Synthesis and radioiodination of new dipeptide coupled with biologically active pyridine moiety

The adsorption of uranium (VI), cesium and strontium ions from aqueous solutions onto a commercial activated carbon obtained by physical activation of coconut shell has been studied in batch systems. In particular the adsorption of uranium, studied as a function of contact time and metal ion concentration, followed pseudo-first-order kinetics. Equilibrium adsorption data were fitted by Langmuir and Freundlich isotherm models and the maximum adsorption capacity of the activated carbon resulted to be 55.32 mg/g. The study showed that the considered activated carbon could be successfully used for uranium adsorption from aqueous solutions. Feasibility of cesium and strontium adsorption onto the same activated carbon has been also investigated. Results showed that no affinities with both of these ions exist.     

Surface characterization and thermodynamics of adsorption of Sr2+, Ce3+, Sm3+, Gd3+, Th4+, UO 2 2+ on activated charcoal from aqueous solution

Surface parameters of the activated charcoal were measured using precise instrumental techniques for dehydration, carbon content, trace metals impurities, anions, bulk, tap and true densities, surface area, pore volume, porosity and average particle diameter. The adsorption of Sr²⁺, Ce³⁺, Sm³⁺, Gd³⁺, Th⁴⁺ and UO ₂ ²⁺ ions on activated charcoal from aqueous solution was studied as a function of temperature. Thermodynamic parameters such as HH ⁰ and S ⁰ were calculated from the slopes and intercepts of the linear variation of lnK ₁ vs. 1/T, whereK ₃ is obtained from Langmuir equation. The results show endothermic heats of adsorption, but negative free energy values indicate that the adsorption process of metal ions on activated charcoal is favored at high temperature. The value of isosteric heat of adsorption, calculated from the Clausius-Clapeyron equation, shows that the surface of the activated charcoal is heterogeneous with respect to activity. A wavelength dispersive x-ray fluorescence spectrometer was used for measuring the concentration of metal ions.     

Effect of pH on the adsorption of Ce3+, Sm3+, Eu3+ and Gd3+ ions on activated charcoal

The adsorption of metal ions such as Ce³⁺, Sm³⁺, Eu³⁺ and Gd³⁺ ions on activated charcoal has been studied as a function of pH. The adsorption mechanism of these ions is discussed in terms of hydrolyzed species formed in aqueous solution at different pH.     

Factors affecting the sorption behavior of Cs<Superscript>+</Superscript> and Sr<Superscript>2+</Superscript> using biosorbent material

In this study, saw dust has been used as precursor for production of low cost activated carbon using potassium hydroxide (KOH) and steam activation technique. The activated carbon was used to remove Cs⁺ and Sr²⁺ ions from aqueous solutions by batch operation, and the extent of adsorption was investigated as a function of solution pH, temperature, shaking time, and initial concentration. The influence of interfering ions was also investigated. The removal of metal ions was pH dependent and the adsorption capacity reaches its maximum 43% and 61.5% at pH 5.0 and 6.0 for Cs⁺ and Sr²⁺ ions, respectively. Thermodynamic studies showed different behaviours where an endothermic, non-spontaneous process was shown for Cs⁺ while an exothermic, spontaneous process was obtained for Sr²⁺. The kinetic data of both ions was described well by pseudo-second order rate equation. The two equilibrium models (Langmuir and Freundlich) have been also applied. Desorption studies indicated that HCl was the most effective desorbing eluent. The investigated adsorbent showed good results towards cesium and strontium removal from aqueous media that could be a promising method due to its low-cost and good efficiency.     

Novel tandem column method for the rapid isolation of radiostrontium from human urine

A method has been developed for the isolation of strontium from human urine for subsequent determination in sample volumes as low as 5–20 mL. This method involves the acidification of the sample using methanesulfonic acid and its decolorization using charcoal, treatment of the filtrate with Diphonix^® resin, and subsequent concentration of strontium on Sr resin. Data from retention model simulations provided the initial conditions which were then optimized by actual column separations. Diphonix^® resin was shown to be effective at removing alkali metal ions from the urine matrix under conditions that retain higher valence ions. The suggested processing method provides 99% recovery of Sr²⁺, a concentration factor of 50, and an expected per sample processing time of less than 1 h.     

