Removal of Copper(II) and Zinc(II) from Aqueous Solutions Using a Lignocellulosic-Based Polymeric Adsorbent Containing Amidoxime Chelating Functional Groups

In this study, the adsorption of Cu(II) and Zn(II) ions from aqueous solutions onto amidoximated polymerized banana stem (APBS) has been investigated. Infrared spectroscopy was used to confirm graft copolymer formation and amidoxime functionalization. The different variables affecting the sorption capacity such as pH of the solution, adsorption time, initial metal ion concentration, and temperature have been investigated. The optimum pH for maximum adsorption was 10.5 (99.99%) for Zn²⁺ and 6.0 (99.0%) for Cu²⁺ at an initial concentration of 10 mg L^?1. Equilibrium was achieved approximately within 3 h. The experimental kinetic data were analyzed using pseudo-first-order and pseudo-second-order kinetic models and are well fitted with pseudo- second-order kinetics. The thermodynamic activation parameters such as ΔG^o, ΔH^o, and ΔS^o were determined to predict the nature of adsorption. The temperature dependence indicates an exothermic process. The experimental isotherm data were well fitted to the Langmuir model with maximum adsorption capacities of 42.32 and 85.89 mg g^?1 for Cu(II) and Zn(II), respectively, at 20°C. The adsorption efficiency was tested using industrial effluents. Repeated adsorption/regeneration cycles show the feasibility of the APBS for the removal of Cu(II) and Zn(II) ions from water and industrial effluents.     

Solid-phase extraction for simultaneous separation and preconcentration of Fe(III) and Zn(II) traces using three chelatants and Ramelak bark-derived activated carbon as a new bio-sorbent

This article introduces a comparative study for the simultaneous separation and preconcentration of Fe(III) and Zn(II) traces in various water samples using three well-known ligands as chelating agents and activated carbon (AC) derived from Ramelak bark as a new bio-sorbent prior to the determination by ?ame atomic absorption spectrometry. The chelating agents were 4,4’-[(4-Cyano-phenyl)methylene]bis(3-methyl-1-phenyl-1H-pyrazol-5-ol) (CMBM), diethyldithiocarbamate (DDTC) and ammonium pyrrolidine dithiocarbamate (APDC). CMBM was synthesized by a procedure reported in the literature. The newly prepared AC was characterized by Scanning Electron Microscopy (SEM) and Fourier-Transform Infrared (FTIR) Spectrometry. The analytical parameters affecting the separation efficiency of the analytes including pH, shaking time, chelating agent volume (concentration), sorbent mass, sample ?ow rate and elution conditions were investigated and discussed. Common coexisting ions did not seriously interfere with the separation, showing the good selectivity of the proposed method. The calibration graph was linear in the range of 0.35–70, 0.50–80, 0.9–100, 0.55–75, 0.75–90 and 1.0–120 ng mL^?1 for Fe-CMBM, Fe-DDTC, Fe-APDC, Zn-CMBM, Zn-DDTC and Zn-APDC, respectively. Under optimized conditions, the limits of detection were 0.11, 0.13, 0.27, 0.16, 0.22 and 0.30 ng mL^?1 for Fe-CMBM, Fe-DDTC, Fe-APDC, Zn-CMBM, Zn-DDTC and Zn-APDC, respectively. The proposed method has been applied to the determination of Fe(III) and Zn(II) in different water samples with satisfactory recovery percentages. The developed method, validated with standard reference materials, was used successfully in determining the concentrations of metal ions in water samples.     

Separation and concentration processes of solutions of Co(II), Ni(II), Cr(III), Fe(III) and Mn(II) by extraction with toluene-dissolved rosin

The extraction and stripping of Co(II), Ni(II), Cr(III) and Fe(III) from aqueous solutions by rosin dissolved in toluene has been investigated. Results obtained show that rosin is better extractant than abietic or n-lauric acids under comparable conditions. From these results, and the data of Mn(II) solvent extraction studied previously under the same conditions, a separation and concentration process for these five cations in aqueous solutions has been designed. Saturated solutions of Fe(III), Cr(III), Mn(II) and finally Co(II) and Ni(II) have been obtained successively by extraction and stripping, by addition of ammonium hydroxide to obtain the appropriate pH value, and by modifying adequately the organic phase/aqueous phase volume ratio.     

