Luminescent zinc(ii) selone macrocyclic ring

The synthesis and photophysical properties of macrocyclic Zn(ii) selone molecule have been reported. The structural property of Zn(ii) selone was elucidated using single crystal X-ray diffraction study. The solid-state structure of zinc(ii) selone molecule exhibits a perfect zinc(ii) selone 28 membered ring system with tetra coordination geometry around zinc(ii) center. The zinc(ii) selone ring system can be considered as the largest zinc(ii) ring system known without any non-interacting centered guest moiety. Detailed trends in photophysical as well as thermal properties were probed. In photoluminescence study, the solid-state sample of zinc(ii) selone ring system emits the bluish-yellow color with considerable quantum yields, while the solution state sample of zinc(ii) selone ring system in DMSO emits bluish-yellow. The luminescence lifetime of zinc(ii) selone was measured using standard time-correlated single photon counting (TCSPC) technique.

The synthesis and photophysical properties of luminescent zinc(ii) selone 28 membered macrocyclic ring system is reported.     

Single molecule magnets of cobalt and zinc homo- and heterometallic coordination polymers prepared by a one-step synthetic procedure

The synthesis of 1D cobalt and zinc monometallic and heterometallic coordination polymers (CPs) was carried out applying one-pot synthetic methods by using either supercritical carbon dioxide or ethanol as the solvent. A collection of four 1D CPs were thus obtained by the combination of a metal (or a mixture of metals) with the linker 1,4-bis(4-pyridylmethyl)benzene. The used metallic complexes were zinc and cobalt hexafluoroacetylacetonate, which can easily incorporate pyridine ligands in the coordination sphere of the metal centre. Independently of the used solvent, the precipitated phases involving Zn(ii), i.e., homometallic CP of Zn(ii) and bimetallic CP of Zn(ii)/Co(ii), were isostructural. Contrarily, homometallic CPs of Co(ii) were precipitated as an isostructural phase of Zn(ii) or with a different structure, depending on the used solvent. All the structures were resolved by XRD using synchrotron radiation. In addition, the magnetic properties of the new CPs involving Co(ii) were studied. Remarkably, at low temperatures with the application of an external field, they acted as field-induced single molecule magnets.

One-pot synthesis of heterometallic (Zn(ii)/Co(ii)) nodes directing CP magnetic behaviour to single molecule magnets.     

Kinetics,thermodynamics, equilibrium,surface modelling,and atomic absorption analysis of selective Cu(ii) removal from aqueous solutions and rivers water using silica-2-(pyridin-2-ylmethoxy)ethan-1-ol hybrid material

The removal of heavy metals is attracting considerable attention due to their undesirable effects on the environment. In this investigation, a new adsorbent based on silica functionalized with pyridin-2-ylmethanol (SiPy) was successfully synthesized to yield to a hybrid material. FTIR, SEM, TGA, and specific surface area analysis were used to characterize the structure and morphology of the SiPy hybrid material. Various heavy metal ions such as Cu(ii), Zn(ii), Cd(ii), and Pb(ii) were selected to examine the adsorption efficiency of the newly prepared adsorbent, optimized at varying solution pH, contact time, concentration, and temperature. The adsorbent SiPy displayed good adsorption capacity of 90.25, 75.38, 55.23, and 35.12 mg g⁻¹ for Cu(ii), Zn(ii), Cd(ii), and Pb(ii), respectively, at 25 min and pH = 6. The adsorption behaviors of metal ions onto the SiPy adsorbent fitted well with the pseudo-second-order kinetic mode and the isotherm was better described by the Langmuir isotherm. The thermodynamic studies disclose spontaneous and endothermic adsorption process. Furthermore, the SiPy adsorbent retained good selectivity and regeneration properties after five adsorption–desorption cycles of Cu(ii). A computational investigation of the adsorption mechanism indicates that the N-pyridine, O-hydroxyl, and ether O-atoms play a predominant role during the capture of Cu(ii), Zn(ii), Cd(ii), and Pb(ii). This study proposes the SiPy adsorbent as an attractive material for the selective removal of Cu(ii) from real river water and real industrial wastewater.

The removal of heavy metals is attracting considerable attention due to their undesirable effects on the environment.     

