Fabrication of carboxymethyl functionalized β-cyclodextrin-modified graphene oxide for efficient removal of methylene blue

In this study, a novel carboxymethyl functionalized β-cyclodextrin-modified graphene oxide (CM-β-CD-GO) adsorbent was designed and fabricated. The CM-β-CD-GO was applied to remove methylene blue (MB) from aqueous solutions. The adsorption mechanism was discussed in detail through the study of pH effect, kinetics, and isotherm models. The adsorption of CM-β-CD-GO for MB displayed high removal rates at the pH range of 6.0–10.0, and the removal efficiency is over 90% within 20 min. The pseudo-second-order model could well describe the kinetic process of MB adsorption, and the adsorption was determined by the multi-step process. The maximum uptake capability of CM-β-CD-GO towards MB was 245.70 mg g⁻¹ at 25 °C according to Langmuir isotherm model. A possible adsorption mechanism that electrostatic attraction, π-π interaction, and host-guest supramolecular interactions supported MB adsorption was proposed. The adsorption capacity of CM-β-CD-GO showed no significant change after five cycles. The structure and morphology of CM-β-CD-GO were characterized by XPS, FT-IR, TGA, PXRD, AFM, SEM, zeta (ζ) potential determination, and Raman spectroscopy. This work provides valuable information for the design of novel adsorbents that specifically and efficiently adsorb cationic dyes contaminants.     

Hydrothermal-assisted sol–gel synthesis of Cd-doped TiO2 nanophotocatalyst for removal of acid orange from wastewater

Journal of Sol-Gel Science and Technology - This research is based on synthesis of titania (TiO2) nanophotocatalyst followed by cadmium (Cd) doping to activate the photocatalyst in visible part of...     

Utilization of silica–chitosan nanocomposite for removal of 152+154Eu radionuclide from aqueous solutions

Journal of Radioanalytical and Nuclear Chemistry - Nano-silica (Si-AL800) was extracted from the thermally treated rice husk ash by acid leaching route. Coating surface of the extracted silica with...     

Synthesis of carboxymethyl β-cyclodextrin bonded Fe3O4@SiO2–NH2 core-shell magnetic nanocomposite adsorbent for effective removal of Pb(II) from wastewater

Journal of Sol-Gel Science and Technology - In this work, a novel functionalized magnetic Fe3O4@SiO2 core-shell nanoparticles grafted with carboxymethyl β-cyclodextrin (CM-β-CD) is...     

Zinc–aluminum layered double hydroxide as a nano-sorbent for removal of Reactive Yellow 84 dye from textile wastewater effluents

In this research, the zinc–aluminum layered double hydroxide (Zn–Al LDH) was synthesized and structurally and morphologically characterized by X-ray diffraction, Fourier transform infrared spectroscopy, transmission electron microscopy and N₂ adsorption–desorption techniques. The obtained nano-structured inorganic material was employed as an innovative nano-sorbent for separation of Reactive Yellow 84 (RY84) dye from aqueous solutions, which can be spectrophotometrically monitored at λ = 359 nm. The effect of several parameters such as type of interlayer anion in Zn–Al LDH structure, pH, sample flow rate, elution conditions, amount of nano-sorbent, sample volume and co-existing ions on the retention efficiency was investigated and optimized. The results showed that trace amounts of the RY84 could be retained using a column packed with 300 mg of the Zn–Al(NO₃ ^?) LDH at pH 8 and stripped by 2.5 mL of 3.0 mol L^?1 NaOH. Under the optimum experimental conditions, the limit of detection and the relative standard deviation were 0.04 μg mL^?1 and 1.8 %, respectively. The calibration graph using the presented solid phase extraction system was linear in the range of 0.15–1.5 μg mL^?1 with a correlation coefficient of 0.9982. The method was successfully applied to removal of RY84 from several textile wastewater effluents.     

Modified nanoporous magnetic cellulose–chitosan microspheres for efficient removal of Pb(II) and methylene blue from aqueous solution

Pyromellitic dianhydride-modified nanoporous magnetic cellulose–chitosan microspheres (PNMCMs) were designed and synthesized to introduce abundant carboxyl groups onto the basic microstructure. The novel microspheres were studied by scanning electron microscopy (SEM), Fourier-transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD) analysis, thermogravimetric analysis (TGA), and X-ray photoelectron spectroscopy (XPS). Subsequently, a batch technique was applied to investigate various environmental parameters that could affect the adsorption behavior of the PNMCMs. Due to its nanoporous structure and large quantity of carboxyl groups, the cellulose/chitosan-based bioadsorbent exhibited excellent adsorption performance for removal of Pb(II) ions and methylene blue (MB) from aqueous solution, with maximum adsorption capacity of 384.6 and 833.3 mg/g, respectively. Furthermore, the adsorption kinetics and isotherms of Pb(II) ions and MB on PNMCMs obeyed the pseudo-second-order and Langmuir isotherm models, and the rate of adsorption was found to be controlled by film diffusion. Finally, the PNMCMs with adsorbed Pb(II) and MB could be easily regenerated using HCl, retaining removal capacity of almost 89% after six repeated uses.     

