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Ciprofloxacin (CIP) is one of the most widely used antibiotics to treat bacterial infections. Consequently, there is concern that it may contaminate water resources due to its high usage level. It is therefore necessary to monitor, trace, and reduce exposure to these antibiotic residues. In the current study, the extraction of CIP from water was performed using a green adsorbent material based on cellulose/polyvinyl alcohol (PVA) decorated with mixed metal oxides (MMO). This cellulose/MMO/PVA adsorbent was synthesized using a simple sol-gel method. The prepared adsorbent materials were then characterized using a range of methods, including scanning electron microscopy, energy-dispersive X-ray spectroscopy, gas adsorption analysis, X-ray diffraction, and Fourier Transform infrared. The impact of pH, adsorbent dose, contact time, and CIP concentration on ciprofloxacin extraction were examined. The equilibrium and kinetic adsorption data were well described using the Freundlich model (R 2  = 0.965). The optimum conditions for CIP adsorption were: pH = 4.5; adsorbent dosage = 0.55 g·L -1 ; contact time = 83 min; and initial CIP concentration = 2 mg·L -1 . The adsorption capacity of the cellulose/MMO/PVA adsorbent for CIP removal was ∼19 mg·g -1 (CIP removal = 86.48 %). This study shows that cellulose/MMO/PVA adsorbents have potential for removing contaminants from aqueous environments., 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, 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.)

Monodisperse restricted-access media bi-functional monomers with molecularly imprinted polymers (RAM-MIPs) were constructed using surface-initiated atom transfer radical polymerization. They were used as solid-phase extraction (SPE) adsorbents to enrich sarafloxacin (SAR) residues from egg samples, and influences on their performance were investigated. Optimum synthesis of RAM-MIPs was achieved by combining a bi-functional monomer (4-vinylpyridine-co-methacrylic acid, 1:3) with an 8:1:32:8 ratio of a template molecule, cross-linker, and restricted-access functional monomer. The SAR imprinting factor of RAM-MIPs was 6.05 and the selectivity coefficient between SAR and other fluoroquinolones was 1.86-2.64. Compared with traditional MIPs, the RAM-MIPs showed better SAR enrichment and selectivity during extraction of a complex protein-containing solution. Empty SPE cartridges were filled with RAM-MIP microspheres as SPE adsorbents. The limit of quantitation for SAR was 4.23 ng g -1 (signal-to-noise ratio = 10) and the mean SAR recovery from spiked egg samples was 94.0-101.3%. Intra-day and inter-day relative standard deviations were 1.1-9% and 1.5-3.3%, respectively., 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 Elsevier B.V. All rights reserved.)

