrogen peroxide was studied showing fast removal of the enrofloxacin at ambient conditionsns. ROS production was identified by electron spin resonance and a spin trapping technique. The distribution of the free radical species indicated production of a high percentage of superoxide (O 2 -. ) radicals as well as hydroxyl radicals; this production is similar to the "radical production" activity of the superoxide dismutase (SOD) enzyme in the presence of hydrogen peroxide. This activity was also tested in the opposite direction, to examine if CuO-NPs show reactivity that potentially mimics the classical SOD enzymatic activity. The CuO-NPs were found to catalyze the dismutation of superoxide to hydrogen peroxide and oxygen in a set of laboratory experiments., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

We investigated individual and combined effects of environmentally representative concentrations of amoxicillin (AMX; 2 μg l -1 ), enrofloxacin (ENR; 2 μg l -1 ), and oxytetracycline (OXY; 1 μg l -1 ) on the aquatic macrophyte Lemna minor. While the concentrations of AMX and ENR tested were not toxic, OXY decreased plant growth and cell division. OXY induced hydrogen peroxide (H 2 O 2 ) accumulation and related oxidative stress through its interference with the activities of mitochondria electron transport chain enzymes, although those deleterious effects could be ameliorated by the presence of AMX and/or ENR, which prevented the overaccumulation of ROS by increasing catalase enzyme activity. L. minor plants accumulated significant quantities of AMX, ENR and OXY from the media, although competitive uptakes were observed when plants were submitted to binary or tertiary mixtures of those antibiotics. Our results therefore indicate L. minor as a candidate for phytoremediation of service waters contaminated by AMX, ENR, and/or OXY., (Copyright © 2020 Elsevier Inc. All rights reserved.)

The overuse or abuse of quinolone antibiotics such as enrofloxacin (ENR) in veterinary medicine results in the presence of their residues in food and environment. Thus, a sensitive method is needed to detect them. Herein, we demonstrate a fluorescence resonance energy transfer (FRET) based aptasensor for ENR detection, using core-shell upconversion nanoparticles (CSUNPs) as an energy donor and graphene oxide (GO) as an energy acceptor. The core-shell structure and Gd3+ doping significantly increased the fluorescence intensity of CSUNPs and the FRET efficiency. The ENR aptamer was conjugated to CSUNPs through ligand exchange, and the π-π stacking between the aptamer and GO brought the aptamer-modified CSUNPs to the surface of the GO sheets, resulting in the formation of a CSUNP-GO complex and the subsequent quenching of CSUNP fluorescence. As a result, an aptasensor was established with the fluorescence of CSUNPs correlated with the ENR concentration within the range of 0.976 ng mL-1 to 62.5 ng mL-1, allowing ENR to be detected at a limit of 0.47 ng mL-1. This method reduced the detection limit by approximately 13-fold in 2 h compared to the commercial enzyme-linked immunosorbent assay (ELISA) kit. The aptasensor could also be applied to detect ENR from commercial milk powder samples with a detection limit of 1.59 ng mL-1, which was far below the regulated maximum residue limit of ENR in milk. The aptasensor could not detect other antibiotics, suggesting its good specificity towards ENR. Our work demonstrates a highly selective, sensitive and cost-effective method for detecting antibiotic residues in veterinary medicine. Since the aptamer can be switched to one recognizing another antibiotic, the aptasensors are used as a plug-and-play platform that can detect a variety of antibiotics.

Antibiotics abuse now poses a global threat to public health. Monitoring their residual levels as well as metabolites are of great importance, still challenges remain in in situ tracing during the circulation. Herein, taking the typical antibacterial Enrofloxacin (ENR) as a subject, a paper-based aptasensor was tailored by manipulating a duo of aptameric moieties to "sandwich" the target in a lateral-flow regime. To visualize the tight-binding sandwich motif more vividly, an irregular yet robust DNA-bridged gold nanoparticles (AuNPs) proximity strategy was developed with recourse to terminal deoxynucleotidyl transferase, of which the nonaggregate constraining feature was unveiled via optical absorption and scanning probe topography. This complex performed exceptionally better in the test strip context than single-particle tags, leading to an enhanced on-chip focusing. Rather than qualitative color developing, further efforts were taken to visualize the readouts in a quantitative manner by exploiting the smartphone camera for pattern recognition along with data processing in a professional App. Overall, this prototyped contraption realized a rapid and ultrasensitive quantification of ENR down to 0.1 μg/L along with a broad linear range over 5 orders of magnitude, plus excellent selectivity and precision even for real samples. Such innovative fusion across DNA-structured nanomanufacturing and intelligent perception provides a prospective and invigorating solution to point-of-care inspection., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

