Effective removal of levofloxacin drug and Cr(VI) from water by a composed nanobiosorbent of vanadium pentoxide@chitosan@MOFs.

Wastewaters is generally polluted with various inorganic and organic contaminants which require effective multipurpose purification technology. In this respect, a novel V2O5@Ch/Cu-TMA nanobiosorbent was constructed via encapsulation of nanoscale metal organic frameworks (Cu-TMA) into vanadium pentoxide-imbedded-chitosan matrix to comprehensively investigate its efficiency in removal of levofloxacin drug (LEVO) (e.g., organic pollutant) and chromium (VI) (e.g., inorganic pollutant) from water. Both LEVO drug and Cr(VI) adsorptions were correlated to pseudo-second order (R2 = 1) and Langmuir isotherm (R2 = 0.9924 for LEVO and R2 = 0.9815 for Cr(VI)). Adsorption of Cr(VI) was confirmed to be spontaneous and endothermic reactions, while LEVO was found to proceed via spontaneous and exothermic reactions based on the thermodynamic parameters. The emerged V2O5@Ch/Cu-TMA is regarded as an excellent nanobiosorbent for removal of inorganic contaminant as Cr(VI) from all natural water samples (tap, sea and wastewater) with percentages range 92.43%-96.95% and organic contaminant as LEVO drug from tap and wastewater (91.99%-97.20%).

Hydrophilic deep eutectic solvents modified phenolic resin as tailored adsorbent for the extraction and determination of levofloxacin and ciprofloxacin from milk.

A reliable and efficient method for the simultaneous extraction and determination of antibiotics of ciprofloxacin and levofloxacin from milk was developed with solid phase extraction based on tailored adsorbent materials of deep eutectic solvents modified phenolic resin (DES-R-SPE). Six types of polyhydric alcohol-based hydrophilic DESs were prepared to modify the phenolic resin with the compositions of 3-aminophenol as a functional monomer, glyoxylic acid as a crosslinker, and polyethylene glycol 6000 as a porogen. And the prepared DES-Rs showed better extraction capacities for the target analytes than the unmodified phenolic resin because of more hydrogen bonding and electrostatic interactions supplied by DESs. The choline chloride-glycerol-based resin (DES1-R) with the highest adsorption amounts was selected and the adsorption behavior of it was studied with static adsorption and the dynamic adsorption performance; the adsorption process followed Freundlich isotherm (R2 ≥ 0.9337) and pseudo-second-order (R2 ≥ 0.9951). The present DES1-R-SPE method showed good linear range from 0.5 to100 µg mL-1 (R2 ≥ 0.9998), good recoveries of spiked milk samples (LEV, 96.7%; CIP, 101.5%), and satisfied repeatability for intra-day and inter-day (LEV, RSD≤5.4%; CIP, RSD≤4.6%).

ß-Cyclodextrin Polymerized in Cross-Flowing Channels of Biomass Sawdust for Rapid and Highly Efficient Pharmaceutical Pollutants Removal from Water.

Water pollution arising from pharmaceuticals has raised great concerns about the potential risks for biosphere and human health. However, rapid and efficient removal of pharmaceutical contaminants from water remains challenging. Wood sawdust, a byproduct of the wood-processing industry, is an abundant, cost-effective, and sustainable material with a unique hierarchically porous microstructure. These features make wood sawdust quite interesting as a filtration material. Here, we report a novel cross-flow filtration composite based on ß-cyclodextrin-polymer-functionalized wood sawdust (ß-CD/WS) in which the pharmaceutical contaminant water flows through the sawn-off vessel channels and the micropores on the surface of the cell walls, generating the turbulence. Such water flow characteristics ensure full contact between pharmaceutical pollutants and ß-CD grafted on the cellulose backbone of wood sawdust, thereby enhancing the water treatment efficiency. Consequently, the ß-CD/WS filter device shows a high removal efficiency of over 97.5% within 90 s for various pharmaceutical contaminants including propranolol, amitriptyline, chlortetracycline, diclofenac, and levofloxacin, and a high saturation uptake capacity of 170, 156, 257, 159, and 185 mg g-1, respectively. The high-performance wood-sawdust-based cross-flow filtration opens new avenues for solving the global water pollution issues, especially those caused by pharmaceutical contaminants.

