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Sample records for cdii coii feiii

  1. Chitosan film loaded with silver nanoparticles-sorbent for solid phase extraction of Al(III), Cd(II), Cu(II), Co(II), Fe(III), Ni(II), Pb(II) and Zn(II).

    Science.gov (United States)

    Djerahov, Lubomir; Vasileva, Penka; Karadjova, Irina; Kurakalva, Rama Mohan; Aradhi, Keshav Krishna

    2016-08-20

    The present study describes the ecofriendly method for the preparation of chitosan film loaded with silver nanoparticles (CS-AgNPs) and application of this film as efficient sorbent for separation and enrichment of Al(III), Cd(II), Cu(II), Co(II), Fe(III), Ni(II), Pb(II) and Zn(II). The stable CS-AgNPs colloid was prepared by dispersing the AgNPs sol in chitosan solution at appropriate ratio and further used to obtain a cast film with very good stability under storage and good mechanical strength for easy handling in aqueous medium. The incorporation of AgNPs in the structure of CS film and interaction between the polymer matrix and nanoparticles were confirmed by UV-vis and FTIR spectroscopy. The homogeneously embedded AgNPs (average diameter 29nm, TEM analysis) were clearly observed throughout the film by SEM. The CS-AgNPs nanocomposite film shows high sorption activity toward trace metals under optimized chemical conditions. The results suggest that the CS-AgNPs nanocomposite film can be feasibly used as a novel sorbent material for solid-phase extraction of metal pollutants from surface waters. PMID:27178907

  2. Coordination of Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Cd(II), Hg(II), Pd(II) and Pt(II) with 2,5-hexanedione bis(thiosemicarbazone), HBTS: crystal structure of cis-[Pd(HBTS)]Cl2 and 1-(2,5-dimethyl-1H-pyrrol-yl)-thiourea.

    Science.gov (United States)

    Jeragh, Bakir; El-Asmy, Ahmed A

    2014-09-15

    Metal complexes of Fe3+, Co2+, Ni2+, Cu2+, Zn2+, Cd2+, Hg2+, Pd2+ or Pt2+ with 2,5-hexanedione bis(thiosemicarbazone), HBTS; have been prepared and spectroscopically investigated. The empirical formulae of the complexes were suggested based on the elemental analysis. Single crystal of Pd(II) has been solved to be cis-form of square-planar geometry by the X-ray crystallography. 1H and 13C NMR spectra have been recorded for HBTS, Zn(II), Cd(II), Hg(II), Pd(II) and Pt(II) complexes, in DMSO-d6, showing the mode of chelation. The ligand acts as a neutral or a binegative tetradentate (N2S2) or neutral bidentate on the basis of FT-IR. The magnetic moments and electronic spectra provide information about the geometry of the complexes which supported by calculating the ligand field parameters for the Co(II) and Fe(III) complexes. The Ni(II) complex has subnormal magnetic moment (0.71 BM) indicative of a mixed stereochemistry of square-planar and tetrahedral structure. [Cu(HBTS-2H)] measured 0.93 BM indicating high interaction between the copper centers. The ligand may be ordered at the top of the spectrochemical series which giving high ligand field splitting energy (10 Dq=17,900 cm(-1) for Co2+ complex). The mass spectra of some complexes proved their stable chemical formulae while the TGA depicts the degradation steps and the final residue. In evaporating the mother liquor during the preparation of HBTS, new compound is obtained naming 1-(2,5-dimethyl-1H-pyrrol-yl)thiourea and its crystal was solved. PMID:24813284

  3. Coordination of Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Cd(II), Hg(II), Pd(II) and Pt(II) with 2,5-hexanedione bis(thiosemicarbazone), HBTS: Crystal structure of cis-[Pd(HBTS)]Cl2 and 1-(2,5-dimethyl-1H-pyrrol-yl)-thiourea

    Science.gov (United States)

    Jeragh, Bakir; El-Asmy, Ahmed A.

    2014-09-01

    Metal complexes of Fe3+, Co2+, Ni2+, Cu2+, Zn2+, Cd2+, Hg2+, Pd2+ or Pt2+ with 2,5-hexanedione bis(thiosemicarbazone), HBTS; have been prepared and spectroscopically investigated. The empirical formulae of the complexes were suggested based on the elemental analysis. Single crystal of Pd(II) has been solved to be cis-form of square-planar geometry by the X-ray crystallography. 1H and 13C NMR spectra have been recorded for HBTS, Zn(II), Cd(II), Hg(II), Pd(II) and Pt(II) complexes, in DMSO-d6, showing the mode of chelation. The ligand acts as a neutral or a binegative tetradentate (N2S2) or neutral bidentate on the basis of FT-IR. The magnetic moments and electronic spectra provide information about the geometry of the complexes which supported by calculating the ligand field parameters for the Co(II) and Fe(III) complexes. The Ni(II) complex has subnormal magnetic moment (0.71 BM) indicative of a mixed stereochemistry of square-planar and tetrahedral structure. [Cu(HBTS-2H)] measured 0.93 BM indicating high interaction between the copper centers. The ligand may be ordered at the top of the spectrochemical series which giving high ligand field splitting energy (10Dq = 17,900 cm-1 for Co2+ complex). The mass spectra of some complexes proved their stable chemical formulae while the TGA depicts the degradation steps and the final residue. In evaporating the mother liquor during the preparation of HBTS, new compound is obtained naming 1-(2,5-dimethyl-1H-pyrrol-yl)thiourea and its crystal was solved.

  4. Can Co(II) or Cd(II) substitute for Zn(II) in zinc fingers?

    Indian Academy of Sciences (India)

    P Rabindra Reddy; M Radhika

    2001-02-01

    Zinc finger domains consist of sequences of amino acids containing cysteine and histidine residues tetrahedrally coordinated to a zinc ion. The role of zinc in a DNA binding finger was considered purely structural due to the absence of redox chemistry in zinc. However, whether other metals e.g. Co(II) or Cd(II) can substitute Zn(II) is not settled. For an answer the detailed interaction of Co(II) and Cd(II) with cysteine methylester and histidine methylester has been investigated as a model for the zinc core in zinc fingers. The study was extended to different temperatures to evaluate the thermodynamic parameters associated with these interactions. The results suggest that zinc has a unique role.

  5. Recovery of Cd(II), Co(II) and Ni(II) from Chloride Medium by Solvent Extraction Using CYANEX 923 and CYANEX 272 I

    International Nuclear Information System (INIS)

    The paper aims to study the extraction and separation of Cd(II), Co(II) and Ni(II) from their mixtures in hydrochloric acid medium with CYANEX 923 in kerosene. Preliminary investigations showed that only Cd(II) is extracted with CYANEX 923 while Co(II) and Ni(II) are not extracted. Different parameters affecting the extraction of Cd(II) with CYANEX 923 such as hydrochloric acid, hydrogen ion, extractant and metal concentrations, temperature investigations were also investigated. The stoichiometry of the extracted metal species investigated was found to be HCdCl3. 2 CYANEX 923. The stripping of the extracted Cd(II) species is obtained with 0.1 M HCl solution. Co(II) was found to be extracted with CYANEX 272 at ph 5.8 leaving Ni(II) in the solution. A developed process for the sequential of Cd(II), Co(II) and Ni(II) from their mixture in hydrochloric acid medium is proposed

  6. Co(II) and Cd(II) Complexes Derived from Heterocyclic Schiff-Bases: Synthesis, Structural Characterisation, and Biological Activity

    Science.gov (United States)

    Ahmed, Riyadh M.; Yousif, Enaam I.; Al-Jeboori, Mohamad J.

    2013-01-01

    New monomeric cobalt and cadmium complexes with Schiff-bases, namely, N′-[(E)-(3-hydroxy-4-methoxyphenyl)methylidene]furan-2-carbohydrazide (L1) and N′-[(E)-(3-hydroxy-4-methoxyphenyl)methylidene]thiophene-2-carbohydrazide (L2) are reported. Schiff-base ligands L1 and L2 were derived from condensation of 3-hydroxy-4-methoxybenzaldehyde (iso-vanillin) with furan-2-carboxylic acid hydrazide and thiophene-2-carboxylic acid hydrazide, respectively. Complexes of the general formula [M(L)2]Cl2 (where M = Co(II) or Cd(II), L = L1 or L2) have been obtained from the reaction of the corresponding metal chloride with the ligands. The ligands and their metal complexes were characterised by spectroscopic methods (FTIR, UV-Vis, 1H, and 13C NMR spectra), elemental analysis, metal content, magnetic measurement, and conductance. These studies revealed the formation of four-coordinate complexes in which the geometry about metal ion is tetrahedral. Biological activity of the ligands and their metal complexes against gram positive bacterial strain Bacillus (G+) and gram negative bacteria Pseudomonas (G−) revealed that the metal complexes become less resistive to the microbial activities as compared to the free ligands. PMID:24027449

  7. Preparation and characterization of Pyridoxine complexes of Fe(III), Mo(VI), Cd(II), Hg(II), and U(VI)

    International Nuclear Information System (INIS)

    Pyridoxine (vit B6) reacts with Fe(III), Mo(VI), Cd(II), Hg(II), and U(VI) in aqueous medium to produce solid stable compounds. The compound were characterized by using elemetal analysis data (C'H'N) and different spectroscopic techniques (IR and UV-visible). Condutance behaviour of aqueous solution and the thermal decomposition nature of the complexes were also studied

  8. Wet oxidative method for removal of 2,4,6-trichlorophenol in water using Fe(III), Co(II), Ni(II) supported MCM41 catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Chaliha, Suranjana [Department of Chemistry, Gauhati University, Guwahati 781014, Assam (India); Bhattacharyya, Krishna Gopal [Department of Chemistry, Gauhati University, Guwahati 781014, Assam (India)], E-mail: krishna2604@sify.com

    2008-02-11

    Chlorophenols in water are resistant to biological oxidation and they have to be destroyed by chemical oxidation. In the present work, Fe(III), Co(II) and Ni(II) incorporated MCM41 mesoporous solids were used as catalysts for oxidation of 2,4,6-trichlorophenol in water with or without the oxidant, H{sub 2}O{sub 2}. The catalysts were prepared by impregnation and were characterized by XRD and FTIR measurements. The parent MCM41, Fe(III), Co(II) and Ni(II) impregnated MCM41 had cation exchange capacity of 20.5, 25.5, 24.2, 26.0 mequiv./100 g, respectively. The catalysts were used after calcination at 773-873 K for 5 h. The reactions were carried out in a high pressure stirred reactor at 0.2 MPa (autogenous) and 353 K under various reaction conditions. The conversion achieved with Fe(III), Co(II) and Ni(II) incorporated MCM41 in 5 h is respectively 59.4, 50.0 and 65.6% with 2,4,6-TCP:H{sub 2}O{sub 2} molar ratio of 1:1, and 60.2, 60.9 and 68.8% in absence of H{sub 2}O{sub 2}. The oxidation has a first order rate coefficient of (1.2-4.8) x 10{sup -3} min{sup -1}. The results show that introduction of Fe(III), Co(II) and Ni(II) into MCM-41 through impregnation produces very effective catalysts for wet oxidation of 2,4,6-trichlorophenol.

  9. Biologically active new Fe(II, Co(II, Ni(II, Cu(II, Zn(II and Cd(II complexes of N-(2-thienylmethylenemethanamine

    Directory of Open Access Journals (Sweden)

    C. SPÎNU

    2008-04-01

    Full Text Available Iron(II, cobalt(II, nickel (II, copper (II, zinc(II and cadmium(II complexes of the type ML2Cl2, where M is a metal and L is the Schiff base N-(2-thienylmethylenemethanamine (TNAM formed by the condensation of 2-thiophenecarboxaldehyde and methylamine, were prepared and characterized by elemental analysis as well as magnetic and spectroscopic measurements. The elemental analyses suggest the stoichiometry to be 1:2 (metal:ligand. Magnetic susceptibility data coupled with electronic, ESR and Mössbauer spectra suggest a distorted octahedral structure for the Fe(II, Co(II and Ni(II complexes, a square-planar geometry for the Cu(II compound and a tetrahedral geometry for the Zn(II and Cd(II complexes. The infrared and NMR spectra of the complexes agree with co-ordination to the central metal atom through nitrogen and sulphur atoms. Conductance measurements suggest the non-electrolytic nature of the complexes, except for the Cu(II, Zn(II and Cd(II complexes, which are 1:2 electrolytes. The Schiff base and its metal chelates were screened for their biological activity against Escherichia coli, Staphylococcus aureus and Pseudomonas aeruginosa and the metal chelates were found to possess better antibacterial activity than that of the uncomplexed Schiff base.

  10. Fe(II, Co(II, Ni(II, Cu(II, Zn(II, Cd(II and Hg(II Complexes of 4'-Nitrobenzylidene-2-Hydroxyl-3,5 Dinitroaniline

    Directory of Open Access Journals (Sweden)

    R. S. Srivastava

    1982-07-01

    Full Text Available Complexes of Fe(II, Co(II, Ni(II, Cu(II Zn(II, Cd(II, and Hg(II with 4'-nitrobenzylidene-2-hydroxy-3,5-dinitroaniline (hereafter abbreviated as nhd have been prepared and characterized by their microanalyses, molar conductance, magnetic susceptibility, electronic and IR spectra. The donor sites of the ligand have been derived from the results of infrared spectra.

  11. Kinetic, equilibrium and thermodynamic investigations of Ni(II, Cd(II, Cu(II and Co(II adsorption on barley straw ash

    Directory of Open Access Journals (Sweden)

    M. Arshadi

    2014-08-01

    Full Text Available This work reports the application of a straw ash from barley as a novel bioadsorbent for the removal of several heavy metals: Ni(II, Cd(II, Cu(II, and Co(II. Equilibrium and kinetic models for heavy metals sorption were developed by considering the effect of the contact time, initial heavy metal ion concentrations, effect of temperature, and initial pH. The adsorption of heavy metal ions have been studied in terms of pseudo-first- and -second-order kinetics, and the Freundlich, Langmuir and Langmuir–Freundlich isotherms models have also been used to the equilibrium adsorption data. The equilibrium data fitted well with the Langmuir–Freundlich model and showed the following affinity order of the material: Ni(II>Cu(II>Co(II>Cd(II. The adsorption kinetics followed the mechanism of the pseudo-second-order equation for all systems studied, confirming chemical sorption as the rate-limiting step of adsorption mechanisms. The thermodynamic parameters (ΔG°, ΔH° and ΔS° indicated that the adsorption of heavy metals ions were feasible, spontaneous and endothermic at 15–80 °C.

  12. Thiocyanato complexes of Co(II), Ni(II), Zn(II), Cd(II), Cr(III) and U(IV) containing unidentate and bidentate auxiliary ligands

    International Nuclear Information System (INIS)

    Several thiocyananato complexes of Co(II), Ni(II), Zn(II), Cd(II), Cr(III) and U(VI) containing some unidentate and bidentate auxiliary ligands have been synthesised and characterized by elemental analyses, magnetic and conductivity measurement, IR and electronic spectral studies. The complexes have the composition [Co(SCN)/sub 2/4L], [Ni(SCN)/sub 2/2L.H/sub 2/O], [Zn(SCN)/sub 2/.2L], [Cd(SCN)/sub 2/.L'] [Cd(SCN)/sub 2/.2L] H/sub 2/O, [UO/sub 2/(NCS)/sub 2/.3L] and UO/sub 2/(NCS)2L'] H/sub 2/O where L=NH/sub 2/-NH/sub 2/; L'=NH/sub 2/CH/sub 2/CH/sub 2/NH/sub 2/ and C/sub 6/H/sub 4/-(NH/sub 2)/sub 2/. The molar conductance data indicate that all the complexes behave as 2:1 electrolyte in DMSO magnetic and spectral data are in support of octahedral geometry for cobalt, nickel, chromium and uranium complexes whereas the zinc and cadmium complexes are probably tetrahedral in nature. (author)

  13. The influence of steric effect and chain length on extraction of the complexes of Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) with 1-alkyl-2-methylimidazoles

    International Nuclear Information System (INIS)

    Extraction of complexes of 1,2-dimethylimidazole, 1-ethyl-2-methylimidazole, 1-propyl-2-methylimidazole and 1-butyl-2-methylimidazole with Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) from aqueous solutions (I = 0.5 at 298 K) with benzyl alcohol was investigated. For each system, the composition of extracted species, their partition constants and the pH1/2 were determined. The most readily extractable were the Cu(II) complexes as well as tetrahedral species of Zn(II), Co(II) and Cd(II). In the case of 1-butyl-2-methylimidazole, the predominating effect on the extraction was exerted by hydrophobicity of the alkyl substituent in position '1' rather than the steric effect. With this extractant extraction of Ni(II) was enhanced, while that of Co(II) compounds was suppressed. The extractability of the complexes increased with increasing length of the 1-alkyl chain. (author)

  14. Coligand-regulated assembly, fluorescence, and magnetic properties of Co(II) and Cd(II) complexes with a non-coplanar dicarboxylate

    International Nuclear Information System (INIS)

    A non-coplanar dicarboxylate ndca (H2ndca=5-norbornene-2,3-dicarboxylic acid), combining with various dipyridyl-typed tectons, constructs six Cd(II)/Co(II) coordination polymers under hydrothermal conditions, namely [Co(ndca)(H2O)]n (1), ([Co(ndca)(bpe)(H2O)]·H2O)n (2), [Co(ndca)(bpa)0.5(H2O)]n (3), [Cd(ndca)(bpe)(H2O)]n (4), ([Cd(ndca)(bpa)(H2O)]·0.5H2O)n (5), and ([Cd(ndca)(bpp) (H2O)]·H2O)n (6) (bpe=1,2-di(4-pyridyl)ethylene, bpa=1,2-bi(4-pyridyl)ethane, and bpp=1,3-bis(4-pyridyl)propane). All these compounds contain various metal(II)–carboxylate motifs, including carboxylate binuclear (2, 4, 5), carboxylate chain (1, 6) and carboxylate layer (3), which are further extended by dipyridyl-typed coligands to afford a vast diversity of the structures with 2D pyknotic layers (1, 6), 2D open layer (5), 2D→3D interpenetrated networks (2,4), and 3D pillared-layer framework (3), respectively. In addition, fluorescent spectra of Cd(II) complexes and magnetic properties of Co(II) complexes are also given. - Graphical abstract: Six various cadmium(II)/cobalt(II)–organic frameworks were constructed by 5-norbornene-2,3-dicarboxylic acid and different bis(pyridine) rod-like tectons, and Cd (II) complexes exhibit blue–violet emissions, whereas Co (II) complexes show antiferromagnetic behaviours. Display Omitted

  15. Synthesis, spectroscopic, antimicrobial and DNA cleavage studies of new Co(II), Ni(II), Cu(II), Cd(II), Zn(II) and Hg(II) complexes with naphthofuran-2-carbohydrazide Schiff base

    Science.gov (United States)

    Halli, Madappa B.; Sumathi, R. B.

    2012-08-01

    A series of Co(II), Ni(II), Cu(II), Cd(II), Zn(II) and Hg(II) complexes have been synthesized with newly synthesized Schiff base derived from naphthofuran-2-carbohydrazide and cinnamaldehyde. The elemental analyses of the complexes are confined to the stoichiometry of the type MLCl2 [M = Co(II) and Cu(II)], ML2Cl2 [M = Ni(II), Cd(II), Zn(II) and Hg(II)] respectively, where L is Schiff base ligand. Structures have been proposed from elemental analyses, IR, electronic, mass, 1H NMR, ESR spectral data, magnetic, and thermal studies. The measured low molar conductance values in DMF indicate that the complexes are non-electrolytes. Spectroscopic studies suggest coordination occurs through azomethine nitrogen and carbonyl oxygen of the ligand with the metal ions. The Schiff base and its complexes have been screened for their antibacterial (Escherichia coli, Staphylococcus aureus, Bacillus subtilis and Salmonella typhi) and antifungal (Aspergillus niger, Aspergillus flavus, Cladosporium and Candida albicans) activities by minimum inhibitory concentration (MIC) method. The DNA cleavage studies by agarose gel electrophoresis method was studied for all the complexes.

  16. Synthesis, spectral characterization and biological evaluation of Mn(II), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) complexes with thiosemicarbazone ending by pyrazole and pyridyl rings.

    Science.gov (United States)

    Yousef, T A; Abu El-Reash, G M; Al-Jahdali, M; El-Rakhawy, El-Bastawesy R

    2014-08-14

    Here we present the synthesis of the new Mn(II), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) complexes with chelating ligand (Z)-(2-((1,3-diphenyl-1H-pyrazol-4-yl)methylene) hydrazinyl)(pyridin-2-ylamino)methanethiol. All the complexes were characterized by elemental analysis, IR, (1)H NMR, UV-vis, magnetic susceptibility measurements and EPR spectral studies. IR spectra of complexes showed that the ligand behaves as NN neutral bidentate, NSN mononegative tridentate and NSNN mononegative tetradentate. The electronic spectra and the magnetic measurements suggested the octahedral geometry for all complexes as well as the EPR confirmed the tetragonal distorted octahedral for Cu(II) complex. Cd(II) complex showed the highest inhibitory antioxidant activity either using ABTS method. The SOD-like activity exhibited those Cd(II) and Zn(II) complexes have strong antioxidative properties. We tested the synthesized compounds for antitumor activity and showed that the ability to kill liver (HePG2) and breast (MCF-7) cancer cells definitely. PMID:24727176

  17. Synthesis, spectral characterization and biological evaluation of Mn(II), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) complexes with thiosemicarbazone ending by pyrazole and pyridyl rings

    Science.gov (United States)

    Yousef, T. A.; Abu El-Reash, G. M.; Al-Jahdali, M.; El-Rakhawy, El-Bastawesy R.

    2014-08-01

    Here we present the synthesis of the new Mn(II), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) complexes with chelating ligand (Z)-(2-((1,3-diphenyl-1H-pyrazol-4-yl)methylene) hydrazinyl)(pyridin-2-ylamino)methanethiol. All the complexes were characterized by elemental analysis, IR, 1H NMR, UV-vis, magnetic susceptibility measurements and EPR spectral studies. IR spectra of complexes showed that the ligand behaves as NN neutral bidentate, NSN mononegative tridentate and NSNN mononegative tetradentate. The electronic spectra and the magnetic measurements suggested the octahedral geometry for all complexes as well as the EPR confirmed the tetragonal distorted octahedral for Cu(II) complex. Cd(II) complex showed the highest inhibitory antioxidant activity either using ABTS method. The SOD-like activity exhibited those Cd(II) and Zn(II) complexes have strong antioxidative properties. We tested the synthesized compounds for antitumor activity and showed that the ability to kill liver (HePG2) and breast (MCF-7) cancer cells definitely.

  18. Synthesis and characterisation of novel ligand type N2O2 and its complexes with Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) ions

    International Nuclear Information System (INIS)

    This work include ligand preparation from the reaction of ethylenediamine with [2,4,6-trihydroxyacetophenon] and KOH (Schiff Base) to give the new tetradentate ligand 2- (1-[2- [1-2, 6- Dihydroxy-4- methyl phenyl) - ethyliden amino]- ethylimino]- ethyl- benzene- 1, 3, 5- triol [H6L]. This ligand was reacted with some metal ions (Co(II), Ni(II), Cu(II), Zn(II), and Cd(II) in methanol (1:1) metal: Ligand ratio in the presence of potassium hydroxide to give a series of new complexes of the general formula [M(H4L)], where: M=Co(II), Ni(II), Cu(II), Zn(II), and Cd(II). All compounds were determined ed by spectroscopic methods (IR, UV, VIS), CHNO analysis, and HPLC, atomic absorption, magnetic susceptibility, (El-mass for the ligand)], microanalysis along with conductivity measurements. From the obtained data the proposed molecular structure was suggested for ([Co(H4L)], [Ni(H4L) and [Cu(H4L)], complexes adopting square planar structure, and [Zn(H4L) and Cd (H4L)] complexes adopting a tetrahedral structure about the metal ions respectively. (author)

  19. Vídeo 2 de 11: Análisis Químico Cualitativo. Identificación de Cationes - Identificación del Catión Co(II): Resolución de la Interferencia con Fe(III)

    OpenAIRE

    Palacios Santander, José María; Cubillana Aguilera, Laura

    2015-01-01

    Vídeo 2 de 11. Análisis Químico Cualitativo. Identificación de Cationes - Identificación del Catión Co(II): Resolución de la Interferencia con Fe(III). En el presente vídeo se describe el proceso de identificación del catión Co(II), así como el procedimiento a seguir para resolver la interferencia con el catión Fe(III).

  20. Spectroscopic and thermal degradation behavior of Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II) and Zn(II) complexes with thiopental sodium anesthesia drug

    Science.gov (United States)

    Refat, Moamen S.

    2013-04-01

    A new series of Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II) and Zn(II) complexes have been synthesized with thiopental sodium anesthesia drug. The elemental analyses of the complexes are confined to stoichiometry of the formulas [M(TPL)3]ṡnH2O (M = Cr(III) or Fe(III); n = 6 or 5), [M(TPL)2(H2O)2]ṡnH2O (M = Mn(II), Co(II) or Ni(II); n = 0 or 4), and [M(TPL)2] (M = Cu(II) or Zn(II); n = 2 or 0) respectively, where TPL is thiopental chelating agent. Structures have been discussed and suggested upon elemental analyses, infrared, Raman, electronic, electron spin resonance, 1H NMR spectral data and magnetic studies. The X-ray powder diffraction (XRD) was performed of metal complexes. The XRD patterns indicate crystalline nature for the complexes. The measured low molar conductance values in dimethylsulfoxide indicate that the complexes are non-electrolyte nature. Spectroscopic discussion refer that coordination take place through three types: Cdbnd N (pyrimidine moiety) nitrogen and C2sbnd S (2-thiolate group) for Cr(III), Mn(II) and Fe(III), C6dbnd O (amido group) oxygen and C2sbnd S (2-thiolate group) for Co(II) and Ni(II), and Cu(II) and Zn(II) ions coordinated via Cdbnd N (pyrimidine moiety) nitrogen, C2dbnd S (2-thiolate group) and C6dbnd O (amido group) oxygen, respectively. The thermal behavior (TG/DTG/DTA) of the complexes was studied and kinetic parameters were determined by Horowitz-Metzger and Coats-Redfern methods. The thiopental and its complexes have been screened for their antimicrobial (G+ and G-) bacteria (Escherichia coli, Staphylococcus aureus, Bacillus subtilis and Pseudomonas aeruginosa) and fungi (Aspergillus flavus and Candida albicans) activities by minimum inhibitory concentration (MIC) method.

  1. Synthesis, investigation and spectroscopic characterization of piroxicam ternary complexes of Fe(II), Fe(III), Co(II), Ni(II), Cu(II) and Zn(II) with glycine and DL-phenylalanine

    Science.gov (United States)

    Mohamed, Gehad G.; El-Gamel, Nadia E. A.

    2004-11-01

    The ternary piroxicam (Pir; 4-hydroxy-2-methyl- N-(2-pyridyl)-2H-1,2-benzothiazine-3-carboxamide 1,1-dioxide) complexes of Fe(II), Fe(III), Co(II), Ni(II), Cu(II) and Zn(II) with various amino acids (AA) such as glycine (Gly) or DL-phenylalanine (PhA) were prepared and characterized by elemental analyses, molar conductance, IR, UV-Vis, magnetic moment, diffuse reflectance and X-ray powder diffraction. The UV-Vis spectra of Pir and the effect of metal chelation on the different interligand transitions are discussed in detailed manner. IR and UV-Vis spectra confirm that Pir behaves as a neutral bidentate ligand coordinated to the metal ions via the pyridine- N and carbonyl group of the amide moiety. Gly molecule acted as a uninegatively monodentate ligand and coordinate to the metal ions through its carboxylic group, in addition PhA acted as a uninegatively bidentate ligand and coordinate to the metal ions through its carboxylic and amino groups. All the chelates have octahedral geometrical structures while Cu(II)- and Zn(II)-ternary chelates with PhA have square planar geometrical structures. The molar conductance data reveal that most of these chelates are non electrolytes, while Fe(III)-Pir-Gly, Co(II)-, Ni(II)-, Cu(II)- and Zn(II)-Pir-PhA cheletes were 1:1 electrolytes. X-ray powder diffraction is used as a new tool to estimate the crystallinity of chelates as well as to elucidate their geometrical structures.

  2. Thermal, spectral, magnetic and biological studies of thiosemicarbazones complexes with metal ions: Cu(II), Co(II), Ni(II), Fe(III), Zn(II), Mn(II) and UO2(VI)

    International Nuclear Information System (INIS)

    Thiosemicarbazones ligands, isatin-3-thiosemicarbazone(HIT) and N-acetylisatin-3-thiosemicarbazone (HAIT), which have tridentate ONN coordinating sites were prepared. The complexes of both ligands with Cu(II), Co(II), Ni(II), Fe(III), Zn(II), Mn(II) and UO2(VI) ions were isolated. The ligands and their metal complexes were characterized by elemental analysis, IR, UV-Vis and mass spectra, also by conductance, magnetic moment and TG-DSC measurements. All the transition metal complexes have octahedral configurations, except Cu-complexes which have planar geometry and the UO2(VI) complexes which have coordination number 8 and may acquire the distorted dodecahedral geometry. Thermal studies explored the possibility of obtaining new complexes. Inversion from octahedral to square-planar configuration occurred upon heating the parent Ni-HIAT complex to form the corresponding pyrolytic product. The antifungal activity against the tested organisms showed that some metal complexes enhanced the activity with respect to the parent ligands. (author)

  3. Structural, spectral analysis and DNA studies of heterocyclic thiosemicarbazone ligand and its Cr(III), Fe(III), Co(II) Hg(II), and U(VI) complexes

    Science.gov (United States)

    Yousef, T. A.; Abu El-Reash, G. M.; El Morshedy, R. M.

    2013-08-01

    The paper presents a combined experimental and computational study of novel Cr(III), Fe(III), Co(II), Hg(II) and U(VI) complexes of (E)-2-((3-hydroxynaphthalen-2-yl)methylene)-N-(pyridin-2-yl)hydrazinecarbothioamide (H2L). The ligand and its complexes have been characterized by elemental analyses, spectral (IR, UV-vis, 1H NMR and 13C NMR), magnetic and thermal studies. IR spectra show that H2L is coordinated to the metal ions in a mononegative bi or tri manner. The structures are suggested to be octahedral for all complexes except Hg(II) complex is tetrahedral. Theoretical calculations have been performed to obtain IR spectra of ligand and its complexes using AM1, MM, Zindo/1, MM+ and PM3, methods. Satisfactory theoretical-experimental agreements were achieved by MM method for the ligand and PM3 for its complexes. DOS calculations carried out by MM (ADF) method for ligand Hg complex from which we concluded that the thiol form of the ligand is more active than thione form and this explains that the most complexation take place in that form. The calculated IR vibrations of the metal complexes, using the PM3 method was the nearest method for the experimental data, and it could be used for all complexes. Also, valuable information are obtained from calculation of molecular parameters for all compounds carried out by the previous methods of calculation (electronegativity of the coordination sites, net dipole moment of the metal complexes, values of heat of formation and binding energy) which approved that the complexes are more stable than ligand. The low value of ΔE could be expected to indicate H2L molecule has high inclination to bind with the metal ions. Furthermore, the kinetic and thermodynamic parameters for the different decomposition steps were calculated using the Coats-Redfern and Horowitz-Metzger methods. Finally, the biochemical studies showed that, complex 2, 4 have powerful and complete degradation effect on DNA. For the foremost majority of cases the

  4. Co(II), Cu(II), Cd(II), Fe(III) and U(VI) complexes containing a NSNO donor ligand: Synthesis, characterization, optical band gap, in vitro antimicrobial and DNA cleavage studies

    Science.gov (United States)

    Yousef, T. A.; Abu El-Reash, G. M.; El-Gammal, O. A.; Bedier, R. A.

    2012-12-01

    A new series of [Co(HPTP)Cl(H2O)2], [Cu(HPTP)Cl], [Cd(HPTP)Cl](H2O)4, [Fe(PTP)Cl(H2O)2](H2O), [UO2(HPTP)(OAc)(H2O)2] complexes of Schiff-bases derived from 4-(2-pyridyl)-3-thiosemicarbazide and pyruvic acid (H2PTP) have been synthesized and characterized by spectroscopic studies. Schiff-base exhibit thiol-thione tautomerism wherein sulfur plays an important role in the coordination. The coordination possibility of the Schiff-bases towards metal ions have been proposed in the light of elemental analyses, spectral (IR, UV-vis, 1H NMR, 13C NMR and ESR), magnetic and thermal studies. IR spectra show that H2PTP is coordinated to the metal ions in a mono or binegative tridentate manner. The electronic spectra of the complexes and their magnetic moments provide information about geometries. The room temperature solid state ESR spectra of the Cu(II) complexes show dx2-y2 as a ground state, suggesting square-planar geometry around Cu(II) center. The molecular parameters: total energy, binding energy, isolated atomic energy, electronic energy, heat of formation, dipole moment, HOMO and LUMO were calculated for the ligand and its complexes. Furthermore, the kinetic and thermodynamic parameters for the different decomposition steps were calculated using the Coats-Redfern and Horowitz-Metzger methods. Also, the optical band gap (Eg) of the metal complexes has been calculated. The optical transition energy (Eg) is direct and equals 3.25, 3.26, 3.34 and 3.27 eV for Co, Cu, Fe and U complexes, respectively. The synthesized ligand, in comparison to its metal complexes is screened for its antibacterial activity against bacterial species, Bacillus thuringiensis, Staphylococcus aureus, Pseudomonas aeruginosa and Escherichia coli. The activity data show that the metal complexes to be more potent/antibacterial than the parent Schiff base ligand against one or more bacterial species. Finally, the biochemical studies showed that, Cu, Cd and Fe complexes have powerful and complete degradation effect on DNA.

  5. On the ortho-positronium quenching reactions promoted by Fe(II), Fe(III), Co(III), Ni(II), Zn(II) and Cd(II) cyanocomplexes

    Science.gov (United States)

    Fantola Lazzarini, Anna L.; Lazzarini, Ennio

    The o-Ps quenching reactions promoted in aqueous solutions by the following six cyanocomplexes: [Fe(CN) 6] 4-; [Co(CN) 6] 3-; [Zn(CN) 4] 2-; [Cd(CN) 6] 2-; [Fe(CN) 6] 3-; [Ni(CN) 4] 2- were investigated. The first four reactions probably consist in o-Ps addition across the CN bond, their rate constants at room temperature, Tr, being ⩽(0.04±0.02) × 10 9 M -1 s -1, i.e. almost at the limit of experimental errors. The rate constant of the fifth reaction, in o-Ps oxydation, at Tr is (20.3±0.4) × 10 9 M -1 s -1. The [Ni(CN) 4] 2-k value at Tr, is (0.27±0.01) × 10 9 M -1 s -1, i.e. 100 times less than the rate constants of o-Ps oxydation, but 10 times larger than those of the o-Ps addition across the CN bond. The [Ni(CN) 4] 2- reaction probably results in formation of the following positronido complex: [Ni(CN) 4Ps] 2-. However, it is worth noting that the existence of such a complex is only indirectly deduced. In fact it arises from comparison of the [Ni(CN) 4] 2- rate constant with those of the Fe(II), Zn(II), Cd(II), and Co(III) cyanocomplexes, which, like the Ni(II) cyanocomplex, do not promote o-Ps oxydation or spin exchange reactions.

  6. Structural and electronic properties of hetero-transition-metal Keggin anions: a DFT Study of alpha/beta-[XW12O40]n- (X = CrVI, VV, TiIV, FeIII, CoIII, NiIII, CoII, and ZnII) relative stability.

    Science.gov (United States)

    Zhang, Fu-Qiang; Zhang, Xian-Ming; Wu, Hai-Shun; Jiao, Haijun

    2007-01-11

    Density functional theory calculations have been carried out to investigate the electronic structures and the alpha/beta relative stability of Keggin-typed [XW(12)O(40)]n- anions with transition metal as heteroatom X (X = Cr(VI), V(V), Ti(IV), Fe(III), Co(III), Ni(III), Co(II) and Zn(II)). Nice agreement in geometries between computation and experiment has been obtained, and the higher stability of the alpha isomer over the beta one has been confirmed. Structural parameter analysis reveals that the {M(3)O(13)} triads in both alpha and beta isomers contract considerably with the increase of the negative anionic charge, while the overall size of both isomers shrinks only slightly. Fragment molecular orbital analysis shows that except alpha/beta-[TiW(12)O(40)]4-, the electronic structures of Keggin anions can be described by the insertion of the e and/or t2 orbital of XO4n- into the frontier orbitals of W(12)O(36) cage, and this leads to the specific redox property, which is different from that of the Keggin anions with main-group elements as heteroatoms. Energy decomposition analysis shows that the enhanced intrinsic stability of the alpha isomer in Td arrangement of W(12)O(36) shell and the larger deformation of the alpha over the beta isomer are two dominating factors and contribute oppositely to the alpha/beta relative stability. PMID:17201398

  7. Synthesis and magnetic properties of Co{sub 1−x}Zn{sub x}Fe{sub 2}O{sub 4} (x=0÷1) nanopowders by thermal decomposition of Co(II), Zn(II) and Fe(III) carboxylates

    Energy Technology Data Exchange (ETDEWEB)

    Stefanescu, Mircea; Bozdog, Marius [University Politehnica Timisoara, Research Institute for Renewable Energy, 2 Piata Victoriei, 300006 Timisoara (Romania); Muntean, Cornelia, E-mail: cornelia.muntean@upt.ro [University Politehnica Timisoara, Research Institute for Renewable Energy, 2 Piata Victoriei, 300006 Timisoara (Romania); Stefanescu, Oana [University Politehnica Timisoara, Research Institute for Renewable Energy, 2 Piata Victoriei, 300006 Timisoara (Romania); Vlase, Titus [West University of Timisoara, 4 B-dul Vasile Parvan, 300223 Timisoara (Romania)

    2015-11-01

    Nanoparticles of cobalt–zinc ferrite Co{sub 1−x}Zn{sub x}Fe{sub 2}O{sub 4} with x varying from 0 to 1.0 were prepared by a new method, the thermal decomposition of carboxylates of Fe(III), Co(II) and Zn(II). The obtained carboxylate precursor was characterized by thermal analysis and FT-IR spectroscopy. The precursor was annealed at 350, 600 and 1000 °C. It was found that the spinel cobalt–zinc ferrite was formed starting at 350 °C, but in mixture with simple oxides γ-Fe{sub 2}O{sub 3}, Co{sub 3}O{sub 4} and ZnO. At 1000 °C Co{sub 1−x}Zn{sub x}Fe{sub 2}O{sub 4} was formed quantitatively as a single, well-crystallized phase. The saturation magnetization of the samples annealed at 1000 °C decreased significantly with increasing Zn{sup 2+} content from 83.93 emu/g (x=0) to 4.92 emu/g (x=1.0). At 350 and 600 °C the saturation magnetization had the same trend, even if there were contributions of other magnetic phases. Obtaining of spinel ferrite was evidenced by X-ray diffractometry and FT-IR spectrometry. Powder morphology was determined by scanning electron microscopy. Magnetic properties of the synthesized ferrites were investigated employing a conventional induction method. - Highlights: • We synthesized Co{sub 1−x}Zn{sub x}Fe{sub 2}O{sub 4} nanoparticles by decomposition of metal-carboxylates. • Decomposition leads to a homogeneous mixture of high reactive amorphous metal oxides. • This new method involves a faster synthesis procedure and yields virtually 100%. • Magnetic properties of Co{sub 1−x}Zn{sub x}Fe{sub 2}O{sub 4} depend on Zn content and annealing temperature.

  8. Aqueous Co(II) adsorption using 8-hydroxyquinoline anchored γ-Fe2O3@chitosan with Co(II) as imprinted ions.

    Science.gov (United States)

    Hossein Beyki, Mostafa; Shemirani, Farzaneh; Shirkhodaie, Mahsa

    2016-06-01

    A novel, bio-based 8-hydroxyquinoline (8-HQ) anchored magnetic chitosan using Co(II) as imprinted ions was prepared and applied for selective removal of Co(II) from aqueous solutions. At first, γ-Fe2O3 has been synthesized by solvent free precipitation route and then combined with 8-hydroxyquinoline anchored chitosan using epichlorohydrin (EPH) as crosslinking agent. The FT- IR spectra showed that 8-HQ has been successfully anchored onto chitosan structure. Moreover, TEM analysis confirmed that the nanocomposite has core-shell structure. The experimental results showed that equilibrium time was 10min moreover, the maximum adsorption capacity of Co(II) with non-imprinted and surface imprinted polymer at pH 8 were 66.6 and 100mgg(-1), respectively. The selectivity coefficient of Co(II) ions relative to Cd(II), Ni(II) and Pb(II) were 11, 42 and 2, respectively. Prepared biosorbent represented good stability and good repeatability after three cycle of sorption and desorption using 0.5molL-(1) of HNO3 as eluent. Kinetic and thermodynamic behavior were also investigated and result showed that cobalt adsorption followed second order model and endothermic path. PMID:26944662

  9. New method for the direct determination of dissolved Fe(III) concentration in acid mine waters

    International Nuclear Information System (INIS)

    A new method for direct determination of dissolved Fe(III) in acid mine water has been developed. In most present methods, Fe(III) is determined by computing the difference between total dissolved Fe and dissolved Fe(II). For acid mine waters, frequently Fe(II) much-gt Fe(III); thus, accuracy and precision are considerably improved by determining Fe(III) concentration directly. The new method utilizes two selective ligands to stabilize Fe(III) and Fe(II), thereby preventing changes in Fe reduction-oxidation distribution. Complexed Fe(II) is cleanly removed using a silica-based, reversed-phase adsorbent, yielding excellent isolation of the Fe(III) complex. Iron(III) concentration is measured colorimetrically or by graphite furnace atomic absorption spectrometry (GFAAS). The method requires inexpensive commercial reagents and simple procedures that can be used in the field. Calcium(II), Ni(II), Pb(II), Al(III), Zn(II), and Cd(II) cause insignificant colorimetric interferences for most acid mine waters. Waters containing >20 mg of Cu/L could cause a colorimetric interference and should be measured by GFAAS. Cobalt(II) and Cr(III) interfere if their molar ratios to Fe(III) exceed 24 and 5, respectively. Iron(II) interferes when its concentration exceeds the capacity of the complexing ligand. Because of the GFAAS elemental specificity, only Fe(II) is a potential interferent in the GFAAS technique. The method detection limit is 2 microg/L using GFAAS and 20 microg/L by colorimetry

  10. New method for the direct determination of dissolved Fe(III) concentration in acid mine waters

    Science.gov (United States)

    To, T.B.; Nordstrom, D.K.; Cunningham, K.M.; Ball, J.W.; McCleskey, R.B.

    1999-01-01

    A new method for direct determination of dissolved Fe(III) in acid mine water has been developed. In most present methods, Fe(III) is determined by computing the difference between total dissolved Fe and dissolved Fe(II). For acid mine waters, frequently Fe(II) >> Fe(III); thus, accuracy and precision are considerably improved by determining Fe(III) concentration directly. The new method utilizes two selective ligands to stabilize Fe(III) and Fe(II), thereby preventing changes in Fe reduction-oxidation distribution. Complexed Fe(II) is cleanly removed using a silica-based, reversed-phase adsorbent, yielding excellent isolation of the Fe(III) complex. Iron(III) concentration is measured colorimetrically or by graphite furnace atomic absorption spectrometry (GFAAS). The method requires inexpensive commercial reagents and simple procedures that can be used in the field. Calcium(II), Ni(II), Pb(II), AI(III), Zn(II), and Cd(II) cause insignificant colorimetric interferences for most acid mine waters. Waters containing >20 mg of Cu/L could cause a colorimetric interference and should be measured by GFAAS. Cobalt(II) and Cr(III) interfere if their molar ratios to Fe(III) exceed 24 and 5, respectively. Iron(II) interferes when its concentration exceeds the capacity of the complexing ligand (14 mg/L). Because of the GFAAS elemental specificity, only Fe(II) is a potential interferent in the GFAAS technique. The method detection limit is 2 ??g/L (40 nM) using GFAAS and 20 ??g/L (0.4 ??M) by colorimetry.A new method for direct determination of dissolved Fe(III) in acid mine water has been developed. In most present methods, Fe(III) is determined by computing the difference between total dissolved Fe and dissolved Fe(II). For acid mine waters, frequently Fe(II)???Fe(III); thus, accuracy and precision are considerably improved by determining Fe(III) concentration directly. The new method utilizes two selective ligands to stabilize Fe(III) and Fe(II), thereby preventing changes

  11. Proteome of Geobacter sulfurreducens grown with Fe(III) oxide or Fe(III) citrate as the electron acceptor.

    Energy Technology Data Exchange (ETDEWEB)

    Ding, Y-H R.; Hixson, Kim K.; Aklujkar, Ma; Lipton, Mary S.; Smith, Richard D.; Lovley, Derek R.; Mester, Tunde

    2008-12-01

    e(III) oxides are the most abundant source of reducible Fe(III) by microorganisms in most soils and sediments, yet few studies on the physiology of Fe(III)-reducing microorganisms during growth on Fe(III) oxide have been conducted because of the technical difficulties in working with cell growth and harvest in the presence of Fe(III) oxides. Geobacter sulfurreducens is a representative of the Geobacter species that predominate in a variety of subsurface environments in which Fe(III) oxide is important. In order to better understand the physiology of Geobacter species during growth on Fe(III) oxide, the proteome of G. sulfurreducens grown on Fe(III) oxide was compared with the proteome of cells grown with soluble Fe(III) citrate. Two-dimensional polyacrylamide gel electrophoresis (2-D PAGE) revealed 19 proteins that were more abundant during growth on Fe(III) oxide than on soluble Fe(III). These included proteins related to protein synthesis, electron transfer and energy production, oxidative stress, protein folding, outer membrane proteins, nitrogen metabolism and hypothetical proteins. Further analysis of the proteome with the accurate mass and time (AMT) tag method revealed additional proteins associated with growth on Fe(III) oxide. These included the outer-membrane c-type cytochrome, OmcS and OmcG, which genetic studies have suggested are required for Fe(III) oxide reduction. Furthermore, several other cytochromes, as yet unstudied, were detected to be significantly up regulated during growth on Fe(III) oxide and other proteins of unknown function were more abundant during growth on Fe(III) oxide than on soluble Fe(III). PilA, the structural protein for pili, which is required for Fe(III) oxide reduction, and other pilin-associated proteins were also more abundant during growth on Fe(III) oxide. Confirmation of the differential expression of proteins known to be important in Fe(III) oxide reduction was observed, and an additional number of previously

  12. Nitrilotriacetate Stimulation of Anaerobic Fe(III) Respiration by Mobilization of Humic Materials in Soil

    OpenAIRE

    Luu, Y.; Ramsay, B. A.; Ramsay, J A

    2003-01-01

    An enrichment culture capable of naphthalene mineralization reduced Fe(III) oxides without direct contact in anaerobic soil microcosms when the Fe(III) was placed in dialysis membranes or entrapped within alginate beads. Both techniques demonstrated that a component in soil, possibly humic materials, facilitated Fe(III) reduction when direct contact between cells and Fe(III) was not possible. The addition of the synthetic Fe(III) chelator, nitrilotriacetic acid (NTA), to soil enhanced Fe(III)...

  13. Removal of Co(II) from waste water using dry cow dung powder : a green ambrosia to soil

    Science.gov (United States)

    Bagla, Hemlata; Khilnani, Roshan

    2015-04-01

    Co(II) is one of the hazardous products found in the waste streams. The anthropogenic activities are major sources of Co(II) in our environment. Some of the well-established processes such as chemical precipitation, membrane process, liquid extraction and ion exchange have been applied as a tool for the removal of this metal ion [1]. All the above methods are not considered to be greener due to some of their shortcomings such as incomplete metal ion removal, high requirement of energy and reagents, generation of toxic sludge or other waste materials which in turn require further treatments for their cautious disposal. The present investigation entails the application of dry cow dung powder (DCP) as an indigenous, inexpensive and eco-friendly material for the removal of Co(II) from aqueous medium. DCP, is naturally available bio-organic, complex, polymorphic humified fecal matter of cow and is enriched with minerals, carbohydrates, fats, proteins, bile pigments, aliphatic-aromatic species such as 'Humic acid' (HA), Fulvic acid, Ulmic acid [2,3]. Batch biosorption experiments were conducted employing 60Co(II) as a tracer and effect of various process parameters such as pH (1-8), temperature (283-363K), amount of biosorbent (5-40 g/L), time of equilibration (0-30 min), agitation speed (0-4000 rpm), concentration of initial metal ions (0.5-20 mg/mL) and interfering effect of different organic as well as inorganic salts were studied. The Kinetic studies were carried out employing various models but the best fitting was given by Lagergren Pseudo-second order model [4] with high correlation coefficient R2 value of 0.999 and adsorption capacity of 2.31 mg/g. The thermodynamic parameters for biosorption were also evaluated which indicated spontaneous and exothermic process with high affinity of DCP for Co(II). Many naturally available materials are used for biosorption of hazardous metal pollutants, where most of them are physically or chemically modified. In this research

  14. Synthesis and characterization of a surface-grafted Cd(II) ion-imprinted polymer for selective separation of Cd(II) ion from aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    Li, Min [State Key Laboratory of Explosion Science and Technology, Beijing Institute of Technology, Beijing 100081 (China); Feng, Changgen, E-mail: cgfeng@cast.org.cn [State Key Laboratory of Explosion Science and Technology, Beijing Institute of Technology, Beijing 100081 (China); Li, Mingyu; Zeng, Qingxuan; Gan, Qiang [State Key Laboratory of Explosion Science and Technology, Beijing Institute of Technology, Beijing 100081 (China); Yang, Haiyan [Research Institute of Tsinghua University in Shenzhen, Shenzhen 518057 (China)

    2015-03-30

    Highlights: • Cd(II) ion-imprinted polymer (Cd(II)-IIP) is prepared. • Cd(II)-IIP shows high stability, good selectivity and reusability. • Cd(II)-IIP can be used as a sorbent for selective removal of Cd(II) ion. - Abstract: A novel Cd(II) ion-imprinted polymer (Cd(II)-IIP) was prepared with surface imprinting technology by using cadmium chloride as a template and allyl thiourea (ATU) as a functional monomer for on-line solid-phase extraction of trace Cd(II) ion and selective separation Cd(II) ion in water samples. The Cd(II)-IIP exhibited good chemical performance and thermal stability. Kinetics studies showed that the equilibrium adsorption was achieved within 8.0 min and the adsorption process can be described by pseudo-second-order kinetic model. Compared to the Cd(II) non-imprinted polymer (Cd(II)-NIP), the Cd(II)-IIP had a higher adsorption capacity and selectivity for Cd(II) ion. The maximum adsorption capacities of the Cd(II)-IIP and Cd(II)-NIP for Cd(II) were 38.30 and 13.21 mg g{sup −1}, respectively. The relative selectivity coefficients of the adsorbent for Cd(II) in the presence of Cu{sup 2+}, Ni{sup 2+}, Co{sup 2+}, Pb{sup 2+} and Zn{sup 2+} were 2.86, 6.42, 11.50, 9.46 and 3.73, respectively. In addition, the Cd(II) ion adsorbed was easy to remove from sorbent and the Cd(II)-IIP exhibited good stability and reusability. The adsorption capacity had no obvious decrease after being used six times. The accuracy of this method was verified by the standard reference material, it was then applied for cadmium ion determination in different types of water samples.

  15. Synthesis and characterization of a surface-grafted Cd(II) ion-imprinted polymer for selective separation of Cd(II) ion from aqueous solution

    International Nuclear Information System (INIS)

    Highlights: • Cd(II) ion-imprinted polymer (Cd(II)-IIP) is prepared. • Cd(II)-IIP shows high stability, good selectivity and reusability. • Cd(II)-IIP can be used as a sorbent for selective removal of Cd(II) ion. - Abstract: A novel Cd(II) ion-imprinted polymer (Cd(II)-IIP) was prepared with surface imprinting technology by using cadmium chloride as a template and allyl thiourea (ATU) as a functional monomer for on-line solid-phase extraction of trace Cd(II) ion and selective separation Cd(II) ion in water samples. The Cd(II)-IIP exhibited good chemical performance and thermal stability. Kinetics studies showed that the equilibrium adsorption was achieved within 8.0 min and the adsorption process can be described by pseudo-second-order kinetic model. Compared to the Cd(II) non-imprinted polymer (Cd(II)-NIP), the Cd(II)-IIP had a higher adsorption capacity and selectivity for Cd(II) ion. The maximum adsorption capacities of the Cd(II)-IIP and Cd(II)-NIP for Cd(II) were 38.30 and 13.21 mg g−1, respectively. The relative selectivity coefficients of the adsorbent for Cd(II) in the presence of Cu2+, Ni2+, Co2+, Pb2+ and Zn2+ were 2.86, 6.42, 11.50, 9.46 and 3.73, respectively. In addition, the Cd(II) ion adsorbed was easy to remove from sorbent and the Cd(II)-IIP exhibited good stability and reusability. The adsorption capacity had no obvious decrease after being used six times. The accuracy of this method was verified by the standard reference material, it was then applied for cadmium ion determination in different types of water samples

  16. Adsorption of Cd(II) by two variable-charge soils in the presence of pectin.

    Science.gov (United States)

    Wang, Ru-Hai; Zhu, Xiao-Fang; Qian, Wei; Zhao, Min-Hua; Xu, Ren-Kou; Yu, Yuan-Chun

    2016-07-01

    Batch experiments were conducted to investigate cadmium(II) (Cd(II)) adsorption by two variable-charge soils (an Oxisol and an Ultisol) as influenced by the presence of pectin. When pectin dosage was less than 30 g kg(-1), the increase in Cd(II) adsorption with the increasing dose of pectin was greater than that when the pectin dosage was >30 g kg(-1). Although both Langmuir and Freundlich equations fitted the adsorption isotherms of Cd(II) and electrostatic adsorption data of Cd(II) by the two soils well, the Langmuir equation showed a better fit. The increase in the maximum total adsorption of Cd(II) induced by pectin was almost equal in both the soils, whereas the increase in the maximum electrostatic adsorption of Cd(II) was greater in the Oxisol than in the Ultisol because the former contained greater amounts of free Fe/Al oxides than the latter, which, in turn, led to a greater increase in the negative charge on the Oxisol. Therefore, the presence of pectin induced the increase in Cd(II) adsorption by the variable-charge soils mainly through the electrostatic mechanism. Pectin increased the adsorption of Cd(II) by the variable-charge soils and thus decreased the activity and mobility of Cd(II) in these soils. PMID:26996909

  17. Sensitive electrochemical sensor using a graphene–polyaniline nanocomposite for simultaneous detection of Zn(II), Cd(II), and Pb(II)

    International Nuclear Information System (INIS)

    Highlights: • Detection limits for Zn, Pb, and Cd using ASV were 1, 0.1, and 0.1 μg L−1, respectively. • G/PANI-modification led to a 3× improvement in signal vs. unmodified electrodes. • ASV on a plastic substrate exhibited better sensitivity than on a paper substrate. • Zn, Pb, and Cd were measured in human serum using method of standard addition. - Abstract: This work describes the development of an electrochemical sensor for simultaneous detection of Zn(II), Cd(II), and Pb(II) using a graphene–polyaniline (G/PANI) nanocomposite electrode prepared by reverse-phase polymerization in the presence of polyvinylpyrrolidone (PVP). Two substrate materials (plastic film and filter paper) and two nanocomposite deposition methods (drop-casting and electrospraying) were investigated. Square-wave anodic stripping voltammetry currents were higher for plastic vs. paper substrates. Performance of the G/PANI nanocomposites was characterized by scanning electron microscopy (SEM) and cyclic voltammetry. The G/PANI-modified electrode exhibited high electrochemical conductivity, producing a three-fold increase in anodic peak current (vs. the unmodified electrode). The G/PANI-modified electrode also showed evidence of increased surface area under SEM. Square-wave anodic stripping voltammetry was used to measure Zn(II), Cd(II), and Pb(II) in the presence of Bi(III). A linear working range of 1–300 μg L−1 was established between anodic current and metal ion concentration with detection limits (S/N = 3) of 1.0 μg L−1 for Zn(II), and 0.1 μg L−1 for both Cd(II) and Pb(II). The G/PANI-modified electrode allowed selective determination of the target metals in the presence of common metal interferences including Mn(II), Cu(II), Fe(III), Fe(II), Co(III), and Ni(II). Repeat assays on the same device demonstrated good reproducibility (%RSD < 11) over 10 serial runs. Finally, this system was utilized for determining Zn(II), Cd(II), and Pb(II) in human serum using the

  18. Synthesis, physicochemical characterization, DFT calculation and biological activities of Fe(III) and Co(II)-omeprazole complexes. Potential application in the Helicobacter pylori eradication

    Science.gov (United States)

    Russo, Marcos G.; Vega Hissi, Esteban G.; Rizzi, Alberto C.; Brondino, Carlos D.; Salinas Ibañez, Ángel G.; Vega, Alba E.; Silva, Humberto J.; Mercader, Roberto; Narda, Griselda E.

    2014-03-01

    The reaction between the antiulcer agent omeprazole (OMZ) with Fe(III) and Co(II) ions was studied, observing a high ability to form metal complexes. The isolated microcrystalline solid complexes were characterized by elemental analysis, X-ray powder diffraction (XRPD), Scanning Electron Microscopy (SEM), magnetic measurements, thermal study, FTIR, UV-Visible, Mössbauer, electronic paramagnetic resonance (EPR), and DFT calculations. The metal-ligand ratio for both complexes was 1:2 determined by elemental and thermal analysis. FTIR spectroscopy showed that OMZ acts as a neutral bidentate ligand through the pyridinic nitrogen of the benzimidazole ring and the oxygen atom of the sulfoxide group, forming a five-membered ring chelate. Electronic, Mössbauer, and EPR spectra together with magnetic measurements indicate a distorted octahedral geometry around the metal ions, where the coordination sphere is completed by two water molecules. SEM and XRPD were used to characterize the morphology and the crystal nature of the complexes. The most favorable conformation for the Fe(III)-OMZ and Co(II)-OMZ complexes was obtained by DFT calculations by using B3LYP/6-31G(d)&LanL2DZ//B3LYP/3-21G(d)&LanL2DZ basis set. Studies of solubility along with the antibacterial activity against Helicobacter pylori for OMZ and its Co(II) and Fe(III) complexes are also reported. Free OMZ and both metal complexes showed antibacterial activity against H. pylori. Co(II)-OMZ presented a minimal inhibitory concentration ˜32 times lower than that of OMZ and ˜65 lower than Fe(III)-OMZ, revealing its promising potential use for the treatment of gastric pathologies associated with the Gram negative bacteria. The morphological changes observed in the cell membrane of the bacteria after the incubation with the metal-complexes were also analyzed by SEM microscopy. The antimicrobial activity of the complexes was proved by the viability test.

  19. Synthesis and characterization of a surface-grafted Cd(II) ion-imprinted polymer for selective separation of Cd(II) ion from aqueous solution

    Science.gov (United States)

    Li, Min; Feng, Changgen; Li, Mingyu; Zeng, Qingxuan; Gan, Qiang; Yang, Haiyan

    2015-03-01

    A novel Cd(II) ion-imprinted polymer (Cd(II)-IIP) was prepared with surface imprinting technology by using cadmium chloride as a template and allyl thiourea (ATU) as a functional monomer for on-line solid-phase extraction of trace Cd(II) ion and selective separation Cd(II) ion in water samples. The Cd(II)-IIP exhibited good chemical performance and thermal stability. Kinetics studies showed that the equilibrium adsorption was achieved within 8.0 min and the adsorption process can be described by pseudo-second-order kinetic model. Compared to the Cd(II) non-imprinted polymer (Cd(II)-NIP), the Cd(II)-IIP had a higher adsorption capacity and selectivity for Cd(II) ion. The maximum adsorption capacities of the Cd(II)-IIP and Cd(II)-NIP for Cd(II) were 38.30 and 13.21 mg g-1, respectively. The relative selectivity coefficients of the adsorbent for Cd(II) in the presence of Cu2+, Ni2+, Co2+, Pb2+ and Zn2+ were 2.86, 6.42, 11.50, 9.46 and 3.73, respectively. In addition, the Cd(II) ion adsorbed was easy to remove from sorbent and the Cd(II)-IIP exhibited good stability and reusability. The adsorption capacity had no obvious decrease after being used six times. The accuracy of this method was verified by the standard reference material, it was then applied for cadmium ion determination in different types of water samples.

  20. Particle Aggregation During Fe(III) Bioreduction in Nontronite

    Science.gov (United States)

    Jaisi, D. P.; Dong, H.; Hi, Z.; Kim, J.

    2005-12-01

    This study was performed to evaluate the rate and mechanism of particle aggregation during bacterial Fe (III) reduction in different size fractions of nontronite and to investigate the role of different factors contributing to particle aggregation. To achieve this goal, microbial Fe(III) reduction experiments were performed with lactate as an electron donor, Fe(III) in nontronite as an electron acceptor, and AQDS as an electron shuttle in bicarbonate buffer using Shewanella putrefaceins CN32. These experiments were performed with and without Na- pyrophosphate as a dispersant in four size fractions of nontronite (0.12-0.22, 0.41-0.69, 0.73-0.96 and 1.42-1.8 mm). The rate of nontronite aggregation during the Fe(III) bioreduction was measured by analyzing particle size distribution using photon correlation spectroscopy (PCS) and SEM images analysis. Similarly, the changes in particle morphology during particle aggregation were determined by analyses of SEM images. Changes in particle surface charge were measured with electrophoretic mobility analyzer. The protein and carbohydrate fraction of EPS produced by cells during Fe(III) bioreduction was measured using Bradford and phenol-sulfuric acid extraction method, respectively. In the presence of the dispersant, the extent of Fe(III) bioreduction was 11.5-12.2% within the first 56 hours of the experiment. There was no measurable particle aggregation in control experiments. The PCS measurements showed that the increase in the effective diameter (95% percentile) was by a factor of 3.1 and 1.9 for particle size of 0.12-0.22 mm and 1.42-1.80 mm, respectively. The SEM image analyses also gave the similar magnitude of increase in particle size. In the absence of the dispersant, the extent of Fe(III) bioreduction was 13.4-14.5% in 56 hours of the experiment. The rate of aggregation was higher than that in the presence of the dispersant. The increase in the effective diameter (95% percentile) was by a factor of 13.6 and 4.1 for

  1. Magnetic and low temperature phonon studies of CoCr2O4 powders doped with Fe(III) and Ni(II) ions

    International Nuclear Information System (INIS)

    Extensive temperature-dependent phonon studies and low-temperature magnetic measurements of CoCr2−xFexO4 (for x=0.5, 1 and 2) and Co0.9Ni0.1Cr2O4 polycrystalline powders are presented. The main aim of these studies was to obtain information on phonon and structural properties of these compounds as well as strength of spin–phonon coupling in the magnetically ordered phases. IR and Raman spectra show that doping of CoCr2O4 with Fe(III) ions leads to broadening of bands and appearance of new bands due to the formation of inverted spinel structure. In contrast to this behavior, doping with 10 mol% of Ni(II) ions leads to weak increase of band width only. Magnetization measured as a function of temperature and external magnetic field showed that magnetic properties of Co0.9Ni0.1Cr2O4 sample are similar to those reported for pure CoCr2O4, i.e., partial substitution of Ni(II) for Co(II) leads to slight shift of the ferrimagnetic phase transition at TC and spiral spin order transition at TS towards lower values. The change of crystallization preference induced by incorporation of increasing concentration of Fe(III) ions in the spinel lattice causes significant increase of TC and decrease of TS. The latter transition disappears completely for higher concentrations of Fe(III). The performed temperature-dependent IR studies revealed interesting anomalous behavior of phonons below TC for CoCr1.5Fe0.5O4 and Co0.9Ni0.1Cr2O4, which was attributed to spin–phonon coupling. - Graphical abstract: Visualization of normal spinel-type AB2O4 structure, where blue octahedrons denote BO6 and red tetrahedrons AO4 units as well as IR and Raman spectra of Co0.9Ni0.1Cr2O4 powder. - Highlights: • TC (TS) increases (decreases) with increasing Fe(III) concentration. • Ni(II) ions doping up to 10 mol% does not change remarkably TC and TS. • Doping with Fe(III) ions causes increase of spinel inversion parameter. • Spin–phonon interactions in Co0.9Ni0.1Cr2O4 and CoCr1.5Fe0.5O4 were

  2. Loading Ag nanoparticles on Cd(II) boron imidazolate framework for photocatalysis

    Science.gov (United States)

    Liu, Min; Zhang, De-Xiang; Chen, Shumei; Wen, Tian

    2016-05-01

    An amine-functionalized Cd(II) boron imidazolate framework (BIF-77) with three-dimensional open structure has been successfully synthesized, which can load Ag nanoparticles (NPs) for photocatalytic degradation of methylene blue (MB).

  3. SINGLE AND DOUBLE IMPRINTED POLYMER FOR SELECTIVE RECOGNITION OF Cd(II) IONS IN AQUEOUS MEDIA

    OpenAIRE

    Ebru Birlik ÖZKÜTÜK; Elif ÖZALP; Gülgün İŞLER

    2010-01-01

    In this paper, we have reported the synthesis of a new single and double-imprinted polymeric material for the separation of Cd(II) ions in aqueous solutions. Chitosan has choosen as the Cd(II) metal complexing big polymer for single and double imprinted polymers. In the synthesis of single imprinted polymer, Cd(II)-complexed chitosan has crosslinked by epichlorohydrin. In the synthesis of double imprinted polymer, Cd(II)-complexed chitosan was reacted with 3-mercaptopropyl-trimethoxysilane. ...