To ensure accurate and reliable measurement results, a whole liquid egg certified reference material (CRM) retaining the resemblance to real samples was first developed for improving measurement quality of enrofloxacin residue in eggs. The CRM raw material naturally containing enrofloxacin was obtained by sampling eggs from laying hens following oral administration of enrofloxacin. The homogenizing and bottling procedure was evaluated and applied on the bulk raw material to prepare the CRM candidate. For characterization of the CRM, liquid chromatography tandem isotope dilution mass spectrometry as a reliable reference method was studied and used for value assignment by all participating laboratories. The certified value was assigned to be 30.6 μg/kg with expanded uncertainty of 3.1 μg/kg (coverage factor k = 2, approximate 95% confidence interval) for enrofloxacin. In addition, homogeneity, long-term stability at -70 °C for one year and short-term stability at -18 °C, 4 °C and room temperature for nine days were assessed., (Copyright © 2019. Published by Elsevier Ltd.)

Poultry litter soil application contributes to sustainability of agricultural systems and is in accordance with the United Nations Sustainable Development Goals (UN-SDG). Poultry litter recommended rates are based on crop nitrogen (N) needs, however, their application can be a potential source of antibiotics and trace elements overload. The aim of the study was to estimate the role of poultry litter application on soil contamination by fluoroquinolones [enrofloxacin (ENR) and ciprofloxacin (CIP)] and trace elements, based on N requirements for crops. Analytical and sampling techniques were used to estimate the loads from poultry litter application. Only CIP was found in poultry litter samples (283 ± 124 µg kg -1 ) and its load was estimated to be of 9.89 ± 4.33 g ha -1 , for the poultry litter application (35 t ha -1 ). The estimated loads (g ha -1 ) of trace elements were: Cr 9.19 ± 3.26, Ni 12.3 ± 4.93, Pb 22.0 ± 8.26, Cu 229 ± 85.6, Mn 691 ± 259 and Zn 1,011 ± 378. These estimates were 900% higher than those recommended by the technical guidance, while N exceeded 600% the recommended application. In order to achieve UN-SDGs, local policies to disseminate knowledge and technologies are required for consolidating sustainable agricultural practices.

Veterinary antibiotics (VAs) have entered the ecosystem principally through the application of organic fertilizer. However, factors influencing the contributions made by the prescribers and users thereof with respect to VAs in poultry manure have not been investigated. The purpose of this paper, therefore, is to identify factors associated with the VA prescription and usage as well as to measure the residual concentration along with the ecological risk of common VAs in poultry litter in Bangladesh. Structured questionnaire surveys were conducted so as to provide an understanding the perspective of prescribers and farmers. Ciprofloxacin (CIP), enrofloxacin (ENR), oxytetracycline (OTC), and doxycycline (DOX) were screened through the use of thin-layer chromatography (TLC) and quantified through high-performance liquid chromatography (HPLC). Also, methods of risk quotient (RQ) were applied to assess ecotoxicity. Most VAs were prescribed without a confirmatory diagnosis. The residue of CIP was dominant with a high concentration, followed by OTC but with a low concentration. A high ecological risk was associated with the use of OTC and DOX whereas the risk associated with the use of CIP and ENR was insignificant to low. The study highlights prescriber and user factors along with the variable ecological risk of VAs in litter.