Herein, we have developed a photocatalytic, fluorescent bismuth phosphate@graphene oxide (BiPO 4 @GO) based magnetic nano-sized-molecularly imprinted polymer (MMIP) for detection, removal, and degradation of ciprofloxacin (CIP) via atom transfer radical polymerization (ATRP) process. CIP is a very popular antibiotic, but their heavy doses in recent time, made them an environmental threat. The imprinted polymer was synthesized using N-vinyl caprolactam, N, N-methylene bis-acrylamide, ZnFe 2 O 4 nanoparticle, and Bi(PO 4 )@GO as a biocompatible monomer, crosslinker, magnetic moiety, and photocatalyst, respectively. The characterization of the molecularly imprinted polymer was systematically evaluated by electrochemical techniques, X-ray diffraction, fluorescence spectroscopy, scanning electron microscopy, etc. The prepared BiPO 4 @GO modified CIP-imprinted magnetic polymer (BiPO 4 @GO-MMIPs) shows high selectivity towards their template/target analyte (i.e., CIP) and used for their visual (via fluorescence study) and trace level detection (via the electrochemical study) in various kind of complex matrix. The dual behaviour i.e. electrochemical and optical sensing of CIP was successfully achieved in a good linear range of 39.0 to 740.0 μg L -1 with detection of limit (LOD) of 0.39 μg L -1 for electrochemical study and 39.0 to 328.0 μg L -1 and LOD of 0.40 μg L -1 for optical study. The prepared BiPO 4 @GO-MMIPs were successfully used for the detection of CIP from complex matrix like blood serum, whole blood, and milk sample as well as removal and degradation of CIP with good efficiency., Competing Interests: Declaration of competing interest None., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Adverse effects of pharmaceutical emerging contaminants (PECs), including antibiotics, in water supplies has been a global concern in recent years as they threaten fresh water security and lead to serious health problems to human, wildlife and the environment. However, detection of these contaminants in water sources, as well as food products, is difficult due to their low concentration. Here, we prepared a new family of magnetic molecular imprinted polymer (MMIP) networks for binding antibiotics via a microemulsion polymerization technique using vinyl silane modified Fe 3 O 4 magnetic nanoparticles. The cross-linked polymer backbone successfully integrated with 20-30 nm magnetic nanoparticles and generated a novel porous polymeric network structure. These networks showed a high binding capacity for both templates, erythromycin and ciprofloxacin at 70 and 32 mg/g. Both MMIPs were also recyclable, retaining 75 % and 68 % of the binding capacity after 4 cycles. These MMIPs have showed a clear preference for binding the template molecules, with a binding capacity 4- to 7-fold higher than the other antibiotics in the same matrix. These results demonstrate our MMIP networks, which offered high binding capacity and selectivity as well as recyclability, can be used for both removal and monitoring hazardous antibiotic pollutants in different sources/samples and food products., Competing Interests: Declaration of Competing Interest There is no conflict of interest to declare., (Copyright © 2019 Elsevier B.V. All rights reserved.)