Adsorption of neodymium ions on activated charcoal from aqeous solutions

Summary A commercial activated charcoal has been tested as an adsorbent for the removal of neodymium ions from aqueous solutions. The adsorption behavior of neodymium ions on activated charcoal from aqueous solutions has been studied as a function of shaking time, neodymium ions concentration and concentration of different acids. Results reveal that the adsorption equilibrium is attained within 30 minutes, and diffusion of neodymium ions into the pores of activated charcoal controls the adsorption process. The adsorption process follows the first order kinetics. The Langmuir isotherm equation was obeyed well in the whole range of concentration studied. The influence of different cations and anions on the adsorption of neodymium ion from aqueous solutions have also been investigated. Approximately 98% of neodymium ions adsorbed onto activated charcoal could be recovered with 40 ml of 3M HNO₃ solutions.     

Adsorption kinetic, isotherm and thermodynamic studies of Sr2+ onto hexagonal tungsten oxide

Hexagonal tungsten oxide (hex-WO₃) with exchangeable sodium and ammonium cations located in hexagonal channel was synthesized by a facile hydrothermal treatment of sodium tungstate dihydrate in concentrated HCl solution in the presence of ammonium sulfate. An attempt was made to assess the potential of hex-WO₃ for the adsorption of Sr²⁺ ions from acidic radioactive waste solutions. Adsorption of Sr²⁺ reached equilibrium very quickly in 2 h in acidic aqueous solution. Maximum removal of Sr²⁺ ions occurred at pH 4. Equilibrium studies showed that the extent of Sr²⁺ ions uptake by hex-WO₃ was better described by the Freundlich isotherm in comparison with the Langmuir model. The thermodynamic parameters showed that the adsorption of Sr²⁺ ions onto hex-WO₃ was spontaneous and exothermic under the studied conditions.     

Removal of Cd(II), Cu(II), and Pb(II) by adsorption onto natural clay: a kinetic and thermodynamic study

In this work, we study the elimination of three bivalent metal ions (Cd²⁺, Cu²⁺, and Pb²⁺) by adsorption onto natural illitic clay (AM) collected from Marrakech region in Morocco. The characterization of the adsorbent was carried out by X-ray fluorescence, Fourier transform infrared spectroscopy and X-ray diffraction. The influence of physicochemical parameters on the clay adsorption capacity for ions Cd²⁺, Cu²⁺, and Pb²⁺, namely the adsorbent dose, the contact time, the initial pH imposed on the aqueous solution, the initial concentration of the metal solution and the temperature, was studied. The adsorption process is evaluated by different kinetic models such as the pseudo-first-order, pseudo-second-order, and Elovich. The adsorption mechanism was determined by the use of adsorption isotherms such as Langmuir, Freundlich, and Temkin models. Experiments have shown that heavy metals adsorption kinetics onto clay follows the same order, the pseudo-second order. The isotherms of adsorption of metal cations by AM clay are satisfactorily described by the Langmuir model and the maximum adsorption capacities obtained from the natural clay, using the Langmuir isotherm model equation, are 5.25, 13.41, and 15.90 mg/g, respectively for Cd(II), Cu(II), and Pb(II) ions. Adsorption of heavy metals on clay is a spontaneous and endothermic process characterized by a disorder of the medium. The values of ΔH are greater than 40 kJ/mol, which means that the interactions between clay and heavy metals are chemical in nature.     