Enrofloxacin (ENR) is a widely used fluoroquinolone (FQ) antibiotic for antibacterial treatment of edible animal. In this study, a rapid and highly specific fluorescence polarization immunoassay (FPIA) was developed for monitoring ENR residues in animal foods. First, ENR was covalently coupled to bovine serum albumin (BSA) to produce specific polyclonal antibodies (pAbs). Three fluorescein-labeled ENR tracers (A, B, and C) with different spacers were synthesized and compared to obtain higher sensitivity. Tracer C with the longest arm showed the best sensitivity among the three tracers. The developed FPIA method showed an IC 50 (50% inhibitory concentration) of 21.49 ng·mL -1 with a dynamic working range (IC 20 -IC 80 ) of 4.30-107.46 ng·mL -1 and a limit of detection (LOD, IC 10 ) of 1.68 ng·mL -1 . The cross-reactivity (CR) of several structurally related compounds was less than 2%. The recoveries of spiked pork liver and chicken samples varied from 91.3% to 112.9%, and the average coefficients of variation were less than 3.83% and 5.13%, respectively. The immunoassay took only 8 min excluding sample pretreatment. This indicated that the established method had high sensitivity, specificity, and the advantages of simplicity. Therefore, the proposed FPIA provided a useful screening method for the rapid detection of ENR residues in pork liver and chicken.

Antibiotics and heavy metals have long-term potential toxicity to the environment, and their residuals in agricultural soils are receiving more and more attention. To evaluate the ecotoxicological effects of enrofloxacin and cadmium on soil enzymatic activities and microbial community structure, soil samples were exposed to individual and combined contaminants over 28 days. The results indicated that the toxic effects of enrofloxacin alone on soil enzymatic activities were relatively small and showed no concentration dependence. In contrast, significant inhibition of soil enzymatic activities was observed upon cadmium contamination by itself. Overall, the combination of two contaminants also has toxic effect on enzymatic activities; an antagonism between enrofloxacin and cadmium was observed. On 14 and 21 days, individual enrofloxacin and cadmium reduced average well color development (AWCD), Shannon, McIntosh, Simpson indices, and substrate utilization, except for Shannon, McIntosh, Simpson indices of the cadmium 0.4 mmol/kg treatment were higher than the control on 21 days. In general, combined treatments led to higher value of these microbial diversity indicators than those found under separate contamination, although there were some exceptions. With the increase in enrofloxacin concentration, the utilization of any carbon source by the microorganisms gradually decreased. In addition, the AWCD value and substrate utilization decreased as time increased. In the separate and combined contaminant treatments, the order of substrate utilization by soil microorganisms was aliphatics > amino acids > saccharides > metabolites. Thus, enrofloxacin and cadmium had a variable but generally negative influence on soil enzymatic activities and microbial community structure.

A colorimetric assay is described for simultaneous detection of multiple analytes related to food safety. It is based on the use of a sandwich aptasensor and terminal deoxynucleotidyl transferase (TdT) which produces a primer for subsequent rolling circle amplification (RCA). Two split aptamer fragments (Apt1 and Apt2) are firstly immobilized, Apt1 on gold nanoparticles (AuNPs), and Apt2 on magnetic beads (MBs). They are then used in a sandwich aptasensor. In the presence of analyte, two probes could specifically recognize target and form a ternary assembly, and the magnetic beads also act to separate rapidly and enrich the target. Then, the extension of template-free DNA is triggered by TdT at the exposed 3'-hydroxy terminals of Apt1. This produces polyA sequences that serve as primers for subsequent RCA. The product of RCA is hybridized with a complementary horse radish peroxidase (HRP) DNA probe. HRP catalyzes the H 2 O 2 -mediated oxidation of tetramethylbenzidine (TMB) and forms a blue chromogenic product. After magnetic separation, the absorption values of the blue product in the supernatant are measured at a wavelength of 600 nm. Based on this dual amplification mechanism, the assay was applied to multiplexed determination of enrofloxacin (ENR), lead(II), Escherichia coli O157:H7 and tropomyosin. Exemplarily, ENR is detectable at concentrations down to 2.5 pg mL -1 with a linear range that extends from 1 pg mL -1 to 1 μg·mL -1 . The assay was validated by analysis of spiked fish samples. Recoveries range between 87.5 and 92.1%. Graphical abstractSchematic representation of a TdT-RCA based aptasensor for multiple analytes related to food safety. It makes use of sandwich aptasensors and TdT-produced universal primer-triggered RCA reaction. dATP: deoxyadenosine triphosphate, TdT: Terminal Deoxynucleotidyl Transferase, RCA: rolling circle amplification, TMB: 3,3',5,5'-Tetramethylbenzidine.