Effective Removal of Levofloxacin from Pharmaceutical Wastewater Using Synthesized Zinc Oxid, Graphen Oxid Nanoparticles Compared with their Combination.

The presence of antibiotic traces in the aquatic system due to the inefficient treatment of the pharmaceutical wastewater represented threats, such as bioaccumulation and antibiotic-resistance, to the environment and human health. Accordingly, for the first time, the current work utilized the photocatalytic degradation and the adsorption approach for Levofloxacin (LEVO) in pharmaceutical wastewater using new designed nano aspects. Therefore, spherical Zinc oxide nanoparticles (ZnONP) sized 17 nm and ultrathin sheet-like structure graphene oxide nanosheets (GONS) with layer thickness ~5 nm were fabricated separately or in a combination between them then characterized via Transmission Electron Microscope (TEM), Scanning Electron Microscope (SEM), X-Ray Diffraction (XRD), Fourier Transforms Infrared Spectroscopy (FTIR), absorption spectra (UV-Vis) and Brunauer-Emmett-Teller (BET). Additionally, several parameters were investigated to evaluate the potential of the removal process, such as pH, the exposure time to UV radiation, the type and concentration of the nanoparticles (NPs) and the initial concentration of the drug using a mixed fractional factorial design. The most effective parameter for LEVO removal was the NPs type followed by the initial drug concentration. Furthermore, an RP-HPLC/UV method was developed and validated for measuring the percentage of removal for LEVO drug. The highest percentage removal for both 50 and 400 µg mL-1 LEVO was 99.2% and 99.6%, respectively, which was achieved using ZnONP/GONS combination at pH 9 ± 0.05 and UV light exposure time 120 min. In addition, the negative antibacterial activity of the treated wastewater sample confirmed the drug removal. The established protocol was successfully applied on wastewater samples collected from a pharmaceutical company that encouraged researchers to mainstream this design to be applied on other pharmaceutical wastewater drugs.

A sustainable ferromanganese biochar adsorbent for effective levofloxacin removal from aqueous medium.

This present study reported the synthesis and characterization of a low-cost, environment friendly and high efficient biochar, ferromanganese modified biochar (Fe/Mn-BC) for the removal of levofloxacin (LEV) from aqueous medium. Fe/Mn-BC was synthesized through the facile co-precipitation of Fe, Mn with vinasse wastes and then pyrolysis under controlled conditions. The characterization of Fe/MnBC was analyzed by scanning electron microscope (SEM), transmission electron microscope (TEM), X-ray diffraction patterns (XPS), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and Raman. Some influencing factors (e.g., pH, Fe/Mn-BC dosage, initial LEV concentration, ionic strength, contact time and temperature) were comprehensively investigated. The results manifested that the adsorption process of LEV onto Fe/Mn-BC was high pH dependence and the maximum adsorption capacity was achieved at pH 5. Moreover, the adsorption capacity of LEV was increased with increasing ionic strength. To gain a clearer perspective on the adsorption behavior of LEV onto Fe/Mn-BC, the adsorption kinetics and isotherms were also performed, revealing pseudo-second-order and Freundlich model had a better fitting effect. Reusability experiments indicated that Fe/Mn-BC could maintain a certain adsorption capacity for LEV after 5 recycles. Overall, this work showed that Fe/Mn-BC was an effective and promising adsorbent for eliminating LEV from aqueous medium.

Separation of Levofloxacin from Industry Effluents Using Novel Magnetic Nanocomposite and Membranes Hybrid Processes.

