Novel coumarin fluorescent dyes: Synthesis, structural characterization and recognition behavior towards Cu(II) and Ni(II)

A series of novel coumarin dyes (3-12) were designed and synthesized. The structures of the dyes were characterized by IR, ¹H NMR, ¹³C NMR, ¹⁹F NMR, MS and single crystal X-ray diffraction. 3-(2-Benzoylhydrazonotrifluoroethyl)-7-(N,N-diethylamino)coumarin (11) could recognize Cu²⁺ and Ni²⁺ selectively in aqueous solution. Upon addition of Cu²⁺ or Ni²⁺ to 11 a blue shift or a bathochromatic shift of the absorption band was observed while the emission band blue-shifted with decrease in the fluorescence intensity. Upon addition of Cu²⁺ the color of the solution of 11 changed from orange to red. The results showed that 11 could be used as an optical chemosensor of Cu²⁺ and Ni²⁺.     

新型salamo衍生物苦味酸铜(Ⅱ)配合物的合成与表征

以丙酮为溶剂,1,3-二胺氧丙烷双缩邻香草醛(H2L)与苦味酸铜反应,制备了一种新型salamo衍生物苦味酸铜(Ⅱ)配合物,其结构经元素分析,1HNMR,IR,TG-DTA及UV表征。结果表明,新型salamo衍生物是一种四齿配体,配合物的可能结构式为[Cu4L2(pic)4(H2O)2].2CH3COCH3.2H2O。     

Fast removal of Pb(II) and Cu(II) from contaminated water by groundwater treatment waste: impact of sorbent composition

ABSTRACT

A non-hazardous groundwater treatment waste (GWTW) was examined as a low-cost sorbent for Pb(II) and Cu(II) ions. The content of the dominant elements in GWTW was as follows: 78% Fe₂O₃, 7.4% P₂O₅, 7.4% CaO and 5.2% SiO₂. The removal of Pb(II) and Cu(II) was fast, and more than 67–95% of ions were accumulated by GWTW during the first 3 min. The sorption capacity of GWTW depends on solution pH, concentration and temperature. Equilibrium data fitted well with Langmuir–Freundlich and Langmuir-partition models. The inherently formed nano-adsorbent could be utilized for the treatment of water contaminated with Pb(II) and Cu(II) ions.     

Modelling of Cr(VI) removal from polluted groundwaters by ion exchange

This work reports the viability and modelling of the removal of Cr(VI) from polluted groundwaters by means of ion exchange using the resin Lewatit MP‐64. Feed groundwaters that contained Cr(VI) at an average concentration of 2431 mg dm^?3 and 1187 mg dm^?3 of chloride and 1735 mg dm^?3 of sulfate as main anions were acidified to a pH of 2.0 prior to the removal process. Dynamic experiments were carried out in a fixed bed column with feed waters at flow rates in the range of 2.78 × 10^?7 m³ s^?1 to 5.55 × 10^?7 m³ s^?1. Regeneration was achieved with NaOH (2 mol dm^?3). From the experimental results, the equilibrium of the ion exchange reaction was successfully modelled, obtaining an equilibrium constant (K′_AB) = 44.90. Finally, a mass balance that included mass transfer resistances in the liquid and solid phases was developed and from the comparison between simulated and experimental data the value of the effective intraparticle diffusivity (D_s) was determined as 1.43 × 10^?12 m² s^?1. Copyright © 2004 Society of Chemical Industry     

Boron removal by ion exchange membranes

Boron removal from aqueous solution was studied through Neosepta-AHA membrane by Donnan dialysis (DD) method as a function of concentration, pH, conduct time, membrane structure and effect of accompanying ions. The feasibility of the system was examined and the highest boron removal was obtained when the pH of the feed phase was 9.5. On the other hand, it was determined that reverse flow transition was accelerated by counter ions and HCO₃⁻ ion was found to be more effective than Cl⁻ and SO₄⁻² ions. It was determined that obtained results of AHA membrane was compared with Neosepta AFN and AMH membranes and the flow rate of boron through Neosepta AHA, AFN and AMH anion exchange membranes were found to be between 3.10⁻⁸−3232.10⁻⁸ mmol cm⁻² s⁻¹ depending on concentration of feed and receiver phases, pH as well as counter ion properties. The order for recovery of boron for membranes was found to be as AFN>AMH>AHA. It could be concluded that the DD method is an appropriate method for boron removal from aqueous solution when an appropriate counter anion was chosen at suitable pH value.     