  4. Experimental and theoretical approaches for Cd(II) biosorption from aqueous solution using Oryza sativa biomass.

    Science.gov (United States)

    Fawzy, Manal; Nasr, Mahmoud; Helmi, Shacker; Nagy, Heba

    2016-11-01

    Biomass of Oryza sativa (OS) was tested for the removal of Cd(II) ions from synthetic and real wastewater samples. Batch experiments were conducted to investigate the effects of operating parameters on Cd(II) biosorption. Fourier transform infrared spectroscopy, scanning electron microscopy, and energy-dispersive x-ray spectroscopy were used to examine the surface characteristics of the Cd(II)-loaded biomass. The maximum removal efficiency of Cd(II) was 89.4% at optimum pH 6.0, biosorbent dose 10.0 g L(-1), initial Cd(II) 50 mg L(-1), and biosorbent particle size 0.5 mm. The applicability of Langmuir and Freundlich isotherms to the sorbent system implied the existence of both monolayer and heterogeneous surface conditions. Kinetic studies revealed that the adsorption process of Cd(II) followed the pseudo-second-order model (r2: 0.99). On the theoretical side, an adaptive neuro-fuzzy inference system (ANFIS) was applied to select the operating parameter that mostly influences the Cd(II) biosorption process. Results from ANFIS indicated that pH was the most influential parameter affecting Cd(II) removal efficiency, indicating that the biomass of OS was strongly pH sensitive. Finally, the biomass was confirmed to adsorb Cd(II) from real wastewater samples with removal efficiency close to 100%. However, feasibility studies of such systems on a large-scale application remain to be investigated. PMID:27185086

  5. Biosorption of Cd(II) and Zn(II) by nostoc commune: isotherm and kinetics studies

    Energy Technology Data Exchange (ETDEWEB)

    Morsy, Fatthy M. [Faculty of Science, Botany Department, Assiut University, Assiut (Egypt); Hassan, Sedky H.A. [Department of Biological Environment, Kangwon National University, Kangwon-do (Korea, Republic of); Koutb, Mostafa [Faculty of Science, Botany Department, Assiut University, Assiut (Egypt); Umm Al-Qura University, Faculty of Applied Science, Biology Department, Mecca (Saudi Arabia)

    2011-07-15

    In this study, Nostoc commune (cyanobacterium) was used as an inexpensive and efficient biosorbent for Cd(II) and Zn(II) removal from aqueous solutions. The effect of various physicochemical factors on Cd(II) and Zn(II) biosorption such as pH 2.0-7.0, initial metal concentration 0.0-300 mg/L and contact time 0-120 min were studied. Optimum pH for removal of Cd(II) and Zn(II) was 6.0, while the contact time was 30 min at room temperature. The nature of biosorbent and metal ion interaction was evaluated by infrared (IR) technique. IR analysis of bacterial biomass revealed the presence of amino, carboxyl, hydroxyl, and carbonyl groups, which are responsible for biosorption of Cd(II) and Zn (II). The maximum biosorption capacities for Cd(II) and Zn(II) biosorption by N. commune calculated from Langmuir biosorption isotherm were 126.32 and 115.41 mg/g, respectively. The biosorption isotherm for two biosorbents fitted well with Freundlich isotherm than Langmuir model with correlation coefficient (r{sup 2} < 0.99). The biosorption kinetic data were fitted well with the pseudo-second-order kinetic model. Thus, this study indicated that the N. commune is an efficient biosorbent for the removal of Cd(II) and Zn(II) from aqueous solutions. (Copyright copyright 2011 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  6. Adsorption studies on Parthenium hysterophorous weed: Removal and recovery of Cd(II) from wastewater

    International Nuclear Information System (INIS)

    The efficiency of parthenium weed as an adsorbent for removing Cd(II) from water has been studied. Parthenium is found to exhibit substantial adsorption capacity over a wide range of initial Cd(II) ions concentration. Effect of time, temperature, pH and concentration on the adsorption of Cd(II) was investigated by batch process. Pseudo-first-order and Pseudo-second-order models were evaluated. The kinetics data for the adsorption process obeyed second-order rate equation. The equilibrium data could be described well by the Langmuir and Freundlich isotherms. Thermodynamic parameters such as ΔHo, ΔSo and ΔGo were calculated. The adsorption process was found to be endothermic and spontaneous. The maximum adsorption of Cd(II) ions (99.7%) in the pH range 3-4 indicated that material could be effectively utilized for the removal of Cd(II) ions from wastewater. The desorption studies showed 82% recovery of Cd(II) when 0.1 M HCl solution was used as effluent

  7. Studies of the polynuclear complexes of labile ligands of vitamin B1 and Zn(II), Cd(II) and Hg(II) with Fe(III)

    International Nuclear Information System (INIS)

    The ligands (complex salts) of vitamin B/sub 1/ (H Vit.) and the chlorides of Zn, Cd and Hg with the general formula, [H Vit]/sup +2/ [MCl/sub 4/]/sup -2/ were prepared and their interactions with iron (III) investigated. It was found that the complex salts of Zn and Cd produced the dinuclear complexes and that of mercury produced a complex without the thiamine moiety. The possible reason for the absence of a Hg complex similar to those of Zn and Cd may be that large size of mercury ion. The complexes were characterized by elementary analyses, infrared and visible spectra, magnetic moment and conductivity measurements.(author)

  8. Biosorption of Cd(II) on jatropha fruit coat and seed coat.

    Science.gov (United States)

    Jain, Niveta; Johnson, Thomas Anish; Johnson, Thoma Anish; Kumar, Amit; Mishra, ShahiVind; Gupta, Navindu

    2015-07-01

    Jatropha (Jatropha curcas L.) seed coat (JSC) and fruit coat (JFC) were investigated for adsorption of Cd(II) from aqueous solutions. JFC and JSC fine powders were characterized using FTIR and SEM which indicated that both the adsorbents have high surface area, pore space on their surface, and anionic sites for metal ion binding. Batch adsorption study was conducted to study the effect of adsorption time, agitation speed, and initial concentration of Cd(II) ion, pH, and temperature on the adsorption of Cd(II) by adsorbents. The equilibrium isotherm, kinetics, and thermodynamics of the adsorption process were studied. Adsorption equilibrium followed both Langmuir and Freundlich isotherm. The adsorption capacity (Q m ) of Cd(II) on JSC and JFC were 22.83 and 21.97 mg g(-1), respectively. The adsorption of Cd(II) on JSC and JFC is endothermic in nature. The change of free energy (∆G) of the biosorption of Cd(II) on JSC ranged from -37.05 to -40.54 kJ mol(-1) and for JFC -34.50 to -37.35 kJ mol(-1). The enthalpy change (∆H) and entropy change (∆S) was 15.84 kJ mol(-1) and -0.17 kJ mol(-1) K(-1) for JSC and 8.77 kJ mol(-1) and -0.14 kJ mol(-1) K(-1) for JFC. Elovich model provided a better correlation of the experimental data in comparison with pseudo-first-order and pseudo-second-order kinetic models. The study indicated that JFC and JSC have good adsorption capacity for Cd(II). PMID:26050066

  9. Preconcentration of Fe(III), Co(II), Ni(II), Cu(II), Zn(II) and Pb(II) with ethylenediamine-modified graphene oxide

    OpenAIRE

    Zawisza, Beata; Baranik, Anna; Malicka, Ewa; Talik, Ewa; Sitko, Rafał

    2015-01-01

    We describe a novel solid phase sorbent that was synthesized by coupling graphene oxide (GO) to ethylenediamine (EDA). This nanomaterial (referred to as GO-EDA) is capable of adsorbing the ions of iron, cobalt, nickel, copper, zinc and lead. The ethylenediamine-modified graphene oxide was characterized by X-ray photoelectron spectroscopy, scanning electron microscopy and Fourier transform infrared spectroscopy. The analytical procedure relies on (a) sorption of metal ions on GO-EDA dispersed ...

  10. The novel approach to Cd(II) extraction by polymer inclusion membrane using TIOA as carrier

    Science.gov (United States)

    Polat, Cüneyt; Eyüpoǧlu, Volkan; Sara, Osman Nuri

    2016-04-01

    In the present study, the novel approach for the extraction of Cd(II) from acidic iodide solutions was achieved by using PVC based polymer inclusion membrane (PIM) technique containing triisooctyl amine (TIOA) as a carrier. PIMs were prepared according to the literature (1) and characterized by in aspects of thickness and surface morphology and molecular characterization. PIM composition was varied to find optimum membrane formation on Cd(II) transport. The effective parameters like thickness, plasticizer type and rate and carrier rate were investigated. Also, as a useful parameter, the concentration in the feed phase was examined to assess the effect on optimized membrane compositions. It was found that the concentration was the most useful parameter in the aqueous phase of Cd(II) transport because the remained I- in the aqueous feed phase unreacted with Cd(II). We recognize that by the time free I- concentration in the feed, the accumulation of the membrane increases and loading capacity of the membrane with CdI42- decreases because of the limited amount of carrier molecules in the PIM. As a result, it is concluded that extraction and separation of Cd(II) from simulated Ni/Cd leach solutions was carried out with higher initial mass transfer and permeation coefficients as 9,07×10-7 mol/m2s and 1,02×10-5 m/s at the optimum conditions respectively.

  11. Solution chemistry effects on sorption behavior of 109Cd(II) on Ca-montmorillonite

    International Nuclear Information System (INIS)

    The sorption of radiocadmium on Ca-montmorillonite as a function of contact time, pH, ionic strength, foreign ions, humic acid (HA) and fulvic acid (FA) was studied using batch technique. The results demonstrated that the sorption of Cd(II) was dependent on ionic strength at pH 9. Outer-sphere surface complexation and/or ion exchange were the main mechanism of Cd(II) sorption on Ca-montmorillonite at low pH, whereas the sorption at high pH was mainly dominated via inner-sphere surface complexation. The sorption of Cd(II) on Ca-montmorillonite was dependent on foreign ions at low pH values, but was independent of foreign ions at high pH values. A positive effect of HA/FA on Cd(II) sorption was found at low pH values, whereas a negative effect was observed at high pH values. The thermodynamic parameters (i.e., ΔH0, ΔS0, ΔG0) were calculated from the temperature dependent sorption isotherms, and the results indicated that the sorption process of Cd(II) on Ca-montmorillonite was spontaneous and endothermic. (author)

  12. SINGLE AND DOUBLE IMPRINTED POLYMER FOR SELECTIVE RECOGNITION OF Cd(II IONS IN AQUEOUS MEDIA

    Directory of Open Access Journals (Sweden)

    Ebru Birlik ÖZKÜTÜK

    2010-12-01

    Full Text Available In this paper, we have reported the synthesis of a new single and double-imprinted polymeric material for the separation of Cd(II ions in aqueous solutions. Chitosan has choosen as the Cd(II metal complexing big polymer for single and double imprinted polymers. In the synthesis of single imprinted polymer, Cd(II-complexed chitosan has crosslinked by epichlorohydrin. In the synthesis of double imprinted polymer, Cd(II-complexed chitosan was reacted with 3-mercaptopropyl-trimethoxysilane. Then, the polymeric beads have crosslinked with tetraethoxysilane (TEOS. The imprinted cadmium ions have removed from the polymeric matrix by 0.1M HNO3 (to prepare Cd(II templates. Optimum pH for rebinding of Cd(II on the single and double-imprinted polymers was 7.0. Equilibrium binding time and sorbent capacity have been found as 120 and 60 min, 342 and 172 mg g-1 for single and double imprinted polymers, respectively. In selectivity studies, it has been found that double imprinted results in increased affinity of the material toward Cd(II ion over other competitor metal ions with the same charge. The prepared single and double-imprinted polymers have repeatedly used and regenerated for thirty times without a significant decrease in polymer binding affinities.

  13. Spectroscopic and Thermogravimetric Investigation of Cd(II Dinonyldithiophosphate: Removal of Cadmium from Aqueous Solutions

    Directory of Open Access Journals (Sweden)

    Nermin Biricik

    2015-01-01

    Full Text Available Dinonyldithiophosphoric acid (HDDTP was synthesised from the reaction of phosphorus pentasulphide and nonyl alcohol. Dinonyldithiophosphate complex of cadmium [Cd(DDTP2] was prepared by mixing solutions of Cd(II with HDDTP in ethanol at room temperature. The acid and its complex were characterised by elemental analysis and spectroscopy. The thermal behaviour of Cd(DNDTP2 was investigated by thermogravimetric analysis. Removal of Cd(II from aqueous media by HDDTP solution was also studied. The optimum conditions for removal of Cd(II were investigated for effects of solvent, pH, contact time, concentration, and inorganic anions. Cd(II was quantitatively removed from aqueous solutions at the pH range of 0.5Cd(II with HDDTP was sufficient for quantitative removing of cadmium from acidic aqueous solutions.

  14. Advanced experimental analysis of controls on microbial Fe(III) oxide reduction. First year progress report

    Energy Technology Data Exchange (ETDEWEB)

    Roden, E.E.; Urrutia, M.M.

    1997-07-01

    'The authors have made considerable progress toward a number of project objectives during the first several months of activity on the project. An exhaustive analysis was made of the growth rate and biomass yield (both derived from measurements of cell protein production) of two representative strains of Fe(III)-reducing bacteria (Shewanellaalga strain BrY and Geobactermetallireducens) growing with different forms of Fe(III) as an electron acceptor. These two fundamentally different types of Fe(III)-reducing bacteria (FeRB) showed comparable rates of Fe(III) reduction, cell growth, and biomass yield during reduction of soluble Fe(III)-citrate and solid-phase amorphous hydrous ferric oxide (HFO). Intrinsic growth rates of the two FeRB were strongly influenced by whether a soluble or a solid-phase source of Fe(III) was provided: growth rates on soluble Fe(III) were 10--20 times higher than those on solid-phase Fe(III) oxide. Intrinsic FeRB growth rates were comparable during reduction of HF0 and a synthetic crystalline Fe(III) oxide (goethite). A distinct lag phase for protein production was observed during the first several days of incubation in solid-phase Fe(III) oxide medium, even though Fe(III) reduction proceeded without any lag. No such lag between protein production and Fe(III) reduction was observed during growth with soluble Fe(III). This result suggested that protein synthesis coupled to solid-phase Fe(III) oxide reduction in batch culture requires an initial investment of energy (generated by Fe(III) reduction), which is probably needed for synthesis of materials (e.g. extracellular polysaccharides) required for attachment of the cells to oxide surfaces. This phenomenon may have important implications for modeling the growth of FeRB in subsurface sedimentary environments, where attachment and continued adhesion to solid-phase materials will be required for maintenance of Fe(III) reduction activity. Despite considerable differences in the rate and

  15. Functionalization of conducting polymer with novel Co(II) complex: Electroanalysis of ascorbic acid

    International Nuclear Information System (INIS)

    We report for the first time the functionalization of a conducting polymer with a metal complex in order to develop a new type of catalytic material exhibiting better electronic communication through their delocalized π electrons. The Co(II) complex having hydroxyl group as functional moiety is chemically coupled with carboxyl group of polyanthranilic acid which itself is a self doped conducting polymer. The covalent linkage between Co(II) and -OH group is confirmed using UV-vis, FT-IR and NMR spectroscopic techniques. The Co(II) complex functionalized polymer does exhibit excellent redox behavior and stability with mixed properties of Co(II) complex and π-conjugated polymer. The material possesses potential benefits in sensors/biosensor applications and it is demonstrated for the electroanalysis of ascorbic acid at a level of nano molar concentration.

  16. Removal of Co(II) from aqueous solution by using hydroxyapatite

    International Nuclear Information System (INIS)

    Herein, hydroxyapatite (HAP) was prepared by aqueous precipitation technique and was characterized by using FT-IR and XRD to determine its chemical functional groups and micro-structure. The removal of cobalt from aqueous solution to HAP was studied by batch technique as a function of various environmental parameters such as contact time, pH, ionic strength, foreign ions, fulvic acid (FA), and temperature under ambient conditions. The results indicated that the sorption of Co(II) on HAP was strongly dependent on pH and ionic strength. The presence of FA enhanced the sorption of Co(II) on HAP at low pH, whereas reduced Co(II) sorption on HAP at high pH. The Langmuir, Freundlich and D-R models were used to simulate the sorption isotherms at three different temperatures of 303.15, 323.15 and 343.15 K. The thermodynamic parameters (ΔHdeg, ΔSdeg and ΔGdeg) calculated from the temperature dependent sorption isotherms indicated that the sorption process of Co(II) on HAP was spontaneous and endothermic. The sorption of Co(II) was dominated by outer-sphere surface complexation and ion exchange at low pH, whereas inner-sphere surface complexation or surface precipitation was the main sorption mechanism at high pH values. The results suggest that the HAP is a suitable material in the preconcentration and solidification of Co(II) from large volumes of aqueous solutions. (author)

  17. Investigation of Co(II) sorption on GMZ bentonite from aqueous solutions by batch experiments

    International Nuclear Information System (INIS)

    In this study, a local bentonite from Gaomiaozi county (Inner Mongolia, China) was converted to Na-bentonite and was characterized by FTIR and XRD to determine its chemical constituents and micro-structure. The removal of cobalt from aqueous solutions by Na-bentonite was investigated as a function of contact time, pH, ionic strength, foreign ions and temperature by batch technique under ambient conditions. The results indicated that the sorption of Co(II) was strongly dependent on pH. At low pH, the sorption of Co(II) was dominated by outer-sphere surface complexation or ion exchange whereas inner-sphere surface complexation was the main sorption mechanism at high pH. The Langmuir, Freundlich, and D-R models were used to simulate the sorption isotherms of Co(II) at the temperatures of 293.15, 313.15 and 333.15 K, respectively. The thermodynamic parameters (ΔG0, ΔS0, ΔH0) of Co(II) sorption on GMZ bentonite calculated from the temperature-dependent sorption isotherms indicated that the sorption of Co(II) on GMZ bentonite was an exothermic and spontaneous process. The Na-bentonite is a suitable material for the preconcentration and solidification of Co(II) from aqueous solutions. (author)

  18. SELECTIVE REMOVAL OF Cd(II) USING DOUBLE IMPRINTED POLYMER FROM SYNTHETIC WATER

    OpenAIRE

    OZKUTUK, Ebru Birlik

    2015-01-01

    The aim of this study is to prepare ion-imprinted polymers which can be used for the selective removal of Cd(II) from synthetic water. Ion-imprinted polymer particles have prepared by molecular imprinting technique using 3-mercaptopropyl-trimethoxysilane as monomer, tetraethoxysilane as crosslinking agent in the presence of Cd(II) and dodecylamine. After that, the template ions have removed using 0.1M HNO3/ethanol. A batch procedure has used for the determination of the characteristics of the...

  19. Preparation, characterization of electrospun meso-hydroxylapatite nanofibers and their sorptions on Co(II)

    International Nuclear Information System (INIS)

    Highlights: • PVA/HA nanofibers could change into meso-HA nanofibers by calcination process. • Sorption of Co(II) on meso-HA was strongly dependent on pH and ionic strength. • Sorption kinetic data were well fitted by the pseudo-second-order rate equation. • Sorption isotherms could be well described by the Langmuir model. • Sorption process of Co(II) on meso-HA nanofibers was spontaneous and endothermic. -- Abstract: In this work, mesoporous hydroxylapatite (meso-HA) nanofibers were prepared via calcination process with polyvinyl alcohol/HA (PVA/HA) hybrid nanofibers fabricated by electrospinning technique as precursors, and the removal efficiency of meso-HA nanofibers toward Co(II) was evaluated via sorption kinetics and sorption isotherms. Furthermore, the sorption behaviors of Co(II) on meso-HA nanofibers were explored as a function of pH, ionic strength, and thermodynamic parameters. There existed hydrogen bonds between HA and PVA matrix in precursor nanofibers which could change into meso-HA nanofibers with main pore diameter at 27 nm and specific surface area at 114.26 m2/g by calcination process. The sorption of Co(II) on meso-HA was strongly dependent on pH and ionic strength. Outer-sphere surface complexation or ion exchange was the main mechanisms of Co(II) adsorption on meso-HA at low pH, whereas inner-sphere surface complexation was the main adsorption mechanism at high pH. The sorption kinetic data were well fitted by the pseudo-second-order rate equation. The sorption isotherms could be well described by the Langmuir model. The thermodynamic parameters (ΔH°, ΔS° and ΔG°) calculated from the temperature-dependent sorption isotherms suggested that the sorption process of Co(II) on meso-HA nanofibers was spontaneous and endothermic

  20. Preparation, characterization of electrospun meso-hydroxylapatite nanofibers and their sorptions on Co(II)

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Hualin, E-mail: hlwang@hfut.edu.cn [School of Chemical Technology, Hefei University of Technology, Hefei, Anhui 230009 (China); Zhang, Peng; Ma, Xingkong; Jiang, Suwei; Huang, Yan; Zhai, Linfeng [School of Chemical Technology, Hefei University of Technology, Hefei, Anhui 230009 (China); Jiang, Shaotong [School of Biotechnology and Food Engineering, Hefei University of Technology, Hefei, Anhui 230009 (China)

    2014-01-30

    Highlights: • PVA/HA nanofibers could change into meso-HA nanofibers by calcination process. • Sorption of Co(II) on meso-HA was strongly dependent on pH and ionic strength. • Sorption kinetic data were well fitted by the pseudo-second-order rate equation. • Sorption isotherms could be well described by the Langmuir model. • Sorption process of Co(II) on meso-HA nanofibers was spontaneous and endothermic. -- Abstract: In this work, mesoporous hydroxylapatite (meso-HA) nanofibers were prepared via calcination process with polyvinyl alcohol/HA (PVA/HA) hybrid nanofibers fabricated by electrospinning technique as precursors, and the removal efficiency of meso-HA nanofibers toward Co(II) was evaluated via sorption kinetics and sorption isotherms. Furthermore, the sorption behaviors of Co(II) on meso-HA nanofibers were explored as a function of pH, ionic strength, and thermodynamic parameters. There existed hydrogen bonds between HA and PVA matrix in precursor nanofibers which could change into meso-HA nanofibers with main pore diameter at 27 nm and specific surface area at 114.26 m{sup 2}/g by calcination process. The sorption of Co(II) on meso-HA was strongly dependent on pH and ionic strength. Outer-sphere surface complexation or ion exchange was the main mechanisms of Co(II) adsorption on meso-HA at low pH, whereas inner-sphere surface complexation was the main adsorption mechanism at high pH. The sorption kinetic data were well fitted by the pseudo-second-order rate equation. The sorption isotherms could be well described by the Langmuir model. The thermodynamic parameters (ΔH°, ΔS° and ΔG°) calculated from the temperature-dependent sorption isotherms suggested that the sorption process of Co(II) on meso-HA nanofibers was spontaneous and endothermic.

  1. Enhanced removal of Cd(II) and Pb(II) by composites of mesoporous carbon stabilized alumina

    Science.gov (United States)

    Yang, Weichun; Tang, Qiongzhi; Wei, Jingmiao; Ran, Yajun; Chai, Liyuan; Wang, Haiying

    2016-04-01

    A novel adsorbent of mesoporous carbon stabilized alumina (MC/Al2O3) was synthesized through one-pot hard-templating method. The adsorption potential of MC/Al2O3 for Cd(II) and Pb(II) from aqueous solution was investigated compared with the mesoporous carbon. The results indicated the MC/Al2O3 showed excellent performance for Cd(II) and Pb(II) removal, the adsorption capacity reached 49.98 mg g-1 for Cd(II) with initial concentration of 50 mg L-1 and reached 235.57 mg g-1 for Pb(II) with initial concentration of 250 mg L-1, respectively. The kinetics data of Cd(II) adsorption demonstrated that the Cd(II) adsorption rate was fast, and the removal efficiencies with initial concentration of 10 and 50 mg L-1 can reach up 99% within 5 and 20 min, respectively. The pseudo-second-order kinetic model could describe the kinetics of Cd(II) adsorption well, indicating the chemical reaction was the rate-controlling step. The mechanism for Cd(II) and Pb(II) adsorption by MC/Al2O3 was investigated by X-ray photoelectron spectroscopy (XPS) and Fourier transformed infrared spectroscopy (FTIR), and the results indicated that the excellent performance for Cd(II) and Pb(II) adsorption of MC/Al2O3 was mainly attributed to its high surface area and the special functional groups of hydroxy-aluminum, hydroxyl, carboxylic through the formation of strong surface complexation or ion-exchange. It was concluded that MC/Al2O3 can be recognized as an effective adsorbent for removal of Cd(II) and Pb(II) in aqueous solution.

  2. Binuclear biologically active Co(II) complexes with octazamacrocycle and aliphatic dicarboxylates

    Science.gov (United States)

    Tanasković, S. B.; Vučković, G.; Antonijević-Nikolić, M.; Stanojković, T.; Gojgić-Cvijović, G.

    2012-12-01

    Four new cationic Co(II) complexes with N,N',N'',N'''-tetrakis (2-pyridylmethyl)-1,4,8,11-tetraazacyclotetradecane (tpmc) and dianion of one the aliphatic dicarboxylic acids: butanedioic acid (succinic) acid = succH2, pentanedioic (glutaric) acid = gluH2, hexanedioic acid (adipic) acid = adipH2 or decanedioic acid (sebacic) acid = sebH2 of general formula [Co2(L)(tpmc)](ClO4)2ṡxY, L2- = succ, x = 1, Y = H2O; L = glu, x = 1, Y = H2O; L = adip, x = 1.5, Y = H2O; L = seb, x = 1, Y = CH3CN were isolated. The composition and charge are proposed based on elemental analyses (C, H, N) and electrical conductivity measurements. UV-Vis and FTIR spectral data and magnetic moments were in accordance with high-spin Co(II) state. It is proposed that in all complexes Co(II) is hexa-coordinated out of cyclam ring and that both carboxylic groups from dicarboxylate bridge participate in coordination. Oxygens from one group are most likely bonded to the same Co(II) ion thus forming a four-membered ring. The in vitro antibacterial/antiproliferative activities of the complexes were in some cases enhanced compared with the simple Co(II) salt and free ligands, tested as controls.

  3. Semi-interpenetrating hybrid membranes containing ADOGEN® 364 for Cd(II) transport from HCl media

    International Nuclear Information System (INIS)

    Graphical abstract: - Highlights: • Semi-interpenetrating hybrid membranes are used for quantitative cadmium(II) recovery. • Optimization of membrane and solutions compositions is performed. • Membranes present increased stability respect to polymer inclusion membranes. • Models for cadmium (II) extraction and transport are proposed. • Excellent selectivity for Cd(II) over Ni(II), Cu(II) and Pb(II) was achieved. - Abstract: Cd(II) transport from 1 mol dm−3 HCl media was investigated across semi-interpenetrating hybrid membranes (SIHMs) that were prepared by mixing an organic matrix composed of ADOGEN® 364 as an extracting agent, cellulose triacetate as a polymeric support and nitrophenyloctyl ether as a plasticizer with an organic/inorganic network (silane phase, SP) composed of polydimethylsiloxane and a crosslinking agent. The stripping phase used was a 10−2 mol dm−3 ethanesulfonic acid solution. The effects of tetraorthoethoxysilane, phenyltrimethoxysilane and N′,N′-bis[3-tri(methoxysilyl)propyl]ethylendiamine as crosslinking agents on the transport were studied. H3PO4 was used as an acid catalyst during the SP synthesis and optimized for transport performance. Solid–liquid extraction experiments were performed to determine the model that describe the transport of Cd(II) via ADOGEN® 364. The transport was found to be chained-carrier controlled with a percolation threshold of 0.094 mmol g−1. The selective recovery of Cd(II) was studied with respect to Ni(II), Zn(II), Cu(II), and Pb(II) at a 1:1 molar ratio, and the optimized membrane system was applied for the recovery of Cd(II) from a real sample consisting of a Ni/Cd battery with satisfactory results. Finally, stability experiments were performed using the same membrane for 14 cycles. The results obtained showed that SIHMs had excellent stability and selectivity, with permeabilities comparable to those of PIMs

  4. Cd(II) removal and recovery enhancement by using acrylamide–titanium nanocomposite as an adsorbent

    International Nuclear Information System (INIS)

    Graphical abstract: - Highlights: • Acrylamide doping initiated 10–20% increase in the particle size. • R-NH2Cd2+ and Cd-O onto the nanocomposite improved Cd(II) adsorption. • Coexisting cations did not make any significant interference of Cd(II) removal. • Increased Ti nanoparticles leads to decrease in mass swelling of acrylamide. - Abstract: Acrylamide (AM) was in-situ doped into titanium during sol–gel reaction and used as an adsorbent for cadmium removal from aqueous solution. The resulting TiO2-AM nanocomposite was characterized by particle size distribution (PSD) and thermogravimetric analysis (TGA). After cadmium adsorption, the nanocomposite was also characterized by Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), scanning electron microscopy/energy-dispersive X-ray (SEM/EDX) and X-ray photoelectron spectroscopy (XPS) analyses. The adsorption behavior of the nanocomposite was examined by kinetic and equilibrium studies in batch conditions. The maximum cadmium binding capacity of TiO2-AM was 322.58 mg g−1 at an optimum pH of 8.0, compared to 86.95 mg g−1 for nano-titanium. Cadmium sorption showed pseudo-second-order kinetics with a rate constant of 4.0 × 10−4 and 9.4 × 10−5 g mg−1 min−1 at an initial Cd(II) concentration of 100 and 500 mg L−1, respectively. Cd (II) adsorption interference of cations (Pb2+, Cu2+, Co2+ and Zn+2) and anions (Cl−, SO42−, CO32−) at pH 8 was very nominal because of favorable complex formation of Cd(II) and amide. The Cd(II) adsorption of 27% that was achieved in the fifth cycle was regenerated with 0.05 N acidic solutions

  5. Carbohydrate oxidation coupled to Fe(III) reduction, a novel form of anaerobic metabolism.

    Science.gov (United States)

    Coates, J D; Councell, T; Ellis, D J; Lovley, D R

    1998-12-01

    An isolate, designated GC-29, that could incompletely oxidize glucose to acetate and carbon dioxide with Fe(III) serving as the electron acceptor was recovered from freshwater sediments of the Potomac River, Maryland. This metabolism yielded energy to support cell growth. Strain GC-29 is a facultatively anaerobic, gram-negative motile rod which, in addition to glucose, also used sucrose, lactate, pyruvate, yeast extract, casamino acids or H2 as alternative electron donors for Fe(III) reduction. Stain GC-29 could reduce NO3(-), Mn(IV), U(VI), fumarate, malate, S2O3(2-), and colloidal S0 as well as the humics analog, 2,6-anthraquinone disulfonate. Analysis of the almost complete 16S rRNA sequence indicated that strain GC-29 belongs in the Shewanella genus in the epsilon subdivision of the Proteobacteria. The name Shewanella saccharophilia is proposed. Shewanella saccharophilia differs from previously described fermentative microorganisms that metabolize glucose with the reduction of Fe(III) because it transfers significantly more electron equivalents to Fe(III); acetate and carbon dioxide are the only products of glucose metabolism; energy is conserved from Fe(III) reduction; and glucose is not metabolized in the absence of Fe(III). The metabolism of organisms like S. saccharophilia may account for the fact that glucose is metabolized primarily to acetate and carbon dioxide in a variety of sediments in which Fe(III) reduction is the terminal electron accepting process. PMID:16887653

  6. Co(II) removal by magnetic alginate beads containing Cyanex 272.

    Science.gov (United States)

    Ngomsik, Audrey-Flore; Bee, Agnès; Siaugue, Jean-Michel; Talbot, Delphine; Cabuil, Valérie; Cote, Gérard

    2009-07-30

    In this study, a series of batch experiments is conducted to investigate the ability of magnetic alginate beads containing Cyanex 272 to remove Co(II) ions from aqueous solutions. Equilibrium sorption experiments show a Co(II) uptake capacity of 0.4 mmol g(-1). The data are successfully modelled with a Langmuir equation. A series of kinetics experiments is then carried out and a pseudo-second order equation is used to fit the experimental data. The effect of pH on the sorption of Co(II) ions is also investigated. Desorption experiments by elution of the loaded beads with nitric acid at pH 1 show that the magnetic alginate beads could be reused without significant losses of their initial properties even after 3 adsorption-desorption cycles. PMID:19157703

  7. Separation of Co(II) from dilute aqueous solutions by precipitate and adsorbing colloid flotation

    International Nuclear Information System (INIS)

    Ion, precipitate and adsorbing colloid flotation of cobalt(II) have been investigated at different pH values, using N-dodecylpyridinium chloride (DPCl). A strong cationic surfactant, and sodium lauryl sulfate (NaLS), a strong anionic surfactant, as collectors. In case of adsorbing colloid flotation, hydrous manganese dioxide was used as an adsorbent. The precipitate flotation curves experimentally obtained with the two tested collectors were compared with the corresponding theoretical one calculated from the data published for Co(II) hydrolysis. The effects of the collector concentration, ageing of the water-MnO2-Co(II) system, bubbling time period, cobalt(II) concentration and foreign salts on the percent removal of Co(II) by adsorbing colloid flotation using DPCl as collector were determined. Removals approaching 100% could be achieved under the optimum conditions. (author) 44 refs.; 6 figs

  8. Sorption Characteristics of Aqueous Co(II) on Preformed Iron Ferrite Impregnated into Phenolsulphonic Formaldehyde Resin

    Energy Technology Data Exchange (ETDEWEB)

    Lee, K. J.; Kim, Y. K.

    2002-02-26

    A series of stepwise procedures to prepare a new organic-inorganic composite magnetic resin with phenolsulphonicformaldehyde and freshly formed iron ferrite was established, based upon wet-and-neutralization method for synthesizing iron ferrite and pearl-polymerization method for synthesizing rigid bead-type composite resin. The composite resin prepared by the above method shows stably high removal efficiency (maximally over 3.1 meq./gresin) to Co(II) species from wastewater in a wide range of solution pH. The wide range of applicable solution pH (i.e. pH 4.09 to 10.32) implies that the composite resin overcomes the limitations of the conventional ferrite process that is practically applicable only to alkaline conditions. It has been found that both ion exchange (by the organic resin constituent) and surface adsorption (by the inorganic adsorbent constituent) are major reaction mechanisms for removing Co(II) from wastewater, but surface precipitation results in the high sorption capacity to Co(II) beyond normal ion exchange capacity of the phenolsulphonic-formaldehyde resin. Standard enthalpy change derived from van't Hoff equation is 32.0 kJ{center_dot}mol-1 conforming to the typical range for chemisorption or ion exchange. In a wide range of equilibrium Co(II) concentration, the overall isotherm is qualitatively explained by the generalized adsorption isotherm concept proposed by McKinley. At the experimental conditions where the composite resin shows equivalent selectivity to Co(II) and other competing reagents (i.e. EDTA and Na), the ratios of Co(II) to other chemicals turn out to be 2:1 and 1:221, respectively. In addition, the selectivity of the PSF-F to Co(II) species is very high (about 72% of Co(II)-removal efficiency) even when the molar ratio of Co(II) to Ca(II) is 1:30. It is anticipated that the composite resin can also be used for column-operation with process-control by applying external magnetic field, since the rigid bead-type composite resin

  9. Separation of gas mixtures using Co(II) carborane-based porous coordination polymers

    Energy Technology Data Exchange (ETDEWEB)

    Bae, Y. S.; Spokoyny, Alexander M.; Farha, Omar K.; Snurr, R. Q.; Hupp, Joseph T.; Mirkin, Chad

    2010-01-01

    Separations of CO{sub 2}/CH{sub 4}, CO{sub 2}/N{sub 2}, and O{sub 2}/N{sub 2} mixtures were studied in three porous coordination polymers made of the same carborane ligand and Co(II) nodes. High selectivities for CO{sub 2} over CH{sub 4} (~47) and CO{sub 2} over N{sub 2} (~95) were obtained, especially in the material with coordinated pyridine. Unusual selectivity for O{sub 2} over N{sub 2} (as high as 6.5) was demonstrated in the materials with open Co(II) sites.

  10. Selection and characterization of DNA aptamers for the development of light-up biosensor to detect Cd(II).

    Science.gov (United States)

    Wang, Hongyan; Cheng, Hui; Wang, Jine; Xu, Lijun; Chen, Hongxia; Pei, Renjun

    2016-07-01

    In order to develop a facile, cost-effective and quick-testing light-up biosensor with excellent specificity for cadmium ions (Cd(II)) detection, a modified selection method based on target-induced release of strands was used to isolate aptamers of Cd (II) with high specificity. Circular Dichroism (CD) data confirmed that one of the selected aptamers underwent a distinct conformational change on addition of Cd (II). A biosensor for Cd(II) was developed based on the Cd(II)-induced release of fluorescence-labeled aptamer from complex with a quencher-labeled short complementary sequence. The sensing platform displayed a Cd(II) concentration-dependent increase of fluorescence intensity in the low micromolar range and had an excellent selectivity in the presence of various interfering metal ions. Such biosensor could potentially be used for the detection of Cd(II) in environmental samples. PMID:27154706

  11. Intercalation of Coordinatively Unsaturated Fe(III) Ion within Interpenetrated Metal-Organic Framework MOF-5.

    Science.gov (United States)

    Holmberg, Rebecca J; Burns, Thomas; Greer, Samuel M; Kobera, Libor; Stoian, Sebastian A; Korobkov, Ilia; Hill, Stephen; Bryce, David L; Woo, Tom K; Murugesu, Muralee

    2016-06-01

    Coordinatively unsaturated Fe(III) metal sites were successfully incorporated into the iconic MOF-5 framework. This new structure, Fe(III) -iMOF-5, is the first example of an interpenetrated MOF linked through intercalated metal ions. Structural characterization was performed with single-crystal and powder XRD, followed by extensive analysis by spectroscopic methods and solid-state NMR, which reveals the paramagnetic ion through its interaction with the framework. EPR and Mössbauer spectroscopy confirmed that the intercalated ions were indeed Fe(III) , whereas DFT calculations were employed to ascertain the unique pentacoordinate architecture around the Fe(III) ion. Interestingly, this is also the first crystallographic evidence of pentacoordinate Zn(II) within the MOF-5 SBU. This new MOF structure displays the potential for metal-site addition as a framework connector, thus creating further opportunity for the innovative development of new MOF materials. PMID:27061210

  12. Radiosensitization by cobalt and Fe(III) complexes

    International Nuclear Information System (INIS)

    The invention concerns the rendering of hypoxic cells more sensitive to irradiation by treatment with a Co(III) to Fe(III) co-ordination compound selected from the group consisting of- (1) compounds having the formula: [CoNnX6-n]y where n has a value of 3 or 4; N is an uncharged nitrogen donor atom that is contained in a ligand; X represents an anionic ligand; and y represents the charge on the complex; (2) compounds having the formula: [CoA2X1D]y1 where A represents a bidentate or tetradentate negative ligand containing N or O donor atoms; X1 and D represent the same or different monodentate ligands; and y1 represents a positive or negative charge on the complex; (3) compounds having the formula: [CoZ3] where Z represents a chelating mononegative ligand; and (4) Compounds of the formula: [FeTT1]+ where T and T1, which may be the same or different, represent mononegative tridentate ligands

  13. Separation for Co(II) on the nickel hexacyanoferrate(II)

    International Nuclear Information System (INIS)

    Communication presents results obtained by the authors on the Co(II) sorption on the nickel hexacyanoferrate(II). Physico-chemical and chemical properties of the inorganic ion exchanger, synthesized in the Institute of Nuclear Physics, Polish Academy of Sciences, Cracow, are described in details. Correlation between main physico-chemical properties of the ion exchanger and its sorption ability is discussed

  14. Synthesis of tridentate-schiff base Co(II) complexes and their electrochemical properties

    International Nuclear Information System (INIS)

    Tridentate Schiff base ligands such as SIPH2, SIPCH2, and HNIPCH2 were prepared by the reaction of salicylaldehyde and 2-hydroxy-1-naphthaldehyde with 2-aminophenol and 2-amino-p-cresol. The structures and properties of ligands and their Co(II) complexes were investigated by elemental analysis, 1H-NMR, IR, UV-Visible spectra, and thermogravimetric analysis. The molar ratio of Schiff base to the metal of complexes was found to be 1:1. Co(II) complexes were contemplated to be hexa-coordinated octahedral configuration containing three water molecules. The redox process of ligands and complexes in DMSO solution containing 0.1 M TBAP as a supporting electrolyte were investigated by cyclic voltammetry with glassy carbon electrode. The redox process of the tridentate Schiff base ligands was totally irreversible. The redox process of Co(II) complexes were irreversible and one electron processes by two steps in diffusion controlled reaction. The reduction potential of the Co(II) complexes was shifted to the positive direction in the order (Co(II)(HNIPC)(H2O)3)>(Co(II)(HNIP)(H2O)3)>(Co(II)(SIPC)(H2O)3)>(Co(II)(SIP )(H2O)3), and their dependence on ligands were not so high.

  15. Spectral, thermal, electrochemical and analytical studies on Cd(II) and Hg(II) thiosemicarbazone complexes

    Science.gov (United States)

    El-Asmy, A. A.; El-Gammal, O. A.; Saleh, H. S.

    2008-11-01

    The coordination characteristic of the investigated thiosemicarbazones towards hazard pollutants, Cd(II) and Hg(II), becomes the first goal. Their complexes have been studied by microanalysis, thermal, electrochemical and spectral (electronic, IR and MS) studies. The substitutent (salicylaldehyde, acetophenone, benzophenone, o-hydroxy- p-methoxybenzophenone or diacetylmonoxime) plays an important role in the complex formation. The coordination sites were the S for thiosemicarbazide (HTS); NN for benzophenone thiosemicarbazone (HBTS); NS for acetophenone thiosemicarbazone (HATS) and salicylaldehyde thiosemicarbazone (H 2STS); NNS or NSO for diacetylmonoxime thiosemicarbazone (H 2DMTS). The stability constants of Hg(II) complexes were higher than Cd(II). The kinetic and thermodynamic parameters for the different thermal decomposition steps in the complexes have been evaluated. The activation energy values of the first step ordered the complexes as: [Cd(H 2STS)Cl 2]H 2O > [Cd(H 2DAMTS)Cl 2] > [Cd(HBTS) 2Cl 2]2H 2O > [Cd(HATS) 2Cl 2]. The CV of [Cd(H 2STS)Cl 2]H 2O and [Hg(HBTS)Cl 2] were recorded. The use of H 2DMTS as a new reagent for the separation and determination of Cd(II) ions from water and some synthetic samples using flotation technique is aimed to be discussed.

  16. Cd(II) removal and recovery enhancement by using acrylamide–titanium nanocomposite as an adsorbent

    Energy Technology Data Exchange (ETDEWEB)

    Sharma, Ajit; Lee, Byeong-Kyu, E-mail: bklee@ulsan.ac.kr

    2014-09-15

    Graphical abstract: - Highlights: • Acrylamide doping initiated 10–20% increase in the particle size. • R-NH{sub 2}Cd{sup 2+} and Cd-O onto the nanocomposite improved Cd(II) adsorption. • Coexisting cations did not make any significant interference of Cd(II) removal. • Increased Ti nanoparticles leads to decrease in mass swelling of acrylamide. - Abstract: Acrylamide (AM) was in-situ doped into titanium during sol–gel reaction and used as an adsorbent for cadmium removal from aqueous solution. The resulting TiO{sub 2}-AM nanocomposite was characterized by particle size distribution (PSD) and thermogravimetric analysis (TGA). After cadmium adsorption, the nanocomposite was also characterized by Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), scanning electron microscopy/energy-dispersive X-ray (SEM/EDX) and X-ray photoelectron spectroscopy (XPS) analyses. The adsorption behavior of the nanocomposite was examined by kinetic and equilibrium studies in batch conditions. The maximum cadmium binding capacity of TiO{sub 2}-AM was 322.58 mg g{sup −1} at an optimum pH of 8.0, compared to 86.95 mg g{sup −1} for nano-titanium. Cadmium sorption showed pseudo-second-order kinetics with a rate constant of 4.0 × 10{sup −4} and 9.4 × 10{sup −5} g mg{sup −1} min{sup −1} at an initial Cd(II) concentration of 100 and 500 mg L{sup −1}, respectively. Cd (II) adsorption interference of cations (Pb{sup 2+}, Cu{sup 2+}, Co{sup 2+} and Zn{sup +2}) and anions (Cl{sup −}, SO{sub 4}{sup 2−}, CO{sub 3}{sup 2−}) at pH 8 was very nominal because of favorable complex formation of Cd(II) and amide. The Cd(II) adsorption of 27% that was achieved in the fifth cycle was regenerated with 0.05 N acidic solutions.

  17. Recycling flue gas desulphurization (FGD) gypsum for removal of Pb(II) and Cd(II) from wastewater.

    Science.gov (United States)

    Yan, Yubo; Li, Qiao; Sun, Xiuyun; Ren, Zhiyuan; He, Fei; Wang, Yalun; Wang, Lianjun

    2015-11-01

    The present study aims to verify the feasibility of directly reusing the flue gas desulphurization (FGD) gypsum generated from coal-fired power plants to adsorptively remove Pb(II) and Cd(II) from wastewater. The Toxicity Characteristic Leaching Procedure (TCLP) test was conducted to evaluate the leachability of toxic heavy metals from FGD gypsum. The adsorption behaviors of FGD gypsum for Pb(II) and Cd(II) such as pH impact, sorption kinetics, sorption isotherms and sorption thermodynamics were studied in a series of batch experiments. The pH studies indicated that the adsorption of Pb(II) and Cd(II) had their best adsorption amounts both at the pH values from 5.0 to 7.0. The kinetic analysis displayed that the adsorption processes both followed the pseudo-second order model well, and the FGD gypsum provided a higher sorption rate for Pb(II). Equilibrium studies showed that the adsorption of Pb(II) and Cd(II) could be properly described by Langmuir isotherms model, and the predicted maximum adsorption capacities were even greater than some specially prepared adsorbents. The thermodynamic investigation confirmed that the removal of Pb(II) and Cd(II) from aqueous medium could carry out spontaneously, and the higher temperature favored the processes. The instrument analysis techniques were also employed to deeply understand the mechanism involved in Pb(II) and Cd(II) removal by FGD gypsum. Overall, good sorption performance together with cost-effective characteristic makes FGD gypsum potentially attractive material for the Pb(II) and Cd(II) removal in industrial wastewater. PMID:26162902

  18. Selective transport of Fe(III) using ionic imprinted polymer (IIP) membrane particle

    Science.gov (United States)

    Djunaidi, Muhammad Cholid; Jumina, Siswanta, Dwi; Ulbricht, Mathias

    2015-12-01

    The membrane particles was prepared from polyvinyl alcohol (PVA) and polymer IIP with weight ratios of 1: 2 and 1: 1 using different adsorbent templates and casting thickness. The permeability of membrane towards Fe(III) and also mecanism of transport were studied. The selectivity of the membrane for Fe(III) was studied by performing adsorption experiments also with Cr(III) separately. In this study, the preparation of Ionic Imprinted Polymer (IIP) membrane particles for selective transport of Fe (III) had been done using polyeugenol as functional polymer. Polyeugenol was then imprinted with Fe (III) and then crosslinked with PEGDE under alkaline condition to produce polyeugenol-Fe-PEGDE polymer aggregates. The agrregates was then crushed and sieved using mesh size of 80 and the powder was then used to prepare the membrane particles by mixing it with PVA (Mr 125,000) solution in 1-Methyl-2-pyrrolidone (NMP) solvent. The membrane was obtained after casting at a speed of 25 m/s and soaking in NaOH solution overnight. The membrane sheet was then cut and Fe(III) was removed by acid to produce IIP membrane particles. Analysis of the membrane and its constituent was done by XRD, SEM and size selectivity test. Experimental results showed the transport of Fe(III) was faster with the decrease of membrane thickness, while the higher concentration of template ion correlates with higher Fe(III) being transported. However, the transport of Fe(III) was slower for higher concentration of PVA in the membrane. IImparticles works through retarded permeation mechanism, where Fe(III) was bind to the active side of IIP. The active side of IIP membrane was dominated by the -OH groups. The selectivity of all IIP membranes was confirmed as they were all unable to transport Cr (III), while NIP (Non-imprinted Polymer) membrane was able transport Cr (III).

  19. Spectroscopic properties of a series of Co(II) coordination polymers and the influence of Co(II) coordination environment on photoelectric property

    Science.gov (United States)

    Jin, Jing; Gong, Yuanyuan; Li, Lei; Han, Xiao; Meng, Qin; Liu, Yonghua; Niu, Shuyun

    2015-02-01

    Four Co(II) coordination polymers, [Co(suc)]n1, [Co(pdc)]n2, {[Co7(suc)4(OH)6(H2O)3] · 8H2O}n3, {[Co(bdc)(phen)(H2O)] · H2O}n4 (H2suc = succinic acid, H2pdc = pyridine-3,4-dicarboxylic acid, H2bdc = 1,2-benzenedicarboxylic acid, phen = 1,10-phenanthroline) were hydrothermally synthesized and characterized by X-ray single-crystal diffraction, surface photovoltage spectroscopy (SPS), electrical conductivity, thermogravimetric analysis (TG), ultraviolet visible and near-infrared absorption spectrum (UV-Vis-NIR), infrared spectrum (IR), and elemental analysis. The structural analyses indicate that the coordination numbers of the Co(II) ions are 4, 5, 6 and 6 for the polymers 1-4, respectively. And polymers 1 and 2 exhibit 3D structure formed by suc2- and pdc2- anions bridging Co(II) ions, respectively. Polymer 3 exhibits a 2D structure with suc2- anions bridging seven-nuclear [Co7(OH)6(H2O)3]3- unit and polymer 4 is a 1D structure bridged by bdc2- anions. The surface photoelectric properties of the cobalt polymers were mainly studied by SPS. The results of SPS reveal that all polymers possess certain photoelectric conversion property in the range of 300-800 nm. The influences of the structure, coordination micro-environment of central metal ion and structural dimensionality on response bands of SPS were discussed.

  20. Perfluorooctanoic acid degradation in the presence of Fe(III) under natural sunlight

    International Nuclear Information System (INIS)

    Highlights: • PFOA was photo-chemically decomposed in the presence of Fe(III) and natural sunlight. • An alternative reaction pathway involves hydroxyl radical as confirmed by EPR. • Common oxidant-persulfate increased PFOA defluorination extent. -- Abstract: Due to the high bond dissociation energy (BDE) of C-F bonds (116 kcal/mol), perfluorooctanoic acid (PFOA) is a highly recalcitrant pollutant. Herein, we demonstrate a novel method to decompose PFOA in the presence of sunlight and ferric iron (Fe(III)). Under such conditions, 97.8 ± 1.7% of 50 μM PFOA decomposed within 28 days into shorter-chain intermediates and fluoride (F−), with an overall defluorination extent of 12.7 ± 0.5%. No PFOA was removed under visible light, indicating that UV radiation is required for PFOA decomposition. Spectroscopic analysis indicates that the decomposition reaction is likely initiated by electron-transfer from PFOA to Fe(III), forming Fe(II) and an unstable organic carboxyl radical. An alternative mechanism for the formation of this organic radical involves hydroxyl radicals, detected by electron paramagnetic resonance (EPR). The observation that PFOA can be degraded by Fe(III) under solar irradiation provides mechanistic insight into a possibly overlooked natural attenuation process. Because Fe(III) is abundant in natural waters and sunlight is essentially free, this work represents a potentially important step toward the development of simple and inexpensive remediation strategies for PFOA-contaminated water

  1. Perfluorooctanoic acid degradation in the presence of Fe(III) under natural sunlight

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Dandan [Beijing Key Laboratory of Water Resource and Environmental Engineering, China University of Geosciences, Beijing 100083 (China); Xiu, Zongming [Department of Civil and Environmental Engineering, Rice University, Houston, TX 77005 (United States); Liu, Fei [Beijing Key Laboratory of Water Resource and Environmental Engineering, China University of Geosciences, Beijing 100083 (China); Wu, Gang [Division of Hematology, Department of Internal Medicine, University of Texas-Medical School at Houston, Houston, TX 77030 (United States); Adamson, Dave; Newell, Charles [GSI Environmental Inc., Houston, TX 77098 (United States); Vikesland, Peter [Department of Civil and Environmental Engineering, Virginia Polytechnic Institute and State University, Blacksburg, VA 24061 (United States); Tsai, Ah-Lim [Division of Hematology, Department of Internal Medicine, University of Texas-Medical School at Houston, Houston, TX 77030 (United States); Alvarez, Pedro J., E-mail: alvarez@rice.edu [Department of Civil and Environmental Engineering, Rice University, Houston, TX 77005 (United States)

    2013-11-15

    Highlights: • PFOA was photo-chemically decomposed in the presence of Fe(III) and natural sunlight. • An alternative reaction pathway involves hydroxyl radical as confirmed by EPR. • Common oxidant-persulfate increased PFOA defluorination extent. -- Abstract: Due to the high bond dissociation energy (BDE) of C-F bonds (116 kcal/mol), perfluorooctanoic acid (PFOA) is a highly recalcitrant pollutant. Herein, we demonstrate a novel method to decompose PFOA in the presence of sunlight and ferric iron (Fe(III)). Under such conditions, 97.8 ± 1.7% of 50 μM PFOA decomposed within 28 days into shorter-chain intermediates and fluoride (F{sup −}), with an overall defluorination extent of 12.7 ± 0.5%. No PFOA was removed under visible light, indicating that UV radiation is required for PFOA decomposition. Spectroscopic analysis indicates that the decomposition reaction is likely initiated by electron-transfer from PFOA to Fe(III), forming Fe(II) and an unstable organic carboxyl radical. An alternative mechanism for the formation of this organic radical involves hydroxyl radicals, detected by electron paramagnetic resonance (EPR). The observation that PFOA can be degraded by Fe(III) under solar irradiation provides mechanistic insight into a possibly overlooked natural attenuation process. Because Fe(III) is abundant in natural waters and sunlight is essentially free, this work represents a potentially important step toward the development of simple and inexpensive remediation strategies for PFOA-contaminated water.

  2. Bioavailability of Fe(III) in natural soils and the impact on mobility of inorganic contaminants

    Energy Technology Data Exchange (ETDEWEB)

    Kosson, David S.; Cowan, Robert M.; Young, Lily Y.; Hacherl, Eric L.; Scala, David J.

    2002-10-03

    Inorganic contaminants, such as heavy metals and radionuclides, can adhere to insoluble Fe(III) minerals resulting in decreased mobility of these contaminants through subsurface environments. Dissimilatory Fe(III)-reducing bacteria (DIRB), by reducing insoluble Fe(III) to soluble Fe(II), may enhance contaminant mobility. The Savannah River Site, South Carolina (SRS), has been subjected to both heavy metal and radionuclide contamination. The overall objective of this project is to investigate the release of inorganic contaminants such as heavy metals and radionuclides that are bound to solid phase soil Fe complexes and to elucidate the mechanisms for mobilization of these contaminants that can be associated with microbial Fe(III) reduction. This is being accomplished by (i) using uncontaminated and contaminated soils from SRS as prototype systems, (ii) evaluating the diversity of DIRBs within the samples and isolating cultures for further study, (iii) using batch microcosms to evaluate the bioavailability of Fe(III) from pure minerals and SRS soils, (iv) developing kinetic and mass transfer models that reflect the system dynamics, and (v) carrying out soil column studies to elucidate the dynamics and interactions amongst Fe(III) reduction, remineralization and contaminant mobility.

  3. Immobilization of Cd(II) in acid soil amended with different biochars with a long term of incubation.

    Science.gov (United States)

    Tan, Xiaofei; Liu, Yunguo; Gu, Yanling; Zeng, Guangming; Wang, Xin; Hu, Xinjiang; Sun, Zhichao; Yang, Zhongzhu

    2015-08-01

    Biochars derived from bamboo, coconut shell, pine wood shavings, and sugarcane bagasse were applied into Ultisol to investigate their effects on Cd(II) immobilization. After 360 days of incubation, the physical/chemical properties of the Ultisol were improved by the addition of different biochars. As a result, the maximum adsorption capacities of soil for Cd(II) were increased from 8.02 to 9.07-11.51 mmol/kg, and bamboo biochar showed the highest effect on Cd(II) immobilization. The Langmuir model (R(2) > 0.983) fitted the data better than the Freundlich model (R (2) were 0.902-0.937). Column leaching experiments suggested that biochar can also increase the immobilization of Cd(II) under leaching conditions. Biochar mainly increased the weak/unstable binding force of Cd(II) by soil, such as ion exchange, electrostatic attraction, physical adsorption, and carbonate precipitation. In addition, a significant enhancement of surface complexation was also observed. PMID:25911285

  4. The electrochemical oxidation of toluene catalysed by Co(II) in N-butyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide.

    Science.gov (United States)

    Balaji, S; Kannan, K; Moon, I S

    2015-12-14

    The electrochemical oxidation of toluene in N-butyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide ([bmpyr](+)[Ntf2](-)) was investigated by using cyclic voltammetry and galvanostatic electrolysis in the presence of Co(II) at a Pt disc working electrode. Cyclic voltammetry (CV) investigations revealed that Co(II)-Co(III) oxidation is a diffusion controlled electron transfer process. The diffusion coefficient values of Co(II) were found to increase from 0.38 × 10(-7) to 1.9 × 10(-7) cm(2) s(-1) as the temperature was increased from 25 °C to 80 °C. The CV peak current for toluene electro-oxidation increased by nearly 7 fold in the presence of Co(II) demonstrating a good catalytic effect. Co(II) catalysed galvanostatic electrolysis of toluene at room temperature has shown that benzaldehyde was formed along with a small quantity of 3-methyl-1-hexanol. PMID:26538114

  5. Spectroscopic, thermal and antibacterial studies on Mn(II) and Co(II) complexes derived from thiosemicarbazone

    OpenAIRE

    SULEKH CHANDRA; MONIKA TYAGI; Moamen S. Refat

    2009-01-01

    Mn(II) and Co(II) complexes having the general composition [M(L)2X2] (where L = 2-pyridinecarboxaldehyde thiosemicarbazone, M = Mn(II) and Co(II), X = Cl- and NO3-) were synthesized. All the metal complexes were characterized by elemental analysis, molar conductance, magnetic susceptibility measurements, mass, IR, EPR, electronic spectral studies and thermogravimetric analysis (TG). Based on the spectral studies, an octahedral geometry was assigned for all the complexes. Thermal studies of th...

  6. Radiosensitization of thymine by Fe(III)-1,2 dihydroxyanthraquinone complex in dilute aqueous solution

    International Nuclear Information System (INIS)

    A complex of Fe(III) with 1,2 dihydroxy 9, 10, anthraquinone (DHA) has been prepared. The metal ion forms a 1:3 complex with DHA. The complex is formed due to the dissociation of one proton per ligand bound to the metal ion. The stability constant of the Fe(III) complex is 1.61 x 1032. The complex reduces the catalytic flow of electrons from NADH to molecular O2 through NADH dehydrogenease over DHA. The Fe(III) complex is seen to be an efficient radiosensitizer towards γ-radiation induced degradation of thymine in a nitrous oxide saturated medium. (author). 31 refs., 2 figs., 1 tab

  7. Determination of stability constants of the Co(II) complexes with weathered coal fulvic acid

    International Nuclear Information System (INIS)

    The stability constants of Co(II) complexes with weathered coal fulvic acid are determined by both Schubert method and Stevenson method at pH = 5.3 +- 0.2, I = 0.001-1.0 mol/kg and (30 +- 1) degree C. The modified Schubert method is also used to estimate the stability constants of Co(II) complexes with the fulvic acid. It is shown that the trend of forming poly nuclei complexes of Co(II)-fulvic acid increases with increasing ionic strength in the solution and that 1:1 and 2:1 type complexes, respectively, are formed at different ionic strength. A comparison between the values of lg β obtained by different methods is made

  8. Removal of Cd(II) from aqueous solution with activated Firmiana Simplex Leaf: Behaviors and affecting factors

    International Nuclear Information System (INIS)

    Cadmium pollution is known to cause severe public health problems. This study is intended to examine the effect of an activated Firmiana Simplex Leaf (FSL) on the removal of Cd(II) from aqueous solution. Results showed that the active Firmiana Simplex Leaf could efficiently remove Cd(II) from wastewater due to the preservation of beneficial groups (amine, carboxyl, and phosphate) at a temperature of 250 deg. C. The adsorbent component, dosage, concentration of the initial solute, and the pH of the solution were all found to have significant effects on Cd(II) adsorption. The kinetic constants were predicted by pseudo-first-order kinetics, and the thermodynamic analysis revealed the endothermic and spontaneous nature of the adsorption. FT-IR and XRD analyses confirmed the strong adsorption between beneficial groups and cadmium ions, and the adsorption capacity was calculated to be 117.786 mg g-1 according to the Langmuir isotherm.

  9. Adsorption and desorption of Cd(II) onto titanate nanotubes and efficient regeneration of tubular structures

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Ting; Liu, Wen; Xu, Nan [Shenzhen Key Laboratory for Heavy Metal Pollution Control and Reutilization, School of Environment and Energy, Peking University Shenzhen Graduate School, Shenzhen 518055 (China); Ni, Jinren, E-mail: nijinren@iee.pku.edu.cn [Department of Environmental Engineering, Peking University, The Key Laboratory of Water and Sediment Sciences, Ministry of Education, Beijing 100871 (China)

    2013-04-15

    Highlights: ► Satisfactory reuse of TNTs due to easy regeneration of tubular structures. ► TNTs regeneration using only 2% of NaOH needed for virgin TNTs preparation. ► Excellent regeneration attributed to steady TNTs skeleton and complex form of TNTs-OCd{sup +}OH{sup −} onto adsorbed TNTs. -- Abstract: Efficient regeneration of desorbed titanate nanotubes (TNTs) was investigated with cycled Cd(II) adsorption and desorption processes. After desorption of Cd (II) from TNTs using 0.1 M HNO{sub 3}, regeneration could be simply achieved with only 0.2 M NaOH at ambient temperature, i.e. 2% of the NaOH needed for virgin TNTs preparation at 130 °C. The regenerated TNTs displayed similar adsorption capacity of Cd(II) even after six recycles, while significant reduction could be detected for desorbed TNTs without regeneration. The virgin TNTs, absorbed TNTs, desorbed TNTs and regenerated TNTs were systematically characterized. As results, the ion-exchange mechanism with Na{sup +} in TNTs was convinced with obvious change of -TiO(ONa){sub 2} by FTIR spectroscopy. The easy recovery of the damaged tubular structures proved by TEM and XRD was ascribed to asymmetric distribution of H{sup +} and Na{sup +} on the surface side and interlayer region of TNTs. More importantly, the cost-effective regeneration was found possibly related to complex form of TNTs-OCd{sup +}OH{sup −} onto the adsorbed TNTs, which was identified with help of X-ray photoelectron spectroscopy, and further indicated due to high relevance to an unexpected mole ratio of 1:1 between exchanged Na{sup +} and absorbed Cd(II)

  10. Synthesis, crystal structure and photo luminescent property of a 3D metal-organic hybrid of Cd(II) constructed by two different bridging carboxylate

    Indian Academy of Sciences (India)

    Biswajit Bhattacharya; Rajdip Dey; Debajyoti Ghoshal

    2013-05-01

    A solvothermal reaction of cadmium (II) nitrate with succinic acid and isonicotinic acid creates a novel 3D metal-organic framework, [Cd3(isonicotinate)2(suc)2] (1). Single crystal X-ray structure determination reveals that complex 1 posses two crystallographically independent Cd(II) centres. The succinate anion acts here as a heptadented ligand and binds five Cd(II) centre simultaneously. The heptacoordinated Cd(II) centres are oxo-bridged by succinate moiety and the hexacoordinated metal centres are terminally connected through four different succinate moiety to make the overall 2D sheet arrangement. In unit cell, the ratio of hexadented Cd(II) and heptadented Cd(II) is 1:2. The new compound was also characterized by luminescence spectra and compared with the luminescence spectra of the pure isonicotinic acid.

  11. Role of Menaquinones in Fe(III) Reduction by Membrane Fractions of Shewanella putrefaciens

    OpenAIRE

    Saffarini, Daad A.; Blumerman, Seth L.; Mansoorabadi, Karen J.

    2002-01-01

    Two Tn5-generated mutants of Shewanella putrefaciens with insertions in menD and menB were isolated and analyzed. Both mutants were deficient in the use of several terminal electron acceptors, including Fe(III). This deficiency was overcome by the addition of menaquinone (vitamin K2). Isolated membrane fractions from both mutants were unable to reduce Fe(III) in the absence of added menaquinone when formate was used as the electron donor. These results indicate that menaquinones are essential...

  12. Coexistence of spin-crossover and magnetic ordering in the dendrimeric Fe(III) complex

    International Nuclear Information System (INIS)

    The magnetic properties of the dendrimeric spin-crossover Fe(III) complex of formula [Fe(L)2]+PF6-, where L = 3,5-di[3,4,5-tris(tetradecyloxy) benzoyl-oxy]benzoyl-4-salicylidene-N'-ethyl-N-ethylene-diamine are reported for the first time. EPR spectroscopy shows that the compound displays a gradual spin-crossover in the temperature range (70-300 K) and undergoes an antiferromagnetic ordering below 10 K. Mossbauer spectroscopy data confirm the existence of magnetic ordering at 5 K in the Fe(III) dendrimeric complex.

  13. Cd(II) complexes with different nuclearity and dimensionality based on 3-hydrazino-4-amino-1,2,4-triazole

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Cai-Xia; Zhang, Jian-Guo, E-mail: zjgbit@bit.edu.cn; Yin, Xin; Jin, Xin; Li, Tong; Zhang, Tong-Lai; Zhou, Zun-Ning

    2015-03-15

    A series of zero- to two-dimensional Cd(II) coordination compounds have been synthesized by the reaction of Cd(II) salts and 3-hydrazino-4-amino-1,2,4-triazole di-hydrochloride (HATr·2HCl). [CdCl{sub 2}(HATr){sub 2}] (1) and [Cd{sub 2}Cl{sub 4}(HATr){sub 2}(H{sub 2}O){sub 2}] (2) have discrete mononuclear and binuclear structures, respectively. [Cd(HATr){sub 2}(ClO{sub 4}){sub 2}]{sub n} (3) presents polymeric 1-D chain and [Cd{sub 2}(NO{sub 3}){sub 2}Cl{sub 2}(HATr){sub 2}]{sub n} (4) shows 2-D frameworks. All Cd(II) ions exhibit distorted octahedral configurations in 1–3, whilst both hexa and heptacoordinated Cd(II) are formed in 4. The HATr ligands adopt chelating coordinated mode in 1, while tri-dentate bridging–chelating mode in 2–4. The chloride ion is a mono-coordinated ligand in 1 and 2, but it bridges two adjacent metal ions in 4. Furthermore, thermal behaviors have been investigated and the results reveal that all complexes have good thermal stability. The impact sensitivity test indicates that complex 3 is sensitive to impact stimuli. - Graphical abstract: Four Cd(II) complexes based on 3-hydrazino-4-amino-1,2,4-triazole ligands exhibit diverse structures from mononuclear to 2D networks. - Highlights: • Cd(II) complexes containing 3-hydrazino-4-amino-1,2,4-triazole ligands. • Mononuclear, binuclear, 1-D and 2-D structures. • Good thermal stability. • Thermal decomposition kinetics.

  14. Cd(II) complexes with different nuclearity and dimensionality based on 3-hydrazino-4-amino-1,2,4-triazole

    International Nuclear Information System (INIS)

    A series of zero- to two-dimensional Cd(II) coordination compounds have been synthesized by the reaction of Cd(II) salts and 3-hydrazino-4-amino-1,2,4-triazole di-hydrochloride (HATr·2HCl). [CdCl2(HATr)2] (1) and [Cd2Cl4(HATr)2(H2O)2] (2) have discrete mononuclear and binuclear structures, respectively. [Cd(HATr)2(ClO4)2]n (3) presents polymeric 1-D chain and [Cd2(NO3)2Cl2(HATr)2]n (4) shows 2-D frameworks. All Cd(II) ions exhibit distorted octahedral configurations in 1–3, whilst both hexa and heptacoordinated Cd(II) are formed in 4. The HATr ligands adopt chelating coordinated mode in 1, while tri-dentate bridging–chelating mode in 2–4. The chloride ion is a mono-coordinated ligand in 1 and 2, but it bridges two adjacent metal ions in 4. Furthermore, thermal behaviors have been investigated and the results reveal that all complexes have good thermal stability. The impact sensitivity test indicates that complex 3 is sensitive to impact stimuli. - Graphical abstract: Four Cd(II) complexes based on 3-hydrazino-4-amino-1,2,4-triazole ligands exhibit diverse structures from mononuclear to 2D networks. - Highlights: • Cd(II) complexes containing 3-hydrazino-4-amino-1,2,4-triazole ligands. • Mononuclear, binuclear, 1-D and 2-D structures. • Good thermal stability. • Thermal decomposition kinetics

  15. Fe(III) mobilisation by carbonate in low temperature environments: Study of the solubility of ferrihydrite in carbonate media and the formation of Fe(III) carbonate complexes

    International Nuclear Information System (INIS)

    Graphical abstract: - Highlights: • We have determined thermodynamic stabilities of Fe(III)-carbonate species. • We have determined the effect of those species on the solubility of ferrihydrite. • Results. • Highlight the importance of two Fe(III)-carbonate: FeOHCO3 and Fe(CO3)33−. - Abstract: The linkage between the iron and the carbon cycles is of paramount importance to understand and quantify the effect of increased CO2 concentrations in natural waters on the mobility of iron and associated trace elements. In this context, we have quantified the thermodynamic stability of mixed Fe(III) hydroxo-carbonate complexes and their effect on the solubility of Fe(III) oxihydroxides. We present the results of carefully performed solubility measurements of 2-line ferrihydrite in the slightly acidic to neutral–alkaline pH ranges (3.8–8.7) under constant pCO2 varying between (0.982–98.154 kPa) at 25 °C. The outcome of the work indicates the predominance of two Fe(III) hydroxo carbonate complexes FeOHCO3 and Fe(CO3)33−, with formation constants log*β°1,1,1 = 10.76 ± 0.38 and log β°1,0,3 = 24.24 ± 0.42, respectively. The solubility constant for the ferrihydrite used in this study was determined in acid conditions (pH: 1.8–3.2) in the absence of CO2 and at T = (25 ± 1) °C, as log*Ks,0 = 1.19 ± 0.41. The relative stability of the Fe(III)-carbonate complexes in alkaline pH conditions has implications for the solubility of Fe(III) in CO2-rich environments and the subsequent mobilisation of associated trace metals that will be explored in subsequent papers

  16. Fe(III), Cr(VI), and Fe(III) mediated Cr(VI) reduction in alkaline media using a Halomonas isolate from Soap Lake, Washington.