HEAVY METAL EXTRACTION WITH THIOCARBAMIC-O-ALKYLESTERS

ABSTRACT

Two types of thiocarbamic-O-alkylesters, four bidentate ligands HL and one bis-bidentate ligand H₂L, were used as extractants for heavy metal ions from aqueous solutions. Silver(I) was extracted as neutral complexes in a yield > 99 %. The underlying stoichiometry and the extraction constants are discussed. The extraction of silver&I) by the bis-bidentate ligand is significantly more effective than the extraction by the analogous bidentate compound. In a dioxane/water mixture neutral, cationic and anionic silver complexes were found by means of pAg and pH potentiometric titrations. The extraction behavior is discussed with regard to the calculated stability constants.     

Selective Transport of Cu(II) across a Polymer Inclusion Membrane with 1-Alkylimidazole from Nitrate Solutions

The selective transport of copper(II), zinc(II), cobalt(II), and nickel(II) ions from nitrate solutions across polymer inclusion membranes (PIMs), which consist of cellulose triacetate as polymeric support, o-nitrophenyl pentyl ether as plasticizer, and 1-alkylimidazole (alkyl from hexyl- to decyl) as ion carrier was reported. PIM was characterized by using atomic force microscopy (AFM) technique. The results show that Cu(II) can be separated very effectively from other transition metal cations as Zn(II), Co(II), and Ni(II) (at a concentration of 10^?3 mol/dm³ each). Alkyl substituents at position 1 of the imidazole ring have been found to affect the hydrophobic properties and initial flux of the transported metal ions. The efficiency of separation of metal ions by 1-alkylimidazole followed the sequence: Cu(II) > Zn(II) > Co(II) > Ni(II). The highest selectivity coefficient for Cu(II) was found with 1-hexylimidazole and its 1 mol/dm³ solution in PIM. Separation of the ions was more effective for the nitrates(V) than for chlorides.     

琥珀酰化壳聚糖-铜(Ⅱ)-苯并咪唑衍生物配合物的合成、表征及抗菌活性

文章利用琥珀酸酐对壳聚糖进行改性,并合成了两个新的配合物:sucts-Cu(Ⅱ)-hpb(1)和sucts-Cu(Ⅱ)-tbz(2)[sucts=琥珀酰化壳聚糖,hpb=2-(2’-吡啶)-苯并咪唑,tbz=2-(4′-噻唑基)苯并咪唑]。应用红外光谱,紫外-可见光谱,原子吸收光谱对配合物进行了表征,采用试管倍比稀释法研究了这些配合物对苏云金杆菌、枯草芽孢杆菌、大肠杆菌和金黄色葡萄球菌的抑制作用。结果表明,两种配合物对四种细菌均有较强的抑菌活性,配合物1、2,最小抑菌浓度(MIC)分别为62.5～125μg.mL-1和125～250μg.mL-1,抗菌效果明显强于自由配体。     

Synthesis, Spectral and Antibacterial Studies of Copper(II) Tetraaza Macrocyclic Complexes

A novel family of tetraaza macrocyclic Cu(II) complexes [CuLX(2)] (where L = N(4) donor macrocyclic ligands) and (X = Cl(-), NO(3) (-)) have been synthesized and characterized by elemental analysis, magnetic moments, IR, EPR, mass, electronic spectra and thermal studies. The magnetic moments and electronic spectral studies suggest square planar geometry for [Cu(DBACDT)]Cl(2) and [Cu(DBACDT)](NO(3))(2) complexes and distorted octahedral geometry to the rest of the ten complexes. The biological activity of all these complexes against gram-positive and gram-negative bacteria was compared with the activity of existing commercial antibacterial compounds like Linezolid and Cefaclor. Six complexes out of twelve were found to be most potent against both gram-positive as well as gram-negative bacteria due to the presence of thio group in the coordinated ligands.     