Magnetic carbon nanocomposite (MCN) was synthesized from waste biomass precursor, pineapple. The prepared adsorbent was characterized using different instrumental techniques and was used to remove levofloxacin (LEV) from effluents. The maximum sorption of LEV was observed at pH 7. Pseudo-2nd-order (PSO) kinetic was found to be the best model that fits well the adsorption kinetics data. For Langmuir adsorption isotherm, the R2 value was higher as compared with other isotherms. The Van't Hoff equation was used for thermodynamic parameters determinations. ΔS° (standard entropy) was positive and ΔG° (standard Gibb's free energy) was negative: -0.37, -1.81, and -3.73 kJmol-1 corresponding to 25, 40, and 60°C. The negative values of ΔG° at different temperatures stipulate that the adsorption of LEV was spontaneous in nature and adsorbent has a considerable affinity for LEV molecules. The MCN was then utilized in hybrid way by connecting with ultrafiltration (UF), nanofiltration (NF), and reverse osmosis (RO) membranes in series and as a result enhanced permeate fluxes were observed. The percent retention of LEV molecules was lower with UF membrane and with NF it was 96%, while it was 100% with RO. For MCN/UF and MCN/NF systems, improvement in % retention was recorded.

Liquid chromatographic enantioseparation of (RS)-etodolac using (S)-levofloxacin and determination of absolute configuration of the diastereomeric derivatives.

(RS)-Etodolac was isolated from commercial tablets and was purified and characterized to be used as racemic standard. A pair of diastereomeric derivatives was synthesized using (S)-levofloxacin as a chiral derivatizing reagent. The derivatization reaction was carried out under conditions of stirring at room temperature (30°C for 1.5 h) as well as under microwave irradiation; the derivatives obtained by the two methods were compared. Reaction conditions for derivatization were optimized with respect to mole ratio of chiral derivatizing reagent and (RS)-etodolac. No racemization was observed throughout the study. Separation of diastereomeric derivatives was successful using C18 column and a binary mixture of methanol and triethyl ammonium phosphate buffer of pH 4.5 (80:20, v/v) as mobile phase at a flow rate of 1 mL min-1 and UV detection at 223 nm. An efficient approach for recognizing chirality and determining the absolute configuration of the diastereomeric derivatives of (RS)-etodolac is described, which in turn is a measure of the enantiomeric purity of (RS)-etodolac since the diastereomeric derivatives were separated and isolated using preparative thin-layer chromatography.

Application of novel ternary deep eutectic solvents as a functional monomer in molecularly imprinted polymers for purification of levofloxacin.

A series of ecofriendly ternary deep eutectic solvents (DESs) with different molar ratios were prepared as candidate functional monomers. Three of the optimal ternary DESs as functional monomers were applied to the preparation of molecularly imprinted polymers (MIPs). After synthesis, the proposed polymers were characterized by elemental analysis (EA), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), Brunauer-Emmett-Teller surface area measurements (BET) and Fourier transform infrared spectroscopy (FT-IR). These MIPs based on ternary DESs with different molar ratios exhibited different absorption capacities of levofloxacin. A sample of levofloxacin (500ng) was dissolved in a millet extractive (10mL). All MIPs were used as SPE adsorbents to purify the extracts. According to characterization result, the ternary DES-3 (1:3:1.5) was joined in the synthetic process of MIP-1. The green ternary DES-3-based MIPs had the best selectivity recovery for levofloxacin (91.4%) from the millet extractive. The best selectivity of MIP-1 was attributed to the novel monomer (ternary DES) in the preparation of the materials. Overall, ternary DES-based MIPs have potential applications as media in many research areas.

Application of Deep Eutectic Solvents in Hybrid Molecularly Imprinted Polymers and Mesoporous Siliceous Material for Solid-Phase Extraction of Levofloxacin from Green Bean Extract.

Deep eutectic solvents (DES) are potential ecofriendly surfactants for the preparation of materials. In this study, both molecularly imprinted polymers (MIPs) and mesoporous siliceous materials (MSMs) were modified by betaine-based DES. Six materials were employed as solid phase extraction (SPE) adsorbents for the rapid purification of levofloxacin. The DES-based materials showed better selective adsorption than the conventional materials. The adsorption curves of DES-MIP showed superior molecular recognition ability and binding capability for levofloxacin compared to the other materials. The limit of detection and limit of quantitation of the method were 0.01 and 0.03 µg/mL for levofloxacin, respectively. The method recoveries at three spiked levels were 97.2 - 100.2% for DES-MIP, with an RSD <1.8%. DES-MIP showed the highest selective recovery (95.2%) for levofloxacin from the green bean extract, and could remove the interferent effectively.