    Science.gov (United States)

    VanEngelen, Michael R; Peyton, Brent M; Mormile, Melanie R; Pinkart, Holly C

    2008-11-01

    Hexavalent chromium is one of the most widely distributed environmental contaminants. Given the carcinogenic and mutagenic consequences of Cr(VI) exposure, the release of Cr(VI) into the environment has long been a major concern. While many reports of microbial Cr(VI) reduction are in circulation, very few have demonstrated Cr(VI) reduction under alkaline conditions. Since Cr(VI) exhibits higher mobility in alkaline soils relative to pH neutral soils, and since Cr contamination of alkaline soils is associated with a number of industrial activities, microbial Cr(VI) reduction under alkaline conditions requires attention.Soda lakes are the most stable alkaline environments on earth, and contain a wide diversity of alkaliphilic organisms. In this study, a bacterial isolate belonging to the Halomonas genus was obtained from Soap Lake, a chemically stratified alkaline lake located in central Washington State. The ability of this isolate to reduce Cr(VI) and Fe(III) was assessed under alkaline (pH = 9), anoxic, non-growth conditions with acetate as an electron donor. Metal reduction rates were quantified using Monod kinetics. In addition, Cr(VI) reduction experiments were carried out in the presence of Fe(III) to evaluate the possible enhancement of Cr(VI) reduction rates through electron shuttling mechanisms. While Fe(III) reduction rates were slow compared to previously reported rates, Cr(VI) reduction rates fell within range of previously reported rates. PMID:18401687

  17. Influence of humic acid imposed changes of ferrihydrite aggregation on microbial Fe(III) reduction

    Science.gov (United States)

    Amstaetter, Katja; Borch, Thomas; Kappler, Andreas

    2012-05-01

    Microbial reduction of Fe(III) minerals at neutral pH is faced by the problem of electron transfer from the cells to the solid-phase electron acceptor and is thought to require either direct cell-mineral contact, the presence of Fe(III)-chelators or the presence of electron shuttles, e.g. dissolved or solid-phase humic substances (HS). In this study we investigated to which extent the ratio of Pahokee Peat Humic Acids (HA) to ferrihydrite in the presence and absence of phosphate influences rates of Fe(III) reduction by Shewanella oneidensis MR-1 and the identity of the minerals formed. We found that phosphate generally decreased reduction rates by sorption to the ferrihydrite and surface site blocking. In the presence of low ferrihydrite concentrations (5 mM), the addition of HA helped to overcome this inhibiting effect by functioning as electron shuttle between cells and the ferrihydrite. In contrast, at high ferrihydrite concentrations (30 mM), the addition of HA did not lead to an increase but rather to a decrease in reduction rates. Confocal laser scanning microscopy images and ferrihydrite sedimentation behaviour suggest that the extent of ferrihydrite surface coating by HA influences the aggregation of the ferrihydrite particles and thereby their accessibility for Fe(III)-reducing bacteria. We further conclude that in presence of dissolved HA, iron reduction is stimulated through electron shuttling while in the presence of only sorbed HA, no stimulation by electron shuttling takes place. In presence of phosphate the stimulation effect did not occur until a minimum concentration of 10 mg/l of dissolved HA was reached followed by increasing Fe(III) reduction rates up to dissolved HA concentrations of approximately 240 mg/l above which the electron shuttling effect ceased. Not only Fe(III) reduction rates but also the mineral products changed in the presence of HA. Sequential extraction, XRD and 57Fe-Mössbauer spectroscopy showed that crystallinity and grain

  18. Dissimilatory Reduction of Fe(III) and Other Electron Acceptors by a Thermus Isolate

    Energy Technology Data Exchange (ETDEWEB)

    Kieft, T. L. [New Mexico Inst. of Mining and Technology, Socorro, NM (United States); Fredrickson, J. K. [Pacific Northwest National Lab., Richland, WA (United States); Onstott, T. C. [Princeton Univ., NJ (United States). Dept. of Geological and Geophysical Sciences; Gorby, Y. A. [Pacific Northwest National Lab., Richland, WA (United States); Kostandarithes, H. M. [Pacific Northwest National Lab., Richland, WA (United States); Bailey, T. J. [Pacific Northwest National Lab., Richland, WA (United States); Kennedy, D. W. [Pacific Northwest National Lab., Richland, WA (United States); Li, S. W. [Pacific Northwest National Lab., Richland, WA (United States); Plymale, A. E. [Pacific Northwest National Lab., Richland, WA (United States); Spadoni, C. M. [Pacific Northwest National Lab., Richland, WA (United States); Gray, M. S. [Pacific Northwest National Lab., Richland, WA (United States)

    1995-10-25

    A thermophilic bacterium that could use O{sub 2}, NO{sub 3}{sup -}, Fe(III), or S{sup o} as terminal electron acceptors for growth was isolated from groundwater sampled at 3.2 km depth in a South African gold mine. This organism, designated SA-01, clustered most closely with members of the genus Thermus, as determined by 16S rDNA gene sequence analysis. The 16S rDNA sequence of SA-01 was >98% similar to that of Thermus strain NMX2 A.1, which was previously isolated by other investigators from a thermal spring in New Mexico. Strain NMX2 A.1 was also able to reduce Fe(III) and other electron acceptors, whereas Thermus aquaticus (ATCC 25104) and Thermus filiformis (ATCC 43280) did not reduce NO{sub 3}{sup -} or Fe(III). Neither SA-01 nor NMX2 A.1 grew fermentatively, i.e., addition of an external electron acceptor was required for anaerobic growth. Thermus SA-01 reduced soluble Fe(III) complexed with citrate or nitrilotriacetic acid (NTA); however, it could only reduce relatively small quantities (0.5 mM) of hydrous ferric oxide (HFO) except when the humic acid analog 2,6-anthraquinone disulfonate (AQDS) was added as an electron shuttle, in which case 10 mM Fe(III) was reduced. Fe(III)-NTA was reduced quantitatively to Fe(II), was coupled to the oxidation of lactate, and could support growth through three consecutive transfers. Suspensions of Thermus SA-01 cells also reduced Mn(IV), Co(III)-EDTA, Cr(VI), and AQDS. Mn(IV)-oxide was reduced in the presence of either lactate or H{sub 2}. Both strains were also able to mineralize NTA to CO{sub 2} and to couple its oxidation to Fe(III) reduction and growth. The optimum temperature for growth and Fe(III) reduction by Thermus SA-01 and NMX2 A.1 is approximately 65 C; optimum pH is 6.5 to 7.0. This is the first report of a Thermus sp. being able to couple the oxidation of organic compounds to the reduction of Fe, Mn or S.

  19. Synthesis and characterization of chromium(III), manganese(II), iron(III), cobalt(II), nickel(II), copper(II), cadmium(II) and dioxouranium(VI) complexes of 4(2-pyridyl)-1-(2,4-dihydroxybenzaldehyde)-3-thiosemicarbazone

    International Nuclear Information System (INIS)

    A few complexes of Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and dioxouranium(VI) with 4(2-pyridyl)-1-(2,4-dihydroxybenzaldehyde)-3-thiosemicarbazone have been synthesised and characterized on the basis of elemental analysis, IR, electronic NMR, and magnetic moment data. An octahedral structure is proposed for the Cr(III), Fe(III), Co(II) and Ni(H3PBT)2 Cl2.2H2O complexes; a tetrahedral structure for the Mn(II) and Ni2(PBT)OAc.H20 complexes and a square planar structure for the Cu(II) complexes. The antimicrobial and antifungal activities of H3PBT and of its metal(II) complexes are investigated. The results reveal that H3PBT exhibits greater antimicrobial activities than its complexes. (author). 34 refs., 4 figs., 2 tabs

  20. Biosorption of Pb(II) and Cd(II) from aqueous solution using green alga (Ulva lactuca) biomass

    International Nuclear Information System (INIS)

    The biosorption characteristics of Pb(II) and Cd(II) ions from aqueous solution using the green alga (Ulva lactuca) biomass were investigated as a function of pH, biomass dosage, contact time, and temperature. Langmuir, Freundlich and Dubinin-Radushkevich (D-R) models were applied to describe the biosorption isotherm of the metal ions by U. lactuca biomass. Langmuir model fitted the equilibrium data better than the Freundlich isotherm. The monolayer biosorption capacity of U. lactuca biomass for Pb(II) and Cd(II) ions was found to be 34.7 mg/g and 29.2 mg/g, respectively. From the D-R isotherm model, the mean free energy was calculated as 10.4 kJ/mol for Pb(II) biosorption and 9.6 kJ/mol for Cd(II) biosorption, indicating that the biosorption of both metal ions was taken place by chemisorption. The calculated thermodynamic parameters (ΔGo, ΔHo and ΔSo) showed that the biosorption of Pb(II) and Cd(II) ions onto U. lactuca biomass was feasible, spontaneous and exothermic under examined conditions. Experimental data were also tested in terms of biosorption kinetics using pseudo-first-order and pseudo-second-order kinetic models. The results showed that the biosorption processes of both metal ions followed well pseudo-second-order kinetics

  1. Crosslinked chitosan/polyvinyl alcohol blend beads for removal and recovery of Cd(II) from wastewater

    International Nuclear Information System (INIS)

    Crosslinked chitosan/poly(vinyl alcohol) (PVA) beads were prepared by suspension of chitosan-PVA aqueous solution in a mixture of toluene and chlorobenzene. Some quantity of the water was distilled out as an azeotrope along with toluene-chlorobenzene and the droplets were chemically crosslinked by adding glutaraldehyde. The prepared crosslinked beads were characterized by FTIR, X-ray diffraction (XRD), and scanning electron microscopy (SEM). The developed beads were used as an adsorbent for the adsorption of Cd(II) from wastewater. Effect of time, temperature, pH, adsorbent dose and adsorbate concentration on the adsorption of Cd(II) were investigated in batch process and pseudo-first and pseudo-second-order kinetic models were also evaluated. The equilibrium adsorption obeyed Langmuir and Freundlich isotherms as well as the thermodynamic parameters such as ΔGo, ΔHo and ΔSo were calculated. From thermodynamic data, it was found that the adsorption process was endothermic and spontaneous. The maximum adsorption of Cd(II) ions was found to be 73.75% at pH 6 and indicated that developed material could be effectively utilized for the removal of Cd(II) ions from wastewater.

  2. Cd(II) complexes with different nuclearity and dimensionality based on 3-hydrazino-4-amino-1,2,4-triazole

    Science.gov (United States)

    Xu, Cai-Xia; Zhang, Jian-Guo; Yin, Xin; Jin, Xin; Li, Tong; Zhang, Tong-Lai; Zhou, Zun-Ning

    2015-03-01

    A series of zero- to two-dimensional Cd(II) coordination compounds have been synthesized by the reaction of Cd(II) salts and 3-hydrazino-4-amino-1,2,4-triazole di-hydrochloride (HATr·2HCl). [CdCl2(HATr)2] (1) and [Cd2Cl4(HATr)2(H2O)2] (2) have discrete mononuclear and binuclear structures, respectively. [Cd(HATr)2(ClO4)2]n (3) presents polymeric 1-D chain and [Cd2(NO3)2Cl2(HATr)2]n (4) shows 2-D frameworks. All Cd(II) ions exhibit distorted octahedral configurations in 1-3, whilst both hexa and heptacoordinated Cd(II) are formed in 4. The HATr ligands adopt chelating coordinated mode in 1, while tri-dentate bridging-chelating mode in 2-4. The chloride ion is a mono-coordinated ligand in 1 and 2, but it bridges two adjacent metal ions in 4. Furthermore, thermal behaviors have been investigated and the results reveal that all complexes have good thermal stability. The impact sensitivity test indicates that complex 3 is sensitive to impact stimuli.

  3. Experimental analysis and mathematical prediction of Cd(II) removal by biosorption using support vector machines and genetic algorithms.

    Science.gov (United States)

    Hlihor, Raluca Maria; Diaconu, Mariana; Leon, Florin; Curteanu, Silvia; Tavares, Teresa; Gavrilescu, Maria

    2015-05-25

    We investigated the bioremoval of Cd(II) in batch mode, using dead and living biomass of Trichoderma viride. Kinetic studies revealed three distinct stages of the biosorption process. The pseudo-second order model and the Langmuir model described well the kinetics and equilibrium of the biosorption process, with a determination coefficient, R(2)>0.99. The value of the mean free energy of adsorption, E, is less than 16 kJ/mol at 25 °C, suggesting that, at low temperature, the dominant process involved in Cd(II) biosorption by dead T. viride is the chemical ion-exchange. With the temperature increasing to 40-50 °C, E values are above 16 kJ/mol, showing that the particle diffusion mechanism could play an important role in Cd(II) biosorption. The studies on T. viride growth in Cd(II) solutions and its bioaccumulation performance showed that the living biomass was able to bioaccumulate 100% Cd(II) from a 50 mg/L solution at pH 6.0. The influence of pH, biomass dosage, metal concentration, contact time and temperature on the bioremoval efficiency was evaluated to further assess the biosorption capability of the dead biosorbent. These complex influences were correlated by means of a modeling procedure consisting in data driven approach in which the principles of artificial intelligence were applied with the help of support vector machines (SVM), combined with genetic algorithms (GA). According to our data, the optimal working conditions for the removal of 98.91% Cd(II) by T. viride were found for an aqueous solution containing 26.11 mg/L Cd(II) as follows: pH 6.0, contact time of 3833 min, 8 g/L biosorbent, temperature 46.5 °C. The complete characterization of bioremoval parameters indicates that T. viride is an excellent material to treat wastewater containing low concentrations of metal. PMID:25224921

  4. Microbial Fe(III) Reduction in Acidic Mining Lake Sediments after Addition of an Organic Substrate and Lime

    International Nuclear Information System (INIS)

    To elucidate the role of Fe(III) reduction in mining lake sediments amended with organic substrates, we performed a large (10 m diameter) enclosure experiment in which sediments were amended with Carbokalk, a waste product from sugar industry containing organic carbon and lime. Fe(III) reduction rates were determined monthly by measuring the accumulation of Fe(II) in the sediments in the field. Fe(III) reduction rates were also determined by incubating sediment samples with synthetic Fe(III) oxyhydroxide under in situ temperature in the laboratory. Sulfate reduction was selectively inhibited in the Fe(III) reduction experiments by addition of sodium molybdate. Sulfate reduction was measured by accumulation of reduced inorganic sulfides in the field and by 35S radiotracer using a core injection technique. Sediment incubation and determination of sulfate reduction rates with radiotracer showed that sulfate reduction and direct microbial Fe(III) reduction occurred simultaneously in the upper centimeters of the sediments and that both processes contributed to alkalinity generation. However, Fe(III) reduction was the initial process and rates were at least 3.5 fold higher than sulfate reduction rates. The results indicate that the presence of suitable anions for Fe(II) precipitation as carbonate or sulfide is needed in order to prevent loss of potential alkalinity by Fe(II) diffusion and reoxidation in the water column

  5. Cd(II) removal from aqueous solution by adsorption on α-ketoglutaric acid-modified magnetic chitosan

    International Nuclear Information System (INIS)

    The present study developed an α-ketoglutaric acid-modified magnetic chitosan (α-KA-Fe3O4/CS) for highly efficient adsorption of Cd(II) from aqueous solution. Several techniques, including transmission electron microscopy (TEM), Fourier transform infrared (FTIR) and vibrating sample magnetometer (VSM), were applied to characterize the adsorbent. Batch tests were conducted to investigate the Cd(II) adsorption performance of α-KA-Fe3O4/CS. The maximum adsorption efficiency of Cd(II) appeared at pH 6.0 with the value of 93%. The adsorption amount was large and even reached 201.2 mg/g with the initial Cd(II) concentration of 1000 mg/L. The adsorption equilibrium was reached within 30 min and commendably described by pseudo-second-order model, and Langmuir model fitted the adsorption isotherm better. Furthermore, thermodynamic parameters, free energy (ΔG), enthalpy (ΔH) and entropy (ΔS) of Cd(II) adsorption were also calculated and showed that the overall adsorption process was endothermic and spontaneous in nature because of positive ΔH values and negative ΔG values, respectively. Moreover, the Cd(II)-loaded α-KA-Fe3O4/CS could be regenerated by 0.02 mol/L NaOH solution, and the cadmium removal capacity could still be kept around 89% in the sixth cycle. All the results indicated that α-KA-Fe3O4/CS was a promising adsorbent in environment pollution cleanup.

  6. Enhanced reduction of Fe(III) oxides and methyl orange by Klebsiella oxytoca in presence of anthraquinone-2-disulfonate.

    Science.gov (United States)

    Yu, Lei; Wang, Shi; Tang, Qing-Wen; Cao, Ming-Yue; Li, Jia; Yuan, Kun; Wang, Ping; Li, Wen-Wei

    2016-05-01

    Klebsiella oxytoca GS-4-08 is capable of azo dye reduction, but its quinone respiration and Fe(III) reduction abilities have not been reported so far. In this study, the abilities of this strain were reported in detail for the first time. As the biotic reduction of Fe(III) plays an important role in the biogeochemical cycles, two amorphous Fe(III) oxides were tested as the sole electron acceptor during the anaerobic respiration of strain GS-4-08. For the reduction of goethite and hematite, the biogenic Fe(II) concentrations reached 0.06 and 0.15 mM, respectively. Humic acid analog anthraquinone-2-disulfonate (AQS) was found to serve as an electron shuttle to increase the reduction of both methyl orange (MO) and amorphous Fe(III) oxides, and improve the dye tolerance of the strain. However, the formation of Fe(II) was not accelerated by biologically reduced AQS (B-AH2QS) because of the high bioavailability of soluble Fe(III). For the K. oxytoca strain, high soluble Fe(III) concentrations (above 1 mM) limit its growth and decolorization ability, while lower soluble Fe(III) concentrations produce an electron competition with MO initially, and then stimulate the decolorization after the electron couples of Fe(III)/Fe(II) are formed. With the ability to respire both soluble Fe(III) and insoluble Fe(III) oxides, this formerly known azo-reducer may be used as a promising model organism for the study of the interaction of these potentially competing processes in contaminated environments. PMID:26762391

  7. Mechanism of Co(II) adsorption by zero valent iron/graphene nanocomposite.

    Science.gov (United States)

    Xing, Min; Xu, Lejin; Wang, Jianlong

    2016-01-15

    Nanoscale zero valent iron (ZVI)/graphene (GF) composite was prepared and characterized by Brunauer-Emmett-Teller (BET) surface area measurement and zeta potential determination. The adsorption isotherm of Co(II) in aqueous solution, as well as the influence of pH values and ionic strengths was studied. The mechanism of Co(II) adsorption by GF was investigated through analyzing the sorption products at initial pH of 3.0, 6.0 and 9.0 using high-resolution transmission electron microscope with energy dispersive X-ray detector (HRTEM-EDX), X-ray diffraction (XRD), vibrating-sample magnetometer (VSM), Raman spectra, X-ray photoelectron spectroscopy (XPS) and X-ray absorption fine structure (XAFS) measurement. The results indicated that Langmuir isotherm model fitted well and the adsorption capacity was 131.58 mg g(-1) at 30°C. Adsorption capacity was not significantly influenced by ionic strength and kept high at pH 4.0∼9.0. The detail information of GF-Co interaction at different initial pH values was obtained using XAFS analysis combined with other characterization methods. Coordination numbers (CN) and interatomic distances (R) of both Fe and Co were given. At pH 3.0 and pH 6.0, the Co-substituted iron oxides transformed to CoFe2O4-like structure, while at pH 9.0 they changed to green rust-like phases. Co occupied preferentially in the octahedral sites in acid solution. The adsorption mechanism of Co(II) was attributed to inner-sphere complexation and dissolution/re-precipitation of the substituted metal oxides. PMID:26368802

  8. Direct Adherence of Fe(III) Particles onto Sheaths of Leptothrix sp. Strain OUMS1 in Culture

    OpenAIRE

    Tatsuki Kunoh; Hideki Hashimoto; Tomoko Suzuki; Naoyuki Hayashi; Katsunori Tamura; Mikio Takano; Hitoshi Kunoh; Jun Takada

    2016-01-01

    Leptothrix species, one of the Fe/Mn-oxidizing bacteria, oxidize Fe(II) and produce extracellular, microtubuar, Fe-encrusted sheaths. Since protein(s) involved in Fe(II) oxidation is excreted from Leptothrix cells, the oxidation from Fe(II) to Fe(III) and subsequent Fe(III) deposition to sheaths have been thought to occur in the vicinity or within the sheaths. Previously, Fe(III) particles generated in MSVP medium amended with Fe(II) salts by abiotic oxidation were directly recruited onto cel...

  9. Does As(III) interact with Fe(II), Fe(III) and organic matter through ternary complexes?

    OpenAIRE

    Catrouillet, Charlotte; Davranche, Mélanie; Dia, Aline; Bouhnik-Le Coz, Martine; Demangeat, Edwige; Gruau, Gérard

    2016-01-01

    International audience Up until now, only a small number of studies have been dedicated to the binding processes of As(III) with organic matter (OM) via ionic Fe(III) bridges; none was interested in Fe (II). Complexation isotherms were carried out with As(III), Fe(II) or Fe(III) and Leonardite humic acid (HA). Although PHREEQC/Model VI, implemented with OM thiol groups, reproduced the experimental datasets with Fe(III), the poor fit between the experimental and modeled Fe(II) data suggeste...

  10. Microbial Reducibility of Fe(III Phases Associated with the Genesis of Iron Ore Caves in the Iron Quadrangle, Minas Gerais, Brazil

    Directory of Open Access Journals (Sweden)

    Ceth W. Parker

    2013-11-01

    Full Text Available The iron mining regions of Brazil contain thousands of “iron ore caves” (IOCs that form within Fe(III-rich deposits. The mechanisms by which these IOCs form remain unclear, but the reductive dissolution of Fe(III (hydroxides by Fe(III reducing bacteria (FeRB could provide a microbiological mechanism for their formation. We evaluated the susceptibility of Fe(III deposits associated with these caves to reduction by the FeRB Shewanella oneidensis MR-1 to test this hypothesis. Canga, an Fe(III-rich duricrust, contained poorly crystalline Fe(III phases that were more susceptible to reduction than the Fe(III (predominantly hematite associated with banded iron formation (BIF, iron ore, and mine spoil. In all cases, the addition of a humic acid analogue enhanced Fe(III reduction, presumably by shuttling electrons from S. oneidensis to Fe(III phases. The particle size and quartz-Si content of the solids appeared to exert control on the rate and extent of Fe(III reduction by S. oneidensis, with more bioreduction of Fe(III associated with solid phases containing more quartz. Our results provide evidence that IOCs may be formed by the activities of Fe(III reducing bacteria (FeRB, and the rate of this formation is dependent on the physicochemical and mineralogical characteristics of the Fe(III phases of the surrounding rock.

  11. Nontronite (NAu-1) Structure Associated with Microbial Fe(III) Reduction in Various Redox Conditions

    Science.gov (United States)

    Koo, T.; Kim, S.; Kim, J.

    2011-12-01

    Shewanella oneidensis MR-1 respires the structural Fe(III) of smectite and promotes illite formation in O2-free environment (Kostka et al., 1996, Kim et al., 2004). Since S. oneidensis is a facultative iron reducing bacterium, it is crucial to understand the structural changes induced by bio-reduction of structural Fe(III) in various redox conditions. Furthermore, the changes in cation exchange capacity (CEC) of bio-reduced nontronite upon the modification of mineral structure has not been extensively studied in terms of Fe-cycling. In this present study, we reported the evolution of nontronite structure at various time points in various redox conditions and corresponding CEC upon reduction and re-oxidation. S. oneidensis MR-1 was incubated in M1 medium with Na-lactate as the electron donor and Fe in nontronite (NAu-1) as the sole electron acceptor at pH 7 in anaerobic chamber for 3 hrs, 12 hrs, 1 day, 2 days, 4 days, 7 days, 14 days, and 21 days. O2 gas bubbling was then applied to the sample at each time point for 24 hours for re-oxidation. The triplet samples at each time point for both reduction and re-oxidation experiments were prepared. The extent of Fe(III) reduction measured by 1,10-phenanthroline method (Stucki and Anderson, 1981) indicated that the structural Fe(III) was reduced up to 8.8% of total Fe(III) within 21 days. XRD data with various treatments such as air dried, glycolated and lithium-saturated showed that K-nontronite may be formed because no discrete 10-Å illite peak was observed in Li-saturated sample upon glycolation. The CEC increased from 747 meg/kg to 1145 meg/kg during Fe(III) reduction and decreased to 954 meg/kg upon re-oxidation, supporting the possible formation of K-nontronite. The direct observation by electron microscopy verified the structural changes in nontonite in various redox conditions. The long-term experiment for 6 months, is in progress in anaerobic chamber, and results will be discussed. Kim, J. W., Dong, H., Seabaugh

  12. Sorption and desorption of Fe(III) on natural and chemically modified zeolite

    International Nuclear Information System (INIS)

    The Fe(III) uptake from aqueous solutions by natural and chemically modified zeolites was investigated using a gradual radioexchange method and AAS technique. The leachability of Fe(III) from loaded zeolites was studied too. The Fe-uptake reached the value of 60 mg x g-1 for the zeolite chemically treated with 6 mol x l-1 solution of NaOH and it is more than twelve times higher than that of the raw zeolite. The leachability of the loaded zeolite samples in water and alkaline solution was up 5%. The leachability of the same zeolites in acid solution depended on the concentration of modifying solution. The leachability at pH = 2.6 in the range 2-20% at pH = 1.9 was many times higher. The results of the radioexchange and AAS methods were compared. (author)

  13. Synthesis and Characterization of 4-Benzyloxybenzaldehyde-4-methyl-3-thiosemicarbazone (Containing Sulphur and Nitrogen Donor Atoms and Its Cd(II Complex

    Directory of Open Access Journals (Sweden)

    Lakshmi Narayana Suvarapu

    2015-12-01

    Full Text Available A chelating agent, 4-benzyloxybenzaldehyde-4-methyl-3-thiosemicarbazone (BBMTSC, containing sulphur and nitrogen donor atoms was synthesized and applied as a ligand for the chelation of Cd(II. Both the BBMTSC and its Cd(II complex were characterized by elemental analysis, UV-Vis absorption spectra, Fourier transform infrared spectroscopy (FT-IR, mass spectra, nuclear magnetic resonance spectroscopy (NMR, X-ray powder diffraction (XRD, and field emission scanning electron microscopy (FESEM. The FTIR spectra confirmed the formation of both BBMTSC and its Cd(II complex. XRD revealed the polycrystalline nature of the synthesized compounds. BBMTSC exhibited a flake-like micro-rod morphology, whereas the Cd(II complex had a flower-like nanorod structure.

  14. Synthesis and Crystal Structure of a Co(II) Complex with Schiff Base and Imidazole Ligand

    Institute of Scientific and Technical Information of China (English)

    WU Lian-Bin; HU Zi-Qiang; LAI Guo-Qiao

    2006-01-01

    The title compound, [Co(C3H4N2)2(C22H18N2O4)]·5H2O (Mr = 659.56), has been prepared and its crystal structure was determined by X-ray diffraction method. The crystal be- longs to monoclinic, space group P21/n, a = 9.6808(2), b = 26.7204(5), c = 12.7993(3)(A), β = 100.9340(10)o, V = 3250.75(12) (A)3, Z = 4, Dc = 1.348 g/cm3, μ= 0.586 mm-1, F(000) = 1380, S = 1.131, R = 0.0689 and wR = 0.1883 for 4782 observed reflections (I > 2σ(I)). The title crystal consists of Co(II) complex and lattice water molecules. The Co(II) complex assumes a distorted octahedral coordination geometry, formed by one Schiff base dianion phenylenediamine-3-me- thoxysali-cylaldehyde and two imidazole ligands. The π-π stacking interaction occurs between nearly parallel benzene rings of the neighboring complexes.

  15. Synthesis and Characterization of 4-Benzyloxybenzaldehyde-4-methyl-3-thiosemicarbazone (Containing Sulphur and Nitrogen Donor Atoms) and Its Cd(II) Complex

    OpenAIRE

    Lakshmi Narayana Suvarapu; Sung-Ok Baek

    2015-01-01

    A chelating agent, 4-benzyloxybenzaldehyde-4-methyl-3-thiosemicarbazone (BBMTSC), containing sulphur and nitrogen donor atoms was synthesized and applied as a ligand for the chelation of Cd(II). Both the BBMTSC and its Cd(II) complex were characterized by elemental analysis, UV-Vis absorption spectra, Fourier transform infrared spectroscopy (FT-IR), mass spectra, nuclear magnetic resonance spectroscopy (NMR), X-ray powder diffraction (XRD), and field emission scanning electron microscopy (FES...

  16. Shewanella oneidensis MR-1-Induced Fe(III) Reduction Facilitates Roxarsone Transformation

    Science.gov (United States)

    Chen, Guowei; Ke, Zhengchen; Liang, Tengfang; Liu, Li; Wang, Gang

    2016-01-01

    Although microbial activity and associated iron (oxy)hydroxides are known in general to affect the environmental dynamics of 4-hydroxy-3-nitrobenzenearsonic acid (roxarsone), the mechanistic understanding of the underlying biophysico-chemical processes remains unclear due to limited experimental information. We studied how Shewanella oneidensis MR-1 –a widely distributed metal-reducing bacterium, in the presence of dissolved Fe(III), affects roxarsone transformations and biogeochemical cycling in a model aqueous system. The results showed that the MR-1 strain was able to anaerobically use roxarsone as a terminal electron acceptor and to convert it to a single product, 3-amino-4-hydroxybenzene arsonic acid (AHBAA). The presence of Fe(III) stimulated roxarsone transformation via MR-1-induced Fe(III) reduction, whereby the resulting Fe(II) acted as an efficient reductant for roxarsone transformation. In addition, the subsequent secondary Fe(III)/Fe(II) mineralization created conditions for adsorption of organoarsenic compounds to the yielded precipitates and thereby led to arsenic immobilization. The study provided direct evidence of Shewanella oneidensis MR-1-induced direct and Fe(II)-associated roxarsone transformation. Quantitative estimations revealed a candidate mechanism for the early-stage environmental dynamics of roxarsone in nature, which is essential for understanding the environmental dynamics of roxarsone and successful risk assessment. PMID:27100323

  17. Direct Adherence of Fe(III Particles onto Sheaths of Leptothrix sp. Strain OUMS1 in Culture

    Directory of Open Access Journals (Sweden)

    Tatsuki Kunoh

    2016-01-01

    Full Text Available Leptothrix species, one of the Fe/Mn-oxidizing bacteria, oxidize Fe(II and produce extracellular, microtubuar, Fe-encrusted sheaths. Since protein(s involved in Fe(II oxidation is excreted from Leptothrix cells, the oxidation from Fe(II to Fe(III and subsequent Fe(III deposition to sheaths have been thought to occur in the vicinity or within the sheaths. Previously, Fe(III particles generated in MSVP medium amended with Fe(II salts by abiotic oxidation were directly recruited onto cell-encasing and/or -free sheaths of L. cholodnii SP-6. In this study, whether this direct Fe(III adherence to sheaths also occurs in silicon-glucose-peptone (SGP medium amended with Fe(0 (SGP + Fe was investigated using another strain of Leptothrix sp., OUMS1. Preparation of SGP + Fe with Fe powder caused turbidity within a few hours due to abiotic generation of Fe(III particles via Fe(II, and the medium remained turbid until day 8. When OUMS1 was added to SGP + Fe, the turbidity of the medium cleared within 35 h as Fe(III particles adhered to sheaths. When primitive sheaths, cell-killed, cell-free, or lysozyme/EDTA/SDS- and proteinase K-treated sheath remnants were mixed with Fe(III particles, the particles immediately adhered to each. Thus, vital activity of cells was not required for the direct Fe(III particle deposition onto sheaths regardless of Leptothrix strains.

  18. Microbial Fe(III) Oxide Reduction in Chocolate Pots Hot Springs, Yellowstone National Park

    Science.gov (United States)

    Fortney, N. W.; Roden, E. E.; Boyd, E. S.; Converse, B. J.

    2014-12-01

    Previous work on dissimilatory iron reduction (DIR) in Yellowstone National Park (YNP) has focused on high temperature, low pH environments where soluble Fe(III) is utilized as an electron acceptor for respiration. Much less attention has been paid to DIR in lower temperature, circumneutral pH environments, where solid phase Fe(III) oxides are the dominant forms of Fe(III). This study explored the potential for DIR in the warm (ca. 40-50°C), circumneutral pH Chocolate Pots hot springs (CP) in YNP. Most probable number (MPN) enumerations and enrichment culture studies confirmed the presence of endogenous microbial communities that reduced native CP Fe(III) oxides. Enrichment cultures demonstrated sustained DIR coupled to acetate and lactate oxidation through repeated transfers over ca. 450 days. Pyrosequencing of 16S rRNA genes indicated that the dominant organisms in the enrichments were closely affiliated with the well known Fe(III) reducer Geobacter metallireducens. Additional taxa included relatives of sulfate reducing bacterial genera Desulfohalobium and Thermodesulfovibrio; however, amendment of enrichments with molybdate, an inhibitor of sulfate reduction, suggested that sulfate reduction was not a primary metabolic pathway involved in DIR in the cultures. A metagenomic analysis of enrichment cultures is underway in anticipation of identifying genes involved in DIR in the less well-characterized dominant organisms. Current studies are aimed at interrogating the in situ microbial community at CP. Core samples were collected along the flow path (Fig. 1) and subdivided into 1 cm depth intervals for geochemical and microbiological analysis. The presence of significant quantities of Fe(II) in the solids indicated that DIR is active in situ. A parallel study investigated in vitro microbial DIR in sediments collected from three of the coring sites. DNA was extracted from samples from both studies for 16S rRNA gene and metagenomic sequencing in order to obtain a

  19. The life cycle of iron Fe(III) oxide: impact of fungi and bacteria

    Science.gov (United States)

    Bonneville, Steeve

    2014-05-01

    Iron oxides are ubiquitous reactive constituents of soils, sediments and aquifers. They exhibit vast surface areas which bind a large array of trace metals, nutrients and organic molecules hence controlling their mobility/reactivity in the subsurface. In this context, understanding the "life cycle" of iron oxide in soils is paramount to many biogeochemical processes. Soils environments are notorious for their extreme heterogeneity and variability of chemical, physical conditions and biological agents at play. Here, we present studies investigating the role of two biological agents driving iron oxide dynamics in soils, root-associated fungi (mycorrhiza) and bacteria. Mycorrhiza filaments (hypha) grow preferentially around, and on the surface of nutrient-rich minerals, making mineral-fungi contact zones, hot-spots of chemical alteration in soils. However, because of the microscopic nature of hyphae (only ~ 5 µm wide for up to 1 mm long) and their tendency to strongly adhere to mineral surface, in situ observations of this interfacial micro-environment are scarce. In a microcosm, ectomycorrhiza (Paxillus involutus) was grown symbiotically with a pine tree (Pinus sylvestris) in the presence of freshly-cleaved biotite under humid, yet undersaturated, conditions typical of soils. Using spatially-resolved ion milling technique (FIB), transmission electron microscopy and spectroscopy (TEM/STEM-EDS), synchrotron based X-ray microscopy (STXM), we were able to quantify the speciation of Fe at the biotite-hypha interface. The results shows that substantial oxidation of biotite structural-Fe(II) into Fe(III) subdomains occurs at the contact zone between mycorrhiza and biotite. Once formed, iron(III) oxides can reductively dissolve under suboxic conditions via several abiotic and microbial pathways. In particular, they serve as terminal electron acceptors for the oxidation of organic matter by iron reducing bacteria. We aimed here to understand the role of Fe(III) mineral

  20. Mechanisms for Electron Transfer Through Pili to Fe(III) Oxide in Geobacter

    Energy Technology Data Exchange (ETDEWEB)

    Lovley, Derek R. [Univ. of Massachusetts, Amherst, MA (United States)

    2015-03-09

    The purpose of these studies was to aid the Department of Energy in its goal of understanding how microorganisms involved in the bioremediation of metals and radionuclides sustain their activity in the subsurface. This information is required in order to incorporate biological processes into decision making for environmental remediation and long-term stewardship of contaminated sites. The proposed research was designed to elucidate the mechanisms for electron transfer to Fe(III) oxides in Geobacter species because Geobacter species are abundant dissimilatory metal-reducing microorganisms in a diversity of sites in which uranium is undergoing natural attenuation via the reduction of soluble U(VI) to insoluble U(IV) or when this process is artificially stimulated with the addition of organic electron donors. This study investigated the novel, but highly controversial, concept that the final conduit for electron transfer to Fe(III) oxides are electrically conductive pili. The specific objectives were to: 1) further evaluate the conductivity along the pili of Geobacter sulfurreducens and related organisms; 2) determine the mechanisms for pili conductivity; and 3) investigate the role of pili in Fe(III) oxide reduction. The studies demonstrated that the pili of G. sulfurreducens are conductive along their length. Surprisingly, the pili possess a metallic-like conductivity similar to that observed in synthetic organic conducting polymers such as polyaniline. Detailed physical analysis of the pili, as well as studies in which the structure of the pili was genetically modified, demonstrated that the metallic-like conductivity of the pili could be attributed to overlapping pi-pi orbitals of aromatic amino acids. Other potential mechanisms for conductivity, such as electron hopping between cytochromes associated with the pili were definitively ruled out. Pili were also found to be essential for Fe(III) oxide reduction in G. metallireducens. Ecological studies demonstrated

  1. Dicarboxylated ethynylarenes as buffer-dependent chemosensors for Cd(II), Pb(II) and Zn(II)

    OpenAIRE

    Fletcher, James T.; Bruck, Brent S.; Deever, Douglas E.

    2013-01-01

    Two dicarboxylated ethynylarenes were prepared efficiently from condensation of 1,3-bis(3-aminoph enylethynyl)benzene with two equivalents of either succinic anhydride or glutaric anhydride. These compounds behave as fluorescent chemosensors selective for Cd(II), Pb(II) and Zn(II) cations under buffered aqueous conditions, with analyte binding observed as bathochromically shifted, intensified fluorescence. It was noteworthy that the fluorescence responses varied significantly with buffer iden...

  2. Mycorrhizal fungi and ectomycorrhiza associated bacteria isolated from an industrial desert soil protect pine seedlings against Cd(II) impact.

    Science.gov (United States)

    Kozdrój, Jacek; Piotrowska-Seget, Zofia; Krupa, Piotr

    2007-08-01

    Effects of mycorrhization with Amanita rubescens or Hebeloma sinapizans and dual inoculation with the fungi and ectomycorrhiza associated bacteria (EMAB) Pseudomonas putida or Bacillus cereus on seedling growth and accumulation of Cd(II) in Pinus sylvestris were studied. Both fungal and bacterial species were isolated from roots of pines growing in an industrial area polluted with high concentrations of heavy metals. During mycorrhization, A. rubescens colonized higher number of pine seedlings than H. sinapizans, especially when EMAB were co-inoculated. In addition, the seedling biometric characteristics (i.e. root and shoot lengths and biomass) were stimulated by treatment with the fungal species alone and dual inoculation with the fungi and EMAB. Amanita rubescens was more efficient in this stimulation than H. sinapizans. The increased growth of pine seedlings was especially seen for co-inoculation with P. putida. Furthermore, elevated accumulation of Cd(II), ranging from 56 microg g(-1) to 72 microg g(-1) dry weight, in underground parts of the inoculated seedlings was found. The seedlings treated with A. rubescens accumulated higher concentrations of the metal than those inoculated with H. sinapizans. Additional treatment of pine seedlings with P. putida resulted in the higher accumulation of Cd(II) in the roots as compared with those inoculated with B. cereus. The results suggest that the growth of pine seedlings in Cd(II)-polluted soil may depend on fungal species forming ectomycorrhizae, species-specific co-inoculation with EMAB and specificity of fungal-EMAB interactions. PMID:17541824

  3. Five chiral Cd(II) complexes with dual chiral components: Effect of positional isomerism, luminescence and SHG response

    International Nuclear Information System (INIS)

    Five chiral Cd(II) complexes with dual chiral components have been synthesized by using a series of (1R,2R)–N1,N2-bis(pyridinylmethyl)cyclohexane-1,2-diamine ligands with different N-positions of pyridyl rings and Cd(NO3)2. The circular dichroism (CD) spectra and second-harmonic generation (SHG) efficiency measurements confirmed that they are of structural chirality in the bulk samples. The luminescent properties indicated that they may have potential applications as optical materials. The formation of discrete mononuclear and binuclear complexes, and one-dimensional chains may be attributed to positional isomerism of the ligands. - Graphical abstract: Five chiral Cd(II) complexes with dual chiral components have been synthesized by using a series of chiral ligands with different N-positions of pyridyl rings. - Highlights: • Five chiral Cd(II) complexes with dual chiral components have been synthesized. • CD spectra and SHG efficiency of the bulk samples have been measured. • The complexes display luminescent properties

  4. Five chiral Cd(II) complexes with dual chiral components: Effect of positional isomerism, luminescence and SHG response

    Energy Technology Data Exchange (ETDEWEB)

    Cheng, Lin, E-mail: lcheng@seu.edu.cn [Pharmaceutical Research Center, School of Chemistry and Chemical Engineering, Southeast University, Nanjing 211189 (China); Jiangsu Province Hi-Tech Key Laboratory for Bio-medical Research, Southeast University, Nanjing 211189 (China); Wang, Jun; Yu, Hai-Yan; Zhang, Xiu-Ying [Pharmaceutical Research Center, School of Chemistry and Chemical Engineering, Southeast University, Nanjing 211189 (China); Gou, Shao-Hua, E-mail: sgou@seu.edu.cn [Pharmaceutical Research Center, School of Chemistry and Chemical Engineering, Southeast University, Nanjing 211189 (China); Jiangsu Province Hi-Tech Key Laboratory for Bio-medical Research, Southeast University, Nanjing 211189 (China); Fang, Lei [Pharmaceutical Research Center, School of Chemistry and Chemical Engineering, Southeast University, Nanjing 211189 (China); Jiangsu Province Hi-Tech Key Laboratory for Bio-medical Research, Southeast University, Nanjing 211189 (China)

    2015-01-15

    Five chiral Cd(II) complexes with dual chiral components have been synthesized by using a series of (1R,2R)–N{sup 1},N{sup 2}-bis(pyridinylmethyl)cyclohexane-1,2-diamine ligands with different N-positions of pyridyl rings and Cd(NO{sub 3}){sub 2}. The circular dichroism (CD) spectra and second-harmonic generation (SHG) efficiency measurements confirmed that they are of structural chirality in the bulk samples. The luminescent properties indicated that they may have potential applications as optical materials. The formation of discrete mononuclear and binuclear complexes, and one-dimensional chains may be attributed to positional isomerism of the ligands. - Graphical abstract: Five chiral Cd(II) complexes with dual chiral components have been synthesized by using a series of chiral ligands with different N-positions of pyridyl rings. - Highlights: • Five chiral Cd(II) complexes with dual chiral components have been synthesized. • CD spectra and SHG efficiency of the bulk samples have been measured. • The complexes display luminescent properties.

  5. Fabrication of titanate nanotubes/iron oxide magnetic composite for the high efficient capture of radionuclides: a case investigation of 109Cd(II)

    International Nuclear Information System (INIS)

    In this paper, the capture of radiocadmium (Cd(II)) by adsorption onto the titanate nanotube/iron oxide (TNT/IOM) magnetic composite as a function of contact time, pH, ionic strength, foreign cation and anion ions, humic acid (HA) and fulvic acid (FA) was studied using batch technique. The results indicated that the adsorption of Cd(II) onto the TNT/IOM magnetic composite was dependent on ionic strength at pH 9.0. Outer-sphere surface complexation were the main mechanism of Cd(II) adsorption onto the TNT/IOM magnetic composite at low pH values, whereas the adsorption was mainly dominated via inner-sphere surface complexation at high pH values. The adsorption of Cd(II) onto the TNT/IOM magnetic composite was dependent on foreign cation and anion ions at low pH values, but was independent of foreign cation and anion ions at high pH values. A positive effect of HA/FA on Cd(II) adsorption onto the TNT/IOM magnetic composite was found at low pH values, while a negative effect was observed at high pH values. From the results of Cd(II) removal by the TNT/IOM magnetic composite, the optimum reaction conditions can be obtained for the maximum removal of Cd(II) from water. It is clear that the best pH values of the system to remove Cd(II) from solution by using the TNT/IOM magnetic composite are 7.0-8.0. Considering the low cost and effective disposal of Cd(II)-contaminated wastewaters, the best condition for Cd(II) capture by the TNT/IOM magnetic composite is at room temperature and solid content of 0.5 g L-1. These results are quite important for estimating and optimizing the removal of Cd(II) and related metal ions by the TNT-based magnetic composite. (author)

  6. Mn(II), Co(II), Zn(II), Fe(III) and U (VI) complexes of 2-acetylpyridine 4N-(2-pyridyl) thiosemicarbazone (HAPT); structural, spectroscopic and biological studies

    Science.gov (United States)

    El-Ayaan, Usama; Youssef, Magdy M.; Al-Shihry, Shar

    2009-11-01

    The present work carried out a study on transition metal ion complexes which have been synthesized from 2-acetylpyridine 4N-(2-pyridyl) thiosemicarbazone (HAPT) 1. These complexes namely [Zn(HAPT)Cl 2] 2, [Mn (HAPT)Cl 2] 3, [Co (HAPT)Cl 2] 4, [Fe(APT)Cl 2(H 2O)] 5 and [UO 2(HAPT)(OAc) 2] 6, were characterized by elemental analysis, spectral (IR, 1H NMR and UV-vis) and magnetic moment measurements. Thermal properties and decomposition kinetics of all compounds are investigated. The interpretation, mathematical analysis and evaluation of kinetic parameters ( E, A, Δ H, Δ S and Δ G) of all thermal decomposition stages have been evaluated using Coats-Redfern equation. The biochemical studies showed that, complexes 3 and 6 have powerful and complete degradation effect on the both DNA and protein. The SOD-like activity exhibited that complex 3 has a strong antioxidative properties. The antibacterial screening demonstrated that, the free ligand (HAPT), complexes 2, 3 and 6 have the maximum and broad activities against Gram-positive and Gram-negative bacterial strains.

  7. Cd(II and Pb(II complexes of the polyether ionophorous antibiotic salinomycin

    Directory of Open Access Journals (Sweden)

    Tanabe Makoto

    2011-09-01

    Full Text Available Abstract Background The natural polyether ionophorous antibiotics are used for the treatment of coccidiosis in poultry and ruminants. They are effective agents against infections caused by Gram-positive microorganisms. On the other hand, it was found that some of these compounds selectively bind lead(II ions in in vivo experiments, despite so far no Pb(II-containing compounds of defined composition have been isolated and characterized. To assess the potential of polyether ionophores as possible antidotes in the agriculture, a detailed study on their in vitro complexation with toxic metal ions is required. In the present paper we report for the first time the preparation and the structure elucidation of salinomycin complexes with ions of cadmium(II and lead(II. Results New metal(II complexes of the polyether ionophorous antibiotic salinomycin with Cd(II and Pb(II ions were prepared and structurally characterized by IR, FAB-MS and NMR techniques. The spectroscopic information and elemental analysis data reveal that sodium salinomycin (SalNa undergoes a reaction with heavy metal(II ions to form [Cd(Sal2(H2O2] (1 and [Pb(Sal(NO3] (2, respectively. Abstraction of sodium ions from the cavity of the antibiotic is occurring during the complexation reaction. Salinomycin coordinates with cadmium(II ions as a bidentate monoanionic ligand through the deprotonated carboxylic moiety and one of the hydroxyl groups to yield 1. Two salinomycin anions occupy the equatorial plane of the Cd(II center, while two water molecules take the axial positions of the inner coordination sphere of the metal(II cation. Complex 2 consists of monoanionic salinomycin acting in polydentate coordination mode in a molar ratio of 1: 1 to the metal ion with one nitrate ion for charge compensation. Conclusion The formation of the salinomycin heavy metal(II complexes indicates a possible antidote activity of the ligand in case of chronic/acute intoxications likely to occur in the stock

  8. Two Isostructural Coordination Polymers Showing Diverse Magnetic Behaviors: Weak Coupling (Ni(II)) and an Ordered Array of Single-Chain Magnets (Co(II)).

    Science.gov (United States)

    Chen, Min; Zhao, Hui; Sañudo, E Carolina; Liu, Chun-Sen; Du, Miao

    2016-04-18

    Two isomorphic 3-D complexes with the formulas [M3(TPTA) (OH)2(H2O)4]n (M = Ni for 1 and Co for 2; H4TPTA = [1,1':4',1″-terphenyl]-2',3,3″,5'-tetracarboxylic acid) have been synthesized and magnetically characterized. Complexes 1 (Ni(II)) and 2 (Co(II)) have the same 1-D rod-shaped inorganic SBUs but exhibit significantly different magnetic properties. Complex 2(Co(II)) is a 3-D arrangement of a 1-D Co(II) single-chain magnet (SCM), while complex 1(Ni(II)) exhibits weak coupling. PMID:27022765

  9. Role of "electron shuttles" in the bioreduction of Fe(III) oxides in humid forest tropical soils.

    Science.gov (United States)

    Peretyazhko, T.; Sposito, G.

    2004-12-01

    Dissimilatory iron-reducing bacteria (DIRB) can reduce Fe(III) oxides either by direct contact between the organisms and the oxide surface or by indirect mechanisms not involving contact. These latter mechanisms can include (i) "electron shuttling" or (ii) soluble Fe(III) complexation with subsequent reduction. In the presence of humic substances, indirect Fe(III) reduction occurs, particularly by mechanism (i). Important electron-accepting groups in humic substances include quinone moieties, complexed Fe(III) and conjugated aromatic moieties. A model compound frequently used to study mechanism (i) is anthraquinone-2,6-disulfonate (AQDS), which is believed to function as an "electron shuttle" in a manner similar to humic substances. We are currently investigating Fe(III) reduction in humid tropical forest soils as affected by "electron shuttles," using AQDS and humic substances in our experiments. The soil samples were collected at the bottom of a toposequence in the Luquillo Experimental Forest, Puerto Rico. Development of anaerobic conditions in these soils occurs due to high precipitation and runoff water inputs. Fourteen-day anoxic incubations of soil suspensions amended with AQDS showed enhanced production of both soluble and particulate forms of Fe(II) as compared to non-amended soil suspensions. Our data indicated clearly that DIRB in the soil could utilize added "electron shuttles" effectively to reduce Fe(III). To examine factors controlling Fe(III) reduction by humic acid (HA), three IHSS HA samples (soil, peat and Leonardite) were both abiotically reduced by H2 treatment and microbially reduced by incubation with a filtrate from a soil suspension, then titrated with three different oxidants (iodine, cyanoferrate, and ferric citrate) to provide chemical and biological estimates of electron-accepting capacity at pH 5 and 7. The results will be discussed in terms of the three oxidants used, the properties of the HA samples, pH, and the effects of chemical

  10. Análisis cualitativo inorgánico. Sistemática de identificación de cationes en disolución. Ejercicio interactivo I.

    OpenAIRE

    Milla González, Miguel

    2016-01-01

    Se analiza un problema en disolución que puede contener alguno de los siguientes cationes: Cu(II), Ni(II), Fe(III), Co(II), Cd(II) y bario. Dada la posible composición del problema, se llevan a cabo algunos ensayos directos para detectar la presencia de determinadas especies metálicas. A continuación se aplica una sistemática sencilla mediante la cual se van identificando los cationes presentes en el problema. Deberá hacerse un informe final del análisis que es corregido. Finalmente se explic...

  11. SIMULTANEOUS DETERMINATION OF HEAVY METAL IONS BY CAILLARY ZONE ELECTROPHORESIS USING A COMPLEX SELECTOR

    OpenAIRE

    Neudachina, L. K.; Lebedeva, E. L.

    2014-01-01

    The usage of diglycylglycine (GGG) was proposed to improve the separation of the complexes of heavy metal ions with EDTA by capillary zone electrophoresis. The tripeptide can interact with the complexes in capillary and thereby acts as a complex selector.The influence of GGG on the electrophoretic behavior of ten metal complexes (Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Cd(II), Pb(II) and Bi(III)) was studied in an acidic media using a negative polarity voltage supply. Three ...

  12. Resistivity and activation energy of CdTe electrodeposited at various Cd(II) concentrations

    Energy Technology Data Exchange (ETDEWEB)

    von Windheim, J.A.; Cocivera, M. (Guelph-Waterloo Centre for Graduate Work in Chemistry, Univ. of Guelph, Guelph, Ontario N1G 2WI (CA))

    1991-01-01

    This paper reports on two methods investigated for incorporating excess cadmium into CdTe electrodeposited from tri-n-butyl-phosphine telluride. These were: (i) variation of the Cd(II):Te concentration ratio in situ from 0.009 to 0.30 and (ii) the diffusion of metallic cadmium at high temperature. Resistivity and light response of various samples were studied after they had been removed from their substrates. Scanning electron microscopy was used to examine the morphology of some of the samples. For the series of films in which the Cd(II):Te concentration ratio was varied in situ the resistivity was found to increase moderately with increasing Cd(II) concentration. However, the activation energy was found to increase significantly only at the highest Cd(II):Te ratio, otherwise it remained more or less constant. The light response was similarly unaffected. When cadmium was diffused into the film, the light response was increased markedly and the resistivity generally decreased while the activation energy remained more or less the same.

  13. Resistivity and activation energy of CdTe electrodeposited at various Cd(II) concentrations

    International Nuclear Information System (INIS)

    This paper reports on two methods investigated for incorporating excess cadmium into CdTe electrodeposited from tri-n-butyl-phosphine telluride. These were: (i) variation of the Cd(II):Te concentration ratio in situ from 0.009 to 0.30 and (ii) the diffusion of metallic cadmium at high temperature. Resistivity and light response of various samples were studied after they had been removed from their substrates. Scanning electron microscopy was used to examine the morphology of some of the samples. For the series of films in which the Cd(II):Te concentration ratio was varied in situ the resistivity was found to increase moderately with increasing Cd(II) concentration. However, the activation energy was found to increase significantly only at the highest Cd(II):Te ratio, otherwise it remained more or less constant. The light response was similarly unaffected. When cadmium was diffused into the film, the light response was increased markedly and the resistivity generally decreased while the activation energy remained more or less the same

  14. Cd(II) Sorption on Montmorillonite-Humic acid-Bacteria Composites

    Science.gov (United States)

    Du, Huihui; Chen, Wenli; Cai, Peng; Rong, Xingmin; Dai, Ke; Peacock, Caroline L.; Huang, Qiaoyun

    2016-01-01

    Soil components (e.g., clays, bacteria and humic substances) are known to produce mineral-organic composites in natural systems. Herein, batch sorption isotherms, isothermal titration calorimetry (ITC), and Cd K-edge EXAFS spectroscopy were applied to investigate the binding characteristics of Cd on montmorillonite(Mont)-humic acid(HA)-bacteria composites. Additive sorption and non-additive Cd(II) sorption behaviour is observed for the binary Mont-bacteria and ternary Mont-HA-bacteria composite, respectively. Specifically, in the ternary composite, the coexistence of HA and bacteria inhibits Cd adsorption, suggesting a “blocking effect” between humic acid and bacterial cells. Large positive entropies (68.1 ~ 114.4 J/mol/K), and linear combination fitting of the EXAFS spectra for Cd adsorbed onto Mont-bacteria and Mont-HA-bacteria composites, demonstrate that Cd is mostly bound to bacterial surface functional groups by forming inner-sphere complexes. All our results together support the assertion that there is a degree of site masking in the ternary clay mineral-humic acid-bacteria composite. Because of this, in the ternary composite, Cd preferentially binds to the higher affinity components-i.e., the bacteria. PMID:26792640

  15. Microbial Fe(III) oxide reduction potential in Chocolate Pots hot spring, Yellowstone National Park.

    Science.gov (United States)

    Fortney, N W; He, S; Converse, B J; Beard, B L; Johnson, C M; Boyd, E S; Roden, E E

    2016-05-01

    Chocolate Pots hot springs (CP) is a unique, circumneutral pH, iron-rich, geothermal feature in Yellowstone National Park. Prior research at CP has focused on photosynthetically driven Fe(II) oxidation as a model for mineralization of microbial mats and deposition of Archean banded iron formations. However, geochemical and stable Fe isotopic data have suggested that dissimilatory microbial iron reduction (DIR) may be active within CP deposits. In this study, the potential for microbial reduction of native CP Fe(III) oxides was investigated, using a combination of cultivation dependent and independent approaches, to assess the potential involvement of DIR in Fe redox cycling and associated stable Fe isotope fractionation in the CP hot springs. Endogenous microbial communities were able to reduce native CP Fe(III) oxides, as documented by most probable number enumerations and enrichment culture studies. Enrichment cultures demonstrated sustained DIR driven by oxidation of acetate, lactate, and H2 . Inhibitor studies and molecular analyses indicate that sulfate reduction did not contribute to observed rates of DIR in the enrichment cultures through abiotic reaction pathways. Enrichment cultures produced isotopically light Fe(II) during DIR relative to the bulk solid-phase Fe(III) oxides. Pyrosequencing of 16S rRNA genes from enrichment cultures showed dominant sequences closely affiliated with Geobacter metallireducens, a mesophilic Fe(III) oxide reducer. Shotgun metagenomic analysis of enrichment cultures confirmed the presence of a dominant G. metallireducens-like population and other less dominant populations from the phylum Ignavibacteriae, which appear to be capable of DIR. Gene (protein) searches revealed the presence of heat-shock proteins that may be involved in increased thermotolerance in the organisms present in the enrichments as well as porin-cytochrome complexes previously shown to be involved in extracellular electron transport. This analysis offers

  16. Moessbauer studies of magnetic and crystal field properties in Fe(III) mixed chelates

    International Nuclear Information System (INIS)

    Moessbauer studies were performed on mixed Fe(III) complexes with two ligands, one of the ligands being N,N-ethylene bis(salicyladimine) and the other N,N-dialkyldithiocarbamate. Moessbauer spectra were measured of four complexes with the dialkyl end group being N-ethyl2, N-butyl2, pyrrolidyl and piperidyl, respectively. Evaluation and comparison of the spectra and the relaxation patterns indicate that the size of the axial zero field splitting constant and consequently the spin of the ground state Kramer's doublet depends on the type of the alkyl group in the N,N-dialkyldithiocarbamate ligand. (A.K.)

  17. Elucidation of the Fe(III) Gallate Structure in Historical Iron Gall Ink

    OpenAIRE

    Ponce, Also; Lynn B. Brostoff; Sarah K. Gibbons; Peter Zavalij; Carol Viragh; Joseph Hooper; Sufian Alnemrat; Gaskell, Karen J.; Bryan Eichhorn

    2016-01-01

    The article of record as published may be found at http://dx.doi.org/10.1021/acs.analchem.6b00088 Synthetic, structural, spectroscopic and aging studies conclusively show that the main colorant of historical iron gall ink (IGI) is an amorphous form of Fe(III) gallate· xH2O (x = ∼1.5−3.2). Comparisons between experimental samples and historical documents, including an 18th century hand-written manuscript by George Washington, by IR and Raman spectroscopy, XRD, X-ray photoelectron spectrosco...

  18. Concurrent nitrate and Fe(III) reduction during anaerobic biodegradation of phenols in a sandstone aquifer

    DEFF Research Database (Denmark)

    Broholm, Mette; Crouzet, C.; Arvin, Erik; Mouvet, C.

    levels relevant for degradation of specific organic compounds in aquifers, cannot always be obtained. Hence, complete mass balances of electron acceptor consumption fur specific organic compounds degradation are difficult to confine. For aquifer materials with low initial Fe(II) content, Fe......(II) determinations on solids and in aqueous phase samples may provide valuable information on Fe(III) reduction. However, in microcosms with natural sediments and where electron acceptors are associated with the sediments, complete mass-balances for substrates and electron accepters are not likely to be obtained. (C...

  19. SYNTHESIS, SPECTRAL CHARACTERIZATION OF Mn(II AND Co(II COMPLEXES WITH THIOSEMICARBAZONES AND SEMICARBAZONES DERIVED FROM PYRIDINE-2- CARBOXALDEHYDE

    Directory of Open Access Journals (Sweden)

    Sulekh Chandra

    2014-02-01

    Full Text Available Mn(II and Co(II complexes are synthesized with L1(Pyridine-2-carboxaldehydethiosemicarbazones and L2 (Pyridne-2-carboxaldehydesemicarbazones. These complexes were characterized by elemental analysis, molar conductance measurements, magnetic suscepectibility measurements, mass, IR, electronic and EPR spectral studies. The molar conductance measurement of the complexes in DMSO corresponds to non electrolytes nature with L1 and formulated as [M(L2X2] where M=Mn(II and Co(II complexes. The molar conductance measurements with L2 lie in the range 208-217 Ω-1cm2mol-1 indicating the electrolytes nature of the complexes thus the complexes formulated as [M(L2]X2 where M=Mn(II and Co(II complexes. On the basis of spectral studies an octahedral geometry has been assigned for Mn(II and Co(II complexes.

  20. SYNTHESIS, SPECTRAL CHARACTERIZATION OF Mn(II) AND Co(II) COMPLEXES WITH THIOSEMICARBAZONES AND SEMICARBAZONES DERIVED FROM PYRIDINE-2- CARBOXALDEHYDE

    OpenAIRE

    Sulekh Chandra; Prem Ballabh

    2014-01-01

    Mn(II) and Co(II) complexes are synthesized with L1(Pyridine-2-carboxaldehydethiosemicarbazones) and L2 (Pyridne-2-carboxaldehydesemicarbazones). These complexes were characterized by elemental analysis, molar conductance measurements, magnetic suscepectibility measurements, mass, IR, electronic and EPR spectral studies. The molar conductance measurement of the complexes in DMSO corresponds to non electrolytes nature with L1 and formulated as [M(L)2X2] where M=Mn(II) and Co(II) complexes. The...

  1. Spectroscopic, thermal and antibacterial studies on Mn(II and Co(II complexes derived from thiosemicarbazone

    Directory of Open Access Journals (Sweden)

    SULEKH CHANDRA

    2009-08-01

    Full Text Available Mn(II and Co(II complexes having the general composition [M(L2X2] (where L = 2-pyridinecarboxaldehyde thiosemicarbazone, M = Mn(II and Co(II, X = Cl- and NO3- were synthesized. All the metal complexes were characterized by elemental analysis, molar conductance, magnetic susceptibility measurements, mass, IR, EPR, electronic spectral studies and thermogravimetric analysis (TG. Based on the spectral studies, an octahedral geometry was assigned for all the complexes. Thermal studies of the compounds suggest that the complexes are more stable than the free ligand. This fact was supported by the kinetic parameters calculated using the Horowitz–Metzger (H–M and Coats–Redfern (C–R equations. The antibacterial properties of the ligand and its metal complexes were also examined and it was observed that the complexes are more potent bactericides than the free ligand.

  2. Defect-induced luminescence in sol-gel silica samples doped with Co(II) at different concentrations

    International Nuclear Information System (INIS)

    The defect-induced luminescence properties of silica samples prepared by the sol-gel method and doped with Co(II) are reported. Silica monoliths doped with different concentrations of Co(II) were laser irradiated (He-Ne 632.8 nm) producing fluorescence. However, this fluorescence is exponentially reduced with the irradiation time, to practically disappear. The rate the fluorescence decays can be well modeled with a double exponential function of the irradiation time, containing two different relaxation times; a baseline is also required to take into account some residual fluorescence. The characteristic times involved in this luminescence quenching process are in the range of seconds. This luminescence suppression can be associated to the local heating produced by the laser irradiation when focused in a small area (2 μm in diameter) on the sample. This heating process reduces physical (grain boundaries, surface states) and chemical (oxygen vacancies produced by the dopant) defects in the sample

  3. Equilibrium, thermoanalytical and spectroscopic studies to characterize phytic acid complexes with Mn(II) and Co(II)

    International Nuclear Information System (INIS)

    Potentiometric studies were carried out to determine the binding degree of phytic acid with Co(II) and Mn(II) ions, in the absence of dioxygen. Equilibrium constants for all major complexes formed are reported, and the results are presented in the form of distribution diagrams showing the concentrations of individual complexes as a function of pH. The formation constants of the complexes show higher values for the species in which the ligand was more deprotonated. Potentiometric data indicates that the species [MH4L]6-, was totally formed at pH 7.0 and the complexes were synthesized from this data. A solid state complex of Mn(II) and Co(II) with phytic acid was synthesized. Thermogravimetry, differential scanning calorimetry, and infrared spectroscopy were used to investigate and characterize the thermal behavior of these compounds. The results led to information on the composition, dehydration, thermal stability and thermal decomposition of the isolated complexes. (author)

  4. Effect of pH and Fe(III) ions on chalcopyrite bioleaching by an adapted consortium from biogas sweetening

    OpenAIRE

    Dorado Castaño, Antonio David; Solé Sardans, Maria Montserrat; Lao Luque, Concepción; Alfonso Abella, María Pura; Gamisans Noguera, Javier

    2012-01-01

    Particle size, pH and Fe(III) ions affect the process of bioleaching of copper from chalcopyrite ores. In the study presented herein a copper sulfide ore was subjected to bioleaching process using a mixed microbial consortium obtained from a biotrickling filter treating high loads of H2S at different mineral particle size, distinct medium pH and various additional Fe(III) ion concentrations as leaching agent. After 1300 h of operation, the total copper recovery achieved a value of 50% in the ...

  5. Simultaneous Determination of Fe(II) and Fe(III) in Pharmaceutical Samples by Post-Column Derivatization/HPLC

    OpenAIRE

    ŞENYUVA, Hamide Z.; SARICA, Deniz Yurtsever; ÖZDEN, Tuncel

    2002-01-01

    A post-column derivatization HPLC method with visible absorbance detection at 521 nm was modified for the simultaneous determination of Fe(II) and Fe(III) in mixtures. The method was applied to pharmaceuticals marketed in Turkey. Iron species were separated on a post-column derivatization HPLC, IonPac CS5A (4x250 mm) analytical column using a pyridine-2,6-dicarboxylic acid based eluent. The determinations of Fe(II) and Fe(III) were also realized by the most common method of FAAS, to...

  6. Iron Oxide Impregnated Morus alba L. Fruit Peel for Biosorption of Co(II): Biosorption Properties and Mechanism

    OpenAIRE

    Janardhan Reddy Koduru; Yoon-Young Chang; Jae-Kyu Yang; Im-Soon Kim

    2013-01-01

    Biosorption is an ecofriendly wastewater treatment technique with high efficiency and low operating cost involving simple process for the removal of heavy metal ions from aqueous solution. In the present investigation, Morus alba L. fruit peel powder (MAFP) and iron oxide impregnated Morus alba L. fruit peel powder (IO-MAFP) were prepared and used for treating Co(II) contaminated aqueous solutions. Further the materials were characterized by using FTIR and SEM-EDX analysis. From FT-IR analysi...

  7. ADSORPTION CHARACTERIZATION OF CO(II) IONS ONTO CHEMICALLY TREATED QUERCUS COCCIFERA SHELL: EQUILIBRIUM, KINETIC AND THERMODYNAMIC STUDIES

    OpenAIRE

    M. Hamdi Karaoglu; Mehmet Uğurlu; İbrahim Kula

    2011-01-01

    Quercus coccifera shell (QCS), a relatively abundant and inexpensive material, is currently being investigated as an adsorbent to remove cobalt(II) from water. Before the adsorption experiments, QCS was subjected to chemical treatment to provide maximum surface area. Then, the kinetics and adsorption mechanism of Co(II) ions on QCS were studied using different parameters such as adsorbent dosage, initial concentration, temperature, contact time, and solution pH. The loaded metals could be des...

  8. Determination of Co(II) and Ni(II)-humate stability constants at high ionic strength NaCl solutions

    International Nuclear Information System (INIS)

    Complexation of Ni(II) and Co(II) by unfractionated humic acid (HA) was measured in 0.3 to 5.0 m NaCl solutions at pH 6 and 20 C, using a solvent extraction technique. The dissociation constants and capacities of the humic acid were investigated in 0.1 to 5.0 m NaCl solutions at 25 C using potentiometric titration methods. (orig.)

  9. Cleavage of recombinant proteins at poly-His sequences by Co(II) and Cu(II)

    OpenAIRE

    Andberg, Martina; Jäntti, Jussi; Heilimo, Sara; Pihkala, Päivi; Paananen, Arja; Koskinen, Ari M P; Söderlund, Hans; Linder, Markus B

    2007-01-01

    Improved ways to cleave peptide chains at engineered sites easily and specifically would form useful tools for biochemical research. Uses of such methods include the activation or inactivation of enzymes or the removal of tags for enhancement of recombinant protein expression or tags used for purification of recombinant proteins. In this work we show by gel electrophoresis and mass spectroscopy that salts of Co(II) and Cu(II) can be used to cleave fusion proteins specifically at sites where s...

  10. Synthesis, crystal structure, spectral characterization and photoluminescence property of three Cd(II) complexes with a pyrazole based Schiff-base ligand

    Science.gov (United States)

    Mandal, Susmita; Saha, Rajat; Saha, Manan; Pradhan, Rajesh; Butcher, Ray J.; Saha, Nitis Chandra

    2016-04-01

    Substituted pyrazole containing Schiff-base ligand, 5-methyl-3-formylpyrazole-N-(2‧-methylphenoxy)methyleneimine, (MPzOA), afforded three new Cd(II) complexes, [Cd(MPzOA)Cl2]2.CH3OH (I), [Cd(MPzOA)2(H2O)2](ClO4)2 (II) and [Cd(MPzOA)(H2O)(NO3)2] (III). In the reported complex species the coordination number and geometry of Cd(II) vary. In complex I and II, Cd(II) adopts six and in (III) it adopts eight coordination modes, with prismatic, octahedral and distorted dodecahedral geometry, respectively. All the complexes are characterized by IR, 1H NMR, UV-Vis spectral parameters and X-ray analyses. The complexes have 1D, 2D and 3D supramolecular frameworks formed by non-covalent interactions, like hydrogen bonding, π … π stacking, C-H … π interactions.