Synergistic Solvent Extraction and Transport of Zn(II) and Cu(II) across Polymer Inclusion Membranes with a Mixture of TOPO and Aliquat 336

Separation of zinc(II) and copper(II) ions from aqueous solutions by synergistic extraction and transport through polymer inclusion membranes (PIMs) has been investigated. A mixture of trioctylphosphine oxide (TOPO) and trioctymethylammonium chloride (Aliquat 336) was used as a selective extractant as well as an ion carrier in polymer membranes. The effects of hydrochloric acid concentration in the aqueous phase and extractants concentration in the organic phase on the separation process of zinc(II) and copper(II) ions have been studied. Zn(II) ions were successfully separated from Cu(II) ions in solvent extraction process using 0.025 M TOPO and 0.06 M Aliquat 336 in kerosene. Polymer inclusion membranes (PIMs) containing a mixture of TOPO and Aliquat 336 as the ion carrier have been prepared and the facilitated transport of Zn(II) and Cu(II) ions has been studied. The influence of membrane composition on the transport kinetic of Zn(II) and Cu(II) has been evaluated. Zn(II) ions were preferably transported from the aqueous solutions containing Cu(II) and above 87% of Zn(II) ions were effectively recovered from the 0.5 M HCl solution as the source phase through PIM into 0.5 M H₂SO₄ as the stripping phase.     

Copper Ion Extraction by a Mixture of Fatty Hydroxamic Acids Synthesized from Commercial Palm Olein

Abstract

A mixture of fatty hydroxamic acids (FHA), synthesized from a commercial palm olein, was evaluated as an extractant for extraction of copper ion from aqueous media. The content of hydroxamic acid groups in the FHA, analyzed by elemental analysis, was 3.52 mmol/g. Copper extraction from aqueous media was studied by solvent extraction technique using octanol as an organic phase. The extraction of copper ion was through the formation of 1∶2 (Cu(II)∶FHA) complex, pH dependent and not affected by the presence of a large amount of Co(II), Ni(II), Cd(II) and Zn(II) ions.     

Synergistic extraction and separation of Fe(III) and Zn(II) using TBP and D2EHPA

Waste chloride pickle liquors from hot-dip galvanizing plants, steel plants and flue dust contain reasonable amounts of heavy metals such as Zn, Cr, Ni, etc. Iron is invariably associated with most of these materials and comes into solution during leaching. Thus, the synergistic extraction of zinc(II) and iron(III) from leach solutions in tri-n-butyl phosphate (TBP)–di(2-ethylhexyl) phosphoric acid (D2EHPA) system diluted in kerosene was investigated. The Zn and Fe concentrations in the leach liquor used in the present study were 2 g/L. Experiments were carried out in the pH range of 0.5–4.0, temperature of 25°C, using sole D2EHPA, sole TBP and D2EHPA–TBP mixtures at different ratios. Results showed that the co-extraction of zinc(II) and iron(III) increased with increasing equilibrium pH using D2EHPA. It is demonstrated that the mixtures of TBP and D2EHPA are more efficient and selective than D2EHPA alone. At low pH values, the separation factor is low when pure D2EHPA is used as an extractant; however, using TBP as a synergist, the separation factor increases and results in a better separation of zinc from iron. Increasing TBP to D2EHPA ratios in the organic phase caused a slight shift to the right in the extraction isotherm of iron and a marked shift to the right in the extraction isotherm of zinc, and the maximum separation factor of 13.3 × 10³ was achieved at a TBP to D2EHPA volume ratio of 4:1 (0.58 M TBP: 0.12 M D2EHPA). Furthermore, the effect of equilibrium pH, organic to aqueous phase ratio and Cl^? concentration on the selective extraction was investigated. Using two extraction stages at the O/A ratio of 2:1 and pH_e (equilibrium pH) of 3 and 1 for zinc and iron, respectively, 99% of zinc(II) and 96.25% of iron(III) were extracted.     

The Effect of the Synthetic Conditions on the Deposition and Distribution of Copper Complexes on Polymer Supports

