Enhanced adsorption for the removal of antibiotics by carbon nanotubes/graphene oxide/sodium alginate triple-network nanocomposite hydrogels in aqueous solutions.

Large-scale abuse of antibiotics has led to serious environmental problems. Some conventional adsorbents such as several biopolymer gels have poor adsorption performance and inadequate mechanical properties. In this paper, carbon nanotubes (CNTs) and graphene oxide (GO), were combined with sodium alginate (SA) to improve the adsorption performance and other properties of traditional adsorbents. With the help of hydrogen peroxide and l-cysteine (L-cys), carbon nanotubes/l-cysteine@graphene oxide/sodium alginate (CNTs/L-cys@GO/SA) triple-network composite hydrogels were prepared. Compared with traditional hydrogels and the double-network hydrogels that are currently being developed, these triple-network composite hydrogels can exploit their three-dimensional structure to improve their adsorption capacity. The independent triple-network structure increases the three-dimensional space, so there are more pores and pollutant adsorption sites to achieve the high-efficient removal of ciprofloxacin. And the adsorption capacity of CNTs/L-cys@GO/SA hydrogels can reach 181 mg g-1 and 200 mg g-1 at 25 °C and 15 °C respectively in weak acidity environment. In fact, CNTs/L-cys@GO/SA hydrogels show better property at low temperature. In addition, the thermal stability, mechanical properties and swelling ability of the triple-network hydrogels have also been improved. The independent multilayer network can retain the excellent properties of the original materials and make the internal space of hydrogels larger. These multinetwork hydrogels have great potential for removing pollutants from wastewater. In addition, the CNTs/L-cys@GO/SA hydrogels show the higher adsorption capacity of ciprofloxacin under the conditions of weak acidity, low temperature and low inorganic salt concentration, so the removal of ciprofloxacin by hydrogels can also be promoted by changing environmental conditions.

Experimental and theoretical aspects of biochar-supported nanoscale zero-valent iron activating H2O2 for ciprofloxacin removal from aqueous solution.

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 (H2O2) has many advantages on promoting the removal of organic contaminants. In this paper, the BC/nZVI activating H2O2 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/H2O2 system. More than 70% of ciprofloxacin was removed in the optimal conditions: acidic condition (pH 3∼4), low doses of H2O2 (20 mM), and temperature of 298 K. The hydroxyl radical (•OH) oxidation was the primary pathway in BC/nZVI/H2O2 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 H2O2 degradation of ciprofloxacin and other fluoroquinolone antibiotics in water treatment plants.

Correlation between pH and molar iron/ligand ratio during ciprofloxacin degradation by photo-Fenton process: Identification of the main transformation products.

Ciprofloxacin has been determined with high frequency in studies involving environmental waters matrixes. However, no study evaluating the correlation between the initial pH and molar iron/organic ligand ratio has been published. This paper describes the degradation of the antibiotic ciprofloxacin by the photo-Fenton process using different sources of iron (Fe2+, Fe3+ and Fe3+-citrate and Fe3+-oxalate, named FeCit and FeOx, respectively) and molar iron/organic ligand ratios at initial pH values of 2.5 and 6.5. The best results at initial pH 2.5 were achieved using FeCit and FeOx at molar iron/organic ligand ratios of 1:1 and 1:3 respectively, when the ciprofloxacin concentration reached values below the quantitation limit of the HPLC after 20 min of treatment. However, at initial pH 6.5, improvements in the results (15% for FeCit, and 46% for FeOx) were achieved by increasing the molar iron/organic ligand ratios to 1:4 (FeCit) and 1:9 (FeOx), respectively. Three transformation products, (C17H19FN3O4, m/z 348; C17H21FN3O5, m/z 366; and C13H12FN2O3, m/z 263) of ciprofloxacin degradation were identified, one of them not yet being reported in the literature (C17H21FN3O5, m/z 366). Their formation and degradation was monitored and the initial steps of their formation and degradation were proposed. The results show that the piperazine ring is more susceptible to hydroxyl radical attack than the quinolone ring, which persists in the intermediates identified. Therefore, this process can be a good alternative for the treatment of this type of pollutant at near-neutral conditions.

Preparation of polysulfone materials on nickel foam for solid-phase microextraction of floxacin in water and biological samples.

Solid-phase microextraction with polysulfone and molecularly imprinted polymers as coating on nickel foam were used to adsorb and enrich floxacin drugs. The preparation method is simple and reproducible to obtain the materials with controlled thickness. After evaluation by scanning electron microscope and various adsorption experiments, the materials were used to adsorb analytes in water samples and biological samples. Coupling with chromatographic analysis, the method recoveries are satisfactory with 90.0-104.8% and 79.31-107.1% for water and biological samples. The method repeatability by intra- and interday experiments shows that the RSD values for water and biological samples were 1.0-9.9% and 1.7-10.3%, with the quantitative limits of three floxacin drugs as 3.0-6.2 µg L-1. Graphical Abstract Preparation diagram of polysulfone material.