Poly(vinylidene fluoride) (PVDF) is known as one of the widely used membrane separation materials with excellent physical and chemical properties. In this work, we combine surface-enhanced Raman scattering (SERS) detection technology, membrane separation technology and molecular imprinting technology (MIT) to improve sensitivity and selectivity for selective detection of the enrofloxacin hydrochloride in water. In this investigation, PVDF membranes were used as the support materials and different experiment parameters were investigated to obtain the best property. Meanwhile, the Ag nanoparticles (Ag NPs) modified by 3-methacryloxypropyltrimethoxysilane (KH-570) were used as the SERS substrates and they were uniformly dispersed on the surface of the membrane. Finally, Ag-based SERS imprinted membranes (ASIMs) with specific recognition property were successfully prepared with enrofloxacin hydrochloride as the template molecule, acrylamide (AM) as the functional monomer, ethylene glycol dimethacrylate (EGDMA) as the cross-linker agent and 2,2'-azobis(2-methylpropionitrile) (AIBN) as the initiator by a facile and versatile precipitation polymerization strategy. Under the optimal condition, it was presented good linear relationship (R 2  = 0.994) between the Raman signal (at 1390.8 cm -1 ) and the concentration (10 -3  mol·L -1 -10 -7  mol·L -1 ) of the templates, and the limit of detection was determined as 10 -7  mol·L -1 . The morphology and characters were investigated and the results proved that the SERS imprinted membranes could be used into the selective detection of antibiotics and it provided a novel approach of antibiotics detection., (Copyright © 2019. Published by Elsevier B.V.)

The presence of a fluoroquinolone base veterinary antibacterial drug enrofloxacin in aqueous media poses a major threat due to its ecotoxicity on aquatic microbiota. Hence, for the first time, an attempt was made to remove enrofloxacin (ENX) from its aqueous solution by employing micellar-enhanced ultrafiltration (MEUF) where cetylpyridinium bromide (CPB), a cationic surfactant was used for micellization. Response surface methodology (RSM) with central composite design (CCD) approach was applied to design the experiment, and to optimize the process parameters, namely, ENX concentration (3-15 mg/L), transmembrane pressure (2-6 kg f /cm 2 ), recirculation flow rate (5.5-7.5 L/min) and CPB concentration (1.4-4.2 mM). The objective of this study was to maximize the permeate flux and rejection coefficient and to find out the optimal process condition for the removal of enrofloxacin from aqueous solution. Though maximum 68.23 L/m 2  h of permeate flux and 94.20% of rejection coefficient were achieved at different process conditions, the optimization study reveals that the predicted optimal values of permeate flux and rejection coefficient are 67.53 L/m 2  h and 89.67% respectively. Modelling was also carried out with the aid of artificial neural network (ANN) to validate the prediction of RSM. The predictability of the model by RSM and ANN was compared statistically by evaluating root-mean-square error (RMSE), absolute average deviation (AAD) and mean absolute error (MAE), where ANN exhibited better predictability. The following set of parameters was proposed for industrial scale up: ENX concentration of 8.4 mg/L, TMP of 5 kg f /cm 2 , recirculation flow rate of 6 L/min and CPB concentration of 2.1 mM., (Copyright © 2019 Elsevier B.V. All rights reserved.)