The influence of conditions (e.g., ratios of components, temperature etc.) on the reaction of Cu(OCOCH₃)₂·2H₂O with polyethylene grafted-polyacrylic on the amount of the metal and the composition of the immobilized Cu(II) complexes was studied. The concentration dependence obeys the Langmuir law. Analysis of the data leads to an evaluation of the stability constant for the Cu(II) complexes (K=300 l/mole at 333 K). The constant corresponds to a Cu(II) fixation value, k=0.35 mole/l (22.22 mg Cu(II)/g). The multistage fixation mechanism for Cu(II) complex formation was demonstrated by the marked atom technique. Cu(II) is fixed by one carboxylate group (to 16 mol% of the supported Cu(II), K ₁=16×10^–2 mole/g) and by two carboxylate groups (K ₂=2.54×10^–3 mole/g) of the grafted ligands. The PE-gr-PAA–Cu(II) system mimics the situation-insoluble support-soluble functional polymer covering and realizes the advantages of both the soluble and the three-dimensional crosslinked polymer. Steady-state magnetic susceptibility measurements and ESR spectroscopy were used to study the distribution of cupric ion attached to a polyethylene-grafted poly(acrylic acid) support. The existence of three types of cupric ion complexes was demonstrated: (1) isolated complexes, (2) complexes bonded by dipole–dipole interactions, and (3) clusters with strong exchange interactions. The mean distances between the isolated ions (¯r22–15 Å) and between the dipole–bound complexes (¯r _agreg7 Å) were estimated. The results obtained were compared to the data for other immobilized catalysts. Preliminary results on the fixation of bimetallic Cu(II) and Pd(II) complexes to the polymers as well as on their distributions were obtained.     

Diastereoselective and Highly Enantioselective Henry Reactions using C1‐Symmetrical Copper(II) Complexes

Catalytic Henry reactions of aliphatic aldehydes and prochiral nitro compounds were investigated using copper(II) complexes of 14 C₁‐symmetrical ligands derived from (1R,2R)(−)‐diaminocyclohexane. β‐Nitro alcohols with syn:anti ratios of up to 5.7 and excellent ee values for both diastereosimers were obtained.     

Low temperature preparation of fluoroalkanes from a mixture of carbon tetrachloride,dichloromethane and anhydrous hydrogen fluoride using a fluorinated γ-alumina supported iron(II,III)/cobalt(II,III) oxide catalyst

1,1,1,2-tetrafluoroethane has been prepared at 473 K under static conditions, from a feedstock of carbon tetrachloride, dichloromethane and anhydrous hydrogen fluoride using a-alumina supported fluorinated Co(II, III)₈₅Fe(II, III)₁₅O_x catalyst. Conversion to hydrofluoroalkanes was ca. 58% efficiency as quantified by liquid phase¹⁹F NMR analysis.     

Selective extraction of In(III), Ga(III) and Zn(II) using a novel extractant with phenylphosphinic acid

A new extractant, [N,N-di(2-ethylhexyl)amino]methylphenylphosphinic acid (DEAPP), was synthesized to de-velop the mutual separation techniques of In(III), Ga(III) and Zn(II). The extraction selectivity for In(III), Ga(I I) and Zn(II) with DEAPP was higher than that of the commercial phosphorus acid extractants such as D2EHPA and PC-88A. The extraction selectivity for metal ions in 1 mol·L?1 aqueous ammonium nitrate solution with DEAPP was in the following order:In(III) N Ga(III) N Zn(II). These selective extraction behaviors indicate that the amino moiety of DEAPP plays an important role in the mutual separation of In(III), Ga(III) and Zn(II). The extraction equilibria of In(I I), Ga(II ) and Zn(II) with DEAPP (=HR) were expressed by the following reactions:In3++2eHRT2?InR3eHRT+3H+, Ga3++1.5eHRT2+NO3??GaR2eHRTeNO3T+2H+, and Zn2++2eHRT2?ZnR2eHRT 2 + 2H+. The extraction equilibrium constants of In(III), Ga(III) and Zn(II) with DEAPP were determined to be Kex,M=1.7 × 104 [dm3·mol?1], 4.17 [(dm3·mol?1)0.5], and 1.55 x 10?2 [–], respectively.     

The Cytotoxic Effect of Copper (II) Complexes with Halogenated 1,3-Disubstituted Arylthioureas on Cancer and Bacterial Cells

A series of eight copper (II) complexes with 3-(4-chloro-3-nitrophenyl)thiourea were designed and synthesized. The cytotoxic activity of all compounds was assessed in three human cancer cell lines (SW480, SW620, PC3) and human normal keratinocytes (HaCaT). The complexes 1, 3, 5, 7 and 8 were cytotoxic to the studied tumor cells in the low micromolar range, without affecting the normal cells. The complexes 1, 3, 7 and 8 induced lactate dehydrogenase (LDH) release in all cancer cell lines, but not in the HaCaT cells. They provoked early apoptosis in pathological cells, especially in SW480 and PC3 cells. The ability of compounds 1, 3, 7 and 8 to diminish interleukin-6 (IL-6) concentration in a cell was established. For the first time, the influence of the most promising Cu (II) complexes on intensities of detoxifying and reactive oxygen species (ROS) scavenging the enzymes of tumor cells was studied. The cytotoxic effect of all copper (II) conjugates against standard and hospital bacterial strains was also proved.     