The study investigated ciprofloxacin (CIP) adsorption capacity of the novel biomaterials prepared from banyan aerial roots by simple thermochemical modification. Pretreated banyan aerial root fibers were modified with a green reagent citric acid (1 M) at 90, 120 and 150 °C, which enhanced the fiber adsorption capacity revealed by characterization and adsorption tests. Several characterization methods were applied to exploring the surface morphologies and physicochemical properties of unmodified banyan aerial roots (UBARs) and modified banyan aerial roots (T-MBARs, T stands for the modification temperature). Based on SEM images and N 2 adsorption/desorption isotherms, the modification resulted in decrease of the specific surface area owing to cellulose molecular linking. In that case, the improved CIP adsorption of MBARs might be attributed to the larger carboxyl quantity and stronger electronegativity manifested via FTIR spectra and zeta potential analysis. Through the adsorption experiments, the optimal pH value of 8 and the suitable absorbent dosage of 0.03 g were obtained. The simulation results showed that the Freundlich model can fit the adsorption thermodynamic data quite well, while the kinetic data was simulated preferably by the pseudo-second-order kinetic equation signifying the chemical adsorption process, and the intra-particle diffusion was involved in the adsorption consisted of three stages. The findings of batch experiments under diverse operations represented that MBARs purified aqueous CIP better than UBARs, closely related to the superior electronegativity. Both characterization and adsorption studies illustrated the dominant role of electrostatic interaction during CIP removal, accompanied by hydrogen bonding and diffusion interaction besides. The present work suggested that MBAR fibers could possess a promising application to ciprofloxacin potent removal from aqueous solutions., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Ciprofloxacin has been frequently detected in water environment, and its removal has become a significant public concern. Biochar-supported nanoscale zero-valent iron (BC/nZVI) to activate hydrogen peroxide (H 2 O 2 ) has many advantages on promoting the removal of organic contaminants. In this paper, the BC/nZVI activating H 2 O 2 degradation of ciprofloxacin was systematically investigated by experimental and theoretical approaches. The morphologies and property analysis showed that nZVI particles distributed uniformly on the biochar surface, which mainly include  - OH, >CO and COC and CO groups. Different reaction conditions were compared to define the optimal conditions for ciprofloxacin removal in BC/nZVI/H 2 O 2 system. More than 70% of ciprofloxacin was removed in the optimal conditions: acidic condition (pH 3∼4), low doses of H 2 O 2 (20 mM), and temperature of 298 K. The hydroxyl radical ( • OH) oxidation was the primary pathway in BC/nZVI/H 2 O 2 degradation of ciprofloxacin process. The theoretical calculation indicated that hydrogen atom abstraction (HAA) pathways were the dominant oxidation pathways contributing 92.3% in overall second‒order rate constants (k) of • OH and ciprofloxacin. The current results are valuable to evaluate the application of BC/nZVI activating H 2 O 2 degradation of ciprofloxacin and other fluoroquinolone antibiotics in water treatment plants., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Water contamination with antibiotics is a serious environmental threat. Ciprofloxacin (CIP) is one of the most frequently detected antibiotics in water. Herein, silica-based magnetic nanosorbents prepared using three seaweed polysaccharides, alginic acid, κ- and λ-carrageenan, were developed and evaluated in the uptake of ciprofloxacin. The sorbents were firstly characterized in detail to assess their morphology and composition. A systematic investigation was conducted to study the adsorption performance towards CIP, by varying the initial pH, contact time and initial CIP concentration. The maximum adsorption capacity was 464, 423 and 1350 mg/g for particles prepared from alginic acid, κ- and λ-carrageenan respectively. These high values indicate that these materials are among the most effective sorbents reported so far for the removal of CIP from water. The kinetic data were consistent with the pseudo-second-order model. The CIP adsorption on λ-carrageenan particles followed a cooperative process with sigmoidal isotherm that was described by the Dubinin-Radushkevich model. The high charge density of λ-carrageenan and the propensity of CIP molecules to self-aggregate may explain the cooperative nature of CIP adsorption. The sorbents were easily regenerated in mild conditions and could be reused in CIP removal up to 4 times without a significant loss of adsorptive properties., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Ciprofloxacin (CIP) is one of most used quinolone antibiotics detected frequently in agricultural soils and vegetables. In the present study, variations in microbial community and CIP removal in rhizospheric soils between two cultivars of Brassica parachinensis L. that accumulate higher and lower CIP (Sijiu and Cutai, respectively) were investigated under CIP stress (0mg/kg in CK, 2.94mg/kg in T1, and 67.11mg/kg in T2). The removal rates of CIP in rhizospheric soils of cultivar Sijiu were higher than those of cultivar Cutai, with a significant difference in T2 (48.7%>39.4%, P<0.05). The pyrosequencing of 16S rRNA and ITS gene indicated that the microbial diversity and community structure in rhizospheric soils of the two cultivars varied significantly. Spirochaeta and Trichosporon might be associated with CIP degradation, and higher relative abundances of Trichosporon in rhizoshperic soils of cultivar Sijiu might be responsible for higher CIP removal. Fourteen bacterial genera and ten fungal genera were screened as potential biomarkers for CIP removal process. The community level physiological profiling in rhizospheric soils of the two cultivars under CIP stress differed significantly, and more C substrates that favored CIP removal were observed in rhizoshperic soils of cultivar Sijiu. Our results demonstrate that variations in microbial community and the utilization of C substrates played important roles in differring the CIP removal in rhizospheric soils between the two cultivars., (Copyright © 2017 Elsevier B.V. All rights reserved.)

An ultra high-performance liquid chromatographic (UHPLC) method with PDA detection was developed and validated for the simultaneous quantification of linezolid and ciprofloxacin in human plasma and applied in hospital acquired pneumonia patients (HAP). The method uses a semi-automated microextraction by packed sorbent for sample preparation. All parameters in the extraction step (pH, sample volume, sample dilution and number of aspiration - ejection cycles) and in the desorption step (percentage of acetonitrile in the solvent of elution and number of aspirations of elution solvent through the device) were statistically significant when the recovery was used as response. The method showed good linearity with correlation coefficients, r 2 >0.9995 for the two drugs, as well as high precision (RSD%<9.77% in each case), accuracy ranged from -6.2% to +8.2. The limit of quantification of the two drugs was established at 0.01 and 0.02μg/mL for ciprofloxacin and linezolid, respectively. Linezolid, ciprofloxacin and internal standard were extracted from human plasma with a mean recovery ranging from 92.4% to 97.4%. During validation, the concentrations of linezolid and ciprofloxacin were found to be stable after 3 freeze-thaw cycles and for at least 24h after extraction. This method will subsequently be used to quantify the drugs dosage in patients with HAP to establish if the dosage regimen given is sufficient to eradicate the infection at the target site., (Copyright © 2016 Elsevier B.V. All rights reserved.)

