Fabrication of a ß-CD-functionalized magnetic microporous organic network for effective enrichment and detection of fluoroquinolone antibiotics in water samples.

Fluoroquinolone (FQ) antibiotics, one of the leading environmental pollutants, have ecotoxic effects that can accumulate through ecosystems and harm human health. The determination of FQs is still difficult due to the complex matrix, many interfering factors, and low concentration. Hence, a magnetic microporous organic network (MON) composite denoted as Fe3O4@MON-NH2@CM-ß-CD with excellent FQ adsorption performance was prepared by ß-CD covalent modification of a MON. Based on the existence of π-π packing, hydrophobic interaction, and hydrogen bonding between Fe3O4@MON-NH2@CM-ß-CD and FQs, a new magnetic solid phase extraction (MSPE) method for the enrichment of FQs was developed. Under optimized MSPE conditions, five FQs were detected by HPLC-UV with good linearity (R2 ≥ 0.9989) in the range of 0.02-1 µg mL-1, and detection limits (S/N = 3) in the range of 0.0014-0.0023 µg mL-1. The satisfactory recoveries ranged from 93.1 to 116.2% with RSDs lower than 8.39% when applied to actual environmental water samples. These results revealed that Fe3O4@MON-NH2@CM-ß-CD as an adsorbent for MSPE had excellent performance for FQ extraction from real samples, and the MON material types were expanded through the functionalization of MONs, which would have great potential for further application in various analytical methods.

Fabrication of fluorinated triazine-based covalent organic frameworks for selective extraction of fluoroquinolone in milk.

A novel fluorinated triazine-based covalent organic frameworks (F-CTFs) was designed and synthesized by using melamine and 2,3,5,6-tetrafluoroterephthalaldehydeas as organic ligands for selective pipette tip solid-phase extraction (PT-SPE) of amphiphilic fluoroquinolones (FQs). The competitive adsorption experiment and mechanism study were carried out and verified that this F-CTFs possesses favorable adsorption affinity for FQs. The abundant fluorine affinity sites endowed the F-CTFs high selectivity to FQs extraction through F-F interactions. The adsorption capacity of F-CTFs can reach up to 109.1 mg g-1 for enrofloxacin. The detailed characterization of the F-CTFs adsorbent involved the application of various techniques to examine its morphology and structure. Under optimized conditions, a method combining F-CTF-based PT-SPE with high-performance liquid chromatography (PT-SPE-HPLC) was established, which exhibited a broad linear range, excellent precision, and an impressively low limit of detection, and could be used for the determination of six FQs in milk, with LODs as low as 0.0010 µg mL-1. The recovery rates during extraction varied between 92.1% and 111.4%, exhibiting RSDs below 6.8% at different spiked concentrations.

Low flow-resistance solid phase extraction of fluoroquinolones in water and food samples by high-pressure wet spinning porous polyimide microfibers.

In this work, porous polyimide microfibers (PI-µF) were prepared by high-pressure wet spinning method, and successfully applied as adsorbents for solid phase extraction (SPE) of fluoroquinolones (FQs) in water and food samples. The PI-µFs of ∼10, 25, 50, 100 µm in diameter could be controlled by the inner diameter of quartz capillary nozzles. The flow resistance of SPE cartridges packed with 10 µm PI microfiber (10-PI-µF) and 25-PI-µF was comparable to or even lower than that of commercial SPE cartridges, while the flow resistance of 50-PI-µF and 100-PI-µF SPE cartridges was increased obviously due to tiny broken pieces. The 10-PI-µF and 25-PI-µF have a specific surface area of 102 m2 g-1 and 76 m2 g-1, mesopores of 22-32 nm, and large breakthrough volume of 110 mL/5 mg and 85 mL/5 mg for FQs, while the 50-PI-µF and 100-PI-µF had much lower specific surface area and hardly had retention for FQs. FQs from tap water, egg and milk samples were then extracted by PI-µF SPE, and analyzed by high performance liquid chromatography-fluorescence detector (HPLC-FLD). SPE parameters as type of elution solvent, elution solvent volume, pH value of sample solution, flow rate of sample solution, and breakthrough volume were first optimized in detail. Under the optimal conditions, the PI-µF SPE/HPLC-FLD method showed high recoveries (96.8%-107%), wide linearity (0.05-50 µg L-1, or 0.01-10 µg L-1), high determination coefficients (R2 ≥0.9992), and low limits of detection (LODs, 0.005-0.014 µg L-1). For the real tap water, egg and milk samples, the recoveries and RSDs were 81-119% and 0.8-9.8%, respectively. The results show that porous microfiber up to 25 µm in diameter is a promising solid-phase extraction adsorbent with the lowest flow resistance that can be used for trace organic pollutants in water and food samples.

