The Synthesis of New N2S2‐Macrocyclic Schiff Base Ligands and Investigation of Their Ion Extraction Capability from Aqueous Media

Abstract

Two new macrocyclic Schiff bases, (5) and (7), containing nitrogen‐sulfur donor atoms were designed and synthesized by reaction of α,α′ bis(o‐aminophenylthio)‐1,2‐xylene with glyoxal and phthaldialdehyde, respectively. The liquid‐liquid extraction of metal picrates such as Ag⁺, Hg²⁺, Cd²⁺, Zn²⁺, Cu²⁺, Ni²⁺, Mn²⁺, K⁺, and Na⁺ from aqueous phase to the organic phase was carried out using the novel ligands. The effect of chloroform and dichloromethane as organic solvents over the metal picrate extractions was investigated at 25±0.1°C by using UV‐visible spectrometry. The extractability and selectivity of the tested metal picrates were evaluated. The values of the extraction constants (log K_ex) were determined for the extracted complexes.     

Evaluation of a (E,E)‐Dioxime Containing Two 15‐Membered Dioxatrithiamacrocycles and its Mononuclear Ni(II) Complex as Ag+ Extractants

Abstract

A macrocyclic vic‐dioxime (1) and its mononuclear Ni(II) complex (2) were studied as extractant. The aqueous solutions of Ag⁺, Mn²⁺, Pb²⁺, Ni²⁺, Cu²⁺, Cd²⁺, and Zn²⁺ picrates were used for extraction experiments. The solutions of the ligands in two different organic solvents were used as organic phases. The metal picrate extractions were carried out at 25±0.1°C by using UV‐visible spectrometry. The most effective transport was observed for Ag⁺ picrate among the tested metal picrates. The effect of pH on the extraction of Ag⁺ picrate was evaluated with the ligands. The ratio of extracted Ag‐complex to chloroform phase was 2:1 (L:M) for (2). In other cases the ratios were 1:1 for both (1) and (2). Molar ratio method was also used to demonstrate the composition. The values of the extraction constants (log K_ex) were determined for the extracted Ag‐complexes.     

New Heavy Metal Ion‐Selective Macrocyclic Ligands with Nitrogen and Sulfur Donor Atoms and their Extractant Properties

Abstract

Two new macrocyclic ligands, containing nitrogen and sulfur donor atoms were designed and synthesized in a multi‐step reaction sequence. The macrocycles with amide group were used in solvent extraction of picrates of metals such as Ag⁺, Hg²⁺, Cd²⁺, Zn²⁺, Cu²⁺, Ni²⁺, Mn²⁺, Co²⁺ and Pb²⁺ from aqueous phase to the organic phase. The metal picrate extractions were investigated at 25±0.1°C by using UV‐visible spectrometry. The extractability and selectivity of the mentioned metal picrates were evaluated according to the organic solvents. The values of the extraction constants (log K_ex) and the complex compositions were determined for the extracted complexes.     

Competitive Adsorption of Ag+, Pb2+, Ni2+, and Cd2+ Ions on Vermiculite

Competitive adsorption of Ag⁺, Pb²⁺, Ni²⁺, and Cd² ions on vermiuculite in a binary, ternary, and quaternary mixture was investigated in batch experiments. The effects of the presence of Ag⁺, Ni²⁺, and Cd²⁺ ions on the adsorption of Pb²⁺ ions were investigated in terms of the equilibrium isotherm. Experimental results indicated that Pb²⁺ ions always favorably adsorbed on vermiculite over Ag⁺, Ni²⁺, and Cd²⁺ ions. The adsorption equilibrium data of Pb²⁺ ions better fitted the Langmuir model than the Freundlich model. The results showed that the pseudo-second-order kinetics model was in good agreement with the experimental results for all metal ions, and the adsorption rate among the metal ions followed Ag⁺ > Pb²⁺ > Ni²⁺ > Cd²⁺. The desorption and regenration study indicated that vermiculite can be used repeatedly and be suitable for the design of a continuous process.     

