Selective solid phase extraction of trace cadmium(II) and lead(II) from biological and natural water samples by ofloxacin-modified-silica gel

Ofloxacin was successfully used as a chemical modifier to improve the reactivity of silica gel in terms of selective binding and extraction of heavy metal ions. This new functionalised silica gel (SG-ofloxacin) was as an effective sorbent for the solid-phase extraction (SPE) of Cd(II) and Pb(II) in biological and natural water samples and their determination by inductively coupled plasma optical emission spectrometry (ICP-OES). Experimental conditions for effective adsorption of trace levels of Cd(II) and Pb(II) were optimised with respect to different experimental parameters using the batch and column procedures. The time for 70% sorption for Cd(II) and Pb(II) was less than 2 min. Complete elution of the adsorbed metal ions from the SG-ofloxacin was carried out using 2.0 mL of 0.5 mol L^?1 of HCl. Common coexisting ions did not interfere with the separation and determination at pH 4.0. The maximum static adsorption capacity of the sorbent at optimum conditions was found to be 39.17 and 48.69 mg g^?1 for Cd(II) and Pb(II), respectively. The detection limits of the method were found to be 0.29 and 0.13 ng mL^?1 for Cd(II) and Pb(II), respectively. The relative standard deviation (RSD) of the method under optimum conditions was lower than 3.0% (n = 5). The method was applied to the recovery of Cd(II) and Pb(II) from the certified reference material (GBW 08301, river sediment) and to the simultaneous determination of these cations in different water and biological samples with satisfactory results and yielding 100-folds enrichment factor.     

Silica gel surface modified with sulfanilamide for selective solid-phase extraction of Cu(II), Zn(II) and Ni(II)

A new chelating matrix has been prepared by immobilising sulfanilamide (SA) on silica gel (SG) surface modified with 3-chloropropyltrimethoxysilane as a sorbent for the solid-phase extraction (SPE) Cu(II), Zn(II) and Ni(II). The determination of metal ions in aqueous solutions was carried out by inductively coupled plasma optical emission spectrometry (ICP-OES). Experimental conditions for effective sorption of trace levels of Cu(II), Zn(II) and Ni(II) were optimised with respect to different experimental parameters using the batch and column procedures. The presence of common coexisting ions does not affect the sorption capacities. The maximum sorption capacity of the sorbent at optimum conditions was found to be 34.91, 19.07 and 23.62 mg g^?1 for Cu(II), Zn(II) and Ni(II), respectively. The detection limit of the method defined by IUPAC was found to be 1.60, 0.50 and 0.61 µg L^?1 for Cu(II), Zn(II) and Ni(II), respectively. The relative standard deviation (RSD) of the method under optimum conditions was 4.0% (n = 8). The method was applied to the recovery of Cu(II), Zn(II) and Ni(II) from the certified reference material (GBW 08301, river sediment) and to the simultaneous determination of these cations in different water samples with satisfactory results.     

Complex formation equilibria of some β-amino-alcohols with lead(II) and cadmium(II) in aqueous solution

A study of complex formation equilibria of some β-amino-alcohols with lead(II) and cadmium(II) ions at 25°C and in 0.5 M KNO₃ is reported. The amino-alcohols considered are 2-amino-1-propanol, 2-amino-1-butanol, 2-amino-1-pentanol and 2-amino-1,3-propanediol. sec-Buthylamine and 2-amino-1-methoxy-propane have been also considered for comparison. The results are discussed in terms of ligand structure, paying attention to the number of hydroxyl groups and to the length of the alkyl residual. A weak contribution of the alcoholic oxygen in the coordination of cadmium(II) and the presence of a mixed hydroxyl species in lead(II) containing systems are hypothesized.     