  11. Removal of Pb(II), Cu(II) and Cd(II) from aqueous solution by some fungi and natural adsorbents in single and multiple metal systems

    International Nuclear Information System (INIS)

    Six fungal and 10 natural biosorbents were analyzed for their Cu(II), Cd(II) and Pb(II) uptake capacity from single, binary and ternary metal ion system. Preliminary screening biosorption of assays revealed 2 fungi (Aspergillus niger and Cunninghamella echinulata) and three natural [Cicer arietinum husk, Moringa oleifera flower and soil (clay)] adsorbents hold considerable high adsorption efficiency and capacity for 3 meta l ions amongst the adsorbents. Further biosorption trials with five elected adsorbents showed a considerable reduction in metal uptake capability of adsorbents in binary- and ternary systems as compared to singly metal system. Cd(II) manifested the highest inhibitory effect on the biosorption of other metal ions, followed by Pb(II) and Cu(II). On account of metal preference, the selectivity order for metal ion towards the studied biomass matrices was Pb(II) (40-90%) > Cd(II) (2-53%) > Cu(II) (2-30%). (author)

  12. Construction of two Cd(II) complexes by flexible adipic acid plus 2-((benzoimidazol-yl)methyl)-1H-tetrazole ligand

    Science.gov (United States)

    Duan, Wanlu; Zhang, Yuhong; Wang, Xiuxiu; Meng, Xiangru

    2015-10-01

    Two new complexes with the formulas [Cd(bimt)(adi)]n (1) and {[Cd(bimt)(adi)0.5Br]·H2O}n (2) were synthesized through reactions of 2-((benzoimidazol-yl)methyl)-1H-tetrazole (bimt) with Cd(II) salts in the presence of adipic acid (H2adi). Single crystal X-ray analysis reveals that complex 1 shows a 1D chain structure in which adipate ligand coordinates to Cd(II) ions with μ3-bridging mode. Complex 2 displays a 2D layer structure with 4-connected (44·62) topology in which adipate ligand coordinates to Cd(II) ions with μ2-bridging mode. These results reveal that the versatile coordination modes of adipate ligands play an important role in controlling the structures of the complexes. In addition, their IR spectra, element analyses, PXRD patterns and luminescent properties are investigated.

  13. Studies on the liquid-liquid extraction and ion and precipitate flotation of Co(II) with decanoic acid

    International Nuclear Information System (INIS)

    The liquid-liquid extraction, ion and precipitate flotation of Co(II) from chloride media of 1*10-4 M initial Co(II) concentration and μ = 0.1 have been investigated using decanoic acid and the results are compared. Organic solvents used were chloroform in the case of liquid-liquid extraction and ethanol (used as a solvent for the collector and a frother) in the case of flotation. From the results it appears that liquid-liquid extraction takes place through the formation of the complex: (CoR2)2(HR)2 but flotation occurs through the formation of a surface active product which has the empirical formula CoR2. The effects of pH and of decanoic acid concentration on the three separation processes were also investigated and the results discussed. Good agreement was observed between the experimental precipitate flotation curves and the theoretical curve calculated from the data published for Co(II) hydrolysis. (author) 30 refs.; 4 figs.; 1 tab

  14. Nanoscaled zero valent iron/graphene composite as an efficient adsorbent for Co(II) removal from aqueous solution.

    Science.gov (United States)

    Xing, Min; Wang, Jianlong

    2016-07-15

    A magnetic graphene, i.e., nanoscaled zero valent iron/graphene (0FG) composite, was prepared, characterized and applied for the removal of Co(II) from aqueous solution. The magnetic graphene (0FG) was synthesized through reduction of graphene oxide (GO) and ferrous ions by potassium borohydride. The kinetics and isotherms of Co(II) adsorption onto 0FG were investigated. The mechanism for Co(II) removal was proposed based on the Fourier transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS) and the X-ray absorption fine structure (XAFS) analysis. The results showed that pseudo second-order models and the Freundlich isotherm model fitted well with the data obtained. The adsorption capacity of 0FG was calculated from the Langmuir isotherm, which was 65.58, 101.60 and 134.27mg/g at 10, 20 and 30°C, respectively. Thermodynamic parameters suggested that the adsorption process was endothermic and spontaneous. Co(2+) was stabilized by γ-FeOOH/γ-Fe2O3/Fe3O4 on the surface of graphene sheets, forming CoFe2O4-like nanocrystals. The coordination numbers and interatomic distances indicated that Co(2+) mainly occupied the octahedral site, while pseudo-tetrahedral coordination may occur by dehydroxylation of Co(O,OH)6. Magnetic graphene is a potential adsorbent for Co(2+) removal. PMID:27115333

  15. Azadirachta indica (Neem) leaf powder as a biosorbent for removal of Cd(II) from aqueous medium

    International Nuclear Information System (INIS)

    A biosorbent, Neem leaf powder (NLP), was prepared from the mature leaves of the Azadirachta indica (Neem) tree by initial cleaning, drying, grinding, washing to remove pigments and redrying. The powder was characterized with respect to specific surface area (21.45 m2 g-1), surface topography and surface functional groups and the material was used as an adsorbent in a batch process to remove Cd(II) from aqueous medium under conditions of different concentrations, NLP loadings, pH, agitation time and temperature. Adsorption increased from 8.8% at pH 4.0 to 70.0% at pH 7.0 and 93.6% at pH 9.5, the higher values in alkaline medium being due to removal by precipitation. The adsorption was very fast initially and maximum adsorption was observed within 300 min of agitation. The kinetics of the interactions was tested with pseudo first order Lagergren equation (mean k 1 = 1.2 x 10-2 min-1), simple second order kinetics (mean k 2 = 1.34 x 10-3 g mg-1 min-1), Elovich equation, liquid film diffusion model (mean k = 1.39 x 10-2 min-1) and intra-particle diffusion mechanism. The adsorption data gave good fits with Langmuir and Freundlich isotherms and yielded Langmuir monolayer capacity of 158 mg g-1 for the NLP and Freundlich adsorption capacity of 18.7 L g-1. A 2.0 g of NLP could remove 86% of Cd(II) at 293 K from a solution containing 158.8 mg Cd(II) per litre. The mean values of the thermodynamic parameters, ΔH, ΔS and ΔG, at 293 K were -73.7 kJ mol-1, -0.24 J mol-1 K-1 and -3.63 kJ mol-1, respectively, showing the adsorption process to be thermodynamically favourable. The results have established good potentiality for the Neem leaf powder to be used as a biosorbent for Cd(II)

  16. Study of mixed ligand complexes of Cd(II) with glycine and L-histidine by polarographic method

    International Nuclear Information System (INIS)

    Mixed ligand complexes of Cd(II) with glycine as a primary ligand and L-histidine as secondary ligand were studied polarographically. The stability constants were determined by the method of DeFord and Hume extended by Schaap and McMasters. All the mixed complexes of the type MXY, MX, Y and MXY2 (where M = Cd (II), X = L-histidine (his), Y = glycine (gly)), undergo a two electron reduction at dropping mercury electrode and the reductions were fully diffusion controlled. (author)

  17. Azadirachta indica (Neem) leaf powder as a biosorbent for removal of Cd(II) from aqueous medium

    Energy Technology Data Exchange (ETDEWEB)

    Sharma, Arunima [Department of chemistry, Gauhati University, Guwahati 781014, Assam (India); Bhattacharyya, Krishna G. [Department of chemistry, Gauhati University, Guwahati 781014, Assam (India)]. E-mail: krishna2604@sify.com

    2005-10-17

    A biosorbent, Neem leaf powder (NLP), was prepared from the mature leaves of the Azadirachta indica (Neem) tree by initial cleaning, drying, grinding, washing to remove pigments and redrying. The powder was characterized with respect to specific surface area (21.45 m{sup 2} g{sup -1}), surface topography and surface functional groups and the material was used as an adsorbent in a batch process to remove Cd(II) from aqueous medium under conditions of different concentrations, NLP loadings, pH, agitation time and temperature. Adsorption increased from 8.8% at pH 4.0 to 70.0% at pH 7.0 and 93.6% at pH 9.5, the higher values in alkaline medium being due to removal by precipitation. The adsorption was very fast initially and maximum adsorption was observed within 300 min of agitation. The kinetics of the interactions was tested with pseudo first order Lagergren equation (mean k {sub 1} = 1.2 x 10{sup -2} min{sup -1}), simple second order kinetics (mean k {sub 2} = 1.34 x 10{sup -3} g mg{sup -1} min{sup -1}), Elovich equation, liquid film diffusion model (mean k = 1.39 x 10{sup -2} min{sup -1}) and intra-particle diffusion mechanism. The adsorption data gave good fits with Langmuir and Freundlich isotherms and yielded Langmuir monolayer capacity of 158 mg g{sup -1} for the NLP and Freundlich adsorption capacity of 18.7 L g{sup -1}. A 2.0 g of NLP could remove 86% of Cd(II) at 293 K from a solution containing 158.8 mg Cd(II) per litre. The mean values of the thermodynamic parameters, {delta}H, {delta}S and {delta}G, at 293 K were -73.7 kJ mol{sup -1}, -0.24 J mol{sup -1} K{sup -1} and -3.63 kJ mol{sup -1}, respectively, showing the adsorption process to be thermodynamically favourable. The results have established good potentiality for the Neem leaf powder to be used as a biosorbent for Cd(II)

  18. Synthesis, characterization and antibacterial activities of Zn(II and Cd(II complexes of a quinazoline-4(3H-one Schiff base

    Directory of Open Access Journals (Sweden)

    Brahman Dhiraj

    2014-01-01

    Full Text Available Zn(II and Cd(II complexes of a Schiff base derived from quinazoline-4(3H one and 2-formylphenoxy acetic acid were prepared and characterized by elemental and different spectroscopic (IR, UV-Visible and NMR analyses. The elemental analysis indicated the formation of the complexes: [ML(AcO].H2O, where M stands for Zn(II and Cd(II and L stands for quinazoline-4(3H-one Schiff base. The molar conductivities of the prepared complexes revealed their non-electrolytic nature. The complexes were also investigated for their antimicrobial activities by using turbidometric assay method.

  19. TD-DFT study of the light-induced spin crossover of Fe(III) complexes.

    Science.gov (United States)

    Saureu, Sergi; de Graaf, Coen

    2016-01-14

    Two light-induced spin-crossover Fe(III) compounds have been studied with time-dependent density functional theory (TD-DFT) to investigate the deactivation mechanism and the role of the ligand-field states as intermediates in this process. The B3LYP* functional has previously shown its ability to accurately describe (light-induced) spin-crossover in Fe(II) complexes. Here, we establish its performance for Fe(III) systems using [Fe(qsal)2](+) (Hqsal = 2-[(8-quinolinylimino)methyl]phenol) and [Fe(pap)2](+) (Hpap = 2-(2-pyridylmethyleneamino)phenol) as test cases comparing the B3LYP* results to experimental information and to multiconfigurational wave function results. In addition to rather accurate high spin (HS) and low spin (LS) state geometries, B3LYP* also predicts ligand-to-metal charge transfer (LMCT) states with large oscillator strength in the energy range where the UV-VIS spectrum shows an intense absorption band, whereas optically allowed π-π* excitations on the ligands were calculated at higher energy. Subsequently, we have generated a two-dimensional potential energy surface of the HS and LS states varying the Fe-N and Fe-O distances. LMCT and metal centered (MC) excited states were followed along the approximate minimal energy path that connects the minima of the HS and LS on this surface. The (2)LMCT state has a minimum in the same region as the initial LS state, where we also observe a crossing with the intermediate spin (IS) state. Upon the expansion of the coordination sphere of the Fe(III) ion, the IS state crosses with the HS state and further expansion of the coordination sphere leads to the excited spin state trapping as observed in experiment. The calculation of the intersystem crossing rates reveals that the deactivation from (2)LMCT → IS → HS competes with the (2)LMCT → IS → LS pathway, in line with the low efficiency encountered in experiments. PMID:26660866

  20. Frequency dependent magneto-transport in charge transfer Co(II) complex

    International Nuclear Information System (INIS)

    A charge transfer chelated system containing ferromagnetic metal centers is the ideal system to investigate the magneto-transport and magneto-dielectric effects due to the presence of both electronic as well as magnetic properties and their coupling. Magneto-transport properties in materials are usually studied through dc charge transport under magnetic field. As frequency dependent conductivity is an essential tool to understand the nature of carrier wave, its spatial extension and their mutual interaction, in the present work, we have investigated frequency dependent magneto-transport along with magnetization behavior in [Co2(II)-(5-(4-PhMe)-1,3,4-oxadiazole-H+-2-thiolate)5](OAc)4 metal complex to elucidate the nature of above quantities and their response under magnetic field in the transport property. We have used the existing model for ac conduction incorporating the field dependence to explain the frequency dependent magneto-transport. It is seen that the frequency dependent magneto-transport could be well explained using the existing model for ac conduction. -Highlights: • Chelated Co(II) complex is synthesized for magneto-transport applications. • Frequency dependent magneto-transport and magnetization behavior are studied. • Nature of carrier wave, its spatial extension is investigated under magnetic field. • Existing model for ac conduction is used with magnetic field dependence

  1. Heterocyclic tri-urea isocyanurate bridged groups modified periodic mesoporous organosilica synthesized for Fe(III) adsorption

    Energy Technology Data Exchange (ETDEWEB)

    Rana, Vijay Kumar [Department of Polymer Science and Engineering, Pusan National University, Busan 609-735 (Korea, Republic of); Department of Chemical Technology, North Maharashtra University Jalgaon-425001 (India); Division of Polymer Science and Engineering, National Chemical Laboratory, Pune-411 008 (India); Selvaraj, M. [Department of Chemical and Biomolecular Engineering, Pusan National University, Geumjeong-gu, Busan 609-735 (Korea, Republic of); Parambadath, Surendran; Chu, Sang-Wook; Park, Sung Soo [Department of Polymer Science and Engineering, Pusan National University, Busan 609-735 (Korea, Republic of); Mishra, Satyendra [Department of Chemical Technology, North Maharashtra University Jalgaon-425001 (India); Singh, Raj Pal [Division of Polymer Science and Engineering, National Chemical Laboratory, Pune-411 008 (India); Ha, Chang-Sik, E-mail: csha@pnu.edu [Department of Polymer Science and Engineering, Pusan National University, Busan 609-735 (Korea, Republic of)

    2012-10-15

    To achieve a high level of heavy metal adsorption, 1,1 Prime ,1 Double-Prime -(1,3,5-triazine-2,4,6-triyl)tris(3-(3-(triethoxysilyl)propyl)urea) (TTPU) was synthesized as a novel melamine precursor and incorporated on the silica surface of periodic mesoporous organosilica (PMO). The melamine modified PMOs (MPMOs) were synthesized under acidic conditions using TTPU, tetraethylorthosilicate (TEOS) and Pluronic P123 as a template and the modified PMOs were characterized using the relevant instrumental techniques. The characteristic materials were used as adsorbents for the adsorption of Fe(III) ions. Fe(III) adsorption studies revealed MPMO-7.5 to be a good absorbent with higher adsorption efficiency than other MPMOs. - Graphical Abstract: A new organosilica precursor, TTPU, has been successfully synthesized and characterized to incorporate on the silica surface of periodic mesoporous organosilica (PMO). The melamine modified PMOs (MPMOs), in particular, the MPMO-7.5 was found to exhibit good adsorption efficiency for Fe(III). Highlights: Black-Right-Pointing-Pointer Synthesis of new melamine modified periodic mesoporous organosilicas (MPMOs). Black-Right-Pointing-Pointer A new organosilica precursor, TTPU, has been successfully synthesized for the MPMOs. Black-Right-Pointing-Pointer The MPMOs were characterized by the relevant instrumental techniques. Black-Right-Pointing-Pointer MPMO-7.5 exhibits higher adsorption efficiency for Fe(III) ions than other MPMOs.

  2. Does As(III) interact with Fe(II), Fe(III) and organic matter through ternary complexes?

    Science.gov (United States)

    Catrouillet, Charlotte; Davranche, Mélanie; Dia, Aline; Bouhnik-Le Coz, Martine; Demangeat, Edwige; Gruau, Gérard

    2016-05-15

    Up until now, only a small number of studies have been dedicated to the binding processes of As(III) with organic matter (OM) via ionic Fe(III) bridges; none was interested in Fe (II). Complexation isotherms were carried out with As(III), Fe(II) or Fe(III) and Leonardite humic acid (HA). Although PHREEQC/Model VI, implemented with OM thiol groups, reproduced the experimental datasets with Fe(III), the poor fit between the experimental and modeled Fe(II) data suggested another binding mechanism for As(III) to OM. PHREEQC/Model VI was modified to take various possible As(III)-Fe(II)-OM ternary complex conformations into account. The complexation of As(III) as a mononuclear bidentate complex to a bidentate Fe(II)-HA complex was evidenced. However, the model needed to be improved since the distribution of the bidentate sites appeared to be unrealistic with regards to the published XAS data. In the presence of Fe(III), As(III) was bound to thiol groups which are more competitive with regards to the low density of formed Fe(III)-HA complexes. Based on the new data and previously published results, we propose a general scheme describing the various As(III)-Fe-MO complexes that are able to form in Fe and OM-rich waters. PMID:26939079

  3. New method for simultaneous determination of Fe(II) and Fe(III) in water using flow injection technique

    International Nuclear Information System (INIS)

    The method exploits the possibilities of flow injection gradient titration in a system of reversed flow with spectrophotometric detection. In the developed approach a small amount of titrant (EDTA) is injected into a stream of sample containing a mixture of indicators (sulfosalicylic acid and 1,10-phenanthroline). In acid environment sulfosalicylic acid forms a complex with Fe(III), whereas 1,10-phenanthroline forms a complex with Fe(II). Measurements are performed at wavelength λ = 530 nm when radiation is absorbed by both complexes. After injection EDTA replaces sulfosalicylic acid and forms with Fe(III) more stable colourless complex. As a result, a characteristic 'cut off' peak is registered with a width corresponding to the Fe(III) concentration and with a height corresponding to the Fe(II) concentration. Calibration was performed by titration of four two-component standard solutions of the Fe(II)/Fe(III) concentrations established in accordance with 22 factorial plan. The method was tested with the use of synthetic samples and then it was applied to the analysis of water samples taken from artesian wells. Under optimized experimental conditions Fe(II) and Fe(III) were determined with precision less than 0.8 and 2.5% (RSD) and accuracy less than 3.2 and 5.1% (relative error) within the concentration ranges of 0.1-3.0 and 0.9-3.5 mg L-1 of both analytes, respectively.

  4. Concurrent nitrate and Fe(III) reduction during anaerobic biodegradation of phenols in a sandstone aquifer

    DEFF Research Database (Denmark)

    Broholm, Mette; Crouzet, C.; Arvin, Erik;

    2000-01-01

    and selected redox sensitive parameters at the end of the experiment. The sandstone material was characterized with respect to oxidation and reduction potential and Fe(II) and Fe(III) speciation prior to use for all microcosms and at the end of the experiments for selected microcosms. The redox conditions......, in the unamended microcosm. For microcosm systems. with solid aquifer materials. dissolution of organic substances from the solid material may occur. A quantitative determination of the speciation (mineral types and quantity) of electron acceptors associated with the solids, at levels relevant for degradation......The biodegradation of phenols (similar to 5, 60, 600 mg 1(-1)) under anaerobic conditions (nitrate enriched and unamended) was studied in laboratory microcosms with sandstone material and groundwater from within an anaerobic ammonium plume in an aquifer, The aqueous phase was sampled and analyzed...

  5. Exploring the biochemistry at the extracellular redox frontier of bacterial mineral Fe(III) respiration

    Energy Technology Data Exchange (ETDEWEB)

    Richardson, David J.; Edwards, Marcus; White, Gaye F.; Baiden, Nanakow; Hartshorne, Robert S.; Fredrickson, Jim K.; Shi, Liang; Zachara, John M.; Gates, Andrew J.; Butt, Julea N.; Clarke, Thomas

    2012-06-01

    Many species of the bacterial Shewanella genus are notable for their ability to respire in anoxic environments utilizing insoluble minerals of Fe(III) and Mn(IV) as extracellular electron acceptors. In Shewanella oneidensis, the process is dependent on the decahaem electron-transport proteins that lie at the extracellular face of the outer membrane where they can contact the insoluble mineral substrates. These extracellular proteins are charged with electrons provided by an inter-membrane electron-transfer pathway that links the extracellular face of the outer membrane with the inner cytoplasmic membrane and thereby intracellular electron sources. In the present paper, we consider the common structural features of two of these outermembrane decahaem cytochromes, MtrC and MtrF, and bring this together with biochemical, spectroscopic and voltammetric data to identify common and distinct properties of these prototypical members of different clades of the outer-membrane decahaem cytochrome superfamily.

  6. Spectrophotometric speciation of Fe(II) and Fe(III) using hydrazone-micelle systems and flow injections

    International Nuclear Information System (INIS)

    Two hydrazones were synthesised, namely salicylhyrazone (SH) and trihydroxyacetophenone (THAPH) were synthesised with the objective of developing a method for determining of Fe(II) and Fe(III) in the presence of each other and hence the total iron.those hydrazones were selected so as to combine the ability of phenolic compounds to complex Fe(III) ions and the complexing characteristics of hydrazones. The complexes of Fe(II)SH and Fe(III)SH as well those of Fe(II)-THAPH and Fe(III)-THAPH had shown maximum absorbance at λ=412 nm which was not not modified by presence of micelles i.e. sodium n-dodecyl sulphate (SDS) and n-hexa dodecyl pyridinium bromide. The maximum absorbance for all complexes takes place around a neutral pH. Generally, in addition, of n-hexa dodecylpyridinium bromide to fe(II)-SH and Fe(III)-SH absorbance of the complexes increases with increasing the concentration of the micelle. The effects of the addition of sodium n-dodecyle sulphate (SDS) to Fe(III)-SH is also studied. Generally, increasing the concentration of the micelle decrease the absorbance of the complexes. To study the effect of the presence of Fe(II) and Fe(III) on the determination of each other,mixtures of Fe(II)-SH and Fe(III)-SH are studied. However, the use of ascorbic acid as a reducing reagent for Fe(III) did not produce the needed results but non reducible results, which may be due to the masking effect of ascorbic acid and thus making the metal not available to the ligand. However, conversion of Fe(II) to Fe(III) prior to the determination was avoided as this requires the use of oxidant, which will oxidise the ligand as well. To establish the condition for the maximum absorbance of THAPH complexes, the effect of the base was investigated by using sodium and ammonium hydroxide. Generally, increasing the concentration of the base decreases the abosrbance. as expected, ammonium hydroxide produced positive results than sodium hydroxide. After establishing the optimum Fi

  7. The adsorption properties of Pb(II) and Cd(II) on functionalized graphene prepared by electrolysis method

    International Nuclear Information System (INIS)

    The functionalized graphene (GNSPF6) was fabricated by simple and fast method of electrolysis with potassium hexafluorophosphate solution as electrolyte under the static potential of 15 V. The characterization results of transmission electron microscopy, atom force microscopy, X-ray photoelectron spectroscopy, X-ray powder diffraction, Raman spectroscopy and thermogravimetric analysis indicate that graphite rod was completely exfoliated to graphene layer containing 30 wt.% PF6- with the average thickness ca. 1.0 nm. Our sample of GNSPF6 was developed for the removal of Pb(II) or Cd(II) ions from water, and the determined adsorption capacities are 406.6 mg/g (pH = 5.1) for Pb(II) and 73.42 mg/g (pH = 6.2) for Cd(II), which is much higher than that by our previous sample of GNSC8P and carbon nanotube. The adsorption processes reach equilibrium in just 40 min and the adsorption isotherms are described well by Langmuir and Freundlich classical isotherms models.

  8. Microporous Cd(II) metal-organic framework as fluorescent sensor for nitroaromatic explosives at the sub-ppm level

    Science.gov (United States)

    Wang, Xing-Po; Han, Lu-Lu; Wang, Zhi; Guo, Ling-Yu; Sun, Di

    2016-03-01

    A novel Cd(II) metal-organic framework (MOF) based on a rigid biphenyltetracarboxylic acid, [Cd4(bptc)2(DMA)4(H2O)2·4DMA] (1) was successfully synthesized under the solvothermal condition and characterized by single-crystal X-ray diffraction and further consolidated by elemental analyses, powder X-ray diffraction (PXRD), infrared spectra (IR) and luminescent measurements. Single crystal X-ray diffraction analysis reveals that compound 1 is 4-connected PtS (Point symbol: {42·84}) network based on [Cd2(COO)4] secondary building units (SBUs). Its inherent porous and emissive characteristics make them to be a suitable fluorescent probe to sense small solvents and nitroaromatic explosives. Compound 1 shows obviously solvent-dependent emissive behaviors, especially for acetone with very high fluorescence quenching effect. Moreover, compound 1 displays excellent sensing of nitroaromatic explosives at sub-ppm level, giving a detection limit of 0.43 ppm and 0.37 ppm for nitrobenzene (NB) and p-nitrotoluene (PNT), respectively. This shows this Cd(II) MOF can be used as fluorescence probe for the detection of nitroaromatic explosives.

  9. Adsorption of Zn(II) and Cd(II) ions onto magnesium and activated carbon composite in aqueous solution

    International Nuclear Information System (INIS)

    Magnesium and coconuts shell activated carbon composite was prepared to selectively remove heavy metals ions in aqueous solution. Zinc(II) and cadmium(II) ions were used to clarify the adsorption capacity of the composite in comparison with no magnesium containing activated carbon. Influence of the initial heavy metal concentration, time course and solution temperature on the adsorption amounts were examined for the two adsorbents, and surface chemistry of the adsorbents was also characterized using Boehm titration. The magnesium composite adsorbed greater amount of Zn(II) and Cd(II) ions than the no magnesium counterpart. The adsorption amount of Cd(II) was not influenced with rise in solution temperature for the composite, whereas decrease in adsorption was observed for the counterpart. The loaded magnesium was estimated to be combined with carbon surface via oxygen bridge. Cadmium(II) was adsorbed onto the composite surface by ion exchange process with releasing equivalent amount of Mg(II) from the carbon surface, while Zn(II) would adsorb onto the composite by not only the ion exchange, but also the electrostatic interaction with the Cπ electrons on the graphite surface from the experimental results.

  10. Geochemical control of microbial Fe(III) reduction potential in wetlands: Comparison of the rhizosphere to non-rhizosphere soil

    Science.gov (United States)

    Weiss, J.V.; Emerson, D.; Megonigal, J.P.

    2004-01-01

    We compared the reactivity and microbial reduction potential of Fe(III) minerals in the rhizosphere and non-rhizosphere soil to test the hypothesis that rapid Fe(III) reduction rates in wetland soils are explained by rhizosphere processes. The rhizosphere was defined as the area immediately adjacent to a root encrusted with Fe(III)-oxides or Fe plaque, and non-rhizosphere soil was 0.5 cm from the root surface. The rhizosphere had a significantly higher percentage of poorly crystalline Fe (66??7%) than non-rhizosphere soil (23??7%); conversely, non-rhizosphere soil had a significantly higher proportion of crystalline Fe (50??7%) than the rhizosphere (18??7%, Prhizosphere Fe(III)-oxide pool in 4 h compared to 23% of the soil Fe(III)-oxide pool. Similarly, microbial reduction consumed 75-80% of the rhizosphere pool in 10 days compared to 30-40% of the non-rhizosphere soil pool. Differences between the two pools persisted when samples were amended with an electron-shuttling compound (AQDS), an Fe(III)-reducing bacterium (Geobacter metallireducens), and organic carbon. Thus, Fe(III)-oxide mineralogy contributed strongly to differences in the Fe(III) reduction potential of the two pools. Higher amounts of poorly crystalline Fe(III) and possibly humic substances, and a higher Fe(III) reduction potential in the rhizosphere compared to the non-rhizosphere soil, suggested the rhizosphere is a site of unusually active microbial Fe cycling. The results were consistent with previous speculation that rapid Fe cycling in wetlands is due to the activity of wetland plant roots. ?? 2004 Federation of European Microbiological Societies. Published by Elsevier B.V. All rights reserved.

  11. Sorption selectivity of birnessite particle edges: a d-PDF analysis of Cd(ii) and Pb(ii) sorption by δ-MnO2 and ferrihydrite.

    Science.gov (United States)

    van Genuchten, Case M; Peña, Jasquelin

    2016-08-10

    Birnessite minerals (layer-type MnO2), which bear both internal (cation vacancies) and external (particle edges) metal sorption sites, are important sinks of contaminants in soils and sediments. Although the particle edges of birnessite minerals often dominate the total reactive surface area, especially in the case of nanoscale crystallites, the metal sorption reactivity of birnessite particle edges remains elusive. In this study, we investigated the sorption selectivity of birnessite particle edges by combining Cd(ii) and Pb(ii) adsorption isotherms at pH 5.5 with surface structural characterization by differential pair distribution function (d-PDF) analysis. We compared the sorption reactivity of δ-MnO2 to that of the nanomineral, 2-line ferrihydrite, which exhibits only external surface sites. Our results show that, whereas Cd(ii) and Pb(ii) both bind to birnessite layer vacancies, only Pb(ii) binds extensively to birnessite particle edges. For ferrihydrite, significant Pb(ii) adsorption to external sites was observed (roughly 20 mol%), whereas Cd(ii) sorption was negligible. These results are supported by bond valence calculations that show comparable degrees of saturation of oxygen atoms on birnessite and ferrihydrite particle edges. Therefore, we propose that the sorption selectivity of birnessite edges follows the same order of that reported previously for ferrihydrite: Ca(ii) < Cd(ii) < Ni(ii) < Zn(ii) < Cu(ii) < Pb(ii). PMID:27183472

  12. Solid phase extraction of Cd(II) and Pb(II) using a magnetic metal-organic framework, and their determination by FAAS

    International Nuclear Information System (INIS)

    We describe a novel magnetic metal-organic framework (MOF) for the preconcentration of Cd(II) and Pb(II) ions. The MOF was prepared from the Fe3O4-pyridine conjugate and the copper(II) complex of trimesic acid. The MOF was characterized by IR spectroscopy, elemental analysis, SEM and XRD. A Box-Behnken design through response surface methodology and experimental design was used to identify the optimal parameters for preconcentration. Extraction time, amount of magnetic MOF and pH value were found to be critical factors for uptake, while type, volume, concentration of eluent, and elution time are critical in the elution step. The ions were then determined by FAAS. The limits of detection are 0.2 and 1.1 μg L−1 for Cd(II), and Pb(II) ions, respectively, relative standard deviations are −1 of Cd(II) and Pb(II) ions), and the enrichment capacity of the MOF is at around 190 mg g−1 for both ions which is higher than the conventional Fe3O4-pyridine material. The magnetic MOF was successfully applied to the rapid extraction of trace quantities of Cd(II) and Pb(II) ions in fish, sediment, and water samples. (author)

  13. Column dynamic studies and breakthrough curve analysis for Cd(II) and Cu(II) ions adsorption onto palm oil boiler mill fly ash (POFA).

    Science.gov (United States)

    Aziz, Abdul Shukor Abdul; Manaf, Latifah Abd; Man, Hasfalina Che; Kumar, Nadavala Siva

    2014-01-01

    This paper investigates the adsorption characteristics of palm oil boiler mill fly ash (POFA) derived from an agricultural waste material in removing Cd(II) and Cu(II) from aqueous solution via column studies. The performance of the study is described through the breakthrough curves concept under relevant operating conditions such as column bed depths (1, 1.5, and 2 cm) and influent metal concentrations (5, 10, and 20 mg/L). The Cd(II) and Cu(II) uptake mechanism is particularly bed depth- and concentration-dependant, favoring higher bed depth and lower influent metal concentration. The highest bed capacity of 34.91 mg Cd(II)/g and 21.93 mg Cu(II)/g of POFA was achieved at 20 mg/L of influent metal concentrations, column bed depth of 2 cm, and flow rate of 5 mL/min. The whole breakthrough curve simulation for both metal ions were best described using the Thomas and Yoon–Nelson models, but it is apparent that the initial region of the breakthrough for Cd(II) was better described using the BDST model. The results illustrate that POFA could be utilized effectively for the removal of Cd(II) and Cu(II) ions from aqueous solution in a fixed-bed column system. PMID:24659435

  14. The impact of functionalized CNT in the network of sodium alginate-based nanocomposite beads on the removal of Co(II) ions from aqueous solutions.

    Science.gov (United States)

    Karkeh-Abadi, Fatemeh; Saber-Samandari, Samaneh; Saber-Samandari, Saeed

    2016-07-15

    Significant efforts have been made to develop highly efficient adsorbents to remove radioactive Co(II) ion pollutants from medical and industrial wastewaters. In this study, amide group functionalized multi-walled carbon nanotube (CNT-CONH2) imprinted in the network of sodium alginate containing hydroxyapatite, and new nanocomposite beads were synthesized. Then, they were characterized using Fourier transform infrared spectroscopy (FTIR), X-ray diffraction analysis (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM) and energy dispersive spectroscopy (EDS). The prepared nanocomposite beads were used as an adsorbent of Co(II) ions from an aqueous solution. The presence and distribution of Co(II) ions in the surface of the nanocomposite beads was confirmed using FESEM, EDS and metal mapping analysis. The effect of various experimental conditions such as time, pH, and initial concentration of the adsorbate solution and temperature on the adsorption capacity of the nanocomposite beads were explored. The maximum Co(II) ions adsorption capacity of the prepared nanocomposite beads with the largest surface area of 163.4m(2)g(-1) was 347.8mgg(-1) in the optimized condition. The adsorption mechanism followed a pseudo-second-order kinetic model. Furthermore, the Freundlich appears to produce better fit than the Langmuir adsorption isotherm. Finally, thermodynamic studies suggest that endothermic adsorption process of Co(II) ions is spontaneous and thermodynamically favorable. PMID:27037477

  15. Role of Fe(III) in preventing humic interference during As(III) detection on gold electrode: Spectroscopic and voltammetric evidence

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Zhong-Gang [Nanomaterials and Environmental Detection Laboratory, Hefei Institutes of Physical Science, Chinese Academy of Sciences, Hefei 230031 (China); Department of Chemistry, University of Science and Technology of China, Hefei 230026 (China); Chen, Xing; Jia, Yong; Liu, Jin-Huai [Nanomaterials and Environmental Detection Laboratory, Hefei Institutes of Physical Science, Chinese Academy of Sciences, Hefei 230031 (China); Huang, Xing-Jiu, E-mail: xingjiuhuang@iim.ac.cn [Nanomaterials and Environmental Detection Laboratory, Hefei Institutes of Physical Science, Chinese Academy of Sciences, Hefei 230031 (China); Department of Chemistry, University of Science and Technology of China, Hefei 230026 (China)

    2014-02-01

    Graphical abstract: - Highlights: • Humic acids interfere with the voltammetric detection of As(III) on gold electrode through adsorption and possible complexation. • Addition of Fe(III) removes this interference and helps in the electroanalytical detection of As(III). • FTIR and XPS studies suggest that the formation of Fe(III)–HA complex prevents adsorption of HA on gold and limits As–HA complex formation. - Abstract: A drawback of As(III) detection using square wave anodic stripping voltammetry (SWASV) is that it is susceptible to interferences from various metals or organic compounds, especially in real sample water. This study attempts to understand the interference of co-existing of Fe(III) and humic acid (HA) molecules to the electrochemical detection of As(III) using Fourier transform infrared (FTIR) spectrum and X-ray photoelectron spectroscopy (XPS). The electrochemical experiments include stripping of As(III) in the solutions containing HA with different concentrations, cyclic voltammetry in 0.5 M H{sub 2}SO{sub 4} in the presence of HA or Fe(III) with/without addition of Fe(III) or HA, and stripping of As(III) in the presence of HA or Fe(III) with/without addition of Fe(III) or HA. FTIR and XPS are employed to confirm the affinity of HA to Fe(III) or As(III) in acidic condition.

  16. Kinetics and mechanisms of Co(II) EDTA oxidation by pyrolusite

    International Nuclear Information System (INIS)

    Monitoring and restoration activities at low-level radioactive waste disposal sites have identified complicated mixtures of inorganic and organic contaminants in soil and groundwater. Metallic contaminants are generally complexed with various chelating agents and organic acids which alter the geochemical behavior of the contaminants in subsurface media. The objective of this study was to provide an improved understanding of the geochemical processes controlling the subsurface transport of radioactive 60Co complexed with ethylenediaminetetraacetic acid (EDTA). Specifically, we investigated the kinetics and mechanisms of Co(II) EDTA2- oxidation to Co(III)EDTA- by the soil mineral pyrolusite β-MnO2. A column displacement technique was utilized to investigate Co(II)EDTA2- to Co(III)EDTA-. The oxidation of Co(II)EDTA2- appeared to involve the reduction of Mn(IV) to both an aqueous Mn2+ species and a theorized Mn(III)-oxide solid phase. The redox reaction was catalytic since the reduction products were gradually reoxidized in the presence of dissolved O2 to form a Mn (IV)-oxide phase. Oxidation of surface-bound Mn2+ and the theorized Mn(III)-oxide was slow relative to Co(II)EDTA2- oxidation, and a reversible loss in the oxidative ability of the β-MnO occurred when exposed to Co(II)EDTA2-. The reduction in catalytic activity of the MnO2 was not the result of direct surface poisoning by Mn2+, but rather was believed to result from the formation of an intermediate Mn(III)-oxide solid phase whose oxidative potential was significantly less than MnO2 was dependent on the rate of MnO2 surface regeneration. The environmental implications of this redox reaction are pronounced, since any Co(III) EDTA- produced is extremely stable, and this enhances the persistence and transport of 60Co in subsurface environments. 52 refs., 7 figs

  17. Novel dipodal Schiff base compounds: Synthesis, characterization and spectroscopic studies

    Science.gov (United States)

    Obali, Aslihan Yilmaz; Ucan, Halil Ismet

    2015-02-01

    Two novel dipodal Schiff base compounds 1,2-benzyloxy-bis-[2-(benzylideneamino)phenol, L1 and 1,2-benzyloxy-bis[3-(benzylideneamino)pyridine], L2 were synthesized. Their sensing actions were confirmed by UV-Vis absorbance and emission spectroscopic studies in presence of Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Sn(II), Cd(II) and Pb(II) in methanol medium (1 × 10-4 M). It was found that the dipodal compounds can selectively bind to Cu(II) and Pb(II) metal ions with a significant change in its emission and absorption spectra, while the addition of other metal ions (Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Sn(II), Cd(II) and Pb(II)) produces insignificant or minor changes. The host-guest complexes formed were determined by Job's plot method. As a chemosensor, L1 and L2 dipodal Schiff base compounds shows a specific selectivity towards Cu(II) and Pb(II) ions in according to all spectroscopic data.

  18. Synthesis and structural characterization of biologically active metal complexes of N1-(N-morpholinoacetyl)-N4-phenyl thiosemicarbazide and 3,4-methylenedioxybenzaldehyde thiosemicarbazone with oxovanadium(IV) chromium(III), manganese(II), iron(III), cobalt(II), nickel(II), copper(II), cadmium(II), uranium(VI), thorium(IV) and silicon(IV)

    International Nuclear Information System (INIS)

    The chelating behaviour of N1-(N-morpholinoacetyl)-N4-phenyl thiosemicarbazide (MPTSC) and 3,4-methylenedioxybenzaldehyde thiosemicarbazone (MDBT) towards oxovanadium(IV), Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Cd(II), dioxouranium(VI), Th(IV) and Si(IV) has been investigated on the basis of elemental analysis, molar conductance, magnetic susceptibility, electronic, infrared, 1H NMR, ESR, thermal and Moessbauer studies. The above studies indicate that MPTSC acts as monobasic bidentate O, S donor towards oxovanadium(IV), Co(II), Ni(II), and Si(IV); monobasic bidentate N, S donor towards Cd(II) and monobasic tridentate O; N, S donor towards Cu(II) and Th(IV), while MDBT acts as neutral bidentate N,S donor towards oxovanadium(IV), Cr(III), Mn(II), Fe(III), dioxouranium(VI) and Th(IV). The ligands and their metal complexes have been screened in vitro for antibacterial and antifungal activities. The results indicate that in some complexes biocidal activity of ligand increases on complexation. (author). 32 refs., 1 fig., 1 tab

  19. Secondary ligand-directed assembly of Co(II) coordination polymers based on a pyridine carboxylate ligand

    International Nuclear Information System (INIS)

    To investigate the influence of hydrogen bonds and secondary ligands on the structures and properties of the resulting frameworks, five new Co(II) compounds have been synthesized by the reactions of Co(II) salts and 3,5-bis(pyridin-4-ylmethoxy)benzoic acid (HL) with four rationally selected dicarboxylic acid ligands. Without secondary ligand, we got one compound [CoL2(H2O)2]n·2nH2O (1), which possesses a 1D chain structure. In the presence of ancillary ligands, namely, 1,3-adamantanedicarboxylic acid (H2adbc), terephthalic acid (H2tpa), thiophene-2,5-dicarboxylic acid (H2tdc) and 1,4-benzenedithioacetic acid (H2bdtc), four 3D structures [Co2L2(adbc)]n·nH2O (2), [Co2L2(tpa)]n (3), [Co2L2(tdc)]n (4), [Co2L2(bdtc)(H2O)]n (5) were obtained, respectively. It can be observed from the architectures of 1–5 that hydrogen bonds and secondary ligands both have great effects on the spatial connective fashions, resulting in the formation of various dimensional compounds. The XRPD, TGA data of title polymers and the magnetic properties for 2 and 5 have also been investigated. - Graphical abstract: The structural differences show that the ancillary ligands have great effects on the spatial connective fashions, resulting in the formation of various dimensional compounds. - Highlights: • Five new Co(II) coordination polymers have been synthesized by solvothermal reactions based on 3,5-bis(pyridin-4-ylmethoxy)benzoic acid (HL). • The long-flexible ligand (HL) is a good candidate to produce interpenetrating architectures. • The secondary dicarboxylic acid ligands play important roles in the spatial connective fashions and the formation of various dimensional compounds. • The magnetism studies show that both 2 and 5 exhibit antiferromagnetic interactions

  20. Kinetics and Thermodynamics of Cd(II Ions Sorption on Mixed Sorbents Prepared from Olive Stone and Date Pit from Aqueous Solution

    Directory of Open Access Journals (Sweden)

    N. Babakhouya

    2010-01-01

    Full Text Available Problem statement: The aim of this study is to remove Cd(II ions from aqueous solutions by adsorption. Mixed sorbent prepared from olive stone and date pit, an agricultural solid by-product was used as adsorbent. Approach: The adsorption experiments of Cd(II onto the mixture of olive stone and date pit were conducted at different parameters such as, percent of olive stone and date pit in the mixture, temperature, initial solution pH and initial Cd(II concentration. Adsorption isotherms were obtained at different percent of olive stone and date pit in the mixture. Results: This adsorption data was fitted with the Langmuir. Kinetic studies revealed that the initial uptake was rapid and equilibrium was established in 20 min for all the studied metals and that the data followed the pseudo-second order reaction. The thermodynamic of Cadmium sorption on the mixed sorbent follows the Langmuir model and the sorption capacity for cadmium increases when we add a small amount of olive stone at date pits (90% of date pits in mixture and 10% of olive stone and a small amount of date pits at olive stone (90% of olive stone and 10% of date pits in mixture. In addition, the thermodynamic parameters, standard free energy (ÄG°, standard enthalpy (ÄH° and standard entropy (ÄS° of the adsorption process were calculated. The sorption of Cd(II onto the mixture of olive stones and dates pit is spontaneous and presents an endothermic nature. The characteristics of the mixture were determined by the analysis of infra red spectral analysis. Conclusion: The results show that the mixture sorbent from olive stone and date pit is an alternative low-cost adsorbent for removing Cd(II.

  1. Transport, fate, and stimulating impact of silver nanoparticles on the removal of Cd(II) by Phanerochaete chrysosporium in aqueous solutions

    International Nuclear Information System (INIS)

    Highlights: • Appropriate concentration of AgNPs can stimulate the biological removal of Cd(II). • Added AgNPs were oxidatively dissolved and transported to the surface of fungus. • AgNPs have undergone coarsening in the process of transport. • Amino, carboxyl, hydroxyl, and other reducing groups were involved in transportion. - Abstract: Despite the knowledge about increasing discharge of silver nanoparticles (AgNPs) into wastewater and its potential toxicity to microorganisms, the interaction of AgNPs with heavy metals in the biological removal process remains poorly understood. This study focused on the effect of AgNPs (hydrodynamic diameter about 24.3 ± 0.37 nm) on the removal of cadmium (Cd(II)) by using a model white rot fungus species, Phanerochaete chrysosporium. Results showed that the biological removal capacity of Cd(II) increased with the concentration of AgNPs increasing from 0.1 mg/L to 1 mg/L. The maximum removal capacity (4.67 mg/g) was located at 1 mg/L AgNPs, and then decreased with further increasing AgNPs concentration, suggesting that an appropriate concentration of AgNPs has a stimulating effect on the removal of Cd(II) by P. chrysosporium instead of an inhibitory effect. Results of Ag+ and total Ag concentrations in the solutions together with those of SEM and XRD demonstrated that added AgNPs had undergone oxidative dissolution and transported from the solution to the surface of fungal mycelia (up to 94%). FTIR spectra confirmed that amino, carboxyl, hydroxyl, and other reducing functional groups were involved in Cd(II) removal, AgNPs transportation, and the reduction of Ag+ to AgNPs

  2. Transport, fate, and stimulating impact of silver nanoparticles on the removal of Cd(II) by Phanerochaete chrysosporium in aqueous solutions

    Energy Technology Data Exchange (ETDEWEB)

    Zuo, Yanan [College of Environmental Science and Engineering, Hunan University, Changsha 410082 (China); Key Laboratory of Environmental Biology and Pollution Control (Hunan University), Ministry of Education, Changsha 410082 (China); Chen, Guiqiu, E-mail: gqchen@hnu.edu.cn [College of Environmental Science and Engineering, Hunan University, Changsha 410082 (China); Key Laboratory of Environmental Biology and Pollution Control (Hunan University), Ministry of Education, Changsha 410082 (China); Zeng, Guangming, E-mail: zgming@hnu.edu.cn [College of Environmental Science and Engineering, Hunan University, Changsha 410082 (China); Key Laboratory of Environmental Biology and Pollution Control (Hunan University), Ministry of Education, Changsha 410082 (China); Li, Zhongwu; Yan, Ming [College of Environmental Science and Engineering, Hunan University, Changsha 410082 (China); Key Laboratory of Environmental Biology and Pollution Control (Hunan University), Ministry of Education, Changsha 410082 (China); Chen, Anwei [College of Resources and Environment, Hunan Agricultural University, Changsha 410128 (China); Guo, Zhi; Huang, Zhenzhen; Tan, Qiong [College of Environmental Science and Engineering, Hunan University, Changsha 410082 (China); Key Laboratory of Environmental Biology and Pollution Control (Hunan University), Ministry of Education, Changsha 410082 (China)

    2015-03-21

    Highlights: • Appropriate concentration of AgNPs can stimulate the biological removal of Cd(II). • Added AgNPs were oxidatively dissolved and transported to the surface of fungus. • AgNPs have undergone coarsening in the process of transport. • Amino, carboxyl, hydroxyl, and other reducing groups were involved in transportion. - Abstract: Despite the knowledge about increasing discharge of silver nanoparticles (AgNPs) into wastewater and its potential toxicity to microorganisms, the interaction of AgNPs with heavy metals in the biological removal process remains poorly understood. This study focused on the effect of AgNPs (hydrodynamic diameter about 24.3 ± 0.37 nm) on the removal of cadmium (Cd(II)) by using a model white rot fungus species, Phanerochaete chrysosporium. Results showed that the biological removal capacity of Cd(II) increased with the concentration of AgNPs increasing from 0.1 mg/L to 1 mg/L. The maximum removal capacity (4.67 mg/g) was located at 1 mg/L AgNPs, and then decreased with further increasing AgNPs concentration, suggesting that an appropriate concentration of AgNPs has a stimulating effect on the removal of Cd(II) by P. chrysosporium instead of an inhibitory effect. Results of Ag{sup +} and total Ag concentrations in the solutions together with those of SEM and XRD demonstrated that added AgNPs had undergone oxidative dissolution and transported from the solution to the surface of fungal mycelia (up to 94%). FTIR spectra confirmed that amino, carboxyl, hydroxyl, and other reducing functional groups were involved in Cd(II) removal, AgNPs transportation, and the reduction of Ag{sup +} to AgNPs.

  3. Influence of humic acid on sorption of Co(II), Sr(II), and Se(IV) on goethite

    OpenAIRE

    Masset, Sonia; Monteil-Rivera, Fanny; Dupont, Laurent; Dumonceau, Jacques; Aplincourt, Michel

    2000-01-01

    International audience This work examined the influence of a leonardite humic acid on the sorption of Co(II), Sr(II), and Se(IV) onto goethite as a function of pH. The sorption of humic acid and ions alone was first studied. The humic acid sorbs appreciably to the goethite surface according to a reversible process, with a maximum sorption of 19 mg of total organic carbon per g of goethite reached at lower pH values ($\\approx$5). Cobalt and selenium are significantly sorbed on goethite whil...

  4. Detection of mitochondrial COII DNA sequences in ant guts as a method for assessing termite predation by ants

    Czech Academy of Sciences Publication Activity Database

    Fayle, Tom; Scholtz, O.; Dumbrell, A. J.; Russell, S.; Segar, Simon T.; Eggleton, P.

    2015-01-01

    Roč. 10, č. 4 (2015), e0122533. E-ISSN 1932-6203 R&D Projects: GA ČR GA14-32302S Grant ostatní: European Social Fund(CZ) CZ1.07/2.3.00/20.0064; European Social Fund(CZ) CZ.1.07/2.3.00/30.0006 Institutional support: RVO:60077344 Keywords : mitochondrial COII DNA sequences Subject RIV: EH - Ecology, Behaviour Impact factor: 3.234, year: 2014 http://journals.plos.org/plosone/article?id=10.1371/journal.pone.0122533

  5. Two field-induced slow magnetic relaxation processes in a mononuclear Co(ii) complex with a distorted octahedral geometry.

    Science.gov (United States)

    Li, Jing; Han, Yuan; Cao, Fan; Wei, Rong-Min; Zhang, Yi-Quan; Song, You

    2016-05-31

    A distorted octahedral Co(II) complex is reported with homoscorpionate ligands. This complex comprised a field-induced single-molecule magnet, showing two slow relaxation processes under a low dc field (magnetic data, we show for the first time that one of the slow relaxation processes in the low dc field originates from intermolecular dipolar interactions. Interestingly, the Raman process is predominant in the spin reversal relaxation process. The origin of the behaviours of the complex was elucidated by ab initio calculations. PMID:27180637

  6. Bis(thiosemicarbazonato) chelates of Co(II), Ni(II), Cu(II), Pd(II) and Pt(II)

    Science.gov (United States)

    Chandra, Sulekh; Singh, R.

    1985-01-01

    Bis chelates of Co(II), Ni(II), Cu(II), Pd(II) and Pt(II) with the enolic form of diethyl ketone and methyl n-propyl thiosemicarbazones were synthesized and characterized by elemental analyses, magnetic moments, i.r. and electronic and electron spin resonance spectral studies. All the complexes were found to have the composition ML 2 [where M = Co(II), Ni(II), Cu(II), Pd(ii) and Pt(II) and L = thiosemicarbazones of diethyl ketone and methyl n-propyl ketone]. Co(II) and Cu(II) complexes are paramagnetic and may have polymeric six-coordinate octahedral and square planar geometries, respectively. The Ni(II), Pd(II) and Pt(II) complexes are diamagnetic and may have square planar geometries. Pyridine adducts (ML 2·2Py) of Ni(II) and Cu(II) complexes were also prepared and characterized.

  7. Sensitive DNA-hybridization biosensors based on gold nanoparticles for testing DNA damage by Cd(II) ions

    International Nuclear Information System (INIS)

    A DNA biosensor was constructed by immobilizing a 20-mer oligonucleotide probe and hybridizing it with its complementary oligomer on the surface of a glassy carbon electrode modified with gold nanoparticles. The properties of the biosensor and its capability of recognizing its complementary sequence were studied by electrochemical impedance spectroscopy. The oxidative stress caused by cadmium ions can be monitored by differential pulse voltammetry using the cobalt(III)tris(1,10-phenanthroline) complex and methylene blue as electrochemical indicators. The biosensor is capable of indicating damage caused by Cd(II) ions in pH 6.0 solution. The results showed that the biosensor can be used for rapid screening for DNA damage. (author)

  8. Removal of Cd(II) and Pb(II) from aqueous solution using dried water hyacinth as a biosorbent

    Science.gov (United States)

    Ibrahim, Hanan S.; Ammar, Nabila S.; Soylak, Mustafa; Ibrahim, Medhat

    2012-10-01

    Possible usages of dried water hyacinth as biosorbent for metal ions were investigated. A model describing the plant is presented on density functional theory DFT and verified experimentally with FTIR. The model shows that water hyacinth is a mixture of cellulose and lignin. Dried shoot and root were found as good sorbent for Cd(II) and Pb(II) at optimum dosage of 5.0 g/l and pH 5.0; equilibrium time was attained within 30-60 min. The removal using root and shoot were nearly equal and reached more than 75% for Cd and more than 90% for Pb. Finally the second-order kinetics was the applicable model. Hydrogen bonds of reactive functional groups like COOH play the key role in the removal process.

  9. Synthesis and characterization of mixed ligand complexes of Zn(II) and Co(II) with amino acids: Relevance to zinc binding sites in zinc fingers

    Indian Academy of Sciences (India)

    P Rabindra Reddy; M Radhika; P Manjula

    2005-05-01

    Mixed ligand complexes of Zn(II) and Co(II) with cysteine, histidine, cysteinemethylester, and histidinemethylester have been synthesized and characterized by elemental analysis, conductivity, magnetic susceptibility measurements, and infrared, 1H NMR, TGA and FAB mass spectra. In these complexes, histidine, and histidinemethylester act as bidentate ligands involving amino and imidazole nitrogens in metal coordination. Similarly, cysteine, and cysteinemethylester also act as bidentate ligands coordinating through thiol sulphur and amino nitrogen. Tetrahedral geometry has been proposed for Zn(II) and Co(II) complexes based on experimental evidence.

  10. Synthesis, structural characterisation and solvatochromism of a Ni(II) and a Co(II) compound with 2-aminopyrimidine as a ligand

    Science.gov (United States)

    Song, Yufei; Massera, Chiara; van Albada, Gerard A.; Lanfredi, Anna Maria Manotti; Reedijk, Jan

    2005-01-01

    Two mononuclear complexes of formula [M(ampym) 2(SCN) 2(H 2O) 2]·2H 2O (M=Ni(II), Co(II); ampym=2-aminopyrimidine) have been synthesized and characterized by X-ray diffraction methods, IR and ligand-field spectra. The Ni(II) and Co(II) compounds, which crystallize in the triclinic space group P-1, are isostructural, and their solid structures are stabilized by hydrogen bonding and π-π interactions between aminopyrimidine rings. The compounds exhibit solvatochromism as evidenced by a UV/Vis study in different solvents.

  11. Equilibrium Fe isotope fractionation between inorganic aqueous Fe(III) and the siderophore complex, Fe(III)-desferrioxamine B

    DEFF Research Database (Denmark)

    Dideriksen, Knud; Baker, Joel A.; Stipp, Susan Louise Svane

    2008-01-01

    In oxic oceans, most of the dissolved iron (Fe) exists as complexes with siderophore-like, strongly coordinating organic ligands. Thus, the isotope composition of the little amount of free inorganic Fe that is available for precipitation and preservation in the geological record may largely...... be controlled by isotope fractionation between the free and complexed iron.We have determined the equilibrium Fe isotope fractionation induced by organic ligand activity in experiments with solutions having co-existing inorganic Fe(III) species and siderophore complexes, Fedesferrioxamine B (at pH 2). The two...... differently complexed Fe(III) pools were separated by addition of Na2CO3, which led to immediate precipitation of the inorganic Fe without causing significant dissociation of Fe-desferrioxamine complexes. Experiments using enriched 57Fe tracer showed that isotopic equilibration between the 57Fe...

  12. Equilibrium and kinetic studies of Pb(II, Cd(II and Zn(II sorption by Lagenaria vulgaris shell

    Directory of Open Access Journals (Sweden)

    Mitić-Stojanović Dragana-Linda

    2012-01-01

    Full Text Available The sorption of lead, cadmium and zinc ions from aqueous solution by Lagenaria vulgaris shell biosorbent (LVB in batch system was investigated. The effect of relevant parameters such as contact time, biosorbent dosage and initial metal ions concentration was evaluated. The Pb(II, Cd(II and Zn(II sorption equilibrium (when 98% of initial metal ions were sorbed was attained within 15, 20 and 25 min, respectively. The pseudo first, pseudo-second order, Chrastil’s and intra-particle diffusion models were used to describe the kinetic data. The experimental data fitted the pseudo-second order kinetic model and intra-particle diffusion model. Removal efficiency of lead(II, cadmium(II and zinc(II ions rapidly increased with increasing biosorbent dose from 0.5 to 8.0 g dm-3. Optimal biosorbent dose was set to 4.0 g dm-3. An increase in the initial metal concentration increases the sorption capacity. The sorption data of investigated metal ions are fitted to Langmuir, Freundlich and Temkin isotherm models. Langmuir model best fitted the equilibrium data (r2 > 0.99. Maximal sorption capacities of LVB for Pb(II, Cd(II and Zn(II at 25.0±0.5°C were 0.130, 0.103 and 0.098 mM g-1, respectively. The desorption experiments showed that the LVB could be reused for six cycles with a minimum loss of the initial sorption capacity.

  13. Evaluation of siderite and magnetite formation in BIFs by pressure-temperature experiments of Fe(III) minerals and microbial biomass

    Science.gov (United States)

    Halama, Maximilian; Swanner, Elizabeth D.; Konhauser, Kurt O.; Kappler, Andreas

    2016-09-01

    Anoxygenic phototrophic Fe(II)-oxidizing bacteria potentially contributed to the deposition of Archean banded iron formations (BIFs), before the evolution of cyanobacterially-generated molecular oxygen (O2), by using sunlight to oxidize aqueous Fe(II) and precipitate Fe(III) (oxyhydr)oxides. Once deposited at the seafloor, diagenetic reduction of the Fe(III) (oxyhydr)oxides by heterotrophic bacteria produced secondary Fe(II)-bearing minerals, such as siderite (FeCO3) and magnetite (Fe3O4), via the oxidation of microbial organic carbon (i.e., cellular biomass). During deeper burial at temperatures above the threshold for life, thermochemical Fe(III) reduction has the potential to form BIF-like minerals. However, the role of thermochemical Fe(III) reduction of primary BIF minerals during metamorphism, and its impact on mineralogy and geochemical signatures in BIFs, is poorly understood. Consequently, we simulated the metamorphism of the precursor and diagenetic iron-rich minerals (ferrihydrite, goethite, hematite) at low-grade metamorphic conditions (170 °C, 1.2 kbar) for 14 days by using (1) mixtures of abiotically synthesized Fe(III) minerals and either microbial biomass or glucose as a proxy for biomass, and (2) using biogenic minerals formed by phototrophic Fe(II)-oxidizing bacteria. Mössbauer spectroscopy and μXRD showed that thermochemical magnetite formation was limited to samples containing ferrihydrite and glucose, or goethite and glucose. No magnetite was formed from Fe(III) minerals when microbial biomass was present as the carbon and electron sources for thermochemical Fe(III) reduction. This could be due to biomass-derived organic molecules binding to the mineral surfaces and preventing solid-state conversion to magnetite. Mössbauer spectroscopy revealed siderite contents of up to 17% after only 14 days of incubation at elevated temperature and pressure for all samples with synthetic Fe(III) minerals and biomass, whereas 6% of the initial Fe(III) was

  14. The influence of Fe(III) on oil biodegradation in excessively moistened soils and sediments

    Science.gov (United States)

    Vodyanitskii, Yu. N.; Trofimov, S. Ya.; Shoba, S. A.

    2015-07-01

    Soils are self-purified from oil slowly, in the north, in particular, where hydromorphic conditions and low temperatures hinder the process. Oxidation of oil hydrocarbons depends on the type of electron acceptors and decreases in the following sequence: denitrification > Mn4+ reduction > Fe3+ reduction > sulfate reduction > methanogenesis. Usually, not all of these redox reactions develop in contaminated excessively moistened soils and sediments. Fe(III) reduction and methanogenesis are the most common: the latter is manifested near the contamination source, while the former develops in less contaminated areas. Fe reduction hinders the methanogenesis. In oil-contaminated areas, Fe reduction is also combined with sulfate reduction, the latter intensifying Fe reduction due to the formation of iron sulfides. Concurrently with oil degradation in excessively moistened soils and sediments, the composition of iron compounds changes due to the increasing Fe(II) share magnetite, as well as siderite and ferrocalcite (in calcareous deposits), and iron sulfides (in S-containing medium) are formed.

  15. Secondary ligand-directed assembly of Co(II) coordination polymers based on a pyridine carboxylate ligand

    Science.gov (United States)

    Cao, Ke-Li; Zhang, Yi-Ping; Cai, Yi-Ni; Xu, Xiao-Wei; Feng, Yun-Long

    2014-07-01

    To investigate the influence of hydrogen bonds and secondary ligands on the structures and properties of the resulting frameworks, five new Co(II) compounds have been synthesized by the reactions of Co(II) salts and 3,5-bis(pyridin-4-ylmethoxy)benzoic acid (HL) with four rationally selected dicarboxylic acid ligands. Without secondary ligand, we got one compound [CoL2(H2O)2]n·2nH2O (1), which possesses a 1D chain structure. In the presence of ancillary ligands, namely, 1,3-adamantanedicarboxylic acid (H2adbc), terephthalic acid (H2tpa), thiophene-2,5-dicarboxylic acid (H2tdc) and 1,4-benzenedithioacetic acid (H2bdtc), four 3D structures [Co2L2(adbc)]n·nH2O (2), [Co2L2(tpa)]n (3), [Co2L2(tdc)]n (4), [Co2L2(bdtc)(H2O)]n (5) were obtained, respectively. It can be observed from the architectures of 1-5 that hydrogen bonds and secondary ligands both have great effects on the spatial connective fashions, resulting in the formation of various dimensional compounds. The XRPD, TGA data of title polymers and the magnetic properties for 2 and 5 have also been investigated.

  16. ADSORPTION CHARACTERIZATION OF CO(II IONS ONTO CHEMICALLY TREATED QUERCUS COCCIFERA SHELL: EQUILIBRIUM, KINETIC AND THERMODYNAMIC STUDIES

    Directory of Open Access Journals (Sweden)

    M. Hamdi Karaoglu

    2011-04-01

    Full Text Available Quercus coccifera shell (QCS, a relatively abundant and inexpensive material, is currently being investigated as an adsorbent to remove cobalt(II from water. Before the adsorption experiments, QCS was subjected to chemical treatment to provide maximum surface area. Then, the kinetics and adsorption mechanism of Co(II ions on QCS were studied using different parameters such as adsorbent dosage, initial concentration, temperature, contact time, and solution pH. The loaded metals could be desorbed effectively with dilute hydrochloric acid, nitric acid, and 0.1 M EDTA. The Langmuir and Freundlich models were used to describe the uptake of cobalt on QCS. The equilibrium adsorption data were better fitted to Langmuir adsorption isotherm model. The maximum adsorption capacity (qm of QCS for Co(II was 33 mg g-1. Various kinetic models were used to describe the adsorption process. The adsorption followed pseudo second-order kinetic model. The intraparticle diffusion was found to be the rate-limiting step in the adsorption process. The diffusion coefficients were calculated and found to be in the range of 3.11×10−6 to 168.78×10−6 cm2s-1. The negative DH* value indicated exothermic nature of the adsorption.

  17. Equilibrium, thermoanalytical and spectroscopic studies to characterize phytic acid complexes with Mn(II) and Co(II)

    Energy Technology Data Exchange (ETDEWEB)

    Carli, Ligia de; Schnitzler, Egon; Rosso, Neiva Deliberali [Universidade Estadual de Ponta Grossa (UEPG), PR (Brazil). Dept. de Quimica], e-mail: ndrosso@uepg.br; Ionashiro, Massao [Universidade Estadual Paulista (UNESP), Araraquara, SP (Brazil). Inst. de Quimica; Szpoganicz, Bruno [Universidade Federal de Santa Catarina (UFSC), Florianopolis, SC (Brazil). Dept. de Quimica

    2009-07-01

    Potentiometric studies were carried out to determine the binding degree of phytic acid with Co(II) and Mn(II) ions, in the absence of dioxygen. Equilibrium constants for all major complexes formed are reported, and the results are presented in the form of distribution diagrams showing the concentrations of individual complexes as a function of pH. The formation constants of the complexes show higher values for the species in which the ligand was more deprotonated. Potentiometric data indicates that the species [MH{sub 4}L]{sup 6-}, was totally formed at pH 7.0 and the complexes were synthesized from this data. A solid state complex of Mn(II) and Co(II) with phytic acid was synthesized. Thermogravimetry, differential scanning calorimetry, and infrared spectroscopy were used to investigate and characterize the thermal behavior of these compounds. The results led to information on the composition, dehydration, thermal stability and thermal decomposition of the isolated complexes. (author)

  18. Synthesis and Crystal Structure of a Co(II) Coordination Polymer Derived from a Flexible Bipyridyl Derivative Ligand

    Institute of Scientific and Technical Information of China (English)

    GONG Ya-Qiong; WANG Rui-Hu; WU Ben-Lai; LOU Ben-Yong; HAN Lei; HONG Mao-Chun

    2005-01-01

    The self-assembly of a flexible bipyridyl ligand 2,2'-bis(4-pyridylmethyle- neoxy)-1,1'-biphenylene (4,4'-bpp) with cobalt(II) center gave rise to a one-dimensional chain complex [Co(μ-4,4'-bpp)2(SCN)2(H2O]n 1 which has been characterized by single-crystal X-ray diffraction. The polymer crystallizes in monoclinic, space group C2/c with unit cell parameters: a = 13.1888(13), b = 24.230(2), c = 15.4218(17) (A), β = 93.291(6)°, V = 4920.1(8) (A)3, Z = 4, C50H42CoN6O5S2, Mr = 929.95, Dc = 1.255 g/cm3, F(000) = 1932 and μ(MoKα) = 0.484 mm-1. The final R and wR are 0.0691 and 0.1670 for 3746 observed reflections with I > 2σ(I). 1 possesses an infinite 1-D polymeric chain structure consisting of the repeated basic square units Co2(μ-4,4'-bpp)2, where the Co(II) center acts as the joint of the square ring. The Co(II) center is coordinated in a slightly distorted octahedral geometry with four nitrogen atoms from four different 4,4'-bpp ligands in the equatorial plane and two trans thiocyanate ligands occupying the axial positions, preventing the formation of an extended framework.