Fixed-bed column study on removal of Mn(II), Ni(II) and Cu(II) from aqueous solution by surfactant bilayer supported alumina

In the present work, the potential of modified alumina for the removal of heavy metals such as Mn(II), Ni(II) and Cu(II) was evaluated in a fixed-bed column operation. The effects of bed depth, flow rate and initial concentration on the removal of Mn(II), Ni(II) and Cu(II) were investigated at the optimum pH. The modified alumina was found to be very efficient for the removal of such heavy metals from water environment. Bed depth service time (BDST) model was best fitted to adsorption data. The theoretical and experimental breakthrough curves were comparable for all heavy metals.     

Chelation of Cu(II), Zn(II), and Fe(II) by Tannin Constituents of Selected Edible Nuts

The tannin fractions isolated from hazelnuts, walnuts and almonds were characterised by colorimetric assays and by an SE-HPLC technique. The complexation of Cu(II) and Zn(II) was determined by the reaction with tetramethylmurexide, whereas for Fe(II), ferrozine was employed. The walnut tannins exhibited a significantly weaker reaction with the vanillin/HCl reagent than hazelnut and almond tannins, but the protein precipitation capacity of the walnut fraction was high. The SE-HPLC chromatogram of the tannin fraction from hazelnuts revealed the presence of oligomers with higher molecular weights compared to that of almonds. Copper ions were most effectively chelated by the constituents of the tannin fractions of hazelnuts, walnuts and almonds. At a 0.2 mg/assay addition level, the walnut tannins complexed almost 100% Cu(II). The Fe(II) complexation capacities of the tannin fractions of walnuts and hazelnuts were weaker in comparison to that of the almond tannin fraction, which at a 2.5 mg/assay addition level, bound Fe(II) by ~90%. The capacity to chelate Zn(II) was quite varied for the different nut tannin fractions: almond tannins bound as much as 84% Zn(II), whereas the value for walnut tannins was only 8.7%; and for hazelnut tannins, no Zn(II) chelation took place at the levels tested.     

Synthesis and characterization of resins with ligands containing guanidinine derivatives. Cu(II) sorption and coordination properties

A new modification direction of acrylonitrile, vinyl acetate and divinylbenzene terpolymers (A, B) are presented. The aminolysis of nitrile groups of the terpolymers using ethylenediamine or hydroxylamine hydrochloride was a first stage of the modification. The resulting amine groups reacted with dicyandiamide (DCDA), cyanamide (CA) and sodium dicyanimide (SDC) in order to obtain the biguanidyl, guanidyl or nitrilguanidyl derivatives in the polymer side chain, respectively. The properties of all obtained resin such as water regain, nitrogen content, amine and carboxyl group concentration and sorption properties towards Cu(II) from nitric acid solutions were determined. The studies of IR spectra of all the resins were performed. Structures of ligand complexes with Cu(II) were studied using electron paramagnetic resonance spectroscopy.     

中空聚丙烯基离子交换纤维的制备及表征

以CaCO_3为成孔剂,通过共混熔融纺丝和酸化制备中空聚丙烯纤维,以纤维为基体,通过引发剂接枝苯乙烯,再经氯甲基化和胺化反应制备强碱性阴离子交换纤维;采用红外光谱、电镜扫描、热重分析等分析手段对制备的离子交换纤维进行了表征,并对其交换容量、溶胀性及动力学吸附性能进行了测试。结果表明:制备的强碱性阴离子交换纤维具有较高的交换容量,约达到3.08 mmol/g,吸附性能良好,含水量大于56%,是一种性能优良的离子交换纤维。     

Preparation and characterization of magnetic polymethylmethacrylate microbeads carrying ethylene diamine for removal of Cu(II), Cd(II), Pb(II), and Hg(II) from aqueous solutions