Enhanced levofloxacin removal from water using zirconium (IV) loaded corn bracts.

The presence of antibiotics in the environment has attracted considerable attention due to their toxicity. In this study, agricultural waste corn bracts (CBs) modified by zirconium cations were utilized to remove levofloxacin (LEV) from wastewater. Zr-modified CBs exhibited a strong adsorption capacity (Qmax = 73 mg/g), and their desorption rate could reach 89% by simply adjusting the pH to 11. FTIR and XPS analyses indicated that the mechanism of LEV adsorption included the complexation between the ketone/carboxyl groups of LEV and the Zr atoms and the π-π electron-donor-acceptor interaction. Zr-modified CBs are economic, effective and nontoxic adsorbents. This material not only removes antibiotics from wastewater but also enables recycling and reuse of agricultural waste.

Integrated liquid chromatography method in enantioselective studies: Biodegradation of ofloxacin by an activated sludge consortium.

Ofloxacin is a chiral fluoroquinolone commercialized as racemate and as its enantiomerically pure form levofloxacin. This work presents an integrated liquid chromatography (LC) method with fluorescence detection (FD) and exact mass spectrometry (EMS) developed to assess the enantiomeric biodegradation of ofloxacin and levofloxacin in laboratory-scale microcosms. The optimized enantioseparation conditions were achieved using a macrocyclic antibiotic ristocetin A-bonded CSP (150×2.1mm i.d.; particle size 5µm) under reversed-phase elution mode. The method was validated using a mineral salts medium as matrix and presented selectivity and linearity over a concentration range from 5µgL(-1) (quantification limit) to 350µgL(-1) for each enantiomer. The method was successfully applied to evaluate biodegradation of ofloxacin enantiomers at 250µgL(-1) by an activated sludge inoculum. Ofloxacin (racemic mixture) and (S)-enantiomer (levofloxacin) were degraded up to 58 and 52%, respectively. An additional degradable carbon source, acetate, enhanced biodegradation up to 23%. (S)-enantiomer presented the highest extent of degradation (66.8%) when ofloxacin was supplied along with acetate. Results indicated slightly higher biodegradation extents for the (S)-enantiomer when supplementation was done with ofloxacin. Degradation occurred faster in the first 3days and proceeded slowly until the end of the assays. The chromatographic results from LC-FD suggested the formation of the (R)-enantiomer during levofloxacin biodegradation which was confirmed by LC-MS with a LTQ Orbitrap XL.

Mineralization of the antibiotic levofloxacin in aqueous medium by electro-Fenton process: kinetics and intermediate products analysis.

The present study investigates the feasibility of using electro-Fenton (EF) process for the oxidative degradation of antibiotic levofloxacin (LEV). The EF experiments have been performed in an electrochemical cell using a carbon-felt cathode. The effect of applied current in the range 60-500 mA and catalyst concentration in the range 0.05-0.5 mM on the kinetics of oxidative degradation and mineralization efficiency have been investigated. Degradation of LEV by hydroxyl radicals was found to follow pseudo-first-order reaction kinetics. The absolute rate constant for oxidative degradation of LEV by hydroxyl radical has been determined by a competition kinetics method and found to be (2.48 ± 0.18) × 10(9) M(-1) s(-1). An optimum current value of 400 mA and a catalyst (Fe(2+)) concentration of 0.1 mM were observed to be optimal for an effective degradation of LEV under our operating conditions. Mineralization of aqueous solution of LEV was performed by the chemical oxygen demand analysis and an almost mineralization degree (>91%) was reached at the end of 6 h of electrolysis. A number of intermediate products have been identified using high performance liquid chromatography and liquid chrmatography-mass spectrometry analyses. Based on these identified reaction intermediates, a plausible reaction pathway has been suggested for the mineralization process. The formation and evolution of [Formula: see text] and [Formula: see text] ions released to the medium during the process were also discussed.

Molecularly imprinted polymers for the solid-phase extraction of four fluoroquilones from milk and lake water samples.