Role of graphene oxide in mitigated toxicity of heavy metal ions on Daphnia magna

Graphene oxide (GO) is increasingly used and inevitably released into aquatic environments, facilitating its interaction with traditional pollutants such as heavy metal ions. However, the potential effect of GO on the toxicity of heavy metal ions to aquatic animals is unknown. This work aims to assess the toxicity of heavy metal ions (Cu(ii), Cd(ii), and Zn(ii)) on Daphnia magna (D. magna) in the presence of GO. GO nanoparticles remarkably reduced the concentrations of heavy metal ions by adsorption and decreased the metal accumulation in D. magna. The maximum desorption rate of heavy metal ions from metal-adsorbed GO was below 5%. At pH 7.8, with addition of 2 mg L⁻¹ GO, the 72 h median lethal concentration (LC₅₀) values of Cu(ii), Cd(ii), and Zn(ii) were increased from 14.3, 38, and 780 μg L⁻¹ to 36.6, 72, and 1010 μg L⁻¹, respectively. The analyses of oxidative stress indicators suggested that the oxidative damage to D. magna by heavy metal ions was reduced after addition of GO at pH 7.8. Moreover, a higher pH level in the growing range (6.5 to 8.5) of D. magna led to weaker toxicity of metal ions with GO addition due to more adsorption and less bioaccumulation. The results revealed the role of GO nanoparticles in the mitigated toxicity of heavy metal ions in the aquatic environment.

Graphene oxide nanoparticles mitigates the biotoxicity of heavy metal ions (Cu(ii), Cd(ii), and Zn(ii)) on aquatic animals (Daphnia magna).     

A green l-cysteine modified cellulose nanocrystals biosorbent for adsorption of mercury ions from aqueous solutions

Using a green biosorbent to remove toxic mercury ions from aqueous solutions is a significant undertaking. In the present study, a novel biosorbent, l-cysteine modified cellulose nanocrystals (Lcys-CNCs), was prepared by functionalizing high surface area cellulose nanocrystals with l-cysteine through periodate oxidation and reductive amination reaction. Lcys-CNCs were characterized by FT-IR, ¹³C CP-MAS NMR, elemental analysis, XPS, zeta potential and SEM. As cellulose nanocrystals are the natural nanomaterial, and l-cysteine contains strong mercury chelating groups, Lcys-CNCs show excellent adsorption capacity for mercury ions. The experimental conditions such as pH, contact time, and initial mercury ion concentration are discussed. The pseudo-second order model can describe the removal kinetics of Hg(ii) more accurately than the pseudo-first order model. The adsorption isotherm study of Hg(ii) followed the Langmuir model of monolayer adsorption. The maximum uptake capacity of Lcys-CNCs was determined to be 923 mg g⁻¹. Lcys-CNCs can remove mercury ions with 93% removal efficiency within 5 min from a 71 mg L⁻¹ solution. For Cd(ii), Pb(ii), Cu(ii) and Zn(ii) ions, Lcsy-CNCs can selectively adsorb Hg(ii) ions and the removal efficiency is 87.4% for Hg(ii). This study suggests Lcsy-CNCs are a green and highly efficient biosorbent for adsorption of mercury ions from aqueous solutions.

A green biosorbent, l-cysteine modified cellulose nanocrystals, was successfully synthesized and applied to adsorb mercury ions from aqueous solutions.     

Separation of iron(iii), zinc(ii) and lead(ii) from a choline chloride–ethylene glycol deep eutectic solvent by solvent extraction

Deep eutectic solvents (DESs) were used as alternatives to the aqueous phase in solvent extraction of iron(iii), zinc(ii) and lead(ii). The selective extraction of iron(iii) and zinc(ii) was studied from a feed of ethaline (1 : 2 molar ratio of choline chloride : ethylene glycol) and lactiline (1 : 2 molar ratio of choline chloride : lactic acid), with the former DES being more selective. A commercial mixture of trialkylphosphine oxides (Cyanex 923, C923) diluted in an aliphatic diluent selectively extracted iron(iii) from a feed containing also zinc(ii) and lead(ii). The subsequent separation of zinc(ii) from lead(ii) was carried out using the basic extractant Aliquat 336 (A336). The equilibration time and the extractant concentration were optimized for both systems. Iron(iii) and zinc(ii) were stripped using 1.2 mol L⁻¹ oxalic acid and 0.5 mol L⁻¹ aqueous ammonia, respectively. An efficient solvometallurgical flowsheet is proposed for the separation and recovery of iron(iii), lead(ii) and zinc(ii) from ethaline using commercial extractants. Moreover, the process was upscaled in a countercurrent mixer-settler set-up resulting in successful separation and purification.