Oriented growth of poly(m-phenylenediamine) on Calotropis gigantea fiber for rapid adsorption of ciprofloxacin.

A facile polymerization of m-phenylenediamine (mPD) in methanol/water (50:50, v/v) was performed via conventional chemical oxidative method by using Calotropis gigantea fiber (CGF) as the natural biotemplate. The as-prepared CGF oriented poly(m-phenylenediamine) (PmPD), i.e. CGF-O-PmPD, exhibits a well defined fiber-oriented morphology. The presence of PmPD layer enables CGF-O-PmPD to present roughen surface with N-rich functional groups that can show high performance for the adsorption of ciprofloxacin. The variables affecting the adsorption capacity were systematically investigated, including contact time, initial concentration, initial pH, ion strength, and so forth. The experimental data reveal that with increasing the amount of mPD from 0.2, 0.5 to 2.0 g, the adsorption capacity for ciprofloxacin shows a monotonic decrease, while the adsorption kinetics show a monotonic increase, with the adsorption percentage from >50%, >60% to >70% within 10 s, demonstrating its superfast adsorption kinetics for ciprofloxacin. In addition, an increasing adsorption capacity is observed over the pH range studied, with the adsorption capacity from 0.73 to 6.7 mg g-1 at pH 2.0 to 64.9-77.3 mg g-1 at pH 10.0. After five adsorption-desorption cycles, the adsorption capacity of CGF-O-PmPD for ciprofloxacin shows no significant decrease, indicating its excellent reusability and potential application in treating antibiotic-containing wastewater.

The effect of some fluoroquinolone family members on biospeciation of copper(II), nickel(II) and zinc(II) ions in human plasma.

The speciation of Cu2+, Ni2+ and Zn2+ ions in the presence of the fluoroquinolones (FQs) moxifloxacin, ofloxacin, levofloxacin and ciprofloxacin, in human blood plasma was studied under physiological conditions by computer simulation. The speciation was calculated using an updated model of human blood plasma including over 6,000 species with the aid of the program Hyss2009. The identity and stability of metal-FQ complexes were determined by potentiometric (310 K, 0.15 mol/L NaCl), spectrophotometric, spectrofluorimetric, ESI-MS and 1H-NMR measurements. In the case of Cu2+ ion the concentration of main low molecular weight (LMW) plasma complex (Cu(Cis)His) is very slightly influenced by all examined FQs. FQs show much higher influence on main plasma Ni2+ and Zn2+ complexes: (Ni(His)2 and Zn(Cys)Cit, respectively. Levofloxacin exhibits the highest influence on the fraction of the main nickel complex, Ni(His)2, even at a concentration level of 3×10⁻5 mol/L. The same effect is seen on the main zinc complex, Zn(Cys)Cit. Calculated plasma mobilizing indexes indicate that ciprofloxacin possesses the highest mobilizing power from plasma proteins, toward copper ion, while levofloxacin is the most influential on nickel and zinc ions. The results obtained indicate that the drugs studied are safe in relation to mobilization of essential metal ions under physiological conditions. The observed effects were explained in terms of competitive equilibrium reactions between the FQs and the main LMW complexes of the metal ions.

Effect of sub-minimum inhibitory concentrations of ciprofloxacin, amikacin and colistin on biofilm formation and virulence factors of Escherichia coli planktonic and biofilm forms isolated from human urine

The aim of this study was to determine the effect of subinhibitory concentrations (sub-MICs) of ciprofloxacin, amikacin and colistin on biofilm formation, motility, curli fimbriae formation by planktonic and biofilm cells of E. coli strains isolated from the urine of patients with various urinary system infections. Quantification of biofilm formation was carried out using a microtiter plate assay and a spectrophotometric method. Bacterial enumeration was used to assess the viability of bacteria in the biofilm. Curli expression was determined by using YESCA agar supplemented with congo red. Using motility agar the ability to move was examined. All the antibiotics used at sub-MICs reduced biofilm formation in vitro, decreased the survival of bacteria, but had no effect on the motility of planktonic as well as biofilm cells. The inhibitory effect of sub-MICs of antimicrobial agents on curli fimbriae formation was dependent on the form in which the bacteria occurred, incubation time and antibiotic used. Our results clearly show that all the three antibiotics tested reduce biofilm production, interfere with curli expression but do not influence motility. This study suggests that ciprofloxacin, amikacin and colistin may be useful in the treatment of biofilm-associated infections caused by E. coli strains