A method based on molecular crowding and ionic liquids as reaction solvents has been used for the synthesis of molecularly imprinted polymers. Levofloxacin was selected as the template, polymethyl methacrylate was the molecular crowding agent, and 1-butyl-3-methylimidazolium tetrafluoroborate (ionic liquid) was selected as the reaction solvent and porogen. The optimized proportion for the mixed porogen was dimethyl sulfoxide/ionic liquid/polymethyl methacrylate 1:1.6:5 in chloroform (150 mg mL(-1) ). The morphology and chemical composition of levofloxacin imprinted polymers were assessed by scanning electron microscopy and Fourier transform infrared spectroscopy. The absorption experiments demonstrated that the levofloxacin imprinted polymers possess high selective recognition property to levofloxacin and analogs, including enrofloxacin, ciprofloxacin and gatifloxacin, which all belong to fluoroquinolones. An extraction method using levofloxacin imprinted polymers as sorbent followed by high-performance liquid chromatography analysis was optimized for the determination of four fluoroquinolones in milk and lake water samples. Under the optimized conditions, good linearity was observed in a range of 5-1000 ng g(-1) with the limit of detection between 0.3 and 0.5 ng g(-1) for the four fluoroquinolones. The recoveries at three spiked levels ranged 82.4-98.3% with the relative standard deviation ≤4.9.

Applications of magnetic surface imprinted materials for solid phase extraction of levofloxacin in serum samples.

In this work, molecularly imprinted magnetic carbon nanotubes (MCNTs@MIPs) was prepared with surface imprinting technique for extraction of levofloxacin in serum samples. The preparation of molecularly imprinted polymers (MIPs) used levofloxacin as template, methacrylic acid as functional monomer, and ethylene glycol dimethacrylate as cross-linker, and the magnetic carbon nanotubes (MCNTs) was synthesized by solvothermal method. The prepared polymers not only can be separated and collected easily by an external magnetic, but also exhibited high specific surface area and high selectivity to template molecules. Kinetic adsorption and static adsorption capacity investigations indicated that the synthesized MCNTs@MIPs had excellent recognition towards levofloxacin. Furthermore, magnetic solid phase extraction (MSPE) using the prepared MCNTs@MIPs as sorbent was then investigated, and an efficient sample cleanup was obtained with recoveries ranged from 78.7 ± 4.8 % to 83.4 ± 4.1%. In addition, several parameters, including the pH of samples, the amount of MCNTs@MIPs, the adsorption and desorption times, and the eluent, were investigated to obtain optimal extraction efficiency. Under the optimal extraction conditions, the stability of the polymer was also evaluated, and the average recovery reduced less than 7.6% after 5 cycles. MCNTs@MIPs successfully applied in the preconcentration and determination of levofloxacin in serum sample suggested that the MSPE method based on the novel polymers could be a promising alternative for selective and efficient extraction of trace amounts of pharmaceutical substances in bio-matrix samples.

In silico and in vitro genotoxicity evaluation of descarboxyl levofloxacin, an impurity in levofloxacin.

It is important to establish the safety of impurities in drug substances or drug products. The assessment of genotoxicity of impurities and the determination of acceptable limits for genotoxic impurities was addressed in some recent guidances as a difficult issue. Descarboxyl levofloxacin is an impurity isolated from levofloxacin, which may impose a risk without associated benefit. However, there is insufficient toxic information about descarboxyl levofloxacin. This study investigated the genotoxicity of this impurity by in silico and in vitro methods. We used Derek, a commercial structure-activity relationship software package, as an in silico tool. The results showed that there was a structural alert (quinoline) in this impurity. Then, the in vitro genotoxicity of descarboxyl levofloxacin was investigated by a modified Ames test and by a chromosomal aberration test, using Chinese hamster lung (CHL) cells. Both assays were conducted in the presence or absence of S-9 mix. The results showed that the test impurity was not mutagenic in the Ames test (31.25-500 µg/plate). Whereas there was a statistically significant increase in the number of metaphase CHL cells with structural aberrations at the concentration of 1 mg/mL with S-9 mix, the aberrations rate was 7.5%. It did not significantly increase the number of structural aberration in CHL cells in the presence (at 250 and 500 µg/mL) or absence of S-9 mix. Based on these assays, descarboxyl levofloxacin could be controlled as a nongenotoxic impurity.