  19. Effect of nitrate enrichment and diatoms on the bioavailability of Fe(III) oxyhydroxide colloids in seawater.

    Science.gov (United States)

    Liu, Feng-Jiao; Huang, Bang-Qin; Li, Shun-Xing; Zheng, Feng-Ying; Huang, Xu-Guang

    2016-03-01

    The photoconversion of colloidal iron oxyhydroxides was a significant source of bioavailable iron in coastal systems. Diatoms dominate phytoplankton communities in coastal and upwelling regions. Diatoms are often exposed to eutrophication. We investigated the effects of different species of diatom, cell density, illumination period, and nitrate additions on the bioavailability of Fe(III) oxy-hydroxide colloids in seawaters. With the increase of illumination period from 1 to 4 h, the ratios of concentrations of total dissolved Fe (DFe) to colloidal iron oxyhydroxides and Fe(II) to DFe increased up to 24.3% and 23.9% for seawater without coastal diatoms, 45.6% and 30.2% for Skeletonema costatum, 44.3% and 29.7% for Thalassiosira weissflogii, respectively. The photochemical activity of coastal diatoms themselves (excluding the dissolved organic matter secreted by algae) on the species transformation of iron in seawater (including the light-induced dissolution of Fe(III) oxyhydroxide colloids and the photo-reduction of Fe(III) into Fe(II)) was confirmed for the first time. There was no significant difference of the ability of S. costatum and Thalassiosira weissflogii on the photoconversion of colloidal iron oxyhydroxides. The photoproduction of dissolved Fe(II) and DFe in the seawater with or without diatoms could be depressed by the nitrate addition. PMID:26766021

  20. Protection of Nitrate-Reducing Fe(II)-Oxidizing Bacteria from UV Radiation by Biogenic Fe(III) Minerals.

    Science.gov (United States)

    Gauger, Tina; Konhauser, Kurt; Kappler, Andreas

    2016-04-01

    Due to the lack of an ozone layer in the Archean, ultraviolet radiation (UVR) reached early Earth's surface almost unattenuated; as a consequence, a terrestrial biosphere in the form of biological soil crusts would have been highly susceptible to lethal doses of irradiation. However, a self-produced external screen in the form of nanoparticular Fe(III) minerals could have effectively protected those early microorganisms. In this study, we use viability studies by quantifying colony-forming units (CFUs), as well as Fe(II) oxidation and nitrate reduction rates, to show that encrustation in biogenic and abiogenic Fe(III) minerals can protect a common soil bacteria such as the nitrate-reducing Fe(II)-oxidizing microorganisms Acidovorax sp. strain BoFeN1 and strain 2AN from harmful UVC radiation. Analysis of DNA damage by quantifying cyclobutane pyrimidine dimers (CPD) confirmed the protecting effect by Fe(III) minerals. This study suggests that Fe(II)-oxidizing microorganisms, as would have grown in association with mafic and ultramafic soils/outcrops, would have been able to produce their own UV screen, enabling them to live in terrestrial habitats on early Earth. PMID:27027418

  1. Kinetic and equilibrium studies of biosorption of Pb(II) and Cd(II) from aqueous solution by macrofungus (Amanita rubescens) biomass

    International Nuclear Information System (INIS)

    The biosorption characteristics of Pb(II) and Cd(II) ions from aqueous solution using the macrofungus (Amanita rubescens) biomass were investigated as a function of pH, biomass dosage, contact time, and temperature. Langmuir, Freundlich and Dubinin-Radushkevich (D-R) models were applied to describe the biosorption isotherm of the metal ions by A. rubescens biomass. Langmuir model fitted the equilibrium data better than the Freundlich isotherm. The maximum biosorption capacity of A. rubescens for Pb(II) and Cd(II) was found to be 38.4 and 27.3 mg/g, respectively, at optimum conditions of pH 5.0, contact time of 30 min, biomass dosage of 4 g/L, and temperature of 20 deg. C. The metal ions were desorbed from A. rubescens using both 1 M HCl and 1 M HNO3. The recovery for both metal ions was found to be higher than 90%. The high stability of A. rubescens permitted ten times of adsorption-elution process along the studies without a decrease about 10% in recovery of both metal ions. The mean free energy values evaluated from the D-R model indicated that the biosorption of Pb(II) and Cd(II) onto A. rubescens biomass was taken place by chemical ion-exchange. The calculated thermodynamic parameters, ΔGo, ΔHo and ΔSo showed that the biosorption of Pb(II) and Cd(II) ions onto A. rubescens biomass was feasible, spontaneous and exothermic under examined conditions. Experimental data were also tested in terms of biosorption kinetics using pseudo-first-order and pseudo-second-order kinetic models. The results showed that the biosorption processes of both Pb(II) and Cd(II) followed well pseudo-second-order kinetics. Based on all results, It can be also concluded that it can be evaluated as an alternative biosorbent to treatment wastewater containing Pb(II) and Cd(II) ions, since A. rubescens is low-cost biomass and has a considerable high biosorption capacity.

  2. Evaluation of thiosemicarbazone derivative as chelating agent for the simultaneous removal and trace determination of Cd(II) and Pb(II) in food and water samples.

    Science.gov (United States)

    Koduru, Janardhan Reddy; Lee, Kap Duk

    2014-05-01

    In the present investigation, prepared N-ethyl-3-carbazolecarbaxaldehyde-3-thiosemicarbazone (ECCT) and employed for the simultaneous removal and determination of trace amounts of Cd(II) and Pb(II) from food and water samples. Cd(II) and Pb(II) gave yellow and orange colored complexes with ECCT in acetate buffer at pH 6.0 with λmax, 380 and 440nm, respectively. Both complexes were easily extractable into kerosene at 1:1(M:L) composition. It was in accordance with Beer's law in the range of 0.0-12.0 and 0.0-10.0μgmL(-1) with 0.999 and 0.997 correlation coefficient for Cd(II) and Pb(II) complexes, respectively, indicated a good linearity between the two variables. The molar absorptivity and Sandell's sensitivity were found to be 0.740×10(4)Lmol(-1)cm(-1), 1.52×10(-3)μgcm(-2) for Cd(II) and 1.809×10(4)L mol(-1)cm(-1), 1.15×10(-3)μgcm(-2) for Pb(II). The precision and accuracy of the method was checked for both metal ions by finding the relative standard deviations (n=8), which were 0.689% and 0.443%, with detection limits of 0.00151μgL(-1) and 0.00264μgL(-1) for Cd(II) and Pb(II), respectively. Further validation using certified reference material, NIST 1568b, resulted in determined concentrations of 0.028±0.253μgg(-1) for Cd(II) and 0.046±0.325μgg(-1) for Pb(II). These determined values agree well with the certified values in the reference materials. The interfering effects of various cations and anions were also studied. The proposed method performance was also evaluated in terms of Student 'T' test and Variance 'F' test, which indicated the significance of the present method parameters, as an inter comparison of the experimental values using ICP-OES. PMID:24360411

  3. Synthesis, spectral characterization and biological activities of Mn(II) and Co(II) complexes with benzyloxybenzaldehyde-4-phenyl-3-thiosemicarbazone

    Science.gov (United States)

    Prathima, B.; Subba Rao, Y.; Ramesh, G. N.; Jagadeesh, M.; Reddy, Y. P.; Chalapathi, P. V.; Varada Reddy, A.

    2011-06-01

    Mn(II) and Co(II) complexes of benzyloxybenzaldehyde-4-phenyl-3-thiosemicarbazone have been synthesized and characterized by the investigations of electronic and EPR spectra and X-ray diffraction. Based on the spectral studies, an octahedral geometry is assigned for the Mn(II) and Co(II) complexes. X-ray powder diffraction studies reveal that Mn(II) and Co(II) complexes have triclinic crystal lattices. The unit cell parameters of the Mn(II) complex are a = 11.0469 Å, b = 6.2096 Å, c = 7.4145 Å, α = 90.646°, β = 95.127°, γ = 104.776°, V = 489.7 Å 3 and those of Co(II) complex are a = 9.3236 Å, b = 10.2410 Å, c = 7.8326 Å, α = 90.694°, β = 99.694°, γ = 100.476°, V = 724.2 Å 3. When the free ligand and its metal complexes are subjected to antibacterial activity, the metal complexes are proved to be more active than the ligand. However with regard to in vitro antioxidant activity, the ligand exhibits greater antioxidant activity than its metal(II) complexes.

  4. Solid phase extraction-inductively coupled plasma spectrometry for adsorption of Co(II) and Ni(II) from radioactive wastewaters by natural and modified zeolites

    International Nuclear Information System (INIS)

    Natural and modified clinoptilolite as low-cost adsorbents have been used for adsorption of Co(II) and Ni(II) from nuclear wastewaters both in batch and continuous experiments. Zeolite X was also synthesized and its ability towards the selected cations was examined. Kinetic and thermodynamic behaviors for the process were investigated and adsorption equilibrium was interpreted in term of Langmuir and Freundlich equations. The effect of various parameters including the initial concentration, temperature, ionic strength and pH of solution were examined to achieve the optimized conditions. The clinoptilolite was shown good sorption potential for Co(II) and Ni(II) ions at pH values 4-6. Based on desorption studies, nearly 74 and 85% of adsorbed Co(II) and Ni(II) were removed from clinoptilolite by HCl. The Na+ and NH4+ forms of clinoptilolite were the best modified forms for the removal of investigated cations. It is concluded that the selectivity of clinoptilolite is higher for Co(II) than Ni(II). The synthesized zeolite showed more ability to remove cobalt and nickel ions from aqueous solution than the natural clinoptilolite. The microwave irradiation was found to be more rapid and effective for ion exchange compared to conventional ion exchange process. (author)

  5. Hydrothermal self-assembly and supercapacitive behaviors of Co(II) ion-modified graphene aerogels in H{sub 2}SO{sub 4} electrolyte

    Energy Technology Data Exchange (ETDEWEB)

    Bao, Qi [Department of Systems Engineering and Engineering Management, City University of Hong Kong, Hong Kong (China); Key Laboratory of Marine Environmental Corrosion and Bio-fouling, Institute of Oceanology, Chinese Academy of Sciences, Qingdao 266071 (China); Hui, K.N., E-mail: bizhui@pusan.ac.kr [School of Materials Science and Engineering, Pusan National University, San 30 Jangjeon-dong, Geumjeong-gu, Busan 609-735 (Korea, Republic of); Hui, K.S., E-mail: kshui@hanyang.ac.kr [Department of Mechanical Convergence Engineering, Hanyang University, 17 Haengdang-dong, Seongdong-gu, Seoul 133-791 (Korea, Republic of); Wang, Yi [Key Laboratory of Marine Environmental Corrosion and Bio-fouling, Institute of Oceanology, Chinese Academy of Sciences, Qingdao 266071 (China); Hong, Xiaoting [Department of Systems Engineering and Engineering Management, City University of Hong Kong, Hong Kong (China)

    2014-08-15

    Highlights: • 3D Co(II) ions modified graphene aerogels were prepared by one-step hydrothermal process. • The aerogel electrodes showed hybrid supercapacitor behaviors. • The aerogel electrodes exhibited high rate capability and long-term cycling stability. - Abstract: Reduced graphene oxide (r-GO) aerogels decorated with divalent cobalt ions were synthesized via a one-pot hydrothermal self-assembly route. The interaction of Co(II) ions with 3D r-GO aerogels was investigated by spectroscopic techniques, including Raman, attenuated total reflectance infrared, and X-ray photoelectron spectroscopies. The excellent electrochemical properties of the aerogels were confirmed by cyclic voltammetry, galvanostatic charge/discharge tests, and electrochemical impedance spectroscopy in an acid electrolyte (1 M H{sub 2}SO{sub 4}). The Co(II) ion-modified r-GO aerogels can be used as high-performance hybrid supercapacitor materials with a specific capacitance of 387.2 F g{sup –1} at 1 A g{sup –1} current density and a good cycling stability without capacity decay over 1000 cycles. The mechanical integrity enhancement of the hybrid r-GO aerogel framework and the improvement in its unique capacitive performance are attributed to the efficient interconnection produced by electro-active Co(II) ions.

  6. Energetic Limitations on Microbial Respiration of Organic Compounds using Aqueous Fe(III) Complexes

    Science.gov (United States)

    Naughton, H.; Fendorf, S. E.

    2015-12-01

    Soil organic matter constitutes up to 75% of the terrestrial carbon stock. Microorganisms mediate the breakdown of organic compounds and the return of carbon to the atmosphere, predominantly through respiration. Microbial respiration requires an electron acceptor and an electron donor such as small fatty acids, organic acids, alcohols, sugars, and other molecules that differ in oxidation state of carbon. Carbon redox state affects how much energy is required to oxidize a molecule through respiration. Therefore, different organic compounds should offer a spectrum of energies to respiring microorganisms. However, microbial respiration has traditionally focused on the availability and reduction potential of electron acceptors, ignoring the organic electron donor. We found through incubation experiments that the organic compound serving as electron donor determined how rapidly Shewanella putrefaciens CN32 respires organic substrate and the extent of reduction of the electron acceptor. We simulated a range of energetically favorable to unfavorable electron acceptors using organic chelators bound to Fe(III) with equilibrium stability constants ranging from log(K) of 11.5 to 25.0 for the 1:1 complex, where more stable complexes are less favorable for microbial respiration. Organic substrates varied in nominal oxidation state of carbon from +2 to -2. The most energetically favorable substrate, lactate, promoted up to 30x more rapid increase in percent Fe(II) compared to less favorable substrates such as formate. This increased respiration on lactate was more substantial with less stable Fe(III)-chelate complexes. Intriguingly, this pattern contradicts respiration rate predicted by nominal oxidation state of carbon. Our results suggest that organic substrates will be consumed so long as the energetic toll corresponding to the electron donor half reaction is counterbalanced by the energy available from the electron accepting half reaction. We propose using the chemical

  7. Flow injection spectrophotometric determination of Fe(III) and V(v)

    International Nuclear Information System (INIS)

    Phenylflourone was synthesized with the objective of developing a method for determining Fe(III) and V(V) in the pressence of micelles using flow injectoin technique. Phenylflourone showed a wavelength of maximum absorption at 412 nm which was not affected by the presence of miccelles i.e. n-hexadodecylpyridinum bromide and sodium n-dodecylsulphate, but they have different effects on the absorbance of PHF. The example of PHF-Fe(III) and PHF-V(V) showed the wavelength of the maximum absorption at 4428 nm and 412 nm, respectively. Presence of micelles shifted the wavelength of the two complexes to a lower one. Generally the addition of micelles increased the absorbance of phenylflourone metal ions complexes except for PHF-V(V) with hexadodecylpyridinum bromide. With flow injection technique two approaches were practiced the use of micelle as a carrier or water as a carrier. Sodium n-dodecylsulphate increased the absorbance of the two complexes when it was used as a carrier or added to the metal ions using water as carrier. On the other hand, the use of n-hexadodecylpyridinum bromide as carrieer increased the absorbance of the complexes but it decreased the absorbance when it was used in conjunction with metal ions and water as a carrier. After establishing the optimum FI conditions for PHF-Fe(III) and PHF-V(V) complexes, the calibration curves were construction and produced semiliner response in the concentration range studied. Ti(IV) III, Mo(VI) showed a positive interference in PHF-Fe(III) and PHF-V(V) complexes, respectively.(Author)

  8. Removal of Cd(II) and Pb(II) from wastewater by using triethylenetetramine functionalized grafted cellulose acetate-manganese dioxide composite.

    Science.gov (United States)

    Yakout, Amr A; El-Sokkary, Ramadan H; Shreadah, Mohamed A; Abdel Hamid, Omnia G

    2016-09-01

    In this manuscript, we have studied the removal of Cd(II) and Pb(II) ions from aqueous solution by using triethylenetetramine functionalized cellulose acetate grafted with the copolymer-manganese dioxide composite. The novel sorbent cellulose was extracted from the mangrove trees (Avicennia marina) and it was then acetylated and grafted with acrylamide. The sorbent composite was designed to interact simultaneously with higher metal loading by complexation-adsorption process. FT-IR, SEM, EDAX and TGA techniques were employed to characterize the cellulose modified composite. Sorption equilibria were established after 30min and their data were described by Langmuir and Freundlich models. The functionalized hybrid cellulose composite showed maximum adsorption capacity 82.06 and 196.84mgg(-1) for Cd(II) and Pb(II), respectively. The studied metal ions were successfully recovered from real wastewater samples of different matrices. PMID:27185155

  9. Crystal structures and luminescence properties of two Cd(II) complexes based on 2-(1H-imidazol-1methyl)-6-methyl-1H-benzimidazole

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Yuhong; Meng, Xiangru; Wen, Yu; Li, Peng; Ma, Lin [Zhengzhou Univ. (China). College of Chemistry and Molecular Engineering; Zhang, Qiuju [Zhengzhou Univ. (China). Clinical Testing Section

    2015-11-01

    Two new complexes, {[Cd(immb)I_2].DMF}{sub n} (1) and {[Cd_3(immb)(btc)_2]. H_2O}{sub n} (2) (immb = 2-(1H-imidazol- 1-methyl)-6-methyl-1H-benzimidazole, btc = 1,2,3-benzenetricarboxylate, DMF = dimethyl formamide), have been synthesized and characterized. Single crystal X-ray diffraction shows that 1 exhibits a chain structure constructed by immb ligands bridging Cd(II) ions. In 2, Cd(II) ions are linked by immb ligands with bridging mode and btc3- anions with the μ{sub 2}-η{sup 2}:η{sup 1} bonding pattern leading to a 2D structure. Luminescent properties have been investigated in the solid state at room temperature.

  10. Secondary ligand-directed assembly of Co(II) coordination polymers based on a pyridine carboxylate ligand

    Energy Technology Data Exchange (ETDEWEB)

    Cao, Ke-Li; Zhang, Yi-Ping; Cai, Yi-Ni; Xu, Xiao-Wei; Feng, Yun-Long, E-mail: sky37@zjnu.cn

    2014-07-01

    To investigate the influence of hydrogen bonds and secondary ligands on the structures and properties of the resulting frameworks, five new Co(II) compounds have been synthesized by the reactions of Co(II) salts and 3,5-bis(pyridin-4-ylmethoxy)benzoic acid (HL) with four rationally selected dicarboxylic acid ligands. Without secondary ligand, we got one compound [CoL{sub 2}(H{sub 2}O){sub 2}]{sub n}·2nH{sub 2}O (1), which possesses a 1D chain structure. In the presence of ancillary ligands, namely, 1,3-adamantanedicarboxylic acid (H{sub 2}adbc), terephthalic acid (H{sub 2}tpa), thiophene-2,5-dicarboxylic acid (H{sub 2}tdc) and 1,4-benzenedithioacetic acid (H{sub 2}bdtc), four 3D structures [Co{sub 2}L{sub 2}(adbc)]{sub n}·nH{sub 2}O (2), [Co{sub 2}L{sub 2}(tpa)]{sub n} (3), [Co{sub 2}L{sub 2}(tdc)]{sub n} (4), [Co{sub 2}L{sub 2}(bdtc)(H{sub 2}O)]{sub n} (5) were obtained, respectively. It can be observed from the architectures of 1–5 that hydrogen bonds and secondary ligands both have great effects on the spatial connective fashions, resulting in the formation of various dimensional compounds. The XRPD, TGA data of title polymers and the magnetic properties for 2 and 5 have also been investigated. - Graphical abstract: The structural differences show that the ancillary ligands have great effects on the spatial connective fashions, resulting in the formation of various dimensional compounds. - Highlights: • Five new Co(II) coordination polymers have been synthesized by solvothermal reactions based on 3,5-bis(pyridin-4-ylmethoxy)benzoic acid (HL). • The long-flexible ligand (HL) is a good candidate to produce interpenetrating architectures. • The secondary dicarboxylic acid ligands play important roles in the spatial connective fashions and the formation of various dimensional compounds. • The magnetism studies show that both 2 and 5 exhibit antiferromagnetic interactions.

  11. Anisotropic Fermi Couplings due to Large Unquenched Orbital Angular Momentum: Q-band 1H, 14N and 11B ENDOR of bistrispyrazolylborate Co(II)

    Science.gov (United States)

    Myers, William K.; Scholes, Charles P.; Tierney, David L.

    2009-01-01

    We report Q-band ENDOR of 1H, 14N, and 11B at the g|| extreme of the EPR spectrum of bistrispyrazolylborate Co(II), Co(Tp)2 and two structural analogs. This trigonally symmetric, high-spin (hs) S = 3/2 Co(II) complex shows large unquenched ground–state orbital angular momentum, which leads to highly anisotropic electronic g-values [g|| = 8.48, g⊥ = 1.02]. The large g-anisotropy is shown to result in large dipolar couplings near g|| and uniquely anisotropic 14N Fermi couplings, which arise from spin transferred to the nitrogen 2s orbital (2.2 %) via anti-bonding interactions with singly occupied metal dx2−y2 and dz2 orbitals. Large, well-resolved 1H and 11B dipolar couplings were also observed. Taken in concert with our previous X-band ENDOR measurements at g⊥ (Myers, et al, Inorg. Chem. 2008, 47, 6701–6710), the present data allow a detailed analysis of the dipolar hyperfine tensors of two of the four symmetry distinct protons in the parent molecule. In the substituted analogs, changes in hyperfine coupling due to altered metal-proton distances give further evidence of an anisotropic Fermi contact interaction. For the pyrazolyl 3H proton, the data indicate a 0.2 MHz anisotropic contact interaction and ~ 4 % transfer of spin away from Co(II). Dipolar coupling also dominates for the axial boron atoms, consistent with their distance from the Co(II) ion, and resolved 11B quadrupolar coupling showed ~ 30 % electronic inequivalence between the B-H and B-C sp3 bonds. This is the first comprehensive ENDOR study of any hs Co(II) species and lays the foundation for future development. PMID:19591466

  12. Preparation of cross-linked magnetic chitosan-phenylthiourea resin for adsorption of Hg(II), Cd(II) and Zn(II) ions from aqueous solutions.

    Science.gov (United States)

    Monier, M; Abdel-Latif, D A

    2012-03-30

    In this study, cross-linked magnetic chitosan-phenylthiourea (CSTU) resin were prepared and characterized by means of FTIR, (1)H NMR, SEM high-angle X-ray diffraction (XRD), magnetic properties and thermogravimetric analysis (TGA). The prepared resin were used to investigate the adsorption properties of Hg(II), Cd(II) and Zn(II) metal ions in an aqueous solution. The extent of adsorption was investigated as a function of pH and the metal ion removal reached maximum at pH 5.0. Also, the kinetic and thermodynamic parameters of the adsorption process were estimated. These data indicated that the adsorption process is exothermic and followed the pseudo-second-order kinetics. Equilibrium studies showed that the data of Hg(II), Cd(II) and Zn(II) adsorption followed the Langmuir model. The maximum adsorption capacities for Hg(II), Cd(II) and Zn(II) were estimated to be 135 ± 3, 120 ± 1 and 52 ± 1 mg/g, which demonstrated the high adsorption efficiency of CSTU toward the studied metal ions. PMID:22277339

  13. Simultaneous determination of Cd(II), Cu(II), Pb(II), and Zn(II) in citrus essential oils by derivative potentiometric stripping analysis.

    Science.gov (United States)

    La Pera, Lara; Saitta, Marcello; Di Bella, Giuseppa; Dugo, Giacomo

    2003-02-26

    Citrus essential oils are widely used in the food, cosmetics, and pharmaceutical industries, so the determination of heavy metals content is of great importance to guarantee their quality. The present work deals with the quantification of Cd(II), Cu(II), Pb(II), and Zn(II) in different varieties of citrus essential oils, using derivative potentiometric stripping analysis. Two different metals extraction procedures, involving concentrated hydrochloric acid treatment and acid-alcoholic dissolution, are tested on lemon, mandarin, sweet orange, and bergamot essential oils, and they give very similar results. Cd(II), Cu(II), Pb(II), and Zn(II) recovery tests spanned from 95 to 100.50%, providing evidence that metals quantification remained unaffected by the cleanup steps of the two procedures. The repeatability of the hydrochloric acid extraction method, applied on different varieties of essential oils, is >95.00% for Cd(II), Cu(II), Pb(II), and Zn(II), whereas the repeatability of the acid-alcoholic dissolution method is >93.00% for Cu and Cd only in lemon oil. Detection limits obtained for the four analytes, using both procedures, ranged from 0.10 to 0.98 ng g(-)(1) in lemon, mandarin, sweet orange, and bergamot essential oils. PMID:12590445

  14. Crystal structure and photoluminescence of a new two-dimensional Cd(II) coordination polymer based on 3-(carboxymethoxy)-2-naphthoic acid

    Energy Technology Data Exchange (ETDEWEB)

    Kong, Zhi-Guo; Guo, Sheng-Nan; Miao, Jia-Qi; An, Miao [Jilin Normal Univ., College of Chemistry, Siping (China); Ministry of Education, Siping (China). Key Lab. of Preparation and Applications of Enviromental Friendly Materials

    2015-11-01

    A new Cd(II) coordination polymer, [Cd(CNA)]{sub n} (1) (H{sub 2}CNA = 3-(carboxymethoxy)-2-naphthoic acid), was hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction. The crystals are monoclinic, space group P{sub 2}1/c with a = 16.9698(18), b = 7.8314(8), c = 8.9553(10) Aa, β = 100.657(2) {sup circle}, V = 1169.6(2) Aa{sup 3}, Z = 4, D{sub calcd.} = 2.03 g cm{sup -3}, μ(MoK{sub α}) = 1.9 mm{sup -1}, F(000) = 696 e, R = 0.0305, wR = 0.0784 for 172 refined parameters and 2285 data. Each CNA anion bridges three Cd(II) cations to give rise to a two-dimensional network structure. Topologically, if each CNA anion is regarded as a linker, and each Cd(II) atom considered as a 4-connected node, the structure is simplified as a 4-connected (4,4) network. The solid state photoluminescent properties of the compound were also studied at room temperature.

  15. Uptake of Cd(II) and Pb(II) by microalgae in presence of colloidal organic matter from wastewater treatment plant effluents

    International Nuclear Information System (INIS)

    The present study addresses the key issue of linking the chemical speciation to the uptake of priority pollutants Cd(II) and Pb(II) in the wastewater treatment plant effluents, with emphasis on the role of the colloidal organic matter (EfOM). Binding of Cd(II) and Pb(II) by EfOM was examined by an ion exchange technique and flow field-flow fractionation coupled to inductively coupled plasma mass spectrometry in parallel to bioassays with green microalga Chlorella kesslerii in ultrafiltrate (<1 kDa) and colloidal isolates (1 kDa to 0.45 μm). The uptake of Cd by C. kesslerii was consistent with the speciation analysis and measured free metal ion concentrations, while Pb uptake was much greater than that expected from the speciation measurement. Better understanding of the differences in the effects of the EfOM on Cd(II) and Pb(II) uptake required to take into account the size dependence of metal binding by EfOM. - Colloids isolated from WWTP effluents decrease Cd uptake, but increase Pb uptake by microalga Chlorella kesslerii.

  16. Crystal structure and photoluminescence of a new two-dimensional Cd(II) coordination polymer based on 3-(carboxymethoxy)-2-naphthoic acid

    International Nuclear Information System (INIS)

    A new Cd(II) coordination polymer, [Cd(CNA)]n (1) (H2CNA = 3-(carboxymethoxy)-2-naphthoic acid), was hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction. The crystals are monoclinic, space group P21/c with a = 16.9698(18), b = 7.8314(8), c = 8.9553(10) Aa, β = 100.657(2) circle, V = 1169.6(2) Aa3, Z = 4, Dcalcd. = 2.03 g cm-3, μ(MoKα) = 1.9 mm-1, F(000) = 696 e, R = 0.0305, wR = 0.0784 for 172 refined parameters and 2285 data. Each CNA anion bridges three Cd(II) cations to give rise to a two-dimensional network structure. Topologically, if each CNA anion is regarded as a linker, and each Cd(II) atom considered as a 4-connected node, the structure is simplified as a 4-connected (4,4) network. The solid state photoluminescent properties of the compound were also studied at room temperature.

  17. Effect of desferrioxamine B and Suwannee River fulvic acid on Fe(III) release and Cr(III) desorption from goethite

    Science.gov (United States)

    Stewart, Angela G.; Hudson-Edwards, Karen A.; Dubbin, William E.

    2016-04-01

    Siderophores are biogenic chelating ligands that facilitate the solubilisation of Fe(III) and form stable complexes with a range of contaminant metals and therefore may significantly affect their biogeochemical cycling. Desferrioxamine B (DFOB) is a trihydroxamate siderophore that acts synergistically with fulvic acid and low molecular weight organic ligands to release Fe from Fe(III) oxides. We report the results of batch dissolution experiments in which we determine the rates of Cr(III) desorption and Fe(III) release from Cr(III)-treated synthetic goethite as influenced by DFOB, by fulvic acid, and by the two compounds in combination. We observed that adsorbed Cr(III) at 3% surface coverage significantly reduced Fe(III) release from goethite for all combinations of DFOB and fulvic acid. When DFOB (270 μM) was the only ligand present, dissolved Fe(III) and Cr(III) increased approximately 1000-fold and 16-fold, respectively, as compared to the ligand-free system, a difference we attribute to the slow rate of water exchange of Cr(III). Suwannee River fulvic acid (SRFA) acts synergistically with DFOB by (i) reducing the goethite surface charge leading to increased HDFOB+ surface excess and by (ii) forming aqueous Fe(III)-SRFA species whose Fe(III) is subsequently removed by DFOB to yield aqueous Fe(III)-DFOB complexes. These observations shed new light on the synergistic relationship between DFOB and fulvic acid and reveal the mechanisms of Fe(III) acquisition available to plants and micro-organisms in Cr(III) contaminated environments.

  18. Spectroscopic evaluation of Co(II), Ni(II) and Cu(II) complexes derived from thiosemicarbazone and semicarbazone

    Science.gov (United States)

    Chandra, Sulekh; Kumar, Anil

    2007-12-01

    Co(II), Ni(II) and Cu(II) complexes were synthesized with thiosemicarbazone (L 1) and semicarbazone (L 2) derived from 2-acetyl furan. These complexes were characterized by elemental analysis, molar conductance, magnetic moment, mass, IR, electronic and EPR spectral studies. The molar conductance measurement of the complexes in DMSO corresponds to non-electrolytic nature. All the complexes are of high-spin type. On the basis of different spectral studies six coordinated geometry may be assigned for all the complexes except Co(L) 2(SO 4) and Cu(L) 2(SO 4) [where L = L 1 and L 2] which are of five coordinated square pyramidal geometry.

  19. Relationship between P and the most reactive fraction of Fe(III) oxyhydroxide in various aquatic and sedimentary environments

    Science.gov (United States)

    Anschutz, Pierre

    2014-05-01

    Phosphorus can experience a series of biogeochemical pathways. Primary P has an igneous origin and occurs mostly as apatite in bedrocks. Once P is dissolved as phosphate ion, it can incorporate organic matter or become adsorbed onto inorganic particles. The liberation of P from organic matter through bacterial respiration produces a subsequent flux back to the biota or a storage in Fe and Al oxyhydroxides, or in authigenic or biogenic phosphate minerals. The adsorption of phosphate on Fe- and Al-oxide and oxyhydroxide has been extensively studied in soil science because phosphorus is a limiting nutrient in terrestrial ecosystems, and sorptive removal of natural or fertilizer phosphorus impacts the production level of crops and forests. Fe(III) oxides/oxyhydroxides are subject to reductive dissolution, and consequently redox conditions play an important role in soil P-bioavailability. The main process of phosphorus removal from the aquatic systems is burial with sediments. Exchange between sediment and overlying water takes place through benthic biogeochemical processes, including organic-P mineralization, redox-driven Fe-P cycling, and benthic phosphorus efflux from sediments. A portion of the pore-water phosphate derived from organic matter mineralization may be adsorbed onto detrital or authigenic iron oxyhydroxides in the oxidized zone of the sediment. Once advected in the reduced zone of sediments through burial or bioturbation, the most reducible fraction of Fe(III) phase can be reduced and solubilized, leading to a release of phosphate. Eventually, P can be buried over long period as relict organic-P, P associated with refractory iron oxides, and apatite. Therefore, Fe-bound P is often the initial sink of P supplied by organic matter, but not the major final sink. Several techniques have been developed to extract P bound to Fe(III) phases. The citrate-dithionite buffered (CDB) solution is one of the most often used solution to measure Fe(III)-bound P. CDB

  20. Reduction of Fe(III), Cr(VI), U(VI), and Tc(VII) by Deinococcus radiodurans R1.

    Science.gov (United States)

    Fredrickson, J K; Kostandarithes, H M; Li, S W; Plymale, A E; Daly, M J

    2000-05-01

    Deinococcus radiodurans is an exceptionally radiation-resistant microorganism capable of surviving acute exposures to ionizing radiation doses of 15,000 Gy and previously described as having a strictly aerobic respiratory metabolism. Under strict anaerobic conditions, D. radiodurans R1 reduced Fe(III)-nitrilotriacetic acid coupled to the oxidation of lactate to CO(2) and acetate but was unable to link this process to growth. D. radiodurans reduced the humic acid analog anthraquinone-2,6-disulfonate (AQDS) to its dihydroquinone form, AH(2)DS, which subsequently transferred electrons to the Fe(III) oxides hydrous ferric oxide and goethite via a previously described electron shuttle mechanism. D. radiodurans reduced the solid-phase Fe(III) oxides in the presence of either 0.1 mM AQDS or leonardite humic acids (2 mg ml(-1)) but not in their absence. D. radiodurans also reduced U(VI) and Tc(VII) in the presence of AQDS. In contrast, Cr(VI) was directly reduced in anaerobic cultures with lactate although the rate of reduction was higher in the presence of AQDS. The results are the first evidence that D. radiodurans can reduce Fe(III) coupled to the oxidation of lactate or other organic compounds. Also, D. radiodurans, in combination with humic acids or synthetic electron shuttle agents, can reduce U and Tc and thus has potential applications for remediation of metal- and radionuclide-contaminated sites where ionizing radiation or other DNA-damaging agents may restrict the activity of more sensitive organisms. PMID:10788374

  1. Reduction of Fe(III), Cr(VI), U(VI), and Tc(VII) by Deinococcus radiodurans R1

    Energy Technology Data Exchange (ETDEWEB)

    Fredrickson, J.K.; Kostandarithes, H.M.; Li, S.W.; Plymake, A.E.; Daly, M.J.

    2000-05-01

    Deinococcus radiodurans is an exceptionally radiation-resistant microorganism capable of surviving acute exposures to ionizing radiation doses of 15,000 Gy and previously described as having a strictly aerobic respiratory metabolism. Under strict anaerobic conditions, D. radiodurans R1 reduced Fe(III)-nitrilotriacetic acid coupled to the oxidation of lactate to CO{sub 2} and acetate but was unable to link this process to growth. D. radiodurans reduced the humic acid analog anthraquinone-2,6-disulfonate (AQDS) to its dihydroquinone form, AH{sub 2}DS, which subsequently transferred electrons to the Fe(III) oxides hydrous ferric oxide and goethite via a previously described electron shuttle mechanism. D. radiodurans reduced the solid-phase Fe(III) oxides in the presence of either 0.1 mM AQDS or leonardite humic acids (2 mg ml{sup {minus}1}) but not in their absence. D. radiodurans also reduced U(VI) and Tc(VII) in the presence of AQDS. In contrast, Cr(VI) was directly reduced in anaerobic cultures with lactate although the rate of reduction was higher in the presence of AQDS. The results are the first evidence that D. radiodurans can reduce Fe(III) coupled to the oxidation of lactate or other organic compounds. Also, D. radiodurans, in combination with humic acids or synthetic electron shuttle agents, can reduce U and Tc and thus has potential applications for remediation of metal- and radionuclide-contaminated sites where ionizing radiation or other DNA-damaging agents may restrict the activity of more sensitive organisms.

  2. Reduction of Fe(III), Cr(VI), U(VI), and Tc(VII) by Deinococcus radiodurans R1

    International Nuclear Information System (INIS)

    Deinococcus radiodurans is an exceptionally radiation-resistant microorganism capable of surviving acute exposures to ionizing radiation doses of 15,000 Gy and previously described as having a strictly aerobic respiratory metabolism. Under strict anaerobic conditions, D. radiodurans R1 reduced Fe(III)-nitrilotriacetic acid coupled to the oxidation of lactate to CO2 and acetate but was unable to link this process to growth. D. radiodurans reduced the humic acid analog anthraquinone-2,6-disulfonate (AQDS) to its dihydroquinone form, AH2DS, which subsequently transferred electrons to the Fe(III) oxides hydrous ferric oxide and goethite via a previously described electron shuttle mechanism. D. radiodurans reduced the solid-phase Fe(III) oxides in the presence of either 0.1 mM AQDS or leonardite humic acids (2 mg ml-1) but not in their absence. D. radiodurans also reduced U(VI) and Tc(VII) in the presence of AQDS. In contrast, Cr(VI) was directly reduced in anaerobic cultures with lactate although the rate of reduction was higher in the presence of AQDS. The results are the first evidence that D. radiodurans can reduce Fe(III) coupled to the oxidation of lactate or other organic compounds. Also, D. radiodurans, in combination with humic acids or synthetic electron shuttle agents, can reduce U and Tc and thus has potential applications for remediation of metal- and radionuclide-contaminated sites where ionizing radiation or other DNA-damaging agents may restrict the activity of more sensitive organisms

  3. Enhanced abiotic and biotic contributions to dechlorination of pentachlorophenol during Fe(III) reduction by an iron-reducing bacterium Clostridium beijerinckii Z

    International Nuclear Information System (INIS)

    A novel Fe(III) reducing bacterium, Clostridium beijerinckii Z, was isolated from glucose amended paddy slurries, and shown to dechlorinate pentachlorophenol (PCP). Fifty percent of added PCP was removed by C. beijerinckii Z alone, which increased to 83% in the presence of both C. beijerinckii Z and ferrihydrite after 11 days of incubation. Without C. beijerinckii Z, the surface-bound Fe(II) also abiotically dechlorinated more than 40% of the added PCP. This indicated that the biotic dechlorination by C. beijerinckii Z is a dominant process causing PCP transformation through anaerobic dechlorination, and that the dechlorination rates can be accelerated by simultaneous reduction of Fe(III). A biochemical electron transfer coupling process between sorbed Fe(II) produced by C. beijerinckii Z and reductive dehalogenation is a possible mechanism. This finding increases our knowledge of the role of Fe(III) reducing genera of Clostridium in dechlorinating halogenated organic pollutants, such as PCP, in anaerobic paddy soils. - Highlights: • A novel Fe(III) reducing bacterium Clostridium beijerinckii Z was isolated and could dechlorinate pentachlorophenol. • Anaerobic transformation of PCP by C. beijerinckii Z could be accelerated by simultaneous reduction of Fe(III). • Biochemical electron transfer coupling between Fe redox cycling and reductive dechlorination was the mechanism involved. • The finding increases our knowledge of Clostridium sp. regarding their multiple functions for dechlorinating pollutants

  4. A Strongly Spin-Frustrated Fe(III) 7 Complex with a Canted Intermediate Spin Ground State of S=7/2 or 9/2.

    Science.gov (United States)

    Mondal, Kartik Chandra; Mereacre, Valeriu; Kostakis, George E; Lan, Yanhua; Anson, Christopher E; Prisecaru, Ion; Waldmann, Oliver; Powell, Annie K

    2015-07-20

    A disk-shaped [Fe(III) 7 (Cl)(MeOH)6 (μ3 -O)3 (μ-OMe)6 (PhCO2 )6 ]Cl2 complex with C3 symmetry has been synthesised and characterised. The central tetrahedral Fe(III) is 0.733 Å above the almost co-planar Fe(III) 6 wheel, to which it is connected through three μ3 -oxide bridges. For this iron-oxo core, the magnetic susceptibility analysis proposed a Heisenberg-Dirac-van Vleck (HDvV) mechanism that leads to an intermediate spin ground state of S=7/2 or 9/2. Within either of these ground state manifolds it is reasonable to expect spin frustration effects. The (57) Fe Mössbauer (MS) analysis verifies that the central Fe(III) ion easily aligns its magnetic moment antiparallel to the externally applied field direction, whereas the other six peripheral Fe(III) ions keep their moments almost perpendicular to the field at stronger fields. This unusual canted spin structure reflects spin frustration. The small linewidths in the magnetic Mössbauer spectra of polycrystalline samples clearly suggest an isotropic exchange mechanism for realisation of this peculiar spin topology. PMID:26073059

  5. Dissimilatory reduction of FeIII (EDTA) with microorganisms in the system of nitric oxide removal from the flue gas by metal chelate absorption

    Institute of Scientific and Technical Information of China (English)

    MA Bi-yao; LI Wei; JING Guo-hua; SHI Yao

    2004-01-01

    In the system of nitric oxide removal from the flue gas by metal chelate absorption, it is an obstacle that ferrous absorbents are easily oxidized by oxygen in the flue gas to ferric counterparts, which are not capable of binding NO. By adding iron metal or electrochemical method, FeIII (EDTA) can be reduced to FeII (EDTA). However, there are various drawbacks associated with these techniques. The dissimilatory reduction of FeIII (EDTA) with microorganisms in the system of nitric oxide removal by metal chelate absorption was investigated. Ammonium salt instead of nitrate was used as the nitrogen source, as nitrates inhibited the reduction of FeIII due to the competition between the two electron acceptors. Supplemental glucose and lactate stimulated the formation of FeII more than ethanol as the carbon sources. The microorganisms cultured at 50℃ were not very sensitive to the other experimental temperature, the reduction percentage of FeIII varied little with the temperature range of 30~50℃. Concentrated Na2CO3 solution was added to adjust the solution pH to an optimal pH range of 6~7. The overall results revealed that the dissimilatory ferric reducing microorganisms present in the mix-culture are probably neutrophilic, moderately thermophilic FeIII reducers.

  6. Equilibrium and kinetic studies of adsorption of Cd(II) from aqueous solution using modified corn stalk

    International Nuclear Information System (INIS)

    This paper describes the adsorption of cadmium ions from aqueous solution using acrylonitrile (AN)-modified corn stalk (AMCS). AMCS was characterized by elemental analysis, scanning electron microscopy, surface area and porosity analyzer, Fourier transform infrared and solid-state CP/MAS 13C NMR spectra, and then used to evaluate the adsorption capacity in different pH values, adsorption isotherm, kinetics and thermodynamics in batch experiments. The results showed that AMCS is found to be an effective adsorbent because of its pore size and functional groups (-CN). The pH of 7.0 was an optimal pH for removal of Cd(II) ion and the Langmuir model provides a better fit to the equilibrium data than the Freundlich model, showing a maximum uptake of 12.73 mg g-1, compared to raw corn stalk (RCS) (3.39 mg g-1). Analysis indicated that pseudo-second-order kinetics controlled the adsorption rate. The activation energy (Ea) was 9.43 kJ mol-1. Thermodynamic parameters such as ΔG, ΔH and ΔS were also evaluated to predict the nature of adsorption process.

  7. Controllable assemblies of Cd(II) supramolecular coordination complexes based on a versatile tripyridyltriazole ligand and halide/pseduohalide anions

    Science.gov (United States)

    Wang, Xi; Guo, Wei; Guo, Ya-Mei

    2015-09-01

    Three Cd(II) complexes [Cd(L)(H2O)Cl2]n (1), [Cd(L)(H2O)Br2]n (2), and [Cd(L)I2]2 (3) have been assembled from CdX2 (1, X = Cl; 2, X = Br; 3, X = I) and a tripyridyltriazole ligand 3-(2-pyridyl)-4-(4-pyridyl)-5-(3-pyridyl)-1,2,4-triazole (L). Complexes 1 and 2 are isostructural and exhibit 1-D loop-like chain, while complex 3 has a distinct dimeric macrocyclic motif. Interestingly, another 1-D chain [Cd(L)I(SCN)]n (4) can be achieved when NH4SCN is introduced into the assembled system of 3. Structural analysis of 1-4 illustrates that the halide and thiocyanate anions in these coordination complexes behave as not only the counteranions, but also the structure directing agents. The fluorescent and thermal properties of 1-4 have also been investigated.

  8. Liquid–liquid extraction of Cd(II) from pure and Ni/Cd acidic chloride media using Cyanex 921: A selective treatment of hazardous leachate of spent Ni–Cd batteries

    Energy Technology Data Exchange (ETDEWEB)

    Choi, Seon-Young [Chungnam National University (CNU), Environmental Engineering, Daejeon 305-764 (Korea, Republic of); Korea Institute of Geoscience and Mineral Resources (KIGAM), Mineral Resources Research Division, Daejeon 305-350 (Korea, Republic of); Nguyen, Viet Tu, E-mail: writtingtu@gmail.com [Korea Institute of Geoscience and Mineral Resources (KIGAM), Mineral Resources Research Division, Daejeon 305-350 (Korea, Republic of); Korea University of Science and Technology (UST), Resources Recycling, Daejeon 305-350 (Korea, Republic of); Lee, Jae-chun, E-mail: jclee@kigam.re.kr [Korea Institute of Geoscience and Mineral Resources (KIGAM), Mineral Resources Research Division, Daejeon 305-350 (Korea, Republic of); Korea University of Science and Technology (UST), Resources Recycling, Daejeon 305-350 (Korea, Republic of); Kang, Ho [Chungnam National University (CNU), Environmental Engineering, Daejeon 305-764 (Korea, Republic of); Pandey, B.D. [CSIR – National Metallurgical Laboratory (NML), Metal Extraction and Forming Division, Jamshedpur 831007 (India)

    2014-08-15

    Highlights: • Cd(II) extraction from acidic chloride waste solutions using Cyanex 921 is optimized. • Chemistry of Cd(II) in HCl solutions is first-ever considered for the extraction mechanism. • Cd(II) species is extracted in Cyanex 921 (L) as a neutral complex HCdCl{sub 3}·4L. • Calculated thermodynamic parameters give an insight into Cd(II) complexation reactions. • Cyanex 921 can be used for the selective treatment of hazardous waste Ni–Cd batteries. - Abstract: The present paper is focused on solvent extraction of hazardous Cd(II) from acidic chloride media by Cyanex 921, a new extractant mixed with 10% (v/v) TBP in xylene. The optimum conditions for extraction and stripping of Cd(II) were investigated with an aqueous feed of 0.1 mol/L Cd(II) in 2.0 mol/L HCl. McCabe–Thiele diagram was in good agreement with the simulation studies, showing the quantitative extraction (99.9%) of Cd(II) within two counter-current stages utilizing 0.30 mol/L Cyanex 921 at O/A ratio of 3/2 in 10 min. Stoichiometry of the complexes extracted was determined and confirmed by numerical treatment and graphical method, revealing the formation of HCdCl{sub 3}·2L and HCdCl{sub 3}·4L for Cyanex 921(L) concentration in the range 0.03–0.1 mol/L and 0.1–1.0 mol/L, respectively. The thermodynamic parameters for the extraction of cadmium were also determined. The stripping efficiency of cadmium from the loaded organic with 0.10 mol/L HCl was 99.6% in a three-stage counter-current process at an O/A ratio of 2/3. Cyanex 921 was successfully applied for the separation of Cd(II) from Ni(II) in the simulated leach liquor of spent Ni–Cd batteries. The study demonstrates the applicability of the present hydrometallurgical approach for the treatment of hazardous waste, the spent Ni–Cd batteries.

  9. Liquid–liquid extraction of Cd(II) from pure and Ni/Cd acidic chloride media using Cyanex 921: A selective treatment of hazardous leachate of spent Ni–Cd batteries

    International Nuclear Information System (INIS)

    Highlights: • Cd(II) extraction from acidic chloride waste solutions using Cyanex 921 is optimized. • Chemistry of Cd(II) in HCl solutions is first-ever considered for the extraction mechanism. • Cd(II) species is extracted in Cyanex 921 (L) as a neutral complex HCdCl3·4L. • Calculated thermodynamic parameters give an insight into Cd(II) complexation reactions. • Cyanex 921 can be used for the selective treatment of hazardous waste Ni–Cd batteries. - Abstract: The present paper is focused on solvent extraction of hazardous Cd(II) from acidic chloride media by Cyanex 921, a new extractant mixed with 10% (v/v) TBP in xylene. The optimum conditions for extraction and stripping of Cd(II) were investigated with an aqueous feed of 0.1 mol/L Cd(II) in 2.0 mol/L HCl. McCabe–Thiele diagram was in good agreement with the simulation studies, showing the quantitative extraction (99.9%) of Cd(II) within two counter-current stages utilizing 0.30 mol/L Cyanex 921 at O/A ratio of 3/2 in 10 min. Stoichiometry of the complexes extracted was determined and confirmed by numerical treatment and graphical method, revealing the formation of HCdCl3·2L and HCdCl3·4L for Cyanex 921(L) concentration in the range 0.03–0.1 mol/L and 0.1–1.0 mol/L, respectively. The thermodynamic parameters for the extraction of cadmium were also determined. The stripping efficiency of cadmium from the loaded organic with 0.10 mol/L HCl was 99.6% in a three-stage counter-current process at an O/A ratio of 2/3. Cyanex 921 was successfully applied for the separation of Cd(II) from Ni(II) in the simulated leach liquor of spent Ni–Cd batteries. The study demonstrates the applicability of the present hydrometallurgical approach for the treatment of hazardous waste, the spent Ni–Cd batteries

  10. A microscale multi-functional metal-organic framework as a fluorescence chemosensor for Fe(III), Al(III) and 2-hydroxy-1-naphthaldehyde.

    Science.gov (United States)

    Kang, Yang; Zheng, Xiang-Jun; Jin, Lin-Pei

    2016-06-01

    A microscale metal-organic framework [Eu(atpt)1.5(phen)(H2O)]n (H2atpt=2-aminoterephthalic acid, phen=1,10-phenanthroline) (Eu-MOF) was synthesized and characterized by elemental analysis, luminescence spectrum, powder X-ray diffraction, dynamic light scattering and scanning electron microscope. The fluorescence response of Eu-MOF to metal ions and aldehydes showed that Eu-MOF is highly selective to Fe(III), Al(III) and 2-hydroxy-1-naphthaldehyde (2-OH-NA). Eu-MOF could be utilized as a multi-functional fluorescence chemosensor for Fe(III), Al(III) and 2-hydroxy-1-naphthaldehyde (2-OH-NA). The detection limit of Fe(III), Al(III) and 2-OH-NA was 45, 10 and 36μM, respectively. The corresponding sensing mechanisms were explored. PMID:26967663

  11. The Influence of the Amide Linkage in the Fe(III) -Binding Properties of Catechol-Modified Rosamine Derivatives.

    Science.gov (United States)

    Queirós, Carla; Leite, Andreia; G M Couto, Maria; Cunha-Silva, Luís; Barone, Giampaolo; de Castro, Baltazar; Rangel, Maria; M N Silva, André; M G Silva, Ana

    2015-10-26

    The two new fluorescent ligands RosCat1 and RosCat2 contain catechol receptors connected to rosamine platforms through an amide linkage and were synthesized by using microwave-assisted coupling reactions of carboxyl- or amine-substituted rosamines with the corresponding catechol units and subsequent deprotection. RosCat1 possesses a reverse amide, whereas RosCat2 has the usual oriented amide bond (HNCO vs. CONH, respectively). The ligands were characterized by means of NMR spectroscopy, mass-spectrometry, and DFT calculations and X-ray crystallography studies for RosCat1. The influence of the amide linkage on the photophysical properties of the fluorescent ligands was assessed in different solvents and showed a higher fluorescence quantum yield for RosCat1. The coordination chemistry of these ligands with a Fe(III) center has been rationalized by mass-spectrometric analysis and semiempirical calculations. Octahedral Fe(III) complexes were obtained by the chelation of three RosCat1 or RosCat2 ligands. Interestingly, the unconventional amide connectivity in RosCat1 imposes the formation of an eight-membered ring on the chelate complex through a "salicylate-type" mode of coordination. PMID:26493881

  12. A new ion-selective electrode based on aluminium tungstate for Fe(III) determination in rock sample, pharmaceutical sample and water sample

    Indian Academy of Sciences (India)

    Mu Naushad

    2008-12-01

    An inorganic cation exchanger, aluminum tungstate (AT), has been synthesized by adding 0.1 M sodium tungstate gradually into 0.1 M aluminium nitrate at pH 1.2 with continuous stirring. The ion exchange capacity for Na+ ion and distribution coefficients of various metal ions was determined on the column of aluminium tungstate. The distribution studies of various metal ions showed the selectivity of Fe(III) ions by this cation exchange material. So, a Fe(III) ion-selective membrane electrode was prepared by using this cation exchange material as an electroactive material. The effect of plasticizers viz. dibutyl phthalate (DBP), dioctylphthalate (DOP), di-(butyl) butyl phosphate (DBBP) and tris-(2-ethylhexylphosphate) (TEHP), has also been studied on the performance of membrane sensor. It was observed that the membrane containing the composition AT: PVC: DBP in the ratio 2 : 20 : 15 displayed a useful analytical response with excellent reproducibility, low detection limit, wide working pH range (1–3.5), quick response time (15 s) and applicability over a wide concentration range of Fe(III) ions from 1 × 10-7 M to 1 × 10-1 M with a slope of 20 ± 1 mV per decade. The selectivity coefficients were determined by the mixed solution method and revealed that the electrode was selective for Fe(III) ions in the presence of interfering ions. The electrode was used for atleast 5 months without any considerable divergence in response characteristics. The constructed sensor was used as indicator electrode in the potentiometric titration of Fe(III) ions against EDTA and Fe(III) determination in rock sample, pharmaceutical sample and water sample. The results are found to be in good agreement with those obtained by using conventional methods.

  13. Complex Formation in a Liquid-Liquid Extraction System Containing Co(II), 4-(2-Thiazolylazo)resorcinol and Monotetrazolium Salt.

    Science.gov (United States)

    Divarova, Vidka; Stojnova, Kirila; Racheva, Petya; Lekova, Vanya

    2016-01-01

    The ion-associated complex formed between anionic chelate of Co(II)-4-(2-Thiazolylazo)resorcinol (TAR) with the monotetrazolium cation of 2-(4-Iodophenyl)-3-(4-nitrophenyl)-5-phenyl-2H-tetrazolium chloride (INT) in the liquid-liquid extraction system Co(II)-TAR-INT-H(2)O-CHCl(3) was studied by the spectrophotometric method. The optimum extraction conditions of Co(II) were found. The extraction equilibria were studied. The equilibrium constants, the recovery factor and some analytical characteristics were calculated. The validity of Beer's law was checked. The molar ratio of the components in the ternary ion-associated complex Co(II)-TAR-INT was determined. The general formula of the complex was suggested. The effect of various foreign ions and reagents on the process of complex formation in the liquid-liquid extraction system was studied. PMID:26970793

  14. Preparation and reactivity of metal-containing monomers. Communication 3. Radiation graft polymerization of Co(II), Ni(II), and Cu(II) acrylates on polyethylene

    International Nuclear Information System (INIS)

    Graft polymerization of Co(II), Ni(II), and Cu(II) acrylates was carried out on polyethylene powder subjected to prior irradiation in the air and graft copolymers were obtained with up to 1.4 mass % metal content. The graft polymerization of metal acrylates on polyethylene proceeds 10 times more slowly than in the case of acrylic acid with virtually the complete absence of thermal homopolymerization. The graft rate is independent of the concentration of the metal-containing monomer in the range from 1 to 10 mass %. The graft polymerization of acrylates is initiated by radicals formed as a result of the decomposition of the hydroperoxide groups with subsequent predominantly bimolecular termination of the growing polymer chains in the case of Co(II) and Ni(II) acrylates and monomolecular termination in the case of Cu(II) acrylate. The effective activation energies for the graft polymerization reactions were determined

  15. Spectral studies on Co(II), Ni(II) and Cu(II) complexes with thiosemicarbazone (L 1) and semicarbazone (L 2) derived from 2-acetyl furan

    Science.gov (United States)

    Chandra, Sulekh; Kumar, Anil

    2007-04-01

    Co(II), Ni(II) and Cu(II) complexes are synthesized with thiosemicarbazone (L 1) and semicarbazone (L 2) derived from 2-acetyl furan. These complexes are characterized by elemental analysis, molar conductance, magnetic susceptibility measurements, mass, IR, electronic and EPR spectral studies. The molar conductance measurements of the complexes in DMSO correspond to non-electrolytic nature except Ni(L) 2(NO 3) 2, which is 1:2 electrolyte. All the complexes are of high-spin type. On the basis of spectral studies an octahedral geometry may be assigned for Co(II) and Ni(II) complexes except nitrato complexes of Ni(II) which is of tetrahedral geometry, whereas tetragonal geometry for Cu(II) complexes.

  16. Spectral, IR and magnetic studies of Mn(II), Co(II), Ni(II) and Cu(II) complexes with pyrrole-2-carboxyaldehyde thiosemicarbazone (L)

    Science.gov (United States)

    Chandra, Sulekh; Kumar, Anil

    2007-11-01

    Mn(II), Co(II), Ni(II) and Cu(II) complexes are synthesized with thiosemicarbazone (L) derived from pyrrole-2-carboxyaldehyde. These complexes are characterized by elemental analysis, molar conductance, magnetic susceptibility measurement, mass, IR, electronic and EPR spectral studies. The molar conductance measurement of the complexes in DMSO indicates that the complexes are non-electrolyte except Co(L) 2(NO 3) 2 and Ni(L) 2(NO 3) 2 complexes which are 1:2 electrolyte. All the complexes are of high-spin type. On the basis of spectral studies an octahedral geometry may be assigned for Mn(II), Co(II) and Ni(II) complexes except Co(L) 2(NO 3) 2 and Ni(L) 2(NO 3) 2 which are of tetrahedral geometry. A tetragonal geometry may be suggested for Cu(II) complexes.

  17. Spectrophotometric study of Co(II, Ni(II, Cu(II, Zn(II, Pd(II and Hg(II complexes with isatin- β-thiosemicarbazone

    Directory of Open Access Journals (Sweden)

    SANDRA S. KONSTANTINOVIC

    2007-10-01

    Full Text Available The composition and stability of the complexes of isatin-b-thiosemicarba­zone with Co(II, Ni(II, Cu(II, Zn(II, Pd(II and Hg(II have been investigated us­ing spectrophotometric method at 30 °C and constant ionic strength of 0.1 mol dm-3 (KNO3 in 70 % ethanol. Experimental results indicate the formation of MeL and MeL2 complexes for Ni(II and Co(II, and MeL for Cu(II, Zn(II, Pd(II and Hg(II complexes, whose stability constants, bn, have been calculated using a com­puteri­zed iterative method of successive approximation.

  18. Removal of Co(II, Cu(II and Pb(II ions by polymer based 2-hydroxyethyl methacrylate: thermodynamics and desorption studies

    Directory of Open Access Journals (Sweden)

    Moradi Omid

    2012-12-01

    Full Text Available Abstract Removal thermodynamics and desorption studies of some heavy metal ions such as Co(II, Cu(II and Pb(II by polymeric surfaces such as poly 2-hydroxyethyl methacrylate (PHEMA and copolymer 2-hydroxyethyl methacrylate with monomer methyl methacrylate P(MMA-HEMA as adsorbent surfaces from aqueous single solution were investigated with respect to the changes in pH of solution, adsorbent composition, contact time and temperature in the individual aqueous solution. The linear correlation coefficients of Langmuir and Freundlich isotherms were obtained and the results revealed that the Langmuir isotherm fitted the experiment results better than Freundlich isotherm. Using the Langmuir model equation, the monolayer removal capacity of PHEMA surface was found to be 0.7388, 0.8396 and 3.0367 mg/g for Co(II, Cu(ΙΙ and Pb(II ions and removal capacity of P(MMA-HEMA was found to be 28.8442, 31.1526 and 31.4465 mg/g for Co(II, Cu(ΙΙ and Pb(II ions, respectively. Changes in the standard Gibbs free energy (ΔG0, standard enthalpy (ΔH0 and standard entropy (ΔS0 showed that the removals of mentioned ions onto PHEMA and P(MMA-HEMA are spontaneous and exothermic at 293–323 K. The maximum desorption efficiency was 75.26% for Pb(II using 0.100 M HNO3, 70.10% for Cu(II using 0.100 M HCl, 59.20% for 0.100 M HCl 63.67% Co(II.

  19. Removal of Co(II, Cu(II and Pb(II Ions by Polymer Based 2-Hydroxyethyl Methacrylate:Thermodynamics and Desorption Studies

    Directory of Open Access Journals (Sweden)

    Omid Moradi

    2012-12-01

    Full Text Available Removal thermodynamics and desorption studies of some heavy metal ions such as Co(II, Cu(II and Pb(II by polymeric surfaces such as poly 2-hydroxyethyl methacrylate (PHEMA and copolymer 2-hydroxyethyl methacrylate with monomer methyl methacrylate P(MMA-HEMA as adsorbent surfaces from aqueous single solution were investigated with respect to the changes in pH of solution, adsorbent composition, contact time and temperature in the individual aqueous solution. The linear correlation coefficients of Langmuir and Freundlich isotherms wereobtained and the results revealed that the Langmuir isotherm fitted the experiment results better than Freundlichisotherm. Using the Langmuir model equation, the monolayer removal capacity of PHEMA surface was found to be0.7388, 0.8396 and 3.0367 mg/g for Co(II, Cu(ΙΙ and Pb(II ions and removal capacity of P(MMA-HEMA was found to be 28.8442, 31.1526 and 31.4465 mg/g for Co(II, Cu(ΙΙ and Pb(II ions, respectively. Changes in the standard Gibbs free energy (ΔG0, standard enthalpy (ΔH0 and standard entropy (ΔS0 showed that the removals of mentioned ions onto PHEMA and P(MMA-HEMA are spontaneous and exothermic at 293–323 K. The maximum desorption efficiency was 75.26% for Pb(II using 0.100 M HNO3, 70.10% for Cu(II using 0.100 M HCl, 59.20% for 0.100 M HCl 63.67% Co(II.

  20. Physicochemical properties of 3,4,5-trimethoxybenzoates of Mn(II, Co(II, Ni(II and Zn(II

    Directory of Open Access Journals (Sweden)

    W. FERENC

    2005-09-01

    Full Text Available The complexes of Mn(II, Co(II, Ni(II, Cu(II and Zn(II with 3,4,5-trimethoxybenzoic acid anion of the formula: M(C10H11O52·nH2O, where n = 6 for Ni(II, n = 1 for Mn(II, Co(II, Cu(II, and n = 0 for Zn, have been synthesized and characterized by elemental analysis, IR spectroscopy, X–ray diffraction measurements, thermogravimetry and magnetic studies. They are crystalline compounds characterized by various symmetry. They decompose in various ways when heated in air to 1273 K. At first, they dehydrate in one step and form anhydrous salts. The final products of decomposition are oxides of the respective metals (Mn2O3, Co3O4, NiO, CuO, ZnO. The solubilities of the analysed complexes in water at 293 K are in the orders of 10-2 – 10-4 mol dm-3. The magnetic susceptibilities of the Mn(II, Co(II, Ni(II and Cu(II complexes were measured over the range of 76–303 K and the magnetic moments were calculated. The results show that the 3,4,5-trimethoxybenzoates of Mn(II, Co(II and Ni(II are high-spin complexes but that of Cu(II forms a dimer [Cu2(C10H11O54(H2O2]. The carboxylate groups bind as monodentate or bidentate chelating or bridging ligands.

  1. Biosorption of Ni(II), Cr(III), and Co(II) from Solutions Using Acalypha hispida Leaf: Kinetics, Equilibrium, and Thermodynamics

    OpenAIRE

    Adesola Babarinde; J. Oyebamiji Babalola; John Adegoke; Osundeko, Adebola O.; Susan Olasehinde; Adetayo Omodehin; Emmanuel Nurhe

    2013-01-01

    Biosorption studies were conducted to study the removal of Ni(II), Cr(III), and Co(II) from aqueous solution of Acalypha hispida leaf. The FTIR spectral characteristics of Acalypha hispida leaf revealed the presence of ioniazable groups that could participate in the binding of metal ions in solution. The kinetic, equilibrium, and thermodynamic studies of the biosorption of the metal ions were investigated using various physicochemical parameters; each parameter was found to affect the biosorp...

  2. Evaluation of the mtDNA-COII Region Based Species Specific Assay for Identifying Members of the Anopheles culicifacies Species Complex.

    Directory of Open Access Journals (Sweden)

    Arulsamy Mary Manonmani

    2013-12-01

    Full Text Available Anopheles culicifacies, a major malarial vector has been recognized as a complex of five sibling species, A, B, C, D and E. These sibling species exhibit varied vectorial capacity, host specificity and susceptibility to malarial parasites/ insecticides. In this study, a PCR assay developed earlier for distinguishing the five individual species was validated on samples of An. culicifacies collected from various parts of India.The samples were initially screened using the rDNA-ITS2 region based primers which categorised the samples into either A/D group or B/C/E group. A proportion of samples belonging to each group were subjected to the mtDNA-COII PCR assay for identifying individual species.Among the 615 samples analysed by rDNA-ITS2 PCR assay, 303 were found to belong to A/D group and 299 to B/C/E group while 13 turned negative. Among 163 samples belonging to A/D group, only one sample displayed the profile characteristic of species A and among the 176 samples falling in the B/C/E group, 51 were identified as species B, 14 as species C and 41 as species E respectively by the mtDNA-COII PCR assay. Samples exhibiting products diagnostic of B/C/E, when subjected to PCR-RFLP assay identified 15 samples as species E.Validation of the mtDNA-COII PCR assay on large number of samples showed that this technique cannot be used universally to distinguish the 5 members of this species complex, as it has been designed based on minor/single base differences observed in the COII region.

  3. Potentiometric study of atenolol as hypertension drug with Co(II, Ni(II, Cu(II and Zn(II transition metal ions in aqueous solution

    Directory of Open Access Journals (Sweden)

    Abdulbaset A. Zaid

    2015-01-01

    Full Text Available Binary and ternary complexes of Co(II, Ni(II, Cu(II and Zn(II with atenolol as hypertension drug and glycine have been determined pH metrically at room temperature and 0.01 M ionic strength (NaClO4 in aqueous solution. The formation of various possible species has been evaluated by computer program and discussed in terms of various relative stability parameters.

  4. Positional isomeric tunable two Co(II) 6-connected 3-D frameworks with pentanuclear to binuclear units: structures, ion-exchange and magnetic properties.

    Science.gov (United States)

    Han, Min-Le; Duan, Ya-Ping; Li, Dong-Sheng; Wang, Hai-Bin; Zhao, Jun; Wang, Yao-Yu

    2014-11-01

    Two new Co(II) based metal-organic frameworks, namely {[Co5(μ3-OH)2(m-pda)3(bix)4]·2ClO4}n (1) and {[Co2(p-pda)2(bix)2(H2O)]·H2O}n (2), were prepared by hydrothermal reactions of Co(II) salt with two isomeric dicarboxyl tectons 1,3-phenylenediacetic acid (m-pda) and 1,4-phenylenediacetic acid (p-pda), along with 1,3-bis(imidazol-L-ylmethyl)benzene (bix). Both complexes 1 and 2 have been characterized by elemental analysis, IR spectroscopy, single-crystal X-ray diffraction, powder X-ray diffraction (PXRD), and thermogravimetric analysis (TGA). 1 shows a 6-connected 3-D pcu cationic framework with pentanuclear [Co5(μ3-OH)2(COO)6(bix)2](2+) units, while 2 exhibits a 6-connected 3-D msw net based on [Co2(μ2-H2O)(COO)2](2+) clusters. The results indicate that the different dispositions of the carboxylic groups of dicarboxylates have an important effect on the overall coordination frameworks. Perchlorate anions in 1 can be partly exchanged by thiocyanate and azide anions, however they are unavailable to nitrate anions. Magnetic susceptibility measurements indicate that both 1 and 2 show weak antiferromagnetic interactions between the adjacent Co(II) ions. PMID:25190003

  5. Preparation of cross-linked magnetic chitosan-phenylthiourea resin for adsorption of Hg(II), Cd(II) and Zn(II) ions from aqueous solutions

    Energy Technology Data Exchange (ETDEWEB)

    Monier, M., E-mail: monierchem@yahoo.com [Chemistry Department, Faculty of Science, Mansoura University, Mansoura (Egypt); Abdel-Latif, D.A. [Chemistry Department, Faculty of Science, Mansoura University, Mansoura (Egypt)

    2012-03-30

    Highlights: Black-Right-Pointing-Pointer Chitosan was chemically modified through the reaction with phenylisothiocyanate. Black-Right-Pointing-Pointer The modified chitosan-phenylthiourea cross-linked with formaldehyde in presence of magnetite to produce modified magnetic resin. Black-Right-Pointing-Pointer The resulted resin characterized by various instrumental methods. Black-Right-Pointing-Pointer The resin was applied to remove Hg{sup 2+}, Cd{sup 2+} and Zn{sup 2+} from aqueous solutions. - Abstract: In this study, cross-linked magnetic chitosan-phenylthiourea (CSTU) resin were prepared and characterized by means of FTIR, {sup 1}H NMR, SEM high-angle X-ray diffraction (XRD), magnetic properties and thermogravimetric analysis (TGA). The prepared resin were used to investigate the adsorption properties of Hg(II), Cd(II) and Zn(II) metal ions in an aqueous solution. The extent of adsorption was investigated as a function of pH and the metal ion removal reached maximum at pH 5.0. Also, the kinetic and thermodynamic parameters of the adsorption process were estimated. These data indicated that the adsorption process is exothermic and followed the pseudo-second-order kinetics. Equilibrium studies showed that the data of Hg(II), Cd(II) and Zn(II) adsorption followed the Langmuir model. The maximum adsorption capacities for Hg(II), Cd(II) and Zn(II) were estimated to be 135 {+-} 3, 120 {+-} 1 and 52 {+-} 1 mg/g, which demonstrated the high adsorption efficiency of CSTU toward the studied metal ions.