The nanoporous carbons (NPC) derived from a one-step carbonization of zeolitic imidazolate framework-8 (ZIF-8) were synthesized and used for ciprofloxacin (CIP) removal from water. The resultant products were characterized by SEM, TEM, FT-IR, Raman, N 2 adsorption-desorption analysis, XRD, TGA and Zeta potential. The optimized NPC-700 (carbonized at 700°C for 2h) exhibited an optimal performance in CIP adsorption removal. CIP adsorption on NPC-700 as a function of contact time, initial CIP concentration, adsorbent dosage, pH, ionic strength and humic acid concentration were investigated. Kinetics of CIP removal was found to follow pseudo-second-order rate equation. Both Langmuir and Freundlich models fitted the adsorption data well and gave similar correlation coefficients (>0.96). However, Freundlich isotherm gave a better fit (r 2 =0.9969), suggesting a multilayer adsorption of CIP onto surface of NPC-700 adsorbent. The maximum adsorption capacity for CIP based on Langmuir model was 416.7mg/g, which was higher than those of other adsorbents. The NPC-700 material showed no apparent loss in CIP adsorption after seven cycles. These features reveal that the metal-organic framework (MOF) derived NPC may be a promising adsorbent for CIP removal from water., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Ferrate(VI) (Fe(VI)) has been known to react with emerging organic contaminants containing electron-rich organic moieties, such as phenols, anilines, olefins, reduced sulfur and deprotonated amines. Oxidation of fluoroquinolone antibiotics, ciprofloxacin (CIP) and enrofloxacin (ENR), by Fe(VI) were investigated for their reaction products and toxicity changes as well as biodegradability of these products. Ten products were identified for both CIP and ENR reactions with Fe(VI) using a high-resolution accurate-mass Orbitrap mass analyzer. Structural changes to the CIP and ENR molecule included dealkylation, formation of alcohols and amides in piperazine ring and oxygen transfer to the double bond in quinolone structure. An enamine formation mechanism was tentatively proposed to facilitate the interpretation of CIP and ENR oxidation pathways. Toxicity evaluation using Microbial Assay for toxicity Risk Assessment (MARA) bioassay indicated that Fe(VI) oxidation products of CIP and ENR contributed negligible antibacterial potency and Fe(VI) oxidation treatment can remove the residual toxicity of CIP and ENR impacted source waters. The Fe(VI) oxidation treatment resulted in formation of relatively more biodegradable products (based on in silico assessment) than their corresponding parent compounds. The results showed that Fe(VI) has a good potential to degrade fluoroquinolone antibiotics and their antimicrobial potency in natural waters., (Copyright © 2016 Elsevier B.V. All rights reserved.)

The series of macroporous monolithic molecularly imprinted monoliths differed by pore size, column length (volume) and amount of template used for imprinting was synthesized using methacrylic acid and glycerol dimethacrylate as co-monomers and antibiotic ciprofloxacin as a template. The prepared monoliths were characterized regarding to their permeability, pore size, porosity, and resistance to the flow of a mobile phase. The surface morphology was also analyzed. The slight dependence of imprinting factor on flow rate, as well as its independence on pore size of macroporous molecularly imprinted monolithic media was observed. The column obtained at different conditions exhibited different affinity of ciprofloxacin to the imprinted sites that was characterized with Kdiss values in the range of 10(-5)-10(-4)M. The solid-phase extraction of ciprofloxacin from such biological liquids as human blood serum, human urine and cow milk serum was performed using the developed monolithic columns. In all cases, the extraction was found to be 95.0-98.6%. Additionally, the comparison of extraction of three fluoroqinolone analogues, e.g. ciprofloxacin, levofloxacin and moxifloxacin, from human blood plasma was carried out. Contrary to ciprofloxacin extracted with more than 95%, this parameter did not exceed 40% for its analogues., (Copyright © 2016 Elsevier B.V. All rights reserved.)