Deep eutectic solvents (DESs) were used as alternatives to the aqueous phase in solvent extraction of iron(iii), zinc(ii) and lead(ii).     

Synthesis and characterization of a surface-grafted Pb(ii)-imprinted polymer based on activated carbon for selective separation and pre-concentration of Pb(ii) ions from environmental water samples

Even the lowest concentration level of lead (Pb) in the human body is dangerous to health due to its bioaccumulation and high toxicity. Therefore, it is very important to develop selective and fast adsorption methods for the removal of Pb(ii) from various samples. In this paper, a new Pb(ii) ion-imprinted polymer (Pb(ii)-IIP) was prepared with surface imprinting technology by using lead nitrate as a template, for the solid-phase extraction of trace Pb(ii) ions in environmental water samples. The imprinted polymer was characterized by X-ray diffraction, Fourier transform infrared spectroscopy, Raman spectroscopy, scanning electron microscopy and N₂ adsorption–desorption isotherms. The separation/pre-concentration conditions for Pb(ii) were investigated, including the effects of pH, shaking time, sample flow rate, elution conditions and interfering ions. Compared with non-imprinted particles, the ion-imprinted polymer had a higher selectivity and adsorption capacity for Pb(ii). The pseudo-second-order kinetics model and Langmuir isotherm model fitted well with the adsorption data. The relative selectivity factor values (α_r) of Pb(ii)/Zn(ii), Pb(ii)/Ni(ii), Pb(ii)/Co(ii) and Pb(ii)/Cu(ii) were 168.20, 192.71, 126.13 and 229.39, respectively, which were all much greater than 1. The prepared Pb(ii)-imprinted polymer was shown to be promising for the separation/pre-concentration of trace Pb(ii) from natural water samples. The adsorption and desorption mechanisms were also proposed.

Even the lowest concentration level of lead (Pb) in the human body is dangerous to health due to its bioaccumulation and high toxicity.     

Membrane partition of bis-(3-hydroxy-4-pyridinonato) zinc(ii) complexes revealed by molecular dynamics simulations

The class of 3-hydroxy-4-pyridinone ligands is widely known and valuable for biomedical and pharmaceutical purposes. Their chelating properties towards biologically-relevant transition metal ions highlight their potential biomedical utility. A set of 3-hydroxy-4-pyridinone Zn(ii) complexes at different concentrations was studied for their ability to interact with lipid phases. We employed umbrella sampling simulations to attain the potential-of-mean force for a set of ligands and one Zn(ii) complex, as these permeated a 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) hydrated bilayer system. In addition, we used conventional molecular dynamics simulations to study the behavior of various Zn(ii) complexes in hydrated bilayer systems. This work discusses: (i) the partition of 3-hydroxy-4-pyridinone ligands to bilayer phases; (ii) self-aggregation in crowded environments of Zn(ii) complexes; and (iii) possible mechanisms for the membrane translocation of Zn(ii) complexes. We observed distinct interactions for the studied complexes, and distinct membrane partition coefficients (K_mem) depending on the considered ligand. The more hydrophobic ligand, 1-hexyl-3-hydroxy-2-methyl-4(1H)-pyridinone, partitioned more favorably to lipid phases (at least two orders of magnitude higher K_mem when compared to the other ligands), and the corresponding Zn(ii) complex was also prone to self-aggregation when an increased concentration of the complex was employed. We also observed that the inclusion of a coordinated water molecule in the parameterization of the Zn(ii) coordination sphere, as proposed in the available crystallographic structure of the complex, decreased the partition coefficient and membrane permeability for the tested complex.

The membrane partition of hydroxypyridinones and of zinc complexes explored by molecular dynamics.     