Preparation and ion-exchange properties of zirconium tungstoarsenate

A new inorganic ion-exchanger, zirconium tugnstoarsenate, has been synthesized which has been characterized by chemical analysis, thermogravimetry, X-ray and infrared spectroscopy. The ion exchanger has been found to be stable in acids and neutral salt solutions. The K_d values for 30 metal ions have been determined at pH 3–4 which show that the exchanger has high affinity for UO ₂ ²⁺ , ZrO²⁺, Cs⁺ and Tl⁺ ions. The variation of K_d for a number of metal ions as a function of concentration of nitric acid and ammonium nitrate has been investigated to elucidate the probable exchange mechanism and to work out conditions for elution. Some binary separations, viz. Sr²⁺−Cs⁺, Sr²⁺−Rb⁺, Sr²⁺−Y³⁺, Fe³⁺−Al³⁺, Fe³⁺−Zn²⁺ and Zn²⁺−Hg²⁺ in trace amounts have been carried out on the column of the exchanger which demonstrate the utility of the exchanger in radionalytical and analytical chemistry.     

Phosphoric acid activated carbon as borderline and soft metal ions scavenger

Three activated carbons have been prepared, two from oil-palm shell and one from coconut shell, by the phosphoric acid activation process. Adsorption isotherms of copper(II) were determined to evaluate and compare the performance of experimental carbons. The obtained data are fitted very well to Langmuir and Freundlich adsorption models. All prepared activated carbons show 4–7-fold high adsorption capacity (q_max 19.5–23/18.6–21?mg?g^?1) than that of the commercial ones (q_max 5.6/2.9?mg?g^?1) under the conducted experimental conditions. The mechanism of adsorption was evaluated from the competitive adsorption of copper(II) and calcium(II) in a binary solution depending on their behaviour as Lewis acid and assessed as inner-sphere complexation. The competitive adsorption of copper(II) with other borderline and soft metal ions was evaluated by the best scavenger using a solution of ternary solute of copper(II), nickel(II) and lead(II). The adsorption selectivity order is determined as follows: Pb?>?Cu???Ni.     

Sorption characteristics of an economical sorbent material used for removal radioisotopes of cesium and europium

Application study for the evaluation of sorption characteristics of sawdust as an economical sorbent material used for decontamination of radioisotopes cesium and europium from aqueous solution has been carried out in the present work. In this respect, sawdust (untreated and treated by HNO₃) has been prepared from the commercial processing of wood for furniture production. Pore properties of the activated carbon such as BET surface area, pore volume, pore size distribution, and pore diameter were characterized by N₂ adsorption and DFT software. Radiotracer method onto sawdust from aqueous solutions was studied in a batch technique with respect to pH, contact time, temperature. The kinetics of adsorption of Eu³⁺ and Cs⁺ have been discussed using five kinetic models namely, pseudo-first-order model, pseudo-second-order model, Elovich equation, intraparticle diffusion model, and modified Freundlich equation that have been tested in order to analysis the experimental data. Kinetic parameters and correlation coefficients were determined. It was shown that the second-order kinetic equation could describe the sorption kinetics for two metal ions. The metal uptake process was found to be controlled by intraparticle diffusion. Thermodynamic parameters, such as ΔH, ΔG and ΔS, have been calculated by using the thermodynamic equilibrium coefficient obtained at different temperatures. The obtained results indicated that endothermic nature of sorption process for both ^152+154Eu and ¹³⁴Cs onto sawdust.     

A benzothiazole-based receptor-immobilised silica nanoparticle as chemosensor for Hg2+

Fluorogenic benzothiazole-based receptor has been easily immobilised onto filter paper and silica nanoparticle by sol-gel reaction. The sensing ability of the benzothiazole-immobilised thin layer filter paper chromatography (TLC-1) was evaluated on the basis of fluorescent changes caused by metal ions that were dropped onto the TLC plate. The TLC-1 exhibited a high affinity and selectivity for Hg²⁺ over other competing metal ions. Therefore, the TLC-1 holds promise as a portable sensor for the detection of Hg²⁺ in aqueous solution. Furthermore, the adsorption capacity of a column packed with SiO₂-1 was evaluated by the application of metal ions under various experimental conditions, such as pH, flow rate and concentration. The SiO2-1 column removed 98% of Hg²⁺ from drinking water containing 10 ppb of Hg²⁺. The adsorption capacity of the SiO₂-1 column was not strongly affected by pH and flow rates.     