In this study, experiments were carried out to investigate the use of as-synthesized single-walled (SWCNT), double-walled (DWCNT) and multi-walled carbon nanotubes (MWCNT) agglomerates for the removal of two antibiotics, Oxytetracycline (OXY) and Ciprofloxacin (CIP) from aqueous solution. The variations of key operating parameters on the removal process were assessed in order to find out the optimum conditions. It includes exposure time, solution pH, temperature, ultrasound assistance and desorption assays. The experimental results revealed that a moderate increase in adsorption was registered between pH 3 and 7 for both antibiotics. The application of ultrasound helped enhancing the removal capacities of OXY for all tested CNTs. For the case of MWCNTs, 1h of ultrasonication increased the adsorption capacity by 44.6%. As for CIP, the ultrasonic treatment did not enhance the overall adsorption, especially for the case of DWCNTS. The Brouers-Sotolongo equation was the best fitting isotherm model. The highest removal capacities were registered using SWCNTS for both antibiotics (724 mg/g for CIP and 554 mg/g for OXY). In addition, ethanol was the solvent that induced the highest desorption percent for the case of CIP (52% for MWCNTs). However, the desorption of OXY was negligible for all solvents (maximum 3.3% for DWCNTs using ethanol)., (Copyright © 2015 Elsevier B.V. All rights reserved.)

In-tube magnetic solid phase microextraction (in-tube MSPME) of fluoroquinolones from water and urine samples based on the use of sodium dodecyl sulfate (SDS) coated Fe3O4 nanoparticles packed tube has been reported. After the preparation of Fe3O4 nanoparticles (NPs) by a batch synthesis, these NPs were introduced into a stainless steel tube by a syringe and then a strong magnet was placed around the tube, so that the Fe3O4 NPs were remained in the tube and the tube was used in the in-tube SPME-HPLC/UV for the analysis of fluoroquinolones in water and urine samples. Plackett-Burman design was employed for screening the variables significantly affecting the extraction efficiency. Then, the significant factors were more investigated by Box-Behnken design. Calibration curves were linear (R(2)>0.990) in the range of 0.1-1000μgL(-1) for ciprofloxacin (CIP) and 0.5-500μgL(-1) for enrofloxacin (ENR) and ofloxacin (OFL), respectively. LODs for all studied fluoroquinolones ranged from 0.01 to 0.05μgL(-1). The main advantages of this method were rapid and easy automation and analysis, short extraction time, high sensitivity, possibility of fully sorbent collection after analysis, wide linear range and no need to organic solvents in extraction., (Copyright © 2015 Elsevier B.V. All rights reserved.)

A semiautomated solid-phase extraction manifold for multiple extractions is presented. The manifold utilizes commercial solid-phase syringe cartridges and automatically introduces and elutes all the solvents during the extraction, reducing the typical workload and stress of the analyst. The manifold consists of a peristaltic pump with solenoid valves in a flow circuit that contains transmissive photomicrosensors. The photomicrosensors were used to control the solvent dispenser and the solvent level inside the cartridge. As solvent-level sensors, the photomicrosensors determined the exact time the solvent reached the top frit to avoid sorbent drying and accurately perform the solvent exchange. The repeatability of the manifold to introduce a particular volume of solvent into the cartridges was measured, and the precisions were between 0.05 and 2.89% (RSD). To evaluate the manifold, the amount of two fluoroquinolones in a fortified blank milk sample was determined. The results of the intra- and inter-day precision of multiple extractions from the fortified milk samples resulted in precisions better than 9.0% (RSD) and confirmed that the arrangement of the semiautomated manifold could adequately be used in solid-phase extraction with commercial cartridges., (Copyright © 2013 Elsevier B.V. All rights reserved.)