His18 promotes reactive oxidative stress production in copper-ion mediated human islet amyloid polypeptide aggregation

Copper ions play a critical role in human islet amyloid polypeptide (hIAPP) aggregation, which has been found in more than 90% of patients with type-2 diabetes (T2D). The role of Cu(ii) in the cell cytotoxicity with hIAPP has been explored in two aspects: inhibiting the formation of fibrillar structures and stimulating the generation of reactive oxygen species (ROS). In this work, we carried out spectroscopic studies of Cu(ii) interacting with several hIAPP fragments and their variants as well. Electron paramagnetic resonance (EPR) measurements and Amplex Red analysis showed that the amount of H₂O₂ generated in hIAPP(11-28) solution co-incubated with Cu(ii) was remarkably more than hIAPP(1-11) and hIAPP(28-37). Furthermore, the H₂O₂ level was seriously reduced when His18 of hIAPP(11-28) was replaced by Arg(R) or Ser(S), indicating that His18 is the key residue of Cu(ii) binding to hIAPP(11-28) to promote H₂O₂ generation. This is likely because the donation of electrons from the peptide to Cu(ii) ions would result in the formation of the redox-active complexes, which could stimulate the formation of H₂O₂. Overall, this study provides further insight into the molecular mechanism of Cu(ii) induced ROS generation.

His18 promotes H₂O₂ production in copper-ion mediated hIAPP aggregation.     

Hydrogels derived from galactoglucomannan hemicellulose with inorganic contaminant removal properties

The adsorption of Cu(ii), Cd(ii), and Pb(ii) ions onto hydrogels derived from modified galactoglucomannan (GGM) hemicellulose was studied. GGM hemicellulose was modified with methacrylate groups (GGM-MA) to incorporate vinyl groups into the polymeric structure, which reacted later with synthetic monomers such as 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS). The results show that all the synthesized hydrogels were capable of adsorbing contaminating ions with high adsorption efficiency during short periods of time. Furthermore, an increase in the content of GGM-MA generated a hydrogel (H3) with a similar ion adsorption property to the other hydrogels but with a lesser degree of swelling. The H3 hydrogel had an adsorption capacity of 60.0 mg g⁻¹ Cd(ii), 78.9 mg g⁻¹ Cu(ii), and 174.9 mg g⁻¹ Pb(ii) at 25 °C. This result shows that modified GGM hemicelluloses can be employed as renewable adsorbents to remove Cu(ii), Cd(ii), and Pb(ii) ions from aqueous solutions.

The adsorption of Cu(ii), Cd(ii), and Pb(ii) ions onto hydrogels derived from modified galactoglucomannan (GGM) hemicellulose was studied.     

Efficient removal of heavy metals from polluted water with high selectivity for Hg(ii) and Pb(ii) by a 2-imino-4-thiobiuret chemically modified MIL-125 metal–organic framework

A highly porous adsorbent based on a metal–organic framework was successfully designed and applied as an innovative adsorbent in the solid phase for the heavy metal removal. MIL-125 was densely decorated by 2-imino-4-thiobiuret functional groups, which generated a green, rapid, and efficacious adsorbent for the uptake of Hg(ii) and Pb(ii) from aqueous solutions. ITB-MIL-125 showed a high adsorption affinity toward mercury(ii) ions of 946.0 mg g⁻¹ due to covalent bond formation with accessible sulfur-based functionality. Different factors were studied, such as the initial concentration, pH, contact time, and competitive ions, under same circumstances at the room temperature. Moreover, the experimental adsorption data were in excellent agreement with the Langmuir adsorption isotherm and pseudo-second order kinetics. At a high concentration of 100 ppm mixture of six metals, ITB-MIL-125 exhibited a high adsorption capacity, reaching more than 82% of Hg(ii) compared to 62%, 30%, 2%, 1.9%, and 1.6% for Pb(ii), Cu(ii), Cd(ii), Ni(ii), and Zn(ii), respectively.

A highly porous adsorbent based on a metal–organic framework was successfully designed and applied as an innovative adsorbent in the solid phase for the heavy metal removal.     

Melamine-based functionalized graphene oxide and zirconium phosphate for high performance removal of mercury and lead ions from water