Magnetic polymethylmethacrylate (mPMMA) microbeads carrying ethylene diamine (EDA) were prepared for the removal of heavy metal ions (i.e., copper, lead, cadmium, and mercury) from aqueous solutions containing different amount of these ions (5–700 mg/L) and at different pH values (2.0–8.0). Adsorption of heavy metal ions on the unmodified mPMMA microbeads was very low (3.6 μmol/g for Cu(II), 4.2 μmol/g for Pb(II), 4.6 μmol/g for Cd(II), and 2.9 μmol/g for Hg(II)). EDA‐incorporation significantly increased the heavy metal adsorption (201 μmol/g for Cu(II), 186 μmol/g for Pb(II), 162 μmol/g for Cd(II), and 150 μmol/g for Hg(II)). Competitive adsorption capacities (in the case of adsorption from mixture) were determined to be 79.8 μmol/g for Cu(II), 58.7 μmol/g for Pb(II), 52.4 μmol/g for Cd(II), and 45.3 μmol/g for Hg(II). The observed affinity order in adsorption was found to be Cu(II) > Pb(II) > Cd(II) > Hg(II) for both under noncompetitive and competitive conditions. The adsorption of heavy metal ions increased with increasing pH and reached a plateau value at around pH 5.0. The optimal pH range for heavy‐metal removal was shown to be from 5.0 to 8.0. Desorption of heavy‐metal ions was achieved using 0.1 M HNO₃. The maximum elution value was as high as 98%. These microbeads are suitable for repeated use for more than five adsorption‐desorption cycles without considerable loss of adsorption capacity. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 81–89, 2000     

Zn-Enhanced Asp-Rich Antimicrobial Peptides: N-Terminal Coordination by Zn(II) and Cu(II), Which Distinguishes Cu(II) Binding to Different Peptides

The antimicrobial activity of surfactant-associated anionic peptides (SAAPs), which are isolated from the ovine pulmonary surfactant and are selective against the ovine pathogen Mannheimia haemolytica, is strongly enhanced in the presence of Zn(II) ions. Both calorimetry and ITC measurements show that the unique Asp-only peptide SAAP3 (DDDDDDD) and its analogs SAAP2 (GDDDDDD) and SAAP6 (GADDDDD) have a similar micromolar affinity for Zn(II), which binds to the N-terminal amine and Asp carboxylates in a net entropically-driven process. All three peptides also bind Cu(II) with a net entropically-driven process but with higher affinity than they bind Zn(II) and coordination that involves the N-terminal amine and deprotonated amides as the pH increases. The parent SAAP3 binds Cu(II) with the highest affinity; however, as shown with potentiometry and absorption, CD and EPR spectroscopy, Asp residues in the first and/or second positions distinguish Cu(II) binding to SAAP3 and SAAP2 from their binding to SAAP6, decreasing the Cu(II) Lewis acidity and suppressing its square planar amide coordination by two pH units. We also show that these metal ions do not stabilize a membrane disrupting ability nor do they induce the antimicrobial activity of these peptides against a panel of human pathogens.     

Removal of Cu(II) and Fe(III) from aqueous solutions by dead sulfate reducing bacteria

The biosorption properties of dead sulfate reducing bacteria (SRB) for the removal of Cu(II) and Fe(III) from aqueous solutions was studied. The effects of the biosorbent concentration, the initial pH value and the temperature on the biosorption of Cu(II) and Fe(III) by the SRB were investigated. FTIR analysis verified that the hydroxyl, carbonyl and amine functional groups of the SRB biosorbent were involved in the biosorption process. For both Cu(II) and Fe(III), an increase in the SRB biosorbent concentration resulted in an increase in the removal percentage but a decrease in the amount of specific metal biosorption. The maximum specific metal biosorption was 93.25 mg?g^–1 at pH 4.5 for Cu(II) and 88.29 mg?g^–1 at pH 3.5 for Fe(III). The temperature did not have a significant effect on biosorption. In a binary metal system, the specific biosorption capacity for the target metal decreased when another metal ion was added. For both the single metal and binary metal systems, the biosorption of Cu(II) and Fe(III) onto a SRB biosorbent was better represented by a Langmuir model than by a Freundlich model.     