A heteropore covalent organic framework for adsorptive removal of Cd(Ⅱ) from aqueous solutions with high efficiency

A heteropore covalent organic framework(COF) integrating tetraphenylethene skeleton and catechol segment is designed and synthesized.It exhibits extremely high stability in water under different pH conditions,which makes it an excellent material for adsorptive removal of Cd(Ⅱ) from aqueous solutions with very fast adsorption kinetics,high uptake capacity,and good recyclability.     

Urease–glutamic dehydrogenase biosensor for screening heavy metals in water and soil samples

A screen-printed three-electrode amperometric biosensor based on urease and the nicotinamide adenine dinucleotide hydrogen (NADH)–glutamic dehydrogenase system was developed and applied to the screening of heavy metals in environmental samples. The development of an amperometric sensor for the monitoring of urease activity was feasible by coupling the urea breakdown reaction catalysed by urease to the reductive ammination of ketoglutarate catalysed by glutamic dehydrogenase (GLDH). The ammonia provided by the urea conversion is required for the conversion of ketoglutarate to glutamate with the concomitant oxidation of the NADH cofactor. NADH oxidation is monitored amperometrically at 0.3 V (vs. Ag/AgCl) after urease immobilization onto the screen-printed three-electrode configuration. Immobilization of urease on the surface of screen-printed electrodes was performed by entrapment in alginate gel and adsorption on the electrode in a nafion film. Low sensitivity to inactivation by metals was recorded after urease entrapment in alginate gel with detection limits of 2.9 and 29.8 mg L^–1 for Hg(II) and Cu(II), respectively. The use of the negatively charged nafion film created a more concentrated environment of cations in proximity to the enzyme, thus enhancing the urease inhibition when compared to gel entrapment. The calculated detection limits were 63.6 and 55.3 g L^–1 for Hg(II) and Cu(II), respectively, and 4.3 mg L^–1 for Cd(II). A significant urease inactivation was recorded in the presence of trace amounts of metals (g L^–1) when the enzyme was used free in solution. Analysis of water and soil samples with the developed nafion-based sensor produced inhibition on urease activity according to their metal contents. The obtained results were in agreement with the standard methods employed for sample analysis. Nevertheless, the use of the amperometric assay (with free urease) proved more feasible for the screening of trace amounts of metals in polluted samples.     

Fabrication and characterization of biocompatible nacre-like structures from α-zirconium hydrogen phosphate hydrate and chitosan

Composite materials with an ordered layered structure resembling that of nacre were fabricated by layer-by-layer assembly making use of presynthesized α-zirconium hydrogenphosphate hydrate (ZrP) platelets and chitosan. These two biocompatible materials were chosen in view of possible applications in the biomedical field, e.g., as bone or joint replacement implants. The effect of different concentrations of the inorganic ZrP platelets and the organic components (chitosan) on the composite assembly and structure was investigated. A high concentration of chitosan (0.1 wt.%) resulted in a misalignment of the inorganic platelets, while at very low concentrations (0.001 wt.%), the substrate was not fully covered by the polymer, again leading to misalignment. Also, the concentration of the α-ZrP platelets affected the composite assembly and structure. The number of dipping cycles was varied between 70 and 220, yielding a maximum thickness of approximately 6 μm. The pH value of the chitosan solution was also varied to investigate its influence on the composite assembly. The mechanical properties of the composites were tested with a nanoindenter. For samples prepared with the same number of dipping cycles, higher values of Young's modulus and hardness were obtained with improved alignment of the platelets in the samples. For samples prepared with 220 dipping cycles, a Young's modulus of 2.6 GPa and a hardness of 70 MPa were observed. Important general relationships are recognized between the preparation parameters, the degree of order within the nacre-like films and the resulting mechanical properties.     