Heavy metal ions are highly toxic and widely spread as environmental pollutants. This work reports the development of two novel chelating adsorbents, based on the chemical modifications of graphene oxide and zirconium phosphate by functionalization with melamine-based chelating ligands for the effective and selective extraction of Hg(ii) and Pb(ii) from contaminated water sources. The first adsorbent melamine, thiourea-partially reduced graphene oxide (MT-PRGO) combines the heavier donor atom sulfur with the amine and triazine nitrogen''s functional groups attached to the partially reduced GO nanosheets to effectively capture Hg(ii) ions from water. The MT-PRGO adsorbent shows high efficiency for the extraction of Hg(ii) with a capacity of 651 mg g⁻¹ and very fast kinetics resulting in a 100% removal of Hg(ii) from 500 ppb and 50 ppm concentrations in 15 second and 30 min, respectively. The second adsorbent, melamine zirconium phosphate (M-ZrP), is designed to combine the amine and triazine nitrogen''s functional groups of melamine with the hydroxyl active sites of zirconium phosphate to effectively capture Pb(ii) ions from water. The M-ZrP adsorbent shows exceptionally high adsorption affinity for Pb(ii) with a capacity of 681 mg g⁻¹ and 1000 mg g⁻¹ using an adsorbent dose of 1 g L⁻¹ and 2 g L⁻¹, respectively. The high adsorption capacity is also coupled with fast kinetics where the equilibrium time required for the 100% removal of Pb(ii) from 1 ppm, 100 ppm and 1000 ppm concentrations is 40 seconds, 5 min and 30 min, respectively using an adsorbent dose of 1 g L⁻¹. In a mixture of six heavy metal ions at a concentration of 10 ppm, the removal efficiency is 100% for Pb(ii), 99% for Hg(ii), Cd(ii) and Zn(ii), 94% for Cu(ii), and 90% for Ni(ii) while at a higher concentration of 250 ppm the removal efficiency for Pb(ii) is 95% compared to 23% for Hg(ii) and less than 10% for the other ions. Because of the fast adsorption kinetics, high removal capacity, excellent regeneration, stability and reusability, the MT-PRGO and M-ZrP are proposed as top performing remediation adsorbents for the solid phase extraction of Hg(ii) and Pb(ii), respectively from contaminated water.

Two novel chelating adsorbents are developed for the effective and selective extraction of Hg(ii) and Pb(ii) ions from contaminated water sources.     

Thiosemicarbazone modified zeolitic imidazolate framework (TSC-ZIF) for mercury(ii) removal from water

Zeolitic imidazolate frameworks (ZIF-8), and their derivatives, have been drawing increasing attention due to their thermal and chemical stability. The remarkable stability of ZIF-8 in aqueous and high pH environments renders it an ideal candidate for the removal of heavy metals from wastewater. In this study, we present the preparation of novel aldehyde-based zeolitic imidazolate frameworks (Ald-ZIF) through the integration of mixed-linkers: 2-methylimidazole (MIM) and imidazole-4-carbaldehyde (AldIM). The prepared Ald-ZIFs were post-synthetically modified with bisthiosemicarbazide (Bisthio) and thiosemicarbazide (Thio) groups, incorporating thiosemicarbazone (TSC) functionalities to the core of the framework. This modification results in the formation of TSC-functionalized ZIF derivatives (TSC-ZIFs). Thiosemicarbazones are versatile metal chelators, hence, adsorption properties of TSC-ZIFs for the removal of mercury(ii) from water were explored. Removal of mercury(ii) from homoionic aqueous solutions, binary and tertiary systems in competition with lead(ii) and cadmium(ii) under ambient conditions and neutral pH are reported in this study. MIM_3.5:Thio₁:Zn improved the removal efficiency of mercury(ii) from water, up to 97% in two hours, with an adsorption capacity of 1667 mg g⁻¹. Desorption of mercury(ii) from MIM_3.5:Thio₁:Zn was achieved under acidic conditions, regenerating MIM_3.5:Thio₁:Zn for five cycles of mercury(ii) removal. TSC-ZIF derivatives, designed and developed here, represent a new class of dynamically functionalized adsorption material displaying the advantages of simplicity, efficiency, and reusability.

Zeolitic imidazolate frameworks Ald-ZIF were obtained by mixing two imidazole-based linkers with zinc(ii). Post-synthetically modified Ald-ZIFs with thiosemicarbazide group improved mercury(ii) removal efficiency from water at a capacity of 1667 mg g⁻¹.     