Polyethyleneimine-functionalized Fe3O4/attapulgite particles for hydrophilic interaction-based magnetic dispersive solid-phase extraction of fluoroquinolones in chicken muscle.

Fluoroquinolone (FQ) residues in foods of animal origin may threaten public health but are challenging to determine because of their low contents and complex matrices. In this study, novel polyethyleneimine-functionalized Fe3O4/attapulgite magnetic particles were prepared by a simple co-mixing method and applied as hydrophilic sorbents for the magnetic dispersive solid-phase extraction (MSPE) of three FQs, i.e., ciprofloxacin, norfloxacin, and enrofloxacin, from chicken muscle samples. The preparation of the magnetic particles was of high reproducibility and the products could be reused many times with high adsorption capacity. The key experimental factors possibly influencing the extraction efficiencies, including sample solution, extraction time, sample loading volume, desorption solution, desorption time, and elution volume were investigated. Under optimum MSPE conditions, the analytes in chicken muscle samples were extracted and then determined by RPLC-MS/MS in MRM mode. Good linearity was obtained for the analytes with correlation coefficients ranged from 0.9975 to 0.9995. The limits of detection were in the range of 0.02-0.08 µg kg-1, and the recoveries of the spiked FQs in chicken muscle samples ranged from 83.9 to 98.7% with relative standard deviations of 1.3-6.8% (n = 3). Compared with the traditional MSPE methods based on hydrophobic mechanism, this hydrophilic interaction-based method significantly simplifies the sample pretreatment procedure and improves repeatability. This method is promising for accurate monitoring of FQs in foods of animal origin.

Ionic Liquid-Functionalized Magnetic Metal-Organic Framework Nanocomposites for Efficient Extraction and Sensitive Detection of Fluoroquinolone Antibiotics in Environmental Water.

Herein, the hydrophobic carboxyl-functionalized ionic liquid (IL-COOH) was encapsulated into the prepared Fe3O4@Zr-MOFs, and the novel water-stable IL-COOH/Fe3O4@Zr-MOF nanocomposites were first synthesized. The polydopamine-functionalized Fe3O4 was introduced to construct the core-shell structure via layer-by-layer modification, and the controlled growth of Zr-MOFs was achieved, which realized the adjustment of charged properties of nanocomposites and simplified the adsorption or extraction process. The IL-COOH/Fe3O4@Zr-MOFs were fully studied by IR, HNMR, XRD, N2 adsorption-desorption isotherms, TEM, EDS mapping, VSM, and so on. Then, they were employed for the selective adsorption and detection of fluoroquinolone antibiotics (FQs). The adsorption isotherms and kinetics demonstrated that the adsorption process followed a pseudo-second-order kinetic model and the Langmuir isotherm model. Among them, IL-COOH/Fe3O4@UiO-67-bpydc showed the best adsorption performance, and the maximum adsorption capacity of ofloxacin was 438.5 mg g-1. Coupled magnetic solid-phase extraction with HPLC-DAD, a convenient, sensitive, and efficient method for extraction and detection of FQs in environmental water, was developed based on IL-COOH/Fe3O4@UiO-67-bpydc. The recoveries of environmental water were ranging from 90.0 to 110.0%, and the detection limits were lower than 0.02 µg L-1. The novel functionalized composites served as solid-phase adsorbents and liquid-phase extractants. This study also provided a promising strategy for designing and preparing multi-functionalized nanocomposites for the removal or detection of pollutants in environmental samples.