Synthesis and Metal‐ion Binding Properties of New N2S4O2‐ and N2S5O2‐Donor Macrocycles

Abstract

Synthetic procedures for new mixed‐donor macrocycle compounds were reported. The macrocyclic compounds were used in solvent extraction metal picrates such as Ag⁺, Hg²⁺, Cd²⁺, Zn²⁺, Cu²⁺, Ni²⁺, Mn²⁺, Pb²⁺, and Co²⁺. The metal picrate extractions were investigated at 25±0.1°C with the aid of UV‐visible spectrometry. It was found that 6,7,9,10,12,13,23,24‐octahydro‐19H,26Hdibenzo[h,t](1,4,7,13,16,22,10,19) dioxatetrathiadiazasiclotetracosine‐20,27(21H,28H)‐dione showed selectivity towards Ag⁺, Hg²⁺, and Cd²⁺ among the other metals. The extraction constants (Log K_ex) and complex compositions were determined for the Ag⁺ and Hg²⁺ complexes for this compound and 9,10,12,13,23,24,26,27,29,30‐decahydro‐5H,15H‐dibenzo‐[h,w][1,4,7,13,16,19,25‐,10,22] dioxapentathiadiazacycloheptacosine‐6,16(7H,17H)‐dione.     

Synergistic and selective extraction of Cd2+ from acidic solution containing Cd2+, Co2+, Ni2+ by triisooctylamine (TIOA) and tributyl phosphate (TBP)

Selective and synergistic extraction of cadmium from acidic iodine solutions containing Cd²⁺, Co²⁺ and Ni²⁺using solvent extraction (SX) technique is presented in this study. The study has highlighted the importance of main and synergistic extractants composition. The mixtures have evident synergistic effects on Cd²⁺ with a synergistic enhancement factor of 2.22. The various experimental parameters were studied to determine the optimum extraction and stripping conditions of Cd²⁺. Under optimum conditions, the maximum extraction efficiency (99.7%) was achieved when using 1.5% (v/v) TIOA and 0.5% (v/v) TBP in dichloromethane within 5 min. Extracted Cd²⁺ was stripped effectively from the organic phase using 2.0 mol/L NaOH solution.     

Liquid-liquid extraction of metal ions,DFT and TD-DFT analysis for some pyrane derivatives with high selectivity for Fe(II) and Pb(II)

Liquid-liquid extraction of metal ions using pyrane derivatives was studied. Fe²⁺, Zn²⁺, Cu²⁺, Co²⁺, Cd²⁺, Ni²⁺, and Pb²⁺ were extracted from the aqueous phase into the organic phase and the extractability for each metal was determined by atomic absorption. Interestingly, a competitive extraction was also investigated and then examined at different pH in order to explore the effect of the different substituent groups on metal extraction. We found high selectivity towards Fe²⁺ (91.8%) and Pb²⁺ (90.7%). In addition, geometry optimizations of the ground and excited-states of the selective ligands in order to get better insight into the geometry and the electronic structure were carried out by DFT and TD-DFT calculations.     

Comparative Study of Zn2+, Cd2+, and Pb2+ Removal From Water Solution Using Natural Clinoptilolitic Zeolite and Commercial Granulated Activated Carbon. Equilibrium of Adsorption

Abstract

The aim of this work is to study the effectiveness of regional, low-cost natural clinoptilolitic zeolite tuff in heavy metal ions removal from aqueous solution, through comparative study with commercial granulated activated carbon. The equilibrium of adsorption of Cd²⁺, Pb²⁺, and Zn²⁺ on both adsorbents have been determined at 25, 35, and 45°C in batch mode. The granulated activated carbon has shown around three times higher adsorption capacity for Cd²⁺ and Zn²⁺ than natural zeolite, and almost the same adsorption capacity for Pb²⁺ as the natural zeolite. The metal ion selectivity series Pb²⁺ > Cd²⁺ > Zn²⁺, on a mass basis, has been obtained on both adsorbents. The Langmuir and Freundlich model have been used to describe the adsorption equilibrium. The thermodynamic parameters were calculated from the adsorption isotherm data obtained at different temperatures. The study of the influence of the acidity of the metal ion aqueous solution has shown an increase of metal ion uptake with increase of the pH. The sorption mechanism of Cd²⁺, Pb²⁺, and Zn²⁺ on natural zeolite changes from ion-exchange to ion-exchange and adsorption of metal-hydroxide with increase of the pH from 2 to 6 (and 7 for Zn²⁺). The preliminary cost calculation, based on adsorbents maximum adsorption capacity and their price, have revealed the potential of natural zeolite as an economic alternative to the granulated activated carbon in the treatment of heavy metal polluted wastewater.     