Solid-phase extraction and preconcentration of cadmium(II) in aqueous solution with Cd(II)-imprinted resin (poly-Cd(II)-DAAB-VP) packed columns

A novel chelating resin (poly-Cd(II)-DAAB-VP) was prepared by metal ion imprinted polymer (MIIP) technique. The resin was obtained by one pot reaction of Cd(II)-diazoaminobenzene-vinylpyridine with cross-linker ethyleneglycoldimethacrylate (EGDMA). Comparing with non-imprinted resin, the poly-Cd(II)-DAAB-VP has higher adsorption capacity and selectivity for Cd(II). The distribution ratio (D) values for the Cd(II)-imprinted resin show increase for Cd(II) with respect to both D values of Zn(II), Cu(II), Hg(II) and non-imprinted resin. The relatively selective factor (α_r) values of Cd(II)/Cu(II), Cd(II)/Zn(II) and Cd(II)/Hg(II), are 51.2, 45.6, and 85.4, which are greater than 1. poly-Cd(II)-DAAB-VP can be used at least 20 times without considerable loss of adsorption capacity. Based on poly-Cd(II)-DAAB-VP packed columns, a highly selective solid-phase extraction (SPE) and preconcentration method for Cd(II) from aqueous solution was developed. The MIIP-SPE preconcentration procedure showed a linear calibration curve within concentration range from 0.093 to 30 μg l⁻¹. The detection limit and quantification limit were 0.093 and 0.21 μg l⁻¹ (3σ) for flame atomic absorption spectrometry (FAAS). The relative standard deviation of the eleven replicate determinations was 3.7% for the determination of 10 μg of Cd(II) in 100 ml water sample. Determination of Cd(II) in certified river sediment sample (GBW 08301) demonstrated that the interfering matrix had been almost removed during preconcentration. The column was good enough for Cd(II) determination in matrixes containing components with similar chemical property such as Cu(II), Zn(II) and Hg(II).     

Mixed-ligand complexes of zinc(II), cobalt(II) and cadmium(II) with sulfur, nitrogen and oxygen ligands. Analysis of the solid state structure and solution behavior. Implications for metal ion substitution in alcohol dehydrogenase

In this paper we characterize new, mixed ligand complexes of zinc(II), cobalt(II) and cadmium(II) with tri-tert-butoxysilanethiolate and 2-(2′-hydroxyethyl)pyridine ligands. Due to the chelating versus non-chelating behavior of 2-(2′-hydroxyethyl)pyridine ligand we have obtained an interesting structural variety in the studied system. The presented coordination patterns together with the results of NMR studies have been used to illustrate a rapid chemical exchange undergoing in methanolic solutions of zinc(II) and cadmium(II) complexes. UV-Vis spectra of cobalt(II) species have also evidenced an exchange in the case of cobalt(II) complex. The relative strength of hydrogen bond formed by hydroxyl group bonded to Zn(II), Co(II) or Cd(II) was evaluated by analysis of structural parameters and position of the OH stretching vibrations in the FT-IR spectra of the complexes in solid state. The data were compared with the activity of zinc (native) alcohol dehydrogenase and alcohol dehydrogenase substituted with cobalt and cadmium ions. The enthalpies of proton abstraction in zinc and cobalt complexes were calculated and found to be very similar. The attempt to apply zinc tri-tert-butoxysilanethiolate as a catalyst in the biomimetic reaction of reduction of N-benzylnicotinamide chloride by ethanol was unsuccessful.     

Complex formation of hypoxanthine and 6-mercaptopurine with Cd(II) ion

Reaction of Cd(II) ion with hypoxanthine (H₂ Y) and with 6-mercaptopurine (H₂ MP) in dioxane-water (50%) leads to the formation of CdY·2H₂O and Cd(HMP)₂·2H₂O, respectively. In methanolic medium Cd(II) and H₂ MP give Cd(MP)·H₂O. These compounds have been characterized by chemical analysis, IR spectra and thermogravimetric analysis. The stability constant of CdY complex at 25±0.1 °C and 1M ionic strength with NaClO₄ in dioxane-water medium is log =10.25±0.05.

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Komplexbildung von Hypoxanthin und 6-Mercaptopurin mit Cd(II)

Zusammenfassung Die Umsetzung von Cd(II)-Ionen mit Hypoxanthin (H₂ Y) und 6-Mercaptopurin (H₂ MP) in Dioxan-Wasser (50%) ergibt die Verbindungen CdY·2H₂O und Cd(HMP)₂·2H₂O. In Methanol entsteht aus Cd(II) und H₂ MP CdMP·H₂O. Die Verbindungen wurden durch chemische Analysen, IR-Spektren und thermogravimetrische Analysen charakterisiert. Die Stabilitätskonstante der Verbindung CdY bei 25°C und bei einer Ionenstärke = 1 (NaClO₄) in Dioxan-Wasser wurde zu lg =10,25±0,05 bestimmt.