Selective extraction and enhanced-sensitivity detection of fluoroquinolones in swine body fluids by liquid chromatography-high resolution mass spectrometry: Application in long-term monitoring in livestock.

To ensure food safety in livestock industries, developing a non-lethal and cost-effective detection method for the long-term monitoring of veterinary antibiotics in animals will be beneficial to avoid unnecessary losses. In this study, a highly-selective extraction using dispersive micro solid-phase extraction method coupled with an enhanced-sensitivity detection by pre-column dilution injection and liquid chromatography-high resolution mass spectrometry was used to determine the restricted fluoroquinolones (FQs) in swine body fluids. The proposed method showed good linear coefficients higher than 0.999, and high sensitivity with the LODs and LOQs in the range of 0.02-0.03 µg/L and 0.06-0.1 µg/L in swine body fluids, respectively. For further evaluation, the adequate recoveries (85.3-112.8%), satisfactory repeatability (intra-day and inter-day precisions of 2.1%-8.2% and 3.8%-13.7%, respectively), and acceptable matrix effect (0.92-1.12) of the FQs were achieved. It has been successfully applied for analysis of the FQs in body fluids without sacrificing animals in the future.

Facile synthesis of magnetic sulfonated covalent organic framework composites for simultaneous dispersive solid-phase extraction and determination of ß-agonists and fluoroquinolones in food samples.

In this work, an efficient method for the determination of ß-agonists and fluoroquinolones was established, based on a mixed-mode sorbent of magnetic sulfonated covalent organic framework composites. By coupling with HPLC-MS/MS, the main factors that affect the extraction procedure were optimized. Under the optimal conditions, the proposed HPLC-MS/MS method was successfully utilized for the extraction of ß-agonists and fluoroquinolones in milk and pork meat samples. The method showed good linearities (R2 ≥ 0.9916), and low LOQs of 0.1-0.2 ng g-1 for ß-agonists and fluoroquinolones. The adsorption mechanism was investigated with the assistance of quantum chemistry calculation method, and it is worth noting that the sorbent relied mainly on the multiple adsorption mechanisms, including π-π stacking, hydrophobic, electrostatic attraction and hydrogen-bonding interactions. This work not only provides a simple method for the preparation of a mixed-mode sorbent, but also a routine analysis strategy for monitoring the illegal use of ß-agonists and fluoroquinolones.

Restricted access media-imprinted nanomaterials based on a metal-organic framework for highly selective extraction of fluoroquinolones in milk and river water.

A new type of restricted access media-imprinted nanomaterials (RAM-MIPs) were successfully prepared on the surface of metal-organic framework by reversible addition fragmentation chain transfer polymerization technology. Then it was applied as a dispersed solid phase extraction (DSPE) material in analysis of fluoroquinolones (ofloxacin, pefloxacin, norfloxacin, enrofloxacin and gatifloxacin) in untreated milk and river water by HPLC-UV detection. The resulted material has a good binding amounts (60.81 mg g-1), rapid binding kinetic (15 min) and satisfactory selectivity as well as has a good ability to eliminate matrix interference. Several major factors affecting DSPE efficiency, pH of sample solution, dosage of RAM-MIPs, adsorption time and volume ratios of elution solvent were primarily optimized. In optimization conditions, RAM-MIPs-DSPE was combined with HPLC-UV to enrich fluoroquinolones in untreated milk and river water, achieving satisfactory linear correlation (R2 > 0.9988), good limits of detection (LOD, 1.02-3.15 µg L-1 for milk and 0.93-2.87 µg L-1 for river water) and better recoveries (80.7-103.5% and 85.1-105.9% with relative standard deviation (RSD) of not higher than 5.3% and 4.7% for milk and river water samples, respectively). The research results illustrate that it provides a simple and efficient method for the direct detection of FQs in complex samples.