  6. The influence of the length and position of alkyl group for the stability of alkylimidazole complexes with Cu(II) and Cd(II)

    International Nuclear Information System (INIS)

    By the liquid - liquid partition method the stability constants of the Cu(II) and Cd(II) complexes with 1-alkyl-imidazoles and 1-alkyl-2-methyl-imidazoles (where alkyl = methyl up to decyl) in aqueous solution have been determined. The measurements were run at 298 K and at a constant ionic strength of the aqueous phase. By the trial-and-error method two to five solvents were tested for each complex out of the following ones: dichloromethane, chloroform, 1,2-dichloroethane, 2-butanol, cyclohexanol, 2-ethyl-1-hexanol, benzyl alcohol, 2-pentanone, 3-methyl-2-butanone, benzene and toluene. Then using atomic absorption spectroscopy or EDTA titration, the concentration of the Cu(II) ion in aqueous phase has been determined. In the case of Cd(II) the aqueous phase was spiked with the 117Cd radionuclide in the form CdCl2 at a concentration of ca 10-5 M. After attaining equilibrium, emission of the β radiation was measured in both phases. Extraction coefficients DM of Cd(II) was obtained from the radiochemical experiments, and for Cu(II) from analytical measurements. In all the systems studied extraction curves (log D vs. pH) have been drawn. For Cu(II) complexes absorption spectra of the organic phase for different pH of the corresponding aqueous phases were taken. The values of the stability constants βn of the investigated complexes were calculated. Log β1 as a function of the number of carbon atoms in the alkyl substituent was investigated for both homologous series of the alkyl-imidazoles. (authors)

  7. A novel sensitive Cu(II) and Cd(II) nanosensor platform: Graphene oxide terminated p-aminophenyl modified glassy carbon surface

    International Nuclear Information System (INIS)

    Graphical abstract: - Highlights: • We electrochemically prepared sensor based on graphene oxide. • The prepared electrode was characterized by using various techniques. • The proposed nanosensor showed good stability, selectivity and high sensitivity. • The proposed nanosensor electrode was used for the analysis of Cd(II) and Cu(II). - Abstract: Graphene oxide (GO) based glassy carbon (GC) electrode has been prepared. Firstly, p-nitrophenyl (NP) modified GC (NP/GC) electrode was prepared via the electrochemical reduction of its tetraflouroborate diazonium salt. After the formation of NP/GC electrode, the negative potential was applied to NP/GC electrode to reduce the nitro groups to amine. p-Aminophenyl (AP) modified GC (AP/GC) electrode was immersed into a graphene oxide solution containing 1-ethyl-3(3-(dimethlyamino)propyl)-carbodiimide. Hence, we constructed GO terminated AP modified GC (GO/AP/GC) electrode. NP/GC, AP/GC and GO/AP/GC electrodes were characterized sequentially using cyclic voltammetry (CV) in the presence of 1.0 mM of potassium ferricyanide in 0.1 M KCl. In addition, GO and GO/AP/GC surfaces were characterized by transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). The GO/AP/GC electrode was used for the analysis of Cd(II) and Cu(II) ions by adsorptive stripping voltammetry. The linearity range and the detection limit of Cd(II) and Cu(II) ions were 1.0 × 10−11–5.0 × 10−10 M and 3.3 × 10−12 M (S/N = 3), respectively

  8. Cellulose microfiber functionalized with N,N'-bis (2-aminoethyl)-1,2-ethanediamine as a solid sorbent for the fast preconcentration of Cd(II) in flow system analysis.

    Science.gov (United States)

    de Oliveira, Fernanda Midori; Somera, Bruna Fabrin; Corazza, Marcela Zanetti; Yabe, Maria Josefa Santos; Segatelli, Mariana Gava; Ribeiro, Emerson Schwingel; Lima, Eder Cláudio; Dias, Silvio Luís Pereira; Tarley, César Ricardo Teixeira

    2011-10-15

    The present paper describes the synthesis of a new chemically modified cellulose microfiber through oxidation with sodium periodate and functionalization with N,N'-bis (2-aminoethyl)-1,2-ethanediamine for the fast and selective preconcentration of Cd(II) ions in flow system analysis. The new sorbent was characterized by FTIR, SEM, and surface area values. The uptake behavior of Cd(II) ions onto this sorbent was evaluated from kinetic data, pseudo-first-order and pseudo-second-order models, as well as from Langmuir, Freundlich and Langmuir-Freundlich adsorption isotherms. The maximum sorption capacity of 4.59 mg g(-1) was estimated by the Langmuir-Freundlich model with fast kinetics for the sorption of Cd(II) described by the pseudo-second-order kinetic model. After characterization, the sorbent was packed in a mini-column, and a fast flow injection preconcentration system for Cd(II) determination by FAAS was developed. The best Cd(II) preconcentration condition, obtained by means of factorial design and response surface methodology, was achieved at pH 9.36 and a flow rate of 10 mL min(-1) followed by elution with 1.0 mol L(-1) nitric acid. By using 78 s preconcentration time, fast and highly sensitive determination of Cd(II) ions could be achieved with a limit of quantification of 0.20 μg L(-1), preconcentration factor of 26, consumption index of 0.5 mL, concentration efficiency of 20 min(-1), and sample throughput of 39 h(-1). The repeatability for 10 replicate determinations was found to be 7.8 and 2.5% for Cd(II) ion concentrations of 5.0 and 100.0 μg L(-1), respectively. The new sorbent efficiency for the interference-free preconcentration of Cd(II) ions was assessed by analysis of tap, mineral and lake waters, as well as synthetic seawater and normal saline waters. Furthermore, complex samples, such as biological samples, could be analysed by the proposed method in accordance with the accuracy attested by analysis of certified reference materials, TORT-2

  9. Uranium(VI) reduction by nanoscale zero-valent iron in anoxic batch systems: The role of Fe(II) and Fe(III)

    Energy Technology Data Exchange (ETDEWEB)

    Yan, Sen; Chen, Yongheng; Xiang, Wu; Bao, Zhengyu; Liu, Chongxuan; Deng, Baolin

    2014-12-01

    The role of Fe(II) and Fe(III) on U(VI) reduction by nanoscale zerovalent iron (nanoFe0) was investigated using two iron chelators 1,10-phenanthroline and triethanolamine (TEA) under a CO2-free anoxic condition. The results showed U(VI) reduction was strongly inhibited by 1,10-phenanthroline and TEA in a pH range from 6.92 to 9.03. For instance, at pH 6.92 the observed U(VI) reduction rates decreased by 80.7% and 82.3% in the presence of 1,10-phenanthroline and TEA, respectively. The inhibition was attributed to the formation of stable complexes between 1,10-phenanthroline and Fe(II) or TEA and Fe(III). In the absence of iron chelators, U(VI) reduction can be enhanced by surface-bound Fe(II) on nanoFe0. Our results suggested that Fe(III) and Fe(II) probably acted as an electron shuttle to mediate the transfer of electrons from nanoFe0 to U(VI), therefore a combined system with Fe(II), Fe(III) and nanoFe0 can facilitate the U(VI) reductive immobilization in the contaminated groundwater.

  10. Sorption of Ni(II), Cu(II) and Fe(III) ions from Aqueous Solutions Using Activated Carbon

    International Nuclear Information System (INIS)

    An activated carbon was tested for its ability to remove transition metal ions from aqueous solutions. Physical, chemical and liquid-phase adsorption characterizations of the carbon were done following standard procedures. Studies on the removal of Ni(II), Cu(II) and Fe(III) ions were attempted by varying adsorbate dose, pH of the metal ion solution and time in batch mode. The equilibrium adsorption data were fitted with Freundlich and Langmuir and the isotherm constants were evaluated, equilibrium time of the different three metal ions were determined. pH was found to have a significant role to play in the adsorption. The processes were endothermic and the thermodynamic parameters were evaluated. Desorption studies indicate that ion-exchange mechanism is operating

  11. Methane Suppression: The Impacts of Fe(III) and Humic Acids on Net Methane Flux from Arctic Tundra Wetlands in Alaska and Finland (Invited)

    Science.gov (United States)

    Lipson, D.; Miller, K.; Lai, C.

    2013-12-01

    Arctic soils contain large reservoirs of carbon (C) that are vulnerable to loss from climatic warming. However the potential global impacts of this C depend on whether it is lost primarily in the form of methane (CH4) or carbon dioxide (CO2), two gases with very different greenhouse warming potentials. In anaerobic environments, the relative production of CH4 vs. CO2 may be controlled by the presence of alternative terminal electron acceptors, which allow more thermodynamically favorable anaerobic respiratory pathways to dominate over methanogenesis. This work investigated how the addition of terminal electron acceptors, ferric iron (Fe(III)) and humic acids, affected net CH4 fluxes from high-latitude wetland ecosystems. We conducted two manipulative field experiments in Barrow, Alaska (71° N) and Finnish Lapland (69° N). The ecosystem in Barrow was known from previous studies to be rich in Fe(III) and to harbor a microbial community that is dominated by Fe(III)- and humic acid-reducing microorganisms. The role of these alternative electron acceptors had not previously been studied at the Finnish site. CH4 and CO2 fluxes were measured using a portable trace gas analyzer from experimental plots, before and after amendments with Fe(III) (in the chelated form, ferric nitrilotriacetic acid), humic acids, or water as a control. Both in the ecosystem with permafrost and naturally high levels of soil Fe (Barrow, AK) and in the ecosystem with no permafrost and naturally low levels of soil Fe (Petsikko, Finland), the addition of the alternative electron acceptors Fe(III) and humic acids significantly reduced net CH4 flux. CO2 fluxes were not significantly altered by the treatments. The reduction in CH4 flux persisted for at least several weeks post-treatment. There was no significant difference between the reduction caused by humic acids versus that from Fe(III). These results show that the suppression of CH4 flux by Fe(III) and humic acids is a widespread phenomenon that

  12. Adsorption of Cu(II), Cd(II) and Ni(II) ions by cross-linked magnetic chitosan-2-aminopyridine glyoxal Schiff's base.

    Science.gov (United States)

    Monier, M; Ayad, D M; Abdel-Latif, D A

    2012-06-01

    The adsorption of Cu(II), Cd(II) and Ni(II) ions from aqueous solution by cross-linked magnetic chitosan-2-aminopyridine glyoxal Schiff's base resin (CSAP) was studied in a batch adsorption system. Cu(II), Cd(II) and Ni(II) removal is pH dependent and the optimum adsorption was observed at pH 5.0. The adsorption was fast with estimated initial rate of 2.7, 2.4 and 1.4 mg/(g min) for Cu(2+), Cd(2+) and Ni(2+) respectively. The adsorption data could be well interpreted by the Langmuir, Freundlich and Temkin model. The maximum adsorption capacities obtained from the Langmuir model were 124±1, 84±2 and 67±2 mg g(-1) for Cu(2+), Cd(2+) and Ni(2+) respectively. The adsorption process could be described by pseudo-second-order kinetic model. Thermodynamic parameters revealed the feasibility, spontaneity and exothermic nature of adsorption. The sorbents were successfully regenerated using EDTA and HCl solutions. PMID:22386793

  13. Isolation and preconcentration of Cd(II) from environmental samples using polypropylene porous membrane in a hollow fiber renewal liquid membrane extraction procedure and determination by FAAS

    International Nuclear Information System (INIS)

    The use of polypropylene porous membrane in a hollow fiber renewal liquid membrane (HFRLM) procedure for determination of Cd(II) in water samples was assessed. Ammonium O,O-diethyl dithiophosphate (DDTP) was used to complex cadmium (II) in an acid medium to obtain a neutral hydrophobic complex. The organic solvent introduced to the sample extracts this complex from the aqueous solution and carries it over the polypropylene membrane porous. The organic solvent is immobilized inside the polypropylene membrane porous, leading to an homogeneous phase. The complex strips the lumen of the membrane where, at higher pH, the complex Cd-DDTP is broken down and Cd(II) is released into the stripping phase. EDTA was used to complex the cadmium (II), helping to trap the analyte in the stripping phase. The optimized variables were: sample pH, DDTP concentration, stripping pH, EDTA concentration, extraction temperature and time, extractor solvent and addition of salt to saturate the sample. The sample volume used was 15 mL and the stripping volume was 165 μL. The analyte enrichment factor was 107, limit of detection 1.5 μg L-1, relative standard deviation 4.0% (15 μg L-1, n = 7) and the working linear range 5-30 μg L-1.

  14. A versatile and highly sensitive probe for Hg(II), Pb(II) and Cd(II) detection individually and totally in water samples.

    Science.gov (United States)

    Zhou, Yu; Tian, Xiang-Li; Li, Yan-Song; Zhang, Yuan-Yuan; Yang, Li; Zhang, Jun-Hui; Wang, Xin-Rui; Lu, Shi-Ying; Ren, Hong-Lin; Liu, Zeng-Shan

    2011-12-15

    The detection of heavy metal ions using enzyme-linked immunosorbent assays (ELISA) has been reported by several research groups. However, highly sensitive and selective detection of total heavy metal ions using ELISA is a major technical limitation. Here we describe the development of a versatile and highly sensitive probe combining goat anti-mice IgG, colloidal gold nanoparticles (AuNPs) and horseradish peroxidase (HRP). We demonstrate the utility of this probe using three kinds of heavy metal complete antigens and three monoclonal antibodies (McAbs) in one ELISA system to establish a high-throughput screening protocol. The procedure was successfully applied to analysis of Hg(II), Pb(II) and Cd(II) individually and totally from different water samples. The sensitivities for the detection of Hg(II), Pb(II) and Cd(II) individually and totally are 27.4, 3.9, 15.8 and 18.2 nM, respectively. And all limit of detection (LODs) are lower than 1.2 nM. The recovery results obtained from the developed technique showed a good correlation (R(2)=0.983) with those from ICP-MS. The major advantage of the probe is the versatility and high sensibility. The probe could be potentially used, upon demand, as a sensitive and versatile detector for a broad range of applications. PMID:21975341

  15. Application of silica fume as a new SP-extractor for trace determination of Zn(II) and Cd(II) in pharmaceutical and environmental samples by square-wave anodic stripping voltammetry

    Science.gov (United States)

    Ahmed, Salwa A.; Gaber, Ahmed A. Abdel; Rahim, Asmaa M. Abdel

    2015-04-01

    In this work, silica fume (SF) is used as a solid-phase extractor for extraction of Zn(II) and Cd(II) from aqueous solutions. Characterization of SF is performed by Fourier transform infrared, X-ray diffraction, transmission and scanning electron microscopy. The optimum experimental conditions for the two metal ions are investigated using batch and column techniques. The maximum adsorption capacity values are found to be 54.13 and 121.28 mg g-1 at the optimum pH 6.0 and 8.0 for Zn(II) and Cd(II), respectively. The equilibrium data are analyzed using the Langmuir, Freundlich, and Temkin isotherms by nonlinear regression analysis. Also, the kinetics analysis revealed that the overall adsorption process is successfully fitted with the pseudo-second-order model. The method is applied for determination of the target metal ions in pharmaceutical and environmental samples using square-wave anodic stripping voltammetry. The limit of detection (LOD) values are 0.102 and 1.43 × 10-3 mg L-1 for Zn(II) and Cd(II), respectively. The percentage recovery values are 98.8-100.5 % which indicate the success of the proposed method for determination of Zn(II) and Cd(II) without interfering effects.

  16. Adsorption of Cd(II) by Mg-Al-CO3- and magnetic Fe3O4/Mg-Al-CO3-layered double hydroxides: Kinetic, isothermal, thermodynamic and mechanistic studies.

    Science.gov (United States)

    Shan, Ran-ran; Yan, Liang-guo; Yang, Kun; Hao, Yuan-feng; Du, Bin

    2015-12-15

    Understanding the adsorption mechanisms of metal cations on the surfaces of solids is important for determining the fate of these metals in water and wastewater treatment. The adsorption kinetic, isothermal, thermodynamic and mechanistic properties of cadmium (Cd(II)) in an aqueous solution containing Mg-Al-CO3- and magnetic Fe3O4/Mg-Al-CO3-layered double hydroxide (LDH) were studied. The results demonstrated that the adsorption kinetic and isotherm data followed the pseudo-second-order model and the Langmuir equation, respectively. The adsorption process of Cd(II) was feasible, spontaneous and endothermic in nature. X-ray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopy were used to explain the adsorption mechanisms. The characteristic XRD peaks and FTIR bands of CdCO3 emerged in the LDH spectra after Cd(II) adsorption, which indicated that the adsorption of Cd(II) by LDHs occurred mainly via CdCO3 precipitation, surface adsorption and surface complexation. Furthermore, the magnetic Fe3O4/Mg-Al-CO3-LDH can be quickly and easily separated using a magnet before and after the adsorption process. PMID:26073520

  17. Fe(II) Sorption On Pyrophyllite: Effect Of Structural Fe(III) (impurity) In Pyrophyllite On Nature Of Layered Double Hydroxide (LDH) Secondary Mineral Formation

    Energy Technology Data Exchange (ETDEWEB)

    Starcher, Autumn N.; Li, Wei; Kukkadapu, Ravi K.; Elzinga, E. J.; Sparks, Donald L.

    2016-06-18

    Fe(II)-Al(III)-LDH (layered double hydroxide) phases have been shown to form from reactions of aqueous Fe(II) with Fe-free Al-bearing minerals (phyllosilicate/clays and Al-oxides). To our knowledge, the effect of small amounts of structural Fe(III) impurities in “neutral” clays on such reactions, however, were not studied. In this study to understand the role of structural Fe(III) impurity in clays, laboratory batch studies with pyrophyllite (10 g/L), an Al-bearing phyllosilicate, containing small amounts of structural Fe(III) impurities and 0.8 mM and 3 mM Fe(II) (both natural and enriched in 57Fe) were carried out at pH 7.5 under anaerobic conditions (4% H2 – 96% N2 atmosphere). Samples were taken up to 4 weeks for analysis by Fe-X-ray absorption spectroscopy and 57Fe Mössbauer spectroscopy. In addition to the precipitation of Fe(II)-Al(III)-LDH phases as observed in earlier studies with pure minerals (no Fe(III) impurities in the minerals), the analyses indicated formation of small amounts of Fe(III) containing solid(s), most probably hybrid a Fe(II)-Al(III)/Fe(III)-LDH phase. The mechanism of Fe(II) oxidation was not apparent but most likely was due to interfacial electron transfer from the sorbed Fe(II) to the structural Fe(III) and/or surface-sorption-induced electron-transfer from the sorbed Fe(II) to the clay lattice. Increase in the Fe(II)/Al ratio of the LDH with reaction time further indicated the complex nature of the samples. This research provides evidence for the formation of both Fe(II)-Al(III)-LDH and Fe(II)-Fe(III)/Al(III)-LDH-like phases during reactions of Fe(II) in systems that mimic the natural environments. Better understanding Fe phase formation in complex laboratory studies will improve models of natural redox systems.

  18. Solvent-templated supramolecular isomerism in 2D coordination polymer constructed by Ni(II)2Co(II) nodes and dicyanamido spacers: drastic change in magnetic behaviours.

    Science.gov (United States)

    Ghosh, Soumavo; Mukherjee, Sandip; Seth, Piya; Mukherjee, Partha Sarathi; Ghosh, Ashutosh

    2013-10-01

    Two heterometallic coordination polymers (CPs) have been prepared using [Ni(II)L]2Co(II) (where H2L = N,N'-bis(salicylidene)-1,3-propanediamine) as nodes and dicyanamido spacers by varying the solvent for synthesis. Structural characterizations revealed that methanol assisted the formation of a two-dimensional (4,4) connected rhombic grid network of [(NiL)2Co(NCNCN)2]∞ (1a) whereas relatively less polar acetonitrile afforded a different superstructure {[(NiL)2Co(NCNCN)2]·CH3CN}∞ (1b) with a two-dimensional (4,4) connected square grid network. The presence of acetonitrile molecules in the structure of 1b seems to change the spatial orientation of the terminal metalloligands [NiL] from pseudo-eclipsed in 1a to staggered-like in 1b around the central Co(II). These structural changes in the nodes together with the conformationally flexible dicyanamido spacers, which are cis coordinated to the Co(II) in both trinuclear units, led to the differences in the final 2D network. Variable-temperature magnetic susceptibility measurements revealed that this supramolecular isomerism led to a drastic transition from spin-frustrated antiferromagnetism for 1a to a dominant ferromagnetic behaviour for 1b. The geometrical differences in Ni2Co coordination clusters (CCs) which are scalene triangular in 1a but nearly linear in 1b, are held responsible for the changes of the magnetic properties. The DFT calculations of exchange interactions between metal centres provide a clear evidence of the role played by the fundamental geometrical factors on the nature and magnitude of the magnetic coupling in these pseudo-polymorphic CPs. PMID:23900267

  19. Adsorption studies of Cd(II) onto Al2O3/Nb2O5 mixed oxide dispersed on silica matrix and its on-line preconcentration and determination by flame atomic absorption spectrometry

    International Nuclear Information System (INIS)

    The present study describes the adsorption characteristic of Cd(II) onto Nb2O5/Al2O3 mixed oxide dispersed on silica matrix. The characterization of the adsorbent has been carried out by infrared spectroscopy (IR), scanning electronic microscopy (SEM), energy dispersive spectroscopy (EDS), energy dispersive X-ray fluorescence analysis (EDXRF) and specific surface area (SBET). From batch experiments, adsorption kinetic of Cd(II) was described by a pseudo-second-order kinetic model. The Langmuir linear isotherm fitted to the experimental adsorption isotherm very well, and the maximum adsorption capacity was found to be 17.88 mg g-1. Using the effective material, a method for Cd(II) preconcentration at trace level was developed. The method was based on on-line adsorption of Cd(II) onto SiO2/Al2O3/Nb2O5 at pH 8.64, in which the quantitative desorption occurs with 1.0 mol L-1 hydrochloric acid towards FAAS detector. The experimental parameters related to the system were studied by means of multivariate analysis, using 24 full factorial design and Doehlert matrix. The effect of SO42-, Cu2+, Zn2+ and Ni2+ foreign ions showed no interference at 1:100 analyte:interferent proportion. Under the most favorable experimental conditions, the preconcentration system provided a preconcentration factor of 18.4 times, consumption index of 1.08 mL, sample throughput of 14 h-1, concentration efficiency of 4.35 min-1, linear range from 5.0 up to 35.0 μg L-1 and limits of detection and quantification of 0.19 and 0.65 μg L-1 respectively. The feasibility of the proposed method for Cd(II) determination was assessed by analysis of water samples, cigarette sample and certified reference materials TORT-2 (Lobster hepatopancreas) and DOLT-4 (Dogfish liver).

  20. Synthesis, spectral studies and biological evaluation of 2-aminonicotinic acid metal complexes

    Science.gov (United States)

    Nawaz, Muhammad; Abbasi, Muhammad Waseem; Hisaindee, Soleiman; Zaki, Muhammad Javed; Abbas, Hira Fatima; Mengting, Hu; Ahmed, M. Arif

    2016-05-01

    We synthesized 2-aminonicotinic acid (2-ANA) complexes with metals such as Co(II), Fe(III), Ni(II), Mn(II), Zn(II), Ag(I),Cr(III), Cd(II) and Cu(II) in aqueous media. The complexes were characterized and elucidated using FT-IR, UV-Vis, a fluorescence spectrophotometer and thermo gravimetric analysis (TGA). TGA data showed that the stoichiometry of complexes was 1:2 metal/ligand except for Ag(I) and Mn(II) where the ratio was 1:1. The metal complexes showed varied antibacterial, fungicidal and nematicidal activities. The silver and zinc complexes showed highest activity against Bacillus subtilis and Bacillus licheniformis respectively. Fusarium oxysporum was highly susceptible to nickel and copper complexes whereas Macrophomina phaseolina was completely inert to the complexes. The silver and cadmium complexes were effective against the root-knot nematode Meloidogyne javanica.

  1. Preparation, spectroscopic investigation and antiproliferative capacity of new metal complexes of (3E)-2-(hydroxyimino)-N-P-Tolyl-3-(P-tolylimino) butanamide

    Science.gov (United States)

    El-Tabl, Abdou Saad; Abd El-wahed, Moshira Mohamed; Abd El-Razek, Samar Ebrahim

    2013-03-01

    Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Cd(II), Sr(II), Hg(II), Tl(I), UO2(II) and ZrO(II) complexes of (3E)-2-(hydroxyimino)-N-P-Tolyl-3-(P-tolylimino) butanamide have been prepared and characterized by elemental analyses, IR, UV-Vis spectra, magnetic moments, conductances, 1H NMR and mass spectra (ligand and its Zn(II) complex), thermal analyses (DTA and TGA) and ESR measurements. The IR data show that, the ligand behaves as monobasic bidentate or neutral bidentate. Molar conductances in DMF indicate that, the complexes are non-electrolytes. ESR spectra of solid Cu(II) complexes at room temperature show axial type (dx2-y2) with covalent bond character in an octahedral environment. Complexes showed inhibitory activity against hepatocellular carcinoma (HepG-2 cell line).

  2. Overall Water Splitting by Sono-Catalysis Using Homogeneous Catalysts of Fe(III) Compounds: Aim of Construction of a Photosynthesis-Like System under Sonication

    Science.gov (United States)

    Harada, Hisashi

    2002-05-01

    The decomposition of water was performed using a sono-catalytic reaction system, which is a joint system of sonochemical and catalytical reactions. By sono-catalysis, overall water splitting was accomplished through the combined effect of these reactions. Water-soluble ferric (Fe(III)) compounds, Pt-black, and metal oxides such as titanium oxide (TiO2) and iron oxide (Fe2O3) were used as catalysts. Homogeneous Fe(III) catalyst was effective for oxygen (O2) generation under sonication, particularly iron ammonium sulfate (iron alum, (FeNH4(SO4)2). Hydrogen (H2) was also evolved by sonication. Thus, overall water (H2O) splitting was accomplished using the sono-catalytic technique. Furthermore, a photosynthesis-like system under sonication is discussed.

  3. Study of Fe(III) adsorption onto Dowex-Marathon resin, as a rate determining step of the U(IV) oxidation in 235U enrichment column

    International Nuclear Information System (INIS)

    The Fe(III) adsorption onto Dowex-Marathon resin was well described by pseudo-second order kinetics with a high correlation factor for all the experimental concentrations. The results were analyzed by Langmuir, Freundlich and Dubinin-Radushkevich isotherm models. The activation energy Ea (7.96 ± 0.2 kJ/mol) indicates a physisorption process as in the case of U(VI) adsorption onto the same resin. The thermodynamic parameters: ΔG deg = (-7.91) / (-13.68) kJ/mol, ΔH deg = 35.60 ± 0.89 kJ/mol and ΔS deg = 143.31 ± 3.58 J/mol K, were determined, the Fe(III) adsorption being spontaneous and endothermic. (author)

  4. Amperometric determination of V(V), Cr(III), Mn(VII), Cr(VI) and Fe(III) with 3-mercaptopropanoic acid

    International Nuclear Information System (INIS)

    Amperometric determination of V(V), Cr(III), Mn(VII), Cr(VI) and Fe(III) is reported with the help of 3-mercaptopropanoic acid (MPSH). The fundamental reaction involved in case of the first two species is complexation while that in case of Mn(VII) is oxidation of MPSH; the last two species do not interact chemically with the acid and the new methods reported are based on the phenomenon of current compensation. Metal ion: MPSH ratio is 1:2 for V(V) and Cr(III), 1:4 for Cr(VI) and 1:0.66 for Fe(III); this ratio for Mn(VII) is 1:1 if the metal ion is used as titrant and 2:1 if MPSH is used in that capacity. Tolerance for diverse foreign ions has also been worked out. (author). 14 refs., 2 tabs

  5. Preparation and reactivity of metal-containing monomers. communication 4. Radiation-induced graft polymerization of acrylamide complexes of Co(II), Ni(II), and Cu(II) on Polyethylene

    International Nuclear Information System (INIS)

    This paper investigates the graft polymerization of MCM with donor-acceptor metal bonds, namely, acrylamide (AA) complexes of Co(II), Ni (II), and Cu(II), on preliminary gamma-irradiated polyethylene (PE) and compares the main parameters of the process with grafting of AA and other acrylic monomers. The initial rate of graft polymerization of the Co(II) and Ni(II) complexes depended linearly on the concentration of the metal-containing monomer in the solution and the concentration of hydroperoxy groups in irradiated polyethylene

  6. Theoretical Modeling of the Magnetic Behavior of Thiacalix[4]arene Tetranuclear Mn(II)2Gd(III)2 and Co(II)2Eu(III)2 Complexes.

    Science.gov (United States)

    Aldoshin, Sergey M; Sanina, Nataliya A; Palii, Andrew V; Tsukerblat, Boris S

    2016-04-01

    In view of a wide perspective of 3d-4f complexes in single-molecule magnetism, here we propose an explanation of the magnetic behavior of the two thiacalix[4]arene tetranuclear heterometallic complexes Mn(II)2Gd(III)2 and Co(II)2Eu(III)2. The energy pattern of the Mn(II)2Gd(III)2 complex evaluated in the framework of the isotropic exchange model exhibits a rotational band of the low-lying spin excitations within which the Landé intervals are affected by the biquadratic spin-spin interactions. The nonmonotonic temperature dependence of the χT product observed for the Mn(II)2Gd(III)2 complex is attributed to the competitive influence of the ferromagnetic Mn-Gd and antiferromagnetic Mn-Mn exchange interactions, the latter being stronger (J(Mn, Mn) = -1.6 cm(-1), Js(Mn, Gd) = 0.8 cm(-1), g = 1.97). The model for the Co(II)2Eu(III)2 complex includes uniaxial anisotropy of the seven-coordinate Co(II) ions and an isotropic exchange interaction in the Co(II)2 pair, while the Eu(III) ions are diamagnetic in their ground states. Best-fit analysis of χT versus T showed that the anisotropic contribution (arising from a large zero-field splitting in Co(II) ions) dominates (weak-exchange limit) in the Co(II)2Eu(III)2 complex (D = 20.5 cm(-1), J = -0.4 cm(-1), gCo = 2.22). This complex is concluded to exhibit an easy plane of magnetization (arising from the Co(II) pair). It is shown that the low-lying part of the spectrum can be described by a highly anisotropic effective spin-(1)/2 Hamiltonian that is deduced for the Co(II)2 pair in the weak-exchange limit. PMID:26974224

  7. Generation of free radicals from model lipid hydroperoxides and H[sub 2]O[sub 2] by Co(II) in the presence of cysteinyl and histidyl chelators

    Energy Technology Data Exchange (ETDEWEB)

    Shi, X.; Kasprzak, K.S. (National Cancer Institute, Frederick, MD (United States)); Dalal, N.S. (West Virginia Univ., Morgantown, WV (United States))

    Electron spin resonance spin trapping was utilized to investigate the generation of free radicals from cumene hydroperoxide (cumene-OOH), tert-butyl hydroperoxide (tert-butyl-OOH), and H[sub 2]O[sub 2] at pH 7.2 by Co(II) in the presence of cysteinyl and histidyl chelating agents. The spin trap used was 5,5-dimethyl-1-pyrroline N-oxide. Incubation of Co(II) with cumene-OOH or tert-butyl-OOH did not generate any detectable amounts of free radicals. However, in the presence of glutathione, cysteine, penicillamine, or N-acetylcysteine, Co(II) generated cumene-OOH-derived carbon-centered radicals, cumene alkoxyl radicals, and hydroxy (OH) radicals. Oxidized glutathione and cysteine used instead of reduced glutathione or cysteine did not generate any free radical, indicating an important role of the -SH group in radical generation. While the addition of diethylenetriaminepentaacetic acid (DTPA) prevented radical generation, deferoxamine had only a slightly inhibitory effect. Similar results to those obtained using cumene-OOH were obtained utilizing tert-butyl-OOH in place of cumene-OOH. The yields of free radicals were in the order of glutathione > cysteine > penicillamine > N-acetylcysteine. Incubation of Co(II) with cumene-OOH or t-butyl-OOH in the presence of the histidyl oligopeptide Gly-Gly-His also generated lipid hydroperoxide-derived free radicals, with the yield being comparable to that obtained using thiols. In contrast, histidine, anserine, homocarnosine, or carnosine did not cause any free radical generation from Co(II) and lipid hydroperoxides. Incubation of Co(II) with H[sub 2]O[sub 2] produced only a small amount of OH radicals. Addition of glutathione to the mixture of Co(II) and H[sub 2]O[sub 2] resulted in generation of both glutathionyl (GS) and OH radicals, which could be inhibited by DTPA and deferoxamine. Deferoxamine nitroxide radical was produced from deferoxamine incubated with Co(II) and H[sub 2]O[sub 2]. 36 refs., 7 figs., 3 tabs.

  8. IR, UV-Vis, magnetic and thermal characterization of chelates of some catecholamines and 4-aminoantipyrine with Fe(III) and Cu(II)

    Science.gov (United States)

    Mohamed, Gehad G.; Zayed, M. A.; El-Dien, F. A. Nour; El-Nahas, Reham G.

    2004-07-01

    The dopamine derivatives participate in the regulation of wide variety of physiological functions in the human body and in medication life. Increase and/or decrease in the concentration of dopamine in human body reflect an indication for diseases such as Schizophrenia and/or Parkinson diseases. α-Methyldopa (α-MD) in tablets is used in medication of hypertension. The Fe(III) and Cu(II) chelates with coupled products of adrenaline hydrogen tartarate (AHT), levodopa (LD), α-MD and carbidopa (CD) with 4-aminoantipyrine (4-AAP) are prepared and characterized. Different physico-chemical methods like IR, magnetic and UV-Vis spectra are used to investigate the structure of these chelates. Fe(III) form 1:2 (M:catecholamines) chelates while Cu(II) form 1:1 chelates. Catecholamines behave as a bidentate mono- or dibasic ligands in binding to the metal ions. IR spectra show that the catecholamines are coordinated to the metal ions in a bidentate manner with O,O donor sites of the phenolic - OH. Magnetic moment measurements reveal the presence of Fe(III) chelates in octahedral geometry while the Cu(II) chelates are square planar. The thermal decomposition of Fe(III) and Cu(II) complexes is studied using thermogravimetric (TGA) and differential thermal analysis (DTA) techniques. The water molecules are removed in the first step followed immediately by decomposition of the ligand molecules. The activation thermodynamic parameters, such as, energy of activation, enthalpy, entropy and free energy change of the complexes are evaluated and the relative thermal stability of the complexes are discussed.

  9. Abundances of Hyperthermophilic Autotrophic Fe(III) Oxide Reducers and Heterotrophs in Hydrothermal Sulfide Chimneys of the Northeastern Pacific Ocean ▿ †

    OpenAIRE

    Ver Eecke, Helene C.; Kelley, Deborah S.; Holden, James F.

    2008-01-01

    The abundances of hyperthermophilic heterotrophs, methanogens, and autotrophic reducers of amorphous Fe(III) oxide in 18 samples of deep-sea hydrothermal vent sulfide chimneys of the Endeavour Segment were measured. The results indicate that conditions favor the growth of iron reducers toward the interiors of these deposits and that of heterotrophs toward the outer surfaces near high-temperature polychaete worms (Paralvinella sulfincola).

  10. Abundances of Hyperthermophilic Autotrophic Fe(III) Oxide Reducers and Heterotrophs in Hydrothermal Sulfide Chimneys of the Northeastern Pacific Ocean ▿ †

    Science.gov (United States)

    Ver Eecke, Helene C.; Kelley, Deborah S.; Holden, James F.

    2009-01-01

    The abundances of hyperthermophilic heterotrophs, methanogens, and autotrophic reducers of amorphous Fe(III) oxide in 18 samples of deep-sea hydrothermal vent sulfide chimneys of the Endeavour Segment were measured. The results indicate that conditions favor the growth of iron reducers toward the interiors of these deposits and that of heterotrophs toward the outer surfaces near high-temperature polychaete worms (Paralvinella sulfincola). PMID:18978076

  11. Mixed ligand complex formation of FeIII with boric acid and typical N-donor multidentate ligands

    Indian Academy of Sciences (India)

    G N Mukherjee; Ansuman Das

    2002-06-01

    Equilibrium study of the mixed ligand complex formation of FeIII with boric acid in the absence and in the presence of 2,2'-bipyridine, 1,10-phenanthroline, diethylenetriamine and triethylenetetramine (L) in different molar ratios provides evidence of formation of Fe(OH)2+, Fe(OH)$^{+}_{2}$, Fe(L)3+, Fe(H2BO4), Fe(OH)(H2BO4)-, Fe(OH)2(H2BO4)2-, Fe(L)(H2BO4) and Fe2(L)2(BO4)+ complexes. Fe(L)$^{3+}_{2}$, Fe(L)2(H2BO4) and Fe2(L)4(BO4)+ complexes are also indicated with 2,2'-bipyridine and 1,10-phenanthroline. Complex formation equilibria and stability constants of the complexes at 25 ± 0 × 1° C in aqueous solution at a fixed ionic strength, = 0.1 mol -3 (NaNO3) have been determined by potentiometric method.

  12. Turn-on fluorogenic and chromogenic detection of Fe(III) and its application in living cell imaging

    Energy Technology Data Exchange (ETDEWEB)

    Sivaraman, Gandhi; Sathiyaraja, Vijayaraj; Chellappa, Duraisamy, E-mail: dcmku123@gmail.com

    2014-01-15

    Two rhodamine-based sensors RDI-1, RDI-2 was designed and synthesized by incorporation of the rhodamine 6G fluorophore and 2-formyl imidazole as the recognizing unit via the imine linkages. RDI-1, RDI-2 exhibits very high selectivity and an excellent sensitivity towards Fe(III) ions in aqueous buffer solution on compared with other probes. The color change from colorless to pink and turn-on fluorescence after binding with iron (III) was observed. Based on jobs plot and ESI-MS studies, the 1:1 binding mode was proposed. Live cell imaging experiments with each probe showed that these probes widely applicable to detect Fe{sup 3+} in living cells. -- Highlights: • Two rhodamine based probes was synthesized and used to recognize iron (III). • The chemosensors can be applied to detect iron(III) ions by color and turn-on fluorescent changes. • The very low detection limit was reported. • The applicability of these probes for live cell fluorescence imaging was studied.

  13. Crystal structure of the coordination polymer [FeIII2{PtII(CN4}3

    Directory of Open Access Journals (Sweden)

    Maksym Seredyuk

    2015-01-01

    Full Text Available The title complex, poly[dodeca-μ-cyanido-diiron(IIItriplatinum(II], [FeIII2{PtII(CN4}3], has a three-dimensional polymeric structure. It is built-up from square-planar [PtII(CN4]2− anions (point group symmetry 2/m bridging cationic [FeIIIPtII(CN4]+∞ layers extending in the bc plane. The FeII atoms of the layers are located on inversion centres and exhibit an octahedral coordination sphere defined by six N atoms of cyanide ligands, while the PtII atoms are located on twofold rotation axes and are surrounded by four C atoms of the cyanide ligands in a square-planar coordination. The geometrical preferences of the two cations for octahedral and square-planar coordination, respectively, lead to a corrugated organisation of the layers. The distance between neighbouring [FeIIIPtII(CN4]+∞ layers corresponds to the length a/2 = 8.0070 (3 Å, and the separation between two neighbouring PtII atoms of the bridging [PtII(CN4]2− groups corresponds to the length of the c axis [7.5720 (2 Å]. The structure is porous with accessible voids of 390 Å3 per unit cell.

  14. Towards the role of metal ions in the structural variability of proteins: CdII speciation of a metal ion binding loop motif

    DEFF Research Database (Denmark)

    Jancsó, Attila; Szunyogh, Dániel; Gyurcsik, Béla;

    2011-01-01

    A de novo designed dodecapeptide (HS), inspired by the metal binding loops of metal-responsive transcriptional activators, was synthesized. The aim was to create a model system for structurally promiscuous and intrinsically unstructured proteins, and explore the effect of metal ions on their...... molecular dynamics simulations demonstrate that it is unstructured with transient and varying helical content. The spectroscopic studies revealed the formation of loop structures with the coordination of the two Cys-thiolates close to each end of the HS peptide, in the presence of one equivalent of CdII per...... peptide is exchanging between a number of structures also in its metal ion bound state(s), as indicated by NMR and PAC data. © 2011 The Royal Society of Chemistry....

  15. Assembly of 4-, 6- and 8-connected Cd(II) pseudo-polymorphic coordination polymers: Synthesis, solvent-dependent structural variation and properties

    Science.gov (United States)

    Li, Zhao-Hao; Xue, Li-Ping; Miao, Shao-Bin; Zhao, Bang-Tun

    2016-08-01

    The reaction of Cd(NO3)2·4H2O, 2,5-thiophenedicarboxylic acid (H2tdc) and 1,2-bis(imidazol-1‧-yl)methane (bimm) by modulating solvent systems yielded three highly connected pseudo-polymorphic coordination polymers based on different dinuclear [Cd2(CO2)2] subunits bridged by carboxylate groups. Single crystal structural analyses reveal structural variation from 4-connected 2D sql layer, 6-connected 2-fold interpenetrated 3D pcu to 8-connected 3D bcu-type network in compounds 1-3. The structural dissimilarity in the structures dependent on the coordination environments of Cd(II) ions and linking modes of mixed ligand influenced by different solvent systems during the synthesis process. Moreover, thermogravimetric and photoluminescence behaviors of 1-3 were also investigated for the first time, and all the complexes emit blue luminescence in the solid state.

  16. Influence of medium acidity on the equilibrium sorption of Zn(II) and Cd(II) ions by cellulose base polymers

    International Nuclear Information System (INIS)

    Influence of medium acidity in pH range of 1-9 on sorption of Zn(II) and Cd(II) ions by oxyethylcellulose, sodium salt of carboxymethylcellulose, ethylcellulose and triacetatecellulose was considered to study sorption properties of cellulose ester base polymeric materials. It has been ascertained that the change in aqueous phase acidity from acid (pH∼1) to low-alkaline (pH∼7-9) one gives rise to increase in zinc and cadmium ions distribution by a factor of 10-12 and 15-18 respectively. A scheme of sorption equilibrium of zinc and cadmium ions in the system studied, depending on pH and considering the state of the ions in the form of cationic aquocomplexes, is suggested. It is shown that the optimal pH value during cadmium ions sorption equals 8, irrespective of polymer sorbent nature

  17. Synthesis of Novel Polymeric Resins by Gamma Irradiation for Separation of In(III) ions from Cd(II) in Aqueous Media

    International Nuclear Information System (INIS)

    In this work, Zn(II)polymethacrylates and poly(acrylamide-acrylic acid) were prepared by gamma irradiation polymerization technique of the corresponding monomer at 30 kGy. The polymeric resins were mixed with Indium ions to determine its capacity in aqueous solutions using batch experiment. The adsorption efficiency of obtained polymeric resins toward In(III) and Cd(II) in different experimental conditions was established. Batch and column methods were applied for separation of indium and cadmium. The effects of various eluants such as H2SO4, NH4NO3, HNO3 and HCl on the recovery of both metal ions were studied. The polymeric resins may be regenerated using 3M HCl solutions.

  18. Study of the Adsorbent-Adsorbate Interactions from Cd(II) and Pb(II) Adsorption on Activated Carbon and Activated Carbon Fiber

    International Nuclear Information System (INIS)

    The adsorption characteristics of Cd(II) and Pb(II) in aqueous solution using granular activated carbon (GAC), activated carbon fiber (ACF), modified ACF (NaACF), and a mixture of GAC and NaACF (GAC/NaACF) have been studied. The surface properties, such as morphology, surface functional groups, and composition of various adsorbents were determined using X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) measurements. The specific surface area, total pore volume, and pore size distribution were investigated using nitrogen adsorption, Brunauer-Emmett-Teller (BET), and Barrett-Joyner-Halenda (BJH) methods. In this study, NaACF showed a high adsorption capacity and rate for heavy metal ions due to the improvement of its ion-exchange capabilities by additional oxygen functional groups. Moreover, the GAC and NaACF mixture was used as an adsorbent to determine the adsorbent-adsorbate interaction in the presence of two competitive adsorbents

  19. The Role of Coulomb Interactions for Spin Crossover Behaviors and Crystal Structural Transformation in Novel Anionic Fe(III Complexes from a π-Extended ONO Ligand

    Directory of Open Access Journals (Sweden)

    Suguru Murata

    2016-05-01

    Full Text Available To investigate the π-extension effect on an unusual negative-charged spin crossover (SCO FeIII complex with a weak N2O4 first coordination sphere, we designed and synthesized a series of anionic FeIII complexes from a π-extended naphthalene derivative ligand. Acetonitrile-solvate tetramethylammonium (TMA salt 1 exhibited an SCO conversion, while acetone-solvate TMA salt 2 was in a high-spin state. The crystal structural analysis for 2 revealed that two-leg ladder-like cation-anion arrays derived from π-stacking interactions between π-ligands of the FeIII complex anion and Coulomb interactions were found and the solvated acetone molecules were in one-dimensional channels between the cation-anion arrays. A desolvation-induced single-crystal-to-single-crystal transformation to desolvate compound 2’ may be driven by Coulomb energy gain. Furthermore, the structural comparison between quasi-polymorphic compounds 1 and 2 revealed that the synergy between Coulomb and π-stacking interactions induces a significant distortion of coordination structure of 2.

  20. The determination of adsorption capacity of anion exchange resin Dowex-Marathon for Ti(IV) and Fe(III) chlorocomplexes

    International Nuclear Information System (INIS)

    Full text: The adsorption capacity of anion exchange resin Dowex-Marathon for Ti(IV) and Fe(III) chlorocomplexes from HCl solution was determined. The measurements were performed for different HCl solution concentrations and temperatures using batch operation as contact method between solution and resin. The Fe(III) adsorption capacities increased with HCl solution concentrations and contact temperatures. In the case of Ti(IV) considerable adsorption capacities were observed only at HCl concentrations >7 M. For the same ion the adsorption capacity does not depend on temperature in the range of 30 - 70 deg C. At 50 deg C there is an important difference between adsorption capacity for Fe(III), (105.7 mg Fe/g dry resin) and for U(VI), (227 mg U/g dry resin), allowing the recovery of uranium adsorption band in the 235U enriching column, using band displacement technique. A solution of TiCl3 0.1 M in HCl >7 M can be utilized as reduction agent at the rear edge of the uranium band, according to the important adsorption capacity of Ti(IV) in those conditions. (author)

  1. Carbon mineralization in Arctic sediments northeast of Svalbard: Mn(IV) and Fe(III) reduction as principal anaerobic respiratory pathways

    DEFF Research Database (Denmark)

    Vandieken, Verona; Nickel, Maren; Jørgensen, Bo Barker

    2006-01-01

    Carbon oxidation rates and pathways were determined in 3 sediments at latitude 79 degrees to 81 degrees N in the Barents Sea, where the ice cover restricts primary production to a few months of the year. Oxygen uptake (1.5 to 3.5 imnol m(-2) d(-1)) and sulfate reduction (= 60 mu mol cm(-3)) and Fe......(III) (>= 108 mu mol cm(-3)), dissimilatory Mn(IV) and Fe(III) reduction contributed between 69 and >= 90% to anaerobic carbon mineralization in the upper 10 cm of the sediments. At 2 of the 3 stations, sulfate reduction rates were below our detection limit of 1 nmol cm(-3) d(-1). Solid Mn and Fe(III) were...... and sulfate reduction at 5 to 10 cm. Rates of microbial carbon oxidation were low compared to those in fjords on the west and south coasts of Svalbard. This is in accordance with the limited organic carbon supply by primary and secondary productivity caused by long periods of ice coverage....

  2. Two new Zn(II) and Cd(II) coordinastion polymers based on amino-tetrazole and phenylcarboxylate: Syntheses, topological structures and photoluminescent properties

    International Nuclear Information System (INIS)

    Two Zn(II) and Cd(II) compounds with the in-situ generated ligand of 5-amino-tetrazolate (atz−) were prepared from the hydrothermal reactions of the corresponding Cd or Zn(II) salts with phenylcarboxylate, and characterized by elemental analysis, IR spectroscopy, and TGA. The results of X-ray crystallographic analysis reveal that compound [Zn2(BZA)(atz)2(OH)]n (1) (BZA=benzoic acid) presents a two-dimensional (2D) “hcb” topological network constructed from the ZnN2O2 tetrahedra. In compound [Cd6(atz)6(PTA)3]n (2) (PTA=terephthalic acid), the identical [Cd3(atz)3)]3+n clusters are connected by atz ligands to generate a 2D cationic layer, and the neighboring cationic layers are pillared by PTA giving birth to 3D network. After simplifying, the complicated 3D network of 2 can be presented as an unprecedented (4, 4, 10)-connected trinodal topology. The formations of the structures show a good example that using the combination of the in-situ generated ligand and other coligand synthetic strategy can construct interesting topological structures. The thermal stabilities and fluorescent properties of the complexes have also been studied. - Graphical abstract: Two d10 metal complexes have been synthesized by employing mixed-ligand synthetic approach. Complex 1 presents a 2D “hcb” topological network. Complex 2 shows an unprecedented (4, 4, 10)-connected trinodal topology. Highlights: ► Coligand synthetic strategy was applied to obtain new MOFs with useful properties. ► Two new Zn(II) and Cd(II) complexes were constructed from the mixed-ligand. ► Topologically, compound 2 presented an unprecedented (4, 4, 10)-connected trinodal topology. ► The two compounds may be excellent candidates for potential photoactive material.

  3. Immobilization of Cu(II), Pb(II) and Cd(II) by the addition of rice straw derived biochar to a simulated polluted Ultisol.

    Science.gov (United States)

    Jiang, Jun; Xu, Ren-kou; Jiang, Tian-yu; Li, Zhuo

    2012-08-30

    To develop new remediation methods for acidic soils polluted by heavy metals, the chemical fractions of Cu(II), Pb(II) and Cd(II) in an Ultisol with and without rice straw biochar were compared and the effect of biochar incorporation on the mobility and bioavailability of these metals was investigated. In light of the decreasing zeta potential and increasing CEC, the incorporation of biochar made the negative soil surface charge more negative. Additionally, the soil pH increased markedly after the addition of biochar. These changes in soil properties were advantageous for heavy metal immobilization in the bulk soil. The acid soluble Cu(II) and Pb(II) decreased by 19.7-100.0% and 18.8-77.0%, respectively, as the amount of biochar added increased. The descending range of acid soluble Cd(II) was 5.6-14.1%, which was much lower than that of Cu(II) and Pb(II). When 5.0 mmol/kg of these heavy metals was added, the reducible Pb(II) for treatments containing 3% and 5% biochar was 2.0 and 3.0 times higher than that of samples without biochar, while the reducible Cu(II) increased by 61.6% and 132.6% for the corresponding treatments, respectively. When 3% and 5% biochar was added, the oxidizable portion of Pb(II) increased by 1.18 and 1.94 times, respectively, while the oxidizable portion of Cu(II) increased by 8.13 and 7.16 times, respectively, primarily due to the high adsorption affinity of functional groups of biochar to Cu(II). The residual heavy metal contents were low and changed little with the incorporation of biochar. PMID:22704774

  4. The influence of H-bonding on the 'ambidentate' coordination behaviour of the thiocyanate ion to Cd(II): a combined experimental and theoretical study.

    Science.gov (United States)

    Hazari, Alokesh; Das, Lakshmi Kanta; Bauzá, Antonio; Frontera, Antonio; Ghosh, Ashutosh

    2014-06-01

    Two new trinuclear hetero-metallic copper(II)-cadmium(II) complexes [(CuL)2Cd(NCS)2] (1) and [(CuL(R))2Cd(SCN)2] (2) have been synthesized using [CuL] and [CuL(R)] as "metalloligands" (where H2L = N,N'-bis(salicylidene)-1,4-butanediamine and H2L(R) = N,N'-bis(2-hydroxybenzyl)-1,4-butanediamine) respectively. Both the complexes were characterized by elemental analysis, various spectroscopic methods and single crystal XRD. Complex 1 is an angular trinuclear species, in which two terminal four-coordinate square planar "metalloligands" [CuL] are coordinated to a central Cd(II) through double phenoxido bridges along with two mutually cis nitrogen atoms of terminal thiocyanate ions. In complex 2, which is linear, in addition to the double phenoxido bridge, two SCN(-) coordinate to the trans positions of the central octahedral Cd(II) via S atoms. Theoretical calculations on the energetic difference between the two possible coordination modes of the thiocyanate anion to the Cd atom reveal that N-coordination is preferred over S-coordination in agreement with the much greater abundance of the reported N-bonded structures. In 2, there is a strong N-H···NCS-Cd H-bonding interaction, the binding energy of which is computed to be approximately -9.3 kcal mol(-1), which is sufficient to compensate the 9.0 kcal mol(-1) of energetic cost due to the unusual Cd-SCN coordination mode. PMID:24715108

  5. Syntheses of polystyrene supported chelating resin containing the Schiff base derived from salicylaldehyde and triethylene tetramine and its copper(II), nickel(II), cobalt(II), iron(III), zinc(II), cadmium(II), molybdenum(VI), zirconium(IV) and uranium(VI) complexes

    International Nuclear Information System (INIS)

    A new polymer-anchored chelating ligand has been synthesized by the reaction of chloromethylated polystyrene (containing 0.94 mmol of Cl per gram of resin and 1% cross-linked with divinylbenzene) and the Schiff base derived from salicylaldehyde and triethylenetetramine. A new series of polystyrene supported, Cu(II), Ni(II), Co(II), Fe(III), Zn(II), Cd(II), Zr(IV), dioxomolybdenum (VI) and dioxouranium (VI) complexes of the formulae PS-LCu, PS-LNi, PS-LCo, PS-LFeCl.DMF, PS-LZn, PS-LCd, PS-LZr(OH)2. DMF, PSLMoO2 and PS-LUO2 (where PS-LH2 = polymer-anchored Schiff base and DMF dimethyl-formamide) have been synthesized and characterised by elemental analysis, infrared, electronic spectra and magnetic susceptibility measurements. The complexes PS-LCu, PS-LNi and PS-LCo have square planar structure, PS-LFeCl.DMF, PS-LMoO2 and PS-LUO2 have octahedral structure, PSLZn and PS-LCd are tetrahedral and PS-LZr(OH)2.DMF is pentagonal bipyramidal. The polymer-anchored Cu(II), Co(II) and Fe(III) complexes are paramagnetic while Ni(II), Zn(II), Cd(II), Zr(IV), dioxomolybdenum(VI) and dioxouranium(VI) complexes are diamagnetic. The negative shift of the v (C=N) (azomethine) and the positive shift of v (C--O)(phenolic) are indicative of ONNO donor behaviour of the polymer-anchored Schiff base. (author)

  6. Studies on coordination and addition compounds and anti microbial activity of some mixed ligand complexes of Au(III), Mo(II), Co(II) and Cd(II) with dibasic acid and heterocyclic amines and addition compounds of As(III) and Sb(III) halides with benzamide and acetophenon

    International Nuclear Information System (INIS)

    Three new mixed ligand complexes of Au(III) and Mo(II) with dibasic acid e.g., homophthalic acid, oxalic acid and heterocylic amines e.g., quinonine, iso-quinonine, bipyridine, Phenylanaline and the two new addition compounds of As(III) and Sb(III) halides with N-donor ligands viz. benzamide and acetophenone and one complex [Cd(DPH)(IQ)2], where IQ = Iso-quinoline and DPH = Deprotonated phthalic acid have been prepared according to the procedure in the literature. Their conventional physical and chemical analyses have been done. Their antibacterial studies against nine gram positive and five gram negative pathogenic bacteria and antifungal activities against eight plant and three human fungi have been evaluated. Kanamycin and Nystatin have been used as a standard for carrying out experiments of antibacterial and antifungal activities, respectively. The minimum inhibitory concentration (MIC) values of these compounds, as antibiotic against two gram positive and two gram negative pathogenic bacteria, have also been carried out and in this case, Amoxacilin antibiotic has been used as a standard antibiotic. (author)

  7. The evolutionary history of the genus Timarcha (Coleoptera, Chrysomelidae) inferred from mitochondrial COII gene and partial 16S rDNA sequences.

    Science.gov (United States)

    Gómez-Zurita, J; Juan, C; Petitpierre, E

    2000-02-01

    The apterous genus Timarcha consists of three subgenera and more than 100 species in its Palearctic distribution, with specialized feeding on few plant families. Fifty-four sequences sampled from 31 taxa of the genus plus three outgroup leaf beetles were studied for their complete cytochrome oxidase II (COII) and a fragment of 16S rDNA mitochondrial genes, representing a total of about 1200 bp. Phylogenetic analyses using maximum-parsimony and distance methods for each gene separately and for the combined data set gave compatible topologies. The subgenus Metallotimarcha consistently appears in a basal position and is well differentiated from the remaining Timarcha, but no clear monophyletic grouping of Timarchostoma and Timarcha s. str. subgenera can be deduced from our analysis. Calibration of the molecular clock has been done using the opening of the Gibraltar Strait after the Messinian salinity crisis (about 5.5 MYA) as the biogeographic event causing disjunction of two particular taxa. Accordingly, the COII evolutionary rate has been estimated to be of 0.76 x 10(-8) substitution/site/year in Timarcha. Relation between phylogeny and host-plant use indicates widening of trophic regime as a derived character in Timarcha. PMID:10679162

  8. The potential impact of microbial Fe(III) reduction on subsurface U(VI) mobility at a low level radioactive waste storage site

    Energy Technology Data Exchange (ETDEWEB)

    Wilkins, M.J.; Livens, F.R.; Vaughan, D.J.; Lloyd, J.R. [Williamson Research Centre for Molecular Environmental Science and School of Earth, Atmospheric and Environmental Sciences, The University of Manchester, Oxford Road, Manchester, M13 9PL (United Kingdom); Beadle, I.; Small, J.S. [British Nuclear Fuels plc, Risley, Warrington WA3 6AS (United Kingdom)

    2005-07-01

    Full text of publication follows: Fe(III) oxy-hydroxides have the potential to be utilised as terminal electron acceptors by indigenous microbial communities in the British Nuclear Fuels (BNFL) low level radioactive waste storage site at Drigg (Cumbria, UK) and these organisms may have a critical control on the biogeochemical cycling of several environmentally important radionuclides. In terms of radiological impact at Drigg, uranium is the most significant contributor to radiological impact and it is strongly influenced by biogeochemical processes. In terms of mass (moles) it is also the most abundant radionuclide in the Drigg inventory. Thus, the potential biotic and abiotic effects of Fe(III) reduction on U(VI) mobility in the Drigg subsurface are of interest. Culture-dependent and molecular techniques showed that the sediments in and around the Drigg site contained a diversity of Fe(III)-reducing bacteria. A series of microcosm experiments were utilised to create environmentally relevant experimental conditions. Microcosms set up using Drigg sediment and synthetic ground water were spiked with 100 {mu}M U(VI) and acetate as an electron donor. U(VI) concentrations in groundwater were measured using a chemical assay while total U levels were determined using ICP-MS. Fe(II) levels were determined using the ferrozine method. Sediment surface areas were measured using BET analysis. The low surface area of the sediments resulted in only a small proportion of the 100 {mu}M U(VI) spike sorbing onto mineral surfaces. The addition of ferri-hydrite to some microcosms resulted in an immediate lowering of soluble U(VI) concentrations, suggesting that the formation of soluble U(VI) complexes were not responsible for the minimal adsorption. The presence of biogenic Fe(II) in the microcosms did not affect the soluble U(VI) concentration. Similarly, soluble U(VI) levels remained unchanged when sediments were spiked with U(VI) post-microbial Fe(III) reduction. However, a

  9. The potential impact of microbial Fe(III) reduction on subsurface U(VI) mobility at a low level radioactive waste storage site

    International Nuclear Information System (INIS)

    Full text of publication follows: Fe(III) oxy-hydroxides have the potential to be utilised as terminal electron acceptors by indigenous microbial communities in the British Nuclear Fuels (BNFL) low level radioactive waste storage site at Drigg (Cumbria, UK) and these organisms may have a critical control on the biogeochemical cycling of several environmentally important radionuclides. In terms of radiological impact at Drigg, uranium is the most significant contributor to radiological impact and it is strongly influenced by biogeochemical processes. In terms of mass (moles) it is also the most abundant radionuclide in the Drigg inventory. Thus, the potential biotic and abiotic effects of Fe(III) reduction on U(VI) mobility in the Drigg subsurface are of interest. Culture-dependent and molecular techniques showed that the sediments in and around the Drigg site contained a diversity of Fe(III)-reducing bacteria. A series of microcosm experiments were utilised to create environmentally relevant experimental conditions. Microcosms set up using Drigg sediment and synthetic ground water were spiked with 100 μM U(VI) and acetate as an electron donor. U(VI) concentrations in groundwater were measured using a chemical assay while total U levels were determined using ICP-MS. Fe(II) levels were determined using the ferrozine method. Sediment surface areas were measured using BET analysis. The low surface area of the sediments resulted in only a small proportion of the 100 μM U(VI) spike sorbing onto mineral surfaces. The addition of ferri-hydrite to some microcosms resulted in an immediate lowering of soluble U(VI) concentrations, suggesting that the formation of soluble U(VI) complexes were not responsible for the minimal adsorption. The presence of biogenic Fe(II) in the microcosms did not affect the soluble U(VI) concentration. Similarly, soluble U(VI) levels remained unchanged when sediments were spiked with U(VI) post-microbial Fe(III) reduction. However, a lowering in

  10. Co-modification of F− and Fe(III) ions as a facile strategy towards effective separation of photogenerated electrons and holes

    International Nuclear Information System (INIS)

    Graphical abstract: - Highlights: • The Fe(III)/F-TiO2 photocatalyst was prepared by a facile, wet chemical method. • Fe(III)/F-TiO2 exhibited higher photocatalytic activity than TiO2, Fe(III)/TiO2 and F-TiO2. • The synergistic effect of Fe(III) and F ions contributed to the enhanced activity of TiO2. - Abstract: The combination of cocatalysts for simultaneously promoting rapid transfer of photogenerated electrons and holes is one of the effective strategies to improve photocatalytic activity of semiconductor photocatalysts. In this study, highly efficient TiO2 photocatalyst with co-modification of F and Fe(III) ions was prepared by a facile two wet-chemical method including Fe(III) ions impregnation and then F-ion adsorption on the TiO2 surface. The photocatalytic results demonstrated that the simultaneously modified Fe(III)/F-TiO2 photocatalyst exhibited obvious enhancement of photocatalytic performance compared with the pure TiO2 and single-component modified Fe(III)/TiO2 and F-TiO2. Based on the present experimental results, we propose a possible synergistic effect of Fe(III) and F ions to illustrate the enhanced photocatalytic activity of Fe(III)/F-TiO2 photocatalyst, namely the Fe(III) ions act as effective active sites to rapidly transfer the photogenerated electrons in the CB of TiO2 and then reduce oxygen, while F ions work as other effective active sites to rapidly transfer the photogenerated holes in the VB of TiO2 and then form free hydroxide radical to oxidize the organic substances. As a result, the transfer rate and the interfacial catalytic reaction of photogenerated electrons and holes were simultaneously accelerated, which resulted in the enhanced photocatalytic performance of Fe(III)/F-TiO2 photocatalyst. Due to the low cost and abundant resource of Fe and F, the obtained photocatalyst is promising for practical application. Furthermore, the present work can provide some good ideas for the rational preparation of new and high

  11. Co-modification of F{sup −} and Fe(III) ions as a facile strategy towards effective separation of photogenerated electrons and holes

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Xuefei; Yu, Rui; Wang, Ping; Chen, Feng [School of Chemistry, Chemical Engineering and Life Sciences, Wuhan University of Technology, Wuhan 430070 (China); Yu, Huogen, E-mail: yuhuogen@whut.edu.cn [School of Chemistry, Chemical Engineering and Life Sciences, Wuhan University of Technology, Wuhan 430070 (China); State Key Laboratory of Silicate Materials for Architectures, Wuhan University of Technology, Wuhan 430070 (China)

    2015-10-01

    Graphical abstract: - Highlights: • The Fe(III)/F-TiO{sub 2} photocatalyst was prepared by a facile, wet chemical method. • Fe(III)/F-TiO{sub 2} exhibited higher photocatalytic activity than TiO{sub 2}, Fe(III)/TiO{sub 2} and F-TiO{sub 2}. • The synergistic effect of Fe(III) and F ions contributed to the enhanced activity of TiO{sub 2}. - Abstract: The combination of cocatalysts for simultaneously promoting rapid transfer of photogenerated electrons and holes is one of the effective strategies to improve photocatalytic activity of semiconductor photocatalysts. In this study, highly efficient TiO{sub 2} photocatalyst with co-modification of F and Fe(III) ions was prepared by a facile two wet-chemical method including Fe(III) ions impregnation and then F-ion adsorption on the TiO{sub 2} surface. The photocatalytic results demonstrated that the simultaneously modified Fe(III)/F-TiO{sub 2} photocatalyst exhibited obvious enhancement of photocatalytic performance compared with the pure TiO{sub 2} and single-component modified Fe(III)/TiO{sub 2} and F-TiO{sub 2}. Based on the present experimental results, we propose a possible synergistic effect of Fe(III) and F ions to illustrate the enhanced photocatalytic activity of Fe(III)/F-TiO{sub 2} photocatalyst, namely the Fe(III) ions act as effective active sites to rapidly transfer the photogenerated electrons in the CB of TiO{sub 2} and then reduce oxygen, while F ions work as other effective active sites to rapidly transfer the photogenerated holes in the VB of TiO{sub 2} and then form free hydroxide radical to oxidize the organic substances. As a result, the transfer rate and the interfacial catalytic reaction of photogenerated electrons and holes were simultaneously accelerated, which resulted in the enhanced photocatalytic performance of Fe(III)/F-TiO{sub 2} photocatalyst. Due to the low cost and abundant resource of Fe and F, the obtained photocatalyst is promising for practical application. Furthermore, the

  12. Direct Involvement of ombB, omaB and omcB Genes in Extracellular Reduction of Fe(III) by Geobacter sulfurreducens PCA

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Yimo; Fredrickson, Jim K.; Zachara, John M.; Shi, Liang

    2015-10-01

    The tandem gene clusters orfR-ombB-omaB-omcB and orfS-ombC-omaC-omcC of the metal-reducing bacterium Geobacter sulfurreducens PCA are responsible for trans-outer membrane electron transfer during extracellular reduction of Fe(III)-citrate and ferrihydrite [a poorly crystalline Fe(III) oxide]. Each gene cluster encodes a putative transcriptional factor (OrfR/OrfS), a porin-like outer-membrane protein (OmbB/OmbC), a periplasmic c-type cytochrome (c-Cyt, OmaB/OmaC) and an outer-membrane c-Cyt (OmcB/OmcC). The individual roles of OmbB, OmaB and OmcB in extracellular reduction of Fe(III), however, have remained either uninvestigated or controversial. Here, we showed that replacements of ombB, omaB, omcB and ombB-omaB with an antibiotic gene in the presence of ombC-omaC-omcC had no impact on reduction of Fe(III)-citrate by G. sulfurreducens PCA. Disruption of ombB, omaB, omcB and ombB-omaB in the absence of ombC-omaC-omcC, however, severely impaired the bacterial ability to reduce Fe(III)-citrate as well as ferrihydrite. These results unequivocally demonstrate an overlapping role of ombB-omaB-omcB and ombC-omaC-omcC in extracellular Fe(III) reduction by G. sulfurreducens PCA. Involvement of both ombB-omaB-omcB and ombC-omaC-omcC in extracellular Fe(III) reduction reflects the importance of these trans-outer membrane protein complexes in the physiology of this bacterium. Moreover, the kinetics of Fe(III)-citrate and ferrihydrite reduction by these mutants in the absence of ombC-omaC-omcC were nearly identical, which clearly show that OmbB, OmaB and OmcB contribute equally to extracellular Fe(III) reduction. Finally, orfS was found to have a negative impact on the extracellular reduction of Fe(III)-citrate and ferrihydrite in G. sulfurreducens PCA probably by serving as a transcriptional repressor.

  13. Synthesis and characterization of Co(II), Ni(II), Cu(II) and Zn(II) complexes of tridentate Schiff base derived from vanillin and DL-α-aminobutyric acid

    Science.gov (United States)

    Nair, M. Sivasankaran; Joseyphus, R. Selwin

    2008-09-01

    Co(II), Ni(II), Cu(II) and Zn(II) complexes of the Schiff base derived from vanillin and DL-α-aminobutyric acid were synthesized and characterized by elemental analysis, IR, electronic spectra, conductance measurements, magnetic measurements, powder XRD and biological activity. The analytical data show the composition of the metal complex to be [ML(H 2O)], where L is the Schiff base ligand. The conductance data indicate that all the complexes are non-electrolytes. IR results demonstrate the tridentate binding of the Schiff base ligand involving azomethine nitrogen, phenolic oxygen and carboxylato oxygen atoms. The IR data also indicate the coordination of a water molecule with the metal ion in the complex. The electronic spectral measurements show that Co(II) and Ni(II) complexes have tetrahedral geometry, while Cu(II) complex has square planar geometry. The powder XRD studies indicate that Co(II) and Cu(II) complexes are amorphous, whereas Ni(II) and Zn(II) complexes are crystalline in nature. Magnetic measurements show that Co(II), Ni(II) and Cu(II) complexes have paramagnetic behaviour. Antibacterial results indicated that the metal complexes are more active than the ligand.