Removal of Cu(II) and Zn(II) Using Lignocellulosic Fiber Derived from Citrus reticulata (Kinnow) Waste Biomass

Abstract

The biosorption of Cu(II) and Zn(II) using dried untreated and pretreated Citrus reticulata waste biomass were evaluated. The Cu(II) and Zn(II) sorption were found to be dependent on the solution pH, the biosorbent dose, the biosorbent particle size, the shaking speed, the temperature, the initial metal ions (800 mg/L), and the contact time. Twenty-eight physical and chemical pretreatments of Citrus reticulata waste biomass were evaluated for the sorption of Cu(II) and Zn(II) from aqueous solutions. The results indicated that biomass pretreated with sulphuric acid and EDTA had maximum Cu(II) and Zn(II) uptake capacity of 87.14 mg/g and 86.4 mg/g respectively. Moreover, the Langmuir isotherm model fitted well than the Freundlich model with R ² > 0.95 for both metal ions. The sorption of Cu(II) and Zn(II) occurred rapidly in the first 120 min and the equilibrium was reached in 240 min. FTIR and SEM studies were also carried out to investigate functional groups present in the biomass and the surface morphological changes of biomass.     

Electrical properties of Cu(II) and Ni(II): N-salicylidene polymethacrylic acid hydrazide complexes

Different types of chelated polymer complexes have been synthesized to obtain improved electrical properties. Compact discs from powders of the chelated polymers were prepared and heated in a specially designed holder. Electrical conductivity and dielectric constant of Cu(II) and Ni(II): N-salicylidene polymethacrylic acid hydrazide samples were measured at a fixed frequency (1600 Hz) throughout the temperature range 25-150°C. The AC conductivity as well as dielectric measurements showed maxima at 85°C. The water molecules which were trapped in the polymer matrix are believed to play the main role in conduction and dielectric behaviour of the polymeric material. From the AC conductance and dielectric constant measurements, the dielectric losses of these polymeric materials were calculated as a function of temperature.     

Synthesis,characterization, and application of yeast-based magnetic bionanocomposite for the removal of Cu(II) from water

Abstract

Due to the amount of yeast residues generated by the industries and their high capacity as biosorbent, this work proposes the use of yeast biomass in natura (YB) or modified with ferromagnetic nanoparticles (Fe₃O₄) (YB-MNP) for Cu(II) removal from water. Synthesized YB-MNP, YB, and magnetite alone (MNP) were characterized by FTIR, XRD, and SEM. It was observed the efficient impregnation of magnetite on the surface of the biomass. Copper sorption was evaluated in batch tests using 100?mg/L of Cu(II) solution at pH 5.5, and the supernatant was analyzed by FAAS for Cu determination. Langmuir, Freundlich, and Dubinin–Radushkevich (D–R) isotherm models were applied to fit the experimental data. A favorable sorption process was observed for all the materials, mainly for the D–R model adjusted to the bionanocomposite data (YB-MNP), with r² = 0.9950 and a low error (χ² = 0.0427) associated to the model. Theoretical and experimentally Cu(II) sorption capacities were fairly similar, 8.6?±?0.1 and 8.3?±?0.2?mg/g, respectively.     

New polymeric structures designed for the removal of Cu(II) ions from aqueous solutions

New polymeric structures obtained by chemical transformations of maleic anhydride/dicyclopentadiene copolymer with triethylenetetraamine, p‐aminobenzoic acid, and p‐aminophenylacetic acid were used for the removal Cu(II) ions from aqueous solutions. The experimental values prove the importance of the chelator nature and of the macromolecular chain geometry for the retention efficiency. The retention efficiency (η_r), the retention capacity (Q _e ), and the distribution coefficient of the metal ion into the polymer matrix (K _d ) are realized by evaluation of residual Cu(II) ions in the effluent waters, by atomic adsorption. Also are discussed the influence of pH, the thermal stability of the polymer, and their polymer–metal complex, as well as the particular aspects regarding the contact procedure and the batch time. Based on the polymers and polymer–metal complexes characterization a potential retention mechanism is proposed. All polymer supports as well theirs metal–complexes are characterized by ATD and FTIR measurements. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1397–1405, 2007     