Determination of fluoroquinolones in milk, honey and water samples by salting out-assisted dispersive liquid-liquid microextraction based on deep eutectic solvent combined with MECC.

A simple and sensitive salting out-assisted dispersive liquid-liquid microextraction method using deep eutectic solvent combined with back extraction and micellar electrokinetic capillary chromatography (SO-DLLME-DES-BE-MECC) was developed for the determination of fluoroquinolones in milk, honey and water samples. Several parameters affecting the extraction efficiency including DES volume, vortex time, centrifugation time, salt type and amount, sample pH and volume, etc. were investigated. Good linearity were obtained for fluoroquinolones in a range of 0.020-3.200 µg mL-1 and 0.030-4.800 µg mL-1 with LODs less than 0.010 µg mL-1. The recoveries were in the ranges of 95.0-104.9%, 90.1-110.2% and 87.8-114.1% for water, honey and milk samples, respectively. The relative standard deviations for reproducibility were all below 7.6%. Under the optimized conditions, the enrichment factors for analytes were achieved in the range from 531 to 858 folds. The presented method was successfully applied for the determination of fluoroquinolones in milk, honey and water samples.

Portable Smartphone-Based QDs for the Visual Onsite Monitoring of Fluoroquinolone Antibiotics in Actual Food and Environmental Samples.

Accurate onsite profiling of fluoroquinolone antibiotics (FQs) is of vital significance for ensuring food safety and estimating environmental pollution. Here, we propose a smartphone-based QD ratiometric fluorescence-sensing system to precisely report the level of FQs. As a proof of concept, we chose gatifloxacin (GFLX, a typical member of FQs) as the model for the analytical target, which could effectively trigger the fluorescence color variation of QDs from bright yellow-green (∼557 nm) to blue (∼448 nm) through the photoinduced electron-transfer (PET) process, thus yielding an evident ratiometric response. Based on this, the level of GFLX can be reported within a wide linear range from 0.85 nM to 3.6 µM. Moreover, this assay owns a high sensitivity with a low detection limit of 0.26 nM for GFLX and a quick sample-to-answer monitoring time of 5.0 min, manifesting that this platform could be fully qualified for onsite requirements. Interestingly, this portable device has successfully been applied for the onsite detection of GFLX in real food (i.e., milk and drinking water) and environmental (i.e., fish-farming water) samples with acceptable results. This developed platform offers a great promise for the point-of-care detection of FQ residues in practical application with the merits of being label-free, low-cost, and rapid, thus opening a new pathway for the onsite evaluation of food safety and environmental health.

Sulphonate functionalized covalent organic framework-based magnetic sorbent for effective solid phase extraction and determination of fluoroquinolones.

Most of the reported covalent organic frameworks (COFs) are hydrophobic, limiting their adsorption application in sample pretreatment field. In this work, sulphonate functionalized magnetic covalent organic frameworks (COFs) composites were first synthesized by loading gold nanoparticles on Fe3O4@COF(TpBD) surface and then functionalized by sodium 3-mercaptopropanesulphonate immobilization via Au-S bonding formation (denoted as Fe3O4@COF(TpBD)@Au-MPS nanocomposites), which were further utilized as adsorbents for magnetic solid-phase extraction (MSPE) of fluoroquinolones. Compared with Fe3O4@COF(TpBD), the composites exhibited higher affinity to fluoroquinolones. Under optimized conditions, the developed MSPE method coupled with HPLC-MS/MS showed good linearity (R2 ≥0.9989) and yielded low limits of detection (0.1-1.0 µg kg-1) for fluoroquinolones. Moreover, the proposed method was successfully applied to extract fluoroquinolones from spiked meats (pork, chicken and bovine). The satisfactory recoveries were in the range of 82-110.2% with the relative standard deviations (RSDs) lower than 7.7%. These results indicated that the Fe3O4@COF(TpBD)@Au-MPS is a promising magnetic adsorbent for trace fluoroquinolones determination in meat samples. This work not only provided a facile strategy for COF functionalization, but also developed an efficient method for detecting fluoroquinolones in foodstuffs.