Assessment of the determination of heavy metals in organic soil improvers by ICP–OES

Directive 86/278/EEC sets maximum levels of heavy metals in sewage sludge used in agriculture to regulate the risk of using these organic soil improvers. The assessment of the compliance of soil improvers with this legislation should be supported on measurements with adequately low uncertainty. This work presents a strategy for assessing the performance of the determination of aqua regia extractable Cu, Zn and Cr in organic soil improvers and urban sewage sludges following EN 13650 standard. The measurement procedure validation involves checking the adequacy of the linear weighted regression model for ICP–OES calibration, the determination of the limit of quantification, the assessment of measurement repeatability, intermediate precision and trueness, and the evaluation of the measurement uncertainty using the differential approach. Routine tests quality control, including the estimated measurement uncertainty, is checked through the analysis of control standards, equivalent to calibrators, and reference materials from proficiency tests. Since the estimated relative expanded uncertainty is smaller than the defined target value (40 %), measurements are fit for assessing compliance of the mass fraction of heavy metals in organic soil improvers with the council directive.     

Ion exchange removal of cesium from Hanford tank waste supernates with SuperLig® 644 resin

SuperLig^Ò 644 ion exchange resin is currently being evaluated for cesium (¹³⁷Cs) removal from radioactive Hanford tank waste supernates as part of the River Protection Project. Testing was performed with actual Hanford tank wastes of widely different compositions using two identical ion exchange columns connected in series each containing approximately 5.5-6.5 ml of SuperLig 644 resin. The ion exchange columns utilized the same resin material that was eluted between the column tests. This was done to demonstrate the performance of the SuperLig 644 resin for cesium removal from waste samples of different compositions, determine the loading and elution profiles, and to validate design assumptions for full-scale column performances. Decontaminated product solutions generated at the same operating temperature and constant residence times (bed volumes per hour) exhibited the same chemical compositions as their feed samples. The compositions of eluate solutions were generally as expected with the exception of uranium and total organic carbon, which where concentrated by the resin. Development of a pretreatment method for the SuperLig 644 resin has been critical to successful column operation with different waste solutions.     

Fabrication of transparent methacrylate zirconium siloxane hybrid materials using sol–gel synthesized oligosiloxane resin

Methacrylate zirconium siloxane (MZS) resin was synthesized by a sol–gel reaction of 3-(trimethoxysilyl)propyl methacrylate, diphenylsilanediol, and zirconium n-propoxide chelated with methacrylic acid. Also, propylene glycol monomethyl ether acetate was added as a solvent to synthesize a homogeneous and long-term stable resin by controlling the reactivity among the precursors. A High condensation degree of the resin and the formation of Si–O–Zr hetero-metal bonds were verified by ²⁹Si NMR and FT-IR spectroscopy. The MZS resin was spin-coated and photo-polymerized to fabricate a highly transparent MZS hybrimer coating film. The refractive index and dielectric constant of the film increased according to the zirconium content, up to 1.59 and 3.65, respectively.     

Calculation of viscosity–temperature curves for glass obtained from four wastewater treatment plants in Egypt

This article establishes the relationship between the chemical composition, temperature and viscosity of glasses obtained from the four sludge treatment plants of urban and industrial wastewater from the Nile Delta in Egypt. In order to determine the working conditions of these glasses and their growth temperature, different techniques have been used: differential thermal analysis, hot stage microscopy and dilatometry. We used a prototype of hot stage microscopy, with the help of an image analysis programme developed in the present study. The chemical composition of major oxides sludge ranging from: SiO₂ (36–48 wt%), Al₂O₃ (9–16 wt%), CaO (5–25 wt%), P₂O₅ (1.5–11 wt%), and Fe₂O₃ (~9 wt%), this composition is close to a basalt rock, being necessary to incorporate some raw materials to adjust it to the basalt rock that has a good viscosity-temperature curve. The glass transition temperatures of the four glasses obtained vary between 650 and 725 °C and the growth occurs between 938 and 1,033 °C. We also obtained the viscosity–temperature curves with the aid of the hot stage microscopy that has allowed us to determine the working temperatures of the four glasses, ranging from 926 to 1,419 °C, depending on the type of forming process used.     

Quantum-chemical modeling of lithium removal from lithium–silicon–silicon carbide composite

The quantum-chemical modeling of the delithiation-induced reorganization of a Li _m Si _n layer applied to the surface of nitrogen-doped silicon carbide is performed by means of non-empirical molecular dynamics in the frame of the gradient-corrected density functional method with the goal for finding promising anode materials for lithium ion batteries. The ratios Li/Si are considered from 8/3 to 1/4. Partial removal of lithium atoms from the surface of the Li _m Si _n layer and annealing at a moderate temperature (400 K) is found to recover rapidly (as soon as within 10 ps) the uniform metal distribution over the layer when the ratio Li/Si is at least 3/4. At lower values of this ratio, the equalization slows down dramatically.     