     

High extraction ability of 1,3-dialkynyl calixarene towards mercury（Ⅱ） ion

The reaction of 1,3-dipropyn-2-yloxycalix[4]arene with mercury(II)acetate could give mercury-containing alkynyl calixarenepolymer.The extraction behavior of 1,3-dipropyn-2-yl-oxycalix[4]arene towards mercury(II)ion was examined.When the moleratio of Hg~(2 )/calixarene was 1:1,the extractive percent can reach to 99.1%,and the extraction capacity was up to 431 mg/g.It couldalso decrease the Hg~(2 )concentration from 5 to 0.85 mg/L,which was only 17%of the national standard of effluent and satisfied thenational standard of drinking water.The extraction process included chemical reaction.     

Synthesis and characterization of mononuclear copper(II) and cadmium(II) complexes with di-(2-picolyl)sulfur

The reaction of Cu(ClO₄)₂·6H₂O and Cd(ClO₄)₂ with di-(2-picolyl)sulfur (dps) leads to the formation of mononuclear complexes [Cu(dps)(H₂O)(ClO₄)](ClO₄) (1) and [Cd(dps)₂](ClO₄)₂ (2). The crystal structure of 1 exhibits a distorted square pyramidal geometry, coordinated by one sulfur and two nitrogen atoms from the dps ligand, one water molecule and one perchlorate oxygen atom. For 2, the environment around cadmium atom is in a distorted octahedron with four nitrogen and two sulfur atoms from the dps ligand. Cyclic voltammetric data show that complexes undergo two waves of a one-electron transfer corresponding to M(II)/M(III) and M(II)/M(I) processes. Spectral and electrochemical behaviors of the complexes are also discussed.     

Ultrasound assisted syntheses of a nano-structured two-dimensional mixed-ligand cadmium(II) coordination polymer and direct thermolyses for the preparation of cadmium(II) oxide nanoparticles

A nano-sized mixed-ligand Cd(II) coordination polymer, {[Cd(bpa)(4,4′-bipy)₂(H₂O)₂](ClO₄)₂}_n (1); bpa = trans-1,2-bis(4-pyridyl)ethane and 4,4′-bipy = 4,4′-bipyridine, has been synthesized by a sonochemical method and characterized by IR and ¹H NMR spectroscopy. Compound 1 grows in one dimension by two different bridging ligands, 4,4′-bipy and bpa. The thermal stability of compound 1 in the bulk form and nano-sized was studied by thermogravimetric (TG) and differential thermal analysis (DTA). The crystallinity of this compound was studied by X-ray powder diffraction and compared with an XRD simulation of the single crystal data. CdO nanoparticles were obtained by direct calcination at 500 °C and decomposition in oleic acid at 200 °C of the nano-sized compound 1. The obtained cadmium(II) oxide nano-particles were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM).     

Zinc(II) and cadmium(II) complexes with PDT: study of the effect of weak interactions on crystal packing

Two new zinc(II) and cadmium(II) complexes, [Zn(PDT)₂(NCS)₂] (1) and [Cd((PDT)₂I_1.6(H₂O)_0.4(OH)_0.4] · 0.4H₂O (2) (“PDT” is the abbreviation of 3-(2-pyridyl)-5, 6-diphenyl-1,2,4-triazine), have been synthesized and characterized by elemental analysis, IR, ¹H NMR spectroscopy, and studied by X-ray crystallography. Zinc(II) in 1 is six coordinate ZnN₆. 2 is a co-crystal with cadmium(II) being 60% six-coordinated with a CdN₄I₂ environment and 40% seven-coordinated with a CdN₄O₂I environment. The supramolecular features in these complexes are guided/controlled by weak directional intermolecular S ··· π, C–H ··· π, C–H ··· I, and π ··· π interactions.     