Adsorption of Cu(ii), Zn(ii), and Pb(ii) from aqueous single and binary metal solutions by regenerated cellulose and sodium alginate chemically modified with polyethyleneimine

In this paper, crosslinked cellulose/sodium alginate (SA) was modified with polyethyleneimine (PEI) as an adsorbent (PEI-RCSA) for comparative and competitive adsorption of Cu(ii), Zn(ii), and Pb(ii) in single and binary aqueous solutions. FTIR, SEM, TGA and specific surface area analysis were used to characterize the structural characteristics of PEI-RCSA. The effects of initial pH of solutions, contact time and initial concentration of heavy metal ions on the adsorption capacity of PEI-RCSA were investigated. The experimental results revealed that the removal of metal ions on the PEI-RCSA was a pH-dependent process with the maximum adsorption capacity at the initial solution pH of 5–6. The adsorption kinetics were followed by a pseudo-second-order kinetics model, and the diffusion properties played a significant role in the control of the adsorption kinetics. Meanwhile, adsorption isotherms were successfully described by the Langmuir model in a single aqueous solution system. The maximum adsorption capacities of PEI-RCSA for Cu(ii), Zn(ii), and Pb(ii) in a single system were 177.1, 110.2 and 234.2 mg g⁻¹, respectively. The binary-component system was better described with the Langmuir competitive isotherm model. The removal efficiencies didn''t change significantly when three adsorption–desorption experimental cycles were conducted. All the above results indicated that PEI-RCSA has promising applications in the treatment of toxic metal pollution.

Crosslinked cellulose/sodium alginate was modified with polyethyleneimine as an adsorbent (PEI-RCSA) for comparative and competitive adsorption of metal ions.     

Amphoteric starch derivatives as reusable flocculant for heavy-metal removal

A pH-responsive amphoteric starch derivative (PRAS) bearing dual functional groups (amino and carboxyl groups) was prepared through etherification of starch with 2-chloro-4,6-diglycino-[1,3,5]-triazine. PRAS exhibits a reversible pH-response property in aqueous solution. The attractive property of PRAS is that it could be used as an effective flocculant for heavy metal-ion (e.g. Cu(ii) and Zn(ii)) removal from wastewater by changing pH. The transition of hydrophobicity–hydrophilicity would produce shrinkage of the polymer matrix, facilitating the release of heavy-metal ions from the saturated flocculant. As an ideal flocculant PRAS displayed outstanding stability and reproducibility, whose remove rate for Cu(ii) and Zn(ii) remained at 93% and 91% after three flocculation/regeneration cycles.

A pH-responsive starch-based flocculants containing both cationic and anionic functional groups has been developed. The saturated flocculant can be facilely regenerated and separated from the solution by applying an external pH stimulus.     

The (CF3C(O)NH)(C6H5CH2NH)2P(O) phosphoric triamide as a novel carrier with excellent efficiency for Cu(ii) in a liquid membrane transport system

Transport of Ag(i), Cd(ii), Co(ii), Cu(ii), Ni(ii), Pb(ii) and Zn(ii) cations across a bulk liquid membrane (BLM) containing N,N′-dibenzyl-N′′-(2,2,2-trifluoroacetyl)-phosphoric triamide (PTC) as a new carrier is studied by atomic absorption spectrometry. The results show selective and efficient transport of the copper(ii) cation from aqueous solution in the presence of the other cations. Various factors are optimized in order to obtain maximum transport efficiency. The PTC ligand is characterized by single crystal X-ray diffraction analysis, IR, NMR (¹⁹F, ³¹P, ¹H, ¹³C) and mass spectroscopy. The complex formation reaction between copper(ii) and PTC is studied by a conductometric method, which shows the 1 : 1 stoichiometry for ligand and copper(ii).

Selective transport of Cu(ii) cation in the presence of six other cations across a bulk liquid membrane containing a novel phosphoric triamide carrier is studied.     

Removal of Pb(ii) and Cd(ii) from wastewater using arginine cross-linked chitosan–carboxymethyl cellulose beads as green adsorbent

A one pot approach has been explored to synthesize crosslinked beads from chitosan (CS) and carboxymethyl cellulose (CM) using arginine (ag) as a crosslinker. The synthesized beads were characterized by FTIR, SEM, EDX, XRD, TGA and XPS analysis. The results showed that CS and CM were crosslinked successfully and the obtained material (beads) was analyzed for adsorption of Cd(ii) and Pb(ii) by using batch adsorption experiments; parameters such as temperature, contact time, pH and initial ion concentration were studied. Different kinetic and thermodynamic models were used to check the best fit of the adsorption data. The results revealed that the kinetics data of the adsorption of Pb(ii) and Cd(ii) ions shows the best fit with the pseudo second order model whereas the thermodynamics data shows the best fit with the Langmuir isotherm with maximum adsorption capacities of 182.5 mg g⁻¹ and 168.5 mg g⁻¹ for Pb(ii) ions Cd(ii) ions, respectively. For the recovery and the regeneration after the one use of the beads, several adsorption–desorption cycles were carried out to check the reusability and recovery of both the metal ion and the adsorbent without the loss of maximum adsorption efficiency.