Development of doubly porous composite adsorbent for the extraction of fluoroquinolones from food samples.

A doubly porous microcomposite polyaniline/graphene oxide/octadecyl-bonded silica magnetite (PANI/GOx/C18-SiO2-Fe3O4) alginate adsorbent was developed and employed to extract fluoroquinolones. The Fe3O4 facilitated rapid and convenient for the separation of the adsorbent from sample solutions. The double porosity of the alginate hydrogel enhanced the surface area of the polyaniline coating. The developed method exhibited good linearity of 0.0010-50 µg L-1 for danofloxacin; 0.0050-50 µg L-1 for norfloxacin, ciprofloxacin and enrofloxacin; and 0.010-50 µg L-1 for sarafloxacin and difloxacin. The limits of detection were between 0.001 and 0.010 µg L-1 with RSD below 9.0%. The PANI/GOx/C18-SiO2-Fe3O4 adsorbent was utilized to extract fluoroquinolones from honey, milk and egg samples and satisfactory extraction recoveries were achieved ranged from 80 to 98%. The developed adsorbent has good stability which can be reused up to 7 times, is simple to prepare and convenient to use for the extraction fluoroquinolones.

Robotic-assisted dynamic large drop microextraction.

By proper design of an innovative extraction device, a lab-made multipurpose autosampler was exploited in the automated performance of the dynamic large drops based microextraction. The pluses of this new analytical strategy were demonstrated in the determination of sulfonamides and fluoroquinolones in surface water samples, by direct immersion single drop microextraction (SDME) and liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) analysis. Operational autosampler features and critical experimental factors influencing SDME, including the extraction mode (static or dynamic), extraction, stirring rate, salt addition, drop size, number of cycles and drop exposition time, were comprehensively investigated using both univariate and multivariate optimization. The lab-made autosampler allowed to performance challenging dynamic and static large drop based SDMEs in an automated and effortless way and with minimal requirements of hardware and software. Large stable drops provided high surface area, enhancing the phase ratio and in consequence increasing the analytes uptake. The best extraction efficiencies were obtained as a result of the synergic interaction between the use of large drops and the automated dynamic mode of extraction. The developed method proved to be a reliable, sensitive, and robust analytical tool, with intraday RSDs ranging between 4.0 and 7.6% (n = 6), and interday RSDs between 4.8 and 9.3% (n = 6), and, LOD and LOQ in the range of 15-50 and 35-100 ng L-1, respectively.

Antibiotics and Resistance Genes in Awash River Basin, Ethiopia.

Among contaminants of emerging concern in the environment, a growing attention has been given to antibiotics and antibiotic-resistant genes (ARGs) due to the rise in their usage and potential ecotoxicological and public health effect. However, the occurrence of these contaminants in the environment is little investigated in developing countries particularly in sub-Saharan regions. In this study, the occurrence of three groups of antimicrobials including tetracycline, sulfonamides and fluoroquinolone, and their corresponding ARGs were investigated in the sediments of Awash River Basin, Ethiopia. Out of twelve studied compounds, sulfadiazine and enrofloxacin showed the highest and lowest detection frequency, respectively. Polymerase chain reaction (PCR) analysis revealed that tetA and tetB occurred in all the samples. The relative abundance of the resistant genes was in the following order: tetA > tetB > sul2 > sul1. Redundancy analysis result indicated that some sediment characteristics were found to have influence on the distribution sul1-resistant gene.

Class-specific determination of fluoroquinolones based on a novel chemiluminescence system with molecularly imprinted polymers.