Syntheses,X-ray structures and properties of a dinuclear cadmium(II)azido and a polymeric cadmium(II)thiocyanato compounds containing bis(tridentate) congregators

One-pot reactions of cadmium(II) perchlorate/nitrate, Schiff bases (pbap/pfap) and pseudohalides (sodium azide/ammonium thiocyanate) in a 2:1:4 molar ratio in MeOH–MeCN solvent mixtures at room temperature result in a dinuclear compound [Cd₂(pbap)(OH₂)₂(N₃)₄] (1) [pbap = N-(1-pyridin-2-ylbenzylidene)-N-[2-(4-{2-[(1-pyridin-2-ylbenzylidene)amino]ethyl}piperazin-1-yl)ethyl]amine] and a polymeric compound [Cd₂(pfap)(μ_1,3-NCS)(μ_1,3-SCN)(NCS)₂]_n (2) [pfap = N-(1-pyridin-2-ylformylidene)-N-[2-(4-{2-[(1-pyridin-2ylformylidene)amino]ethyl}piperazin-1-yl)ethyl]-amine]. X-ray crystal structural analyses reveal a bis(tridentate) congregation behaviour of the hexadentate blocker (pbap/pfap) encapsulating two metal centers. Each cadmium(II) center in 1 and 2 is in a distorted octahedral geometry with CdN₅O and CdN₅S chromophores, respectively. In 1, the dinuclear units participate in intermolecular O–H?N hydrogen bonding between bound water O atoms and terminal azide N atoms, in combination with C–H?π interactions, resulting in a 3D supramolecular network with an intramolecular Cd?Cd distance of 6.473(2) Å. In the crystal lattice, the covalent 1D chain of 2 is further engaged in face-to-face π?π interactions from two terminal pyridine rings, which stabilizes the chain with an intradimer Cd?Cd separation of 6.640(5) Å. Both the complexes display intraligand ¹(π–π^∗) fluorescence and intraligand ³(π–π^∗) phosphorescence in glassy solutions.     

Selective solid-phase extraction of nickel(II) using a surface-imprinted silica gel sorbent

A new Ni(II)-imprinted amino-functionalized silica gel sorbent with excellent selectivity for nickel(II) was prepared by an easy one-step reaction by combining a surface imprinting technique for selective solid-phase extraction (SPE) of trace Ni(II) in water samples prior to its determination by inductively coupled plasma atomic emission spectrometry (ICP-AES). Compared with non-imprinted polymer particles, the ion-imprinted polymers (IIPs) had higher selectivity and adsorption capacity for Ni(II). The maximum static adsorption capacity of the ion-imprinted and non-imprinted sorbent for Ni(II) was 12.61 and 4.25 mg g⁻¹, respectively. The relatively selective factor (α_r) values of Ni(II)/Cu(II), Ni(II)/Co(II), Ni(II)/Zn(II) and Ni(II)/Pd(II) were 45.99, 32.83, 43.79 and 28.36, which were greater than 1. The distribution ratio (D) values of Ni(II)-imprinted polymers for Ni(II) were greatly larger than that for Cu(II), Co(II), Zn(II) and Pd(II). The detection limit (3σ) was 0.16 ng mL⁻¹. The relative standard deviation of the method was 1.48% for eight replicate determinations. The method was validated by analyzing two certified reference materials (GBW 08618 and GBW 08402), the results obtained is in good agreement with standard values. The developed method was also successfully applied to the determination of trace nickel in plants and water samples with satisfactory results.     

Synthesis,structure and properties of three one-dimensional coordination polymers {[M(II)L(NCS)2](DMF)2} n (M(II)=cadmium(II), zinc(II), manganese(II); L=1,4-bis[2-(2-pyridyl)benzimidazolato]butane)

A tetradentate N-donor ligand 1,4-bis[2-(2-pyridyl)benzimidazolato]butane (L) was prepared for construction of a coordination framework. Three one-dimensional coordination polymers {[M(II)L(NCS)₂](DMF)₂} _n (M(II) = cadmium(II), 1, zinc(II), 2, manganese(II), 3) were obtained by reaction of metal ions and L in the presence of KSCN in DMF/water. The complexes are isostructural and consist of 1D zigzag [M(II)L(NCS)₂] _n chains and DMF molecules. Within the chains, the metal atoms are each octahedrally coordinated by four N atoms of L and two N atoms of the SCN^? anions. Complexes 1 and 2 in the solid state at room temperature exhibit intense photoluminescence at 453 and 433 nm, respectively.     