Kinetics of ligand exchange reaction of Cu(II)-ammine complex with poly(vinyl alcohol) in aqueous solution

The kinetics of the ligand exchange reaction of the Cu(II)-ammine complex with poly(vinyl alcohol) (PVA) has been studied by a stopped-flow method at pH 9–10, at μ=0.1 (NH₄Cl) and at 25°C. The reaction is initiated by the formation of unstable [Cu(NH₃)₃]²⁺ by the attack of H⁺ on Cu(II)-ammine complex, and proceeds through the mixed complex {[Cu(NH₃)₃(O?PVA)]²⁺}. This step may be rate-determining, followed by a rapid reaction. Finally, the Cu(II) ion is taken up by PVA. The rate is given by d[Cu(II)?PVA]/dt=k[H⁺]{[Cu(NH₃)₄]²⁺}[PVA]/[NH₄Cl], where k=k₁ + k′₂[H⁺], k₁=4.25× 10s^?1 and k′₂=5.20× 10¹¹l mol^?1s^?1.     

离子交换法处理含Cr(Ⅵ)废水的研究

采用201×7强碱性阴离子交换树脂处理模拟含Cr(Ⅵ)废水,探讨了废水酸度、交换时间、浓度对Cr(Ⅵ)去除率的影响以及树脂再生所需的合适温度和再生剂浓度。结果表明,201×7强碱性阴离子交换树脂处理模拟含Cr(Ⅵ)废水,具有交换容量大、交换效果好、树脂再生条件较简单等优点。并对实际含铬废水进行了处理,废水中Cr(Ⅵ)的初始浓度为1 540 mg/L,处理量达52 BV(床体积)时,出水中Cr(Ⅵ)的浓度仍小于0.5 mg/L,达到国家排放标准。树脂交换容量约80 mg/g。用8%NaOH溶液,在50℃条件下进行再生效果较好,再生率大于95%,可实现树脂的重复使用。     

Adsorption of Cu(II) from aqueous solutions by tannins immobilized on collagen

Novel adsorbents were prepared by immobilizing tannins on collagen fibre matrices. Their adsorption properties, including adsorption equilibrium, adsorption kinetics, and column adsorption kinetics to Cu(II) were investigated. Immobilized Myrica rubra tannin and black wattle tannin exhibited significantly higher adsorption capacity than larch tannin and the adsorption isotherms of these three immobilized tannins can be described by the Freundlich model. Detailed adsorption studies of immobilized black wattle tannin to Cu(II) indicated that temperature had little effect on the adsorption isotherms whereas the effect of pH was significant. Adsorption rate data fitted well to a pseudo‐second‐order rate model, and the adsorption capacity calculated by this model was consistent with the result of actual measurement at relatively higher adsorption temperatures. Immobilized black wattle tannin also had excellent column adsorption kinetic properties and high binding capacity. The adsorptivity of the column was stable even after repeated adsorption–desorption cycles. Copyright © 2004 Society of Chemical Industry     

Biosorption of copper (II) from aqueous solutions by wheat shell

The adsorption capacity of wheat shell for copper (II) was studied at various pH (2-7), agitation speeds (50-250 rpm) and initial metal ion concentrations (Co, from 10 to 250 mg.L⁻¹). Maximum biosorption of copper onto wheat shell occurred at 240 rpm agitation speed and at pH between 5 and 6. The biosorption values of copper (11) were increased with increasing pH from 2 to 5 and decreased with increasing copper/wheat shell (x/m) ratios from 0.83 to 10.84 mgCu(II).g⁻¹ wheat shell. The biosorption efficiencies at these x/m ratios were 99% and 52%, respectively, at the end of the 120 min contact time (t). The equilibrium isotherms and kinetics were obtained from batch adsorption experiments at 298 K. It was observed that wheat shell was a suitable biosorbent for removing Cu(II) from aqueous solutions.