  14. Solid phase extraction of Cd(II) and Pb(II) ions based on a novel functionalized Fe3O4@ SiO2 core-shell nanoparticles with the aid of multivariate optimization methodology.

    Science.gov (United States)

    Tadjarodi, Azadeh; Abbaszadeh, Abolfazl; Taghizadeh, Mohsen; Shekari, Nafiseh; Asgharinezhad, Ali Akbar

    2015-04-01

    This work describes novel Fe3O4@SiO2 core-shell nanoparticles functionalized with phenyl isothiocyanate and its application in the preconcentration of Cd(II) and Pb(II) ions. The parameters affecting the preconcentration procedure were optimized by a Box-Behnken design through response surface methodology. Three variables (extraction time, magnetic sorbent amount, and pH value) were selected as the main factors affecting the sorption step, while four variables (type, volume and concentration of the eluent; and elution time) were selected as effective factors of elution step in the optimization study. Following the sorption and elution, the ions were quantified by FAAS. The limits of detection were 0.05 and 0.9ngmL(-1) for Cd(II) and Pb(II) ions, respectively. The relative standard deviations were less than 6.4%. The sorption capacity (in mg g(-1)) of this new sorbent is 179 for Cd(II) and 156 for Pb(II). Finally, this nanocomposite was successfully applied to the rapid extraction of trace quantities of heavy metal ions from fish, sediment, soil, and water samples and satisfactory results were obtained. PMID:25686967

  15. Influence of pseudohalide anions on the structural assembly of Cd(II) coordination polymers with 3,4-bis(3-pyridyl)-5-(4-pyridyl)-1,2,4-triazole

    Science.gov (United States)

    Chen, Jing; Li, Ming-Ze; Sun, Nan; Guo, Jian-Hua

    2016-02-01

    Four CdII coordination polymers, namely {[Cd(L334)(Cl)2](CH3OH)}n (1), [Cd(L334)(Cl)(dca)]n (2), {[Cd(L334)(Cl)1.33(N3)0.67](H2O)}n (3), and {[Cd(L334)(SCN)2(H2O)](H2O)1.5(CH3OH)}n (4), have been synthesized by the conventional reactions of CdCl2 and 3,4-bis(3-pyridyl)-5-(4-pyridyl)-1,2,4-triazole (L334) or in the presence of different pseudohalides dicyanamide (dca), azide (N3), and thiocyanate (SCN), respectively as auxiliary ligands. Complexes 1-3 exhibit the isostructural 2D layered network structures, whereas complex 4 shows a distinct 2D network with dimeric CdII subunits. The structural discrepancy in 1-4 indicates the significant influence of pseudohalide anions on the structural assembly of CdII coordination polymers with 3,4-bis(3-pyridyl)-5-(4-pyridyl)-1,2,4-triazole. In addition, thermogravimetric and fluorescent properties for all complexes and the ligand have also been investigated.

  16. Synthesis, characterization, in vitro antimicrobial and DNA cleavage studies of Co(II), Ni(II) and Cu(II) complexes with ONOO donor coumarin Schiff bases

    Science.gov (United States)

    Patil, Sangamesh A.; Unki, Shrishila N.; Kulkarni, Ajaykumar D.; Naik, Vinod H.; Badami, Prema S.

    2011-01-01

    A series of Co(II), Ni(II) and Cu(II) complexes have been synthesized with Schiff bases derived from 2-hydroxy-1-naphthaldehyde and 2-oxo-2H-chromene-3-carbohydrazide/6-bromo-2-oxo-2H-chromene-3-carbohydrazide. The chelation of the complexes has been proposed in the light of analytical, spectral (IR, UV-Vis, 1H NMR, ESR, FAB-mass and fluorescence), magnetic and thermal studies. The measured molar conductance values indicate that, the complexes are non-electrolytic in nature. The redox behavior of the complexes was investigated with electrochemical method by using cyclic voltammetry. The Schiff bases and their metal complexes have been screened for their in vitro antibacterial ( Escherichia coli, Staphylococcus aureus, Bacillus subtilis and Salmonella typhi) and antifungal activities ( Candida albicans, Cladosporium and Aspergillus niger) by MIC method. The DNA cleavage is studied by agarose gel electrophoresis method.

  17. Calculation of the geometry of the Co(II) and Ni(II) complexes with L-histidine in aqueous solutions from PMR data

    International Nuclear Information System (INIS)

    Previously obtained PMR data from an investigation of the complexation of cobalt(II) and nickel(II) with L-histidine have been used to separate overall paramagnetic shifts into their contact and dipolar components. The geometry of the complexes Co(his)2 and Ni(his)2 has been calculated from the latter. Good agreement between the calculated and x-ray structural data has been obtained under the assumption that the magnetic moment remains axially isotropic when its direction is varied. Such correspondence was not obtained for the 1:1 complexes due to the triaxial anisotropy of the magnetic moment, which is possible for these complexes. Conclusions regarding the geometry of the histidine complexes of Co(II) and Ni(II) in aqueous solutions and the solid phase have been drawn

  18. Self-assembly of a Co(II) dimer through H-bonding of water molecules to a 3D open-framework structure

    Indian Academy of Sciences (India)

    Sujit K Ghosh; Parimal K Bharadwaj

    2005-01-01

    Reaction of pyridine-2,4,6-tricarboxylic acid (ptcH3) with Co(NO3)2.6H2O in presence of 4,4'-bipyridine (4,4'-bpy) in water at room temperature results in the formation of {[Co2(ptcH)2(4,4'-bpy)(H2O)4].2H2O}, (1). The solid-state structure reveals that the compound is a dimeric Co(II) complex assembled to a 3D architecture via an intricate intra- and inter-molecular hydrogen-bonding interactions involving water molecules and carboxylate oxygens of the ligand ptcH2-. Crystal data: monoclinic, space group 21/, = 11.441(5) Å, = 20.212(2) Å, = 7.020(5) Å, = 103.77(5)°, = 1576.7(1) Å3, = 2, 1 = 0.0363, 2 = 0.0856, = 1.000.

  19. Spectroscopic and biological approach of Ni(II), Cu(II) and Co(II) complexes of 4-methoxy/ethoxybenzaldehyde thiosemicarbazone glyoxime.

    Science.gov (United States)

    Babahan, Ilknur; Eyduran, Fatih; Coban, Esin Poyrazoglu; Orhan, Nil; Kazar, Didem; Biyik, Halil

    2014-01-01

    Two novel vicinal dioxime ligands containing (4-methoxybenzaldehyde thiosemicarbazone glyoxime (L(1)H2) or 4-ethoxybenzaldehyde thiosemicarbazone glyoxime (L(2)H2)) thiosemicarbazone units were synthesized and characterized using (1)H NMR, (13)C NMR, HMQC, MS, infrared and, UV-VIS. spectroscopy, elemental analysis, and magnetic susceptibility measurements. Mononuclear nickel(II), copper(II) and cobalt(II) complexes with a metal:ligand ratio of 1:2 for L(1)H2 and L(2)H2 were also synthesized. The effect of pH and solvent on the absorption spectra of both ligands and complexes was determined. IR spectra show that the ligands act in a bidentate manner and coordinates N4 donor groups of the ligands to Ni(II), Cu(II) and Co(II) ions. The detection of H-bonding (O-H⋯O) in the [M(LH)2] metal complexes by IR spectra supported the square-planar MN4 coordination of mononuclear complexes. The antimicrobial activities of compounds L(1)H2, L(2)H2, and their Ni(II), Cu(II) and Co(II) complexes were evaluated using the disc diffusion method against 12 bacteria and 4 yeasts. The minimal inhibitory concentrations (MICs) against 7 bacteria and 3 yeasts were also determined. Among the test compounds attempted, L(1)H2, [Ni(L1H)2], [Cu(L1H)2], L2H2, [Ni(L2H)2] and [Cu(L2H)2] showed some activities against certain Gram-positive bacteria and some of the yeasts tested. PMID:24239764

  20. Structural and magnetic characterization of mixed valence Co(II, III)xZn1−xO epitaxial thin films

    International Nuclear Information System (INIS)

    In this article, we report on the Co atom incorporation, secondary phase formation and composition-dependent magnetic and optical properties of mixed valence Co(II, III)xZn1−xO epitaxial thin films grown by pulsed laser deposition. The intended total Co concentration is varied between ∼6–60 at.% with relatively higher concentration of +3 over +2 charge state. Mixed valence Co(II, III) shows high solubility in ZnO (up to 38 at.%) and ferromagnetism is observed in samples with total Co incorporation of ∼29 and 38 at.%. Electron diffraction pattern and high resolution transmission electron microscopy images reveal single crystalline nature of the thin films with wurtzite structure. Co oxide interlayer, with both rock salt and spinel structure, are observed to be formed between the substrate and wurtzite film for total Co concentration at ∼17 at.% and above. Magnetization shows composition dependence with a saturation moment value of ∼93 emu cm−3 and a coercive field of ∼285 Oe observed for ∼38 at.% Co:ZnO films. Ferromagnetism was not observed for films with Co concentration 17 and 9 at.%. The Co oxide interlayer does not show any ferromagnetism. All the films are n-type with carrier concentration ∼1019 cm−3. The observed magnetism is probably resulting from direct antiferromagntic exchange interaction between Co2+ and Co3+ ions favored by heavy Co alloying giving rise to ferrimagnetism in the system. - Highlights: • Mixed valence Co doped ZnO ferromagnetic single crystal thin film. • Secondary phase formation in terms of CoO and Co3O4 and magnetism is observed only for high Co alloying. • Cathodoluminescence (CL) data showing increase in band gap with Co concentrations

  1. The contribution of Fe(III) and humic acid reduction to ecosystem respiration in drained thaw lake basins of the Arctic Coastal Plain

    Science.gov (United States)

    Lipson, David A.; Raab, Theodore K.; Goria, Dominic; Zlamal, Jaime

    2013-04-01

    research showed that anaerobic respiration using iron (Fe) oxides as terminal electron acceptor contributed substantially to ecosystem respiration (ER) in a drained thaw lake basin (DTLB) on the Arctic coastal plain. As DTLBs age, the surface organic layer thickens, progressively burying the Fe-rich mineral layers. We therefore hypothesized that Fe(III) availability and Fe reduction would decline with basin age. We studied four DTLBs across an age gradient, comparing seasonal changes in the oxidation state of dissolved and extractable Fe pools and the estimated contribution of Fe reduction to ER. The organic layer thickness did not strictly increase with age for these four sites, though soil Fe levels decreased with increasing organic layer thickness. However, there were surprisingly high levels of Fe minerals in organic layers, especially in the ancient basin where cryoturbation may have transported Fe upward through the profile. Net reduction of Fe oxides occurred in the latter half of the summer and contributed an estimated 40-45% to ecosystem respiration in the sites with the thickest organic layers and 61-63% in the sites with the thinnest organic layers. All sites had high concentrations of soluble Fe(II) and Fe(III), explained by the presence of siderophores, and this pool became progressively more reduced during the first half of the summer. Redox titrations with humic acid (HA) extracts and chelated Fe support our view that this pattern indicates the reduction of HA during this interval. We conclude that Fe(III) and HA reductions contribute broadly to ER in the Arctic coastal plain.

  2. Two new Zn(II) and Cd(II) coordinastion polymers based on amino-tetrazole and phenylcarboxylate: Syntheses, topological structures and photoluminescent properties

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Dong-Sheng, E-mail: liudongsheng@jgsu.edu.cn [School of Chemistry and Chemical Engineering, Institute of Applied Chemistry, Jinggangshan University, Ji' an, Jiangxi 343009 (China); College of Chemistry and Chemical Engineering, Fuzhou University, Fuzhou, Fujian 350108 (China); Sui, Yan; Chen, Weng-Tong; Huang, Jian-Gen [School of Chemistry and Chemical Engineering, Institute of Applied Chemistry, Jinggangshan University, Ji' an, Jiangxi 343009 (China); Chen, Jian-Zhong [College of Chemistry and Chemical Engineering, Fuzhou University, Fuzhou, Fujian 350108 (China); Huang, Chang-Cang, E-mail: cchuang@fzu.edu.cn [College of Chemistry and Chemical Engineering, Fuzhou University, Fuzhou, Fujian 350108 (China)

    2012-12-15

    Two Zn(II) and Cd(II) compounds with the in-situ generated ligand of 5-amino-tetrazolate (atz{sup -}) were prepared from the hydrothermal reactions of the corresponding Cd or Zn(II) salts with phenylcarboxylate, and characterized by elemental analysis, IR spectroscopy, and TGA. The results of X-ray crystallographic analysis reveal that compound [Zn{sub 2}(BZA)(atz){sub 2}(OH)]{sub n} (1) (BZA=benzoic acid) presents a two-dimensional (2D) 'hcb' topological network constructed from the ZnN{sub 2}O{sub 2} tetrahedra. In compound [Cd{sub 6}(atz){sub 6}(PTA){sub 3}]{sub n} (2) (PTA=terephthalic acid), the identical [Cd{sub 3}(atz){sub 3})]{sup 3+}{sub n} clusters are connected by atz ligands to generate a 2D cationic layer, and the neighboring cationic layers are pillared by PTA giving birth to 3D network. After simplifying, the complicated 3D network of 2 can be presented as an unprecedented (4, 4, 10)-connected trinodal topology. The formations of the structures show a good example that using the combination of the in-situ generated ligand and other coligand synthetic strategy can construct interesting topological structures. The thermal stabilities and fluorescent properties of the complexes have also been studied. - Graphical abstract: Two d{sup 10} metal complexes have been synthesized by employing mixed-ligand synthetic approach. Complex 1 presents a 2D 'hcb' topological network. Complex 2 shows an unprecedented (4, 4, 10)-connected trinodal topology. Highlights: Black-Right-Pointing-Pointer Coligand synthetic strategy was applied to obtain new MOFs with useful properties. Black-Right-Pointing-Pointer Two new Zn(II) and Cd(II) complexes were constructed from the mixed-ligand. Black-Right-Pointing-Pointer Topologically, compound 2 presented an unprecedented (4, 4, 10)-connected trinodal topology. Black-Right-Pointing-Pointer The two compounds may be excellent candidates for potential photoactive material.

  3. A series of Cd(II) complexes with π-π stacking and hydrogen bonding interactions: Structural diversities by varying the ligands

    International Nuclear Information System (INIS)

    Seven new Cd(II) complexes consisting of different phenanthroline derivatives and organic acid ligands, formulated as [Cd(PIP)2(dnba)2] (1), [Cd(PIP)(ox)].H2O (2), [Cd(PIP)(1,4-bdc)(H2O)].4H2O (3), [Cd(3-PIP)2(H2O)2].4H2O (4), [Cd2(3-PIP)4(4,4'-bpdc)(H2O)2].5H2O (5), [Cd(3-PIP)(nip)(H2O)].H2O (6), [Cd2(TIP)4(4,4'-bpdc)(H2O)2].3H2O (7) (PIP=2-phenylimidazo[4,5-f]1,10-phenanthroline, 3-PIP=2-(3-pyridyl)imidazo[4,5-f]1,10-phenanthroline, TIP=2-(2-thienyl)imidazo[4,5-f]1,10-phenanthroline, Hdnba=3,5-dinitrobenzoic acid, H2ox=oxalic acid, 1,4-H2bdc=benzene-1,4-dicarboxylic acid, 4,4'-H2bpdc=biphenyl-4,4'-dicarboxylic acid, H2nip=5-nitroisophthalic acid) have been synthesized under hydrothermal conditions. Complexes 1 and 4 possess mononuclear structures; complexes 5 and 7 are isostructural and have dinuclear structures; complexes 2 and 3 feature 1D chain structures; complex 6 contains 1D double chain, which are further extended to a 3D supramolecular structure by π-π stacking and hydrogen bonding interactions. The N-donor ligands with extended π-system and organic acid ligands play a crucial role in the formation of the final supramolecular frameworks. Moreover, thermal properties and fluorescence of 1-7 are also investigated. -- Graphical abstract: Seven new supramolecular architectures have been successfully isolated under hydrothermal conditions by reactions of different phen derivatives and Cd(II) salts together with organic carboxylate anions auxiliary ligands. Display Omitted Research highlights: → Complexes 1-7 are 0D or 1D polymeric structure, the π-π stacking and H-bonding interactions extend the complexes into 3D supramolecular network. To our knowledge, systematic study on π-π stacking and H-bonding interactions in cadmium(II) complexes are still limited. → The structural differences among the title complexes indicate the importance of N-donor chelating ligands for the creation of molecular architectures. → The thermal and fluorescence properties

  4. Role of microbial Fe(III) reduction and solution chemistry in aggregation and settling of suspended particles in the Mississippi River Delta plain, Louisiana, USA

    Science.gov (United States)

    Jaisi, D.P.; Ji, S.; Dong, H.; Blake, R.E.; Eberl, D.D.; Kim, J.

    2008-01-01

    River-dominated delta areas are primary sites of active biogeochemical cycling, with productivity enhanced by terrestrial inputs of nutrients. Particle aggregation in these areas primarily controls the deposition of suspended particles, yet factors that control particle aggregation and resulting sedimentation in these environments are poorly understood. This study was designed to investigate the role of microbial Fe(III) reduction and solution chemistry in aggregation of suspended particles in the Mississippi Delta. Three representative sites along the salinity gradient were selected and sediments were collected from the sediment-water interface. Based on quantitative mineralogical analyses 88-89 wt.% of all minerals in the sediments are clays, mainly smectite and illite. Consumption of SO421 and the formation of H2S and pyrite during microbial Fe(III) reduction of the non-sterile sediments by Shewanella putrefaciens CN32 in artificial pore water (APW) media suggest simultaneous sulfate and Fe(III) reduction activity. The pHPZNPC of the sediments was ??? 3.5 and their zeta potentials at the sediment-water interface pH (6.9-7.3) varied from -35 to -45 mV, suggesting that both edges and faces of clay particles have negative surface charge. Therefore, high concentrations of cations in pore water are expected to be a predominant factor in particle aggregation consistent with the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. Experiments on aggregation of different types of sediments in the same APW composition revealed that the sediment with low zeta potential had a high rate of aggregation. Similarly, addition of external Fe(II) (i.e. not derived from sediments) was normally found to enhance particle aggregation and deposition in all sediments, probably resulting from a decrease in surface potential of particles due to specific Fe(II) sorption. Scanning and transmission electron microscopy (SEM, TEM) images showed predominant face-to-face clay aggregation in native

  5. Direct Involvement of ombB, omaB and omcB Genes in Extracellular Reduction of Fe(III by Geobacter sulfurreducens PCA

    Directory of Open Access Journals (Sweden)

    Yimo eLiu

    2015-10-01

    Full Text Available The tandem gene clusters orfR-ombB-omaB-omcB and orfS-ombC-omaC-omcC of the metal-reducing bacterium Geobacter sulfurreducens PCA are responsible for trans-outer membrane electron transfer during extracellular reduction of Fe(III-citrate and ferrihydrite [a poorly crystalline Fe(III oxide]. Each gene cluster encodes a putative transcriptional factor (OrfR/OrfS, a porin-like outer-membrane protein (OmbB/OmbC, a periplasmic c-type cytochrome (c-Cyt, OmaB/OmaC and an outer-membrane c-Cyt (OmcB/OmcC. The individual roles of OmbB, OmaB and OmcB in extracellular reduction of Fe(III, however, have remained either uninvestigated or controversial. Here, we showed that replacements of ombB, omaB, omcB and ombB-omaB with an antibiotic gene in the presence of ombC-omaC-omcC had no impact on reduction of Fe(III-citrate by G. sulfurreducens PCA. Disruption of ombB, omaB, omcB and ombB-omaB in the absence of ombC-omaC-omcC, however, severely impaired the bacterial ability to reduce Fe(III-citrate as well as ferrihydrite. These results unequivocally demonstrate an overlapping role of ombB-omaB-omcB and ombC-omaC-omcC in extracellular Fe(III reduction by G. sulfurreducens PCA. Involvement of both ombB-omaB-omcB and ombC-omaC-omcC in extracellular Fe(III reduction reflects the importance of these trans-outer membrane protein complexes in the physiology of this bacterium. Moreover, the kinetics of Fe(III-citrate and ferrihydrite reduction by these mutants in the absence of ombC-omaC-omcC were nearly identical, which suggests that absence of any protein subunit eliminates function of OmaB/OmbB/OmcB protein complex. Finally, orfS was found to have a negative impact on the extracellular reduction of Fe(III-citrate and ferrihydrite in G. sulfurreducens PCA probably by serving as a transcriptional repressor.

  6. Propiedades de los iones Fe(II) y Fe(III) en disolución. Reacciones con reactivos generales y especiales. Ensayos de identificación.

    OpenAIRE

    2015-01-01

    Se muestran las características analíticas de los cationes Fe(II) y Fe(III) en disolución presentando las reacciones químicas de los mismos frente a los reactivos generales y a los reactivos especiales. Estas reacciones van acompañadas de fotos que permiten apreciar los cambios de colores de las disoluciones y precipitados que aparecen en la disolución de ensayo. La descriptiva finaliza con pruebas de identificación de cada ión en ausencia de especies interferentes.

  7. Variegatic acid from Serpula lacyrmans reduces FeIII and interacts with other fungal metabolites for location-specific generation and scavenging of reactive oxygen species

    OpenAIRE

    Zhu, Yuan; MAHANEY, JAMES; Jellison, Jody; Cao, Jinzhen; Gressler, Julia; Hoffmeister, Dirk; Goodell, Barry

    2016-01-01

    This study aims to clarify the role of variegatic acid (VA) secreted from Serpula lacyrmans in a chelator-mediated Fenton (CMF) system, including FeIII reduction and the generation of reactive oxygen species (ROS) in the presence of H2O2 and oxalate. As the principle component of the fungal extracellular matrix (ECM), β-glucan isolated from Basidiomycota species was also assessed in scavenging ROS with regard to its potential as a protective barrier for fungal hyphae. Our results demonstrate ...

  8. Homogeneous (Fe(III) and Heterogeneous (TiO2) Photocatalysts for Pollutants Removal from the Aquatic Compartment: Comparison and Complementarity

    Czech Academy of Sciences Publication Activity Database

    Měšťánková, H.; Mailhot, G.; Krýsa, J.; Jirkovský, Jaromír; Bolte, M.

    Goslar : CUTEC, 2004 - (Vogelpohl, A.), s. 198-203 [International Conference on Oxidation Technologies for Water and Wastewater Treatment /3./. Goslar (DE), 18.05.2003-22.05.2003] R&D Projects: GA ČR GA203/02/0983; GA ČR GA104/02/0662 Grant ostatní: Barrande(FR) 203/20 Institutional research plan: CEZ:AV0Z4040901 Keywords : Fe(III) aquacomplexes * photocatalyst * photodegradation process Subject RIV: CF - Physical ; Theoretical Chemistry

  9. Preconcentration of Cu(II), Fe(III) and Pb(II) with 2-((2-aminoethylamino)methyl)phenol-functionalized activated carbon followed by ICP-OES determination.

    Science.gov (United States)

    He, Qun; Hu, Zheng; Jiang, Yin; Chang, Xijun; Tu, Zhifeng; Zhang, Lina

    2010-03-15

    A procedure for separation and preconcentration trace amount of Cu(II), Fe(III) and Pb(II) by 2-((2-aminoethylamino)methyl)phenol-functionalized activated carbon (AC-AMP) packed column has been proposed. Under the optimized conditions (pH 4, flow rate 2.0 mL min(-1)), Cu(II), Fe(III) and Pb(II) were retained on the column, then quantitatively eluted by 2 mL 1 mol L(-1) nitric acid solution and determined by inductively coupled plasma-optical emission spectrometry (ICP-OES). The tolerance limits of electrolytes were very high. The adsorption capacity of AC-AMP was found to be 12.1, 67.1, and 16.2 mg g(-1) for Cu(II), Fe(III), and Pb(II), respectively. According to the definition of International Union of Pure and Applied Chemistry, the detection limits (3 sigma) of this method for Cu(II), Fe(III) and Pb(II) were 0.27, 0.41 and 0.16 microg L(-1), respectively. The relative standard deviation under optimum conditions is less than 3.0% (n=11). The proposed method has been validated by analyzing a certified reference material and successfully applied to the preconcentration and determination of Cu(II), Fe(III), and Pb(II) in actual samples with satisfactory results. PMID:19926213

  10. Synthesis, crystal structure and spectroscopy of bioactive Cd(II) polymeric complex of the non-steroidal anti-inflammatory drug diclofenac sodium: Antiproliferative and biological activity

    Science.gov (United States)

    Tabrizi, Leila; Chiniforoshan, Hossein; McArdle, Patrick

    2015-02-01

    The interaction of Cd(II) with the non-steroidal anti-inflammatory drug diclofenac sodium (Dic) leads to the formation of the complex [Cd2(L)41.5(MeOH)2(H2O)]n(L = Dic), 1, which has been isolated and structurally characterized by X-ray crystallography. Diclofenac sodium and its metal complex 1 have also been evaluated for antiproliferative activity in vitro against the cells of three human cancer cell lines, MCF-7 (breast cancer cell line), T24 (bladder cancer cell line), A-549 (non-small cell lung carcinoma), and a mouse fibroblast L-929 cell line. The results of cytotoxic activity in vitro expressed as IC50 values indicated the diclofenac sodium and cadmium chloride are non active or less active than the metal complex of diclofenac (1). Complex 1 was also found to be a more potent cytotoxic agent against T-24 and MCF-7 cancer cell lines than the prevalent benchmark metallodrug, cisplatin, under the same experimental conditions. The superoxide dismutase activity was measured by Fridovich test which showed that complex 1 shows a low value in comparison with Cu complexes. The binding properties of this complex to biomolecules, bovine or human serum albumin, are presented and evaluated. Antibacterial and growth inhibitory activity is also higher than that of the parent ligand compound.

  11. Crystal structure of a Cd(II) polymeric complex obtained from a proton-transfer compound containing piperazine and oxalic acid

    International Nuclear Information System (INIS)

    The reaction of cadmium(II) nitrate hexahydrate with the proton-transfer compound (pipzH2)(ox) (where pipz=piperazine and oxH2=oxalic acid), in aqueous solution leads to the formation of the title polymeric compound (C2H6CdO7)n. This compound crystallizes in the triclinic system, space group Pi with two formula in the unit cell. The unit cell parameters are: a=5.998 (4) A, b=6.634 (5) A, c=8.482 (6) A, α=74.679 (10) degree, β=74.348 (11) degree and γ=81.112(11) degree. The final R value was 0.087 for 1309 measured reflections. The CdII ion is seven-coordinated by five O atoms of oxalate ions as tetradentate bridging ligands and two O atoms of coordinated water molecules with distorted pentagonal bi pyramid geometry around the central atom. The asymmetric unit also contains one water molecule. The crystal structure is stabilized by O-H...O hydrogen bonds, linking the molecules into a three-dimensional framework, which results in the formation of a supramolecular structure

  12. Removal of Cd(II), Zn(II) and Pb(II) from aqueous solutions by brown marine macro algae: Kinetic modelling

    Energy Technology Data Exchange (ETDEWEB)

    Freitas, Olga M.M. [LRSE - Laboratory of Separation and Reaction Engineering, Faculdade de Engenharia da Universidade do Porto, Rua Dr. Roberto Frias 4200-465 Porto (Portugal); REQUIMTE, Instituto Superior de Engenharia do Porto, Rua Dr. Bernardino de Almeida 431 4200-072 Porto (Portugal); Martins, Ramiro J.E. [Departamento de Engenharia Quimica e Biologica, Escola Superior de Tecnologia, Instituto Politecnico de Braganca, Campus de Santa Apolonia, 5301-857 Braganca (Portugal); LRSE - Laboratory of Separation and Reaction Engineering, Faculdade de Engenharia da Universidade do Porto, Rua Dr. Roberto Frias 4200-465 Porto (Portugal); Delerue-Matos, Cristina M. [REQUIMTE, Instituto Superior de Engenharia do Porto, Rua Dr. Bernardino de Almeida 431 4200-072 Porto (Portugal); Boaventura, Rui A.R. [Departamento de Engenharia Quimica, Faculdade de Engenharia da Universidade do Porto, Rua Dr. Roberto Frias, 4200-465 Porto (Portugal); LRSE - Laboratory of Separation and Reaction Engineering, Faculdade de Engenharia da Universidade do Porto, Rua Dr. Roberto Frias 4200-465 Porto (Portugal)], E-mail: bventura@fe.up.pt

    2008-05-01

    Specific marine macro algae species abundant at the Portuguese coast (Laminaria hyperborea, Bifurcaria bifurcata, Sargassum muticum and Fucus spiralis) were shown to be effective for removing toxic metals (Cd(II), Zn(II) and Pb(II)) from aqueous solutions. The initial metal concentrations in solution were about 75-100 mg L{sup -1}. The observed biosorption capacities for cadmium, zinc and lead ions were in the ranges of 23.9-39.5, 18.6-32.0 and 32.3-50.4 mg g{sup -1}, respectively. Kinetic studies revealed that the metal uptake rate was rather fast, with 75% of the total amount occurring in the first 10 min for all algal species. Experimental data were well fitted by a pseudo-second order rate equation. The contribution of internal diffusion mechanism was significant only to the initial biosorption stage. Results indicate that all the studied macro algae species can provide an efficient and cost-effective technology for eliminating heavy metals from industrial effluents.

  13. Selective removal of Pb(II), Cd(II), and Zn(II) ions from waters by an inorganic exchanger Zr(HPO3S)2

    International Nuclear Information System (INIS)

    The present study reported synthesis of a new inorganic exchanger, i.e., zirconium hydrogen monothiophosphate [Zr(HPO3S)2, denoted ZrPS] and its selective sorption toward Pb(II), Cd(II) and Zn(II) ions. ZrPS sorption toward all the three metals is dependent upon solution pH due to the ion-exchange nature. As compared to another inorganic exchanger zirconium phosphate [Zr(HPO4)2, denoted ZrP], ZrPS exhibits highly selective sorption toward these toxic metals from the background of calcium ions at great levels. Such sorption preference is mainly attributed to the presence of -SH group in ZrPS, as further demonstrated by FT-IR analysis and XPS study. Moreover, ZrPS particles preloaded with heavy metals could be efficiently regenerated with 6 M HCl for multiple use without any noticeable capacity loss. All the experimental results indicated that ZrPS is a promising sorbent for enhanced heavy metals removal from contaminated water.

  14. Photocurrent-generating properties of bulk and few-layered Cd(ii) coordination polymers based on a rigid dicarboxylate ligand.

    Science.gov (United States)

    Jiang, Peng Gang; Zhang, Pan; Gong, Yun; Lin, Jian Hua

    2016-03-21

    Based on a rigid ligand, 2,5-bis[3'-carboxyl-phenyl] pyridine (H2L), two coordination polymers (CPs) formulated as Cd3L3(DMF)4 (1) and CdL(DMF)·DMF (2) were solvothermally synthesized and characterized by single-crystal X-ray diffraction. CP 1 is a uninodal 6-connected 3D network with a {4(4)·6(10)·8}-mab topology, in which the Cd3 unit with a CdCd separation of 3.61 Å is observed. CP 2 exhibits a uninodal 2D layer with a 4(4)-sql topology, in which Cd(ii) ions are linked into a Cd-O-Cd chain with a CdCd separation of 3.91 Å. DFT calculations indicate that CP 1 possesses a more narrow band gap than CP 2, and CP 1 yields higher photocurrent density upon visible light illumination than CP 2. In the present work, the few-layered CP 2 has been in situ synthesized, and it shows enhanced photocurrent density with respect to the bulk CP, which is probably associated with the large fraction of uncoordinated surface atoms and dangling bonds in the nanosheet of CP 2. PMID:26846935

  15. Solvent extraction of Sc(III), Zr(IV), Th(IV), Fe(III), and Lu(III) with thiosubstituted organophosphinic acid extractants

    International Nuclear Information System (INIS)

    The solvent extraction of Sc(III), Zr(IV), Th(IV), Fe(III) and Lu(III) with Cyanex 302 (bis(2,4,4-trimethylpentyl)monothiphosphinic acid) and Cyanex 301 (bis(2,4,4-trimethylpentyl)dithiophosphinic acid) in n-hexane from acidic aqueous solutions has been investigated systematically. The effect of equilibrium aqueous acidity on the extraction with these reagents was studied. The separation of Th(IV), Fe(III) and Lu(III) from Sc(III), or the separation of other metals from Lu(III) with Cyanex 302, can be achieved by controlling the aqueous acidity. However, Cyanex 301 exhibited a poor selectivity for the above metals, except for Lu(III). The extraction of these metals with Cyanex 272, Cyanex 302 and Cyanex 301 has been compared. The stripping percentages of Sc(III) for Cyanex 302 and Cyanex 301 in a single stage are near 78% and 75% with 3.5 mol/L and 5.8 mol/L sulphuric acid solutions, respectively. The effects of extractant concentration and temperature on the extraction of Sc(III) were investigated. The stoichiometry of the extraction of Sc(III) with Cyanex 302 was determined. The role of different components of Cyanex 302 in the extraction of Sc(III) was discussed. 18 refs., 10 figs

  16. INVESTIGATION OF THE TRANSFORMATION OF URANIUM UNDER IRON-REDUCING CONDITIONS: REDUCTION OF UVI BY BIOGENIC FEII/FEIII HYDROXIDE (GREEN RUST)

    Energy Technology Data Exchange (ETDEWEB)

    O' Loughlin, Edward J.; Scherer, Michelle M.; Kemner, Kenneth M.

    2006-12-31

    The recent identification of green rusts (GRs) as products of the reduction of FeIII oxyhydroxides by dissimilatory iron-reducing bacteria, coupled with the ability of synthetic (GR) to reduce UVI species to insoluble UO2, suggests that biogenic green rusts (BioGRs) may play an important role in the speciation (and thus mobility) of U in FeIII-reducing environments. The objective of our research was to examine the potential for BioGR to affect the speciation of U under FeIII-reducing conditions. To meet this objective, we designed and executed a hypothesis-driven experimental program to identify key factors leading to the formation of BioGRs as products of dissimilatory FeIII reduction, to determine the key factors controlling the reduction of UVI to UIV by GRs, and to identify the resulting U-bearing mineral phases. The results of this research significantly increase our understanding of the coupling of biotic and abiotic processes with respect to the speciation of U in iron-reducing environments. In particular, the reduction of UVI to UIV by BioGR with the subsequent formation of U-bearing mineral phases may be effective for immobilizing U in suboxic subsurface environments. This information has direct applications to contaminant transport modeling and bioremediation engineering for natural or enhanced in situ remediation of subsurface contamination.

  17. Coprecipitation of Pu(IV) with Fe(III) and Cr(III) hydroxides from nitrate-acetate solutions in hydrothermal conditions modeling deep disposal of liquid radioactive wastes

    International Nuclear Information System (INIS)

    Precipitation of Fe(III), Cr(III), Ni(II), Mn(II) and coprecipitation of Pu with Fe(III) and Cr(III) from nitrate-acetate solutions are investigated. It is shown that plutonium coprecipitates in noticeable degree at pH≥4. Plutonium is included in precipitate composition only when FeOOH phase is forming; formation of Pu(IV) compound with Fe2O3 does not observed. In conditions studied in water phase plutonium can exist in oxidation state +4 forming monoacetate or hydroxyacetate complexes

  18. Synthesis and X-ray structure analysis of a new binuclear Schiff base Co(II) complex with the ligand N,N'-bis(3-methoxysalicylidene)-1,4-butanediamine

    International Nuclear Information System (INIS)

    The title binuclear complex, tris[N,N-bis(3-methoxysalicylidene)-1,4-diaminobutane] dicobalt(II), C60H70Co2N6O15, was prepared by the reaction of the tetradentate Schiff base ligand bis(3-methoxysalicylidene)-1,4-diaminobutane and Co(CH3COO)2 . 4H2O in a ethanol solution and structurally characterized by single-crystal X-ray diffraction. This complex has a dinuclear structure where two Co(II) ions are bridged by one N0,N'-bis(3-methoxysalicylidene)-1,4-diaminobutane. The two Co(II) ions, have two distorted octahedral coordination involving two O and two N atoms.

  19. Electronic, epr and magnetic studies of Co(II), Ni(II) and Cu(II) complexes with thiosemicarbazone (L 1) and semicarbazone (L 2) derived from pyrole-2-carboxyaldehyde

    Science.gov (United States)

    Chandra, Sulekh; Kumar, Anil

    2007-07-01

    Co(II), Ni(II) and Cu(II) complexes are synthesized with thiosemicarbazone (L 1) and semicarbazone (L 2) derived from pyrole-2-carboxyaldehyde. These complexes are characterized by elemental analysis, molar conductance, magnetic susceptibility measurements, mass, IR, electronic and EPR spectral studies .The molar conductance measurements of the complexes in DMSO correspond to non-electrolytic nature except Co(L 1) 2(NO 3) 2 and Ni(L 1) 2(NO 3) 2 complexes which are 1:2 electrolytes. All the complexes are of high-spin type. On the basis of spectral studies an octahedral geometry may be assigned for Co(II) and Ni(II) complexes except Co(L 1) 2(NO 3) 2 and Ni(L 1) 2(NO 3) 2 which are of tetrahedral geometry. A tetragonal geometry may be suggested for Cu(II) complexes.

  20. Cloud point extraction and simultaneous spectrophotometric determination of V(V), Co(II) and Cu(II) ions in water samples by 5-Br-PADAP using partial least squares regression

    International Nuclear Information System (INIS)

    In this work, a new method has been proposed to simultaneously determine V(V), Co(II) and Cu(II) ions from aqueous solution by spectrophotometry after cloud point extraction using partial least squares regression (PLS). The metal ions in 10 ml of aqueous solution (containing 0.2 M sodium acetate buffer solution, pH 3.5) were formed complexes with 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol (5-Br-PADAP). Then, Triton X-114 (2 %, v/v) was added to the solution. By increasing the temperature of the solution up to 55 deg C, a phase separation occurred. After centrifugation at 3,000 rpm for 10 min, the surfactant-rich phase was dissolved and diluted to 0.5 mL with ethanol. The metal ions were then determined using spectrophotometry. At these optimal extraction and operating conditions, linearity was obeyed in the range 7-300, 3-100 and 15-700 ng mL-1 of V(V), Co(II) and Cu(II), with the detection limit of 2.2, 1.0 and 4.5 ng mL-1, respectively. The relative predictive error for the simultaneous determination of 15 test samples of different concentrations of V(V), Co(II) and Cu(II) was 3.28, 3.64 and 4.04 %, respectively. The root mean square error of prediction for applying the PLS method to 15 synthetic samples in the linear ranges of these metal ions was 3.4, 1.6 and 18.1 ng mL-1. The interference effect of some anions and cations was also tested. The proposed method has been applied successfully to the simultaneous determination of V(V), Co(II) and Cu(II) ions in real matrix samples with the recoveries of 96.75-104.80 %. (author)

  1. Ammonia-modified Co(II) sites in zeolites: spin and electron density redistribution through the Co(II)-NO bond.

    Science.gov (United States)

    Stępniewski, Adam; Radoń, Mariusz; Góra-Marek, Kinga; Broclawik, Ewa

    2016-02-01

    Electronic factors essential for the bonding of a non-innocent NO ligand to ammonia-modified Co(2+) sites in cobalt-exchanged zeolites are examined for small cluster models using DFT and advanced correlated wave function calculations. The analysis of charge transfer processes between the NO ligand and the cobalt center involves two protocols: valence-bond expansion of the multiconfiguration CASSCF wave function (in terms of fragment-localized active orbitals) and spin-resolved natural orbitals for chemical valence (SR-NOCV). Applicability of SR-NOCV analysis to transition metal complexes involving non-innocent fragments is critically assessed and the approach based on the CASSCF wave function turns out to be much more robust and systematic for all studied models. It is shown that the character and direction of electron density redistribution through the Co-N-O bond, quantified by relative share of the Co(II)-NO(0), Co(III)-NO(-), and Co(I)-NO(+) resonance structures in the total wave function, fully rationalize the activation of the N-O bond upon NH3 co-ligation (evidenced by calculated and measured red-shift of the NO stretching frequency and commonly ascribed to enhanced backdonation). The huge red-shift of νN-O is attributed to an effective electron transfer between the ammonia-modified Co(ii) centers and the NO antibonding π*-orbitals (related to the increased share of the Co(III)-NO(-) form). Unexpectedly, the effect is stronger for the singlet complex with three NH3 ligands than for that with five NH3 ligands bound to the cobalt center. Our results also indicate that high-efficiency electron transfers between the Co(ii) center and the NO ligand may be enabled for the selected spin state and disabled for the other spin state of the adduct. This illustrates how the cobalt center may serve to fine-tune the electronic communication between the NO ligand and its binding site. PMID:26761131

  2. Isolation and characterization of the tertiary amine Alamine 304 hydrochioride. Its application on the extraction of Co(II, Au(III and Pt(IV

    Directory of Open Access Journals (Sweden)

    López-Delgado, Aurora

    2000-06-01

    Full Text Available Amine Alamine 304 dissolved in xylene reacts with hydrochloric acid to form the amine chloride (R3NH+Cl- and the amine dichloride (R3NH2Cl2. The former compound was isolated and characterized by chemical analysis, X-ray powder diffraction, infrared spectroscopy and scanning electron microscopy. Lattice parameters of the isolated amine chloride were determined and refined by least-square numerical treatment (monoclinic cell, with a = 29.017(4 Å, b = 14.564(7 Å, c = 5.043(1 Å, b = 95.68(3 ° and V = 2,120 Å3. The amine chloride is a potential anion-exchanger with metals, thus data on the liquid-liquid extraction of Co(II, Au(III and Pt(IV are also reported.

    La amina Alamine 304 disuelta en xileno reacciona con el ácido clorhídrico para formar el cloruro de la amina (R3NH+Cl- y el dicloruro de amina (R3NH2Cl2. El primero de estos compuestos se aisló y caracterizó mediante análisis químico, difracción de rayos X, espectroscopia de IR y microscopía electrónica de barrido. Se determinaron y refinaron los parámetros de red del cloruro de amina (monoclínico, a = 29,017(4 Å, b = 14,564(7 Å, c = 5,043(1 Å, b = 95,68(3 ° y V = 2.120 Å3. El cloruro de amina actúa como un intercambiador aniónico con ciertos metales, por lo que se incluyen datos sobre la extracción líquido-líquido de Co(II, Au(III y Pt(IV.

  3. Uptake of waterborne 109Cd(II) in the scallop (Chlamys islandica) studied by in vivo gamma counting and quantitative whole-body autoradiography

    International Nuclear Information System (INIS)

    Scallops caught in the North coast of the Gulf of St. Lawrence (Quebec, Canada) have been found to contain elevated levels of cadmium (Cd), though this area is far from any point source of pollution. Concentrations observed ranges from 2 to more than 20 mg/kg (w.w.) in the whole animal. This exceeds the European guidelines of 1 mg Cd/kg set for molluscs and have led to the refusal of scallop stocks from the area mentioned above. Relatively little is known about the uptake of Cd by scallops, apart from the fact that they often exhibit high concentrations of this metal in their tissues, especially in the digestive gland. To better understand the fate of Cd in scallop, we have exposed Chlamys islandica (60- 80 mm shell height) to waterborne 109Cd(II) (nominal concentration 37 kBq/L, closed system) for 45 hours. Accumulation of Cd was followed over time by non-destructive in vivo gamma counting (IVGC). At the termination of the exposure period, scallops were then placed in clean running seawater and radioactivity loss was monitored for 35 d. Results from IVGC were used to quantify the kinetics of uptake and elimination. Six of these scallops were sampled at t = 0, 7, and 35 d during the depuration period and used for whole-body autoradiography to precisely determined the distribution of the accumulated 109Cd. Preliminary analysis of data from IVGC showed that scallop rapidly accumulated 109Cd(II) from the water and that elimination was bi-exponential, with 30-35% of the radioactivity being eliminated within 2 d while the remaining 65-70% was eliminated at a slower rate, with half-life values ranging from 20 to 140 d (average 73 ± 52 d). Whole-body autoradio-graphy shows that 109Cd was distributed in all tissues of the scallop, the highest concentration being found in the kidney and the lowest in the muscle. Actually, the concentration of the radiolabel in the kidney is some 10 times higher than in any other tissue. Despite of its small size (ca. 1% of soft tissue

  4. Potentiometric studies on the complexes of tetracycline (TC) and oxytetracycline (OTC) with some metal ions

    International Nuclear Information System (INIS)

    The interaction of Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Zn(II), Cd(II), Hg(II), Pb(II), Al(III), and UO2(II) ions with tetracycline (TC) were studied by potentiometric pH titrations. The formation constants of the different binary complexes formed in such systems have been determined at 25±0.1 deg C and μ=0.1 moll-1 (NaNO3). Potentiometric pH equilibrium measurements have been made under the same conditions for the interaction of oxytetracycline (OTC) and Cu(II), Cd(II), Pb(II), and UO2(II). The formation of (1:1) binary complexes are inferred from the potentiometric pH titration curves. The protonation constants of TC and OTC were also determined under the same conditions and refined (ESAB2M computer program). The transition metal stability constants are consistent with the Irving-Williams series. (authors)

  5. Application of Zr/Ti-Pic in the adsorption process of Cu(II), Co(II) and Ni(II) using adsorption physico-chemical models and thermodynamics of the process; Aplicacao de Zr/Ti-PILC no processo de adsorcao de Cu(II), Co(II) e Ni(II) utilizando modelos fisico-quimicos de adsorcao e termodinamica do processo

    Energy Technology Data Exchange (ETDEWEB)

    Guerra, Denis Lima; Airoldi, Claudio [Universidade Estadual de Campinas (UNICAMP), SP (Brazil). Inst. de Quimica. Dept. de Quimica Inorganica]. E-mail: dlguerra@iqm.unicamp.br; Lemos, Vanda Porpino; Angelica, Romulo Simoes [Universidade Federal do Para (UFPa), Belem (Brazil); Viana, Rubia Ribeiro [Universidade Federal do Mato Grosso (UFMT), Cuiaba (Brazil). Inst. de Ciencias Exatas e da Terra. Dept. de Recursos Minerais

    2008-07-01

    The aim of this investigation is to study how Zr/Ti-Pic adsorbs metals. The physico-chemical proprieties of Zr/Ti-Pic have been optimized with pillarization processes and Cu(II), Ni(II) and Co(II) adsorption from aqueous solution has been carried out, with maximum adsorption values of 8.85, 8.30 and 7.78 x-1 mmol g{sup -1}, respectively. The Langmuir, Freundlich and Temkin adsorption isotherm models have been applied to fit the experimental data with a linear regression process. The energetic effect caused by metal interaction was determined through calorimetric titration at the solid-liquid interface and gave a net thermal effect that enabled the calculation of the exothermic values and the equilibrium constant. (author)

  6. Soft metal ions, Cd(II) and Hg(II), induce triple-stranded alpha-helical assembly and folding of a de novo designed peptide in their trigonal geometries.

    OpenAIRE

    Li, X; K. Suzuki; Kanaori, K; Tajima, K; Kashiwada, A.; Hiroaki, H; Kohda, D; Tanaka, T

    2000-01-01

    We previously reported the de novo design of an amphiphilic peptide [YGG(IEKKIEA)4] that forms a native-like, parallel triple-stranded coiled coil. Starting from this peptide, we sought to regulate the assembly of the peptide by a metal ion. The replacement of the Ile18 and Ile22 residues with Ala and Cys residues, respectively, in the hydrophobic positions disrupted of the triple-stranded alpha-helix structure. The addition of Cd(II), however, resulted in the reconstitution of the triple-str...

  7. Synthesis, spectral and thermal studies of pyridyl adducts of Zn(II) and Cd(II) dithiocarbamates, and their use as single source precursors for ZnS and CdS nanoparticles

    OpenAIRE

    Damian C. Onwudiwe; Strydom, Christien A.; Jordaan, Anine; Oluwafemi, Oluwatobi S.; Hosten, Eric

    2014-01-01

    The synthesis, spectroscopic characterisation, and thermal studies of pyridyl adducts of Zn(II) and Cd(II) complexes of N-ethyl-N-phenyl dithiocarbamate, represented as [ZnL2py] and [CdL2py2], are reported. Single-crystal X-ray structural analysis of the Zn compound showed that it is five-coordinate with four sulphurs from dithiocarbamate and one nitrogen from pyridine in a distorted square pyramidal geometry. The thermogravimetric studies indicate that the zinc and cadmium compou...

  8. The thermodynamic characteristics of formation of mono- and binuclear biladiene Ni(II), Cu(II), Zn(II), Cd(II), and Hg(II) chelates in dimethylformamide solutions

    International Nuclear Information System (INIS)

    Thermodynamics of 1,2,3,7,8,12,13,17,18,19-decamethylbiladiene-a,c complexing with Ni(II), Cu(II), Zn(II), Cd(II) and Hg(II) acetates was studied. Fairmont enthalpies of corresponding metal complexes were analyzed using titration calorimetry. This allowed to calculate full set of thermodynamic properties of processes. Binuclear heteroligand complexes [M2L(AcO)2)] (M = Cd, Hg) formation is most entropy favorable processes, that is evidently conditioned by the deliverance of large number of DMFA molecules from coordinating spheres of two solvate-cations when tetrapyrrole ligand coordination, and it demonstrates high thermodynamic stability of given ligands

  9. Green oxidation of alkenes in ionic liquid solvent by hydrogen peroxide over high performance Fe(III) Schiff base complexes immobilized on MCM-41

    Indian Academy of Sciences (India)

    Mohammad Taghi Goldani; Ali Mohammadi; Reza Sandaroos

    2014-05-01

    A series of Fe(III) Schiff base complexes immobilized on MCM-41 were prepared and characterized by various physicochemical and spectroscopic methods. The complexes were used for oxidation of cyclohexene by 30% hydrogen peroxide in the presence and absence of ethylmethyl imidazolium chloride (EMIM) ionic liquid as solvent. The immobilized complexes proved to be effective catalysts and generally exhibited much higher catalytic performance than their homogeneous analogue. Catalytic performance of the complexes was also found to be closely related to the Schiff base ligands used. Additionally, ion liquid solvent efficiently improved all the catalytic performances. Finally, the reaction was extended to different alkenes using the heterogeneous complex 2-L4. Among all the alkenes, those containing -electron-withdrawing groups and trans-orientations exhibited lower tendency for oxidation.

  10. A Mononuclear Co(II) Coordination Complex Locked in a Confined Space and Acting as an Electrochemical Water-Oxidation Catalyst: A "Ship-in-a-Bottle" Approach.

    Science.gov (United States)

    Manna, Paulami; Debgupta, Joyashish; Bose, Suranjana; Das, Samar K

    2016-02-12

    Preparing efficient and robust water oxidation catalyst (WOC) with inexpensive materials remains a crucial challenge in artificial photosynthesis and for renewable energy. Existing heterogeneous WOCs are mostly metal oxides/hydroxides immobilized on solid supports. Herein we report a newly synthesized and structurally characterized metal-organic hybrid compound [{Co3 (μ3 -OH)(BTB)2(dpe)2} {Co(H2O)4(DMF)2}0.5]n ⋅n H2O(Co-WOC-1) as an effective and stable water-oxidation electrocatalyst in an alkaline medium. In the crystal structure of Co-WOC-1, a mononuclear Co(II) complex {Co(H2O)4(DMF)2}(2+) is encapsulated in the void space of a 3D framework structure and this translationally rigid complex cation is responsible for a remarkable electrocatalytic WO activity, with a catalytic turnover frequency (TOF) of 0.05 s(-1) at an overpotential of 390 mV (vs. NHE) in 0.1 m KOH along with prolonged stability. This host-guest system can be described as a "ship-in-a-bottle", and is a new class of heterogeneous WOC. PMID:26757444

  11. Ammonia-modified Co(II) sites in zeolites: IR spectroscopy and spin-resolved charge transfer analysis of NO adsorption complexes.

    Science.gov (United States)

    Góra-Marek, Kinga; Stępniewski, Adam; Radoń, Mariusz; Broclawik, Ewa

    2014-11-21

    IR spectroscopic studies and quantum chemical modeling (aided by the analysis of charge transfer processes between co-adsorbed ammonia and the Co(II)-NO adduct) evidence that donor ammonia molecules, ligated to extraframework Co(2+) centers in zeolites, vitally affect the strength of the N-O bond. Calculations indicate that versatility of ammine nitrosyl complexes, differing in the number of NH3 ligands as well as in the geometry and electronic structure of the Co-N-O unit (showing variable activation of NO) may co-exist in zeolite frameworks. However, only combined analysis of experimental and calculation results points to the adducts with three or five NH3 coligands as decisive. The novel finding concerning the interpretation of discussed IR spectra is the assignment of the most down-shifted bands at 1600-1615 cm(-1) to the N-O stretch in the singlet [Co(NH3)3(NO)](2+) adduct, in place of tentative ascription to pentaammine adducts. Theory indicates also that the Co(ii) center (with manifold of close-lying electronic and spin states) acts as a tunable electron donor where the spin state may open or close specific channels transferring electron density from the donor ligands (treated as the part of environment) to the NO molecule. PMID:25245279

  12. Suppressing of slow magnetic relaxation in tetracoordinate Co(II) field-induced single-molecule magnet in hybrid material with ferromagnetic barium ferrite

    Science.gov (United States)

    Nemec, Ivan; Herchel, Radovan; Trávníček, Zdeněk

    2015-01-01

    The novel field-induced single-molecule magnet based on a tetracoordinate mononuclear heteroleptic Co(II) complex involving two heterocyclic benzimidazole (bzi) and two thiocyanido ligands, [Co(bzi)2(NSC)2], (CoL4), was prepared and thoroughly characterized. The analysis of AC susceptibility data resulted in the spin reversal energy barrier U = 14.7 cm−1, which is in good agreement with theoretical prediction, Utheor. = 20.2 cm−1, based on axial zero-field splitting parameter D = −10.1 cm−1 fitted from DC magnetic data. Furthermore, mutual interactions between CoL4 and ferromagnetic barium ferrite BaFe12O19 (BaFeO) in hybrid materials resulted in suppressing of slow relaxation of magnetization in CoL4 for 1:2, 1:1 and 2:1 mass ratios of CoL4 and BaFeO despite the lack of strong magnetic interactions between two magnetic phases. PMID:26039085

  13. Supramolecular complexes of Co(II), Ni(II) and Zn(II) p-hydroxybenzoates with caffeine: Synthesis, spectral characterization and crystal structure

    Science.gov (United States)

    Taşdemir, Erdal; Özbek, Füreya Elif; Sertçelik, Mustafa; Hökelek, Tuncer; Çelik, Raziye Çatak; Necefoğlu, Hacali

    2016-09-01

    Three novel complexes Co(II), Ni(II) and Zn(II) containing p-hydroxybenzoates and caffeine ligands were synthesized and characterized by elemental analysis, FT-IR and UV-vis Spectroscopy, molar conductivity and single crystal X-ray diffraction methods. The thermal properties of the synthesized complexes were investigated by TGA/DTA. The general formula of the complexes is [M(HOC6H4COO)2(H2O)4]·2(C8H10N4O2)·8H2O (where: M: Co, Ni and Zn). The IR studies showed that carboxylate groups of p-hydroxybenzoate ligands have monodentate coordination mode. The M2+ ions are octahedrally coordinated by two p-hydroxybenzoate ligands, four water molecules leading to an overall MO6 coordination environment. The medium-strength hydrogen bondings involving the uncoordinated caffeine ligands and water molecules, coordinated and uncoordinated water molecules and p-hydroxybenzoate ligands lead to three-dimensional supramolecular networks in the crystal structures.

  14. DNA cleavage, antimicrobial, spectroscopic and fluorescence studies of Co(II), Ni(II) and Cu(II) complexes with SNO donor coumarin Schiff bases

    Science.gov (United States)

    Patil, Sangamesh A.; Naik, Vinod H.; Kulkarni, Ajaykumar D.; Badami, Prema S.

    2010-01-01

    A series of Co(II), Ni(II) and Cu(II) complexes of the type ML 2 have been synthesized with Schiff bases derived from methylthiosemicarbazone and 5-formyl-6-hydroxy coumarin/8-formyl-7-Hydroxy-4-methylcoumarin. The complexes are insoluble in common organic solvents but soluble in DMF and DMSO. The measured molar conductance values in DMF indicate that, the complexes are non-electrolytes in nature. In view of analytical, spectral (IR, UV-vis, ESR, FAB-mass and fluorescence), magnetic and thermal studies, it has been concluded that, all the metal complexes possess octahedral geometry in which ligand is coordinated to metal ion through azomethine nitrogen, thione sulphur and phenolic oxygen atom via deprotonation. The redox behavior of the metal complexes was investigated by using cyclic voltammetry. The Schiff bases and their complexes have been screened for their antibacterial ( Escherichia coli, Staphylococcus aureus, Pseudomonas aeruginosa and Salmonella typhi) and antifungal activities ( Aspergillus niger, Aspergillus flavus and Cladosporium) by Minimum Inhibitory Concentration method. The DNA cleavage is studied by agarose gel electrophoresis method.

  15. Synthesis, DFT Calculation, and Antimicrobial Studies of Novel Zn(II), Co(II), Cu(II), and Mn(II) Heteroleptic Complexes Containing Benzoylacetone and Dithiocarbamate

    Science.gov (United States)

    Ekennia, Anthony C.; Onwudiwe, Damian C.; Olasunkanmi, Lukman O.; Osowole, Aderoju A.; Ebenso, Eno E.

    2015-01-01

    Heteroleptic complexes of zinc(II), copper(II), manganese(II), and cobalt(II) of the types [MLL′(H2O)2]·nH2O and [MLL′]·nH2O have been synthesized using sodium N-methyl-N-phenyldithiocarbamate (L) and benzoylacetone (L′). The metal complexes were characterized by elemental analysis, electrical conductance, magnetic susceptibility, infrared (IR), and UV-visible spectroscopic studies. The electrical conductance measurements revealed the nonelectrolytic nature of the synthesized complexes. The results of the elemental analyses, magnetic susceptibility measurements, and electronic spectra inferred that the Zn(II) complex adopted a four-coordinate geometry while the Co(II), Cu(II), and Mn(II) complexes assumed octahedral geometries. The IR spectra showed that the metal ions coordinated with the ligands via the S- and O-donor atoms. The geometry, electronic, and thermodynamic parameters of the complexes were obtained from density functional theory (DFT) calculations. The spin density distributions, relative strength of H–bonds, and thermodynamic parameters revealed that the order of stability of the metal complexes is Mn Zn. The agar diffusion methods were used to study the antimicrobial activity of the complexes against two Gram positive bacteria (S. aureus and S. pneumoniae), one Gram negative bacterium (E. coli), and two fungi organisms (A. niger and A. candida) and the complexes showed a broad spectrum of activities against the microbes. PMID:26681931

  16. Studies on the liquid-liquid extraction and precipitate flotation of the second kind of Co(II) using 8-hydroxy quinoline

    International Nuclear Information System (INIS)

    The liquid-liquid extraction and precipitate flotation of the second kind (i.e., without the use of surfactant collectors) have been investigated for Co(II) using 8-hydroxy quinoline (Hq) and the results are compared. Organic solvents used were chloroform in the case of liquid-liquid extraction and ethanol (used as solvent for the collector and as a frothier) in the case of flotation. From the results it appears that liquid-liquid extraction occurs through the formation of the adduct Coq2(Hq) but flotation takes place trough the formation of the precipitate Coq2. Unlike precipitate flotation of the first kind, precipitate flotation of the second kind has the advantage that the recovery is not affected by the ionic strength of the medium. An induction time of about 5 minutes is required to attain the maximum flotation results. The effects of pH and Hq concentration on both of the extraction processes were also investigated and the results are discussed. (author). 45 refs., 8 figs

  17. MtDNA COI-COII marker and drone congregation area: an efficient method to establish and monitor honeybee (Apis mellifera L.) conservation centres.

    Science.gov (United States)

    Bertrand, Bénédicte; Alburaki, Mohamed; Legout, Hélène; Moulin, Sibyle; Mougel, Florence; Garnery, Lionel

    2015-05-01

    Honeybee subspecies have been affected by human activities in Europe over the past few decades. One such example is the importation of nonlocal subspecies of bees which has had an adverse impact on the geographical repartition and subsequently on the genetic diversity of the black honeybee Apis mellifera mellifera. To restore the original diversity of this local honeybee subspecies, different conservation centres were set up in Europe. In this study, we established a black honeybee conservation centre Conservatoire de l'Abeille Noire d'Ile de France (CANIF) in the region of Ile-de-France, France. CANIF's honeybee colonies were intensively studied over a 3-year period. This study included a drone congregation area (DCA) located in the conservation centre. MtDNA COI-COII marker was used to evaluate the genetic diversity of CANIF's honeybee populations and the drones found and collected from the DCA. The same marker (mtDNA) was used to estimate the interactions and the haplotype frequency between CANIF's honeybee populations and 10 surrounding honeybee apiaries located outside of the CANIF. Our results indicate that the colonies of the conservation centre and the drones of the DCA show similar stable profiles compared to the surrounding populations with lower level of introgression. The mtDNA marker used on both DCA and colonies of the conservation centre seems to be an efficient approach to monitor and maintain the genetic diversity of the protected honeybee populations. PMID:25335970

  18. Suppressing of slow magnetic relaxation in tetracoordinate Co(II) field-induced single-molecule magnet in hybrid material with ferromagnetic barium ferrite.

    Science.gov (United States)

    Nemec, Ivan; Herchel, Radovan; Trávníček, Zdeněk

    2015-01-01

    The novel field-induced single-molecule magnet based on a tetracoordinate mononuclear heteroleptic Co(II) complex involving two heterocyclic benzimidazole (bzi) and two thiocyanido ligands, [Co(bzi)2(NSC)2], (CoL4), was prepared and thoroughly characterized. The analysis of AC susceptibility data resulted in the spin reversal energy barrier U = 14.7 cm(-1), which is in good agreement with theoretical prediction, U(theor). = 20.2 cm(-1), based on axial zero-field splitting parameter D = -10.1 cm(-1) fitted from DC magnetic data. Furthermore, mutual interactions between CoL4 and ferromagnetic barium ferrite BaFe12O19 (BaFeO) in hybrid materials resulted in suppressing of slow relaxation of magnetization in CoL4 for 1:2, 1:1 and 2:1 mass ratios of CoL4 and BaFeO despite the lack of strong magnetic interactions between two magnetic phases. PMID:26039085

  19. Development of a C3-symmetric benzohydroxamate tripod: Trimetallic complexation with Fe(III), Cr(III) and Al(III)

    Science.gov (United States)

    Baral, Minati; Gupta, Amit; Kanungo, B. K.

    2016-06-01

    The design, synthesis and physicochemical characterization of a C3-symmetry Benzene-1,3,5-tricarbonylhydroxamate tripod, noted here as BTHA, are described. The chelator was built from a benzene as an anchor, symmetrically extended by three hydroxamate as ligating moieties, each bearing O, O donor sites. A combination of absorption spectrophotometry, potentiometry and theoretical investigations are used to explore the complexation behavior of the ligand with some trivalent metal ions: Fe(III), Cr(III), and Al(III). Three protonation constants were calculated for the ligand in a pH range of 2-11 in a highly aqueous medium (9:1 H2O: DMSO). A high rigidity in the molecular structure restricts the formation of 1:1 (M/L) metal encapsulation but shows a high binding efficiency for a 3:1 metal ligand stoichiometry giving formation constant (in β unit) 28.73, 26.13 and 19.69 for [M3L]; Mdbnd Fe(III), Al(III) and Cr(III) respectively, and may be considered as an efficient Fe-carrier. The spectrophotometric study reveals of interesting electronic transitions occurred during the complexation. BTHA exhibits a peak at 238 nm in acidic pH and with the increase of pH, a new peak appeared at 270 nm. A substantial shifting in both of the peaks in presence of the metal ions implicates a s coordination between ligand and metal ions. Moreover, complexation of BTHA with iron shows three distinct colors, violet, reddish orange and yellow in different pH, enables the ligand to be considered for the use as colorimetric sensor.

  20. Speciative Determination of Dissolved Inorganic Fe(II, Fe(III and Total Fe in Natural Waters by Coupling Cloud Point Extraction with FAAS

    Directory of Open Access Journals (Sweden)

    Ramazan GÜRKAN

    2013-12-01

    Full Text Available A new cloud point extraction (CPE method for the preconcentration of trace iron speciation in natural waters prior to determination by flame atomic absorption spectrometry (FAAS was developed in the present study. In this method, Fe(II sensitively and selectively reacts with Calcon carboxylic acid (CCA in presence of cetylpyridinium chloride (CPC yielding a hydrophobic complex at pH 10.5, which is then entrapped in surfactant-rich phase. Total Fe was accurately and reliably determined after the reduction of Fe(III to Fe(II with sulfite. The amount of Fe(III in samples was determined from the difference between total Fe and Fe(II. CPC was used not only as an auxiliary ligand in CPE, but also as sensitivity enhancement agent in FAAS. The nonionic surfactant, polyethylene glycol tert-octylphenyl ether (Triton X-114 was used as an extracting agent. The analytical variables affecting CPE efficiency were investigated in detail. The preconcentration/enhancement factors of 50 and 82 respectively, were obtained for the preconcentration of Fe(II with 50 mL solution. Under the optimized conditions, the detection limit of Fe(II in linear range of 0.2-60 μg L-1 was 0.06 μg L-1. The relative standard deviation was 2.7 % (20 μg L-1, N: 5, recoveries for Fe(II were in range of 99.0-102.0% for all water samples including certified reference materials (CRMs. In order to verify its accuracy, two CRMs were analyzed and the results obtained were statistically in good agreement with the certified values.

  1. SPE coupled to AAS trace determination of Cd(II) and Zn(II) in food samples using amine functionalized GMA-MMA-EGDMA terpolymer: Isotherm and kinetic studies.

    Science.gov (United States)

    Islam, Aminul; Kumar, Suneel; Zaidi, Noushi; Ahmad, Hilal

    2016-12-15

    An ethylenediamine functionalized glycidyl methacrylate (GMA) based terpolymeric chelating resin was synthesized for the separation and preconcentration of Cd(II) and Zn(II) by SPE from bread, rice and fruit juice prior to FAAS determination. The resin was characterized by FT-IR, TGA/DTA, SEM, BET analysis and EDS. Synthesized resin shows a good capacity of 53.96mgg(-1) for Cd(II) and 24.19mgg(-1) for Zn(II) at pH 8.0. Five isotherm equilibrium models were studied to explain the sorption phenomenon out of which Langmuir, Dubinin-Radushkevich, Scatchard and Temkin models were found to be the best fitted. The limit of detection (LOD) and limit of quantification (LOQ) were observed to be 1.5 and 5.1μgL(-1) for Cd and 1.2 and 4.1μgL(-1) for Zn. The reliability of the method was investigated by the analysis of SRM and the recovery of analytes from various spiked food samples. PMID:27451247

  2. Coordination behavior of new bis Schiff base ligand derived from 2-furan carboxaldehyde and propane-1,3-diamine. Spectroscopic, thermal, anticancer and antibacterial activity studies

    Science.gov (United States)

    Mohamed, Gehad G.; Zayed, Ehab M.; Hindy, Ahmed M. M.

    2015-06-01

    Novel bis Schiff base ligand, [N1,N3-bis(furan-2-ylmethylene)propane-1,3-diamine], was prepared by the condensation of furan-2-carboxaldehyde with propane-1,3-diamine. Its conformational changes on complexation with transition metal ions [Co(II), Ni(II), Cu(II), Mn(II), Cd(II), Zn(II) and Fe(III)] have been studied on the basis of elemental analysis, conductivity measurements, spectral (infrared, 1H NMR, electronic), magnetic and thermogravimetric studies. The conductance data of the complexes revealed their electrolytic nature suggesting them as 1:2 (for bivalent metal ions) and 1:3 (for Fe(III) ion) electrolytes. The complexes were found to have octahedral geometry based on magnetic moment and solid reflectance measurements. Thermal analysis data revealed the decomposition of the complexes in successive steps with the removal of anions, coordinated water and bis Schiff base ligand. The thermodynamic parameters were calculated using Coats-Redfern equation. The Anticancer screening studies were performed on human colorectal cancer (HCT), hepatic cancer (HepG2) and breast cancer (MCF-7) cell lines. The antimicrobial activity of all the compounds was studied against Gram negative (Escherichia coli and Proteus vulgaris) and Gram positive (Bacillus vulgaris and Staphylococcus pyogones) bacteria. It was observed that the coordination of metal ion has a pronounced effect on the microbial activities of the bis Schiff base ligand. All the metal complexes have shown higher antimicrobial effect than the free bis Schiff base ligand.