With more pharmaceuticals and personal care products detected in the surface and waste waters, studies on interactions between these contaminants and soils or sediments have attracted great attention. In this study, the removal of ciprofloxacin (CIP), a fluoroquinolone antibiotic, by birnessite, a layered manganese oxide, in aqueous solution was investigated by batch studies supplemented by X-ray diffraction (XRD) and Fourier transform infrared analyses. Stoichiometric release of exchangeable cations accompanying CIP removal from water confirmed cation exchange as the major mechanism for CIP uptake by birnessite. Interlayer expansion after CIP adsorption on birnessite as revealed by XRD analyses indicated that intercalation contributed significantly to CIP uptake in addition to external surface adsorption. Correlation of CIP adsorption to specific surface area and cation exchange capacity suggested that the former was the limiting factor for CIP uptake. At the adsorption maximum, CIP molecules formed a monolayer on the birnessite surfaces. The adsorbed CIP could be partially removed using a cationic surfactant at a low initial concentration and mostly removed by AlCl3 at a higher initial concentration, which further supported the cation exchange mechanism for CIP removal by birnessite. The results indicated that the presence of layered Mn-oxide in the soil and waste water treatment systems may provide host for CIP accumulation., (Copyright © 2013 Elsevier B.V. All rights reserved.)

Response surface methodology (RSM) was utilized for rapid and systematic optimization of on-line solid-phase extraction (SPE) parameters to maximize the response and separation of WM-5. The optimization was performed with Box-Behnken designs. Four major parameters were investigated for their contributions to the response and separation of WM-5, with a total of 29 experiments being performed for each instrument, respectively. Quantitative determination of WM-5 in mouse plasma was performed to evaluate the statistical significance of the parameters on chromatographic response. A fully automated on-line SPE and high-performance liquid chromatography (HPLC) with diode array detection (DAD) method was developed for the determination of WM-5 in mouse plasma. Calibration curve with good linearity (r=0.9989) was obtained in the range of 20-4000 ng/mL in mouse plasma. The limit of detection (LOD) and lower limit of quantification (LLOQ) of the assay were 6 ng/mL and 20 ng/mL, respectively. The overall intra-day and the inter-day variations were less than 1.90%. The recovery of the method was in the range of 93.74-96.33% with RSD less than 3.06%. The optimized method demonstrated good performance in terms of specificity, LLOQ, linearity, recovery, precision and accuracy, and was successfully applied to quantify WM-5 in mouse plasma to support the pharmacokinetic study., (Copyright © 2013 Elsevier B.V. All rights reserved.)

An understanding of the interaction mechanisms of antibiotics with environmentally relevant sorbents is important to determine the environmental fate of antibiotics and to develop wastewater treatment strategies. Magnetite (Fe(3)O(4)(s)) is ubiquitous in the environment and occurs as a secondary corrosion product of iron nanoparticles that are commonly used as a remediation material. In this study, we aimed to assess the sorption mechanisms of ciprofloxacin (CIP), an important class of fluoroquinolone antibiotics, with magnetite nanoparticles using a combination of wet chemical and in situ ATR-FTIR spectroscopic measurements. Ciprofloxacin sorption was characterized as a function of pH (3.4-8.0), CIP concentration (1-500 μM), ionic strength (0.5, 0.1, and 0.01 M NaCl), and competing anion such as phosphate (0.1mM) to cover a broad range of environmentally relevant geochemical conditions. Results indicated a bell-shaped sorption envelop where sorption of CIP on nano-Fe(3)O(4)(s) increased from 45% to 80% at pH 3.44-5.97; beyond that sorption gradually decreased to a value of 25% at pH 8.39. Phosphate had negligible effect on CIP sorption. In situ ATR-FTIR results indicated inner-sphere coordination of CIP at the magnetite surface mediated by carboxylic acid groups. Results suggest that nano-Fe(3)O(4)(s) has the potential to remove CIP from wastewater effectively., (Copyright © 2012 Elsevier B.V. All rights reserved.)