Selective solid-phase extraction of trace cadmium(II) with an ionic imprinted polymer prepared from a dual-ligand monomer

A novel dual-ligand reagent (2Z)-N,N′-bis(2-aminoethylic)but-2-enediamide, was synthesized and applied to prepare metal ion-imprinted polymers (IIPs) materials by ionic imprinted technique for selective solid-phase extraction (SPE) of trace Cd(II) from aqueous solution. In the first step, Cd(II) formed coordination linkage with the two ethylenediamine groups of the synthetic monomer. Then the complex was copolymerized with pentaerythritol triacrylate (crosslinker) in the presence of 2,2′-azobisisobutyronitrile as initiator. Subsequently, the imprinted Cd(II) was completely removed by leaching the dried and powdered materials particles with 0.5 M HCl. The obtained IIPs particles exhibited excellent selectivity for target ion. The distribution ratio (D) values of Cd(II)-IIPs for Cd(II) were greatly larger than that for Cu(II), Zn(II) and Hg(II). The relative selective factor (α_r) values of Cd(II)/Cu(II), Cd(II)/Zn(II) and Cd(II)/Hg(II) were 25.5, 35.3 and 62.1. The maximum static adsorption capacity of the ion-imprinted and non-imprinted sorbent for Cd(II) was 32.56 and 6.30 mg g⁻¹, respectively. Moreover, the times of adsorption equilibration and complete desorption were remarkably short. The prepared Cd(II)-IIPs were shown to be promising for solid-phase extraction coupled with inductively coupled plasma atomic emission spectrometry (ICP-AES) for the determination of trace Cd(II) in real samples. The precision (R.S.D.) and detection limit (3σ) of the method were 2.4% and 0.14 μg L⁻¹, respectively. The column packed with Cd(II)-IIPs was good enough for Cd(II) separation in matrixes containing components with similar chemical behaviour such as Cu(II), Zn(II) and Hg(II).     

Solid phase extraction of trace Hg(II) on silica gel modified with 2-(2-oxoethyl)hydrazine carbothioamide and determination by ICP-AES

In this work, a new 2-(2-oxoethyl)hydrazine carbothioamide modified silica gel (SG-OHC) sorbent was prepared and applied for preconcentration of trace mercury(II) prior to the measurement by inductively coupled plasma atomic emission spectrometry (ICP-AES). The optimization of some analytical parameters affecting the adsorption of the analyte such as acidity, shaking time, sample flow rate and volume, eluent condition, and interfering substances were investigated. At pH 3, the maximum static adsorption capacity of Hg(II) onto the SG-OHC was 37.5 mg g⁻¹. The quantitative recovery (>95%) of Hg(II) could be obtained using 2 mL of 0.5 mol L⁻¹ HCl and 1% CS(NH₂)₂ solution as eluent. Common coexisting substances did not interfere with the separation of mercury(II) under optimal conditions. The detection limit of present method was 0.10 ng mL⁻¹, and the relative standard deviation (RSD) was lower than 4.0% (n = 8). The prepared sorbent was successfully applied for the preconcentration of trace Hg(II) in certified and water samples with satisfactory results.     

Synthesis and spectroscopic characterization of cadmium(II) complexes of thiones and thiocyanate

Cadmium(II) complexes of thiones and thiocyanate, [(>C=S)₂Cd(SCN)₂], have been prepared and characterized by IR and NMR spectroscopy. An upfield shift in the >C=S resonance of thiones in the ¹³C NMR and downfield shift in N–H resonance in ¹H NMR are consistent with sulfur coordination to cadmium(II). The presence of ν(N–H) of thiones in IR spectra of the complexes indicates the thione forms of the ligands in the solid state; some contribution of the thiolate form was observed in one complex. The appearance of a band around 2100 cm^?1 in IR and a resonance around 132 ppm in ¹³C NMR indicates the binding of thiocyanate to cadmium(II).     