A ultrasensitive chemiluminescence (CL) method for the determination of fluoroquinolones (FQs) in milk was proposed based on the enhancement effect of FQs on the CL reaction between cerium(IV) and methoxylated Cypridina luciferin analogs (MCLA). Prior to the CL determination, molecularly imprinted polymers (MIPs) with superior recognition performances were adopted to the clean-up and extraction of the family of FQs. Then the developed CL system coupling with MIPs (MIP-CL) was applied to the selective determination of FQs in milk. Under the optimized conditions, the method was validated with respect to linearity, precision, accuracy, limits of detection and quantification. The relative standard deviation (RSD) on intra-day assay was below 5.1%, and detection limit was as low as 0.10 nmol/L. The consistency of this method and HPLC method was compared and validated by the paired t-test. The results indicated that the proposed method allowed class-specific determination of FQs in complex matrices.

Preparation of highly fluorinated and boron-rich adsorbent for magnetic solid-phase extraction of fluoroquinolones in water and milk samples.

Effective extraction is an indispensable procedure for the sensitive analysis of fluoroquinolones (FQs) in complex samples. According to the molecular properties of FQs, a new highly fluorinated and boron-rich adsorbent (FBA) was synthesized and employed as the extraction phase of magnetic solid-phase extraction (MSPE). Results revealed that the prepared FBA displayed satisfactory extraction capability for FQs through fluorophilic and B-N coordination interactions. Besides, the synthesized FBA also exhibited strong magnetic responsiveness and good life-span. Under the most favorable conditions, the FBA/MSPE was combined with high-performance liquid chromatography with diode array detection (HPLC-DAD) to sensitively quantify trace levels of FQs in environmental water and milk samples. The developed approach showed good linearity within the studied concentration range, satisfactory precision and low limits of detection (0.0049-0.016 µg/L for water sample and 0.010-0.046 µg/kg for milk sample). In the analysis of target FQs in real samples, the recoveries of different fortified concentrations were in the ranges of 80.1-120% and 78.9-119% for water and milk samples, respectively. The relative standard deviations for reproducibility were all below 11%. The results well evidence that the introduced FBA/MSPE is a promising extraction technology for FQs, and the established FBA/MSPE-HPLC/DAD approach is suitable to measure low concentrations of FQs in water and milk samples.

High-Throughput and High-Efficient Micro-solid Phase Extraction Based on Sulfonated-Polyaniline/Polyacrylonitrile Nanofiber Mats for Determination of Fluoroquinolones in Animal-Origin Foods.

We herein describe a high-throughput 96-well plate micro-solid phase extraction sample preparation technique based on novel sulfonated-polyaniline/polyacrylonitrile nanofiber mats (sulfonated-PANI/PAN NFMs) for multiresidue detection of fluoroquinolones (FQs) in various animal-origin food samples. Through the double-modification of polyaniline and sulfonic acid, the resulting functionalized sulfonated-PANI/PAN NFMs present high extraction efficiency for FQs. Compared with the existing methods, this approach demonstrates its advantages of being suitable for more sample matrices (milk, animal muscle, liver, kidney, and egg), lower sample amount (0.5 g), lower sorbent requirement (5.0 mg), lower volume of organic solvent (0.7 mL), shorter time (0.2 min per sample), and high sensitivity (0.012-0.06 µg·kg-1). In addition, sulfonated-PANI/PAN NFMs possess excellent reusability which could be reused 10 times without an obvious decrease in extraction efficiency. Combined with ultra performance liquid chromatography-tandem mass spectrometry, the novel sample preparation technique can be expected as an efficient method for routine trace FQ residue monitoring in animal-origin food samples.

Water-dispersible pH/thermo dual-responsive microporous polymeric microspheres as adsorbent for dispersive solid-phase extraction of fluoroquinolones from environmental water samples and food samples.