Water and wastewater effluents contain a vast range of chemicals in mixtures that have different chemical structures and characteristics. This study presents a treatment technology for the removal of mixtures of antibiotic residues (sulfamethoxazole (SMX), oxytetracycline (OTC) and ciprofloxacin (CIP)) from contaminated water. The treatment combines pH modification of the water to an optimal value, followed by a photolytic treatment using direct polychromatic ultraviolet (UV) irradiation by medium pressure UV lamp. The pH adjustment of the treated water leads to structural modifications of the pollutant's molecule thus may enhance direct photolysis by UV light. Results showed that an increase of water pH from 5 to 7 leads to a decrease in degradation rate of SMX and an increase in degradation rate of OTC and CIP, when studied separately and not in a mixture. Thus, the optimal pH values for UV photodegradation in a mixture, involve initial photolysis at pH 5 and then gradually changing the pH from 5 to 7 during the UV exposure. For example, this resulted in 99% degradation of SMX at pH 5 and enhanced degradation of OTC and CIP from 54% and 26% to 91% and 96% respectively when pH was increased from 5 to 7. Thus the pH induced photolytic treatment has a potential in improving treatment of antibiotics in mixtures., ((c) 2009 Elsevier B.V. All rights reserved.)

A supercritical fluid extraction method combined with high-performance liquid chromatography-fluorescence detection was developed for the determination of enrofloxacin, danofloxacin, and ciprofloxacin in pig muscle, lung, and kidney samples. The optimal SFE conditions were 80 degrees C, 300 kg/cm(2), 30% methanol for 40 min as a dynamic extraction time, in addition to 0.2g Na(4)EDTA and 7.0 g sea sand in the extraction vessel. The use of Na(4)EDTA and sea sand on SFE extraction resulted in improvement of the recoveries of ciprofloxacin, a polar and hydrophilic compound, as well as enrofloxacin and danofloxacin. Overall, the recoveries ranged from 86.7 to 113.1% using the Na(4)EDTA/sea sand-assisted SFE extraction method. The Na(4)EDTA/sea sand-assisted SFE-HPLC-FLD validated method was successfully carried out in pig tissues, and proved to be specific, sensitive, reliable, and accurate. The method was also applied satisfactorily for accurate quantitative residue analysis in incurred pig tissues.

A simple and rapid method for the determination of residues of enrofloxacin and its metabolite ciprofloxacin in edible tissues of farm animals using turbulent flow chromatography/tandem mass spectrometry (TFC-MS/MS) is described. The tissue samples were extracted with a mixture of acetonitrile, water and formic acid. After addition of internal standard solution, an aliquot of the extract was injected into the turbulent flow chromatography system. Matrix components contained in the injected sample were separated from the retained analytes on a polymer-based extraction column suited for pretreatment of samples at high flow rates. The analytes were eluted to an analytical column and the quantitative determination was performed using a tandem mass spectrometric detector. The run time for the analysis was 4 min. The limit of quantitation (LOQ) was 25 microgkg(-1) for each analyte and tissue material. Validation was performed in edible tissues of cattle, pig, turkey and rabbit in the range from 25 microgkg(-1) to at least twice the MRL. Mean recovery rates for the tissues of the different species were in the range from 72 to 105% with a coefficient of variation (CV) between 4.3 and 18%.

Since its extensive development in the early 1980s, SFE has attracted considerable attention as a sample-preparation procedure. However, other different sample preparation procedures, including precipitation, liquid- and/or solid-phase extraction in biological fluids, also remain in use. In this investigation, SFE was introduced to isolate and identify orbifloxacin from plasma and milk. Four parameters, including the temperature and the pressure of supercritical fluid, modifier ratios, and dynamic extraction time, were evaluated and optimized to obtain the best yield of the analyte from the biological fluids. Determinations of the orbifloxacin (OBFX) in the extracts were carried out using HPLC-FLD. The optimum conditions of the extraction process that yielded the maximum analyte extraction efficiencies were 150 degrees C vs. 60 degrees C, 250 kg cm(-2), 30% vs. 35% methanol, and 40 min vs. 20 min, for plasma and milk, respectively. The linearity of the calibration curves as well as the instrument LODs/LOQs were evaluated. Good linearity (at least r(2) > or = 0.999) of the calibration curves was obtained over the range from 0.2 to 0.01 microg mL(-1). The method showed a good recovery rate (74.2-127.73%) and precision (RSDs: 1.64-20%). The instrumental LOD and LOQ values were 0.004 microg mL(-1) vs. 0.01 microg mL(-1) or 0.006 microg mL(-1) vs. 0.02 microg mL(-1), for plasma and milk, respectively. The method was successfully applied to estimate the pharmacokinetic variables of orbifloxacin in lactating does. To the best of our knowledge, this is the first time that SFE has been applied to isolate an antimicrobial agent from biological fluids. This method is promising for clinical applications and for pharmacokinetic studies of various pharmaceuticals in biological fluids.