Removal of Cd2+, Cu2+, Ni2+, and Pb2+ ions from aqueous solutions using tururi fibers as an adsorbent

This work investigates the removal of Cd²⁺, Cu²⁺, Ni²⁺, and Pb²⁺ ions from aqueous solutions using tururi fibers as an adsorbent under both batchwise and fixed‐bed conditions. It was found that modification of the tururi fibers with sodium hydroxide increased the adsorption efficiencies of all metal ions studied. The fractional factorial design showed that pH, adsorbent mass, agitation rate, and initial metal concentration influenced each metal adsorption differently. The kinetics showed that multi‐element adsorption equilibria were reached after 15 min following pseudo‐second‐order kinetics. The Langmuir, Freundlich, and Redlich–Peterson models were used to evaluate the adsorption capacities by tururi fibers. The Langmuir model was found to be suitable for all metal ions. Breakthrough curves revealed that saturation of the bed was reached in 160.0 mL with Cd²⁺ and Cu²⁺, and 52.0 mL with Ni²⁺ and Pb²⁺. The Thomas model was applied to the experimental data of breakthrough curves and represented the data well. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40883.     

Welan Gum-Modified Cellulose Bead as an Effective Adsorbent of Heavy Metal Ions (Pb2+, Cu2+, and Cd2+) in Aqueous Solution

A novel welan gum-modified cellulose adsorbent was prepared through emulsification, regeneration, and modification. SEM and FTIR were used to characterize the modified cellulose adsorbent. The adsorption isotherms of metal ions on the adsorbent were well fitted by Langmuir model, with the maximum adsorption capacities of 83.6, 77.0, and 67.4 mg/g for Cd²⁺, Pb²⁺, and Cu²⁺, respectively. The adsorption kinetics was well described using the pseudo-first-order model. Moreover, the adsorption capacities for the three metal ions increased with the increase of temperature, and the optimal pH was 5. Furthermore, the thermodynamic analysis indicated that the adsorption processes were spontaneous and endothermic.     

L-cystein modified bentonite-cellulose nanocomposite (cellu/cys-bent) for adsorption of Cu2+, Pb2+, and Cd2+ ions from aqueous solution

In this study, L-cystein modified bentonite-cellulose (cellu/cys-bent) nanocomposite was synthesized and characterized by XRD, FTIR, SEM with EDS, TGA, and TEM techniques. In order to optimize the process the effect of various operational parameters such as pH, adsorbent dosage, contact time, and temperature were also investigated. The adsorption experiments were carried out in initial concentrations range of 20-100 mg L^?1and the adsorbent affinity for metal ions was found to be in order of Cu²⁺ > Pb²⁺ > Cd²⁺. The optimum pH for adsorption of Cu²⁺ and Cd²⁺ was observed at 5 while for Pb²⁺ it was pH 6. Based on the Langmuir model, the maximum adsorption capacity of Cu²⁺, Pb²⁺, and Cd²⁺ at 50^?C was found to be 32.36, 18.52, and 16.12 mg g^?1, respectively. The Langmuir isotherm and pseudo-second order model were found to be better fitted than the other isotherms and kinetic models. The results of thermodynamic parameters confirmed the process to be endothermic and spontaneous in nature.     

C,N‐Pyridylpyrazole‐Based Ligands: Synthesis and Preliminary Use in Metal Ion Extraction

Abstract

The synthesis of new N‐donor pyridylpyrazole ligands with a functionalized arm is described. The complexation capabilities of these compounds towards bivalent metal ions (Hg²⁺, Cd²⁺, Pb²⁺, Cu²⁺, and Zn²⁺) and alkali metal ions (K⁺, Na⁺, and Li⁺) were investigated using the liquid‐liquid extraction process. The percentage limits of extraction were determined by atomic absorption measurements.     