Multifunctional polymeric microspheres were prepared using hyper-cross-linking chemistry combined with surface-initiated atom transfer radical polymerization. The synthesized microspheres exhibited good water dispersibility, a high surface area, and pH/thermo dual-responsiveness. Fluoroquinolones (FQs), which contains a hydrophilic piperazine ring and hydrophobic fluorine atoms, were used as target analytes to assess the performance of the microspheres as a sorbent for dispersive solid-phase extraction (d-SPE). The d-SPE experimental parameters, including extraction time, amount of microspheres, extraction temperature, and sample solution pH, as well as the desorption conditions, were systematically studied. Coupled with LCMS/MS, an analytical method for analysis of trace-level FQs in water samples was developed and validated. Under optimal conditions, linearity with correlation coefficients (r) of >0.99 was achieved in the concentration range of 0.02-10 µg L-1. The limits of detection and quantification for the selected FQs were 5.0-6.7 and 12-20 ng L-1, respectively. High recovery values (93.1%-97.2%), a high enrichment factor (˜180), and good precision (RSD < 8%, n = 6) were obtained for FQ determination in spiked purified water samples. It was proposed that hydrophilic-hydrophobic transition induced by stretching and shrinking of polymer chains under different pH and temperature conditions offered good control of the surface wettability and altered the extraction behavior. The developed method was validated and was successfully applied to the analysis of FQs in environmental water samples, meat and milk samples. These results demonstrated that the water-dispersible polymeric microspheres have good potential for use in separation and extraction techniques.

Three-dimensional hierarchical frameworks based on molybdenum disulfide-graphene oxide-supported magnetic nanoparticles for enrichment fluoroquinolone antibiotics in water.

Recently, water pollution caused by antibiotics is rapidly increasing. Thus, developing efficient, fast and sensitive detection methods for environmental antibiotics monitoring are still remaining elusive. Herein, a method for antibiotics analysis including lecofloxacin, pazcofloxacin and gatifloxacin in water by high performance liquid chromatography (HPLC) using molybdenum disulfide-graphene oxide-supported magnetic nanoparticles (Fe3O4/GO/MoS2) as the adsorbent of magnetic solid-phase extraction was developed. The as-prepared magnetic Fe3O4/GO/MoS2 nanocomposite exhibited good enrichment capability toward fluoroquinolone antibiotics and the analytes were absorbed within a short time ca. 2 min. The main drive forces of Fe3O4/GO/MoS2 nanocomposite and antibiotics were most likely attributed to hydrogen bonding and electrostatic attraction. A sensitive and effective MSPE-HPLC method was developed with low detection limits (LODs) ranging from 0.25 to 0.50 ng mL-1. The recoveries obtained from the analysis of water sample were between 85.6% and 106.1% with relative standard deviations (RSDs, n = 5) lower than 9.5%. The developed method has a good potential for the analysis of organic contaminants in water with low cost and high sensitivity. Therefore, this finding is a promising strategy for designing high efficiency and fast antibiotics detection system.

Molecularly imprinted polymer-hollow fiber microextraction of hydrophilic fluoroquinolone antibiotics in environmental waters and urine samples.

In the present work, the preparation of a new selective molecularly imprinted polymer (MIP) for the family of fluoroquinolones (FQs) in the pores of polypropylene hollow fibers (HFs) is proposed. The resulting MIP-HFs, which combine solid-phase microextraction (SPME) and molecular imprinting technologies, were used to develop a selective microextraction methodology (MIP-HFM) to determine selected FQs danofloxacin, norfloxacin, enrofloxacin and ciprofloxacin in real samples of environmental and biological interest. Measurements during the optimization of the MIP-HFM and its application to the analyses of real samples were performed by HPLC-UV and HPLC-MS/MS. In order to establish optimum rebinding conditions, the effect of key experimental parameters such as loading media, extraction time and stirring-rate were studied. The developed MIP composites exhibited recognition properties towards the selected hydrophilic antibiotics in non-polar media (toluene) and in polar protic systems such as methanol and methanol/water solutions, up to 20% water content. Recoveries by the developed method for all FQs tested in surface water, groundwater and urine spiked with the analytes of interest at two different concentration levels were within 9.4-24.5 %, with a relative standard deviation, generally <20% (n = 3). The detection limits were within 0.1-10 µg L-1, depending upon the antibiotic and the type of sample.