This paper describes a new method for the effective extraction, clean-up and chromatographic analysis of residues of four fluoroquinolones (ciprofloxacin, enrofloxacin, danofloxacin and sarafloxacin) in powdered infant formulae and follow-on preparations. Samples were reconstituted following the manufacturer's recommendations and treated with trichloroacetic acid in methanol 10% (w/v) for deproteinization. Two solid-phase extraction cartridges have been evaluated for sample clean-up and preconcentration, Strata Screen A and Strata X and the later provided the best recoveries for all the analytes tested. Chromatographic analysis has been carried out using a polar endcapped column (AQUA C(18)) and fluorescence detection, with lomefloxacin (LOME) as internal standard. Method validation has been performed according to European Commission Decision 2002/657/EC criteria, in terms of linearity, recovery, precision, specificity, decision limit (CC(alpha)) and detection capability (CC(beta)). Typical recoveries ranged between 70 and 110% at levels below and above the maximum residue limits of the target analytes in bovine milk, with an excellent intralab reproducibility (RSDs<7%). Matrix effects did not significantly affect method accuracy, as evidenced by analyzing different brands of milk. The method has been successfully applied to the analysis of 100 samples of infant and follow-on formulae of the Spanish and Latin American market, using LC-MS/MS as confirmatory technique.

A simple, reliable microemulsion electrokinetic chromatography (MEEKC) method is developed for the simultaneous separation of seven fluoroquinolones (FQs). The best separation is achieved in a carrier electrolyte containing 1% (v/v) heptane, 100 mmol/L sodium dodecyl sulfate (SDS), 10% (v/v) 1-butanol, and 8 mmol/L phosphate-sodium tetraborate buffer at pH 7.30. The proposed method was directly applied to the determination of ciprofloxacin (CPF) and lomefloxacin (LMF) in urine samples of subjects administered either with CPF or LMF.

Continuous-flow and static dialysis coupled on-line to liquid chromatography was evaluated and an automated method for determination of ciprofloxacin in biological samples developed. A trace enrichment column packed with C18 material and coupled with a continuous dialysis and reversed-phase HPLC system with fluorescence detection enabled determination of ciprofloxacin in human blood serum at the 0.1-nmol/l level. The amount of analyte preconcentrated and loaded on the HPLC system was linearly proportional to the concentration in the dialysed sample over more than 4 orders of magnitude (up to 1 x 10(-6) M). Data for linearity, repeatability and detectability for each particular set-up are given. The trace enrichment step eliminates band broadening caused by solvents different from those of the eluent and affecting retention of ciprofloxacin on the analytical column (increase in k') due to the on-column change of eluent composition. In analysis of human serum samples phthalates leached from plastic materials may interfere due to coelution with the analyte.

The parameters influencing dialytic separation of ciprofloxacin (CF) fluoroquinolone were investigated. Dialysis with a porous cellulose acetate membrane was on-line coupled with HPLC and the analysis of dialysate was made by isocratic ion-pairing liquid chromatography using a reversed-phase analytical column and fluorescence detection. Optimisation of the experimental conditions for selective dialytic enrichment are described and explanations of some phenomena affecting dialysis efficiency discussed. By the use of a neutral donor (pH approximately 7) and acidic acceptor solution (pH < 4) a substantial enrichment of quinolones was achieved. Accumulation of CF in the acidic acceptor phase is based on the protonation of the analyte in the acceptor compartment. Continuous-flow of donor solution and a stagnant acceptor solution gave high dialysis efficiency in 5-15 min. Effects of interfering substances present in real samples on the variation of dialysis efficiency can be minimised by successive dialysis runs of the original and spiked samples.