Adsorption behaviors of strontium using macroporous silica based hexagonal tungsten oxide

A novel macroporous silica-based hexagonal tungsten oxide (h-WO₃/SiO₂) with exchangeable sodium cations located in hexagonal tunnel structure was synthesized by a facile hydrothermal treatment of sodium tungstate dihydrate with 1 mol/L HCl solution. Utilization of the h-WO₃/SiO₂ adsorbent to remove aqueous strontium was investigated under the condition of various pH values, contact time, the initial concentration of metal ions, salt ion concentration, and coexisting ions. According to the experimental data, Sr²⁺ adsorption equilibrium was achieved within 15 min in acidic solution, and the maximum removal capacity of Sr²⁺ occurred at pH 4. The kinetic adsorption of Sr²⁺ on h-WO₃/SiO₂ was controlled by pseudo second-order model, and the saturated adsorption of Sr²⁺ on h-WO₃/SiO₂ was better described by Langmuir and Redlich-Peterson isotherm models compared with the Freundlich isotherm model. The distribution coefficient of Sr²⁺ was more than 2000 cm³/g in the presence of Ca²⁺, Mg²⁺, La³⁺, and Eu³⁺, indicating that the h-WO₃/SiO₂ showed excellent selectivity towards Sr²⁺ in pH 4.     

Highly efficient removal of diazinon pesticide from aqueous solutions by using coconut shell-modified biochar

This study evaluates the adsorption of diazinon from aqueous solutions onto coconut shell-modified biochar using a batch system. The amount of dosage and initial pH are the main parameters being studied to obtain maximum adsorption capacity of the probe molecules. The carbonized coconut shell biochar (BC1), activated coconut shell biochar (BC2), chemically modified phosphoric acid (BC3) and sodium hydroxide coconut shell biochar (BC4) were prepared and tested as variables in the adsorption experiment. The characteristic of biochar via SEM, EDX and BET analysis revealed the large porous of surface morphology and slight changes in the composition with high surface area (405.97 – 508.07 m²/g) by following the sequence of BC3 > BC2 > BC4. Diazinon removal percentage as high as 98.96% was achieved at pH 7 with BC3 as adsorbent dosing at 5.0 g/L. The high coefficient of determination, R² with a small value of ERRSQ and χ² error analysis present the BC1 (0.9971) and BC2 (0.9999) are best fitted with Freundlich isotherm indicates multilayer sorption onto heterogeneous surface whereby the Langmuir isotherm model is the best fitting is described of monolayer adsorption process onto the homogenous surface of BC3 and BC4. The results indicated the maximum adsorption capacity (q_m) was achieved by BC3 with 10.33 mg/g, followed by BC2 (9.65 mg/g) in accordance to the Langmuir isotherm while Freundlich isotherm showed the highest adsorption capacity (k_F) with 1.73 mg/g (L/mg)^1/n followed by BC4 with 0.63 mg/g (L/mg)^1/n at favorable adsorption isotherm (1 ≤ n ≤ 10). Thus, the results obtained depicted that BC2 and BC3 are highly efficient adsorbents and both exhibit great potential in removing diazinon from aqueous solutions.     

Using Zeolite/Polyvinyl alcohol/sodium alginate nanocomposite beads for removal of some heavy metals from wastewater