Antimicrobial activity of new carboxymethyl chitosan–carbon nanotube biocomposites and their swell ability in different pH media

New carboxymethyl chitosan–carbon nanotube (CMCS-CNT) biocomposites were prepared and characterized by Fourier transform infrared spectroscopy, transmission electron microscopy, scanning electron microscopy, X-ray diffraction, and normal photography. The recorded images of the CMCS-CNT biocomposites showed homogeneous distribution of carbon nanotubes into the carboxymethyl chitosan (CMCS) matrix. Their antimicrobial activity and swell ability in different pH media have been investigated. They showed a higher antimicrobial activity against tested gram-positive and gram-negative bacteria. The inhibition zone diameters are closer to that recorded for the commonly used antibiotics. They showed an increase in the swell ability in different pH media relative to the parent CMCS. It would be expected that these nanobiocomposites are promising candidates for medical applications.     

The effect of heavy metals on the anthracene–Me-β-cyclodextrin host–guest inclusion complexes

Anthracene was used to form an inclusion complex with methylated-β-cyclodextrin (Me-β-CD) in water. In aqueous Me-β-CD solution, typical fluorescence emission of anthracene was observed. Benesi–Hildebrand's method was used to obtain the stoichiometry of the anthracene–Me-β-CD complex. The Stern–Volmer quenching constants, K_sv, and fluorescence quantum yields were calculated according to changes in the fluorescence emission intensity of anthracene–Me-β-CD inclusion complexes by adding various amounts of Pb²⁺ and Cd²⁺ salts in water. The K_sv values and fluorescence quantum yields indicate that Pb²⁺ salts quench the anthracene–Me-β-CD inclusion complexes more efficiently than Cd²⁺ salts.     

Kinetic investigation for sorption of europium and samarium from aqueous solution using resorcinol–formaldehyde polymeric resin

Kinetic study for Eu³⁺ and Sm³⁺ sorption on resorcinol–formaldehyde (RF) polymeric material has been performed using batch method. The sorption process of Eu³⁺ and Sm³⁺ was carried out at different contact time, pH of medium, initial ion concentration and temperature. The experimental data indicated that, RF could be used as an efficient sorbent for Eu³⁺ and Sm³⁺. The sorption kinetic for Eu³⁺ and Sm³⁺ onto RF polymeric resin takes about 1 h to reach equilibrium which is considered as a fast kinetic process. Sorption results were fitted using different kinetic models such as pseudo-first-order, pseudo-second order and intraparticle diffusion models. The results indicated that the sorption of both Eu³⁺ and Sm³⁺ onto RF resin is highly fit with the pseudo-second order model. Moreover, the obtained results showed that the maximum separation factor between Eu³⁺ and Sm³⁺ was obtained at pH 3. Therefore, RF resin is considered as a promising material for sorption of Eu³⁺ and Sm³⁺ form aqueous solution.     

Alginate–chitosan micro- and nanoparticles for transmucosal delivery of proteins

The properties of protein-containing micro- and nanoparticles that were produced from alginate and chitosan using the methods of layer-by-layer polyelectrolyte adsorption and ionotropic gelation have been compared. The encapsulation efficiency of proteins (aprotinin, interferon, and human insulin), the size and ζ-potential of the particles, the mucin binding, and the protein release under physiological conditions have been studied. The prospects for the possible mucosal application of the particles are discussed.     

Speciation of heavy metals in environmental water by ion chromatography coupled to ICP–MS

Biogenic (e.g. phytochelatins, porphyrins, DOM) as well as anthropogenic (e.g. NTA, EDTA, phosphonates) chelators affect the mobility and cycling of heavy metals in environmental waters. Since such chelators can form strongly bound anionic heavy metal complexes that are stable and highly mobile, anion-exchange chromatography coupled to ICP-MS was investigated. A narrow bore HPLC system was connected to a micro concentric nebuliser for in-line sample introduction. A new chromatographic procedure based on a synthetic hydrophilic quaternary ammonium anion exchanger in combination with nitrate as a strong eluent anion, and gradient elution, provided high separation selectivity and a large analytical window. Low detection limits (nmol L(-1)) were achieved by on-column matrix removal and sample preconcentration. This allowed the method to be successfully applied to different environmental research areas. In ecotoxicological studies of heavy metal effects on algae low concentrations of metal EDTA complexes were determined in nutrient solutions without interference from high (buffer) salt concentrations. In groundwater, infiltrated by a polluted river, mobile metal EDTA species were observed. In river water of different pollution levels beside CuEDTA other anionic Cu-complexes were found in nmol L(-1) concentrations.