Poly(2‐acrylamido glycolic acid‐co‐2‐acrylamido‐2‐methyl‐1‐propane sulfonic acid): Synthesis,characterization, and retention properties for environmentally impacting metal ions

Poly(2‐acrylamido glycolic acid‐co‐2‐acrylamido‐2‐methyl‐1‐propane sulfonic acid) [P(AGA‐co‐APSA)] was synthesized by radical polymerization in an aqueous solution. The water‐soluble polymer, containing secondary amide, hydroxyl, carboxylic, and sulfonic acid groups, was investigated, in view of their metal‐ion‐binding properties, as a polychelatogen with the liquid‐phase polymer‐based retention technique under different experimental conditions. The investigated metal ions were Ag⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Cd²⁺, Pb²⁺, and Cr³⁺, and these were studied at pHs 3, 5, and 7. P(AGA‐co‐APSA) showed efficient retention of all metal ions at the pHs studied, with a minimum of 60% for Co(II) at pH 3 and a maximum close to 100% at pH 7 for all metal ions. The maximum retention capacity (n metal ion/n polymer) ranged from 0.22 for Cd²⁺ to 0.34 for Ag⁺. The antibacterial activity of Ag⁺, Cu²⁺, Zn²⁺, and Cd²⁺ polymer–metal complexes was studied, and P(AGA‐co‐APSA)–Cd²⁺ presented selective antibacterial activity for Staphylococcus aureus with a minimum inhibitory concentration of 2 μg/mL. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

SORPTION PROCESSES OF NATURAL IRANIAN BENTONITE EXCHANGED WITH CD2+, CU2+, NI2+, AND PB2+ CATIONS

Experimental studies on the retention of cadmium (Cd²⁺), copper (Cu²⁺), nickel (Ni²⁺), and lead (Pb²⁺) by bentonite samples from Iran were conducted using single- and multiple-component solutions. Based on the sorption capacity of bentonite the following order was obtained for single- and multiple-component solutions: Pb²⁺ > Cd²⁺ > Ni²⁺ > Cu²⁺. The maximum adsorption capacities of bentonite with metals in single- and multiple-component solutions were 29.5%, 22.5%, 19.2%, and 17.1% and 13.5%, 13.4%, 12.1%, and 9.1% for Pb²⁺, Cd²⁺, Ni²⁺, and Cu²⁺, respectively. Desorption isotherms of Cd²⁺, Cu²⁺, Ni²⁺, and Pb²⁺ deviated significantly from the sorption isotherms, thereby indicating irreversible or very slowly reversible sorption. Finally, soil solution saturation indices and metal speciation were assessed using the Visual MINTEQ 2.6 program and the probability of mineral precipitation was supported by scanning electron microscopy.     

Ligating behavior and metal uptake of N‐sulphonylpolyamine chelating resins anchored on polystyrene‐divinylbenzene beads

Amberlite XAD‐2 has been functionalized by coupling through –SO₂‐with ethylenediamine, propylenediamine, and diethylenetriamine to give the corresponding polyamine chelating resins I–III. The solid metallopolymer complexes of the synthesized chelating resins with Cu²⁺, Zn²⁺, Cd²⁺, and Pb²⁺ were synthesized. The polyamine derivatives and their metal complexes were characterized by elemental analysis, spectral (IR, UV/V, and ESR), and magnetic studies. The batch equilibrium method was utilized for using the chelating polyamines for the removal of Cu⁺², Zn⁺², Cd⁺², and Pb⁺² ions from aqueous solutions at different pH values and different shaking times at room temperature. The selective extraction of Cu⁺² from a mixture of the four metal ions and the metal capacities of the chelating resins were evaluated using atomic absorption spectroscopy. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1839–1846, 2005     

Biosorption of aquatic Pb2+, Hg2+, and Cd2+ using a combined biosorbent—Aspergillus niger-Treated Rice Straw

The biosorbent used for removal of Pb²⁺, Hg²⁺, and Cd²⁺ from aqueous solutions was rice straw fermented by Aspergillus niger (ARS), and raw rice straw (RRS) was used as a control. When inoculum size, material–water ratio, and temperature were 10⁶, 100%, and 303K, respectively, the optimized spore number was 10⁹. The ARS exhibited a lager pore biosorption, which was better than RRS. The biosorption mechanism was involved in chelation with functional groups such as C-H, C = O, C-O, and C = C, and the biosorption data obtained were well described by the pseudo-second-order kinetic equation and the Freundlich isotherm model.     