The Extraction and Separation of Ho,Y, and Er(III) with the Mixtures of Cyanex 302 and Another Organic Extractant

Abstract

The extraction and separation of Ho, Y, and Er(III) with the mixtures of bis(2,4,4‐trimetylpentyl)monothiophosphinic acid (Cyanex 302) and another organic extractant, such as acidic organic extractant (di‐2‐ethylhexyl phosphoric acid P204, 2‐ethylhexyl phosphoric acid mono‐2‐ethylhexyl ester P507, di‐2‐ethylhexyl phosphinic acid P229, and sec‐nonylphenoxy acetic acid CA‐100), neutral organic extractant (tri‐n‐butyl phosphate TBP, di‐(1‐metylheptyl)metyl phosphate P350, and branched trialkylphosphinic oxide Cyanex 925) or primary amine N1923, has been investigated in this paper. The extractability and separation ability for the Ho, Y, and Er with the mixtures of Cyanex 302 and organic extractants has been compared. The synergistic effect of the Ho, Y, and Er extraction with the mixtures of Cyanex 302 and P229, Cyanex 925, CA‐100, or N1923 has been explored and the synergistic enhancement coefficients have been calculated. At last, the Y³⁺ synergistic extraction with the mixtures of Cyanex 302 and CA‐100 has been determined and the extracted complex has been deduced.     

Homogeneous catalysts for ethylene polymerization based on bis(imino)pyridine complexes of iron, cobalt, vanadium and chromium

Results of a comparative study of ethylene polymerization activity and the structure of polyethylene (PE) produced over homogeneous catalysts based on bis(imino)pyridine complexes with close ligand frameworks and different transition metal centers (Fe(II), Co(II), Cr(III) and V(III)) are reported. The effects of the activator nature and polymerization conditions on the activity of these complexes and the resulting PE structure (molecular weight, molecular weight distribution, content of methyl and vinyl groups) have been studied. The experimental data obtained under comparable conditions demonstrate a pronounced effect of transition metal center on the catalytic properties of bis(imino)pyridine complexes (polymerization activity, copolymerization reactivity, thermal stability, PE structure, composition of optimal activator, formation of single-site or multiple-site catalytic system).     

Supported catalysts based on 2,6-bis(imino)pyridyl complex of Fe(II): DRIFTS study of the catalyst formation and data on ethylene polymerization

The supported catalysts for ethylene polymerization were prepared by interaction of 2,6-bis[1-(2,6-dimetilphenylimino)-ethyl]pyridineiron(II) dichloride (LFeCl₂) with silica and alumina. The catalysts exhibit high and stable activity at ethylene polymerization in presence of Al(i-Bu)₃ as co-catalyst. LFeCl₂ interaction with surface functional groups of the supports was studied by means of DRIFTS. LFeCl₂ adsorbed on the support surface mainly retains its structure. LFeCl₂ is strongly bounded to the support due to formation of multiple bonds between LFeCl₂ and surface functional groups of the supports. DRIFTS data on the state of the surface iron compounds have been obtained using CO as probe molecule.     

Extraction of Copper(II) Ions from Chloride and Sulphate Solutions Using Hydrophobic Pyridyl Ketoximes

Hydrophobic pyridyl ketoximes: 1-(2-pyridyl)tridecan-1-one oxime, 1-(3-pyridyl)tridecan-1-one oxime and 1-(4-pyridyl)tridecan-1-one oxime have been synthesized and investigated as extractants of copper(II) ions. Removal of metal ions was conducted from chloride, sulphate, and sulphate/chloride solutions. The influence of pH of aqueous solutions, copper(II), chloride, and sulphate ions and ligand concentration for extraction process were studied. Copper(II) extraction by hydrophobic 2-, 3-, and 4-pyridyl ketoximes from sulphate solutions is not possible. However, addition of chloride ions to initial sulphate media enables metal removal. The oxime of 1-(2-pyridyl)tridecane-1-one was determined as the strongest extractant of the tested oximes, but metal stripping was impossible. For the rest of the studied extractants the stripping process could be done using water or diluted mineral acid.