The presence and concentrations of 25 antibiotics in Dalian coastal water of the Bohai Sea were investigated using solid-phase extraction coupled with high-performance liquid chromatography tandem mass spectrometry. Results showed that antibiotics were widely detected in this region with total concentration ranging from 22.6 to 2402.4 ng/L. Enrofloxacin and trimethoprim were 100% detected followed by sulfamethoxazole with a detection rate of 90.9%. No significant correlations were found between antibiotics concentrations and sample parameters such as dissolved organic carbon, salinity, and distance from the coast, suggesting that concentrations and distributions of the antibiotics in this area were source-dependent. Antibiotic concentration in the sample from an offshore cage-culture area was the highest. Based on composition profiles, mariculture was supposed to be an important source of antibiotics. According to the assessment, individual antibiotic posed low to moderate risk, while the antibiotic mixture presented high risk. Enrofloxacin, clarithromycin and sulfamethoxazole, the top three contributors to the mixture risk quotients for each site, need priority control in this area. Besides, levels of enrofloxacin were high enough to exert a selective pressure on bacteria that may lead to an increase in the prevalence of resistance., (Copyright © 2019 Elsevier Inc. All rights reserved.)

Enrofloxacin (ENR) is one of the environmental pollutants need to remove in many wastewater treatment processes. Traditional methods for measuring ENR are often complex and time-consuming. Due to their low cost and high efficiency, fluorescent carbon dots can be used for detecting many pharmaceuticals. In this contribution, nitrogen doped fluorescent carbon dots (N-CDs) were firstly synthesized with a fluorescence quantum yield of 20.5%. The N-CDs can emit strong blue fluorescence when excited at 368 nm and there exist a large amount of carboxyl, hydroxyl and amine groups on their surfaces. In addition, the fluorescence of N-CDs could be quenched in the presence of Cu 2+ , which could be gradually restored upon adding ENR. Thereby, a rapid and sensitive fluorescent sensing strategy based on the fluorescence recovery of the N-CDs-Cu 2+ system was designed for selective detection of ENR. The possible sensing mechanism was also proposed in terms of the results of resonance Rayleigh scattering, UV-vis absorption and Fourier transform infrared (FITR) spectra. Under the optimal condition, a good linear relationship was obtained for ENR determination with concentrations ranging from 1.0 to 15.0 μg·mL -1 and the detection limit of 0.16 μg·mL -1 was achieved. Finally the proposed sensing system was applied for the detection of ENR in real water samples with satisfactory results., (Copyright © 2019. Published by Elsevier B.V.)

The use of the heterologous competitive strategy has become a vital method to improve the sensitivity of ELISA. In this work, we prepared an anti-enrofloxacin (ENR) mAb with ENR-bovine serum albumin (BSA) as immunogen. The molecular descriptors of quinolones were then used to screen heterologous coating antigens for the detection of ENR based on an ensemble learning method to improve the sensitivity of the ELISA. Results indicated that 6 of the 7 selected heterologous competitive antigens could enhance the sensitivity of ELISA. The ELISA sensitivity for the detection of ENR with sarafloxacin-BSA as heterologous coating antigen was improved 10-fold (in PBS) and 6-fold (in milk) compared with that with ENR-BSA as homologous antigen. The strategy can effectively screen suitable heterologous competitive antigens to improve the sensitivity of ELISA, followed by preparation of mAb with no additional modification to the corresponding immunogen., (Copyright © 2019 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.)

Colorimetric nanosensors formed of polydiacetylene (PDA), triblock copolymer (L64 or F68), and sodium dodecyl sulfate (SDS), so-called nanoblends, were developed to detect enrofloxacin (ENRO) in aqueous media. The nanosensors show hydrodynamic diameter ranging from 234.2 ± 3.5 to 801.6 ± 17.8 nm for SDS concentrations of 13.0-21.0 mM, respectively. The lowest limit of detection was 0.054 µM, which is five times smaller than the maximum limit allowed by the European Union. The response surfaces showed that both the SDS and ENRO concentrations influenced the colorimetric response (p < 0.05), and kinetic rate of colorimetric transition (R CT ). SDS concentration between 11.0 and 14.0 mM in the nanoblend yielded the most sensitive nanosensors for detecting ENRO. When L64 was replaced by F68, the colorimetric response of the nanoblends was similar, but PDA/F68/SDS showed a slower R CT than PDA/L64/SDS. The developed nanosensor is a sensitive and simple device for the fast detection of ENRO., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