Chemically modified silica gel with p-dimethylaminobenzaldehyde for selective solid-phase extraction and preconcentration of Cr(III), Cu(II), Ni(II), Pb(II) and Zn(II) by ICP-OES

Silica gel-bound amines phase modified with p-dimethylaminobenzaldehyde (p-DMABD) was prepared based on chemical immobilization technique. The product (SG-p-DMABD) was used as an adsorbent for the solid-phase extraction (SPE) Cr(III), Cu(II), Ni(II), Pb(II) and Zn(II) prior to their determination by inductively coupled plasma optical emission spectrometry (ICP-OES). The uptake behaviors of SG-p-DMABD for extracting these metal ions were studied using batch and column procedures. For the batch method, the optimum pH range for Cr(III) and Ni(II) extraction was ≥ 3, for Cu(II), Pb(II) and Zn(II) extraction it was ≥ 4. For simultaneous enrichment and determination of all the metals on the newly designed adsorbent, the pH value if 4.0 was selected. All the metal ions can be desorbed with 2.0 mL of 0.5 mol L^− 1 of HCl. The results indicate that SG-p-DMABD has rapid adsorption kinetics using the batch method. The adsorption capacity for these metal ions is in the range of 0.40-1.15 mmol g^− 1, with a high enrichment factor of 125. The presence of commonly coexisting ions does not affect the sorption capacities. The detection limits of the method were found to be 1.10, 0.69, 0.99, 1.10 and 6.50 μg L^− 1 for Cr(III), Cu(II), Ni(II), Pb(II) and Zn(II), respectively. The relative standard deviation (RSD) of the method under optimum conditions was 5.0% (n = 8) for all metal ions. The method was applied to the preconcentration of Cr(III), Cu(II), Ni(II), Pb(II) and Zn(II) from the certified reference material (GBW 08301, river sediment) and water samples with satisfactory results.     

Determination of Fe(II), Cu(II) and Ag(I) by using silica gel loaded with 1,10-phenanthroline

The modified silica gel with 1,10-phenanthroline adsorbed was obtained. The adsorption from aqueous solutions onto loaded silica gel of Fe(II), Cu(II) and Ag(I) and their complexes was studied. The loaded silica gel was applied to Fe(II), Cu(II) and Ag(I) reflectance spectroscopy determinations in water (detection limits 0.08, 0.03 and 0.01 ppm respectively). Visual test scales for Fe, Cu and Ag ion determinations in water were worked out.     

Synthesis,structures, and fluorescence of two cadmium(II) coordination polymers with a semirigid bis-benzimidazole

Compounds [CdLCl₂] _n (1) and {[Cd(L)₂(ClO₄)]·ClO₄} _n (2), where L?=?1,3-bis(5,6-dimethylbenzimidazol-1-ylmethyl)benzene, have been synthesized by hydrothermal method, and characterized by element analysis, IR spectra, Powder XRD, and X-ray crystallographic diffraction. Cd(II) in 1 and 2 are both trigonal bipyramidal. Different cadmium salts of chloride and perchlorate lead to different configurations of [Cd₂L₂]²⁺, trans-form in 1 but trans and cis-forms in 2. The 1-D beaded chains of 1 are further linked to generate a 3-D supramolecular architecture by strong π–π stacking interactions as well as intermolecular C–H?···?Cl hydrogen bonds. In 2, the 1-D beaded chains are further assembled by intermolecular C–H?···?O hydrogen bonds to form a 2-D layer. Solid-state fluorescent properties of 1 and 2 were investigated at room temperature.     

Solid-phase extraction and preconcentration of trace Pb(II) from water samples with folic acid modified silica gel

A chelating matrix prepared by immobilising folic acid on silica gel-bound amine phase was used as a new solid-phase extractant. This sorbent has been developed only for preconcentration of trace Pb(II) prior to determination by inductively coupled plasma atomic emission spectrometry (ICP-AES). Experimental conditions were investigated by batch and column procedures. The optimum pH value for the separation of Pb(II) on the new sorbent was 4.0. The adsorbed Pb(II) was quantitatively eluted by 2.0?cm³ of 0.5?mol?dm^?3 of HCl. Common coexisting ions did not interfere with the separation and determination of Pb(II). The maximum static adsorption capacity of the sorbent under optimum conditions was found to be 69.23?mg?g^?1 for Pb(II). The detection limit of the method defined by International Union of Pure and Applied Chemistry was 0.28?ng?cm^?3. The relative standard deviation (RSD) of the method was lower than 2.0% (n?=?8). The developed method has been validated by analysing certified reference materials and successfully applied to the determination of Pb(II) in water samples with satisfactory results.