Cd2+, Cu2+, Pb2+, Sr2+, and Y3+ binding characteristics of 17β‐estradiol molecularly imprinted polymer particles incorporated with dicyclohexano‐18‐crown‐6 for urine bioassay

The metal ion binding characteristics of molecularly imprinted polymer (MIP) submicron particles prepared using 17β‐estradiol (E2) as a template, and incorporated with dicyclohexano‐18‐crown‐6 (DCH18C6), were studied using differential pulse anodic stripping voltammetry. When Sr²⁺ was added to DCH18C6‐E2‐MIP particles already occupied by Cd²⁺, Cu²⁺, and Pb²⁺ inside the binding sites, a displacement reaction was observed: Cd²⁺/Cu²⁺/Pb²⁺‐DCH18C6‐E2‐MIP + Sr²⁺ = Sr²⁺‐DCH18C6‐E2‐MIP + Cd²⁺/Cu²⁺/Pb²⁺. This demonstrated that DCH18C6 had stronger binding affinity for Sr²⁺ than Cd²⁺ Cu²⁺ or Pb²⁺. Strong DCH18C6 binding affinity was also observed for Y³⁺. Atomic emission spectrometry showed that DCH18C6‐E2‐MIP particles (150 mg/mL) resulted in 52% binding of Sr²⁺ (2000 ppm, at pH 6.3 ± 0.1 and ionic strength of 0.1M NaNO₂). © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Sorption Studies of Terpolymers Based on p-Nitrophenol,Triethylenetetramine, and Formaldehyde

Terpolymer resins have been synthesized by condensation of p-nitrophenol, triethylenetetramine, and formaldehyde in the presence of 2 M NaOH as a catalyst with different molar proportions of monomers. Newly synthesized terpolymers were proved to be selective chelation ion exchangers for metal ions like Fe³⁺, Cu²⁺, Ni²⁺, Co²⁺, Zn²⁺, Cd²⁺, Hg²⁺, and Pb²⁺. A batch equilibrium study was carried out over a wide pH range, shaking time, and in media of various ionic strengths of different electrolytes and shows higher selectivity for Hg²⁺, Cd²⁺, and Pb²⁺. Distribution ratios of metal ions were found to be increased by increasing pH of solutions; hence the resins can be used to recover certain metals from waste solutions and removal of iron from boiler water.     

An investigation into transition metal ion binding properties of silk fibers and particles using radioisotopes

Silk is a structural protein fiber that is stable over a wide pH range making it attractive for use in medical and environmental applications. Variation in amino acid composition has the potential for selective binding for ions under varying conditions. Here we report on the metal ion separation potential of Mulberry and Eri silk fibers and powders over a range of pH. Highly sensitive radiotracer probes, ⁶⁴Cu²⁺, ¹⁰⁹Cd²⁺, and ⁵⁷Co²⁺ were used to study the absorption of their respective stable metal ions Cu²⁺, Cd²⁺, and Co²⁺ into and from the silk sorbents. The total amount of each metal ion absorbed and time taken to reach equilibrium occurred in the following order: Cu²⁺ > Cd²⁺ > Co²⁺. In all cases the silk powders absorbed metal ions faster than their respective silk fibers. Intensive degumming of the fibers and powders significantly reduced the time to absorb respective metal ions and the time to reach equilibrium was reduced from hours to 5–15 min at pH 8. Once bound, 45–100% of the metal ions were released from the sorbents after exposure to pH 3 buffer for 30 min. The transition metal ion loading capacity for the silk sorbents was considerably higher than that found for commercial ion exchange resins (AG MP‐50 and AG 50W‐X2) under similar conditions. Interestingly, total Cu²⁺ bound was found to be higher than theoretically predicted values based on known specific Cu²⁺ binding sites (AHGGYSGY), suggesting that additional (new) sites for transition metal ion binding sites are present in silk fibers. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

A Study of Complexation-ability of Neutral Schiff Bases to Some Metal Cations

The constants of the extraction equilibrium and the distribution for dichloromethane as an organic solvent having low dielectric constant of metal cations with chiral Schiff bases, benzaldehydene-(S)-2-amino-3-phenylpropanol (I), ohydroxybenzaldehydene-( S)-2-amino-3-phenyl-propanol (II), benzaldehydene-(S)-2- amino-3-methylbutanol (III) with anionic dyes [4-(2-pyridylazo)-resorcinol mono sodium monohydrate (NaPar), sodium picrat (NaPic) and potassium picrat (KPic)] and some heavy metal chlorides were determined at 25 ºC. All the ligands have given strongest complexation for NaPar. In contrast, similar behaviour for both alkali metal picrates is not apparent in the complexation of corresponding ligands.