The current investigation deals with how chemically activated carbon derived from industrial paper sludge (ACPS) performs on sorptive removal of enrofloxacin (ENF), an antibacterial drug from its water solution. Thermogravimetric (TGA) and proximate analysis of raw paper sludge (RPS) were conducted. ACPS was characterized with proximate analysis, XRD, FT-IR, SEM and BET. The influence of five operational parameters viz. adsorbate concentration (initial), dose of adsorbent, pH, temperature, and contact time on the adsorption of ENF onto ACPS has been conducted using batch experiments. The process of adsorption was optimized through ANN (artificial neural network) in addition to RSM (response surface methodology). The maximum percentage removal (95.85%) was achieved at initial ENF concentration 12 mg/g, adsorbent dose 1.2 g/L, contact duration of 18 h and temperature 20 °C. Kinetic data were best fitted into pseudo-second order kinetic model and adsorption equilibrium study indicates that the adsorption process follows Langmuir isotherm model. Adsorption capacity was noted to have a highest value of 44.44 mg/g. A study on thermodynamics of the adsorption process suggests that it exhibits spontaneity, being essentially exothermic. Cost analysis and reusability study confirm that adsorbent produced from industrial paper sludge is cost-effective and reusable. Therefore, ACPS as adsorbent has potency for removing ENF from aqueous solution., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Application of anaerobically digested sludges and manure (digestates) to agricultural fields reduces the need for fertilizer application, but might also pose environmental risks due to the introduction of various pollutants -including metal trace elements and pharmaceuticals- to amended soils. The simultaneous presence of different contaminants can affect plant uptake, altering the performance of phytoremediation. This work aims to investigate and compare the single and combined effects of Enrofloxacin (Enro) and Cu on their plant uptake from digestate solutions. Plant uptake experiments were carried out by exposing, for 5 days, Phragmites australis to three different concentrations of a liquid digestate doped with Cu and/or Enro. Contaminant concentrations were afterward determined in both plant tissues and digestate solutions. Contaminant speciation in solution and Cu speciation in plant roots were also assessed. Cu plant uptake (mostly in plant roots, Cu concentration varied between 55 and 254 μg·g -1 ) was observed, especially at low concentration of digestate. At high digestate concentration, Cu uptake decreased due to the formation of Cu-DOC complexes rendering Cu less bioavailable. The presence of the antibiotic slightly further reduced Cu plant uptake due to the formation of Cu-Enro complexes. Plant roots also accumulated Enro, an accumulation also higher for the lowest concentration of digestate (an increase of 40%), and that slightly increased in the presence of Cu (up to 226 μg·g -1 ). However, proportion of free Enro in solution decreased (up to 70%) in the presence of Cu due to complexation. Cu speciation in plant roots confirmed the implication of the complexation in the uptake of Cu and Enro when they are simultaneously present in solution. Thus, the presence of amendments (such as digestates) increasing the DOC content, in addition to the interactions between contaminants, should be taken into account for field crop soils as well as for phytoremediation technologies., (Copyright © 2019 Elsevier B.V. All rights reserved.)

We designed and synthesized a novel covalent organic framework (COF) by condensation polymerization of 1,3,6,8-tetrakis(4-formylphenyl)pyrene and melamine through imine bonds (represented by Py-M-COF). The basic characterizations revealed that the Py-M-COF not only exhibited an extended π-conjugation framework, a large specific surface area (495.5 m 2 g -1 ), big pore cavities, and nanosheet-like structure but also possessed rich functional groups, such as C˭C, C˭N, C˭O, and NH 2 . These features endowed the Py-M-COF with high charge carrier mobility, further improving the strong immobilization of DNA aptamer strands via π-π stacking interaction and electrostatic interaction. As such, the Py-M-COF-based electrochemical aptasensors are ultrasensitive in detecting different antibiotics, including enrofloxacin (ENR) and ampicillin (AMP), yielding extremely low detection limits of 6.07 and 0.04 fg mL -1 (S/N = 3) toward ENR and AMP, respectively, along with other excellent sensing performances. This biosensing platform based on Py-M-COF has potential applications for the sensitive detection of antibiotics or other analytes by replacing the corresponding aptamers., (Copyright © 2019 Elsevier B.V. All rights reserved.)