Remediation of Pb(ii) and Cd(ii) containing wastewater by arginine crosslinked chitosan/carboxymethyl cellulose beads.     

Recovery of cobalt from dilute aqueous solutions using activated carbon–alginate composite spheres impregnated with Cyanex 272

A novel adsorbent was designed for selective recovery of cobalt(ii) from synthetic binary cobalt(ii)–nickel(ii) and cobalt(ii)–manganese(ii) solutions, a synthetic multi-element solution and a real aqueous waste stream from the petrochemical sector. The adsorbent consisted of shaped activated carbon–alginate spheres impregnated with Cyanex 272. The synthesis was followed by characterisation using SEM, infrared spectroscopy, BET analysis and elemental analysis. Good selectivity for cobalt(ii) over nickel(ii) could be achieved during adsorption, while this was not the case for cobalt(ii) over manganese(ii). Cobalt(ii) and manganese(ii) were therefore fully adsorbed and stripped using a dilute sulphuric acid solution. The adsorbent was shown to be reusable in a column setup. Finally, the adsorbent material was used for the purification of a real aqueous waste stream from the petrochemical sector.

Waste water was purified from cobalt(ii) and manganese(ii) by adsorption and desorption on shaped and impregnated activated carbon spheres.     

Studies on a glutathione coated hollow ZnO modified glassy carbon electrode; a novel Pb(ii) selective electrochemical sensor

Herein, we report the electrochemical detection of heavy metal ions such as Pb(ii), Cd(ii) and Hg(ii) ions while using glutathione coated hollow ZnO modified glassy carbon electrode (Glu-h-ZnO/GCE). An excellent voltammetric response of the modified electrode towards these metal ions was observed by different voltammetric techniques. Among the different target metal ions, a selective electrochemical response (sensitivity = 4.57 μA μM⁻¹) for the detection of Pb(ii) ions was obtained with differential pulse voltammetric (DPV) measurements. Besides, under optimal experimental conditions and in the linear concentration range of 2–18 μM, a very low detection limit of 0.42 μM was obtained for Pb(ii) ion. The observed electrochemical behaviour of Glu-h-ZnO/GCE towards these metal ions is in conformity with the band gap of the composite in the presence of various test metal ions. The band gap studies of the composite and various “Composite-Metal Ion” systems were obtained by reflectance as well as by computational methods where results are in close agreement, justifying the observed electrochemical behaviour of the systems. The lowest band gap value of the “Composite-Pb” system may be the reason for the excellent electrochemical response of the Glu-h-ZnO modified GCE towards the detection of Pb(ii) ion.

Decrease in the band gap of the "Composite-Metal" systems in comparison to pure composite is a key factor in the electrochemical detection of heavy metal ions such as Pb(ii), Cd(ii) and Hg(ii) ions while using glutathione coated hollow ZnO modified glassy carbon electrode (Glu-h-ZnO/GCE).     

Selective removal of silver(i) using polymer inclusion membranes containing calixpyrroles

This paper discusses the results of studies on the transport of Ag(i) across polymer inclusion membranes (PIMs), derivatives of calixpyrroles with methyl (KP1) and carboxyl (KP2) groups, as ion carriers, o-nitrophenyl pentyl ether (o-NPPE) as a plasticizer and cellulose triacetate (CTA) as support. The influence of the pH of the source phase, metal concentration, stripping phase as well as carrier and plasticizer concentration on the efficiency of Ag(i) transport through PIM is presented. Long-term experiments with a supported liquid membrane and a plasticizer membrane demonstrate the durability of the studied PIMs. The obtained results indicate that the competitive transport of Cu(ii), Zn(ii), Ag(i) and Cd(ii) from the aqueous nitrate source phase through KP1 and KP2 is an effective separation method for Ag(i) ions. The prepared PIMs were characterized by scanning electron microscopy (SEM), and atomic force microscopy (AFM) techniques.

The transport of Ag(i) across polymer inclusion membranes is reported with derivatives of calixpyrroles with methyl (KP1) and carboxyl (KP2) groups as ion carriers, o-nitrophenyl pentyl ether as a plasticizer and cellulose triacetate as support.