Functionalized Polyvinyl alcohol/sodium alginate (PVA/SA) beads were synthesized via blending Polyvinyl alcohol (PVA) with sodium alginate (SA) and the glutaraldehyde was used as a cross-linking agent. The zeolite nanoparticles (Zeo NPs) incorporated PVA/SA resulting Zeo/PVA/SA nanocomposite (NC) beads were synthesized for removal of some heavy metal from wastewater. The synthesizes beads were characterized via Fourier transforms infrared spectroscopy (FTIR), X-ray diffraction (XRD), particle size analyzer (PSA), and scanning electron microscope (SEM). The adsorption kinetics of the selected metal ions onto Zeo/PVA/SA NC beads followed the pseudo-first-order model (PFO) and the adsorption isotherm model was well fitted by the Langmuir model. Moreover, the thermodynamic studies were also examined; the outcomes showed that the adsorption mechanisms of the selective metal ions were endothermic, the chemical in nature, spontaneous adsorption on the surface of the Zeo/PVA/SA NC beads. The removal efficiency using Zeo/PVA/SA NC modified beads reached maximum at the pH value of 6.0 for Pb²⁺, Cd²⁺, Sr²⁺, Cu²⁺, Zn²⁺, Ni²⁺, Mn²⁺ and Li²⁺ with 99.5, 99.2, 98.8, 97.2, 95.6, 93.1, 92.4 and 74.5%, respectively, while the highest removal are achieved at pH = 5 for Fe³⁺ and Al³⁺ with 96.5 and 94.9%, respectively and decreased at lower or higher pH values. The survival count (%) of the E. coli cells were 34% on the SA beads, 11% on the PVA/SA, and 1% on the Zeo/PVA/SA NC modified beads, after 120 min exposure at 25 °C. Reusability experimental displays that the synthesized beads preserved a significant decrease in the sorption capacity after 10 repeating cycles. The Zeo/PVA/SA NC beads were able to eliminate 60–99.8% of Al³⁺, Fe³⁺, Cr³⁺, Co²⁺, Cd²⁺, Zn²⁺, Mn²⁺, Ni²⁺, Cu²⁺, Li²⁺, Sr²⁺, Si²⁺, V²⁺, and Pb²⁺ ions from the natural wastewater samples collected from 10th Ramadan City, Cairo, Egypt.     

The use of ESI-MS to probe the binding of divalent cations to calmodulin

Proteins have evolved with distinct sites for binding particular metal ions. This allows metalloproteins to perform a myriad of specialized tasks with conformations tailor-made by the combination of its primary sequence and the effect on this of the ligated metal ion. Here we investigate the selectivity of the calcium trigger protein calmodulin for divalent metal ions. This ubiquitous and highly abundant protein exists in equilibrium between its apo and its holo form wherein four calcium ions are bound. Amongst its many functions, calmodulin modulates the calcium concentration present in cells, but this functional property renders it a target for competition from other metal ions. We study the competition posed by four other divalent cations for the calcium binding sites in calmodulin using electrospray ionization mass spectrometry (ESI-MS). We have chosen two other group II cations Mg²⁺, Sr²⁺, and two heavy metals Cd²⁺, Pb²⁺. The ease with which each of these metals binds to apo and to holo CaM[4Ca] is described. We find that each metal ion has different properties with respect to calmodulin binding and competition with calcium. The order of affinity for apo CaM is Ca²⁺ ≫ Sr²⁺ ∼ Mg²⁺ > Pb²⁺ ∼ Cd²⁺. In the presence of calcium the affinity alters to Pb²⁺ > Ca²⁺ > Cd²⁺ > Sr²⁺ > Mg²⁺. Once complexes have been formed between the metal ions and protein (CaM:[xM]) we investigate whether the structural change which must accompanies calcium ligation to allow target binding takes place for a given CaM:[xM] system. We use a 20 residue target peptide, which forms the CaM binding site within the enzyme neuronal nitric-oxide synthase. Our earlier work (Shirran et al. 2005) [1] has demonstrated the particular selectivity of this system for CaM:4Ca²⁺. We find that along with Ca²⁺ only Pb²⁺ forms complexes of the form CaM:4M²⁺:nNOS. This work demonstrates the affinity for calcium above all other metals, but also warns about the ability of lead to replace calcium with apparent ease.     

A highly selective fluorescent sensor for Ca2+ and Sr2+ based on diarylethene with a furan-carbohydrazide unit

A fluorescent sensor based on diarylethene has been designed and synthesized. The sensor not only exhibited excellent photochromic properties, but also has distinguishing ability for Ca²⁺ and Sr²⁺ from other metal ions. Upon addition of Ca²⁺ and Sr²⁺, its emission intensity enhanced 27-fold and 24-fold respectively, accompanied by the emission peak shifted from 439 nm to 484 nm for Ca²⁺, and to 479 nm for Sr²⁺. The 1:1 stoichiometry between the sensor and the two ions was confirmed by Job's plot and HRMS. The LOD for Ca²⁺ and Sr²⁺ was determined to be 9.4 × 10^?8 mol L^?1 and 7.2 × 10^?8 mol L^?1, respectively. Furthermore, the sensor was applied in the detection of Ca²⁺ and Sr²⁺ in practical samples successfully.     

Heavy metal ions removal by nano-sized spherical polymer brushes

Nano-sized spherical polymer brushes(SPBs) consisting of both a polystyrene(PS) core and a brush shell of poly(acrylic acid)(PAA), poly(N-acrylcysteamine)(PSH), or poly(N-acrylcysteamine-co-acrylic acid)(P(SH-co-AA)), were prepared by photo-emulsion polymerization. The core-shell structure was observed by dynamic light scattering and transmission electron microscopy. Due to the strengthened Donnan effect, the PAA brush can adsorb heavy metal ions. Effects of the contact time, thickness of PAA brush and pH value on the adsorption results were investigated. Due to the coordination between the mercapto groups and heavy metal ions as well as the electrostatic interactions, SPBs with mercapto groups are capable to remove heavy metal ions selectively from aqueous solutions. The order of adsorption capacity of the heavy metal ions by SPBs with mercapto groups is: Hg2+ ≈ Au3+ Pb2+ Cu2+ Ni2+. The adsorbed heavy metal ions can be eluted from SPB by aqueous HCl solution, and the SPBs can be recovered. After three regenerations the recovered SPBs still maintain their adsorption capacity.     

Binding heavy metal ions with polymerized onion skin

Red onion skin is highly effective for binding heavy metal ions from aqueous solutions. Color leaching can be prevented and the physical characteristics of the substrate can be improved by treatment with formaldehyde in an acidic medium. Batch and column experiments have been conducted with Cu²⁺, Cd²⁺, Zn²⁺, Ni²⁺, Hg²⁺, and Pb²⁺. Almost quantitative removal of the metal ions from solution can be achieved by using columns of the treated onion skin. Competition of the various metal ions for the substrate has been investigated. The capacity of the substrate in the majority of the metal ions studied is well above 1 meq/g. The use of polymerized onion skin to remove heavy metal ions from domestic and industrial wastewater to safe levels has been recommended as a cheap and effective alternative for commercial ion-exchange resins.     

Chemically modified kapok fiber for fast adsorption of Pb2+, Cd2+, Cu2+ from aqueous solution

Kapok fiber, a natural hollow fiber with thin shell and large cavity, has rarely been used as adsorbent for heavy metal ions. In this paper, kapok fibers were modified with diethylenetriamine pentaacetic acid (DTPA) after hydrophilicity treatment. The adsorption behavior of the resultant kapok-DTPA influenced by pH, adsorption time and initial concentration of metal ion was investigated. The results demonstrate that adsorption equilibrium was reached within 2 min for Pb²⁺ and Cd²⁺. Adsorption kinetics showed that the adsorption rate was well fitted by pseudo-second-order rate model. The adsorption isotherms were studied, and the best fit was obtained in the Langmuir model. The maximum adsorption capacities of kapok-DTPA were 310.6 mg g^?1 for Pb²⁺, 163.7 mg g^?1 for Cd²⁺, 101.0 mg g^?1 for Cu²⁺, respectively. After eight desorption and re-adsorption loops, the lost adsorption capacities for Pb²⁺ and Cu²⁺ were less than 10 %. Because of the large specific area derived from the hollow fiber structure, kapok-DTPA exhibited much better adsorption capacity compared with many other reported adsorbents based on natural materials.