  3. Characterization of sodium dodecyl sulfate modified iron pillared montmorillonite and its application for the removal of aqueous Cu(II) and Co(II)

    International Nuclear Information System (INIS)

    Anionic surfactant modified Fe-pillared montmorillonites were prepared by Fe-hydrate solution and sodium dodecyl sulfate (SDS) solution. These organo-inorgano complex montmorillonites were divided into three types (CM1, CM2 and CM3) depending on different intercalation processes. X-ray diffraction spectra, the Fourier transform infrared (FTIR) spectra were used to analyze the structure of the raw and modified montmorillonites. X-ray photoelectron spectra of the simples have been studied to determine spectral characteristics to allow the identification of Fe(III) hydroxide. The specific surface area of the host montmorillonite (M0) is 73.2 m2/g, while for the modified montmorillonites it is 114.0 m2/g, 117.2 m2/g, and 115.8 m2/g, respectively. The mesopore volumes of the montmorillonites decrease after modification. Ions of copper and cobalt were selected as adsorbates to evaluate the adsorption performance of each montmorillonite. The adsorption data was analyzed by both Freundlich and Langmuir isotherm models and the data was well fit by the Langmuir isotherm model. The adsorption was efficient and significantly influenced by metal speciation, metal concentration, contact time, and pH. Higher adsorption capacity of the modified montmorillonites were obtained at pH 5-6. The results of desorption indicated that the metal ions were covalently bound to the modified montmorillonites.

  4. Ternary metal complexes of guaifenesin drug: Synthesis, spectroscopic characterization and in vitro anticancer activity of the metal complexes.

    Science.gov (United States)

    Mahmoud, W H; Mahmoud, N F; Mohamed, G G; El-Sonbati, A Z; El-Bindary, A A

    2015-01-01

    The coordination behavior of a series of transition metal ions named Cr(III), Fe(III), Mn(II), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) with a mono negative tridentate guaifenesin ligand (GFS) (OOO donation sites) and 1,10-phenanthroline (Phen) is reported. The metal complexes are characterized based on elemental analyses, IR, (1)H NMR, solid reflectance, magnetic moment, molar conductance, UV-vis spectral studies, mass spectroscopy, ESR, XRD and thermal analysis (TG and DTG). The ternary metal complexes were found to have the formulae of [M(GFS)(Phen)Cl]Cl·nH2O (M=Cr(III) (n=1) and Fe(III) (n=0)), [M(GFS)(Phen)Cl]·nH2O (M=Mn(II) (n=0), Zn(II) (n=0) and Cu(II) (n=3)) and [M(GFS)(Phen)(H2O)]Cl·nH2O (M=Co(II) (n=0), Ni(II) (n=0) and Cd(II) (n=4)). All the chelates are found to have octahedral geometrical structures. The ligand and its ternary chelates are subjected to thermal analyses (TG and DTG). The GFS ligand, in comparison to its ternary metal complexes also was screened for their antibacterial activity on gram positive bacteria (Bacillus subtilis and Staphylococcus aureus), gram negative bacteria (Escherichia coli and Neisseria gonorrhoeae) and for in vitro antifungal activity against (Candida albicans). The activity data show that the metal complexes have antibacterial and antifungal activity more than the parent GFS ligand. The complexes were also screened for its in vitro anticancer activity against the Breast cell line (MFC7) and the results obtained show that they exhibit a considerable anticancer activity. PMID:26067934

  5. The meloxicam complexes of Co(II) and Zn(II): Synthesis, crystal structures, photocleavage and in vitro DNA-binding

    Science.gov (United States)

    Sanatkar, Tahereh Hosseinzadeh; Hadadzadeh, Hassan; Simpson, Jim; Jannesari, Zahra

    2013-10-01

    Two neutral mononuclear complexes of Co(II) and Zn(II) with the non-steroidal anti-inflammatory drug meloxicam (H2mel, 4-hydroxy-2-methyl-N-(5-methyl-2-thiazolyl)-2H-1,2-benzothiazine-3-carboxammide-1,1-dioxide), [Co(Hmel)2(EtOH)2] (1), and [Zn(Hmel)2(EtOH)2] (2), were synthesized and characterized by elemental analysis, IR and UV-Vis spectroscopy and their solid-state structures were studied by single-crystal diffraction. The complexes have a distorted octahedral geometry around the metal atom. The experimental data indicate that the meloxicam acts as a deprotonated bidentate ligand (through the amide oxygen and the nitrogen atom of the thiazolyl ring) in the complexes, and a strong intramolecular hydrogen bond between the amide N-H function and the enolate O atom stabilizes the ZZZ conformation of meloxicam ligands. Absorption, fluorescence spectroscopy and cyclic voltammetry have been used to investigate the binding of the complexes with fish sperm DNA (FS-DNA). Additionally, the photocleavage studies have been also used to investigate the binding of the complexes with plasmid DNA. The interaction of the complexes with DNA was monitored by a blue shift and hyperchromism in the UV-Vis spectra attributed to an electrostatic binding mode. A competitive study with ethidium bromide (EB) has shown that the complexes can displace the DNA-bound EB indicating that they bind to DNA in strong competition with EB. The experimental results show that the complexes can cleave pUC57 plasmid DNA.

  6. Simultaneous determination of Fe(III) and Al(III) by first-derivative spectrophotometry and partial least-squares (PLS-2) method - application to post-haemodialysis fluids.

    Science.gov (United States)

    Aguerssif, Nadia; Benamor, Mohamed; Kachbi, Malek; Draa, Mohamed Tahar

    2008-01-01

    Derivative spectrophotometry (graphical method) and partial least-squares regression (numerical method) methods were developed for the spectrophotometric multi-component analysis of post-haemodialysis fluids and synthetic mixtures containing Al(III) and Fe(III) without any chemical separation. The complexes of these metal ions with chrome azurol S were formed immediately at pH 5.5 and were stable for at least 3h. The graphical method is based on the use of first-derivative spectra for evaluation because working wavelength determination was more precise and spectral overlap was less than in the ordinary spectra. Two wavelengths at which the complexes exhibited maximum absorption values for Fe(III) and Al(III) were selected as analytical wavelengths, i.e., 675 and 623.5 nm, respectively. Lambert-Beer's law is obeyed between 0.0896-8.064 microg/mL Fe(III) and 0.054-0.486 microg/mL Al(III). Limits of detection for Fe(III) and Al(III) were 0.056 and 0.044 microg/mL, respectively. The reproducibility, expressed as variation coefficients, for two sets of 10 standard mixtures containing 3.584 microg/mL Fe(III) and 0.27 microg/mL Al(III) were 1.9% and 2% for iron and aluminium, respectively. In the numerical method, a training set was randomly prepared by using 14 samples. The concentration of each component has been varied in the linear range of the analytical signal. The spectral regions between 510 and 720 nm were selected for the analysis of the binary mixture of Fe(III)/Al(III). The proposed methods were validated by using synthetic binary mixtures and applied to the simultaneous determination of Fe(III) and Al(III) in post-haemodialysis samples. The obtained results were compared with each other; in general, both multi-component methods gave rise to similar recovery results for laboratory-prepared mixtures and real samples. PMID:18755392

  7. The outer membrane protein Omp35 affects the reduction of Fe(III, nitrate, and fumarate by Shewanella oneidensis MR-1

    Directory of Open Access Journals (Sweden)

    Myers Charles R

    2004-06-01

    Full Text Available Abstract Background Shewanella oneidensis MR-1 uses several electron acceptors to support anaerobic respiration including insoluble species such as iron(III and manganese(IV oxides, and soluble species such as nitrate, fumarate, dimethylsulfoxide and many others. MR-1 has complex branched electron transport chains that include components in the cytoplasmic membrane, periplasm, and outer membrane (OM. Previous studies have implicated a role for anaerobically upregulated OM electron transport components in the use of insoluble electron acceptors, and have suggested that other OM components may also contribute to insoluble electron acceptor use. In this study, the role for an anaerobically upregulated 35-kDa OM protein (Omp35 in the use of anaerobic electron acceptors was explored. Results Omp35 was purified from the OM of anaerobically grown cells, the gene encoding Omp35 was identified, and an omp35 null mutant (OMP35-1 was isolated and characterized. Although OMP35-1 grew on all electron acceptors tested, a significant lag was seen when grown on fumarate, nitrate, and Fe(III. Complementation studies confirmed that the phenotype of OMP35-1 was due to the loss of Omp35. Despite its requirement for wild-type rates of electron acceptor use, analysis of Omp35 protein and predicted sequence did not identify any electron transport moieties or predicted motifs. OMP35-1 had normal levels and distribution of known electron transport components including quinones, cytochromes, and fumarate reductase. Omp35 is related to putative porins from MR-1 and S. frigidimarina as well as to the PorA porin from Neisseria meningitidis. Subcellular fraction analysis confirmed that Omp35 is an OM protein. The seven-fold anaerobic upregulation of Omp35 is mediated post-transcriptionally. Conclusion Omp35 is a putative porin in the OM of MR-1 that is markedly upregulated anaerobically by a post-transcriptional mechanism. Omp35 is required for normal rates of growth on Fe(III

  8. Hydrothermal syntheses and single crystal structural characterization of M(H2O)6(OPTA)2 [M = Co(II), Ni(II), Zn(II); OPTA = 1-oxopyridinium-2-thioacetato

    Indian Academy of Sciences (India)

    S Kumaresan; P Ramadevi; R D Walsh; A McAneny; C H Lake

    2006-05-01

    A new class of compounds of the family M(H2O)6(OPTA)2 (where M = Co(II), Ni(II), and Zn(II); OPTA = 1-oxopyridinium-2-thioacetato) was prepared from the appropriate metal acetates, 1-oxopyridinium-2-thioacetic acid (OPTAH), and potassium hydroxide in hydrothermal media and structurally characterized. The structure is constructed from M(H2O)$_{6}^{2+}$ and two anions of OPTAH (C7H6NO3S) linked through hydrogen bonding into an extended network.

  9. Synthesis, structure, thermostability and luminescence properties of Zn(II) and Cd(II) coordination polymers based on dimethysuccinate and flexible 1,4-bis(imidazol-1-ylmethyl)benzene ligands.

    Science.gov (United States)

    Liu, Yang; Feng, Yong Lan; Fu, Wei Wei

    2016-09-01

    The design and synthesis of functional coordination polymers is motivated not only by their structural beauty but also by their potential applications. Zn(II) and Cd(II) coordination polymers are promising candidates for producing photoactive materials because these d(10) metal ions not only possess a variety of coordination numbers and geometries, but also exhibit luminescence properties when bound to functional ligands. It is difficult to predict the final structure of such polymers because the assembly process is influenced by many subtle factors. Bis(imidazol-1-yl)-substituted alkane/benzene molecules are good bridging ligands because their flexibility allows them to bend and rotate when they coordinate to metal centres. Two new Zn(II) and Cd(II) coordination polymers based on mixed ligands, namely, poly[[μ2-1,4-bis(imidazol-1-ylmethyl)benzene-κ(2)N(3):N(3')]bis(μ3-2,2-dimethylbutanoato-κ(3)O(1):O(4):O(4'))dizinc(II)], [Zn2(C6H8O4)2(C14H14N4)]n, and poly[[μ2-1,4-bis(imidazol-1-ylmethyl)benzene-κ(2)N(3):N(3')]bis(μ3-2,2-dimethylbutanoato-κ(5)O(1),O(1'):O(4),O(4'):O(4))dicadmium(II)], [Cd2(C6H8O4)2(C14H14N4)]n, have been synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction, elemental analysis, IR spectroscopy and thermogravimetric analysis. Both complexes crystallize in the monoclinic space group C2/c with similar unit-cell parameters and feature two-dimensional structures formed by the interconnection of S-shaped Zn(Cd)-2,2-dimethylsuccinate chains with 1,4-bis(imidazol-1-ylmethyl)benzene bridges. However, the Cd(II) and Zn(II) centres have different coordination numbers and the 2,2-dimethylsuccinate ligands display different coordination modes. Both complexes exhibit a blue photoluminescence in the solid state at room temperature. PMID:27585928

  10. Bioactivity of pyridine-2-thiolato-1-oxide metal complexes: Bi(III), Fe(III) and Ga(III) complexes as potent anti-Mycobacterium tuberculosis prospective agents.

    Science.gov (United States)

    Machado, Ignacio; Marino, Leonardo Biancolino; Demoro, Bruno; Echeverría, Gustavo A; Piro, Oscar E; Leite, Clarice Q F; Pavan, Fernando R; Gambino, Dinorah

    2014-11-24

    In the search for new therapeutic tools against tuberculosis and to further address the therapeutic potential of pyridine-2-thiol 1-oxide (Hmpo) metal complexes, two new octahedral [M(III)(mpo)3] complexes, with M = Ga or Bi, were synthesized and characterized in the solid state and in solution. Attempts to crystallize [Ga(III)(mpo)3] in CH2Cl2 led to single crystals of the reaction product [GaCl(mpo)2], where the gallium(III) ion is in a square basis pyramidal environment, trans-coordinated at the basis to two pyridine-2-thiolato 1-oxide anions acting as bidentate ligands through their oxygen and sulfur atoms. The biological activity of the new [M(III)(mpo)3] complexes together with that of the previously reported Fe(III) analogous compound and the pyridine-2-thiol 1-oxide sodium salt (Na mpo) was evaluated on Mycobacterium tuberculosis. The compounds showed excellent activity, both in the standard strain H37Rv ATCC 27294 (pan-susceptible) and in five clinical isolates that are resistant to the standard first-line anti-tuberculosis drugs isoniazid and rifampicin. These pyridine-2-thiol 1-oxide derivatives are promising compounds for the treatment of resistant tuberculosis. PMID:25261824

  11. Fe(III) hydroxide nucleation and growth on quartz in the presence of Cu(II), Pb(II), and Cr(III): metal hydrolysis and adsorption.

    Science.gov (United States)

    Dai, Chong; Hu, Yandi

    2015-01-01

    Fe(III) hydroxide nanoparticles are an essential carrier for aqueous heavy metals. Particularly, iron hydroxide precipitation on mineral surfaces can immobilize aqueous heavy metals. Here, we used grazing-incidence small-angle X-ray scattering (GISAXS) to quantify nucleation and growth of iron hydroxide on quartz in 0.1 mM Fe(NO3)3 solution in the presence of Na(+), Cu(2+), Pb(2+), or Cr(3+) at pH = 3.7 ± 0.1. In 30 min, the average radii of gyration (R(g)) of particles on quartz grew from around 2 to 6 nm in the presence of Na(+) and Cu(2+). Interestingly, the particle sizes remained 3.3 ± 0.3 nm in the presence of Pb(2+), and few particles formed in the presence of Cr(3+). Quartz crystal microbalance dissipation (QCM-D) measurements showed that only Cr(3+) adsorbed onto quartz, while Cu(2+) and Pb(2+) did not. Cr(3+) adsorption changed the surface charge of quartz from negative to positive, thus inhibiting the precipitation of positively charged iron hydroxide on quartz. Masses and compositions of the precipitates were also quantified. This study provided new insights on interactions among quartz, iron hydroxide, and metal ions. Such information is helpful not only for environmental remediation but also for the doping design of iron oxide catalysts. PMID:25496643

  12. Texturing a pyramid-like structure on a silicon surface via the synergetic effect of copper and Fe(III) in hydrofluoric acid solution

    Science.gov (United States)

    Cao, Ming; Li, Shaoyuan; Deng, Jianxin; Li, Yuping; Ma, Wenhui; Zhou, Yang

    2016-05-01

    An innovative approach is proposed to texture a pyramid structure on a silicon surface via Cu-catalyzed chemical etching in the HF/FeCl3 system. The surface and cross-section morphologies of the formed pyramid structure were examined by scanning electron microscopy and atomic force microscopy. The results revealed that numerous silicon pyramid-like structures with hemlines of 0.1 ∼ 3 μm and height of 0.1 ∼ 2 μm are close together, and the top angle of the pyramid structure is 90°. Additionally, the systematic study of the effects of the etching time and the concentration of FeCl3 on the pyramid-like structures by the atom configuration model of silicon crystal faces demonstrated that the etching proceeds preferentially along the directions of silicon. A formation mechanism of the pyramid-like structure is proposed. The results imply that the synergetic effect of Cu nanoparticles and Fe(III) could conveniently generate a pyramid-like architecture on the surface of silicon in hydrofluoric acid solution.

  13. Coordination polymers of Fe(iii) and Al(iii) ions with TCA ligand: distinctive fluorescence, CO2 uptake, redox-activity and oxygen evolution reaction.

    Science.gov (United States)

    Dhara, Barun; Sappati, Subrahmanyam; Singh, Santosh K; Kurungot, Sreekumar; Ghosh, Prasenjit; Ballav, Nirmalya

    2016-04-19

    Fe and Al belong to different groups in the periodic table, one from the p-block and the other from the d-block. In spite of their different groups, they have the similarity of exhibiting a stable 3+ oxidation state. Here we have prepared Fe(iii) and Al(iii) based coordination polymers in the form of metal-organic gels with the 4,4',4''-tricarboxyltriphenylamine (TCA) ligand, namely Fe-TCA and Al-TCA, and evaluated some important physicochemical properties. Specifically, the electrical conductivity, redox-activity, porosity, and electrocatalytic activity (oxygen evolution reaction) of the Fe-TCA system were noted to be remarkably higher than those of the Al-TCA system. As for the photophysical properties, almost complete quenching of the fluorescence originating from TCA was observed in case of the Fe-TCA system, whereas for the Al-TCA system a significant retention of fluorescence with red-shifted emission was observed. Quantum mechanical calculations based on density functional theory (DFT) were performed to unravel the origin of such discriminative behaviour of these coordination polymer systems. PMID:26961352

  14. Studies on some salicylaldehyde Schiff base derivatives and their complexes with Cr(III), Mn(II), Fe(III), Ni(II) and Cu(II)

    Science.gov (United States)

    Abdel-Latif, S. A.; Hassib, H. B.; Issa, Y. M.

    2007-07-01

    The formation constants of some transition metal ions Cr(III), Mn(II), Fe(III), Ni(II) and Cu(II) binary complexes containing Schiff bases resulting from condensation of salicylaldehyde with aniline (I), 2-aminopyridine (II), 4-aminopyridine (III) and 2-aminopyrimidine (IV) were determined pH-metrically in ethanolic medium (80%, v/v). The formation constants were determined for all binary complexes. The important infrared (IR) spectral bands corresponding to the active groups in the four ligands and the solid complexes under investigation were studied. The solid complexes have been synthesized and studied by thermogravimetric analysis. The thermal dehydration and decomposition of these complexes were studied kinetically using the integral method applying the Coats-Redfern equation. It was found that the thermal decomposition of the complexes follow second order kinetics. The thermodynamic parameters of the decomposition are also reported. The electronic absorption spectra of the investigated ligands were carried out to determine the p Ka values spectrophotometrically.

  15. Structure, infrared and Raman spectroscopic studies of newly synthetic AII(SbV0.50FeIII0.50)(PO4)2 (Adbnd Ba, Sr, Pb) phosphates with yavapaiite structure

    Science.gov (United States)

    Aatiq, Abderrahim; Tigha, My Rachid; Fakhreddine, Rachid; Bregiroux, Damien; Wallez, Gilles

    2016-08-01

    The synthesis and structural study of three new AII(SbV0.5FeIII0.5)(PO4)2 (Adbnd Ba, Sr, Pb) phosphates belonging to the Asbnd Sbsbnd Fesbnd Psbnd O system were reported here for the first time. Structures of [Ba], [Sr] and [Pb] compounds, obtained by solid state reaction in air atmosphere, were determined at room temperature from X-ray powder diffraction using the Rietveld method. BaII(SbV0.5FeIII0.5)(PO4)2 features the yavapaiite-type structure, with space group C2/m, Z = 2 and a = 8.1568(4) Å; b = 5.1996(3) Å c = 7.8290(4) Å; β = 94.53(1)°. AII(SbV0.5FeIII0.5)(PO4)2 (Adbnd Sr, Pb) compounds have a distorted yavapaiite structure with space group C2/c, Z = 4 and a = 16.5215(2) Å; b = 5.1891(1) Å c = 8.0489(1) Å; β = 115.70(1)° for [Sr]; a = 16.6925(2) Å; b = 5.1832(1) Å c = 8.1215(1) Å; β = 115.03(1)° for [Pb]. Raman and Infrared spectroscopic study was used to obtain further structural information about the nature of bonding in selected compositions.

  16. Supramolecular 2D/3D isomerism in a compound containing heterometallic Cu(II)2Co(II) nodes and dicyanamide bridges.

    Science.gov (United States)

    Biswas, Saptarshi; Gómez-García, Carlos J; Clemente-Juan, Juan M; Benmansour, Samia; Ghosh, Ashutosh

    2014-03-01

    Three new heterometallic copper(II)-cobalt(II) complexes [(CuL(2))2Co{dca}2]·H2O(1), [(CuL(1))2Co{dca}2]n (2a), and [(CuL(1))2Co{dca}2]n (2b) [dca(-) = dicyanamide = N(CN)2(-)] have been synthesized by reacting the "metallo-ligand" [CuL(1)] or [CuL(2)] with cobalt(II) perchlorate and sodium dicyanamide in methanol-water medium (where H2L(1) = N,N'-bis(salicylidene)-1,3-propanediamine and H2L(2) = N,N'-bis(α-methylsalicylidene)-1,3-propanediamine). The three complexes have been structurally and magnetically characterized. Complex 1 is a discrete trinuclear species in which two metallo-ligands coordinate to a cobalt(II) ion through the phenoxido oxygen atoms along with two terminally coordinated dicyanamide ions. On the other hand, complexes 2a and 2b are one of the very scarce examples of supramolecular isomers since they present the same [(CuL(1))2Co{dca}2] trinuclear units (very similar to the trinuclear core in 1) and differ only in their superstructures. Thus, although each Cu2Co trimer in 2a and 2b is connected to four other Cu2Co trimers through four μ1,5-dca(-) bridges, 2a presents a square two-dimensional structure (each Cu2Co trimer is connected to four in-plane Cu2Co trimers); whereas, 2b shows a triangular three-dimensional lattice (each Cu2Co trimer is connected to three in-plane and one out-of-plane trimers). Variable-temperature magnetic susceptibility measurements show the presence of moderate antiferromagnetic exchange interactions (ferrimagnetic) in all the cases mediated through the double phenoxido bridges that have been fitted with an anisotropic model including spin-orbit coupling in the central Co(II) ion. PMID:24552535

  17. Solid phase extraction of Cd(II), Pb(II), Zn(II) and Ni(II) from food samples using multiwalled carbon nanotubes impregnated with 4-(2-thiazolylazo)resorcinol

    International Nuclear Information System (INIS)

    Multiwalled carbon nanotubes were impregnated with 4-(2-thiazolylazo)resorcinol and used for the separation and preconcentration of Cd(II), Pb(II), Zn(II) and Ni(II) ions from food samples. The analytes were quantitatively recovered at pH 7. 0 and eluted with 3 mol L-1 acetic acid. The effects of pH value, flow rate, eluent type and sample volume on the recoveries, and the effects of alkali, earth alkali and transition metals on the retention of the analytes were studied. The method was validated using the standard certified reference materials SRM 1570A (spinach leaves) and IAEA 336 (lichen), and the results were found to be compatible with the certified values of reference materials. The new enrichment procedure was applied to the determination of these ions in various food samples. (author)

  18. Estudio del equilibrio y cinética de adsorción de Cd(II), Ni(II) y Cr(VI) usando Quitosano y Quitosano modificado con cobre

    OpenAIRE

    Benavente, M.; Castro, S; N. Betanco; F. Canelo; López, X. (Xosé); García, A.

    2013-01-01

    En este trabajo, se estudió el equilibrio y la cinética de adsorción de Cd(II), Ni(II) en quitosano y Cr(VI) en quitosano modificado con cobre. Para ello, soluciones de iones metálicos a diferentes concentraciones, fueron puestas en contacto con el adsorbente y se agitaron por un período de 3 – 4 h. Al final del proceso, las muestras fueron analizadas en un espectrómetro de absorción atómica. Los datos experimentales del equilibrio de adsorción de los iones metálicos fueron evaluados aplicand...

  19. Spectroscopic and thermal characterization of Cu(II), Co(II), Ni(II) and Mn(II) complexes of fluorescent dye 4-N,N-dimethyl-ethanolamine-N-allyl-1,8-naphthalimide (4DMEAN)

    Science.gov (United States)

    Refat, Moamen S.; Killa, Hamada M. A.; Fetooh, Hammad

    2010-11-01

    Compounds having general formula: [M(4DMEAN) X (Cl) 2(H 2O) Y]· ZH 2O, where (M = Cu(II), Co(II), Ni(II) and Mn(II), 4DMEAN = 4-N,N-dimethyl-ethanolamine-N-allyl-1,8-naphthalimide, X = 1 or 2, Y = 0 or 2 and Z = 1, 2, 4 or 6) have been prepared. The resulted compounds were characterized by elemental analysis, conductivity measurements, magnetic measurements, (infrared, 1H NMR, mass and electronic) spectra and thermogravimetric analysis. The results were suggested that all 4DMEAN complexes formed have a 1:1 M ratio (metal: 4DMEAN) except for Co(II) complex exist as 1:2. The 4DMEAN ligand acts as a neutral bidentate through both of the oxygen atom of ( sbnd C sbnd OCH 2) group and the lone pair of electron on the nitrogen atom of (N(CH 3) 2 group. The molar conductance measurements proved that the 4DMEAN complexes are non-electrolytes. The kinetic thermodynamic parameters such as: E*, Δ H*, Δ S* and Δ G* were estimated from the DTG curves.

  20. Coordination behavior of tetraaza [N₄] ligand towards Co(II), Ni(II), Cu(II), Cu(I) and Pd(II) complexes: synthesis, spectroscopic characterization and anticancer activity.

    Science.gov (United States)

    El-Boraey, Hanaa A

    2012-11-01

    Novel eight Co(II), Ni(II), Cu(II), Cu(I) and Pd(II) complexes with [N(4)] ligand (L) i.e. 2-amino-N-{2-[(2-aminobenzoyl)amino]ethyl}benzamide have been synthesized and structurally characterized by elemental analysis, spectral, thermal (TG/DTG), magnetic, and molar conductivity measurements. On the basis of IR, mass, electronic and EPR spectral studies an octahedral geometry has been proposed for Co(II), Ni(II) complexes and Cu(II) chloride complex, square-pyramidal for Cu(I) bromide complex. For Cu(II) nitrate complex (6), Pd(II) complex (8) square planar geometry was proposed. The EPR data of Cu(II) complexes in powdered form indicate d(x2-y2) ground state of Cu(II) ion. The antitumor activity of the synthesized ligand and some selected metal complexes has been studied. The palladium(II) complex (8) was found to display cytotoxicity (IC(50)=25.6 and 41 μM) against human breast cancer cell line MCF-7 and human hepatocarcinoma HEPG2 cell line. PMID:22765944

  1. Coordination behavior of tetraaza [N4] ligand towards Co(II), Ni(II), Cu(II), Cu(I) and Pd(II) complexes: Synthesis, spectroscopic characterization and anticancer activity

    Science.gov (United States)

    El-Boraey, Hanaa A.

    2012-11-01

    Novel eight Co(II), Ni(II), Cu(II), Cu(I) and Pd(II) complexes with [N4] ligand (L) i.e. 2-amino-N-{2-[(2-aminobenzoyl)amino]ethyl}benzamide have been synthesized and structurally characterized by elemental analysis, spectral, thermal (TG/DTG), magnetic, and molar conductivity measurements. On the basis of IR, mass, electronic and EPR spectral studies an octahedral geometry has been proposed for Co(II), Ni(II) complexes and Cu(II) chloride complex, square-pyramidal for Cu(I) bromide complex. For Cu(II) nitrate complex (6), Pd(II) complex (8) square planar geometry was proposed. The EPR data of Cu(II) complexes in powdered form indicate dx2-y2 ground state of Cu(II) ion. The antitumor activity of the synthesized ligand and some selected metal complexes has been studied. The palladium(II) complex (8) was found to display cytotoxicity (IC50 = 25.6 and 41 μM) against human breast cancer cell line MCF-7 and human hepatocarcinoma HEPG2 cell line.

  2. A new one-dimensional Cd(II) coordination polymer with a two-dimensional layered structure incorporating 2-[(1H-imidazol-1-yl)methyl]-1H-benzimidazole and benzene-1,2-dicarboxylate ligands.

    Science.gov (United States)

    Huang, Qiu Ying; Lin, Xiao Yi; Meng, Xiang Ru

    2016-06-01

    The N-heterocyclic ligand 2-[(1H-imidazol-1-yl)methyl]-1H-benzimidazole (imb) has a rich variety of coordination modes and can lead to polymers with intriguing structures and interesting properties. In the coordination polymer catena-poly[[cadmium(II)-bis[μ-benzene-1,2-dicarboxylato-κ(4)O(1),O(1'):O(2),O(2')]-cadmium(II)-bis{μ-2-[(1H-imidazol-1-yl)methyl]-1H-benzimidazole}-κ(2)N(2):N(3);κ(2)N(3):N(2)] dimethylformamide disolvate], {[Cd(C8H4O4)(C11H10N4)]·C3H7NO}n, (I), each Cd(II) ion exhibits an irregular octahedral CdO4N2 coordination geometry and is coordinated by four O atoms from two symmetry-related benzene-1,2-dicarboxylate (1,2-bdic(2-)) ligands and two N atoms from two symmetry-related imb ligands. Two Cd(II) ions are connected by two benzene-1,2-dicarboxylate ligands to generate a binuclear [Cd2(1,2-bdic)2] unit. The binuclear units are further connected into a one-dimensional chain by pairs of bridging imb ligands. These one-dimensional chains are further connected through N-H...O hydrogen bonds and π-π interactions, leading to a two-dimensional layered structure. The dimethylformamide solvent molecules are organized in dimeric pairs via weak interactions. In addition, the title polymer exhibits good fluorescence properties in the solid state at room temperature. PMID:27256695

  3. Synthesis of amino functionalized magnetic graphenes composite material and its application to remove Cr(VI), Pb(II), Hg(II), Cd(II) and Ni(II) from contaminated water

    Energy Technology Data Exchange (ETDEWEB)

    Guo, Xiaoyao [School of Resources and Environment, University of Jinan, Jinan 250022 (China); Du, Bin, E-mail: dubin61@gmail.com [School of Resources and Environment, University of Jinan, Jinan 250022 (China); Wei, Qin, E-mail: sdjndxwq@163.com [School of Chemistry and Chemical Engineering, University of Jinan, Jinan 250022 (China); Yang, Jian [School of Resources and Environment, University of Jinan, Jinan 250022 (China); Hu, Lihua [School of Chemistry and Chemical Engineering, University of Jinan, Jinan 250022 (China); Yan, Liangguo; Xu, Weiying [School of Resources and Environment, University of Jinan, Jinan 250022 (China)

    2014-08-15

    Highlights: • Graphenes magnetic composite nanoparticles (Fe{sub 3}O{sub 4}-GS) were used to adsorb metal ions. • The adsorption of metal ions onto Fe{sub 3}O{sub 4}-GS could be well interpreted by the Freundlich equation. • The adsorption of metal ions onto Fe{sub 3}O{sub 4}-GS fit pseudo-second order kinetic model. • Thermodynamic studies illustrated that the adsorption process was endothermic and spontaneous in nature. - Abstract: In the present study, a kind of graphenes magnetic material (Fe{sub 3}O{sub 4}-GS) was prepared by compositing graphene sheet with ferroferric oxide, and shown to be effictive for removing Cr(VI), Pb(II), Hg(II), Cd(II) and Ni(II) ions from aqueous solution. The synthesized sorbent was characterized by SEM, TEM, FTIR, XRD, XPS and BET, respectively. The pH{sub ZPC} value of the sorbent was estimated to be 3.5 by alkaline-titration methods. Fe{sub 3}O{sub 4}-GS can be simply recovered from water with magnetic separation at low magnetic field within one minute. The sorption capacities of the metals were 17.29, 27.95, 23.03, 27.83 and 22.07 mg g{sup −1} for Cr(VI), Pb(II), Hg(II), Cd(II) and Ni(II), respectively. Kinetic data showed good correlation with pseudo-second-order equation and the Freundlich model was found to fit for the isotherm data of all the heavy metal ions. It was found that the metals sorption was accomplished mainly via chelation or ion exchange. The results of thermodynamic studies illustrate that the adsorption process was endothermic and spontaneous in nature.

  4. Mixed ligand two dimensional Cd(ii)/Ni(ii) metal organic frameworks containing dicarboxylate and tripodal N-donor ligands: Cd(ii) MOF is an efficient luminescent sensor for detection of picric acid in aqueous media.

    Science.gov (United States)

    Rachuri, Yadagiri; Parmar, Bhavesh; Bisht, Kamal Kumar; Suresh, Eringathodi

    2016-05-01

    Two dimensional metal organic frameworks (MOFs) [Cd(5-BrIP)(TIB)]n () and [Ni2(5-BrIP)2(TIB)2]n (), involving the aromatic polycarboxylate ligand 5-bromo isophthalic acid (H2BrIP), flexible tripodal ligand 1,3,5-tris(imidazol-1-ylmethyl)benzene (TIB) and Cd(ii)/Ni(ii) metal nodes have been synthesized by different methods. These compounds were characterized by various analytical methods, and variable temperature X-ray diffraction data showed thermal stability of both MOFs up to 350 °C. Phase purity as well as water stability of the MOFs were established by powder X-ray diffraction, and the structural diversity of the compounds were investigated by single-crystal X-ray diffraction. Both the MOFs are mixed ligand 2D nets, and the topology of the network can be described as a binodal 3,5-c connected net with 3,5L2 topology having the point symbol {4(2)·6(7)·8}{4(2)·6}. Sensing of picric acid [2,4,6-trinitrophenol, TNP] by luminescence quenching among a large range of nitroanalytes in aqueous phase by the Cd(ii) luminescent MOF (LMOF) were been investigated. Structural studies on 1 : 1 co-crystals () of TIB and TNP were carried out. The selective and sensitive fluorescence quenching response of towards electron-deficient TNP over other nitro analytes in aqueous phase was demonstrated by fluorescence quenching titration. Concomitant occurrence of electron transfer/energy transfer processes and electrostatic interaction favours the selective sensing of TNP. A Cd(ii) LMOF ()-coated paper strip that we developed demonstrated fast and selective response to TNP, by the complete quenching of the blue fluorescence upon excitation of the paper strip at 365 nm radiation in its presence. PMID:27067118

  5. Experimental and molecular modeling studies of the interaction of the polypyridyl Fe(II) and Fe(III) complexes with DNA and BSA

    Science.gov (United States)

    Behnamfar, Mohammad Taghi; Hadadzadeh, Hassan; Simpson, Jim; Darabi, Farivash; Shahpiri, Azar; Khayamian, Taghi; Ebrahimi, Malihe; Amiri Rudbari, Hadi; Salimi, Mona

    2015-01-01

    Two mononuclear iron complexes, [Fe(tppz)2](PF6)2·H2O (1) and Fe(tppz)Cl3·2CHCl3 (2) where tppz is (2,3,5,6-tetra(2-pyridyl)pyrazine), have been synthesized and characterized by elemental analysis, spectroscopic methods (UV-Vis and IR) and single crystal X-ray structure analysis. The interaction of (1) as the nitrate salt ([Fe(tppz)2](NO3)2) with calf-thymus DNA (CT-DNA) has been monitored by UV-Vis spectroscopy, competitive fluorescence titration, circular dichroism (CD), voltammetric techniques, viscosity measurement, and gel electrophoresis. Gel electrophoresis of DNA with [Fe(tppz)2](NO3)2 demonstrated that the complex also has the ability to cleave supercoiled plasmid DNA. The results have indicated that the complex binds to CT-DNA by three binding modes, viz., electrostatic, groove and partial insertion of the pyridyl rings between the base stacks of double-stranded DNA. Molecular docking of [Fe(tppz)2](NO3)2 with the DNA sequence d(ACCGACGTCGGT)2 suggests the complex fits into the major groove. The water-insoluble complex (2) can catalyze the cleavage of BSA at 40 °C. There are no reports of the catalytic effect of polypyridyl metal complexes on the BSA cleavage. Molecular docking of (2) with BSA suggests that, when the chloro ligands in the axial positions are replaced by water molecules, the BSA can interact with the Fe(III) complex more easily.

  6. Evidence for microbial Fe(III) reduction in anoxic, mining-impacted lake sediments (Lake Coeur d'Alene, Idaho)

    Energy Technology Data Exchange (ETDEWEB)

    Cummings, D.E.; March, A.W.; Bostick, B.; Spring, S.; Caccavo, F. Jr.; Fendorf, S.; Rosenzweig, R.F.

    2000-01-01

    Mining-impacted sediments of Lake Coeur d'Alene, Idaho, contain more than 10% metals on a dry weight basis, approximately 80% of which is iron. Since iron (hydr)oxides adsorb toxic, ore-associated elements, such as arsenic, iron (hydr)oxide reduction may in part control the mobility and bioavailability of these elements. Geochemical and microbiological data were collected to examine the ecological role of dissimilatory Fe(III)-reducing bacteria in this habitat. The concentration of mild-acid-extractable Fe(II) increased with sediment depth up to 50 g kg{sup {minus}1}, suggesting that iron reduction has occurred recently. The maximum concentrations of dissolved Fe(II) in interstitial water (41 mg liter{sup {minus}1}) occurred 10 to 15 cm beneath the sediment-water interface, suggesting that sulfidogenesis may not be the predominant terminal electron-accepting process in this environment and that dissolved Fe(II) arises from biological reductive dissolution of iron (hydr)oxides. The concentration of sedimentary magnetite (Fe{sub 3}O{sub 4}), a common product of bacterial Fe(III) hydroxide reduction, was as much as 15.5 g kg{sup {minus}1}. Most-probable-number enrichment cultures revealed that the mean density of Fe(III)-reducing bacteria was 8.3 x 10{sup 5} cells g (dry weight) of sediment{sup {minus}1}. Two new strains of dissimilatory Fe(III)-reducing bacteria were isolated from surface sediments. Collectively, the results of this study support the hypothesis that dissimilatory reduction of iron has been and continues to be an important biogeochemical process in the environment examined.

  7. Supramolecular architectures in Co(II) and Cu(II) complexes with thiophene-2-carboxylate and 2-amino-4,6-dimethoxypyrimidine ligands.

    Science.gov (United States)

    Karthikeyan, Ammasai; Thomas Muthiah, Packianathan; Perdih, Franc

    2016-05-01

    The coordination chemistry of mixed-ligand complexes continues to be an active area of research since these compounds have a wide range of applications. Many coordination polymers and metal-organic framworks are emerging as novel functional materials. Aminopyrimidine and its derivatives are flexible ligands with versatile binding and coordination modes which have been proven to be useful in the construction of organic-inorganic hybrid materials and coordination polymers. Thiophenecarboxylic acid, its derivatives and their complexes exhibit pharmacological properties. Cobalt(II) and copper(II) complexes of thiophenecarboxylate have many biological applications, for example, as antifungal and antitumor agents. Two new cobalt(II) and copper(II) complexes incorporating thiophene-2-carboxylate (2-TPC) and 2-amino-4,6-dimethoxypyrimidine (OMP) ligands have been synthesized and characterized by X-ray diffraction studies, namely (2-amino-4,6-dimethoxypyrimidine-κN)aquachlorido(thiophene-2-carboxylato-κO)cobalt(II) monohydrate, [Co(C5H3O2S)Cl(C6H9N3O2)(H2O)]·H2O, (I), and catena-poly[copper(II)-tetrakis(μ-thiophene-2-carboxylato-κ(2)O:O')-copper(II)-(μ-2-amino-4,6-dimethoxypyrimidine-κ(2)N(1):N(3))], [Cu2(C5H3O2S)4(C6H9N3O2)]n, (II). In (I), the Co(II) ion has a distorted tetrahedral coordination environment involving one O atom from a monodentate 2-TPC ligand, one N atom from an OMP ligand, one chloride ligand and one O atom of a water molecule. An additional water molecule is present in the asymmetric unit. The amino group of the coordinated OMP molecule and the coordinated carboxylate O atom of the 2-TPC ligand form an interligand N-H...O hydrogen bond, generating an S(6) ring motif. The pyrimidine molecules also form a base pair [R2(2)(8) motif] via a pair of N-H...N hydrogen bonds. These interactions, together with O-H...O and O-H...Cl hydrogen bonds and π-π stacking interactions, generate a three-dimensional supramolecular architecture. The one

  8. Synthesis, characterisation and electrochemical behaviour of Cu(II), Co(II), Ni(II) and Zn(II) complexes derived from acetylacetone and p-anisidine and their antimicrobial activity

    Indian Academy of Sciences (India)

    N Raman; V Muthuraj; S Ravichandran; A Kulandaisamy

    2003-06-01

    Neutral tetradentate N2O2 type complexes of Cu(II), Ni(II), Co(II) and Zn(II) have been synthesised using the Schiff base formed by the condensation of acetylacetone and p-anisidine. Microanalysis, molar conductance, magnetic susceptibility, IR, UV-Vis, 1H NMR, CV and EPR studies have been carried out to determine the structure of the complexes. From the data, it is found that all the complexes possess square-planar geometry. The EPR spectrum of the copper complex in DMSO at 300 K and 77 K was recorded and its salient features are reported. All the title complexes were screened for antimicrobial activity by the well diffusion technique using DMSO as solvent. The minimum inhibitory concentration (MIC) values were calculated at 37°C for a period of 24 h. It has been found that all the complexes are antimicrobially active and show higher activity than the free ligand.

  9. 31P and 1H NMR studies of the structure of enzyme-bound substrate complexes of lobster muscle arginine kinase: Relaxation measurements with Mn(II) and Co(II)

    International Nuclear Information System (INIS)

    The paramagnetic effects of Mn(II) and Co(II) on the spin-lattice relaxation rates of 31P nuclei of ATP and ADP and of Mn(II) on the spin-lattice relaxation rate of the δ protons of arginine bound to arginine kinase from lobster tail muscle have been measured. Temperature variation of 31P relaxation rates in E-MnADP and E-MnATP yields activation energies (ΔE) in the range 6-10 kcal/mol. Thus, the 31P relaxation rates in these complexes are exchange limited and cannot provide structural information. However, the relaxation rates in E-CoADP and E-CoATP exhibit frequency dependence and ΔE values in the range 1-2 kcal/mol; i.e., these rates depend upon 31P-Co(II) distances. These distances were calculated to be in the range 3.2-4.5 angstrom, appropriate for direct coordination between Co(II) and the phosphoryl groups. The paramagnetic effect of Mn(II) on the 1H spin-lattice relaxation rate of the δ protons of arginine in the E-MnADP-Arg complex was also measured at three frequencies. From the frequency dependence of the relaxation rate an effective τC of 0.6 ns has also been calculated, which is most likely to be the electron spin relaxation rate (τS1) for Mn(II) in this complex. The distance estimated on the basis of the reciprocal sixth root of the average relaxation rate of the δ protons was 10.9 ± 0.3 angstrom

  10. Spin-State Energetics of Fe(III) and Ru(III) Aqua Complexes: Accurate ab Initio Calculations and Evidence for Huge Solvation Effects.

    Science.gov (United States)

    Radoń, Mariusz; Gąssowska, Katarzyna; Szklarzewicz, Janusz; Broclawik, Ewa

    2016-04-12

    Aqua complexes of transition metals are useful models for understanding the electronic structure of metal-oxide species relevant in photocatalytic water splitting. Moreover, spin-forbidden d-d transitions of aqua complexes provide valuable experimental data of spin-state energetics, which can be used for benchmarking of computational methods. Here, low-energy spin states of Fe(III) and Ru(III) aqua complexes are studied with an array of DFT and high-level wave function methods (CASPT2, RASPT2, NEVPT2, CCSD(T)-F12, and other coupled cluster methods up to full CCSDT). The results from single-reference and multireference methods are cross-checked, and the amount of multireference character for both considered spin states of [Fe(H2O)6](3+) is carefully analyzed. In addition to small [M(H2O)6](3+) clusters (M = Fe, Ru), we also employ larger models [M(H2O)6·(H2O)12](3+), with explicit water molecules in the second coordination sphere, to describe the situation in aqueous solution. By comparing the results for both types of models, our calculations evidence large and systematic solvation effects on the spin-state energetics. It is found that, due to the interaction with hydrogen-bonded water molecules in the second coordination sphere, the first coordination sphere undergoes a noticeable contraction and deformation. In consequence, the presence of solvation shell affects the relative energies of spin states by as much as 3-4 × 10(3) cm(-1) (∼10 kcal/mol). Once this solvation effect is accounted for, the spin-state energetics from CCSD(T) and NEVPT2 calculations turn out to be in an excellent agreement with the experimental estimates, which was not the case for isolated [M(H2O)6](3+) species is gas phase. We thus postulate that significant discrepancies between theory and experimental data for [Fe(H2O)6](3+) that were previously reported in the literature may be plausibly resolved and attributed to the neglect of explicit solvation effects and also, to some extent, to

  11. Estudio del equilibrio y cinética de adsorción de Cd(II, Ni(II y Cr(VI usando Quitosano y Quitosano modificado con cobre

    Directory of Open Access Journals (Sweden)

    M. Benavente

    2013-04-01

    Full Text Available En este trabajo, se estudió el equilibrio y la cinética de adsorción de Cd(II, Ni(II en quitosano y Cr(VI en quitosano modificado con cobre. Para ello, soluciones de iones metálicos a diferentes concentraciones, fueron puestas en contacto con el adsorbente y se agitaron por un período de 3 – 4 h. Al final del proceso, las muestras fueron analizadas en un espectrómetro de absorción atómica. Los datos experimentales del equilibrio de adsorción de los iones metálicos fueron evaluados aplicando las isotermas de Langmuir y Freundlich; mientras los datos cinéticos fueron evaluados utilizando los modelos cinéticos de pseudo-primer orden y pseudo-segundo orden. Los resultados del proceso demostraron que los iones fueron eficazmente adsorbidos por el quitosano (Cd y Ni y por el Cu-quitosano (Cr. Además, se comprobó que los datos experimentales del equilibrio de adsorción de Cr(VI y Ni(II se ajustan al modelo de Langmuir; mientras que los datos experimentales del Cd(II fueron mejor ajustados por el modelo de Freundlich. Mediante el uso de la isoterma de Langmuir se determinó la capacidad máxima de adsorción de cromo (29.7 mg/g Cu-quitosano, cadmio (102.0 mg/g quitosano y níquel (83.31 mg/g quitosano. Los resultados de la cinética de adsorción de los iones metálicos mostraron que los datos experimentales fueron mejor ajustados por el modelo de pseudo-segundo orden; es decir, el paso limitante en la velocidad es la reacción de adsorción y no la transferencia de masa.

  12. Preparation, structure and stability of Fe(II), Co(II), Ni(II) and Zr(IV)-containing layered double hydroxides

    International Nuclear Information System (INIS)

    insignificantly lower than those values (-3612.74, -3604.67, 3593.13 kJ/mol) for Fe(II)-, Co(II)-, Ni(II)-containing (xFe = xCo = xNi = 0.1) solids, respectively. This can indicate that the substitution of Fe2+, Co2+ and Ni2+ into the brucite-like layers of LDHs does not affect so significantly on the stability of LDHs as was observed in the case of Zr4+ substitution. Molar Gibbs free energies of hydrotalcite solids at 25 C with variable content of substituted Fe2+ have been estimated as well. This allowed providing reasonable estimates for pure Mg-Al hydrotalcite composition (-3619.04±15.27 kJ/mol) as well as for and Fe(II)-Al LDH (-2703.61±191.93 kJ/mol) at 25 C. Estimation of the standard molar entropy of the hydrotalcite end-member by applying Helgeson's methods and using results of co-precipitation experiments at variable temperatures let us to conclude that derivation of more precise Sof values would require calorimetric measurements. Moreover, for the further investigations with Fe2+, Co2+, Ni2+ and Zr4+ LDHs additional careful designed syntheses, ion-exchange experiments and dissolution tests will be performed. These studies will provide more information about thermodynamic properties (i.e. standard molar Gibbs free energies, entropies and heat capacities) of LDHs in order to predict their behavior and retention properties at conditions of nuclear waste repositories. (authors)

  13. Extraction of Pd(II), Pt(IV), Fe(III), Zn(II), Cu(II) and Ag(I) From Hydrochloric Acid Solutions with Selected Cyanamides as a Novel Extractants

    International Nuclear Information System (INIS)

    Three of structurally related novel extractants namely; N, Ndihexylcyanamide( DHCY), N,N-di(2-ethylhexyl)cyanamide (DEHCY) and N, N-d-octyl cyanamid (DOCY) were synthesized in our laboratory and characterized by different techniques. The general method for synthesizing the above extractants was to react relevant secondary amines with cyanogen bromide in presence of sodium acetate anhydride. Their extracting ability for Pd(II), Pt(IV), Fe(III), Zn(II), Cu(II) and Ag(I) from hydrochloric acid media in toluene as diluent has been studied. The extraction of hydrochloric acid was studied also. Pd(II) was strongly extracted by the extractants used at low hydrochloric acid concentration and the extraction decreased with increasing hydrochloric concentration while the reverse in extraction behavior was found in is the case of Pt(IV), Fe(III) and Zn(II) extraction. Both Cu(II) and Ag(I) were found to be poor extracted with this synthesized extractants. Hydrochloric acid was extracted only in its high concentration region. A systematic investigation has been carried out on the extraction of Pd(II) by using two synthesized extractants. Pd(II) was extracted as a solvated complex with the composition, metal:chloride ion:extractant = l:2:2 the extracted species was also studied using IR spectra

  14. Synthesis and characterization of dopamine substitue tripodal trinuclear [(salen/salophen/salpropen)M] (Mdbnd Cr(III), Mn(III), Fe(III) ions) capped s-triazine complexes: Investigation of their thermal and magnetic properties

    Science.gov (United States)

    Uysal, Şaban; Koç, Ziya Erdem

    2016-04-01

    In this work, we aimed to synthesize and characterize a novel tridirectional ligand including three catechol groups and its novel tridirectional-trinuclear triazine core complexes. For this purpose, we used melamine (2,4,6-triamino-1,3,5-triazine) (MA) as starting material. 2,4,6-tris(4-carboxybenzimino)-1,3,5-triazine (II) was synthesized by the reaction of an equivalent melamine (I) and three equivalent 4-carboxybenzaldehyde. 4,4‧,4″-((1E,1‧E,1″E)-((1,3,5-triazine-2,4,6-triyl)tris(azanylylidene))tris(methanylylidene))tris(N-(3,4-dihydroxyphenethyl)benzamide) L (IV) was synthesized by the reaction of one equivalent (II) and three equivalent dopamine (3,4-dihydroxyphenethylamine) (DA) by using two different methods. (II, III, IV) and nine novel trinuclear Cr(III), Mn(III) and Fe(III) complexes of (IV) were characterized by means of elemental analyses, 1H NMR, FT-IR spectrometry, LC-MS (ESI+) and thermal analyses. The metal ratios of the prepared complexes were performed using Atomic Absorption Spectrophotometry (AAS). We also synthesized novel tridirectional-trinuclear systems and investigated their effects on magnetic behaviors of [salen, salophen, salpropen Cr(III)/Mn(III)/Fe(III)] capped complexes. The complexes were determined to be low-spin distorted octahedral Mn(III) and Fe(III), and distorted octahedral Cr(III) all bridged by catechol group.

  15. Preparation, spectroscopic, thermal, antihepatotoxicity, hematological parameters and liver antioxidant capacity characterizations of Cd(II), Hg(II), and Pb(II) mononuclear complexes of paracetamol anti-inflammatory drug

    Science.gov (United States)

    El-Megharbel, Samy M.; Hamza, Reham Z.; Refat, Moamen S.

    2014-10-01

    Keeping in view that some metal complexes are found to be more potent than their parent drugs, therefore, our present paper aimed to synthesized Cd(II), Hg(II) and Pb(II) complexes of paracetamol (Para) anti-inflammatory drug. Paracetamol complexes with general formula [M(Para)2(H2O)2]·nH2O have been synthesized and characterized on the basis of elemental analysis, conductivity, IR and thermal (TG/DTG), 1H NMR, electronic spectral studies. The conductivity data of these complexes have non-electrolytic nature. Comparative antimicrobial (bacteria and fungi) behaviors and molecular weights of paracetamol with their complexes have been studied. In vivo the antihepatotoxicity effect and some liver function parameters levels (serum total protein, ALT, AST, and LDH) were measured. Hematological parameters and liver antioxidant capacities of both Para and their complexes were performed. The Cd2+ + Para complex was recorded amelioration of antioxidant capacities in liver homogenates compared to other Para complexes treated groups.

  16. Highly efficient simultaneous ultrasonic-assisted adsorption of Pb(II), Cd(II), Ni(II) and Cu (II) ions from aqueous solutions by graphene oxide modified with 2,2'-dipyridylamine: Central composite design optimization.

    Science.gov (United States)

    Zare-Dorabei, Rouholah; Ferdowsi, Somayeh Moazen; Barzin, Ahmad; Tadjarodi, Azadeh

    2016-09-01

    In present work, a graphene oxide chemically modified with 2,2'-dipyridylamine (GO-DPA), was synthesized by simple, fast and low-cost process for the simultaneous adsorption of four toxic heavy metals, Pb(II), Cd(II), Ni(II) and Cu(II), from aqueous solutions. The synthesized adsorbent was characterized by FT-IR, XRD, XPS, SEM and AFM measurements. The effects of variables such as pH solution, initial ion concentrations, adsorbent dosage and sonicating time were investigated on adsorption efficiency by rotatable central composite design. The optimum conditions, specified as 8mg of adsorbent, 20mgL(-1) of each ion at pH 5 and short time of 4min led to the achievement of a high adsorption capacities. Ultrasonic power had important role in shortening the adsorption time of ions by enhancing the dispersion of adsorbent in solution. The adsorption kinetic studies and equilibrium isotherms for evaluating the mechanism of adsorption process showed a good fit to the pseudo-second order and Langmuir model, respectively. The maximum adsorption capacities (Qm) of this adsorbent were 369.749, 257.201, 180.893 and 358.824mgg(-1) for lead, cadmium, nickel and copper ions, respectively. The removal performance of adsorbent on the real wastewater samples also showed the feasibility of adsorbent for applying in industrial purposes. PMID:27150770

  17. Molecular structures, charge distributions, and vibrational analyses of the tetracoordinate Cu(II), Zn(II), Cd(II), and Hg(II) bromide complexes of p-toluidine investigated by density functional theory in comparison with experiments

    Science.gov (United States)

    Bardakçı, Tayyibe; Kumru, Mustafa; Altun, Ahmet

    2016-07-01

    The Cu(II), Zn(II), Cd(II), and Hg(II) bromide complexes of p-toluidine have been studied with B3LYP calculations by using def2-TZVP basis set at the metal atoms and using def2-TZVP and 6-311G+(d,p) basis sets at the remaining atoms. Both basis set combinations give analogous results, which validate the use of quickly converging 6-311G+(d,p) basis set in future studies. The molecular structures, atomic charge and spin distributions, and harmonic vibrational frequencies of the complexes have been calculated. The Zn, Cd and Hg complexes have been found to have distorted tetrahedral environments around the metal atoms whereas Cu complex has a square planar geometry. The NBO charge analysis have been found more accurate and less misleading compared with the Mulliken scheme. The present vibrational spectra calculations allow accurate assignment of the vibrational bands, which otherwise assigned tentatively in previous experimental-only studies.

  18. Syntheses, crystal structures and fluorescent properties of Cd(II), Hg(II) and Ag(I) coordination polymers constructed from 1H-1,2,4-triazole-1-acetic acid

    International Nuclear Information System (INIS)

    Three new d10 coordination polymers, namely [Cd(taa)Cl]n1, [Hg(taa)Cl]n2, and [Ag1.5(taa)(NO3)0.5]n3 (taa=1H-1,2,4-triazole-1-acatate anion) have been prepared and characterized by elemental analysis, IR, and single crystal X-ray diffraction. Compound 1 consists of two-dimensional layers constructed by carboxyl-linked helical chains, which are further linked through carboxyl group to generate a unique 3D open framework. Topological analysis reveals that the structure of 1 can be classified as an unprecedented (3,8)-connected network with the Schlaefli symbol (4.52)2(42.58.614.73.8). Compound 2 manifests a doubly interpenetrated decorated α-polonium cubic network with the Schlaefli symbol of (410.62.83). Compound 3 consists of 2D puckered layers made up of Ag centers and taa- bridges. In addition, all of these compounds are photoluminescent in the solid state with spectra that closely resemble those of the ligand precursor. - Graphical abstract: Three new compounds based on 1H-1,2,4-triazole-1-acetic acid and Cd(II), Hg(II) and Ag(I) salts display luminescent properties and may be potential candidates for luminescent materials.

  19. Synthesis, spectral and thermal studies of pyridyl adducts of Zn(II) and Cd(II) dithiocarbamates, and their use as single source precursors for ZnS and CdS nanoparticles.

    Science.gov (United States)

    Onwudiwe, Damian C; Strydom, Christien A; Oluwafemi, Oluwatobi S; Hosten, Eric; Jordaan, Anine

    2014-06-21

    The synthesis, spectroscopic characterisation, and thermal studies of pyridyl adducts of Zn(II) and Cd(II) complexes of N-ethyl-N-phenyl dithiocarbamate, represented as [ZnL2py] and [CdL2py2], are reported. Single-crystal X-ray structural analysis of the Zn compound showed that it is five-coordinate with four sulphurs from dithiocarbamate and one nitrogen from pyridine in a distorted square pyramidal geometry. The thermogravimetric studies indicate that the zinc and cadmium compounds undergo fast weight loss, and the temperature at maximum rate of decomposition is at 277 °C and 265 °C respectively, to give the metal (Zn or Cd) sulphide residues. These compounds were used as single molecule precursors to produce nanocrystalline MS (M = Zn, Cd) after thermolysis in hexadecylamine. The morphological and optical properties of the resulting MS nanocrystallites were investigated using transmission electron microscopy (TEM), scanning electron microscopy (SEM), UV-Vis absorption and photoluminescence (PL) spectroscopy, and powdered X-ray diffraction (XRD). By varying the growth time, the temporal evolution of the optical properties and morphology of the nanocrystals were investigated. PMID:24769861

  20. Synthesis, Characterization and Thermal Studies of Zn(II), Cd(II) and Hg(II) Complexes of N-Methyl-N-Phenyldithiocarbamate: The Single Crystal Structure of [(C6H5)(CH3)NCS2]4Hg2

    Science.gov (United States)

    Onwudiwe, Damian C.; Ajibade, Peter A.

    2011-01-01

    Zn(II), Cd(II) and Hg(II) complexes of N-methyl-N-phenyl dithiocarbamate have been synthesized and characterized by elemental analysis and spectral studies (IR, 1H and 13C-NMR). The single crystal X-ray structure of the mercury complex revealed that the complex contains a Hg centre with a distorted tetrahedral coordination sphere in which the dinuclear Hg complex resides on a crystallographic inversion centre and each Hg atom is coordinated to four S atoms from the dithiocarbamate moiety. One dithiocarbamate ligand acts as chelating ligand while the other acts as chelating bridging ligand between two Hg atoms, resulting in a dinuclear eight-member ring. The course of the thermal degradation of the complexes has been investigated using thermogravimetric and differential thermal analyses techniques. Thermogravimetric analysis of the complexes show a single weight loss to give MS (M = Zn, Cd, Hg) indicating that they might be useful as single source precursors for the synthesis of MS nanoparticles and thin films. PMID:21673933

  1. Synthesis, Spectroscopy, Theoretical, and Electrochemical Studies of Zn(II, Cd(II, and Hg(II Azide and Thiocyanate Complexes of a New Symmetric Schiff-Base Ligand

    Directory of Open Access Journals (Sweden)

    Morteza Montazerozohori

    2013-01-01

    Full Text Available Synthesis of zinc(II/cadmium(II/mercury(II thiocyanate and azide complexes of a new bidentate Schiff-base ligand (L with general formula of MLX2 (M = Zn(II, Cd(II, and Hg(II in ethanol solution at room temperature is reported. The ligand and metal complexes were characterized by using ultraviolet-visible (UV-visible, Fourier transform infrared (FT-IR, 1H- and 13C-NMR spectroscopy and physical characterization, CHN analysis, and molar conductivity. 1H- and 13C-NMR spectra have been studied in DMSO-d6. The reasonable shifts of FT-IR and NMR spectral signals of the complexes with respect to the free ligand confirm well coordination of Schiff-base ligand and anions in an inner sphere coordination space. The conductivity measurements as well as spectral data indicated that the complexes are nonelectrolyte. Theoretical optimization on the structure of ligand and its complexes was performed at the Becke’s three-parameter hybrid functional (B3 with the nonlocal correlation of Lee-Yang-Parr (LYP level of theory with double-zeta valence (LANL2DZ basis set using GAUSSIAN 03 suite of program, and then some theoretical structural parameters such as bond lengths, bond angles, and torsion angles were obtained. Finally, electrochemical behavior of ligand and its complexes was investigated. Cyclic voltammograms of metal complexes showed considerable changes with respect to free ligand.

  2. Formation, reactivity, and aging of ferric oxide particles formed from Fe(II) and Fe(III) sources: Implications for iron bioavailability in the marine environment

    Science.gov (United States)

    Bligh, Mark W.; Waite, T. David

    2011-12-01

    Freshly formed amorphous ferric oxides (AFO) in the water column are potentially highly reactive, but with reactivity declining rapidly with age, and have the capacity to partake in reactions with dissolved species and to be a significant source of bioavailable iron. However, the controls on reactivity in aggregated oxides are not well understood. Additionally, the mechanism by which early rapid aging occurs is not clear. Aging is typically considered in terms of changes in crystallinity as the structure of an iron oxide becomes more stable and ordered with time thus leading to declining reactivity. However, there has been recognition of the role that aggregation can play in determining reactivity, although it has received limited attention. Here, we have formed AFO in seawater in the laboratory from either an Fe(II) or Fe(III) source to produce either AFO(II) or AFO(III). The changes in reactivity of these two oxides following formation was measured using both ligand-promoted dissolution (LPD) and reductive dissolution (RD). The structure of the two oxides was examined using light scattering and X-ray adsorption techniques. The dissolution rate of AFO(III) was greater than that of AFO(II), as measured by both dissolution techniques, and could be attributed to both the less ordered molecular structure and smaller primary particle size of AFO(III). From EXAFS analysis shortly (90 min) following formation, AFO(II) and AFO(III) were shown to have the same structure as aged lepidocrocite and ferrihydrite respectively. Both oxides displayed a rapid decrease in dissolution rate over the first hours following formation in a pattern that was very similar when normalised. The early establishment and little subsequent change of crystal structure for both oxides undermined the hypothesis that increasing crystallinity was responsible for early rapid aging. Also, an aging model describing this proposed process could only be fitted to the data with kinetic parameters that were

  3. A study on the use of nano/micro structured goethite and hematite as adsorbents for the removal of Cr(III, Co(II, Cu(II, Ni(II, and Zn(II metal ions from aqueous solutions.

    Directory of Open Access Journals (Sweden)

    Hala Hafez

    2012-06-01

    Full Text Available Numerous adsorbents for the removal of heavy metals from aqueous solutions are in various stages of research. The main goal for most of this research is to develop low-cost and environmentally friendly materials for the removal of heavy metals from contaminated groundwater, surface water, and drinking water. Materials that have ion exchange sites are expected to be able to efficiently remove heavy metals from water. Iron oxides, especially in the micro/nano structured forms, are good candidates for the removal of toxic heavymetal ions from water due to their structural properties. In the present work the efficiency of synthesized micro/nano particles of goethite and hematite for the removal of Cr(III, Co(II , Cu(II, Ni(II and Zn(II ions from water was compared. The absorbent capability of goethite as a function of pH, contact time, and initialmetal ion concentration was studied. The results showed that maximum absorption for all metal ions using goethite occurred at a pH=5.3, which was a common trend for all metal ions. At this pH and after one hour contact time goethite was able to adsorb about 100% of the Cu ions (50mg/g, 85% (42.5 mg/g of the Ni ions, 70% (35mg/g of the Cr and Co ions and 60% (30 mg/g of Zn ions from the solutions. Whereas and under the same conditions hematite was able to adsorb 20% (10mg/g of the Cu ions, 85% (42.5mg/g of the Ni ions, 95% (47.5mg/g of the Cr ions, 80% (40mg/g of the Zn ions, and 70% (35mg/g of the Co ions. Both oxides are equally efficient for the removal of Co(II and Ni(II from water. However, goethite is a much more efficient candidate than hematite for the removal of Cu(II,while hematite is more efficient adsorbent for Zn(II and Cr(III. The adsorption affinity of the five metallic cations to goethite is Cu > Ni > Co ~ Cr > Zn, whereas the adsorption affinity of the cations to hematite is Cr > Ni > Zn > Co > Cu. Under the conditions used in the batch experiments (mass of goethite 2g/l maximumadsorption of

  4. Synthesis of polystyrene supported chelating resin containing an oxygen-nitrogen donor bidentate Schiff base and its nickel(II), cobalt(II), copper(II), iron(III), zinc(II), molybdenum(VI) and uranium(VI) complexes

    International Nuclear Information System (INIS)

    A new bidentate oxygen-nitrogen donor Schiff base supported on polystyrene matrix has been synthesized by the reaction of aminomethylated polystyrene and salicylaldehyde. The chelating resin reacts with metal complex/metal salt and forms metal bound polymers of the formulae: PS-LNi(CH3COO).3DMF, PS-LCo(CH3COO).DMF, PS-LCu(CH3COO).DMF, PS-LCu(CH3COO).CH3OH, PS-LFeCL2.2DMF, PS-LZnCl.CH3OH, PS-LCd(CH3COO).DMF, PS-LCdCl.CH3OH, PS-LMoO2(acetylacetonato) and PS-LUO2(CH3COO).DMF (where PS-L=deprotonated anion of polymer-anchored ligand). The metal bound polymers have been characterized by elemental analysis, IR, electronic spectra and magnetic susceptibility measurements. The complexes PS-LNi(CH3COO).3DMF, PS-LCo(CH3COO).DMF, PS-LCu(CH3COO).DMF, PS-LCu(CH3COO).CH3OH and PS-LFeCl2.2DMF are paramagnetic while the Zn(II), Cd(II), Mo(VI) and U(VI) complexes are diamagnetic. The Co(II) and Cu(II) complexes exhibit a square planar structure, whereas Ni(II), Fe(III), Mo(VI) and U(VI) complexes are octahedral and Zn(II) and Cd(II) complexes are tetrahedral. (author). 29 refs., 1 tab

  5. Influence of Reactive Transport on the Reduction of U(VI) in the Presence of Fe(III) and Nitrate: Implications for U(VI) Immobilization by Bioremediation / Biobarriers- Final Report

    Energy Technology Data Exchange (ETDEWEB)

    B.D. Wood

    2007-01-01

    Subsurface contamination by metals and radionuclides represent some of the most challenging remediation problems confronting the Department of Energy (DOE) complex. In situ remediation of these contaminants by dissimilatory metal reducing bacteria (DMRB) has been proposed as a potential cost effective remediation strategy. The primary focus of this research is to determine the mechanisms by which the fluxes of electron acceptors, electron donors, and other species can be controlled to maximize the transfer of reductive equivalents to the aqueous and solid phases. The proposed research is unique in the NABIR portfolio in that it focuses on (i) the role of flow and transport in the initiation of biostimulation and the successful sequestration of metals and radionuclides [specifically U(VI)], (ii) the subsequent reductive capacity and stability of the reduced sediments produced by the biostimulation process, and (iii) the potential for altering the growth of biomass in the subsurface by the addition of specific metabolic uncoupling compounds. A scientifically-based understanding of these phenomena are critical to the ability to design successful bioremediation schemes. The laboratory research will employ Shewanella putrefaciens (CN32), a facultative DMRB that can use Fe(III) oxides as a terminal electron acceptor. Sediment-packed columns will be inoculated with this organism, and the reduction of U(VI) by the DMRB will be stimulated by the addition of a carbon and energy source in the presence of Fe(III). Separate column experiments will be conducted to independently examine: (1) the importance of the abiotic reduction of U(VI) by biogenic Fe(II); (2) the influence of the transport process on Fe(III) reduction and U(VI) immobilization, with emphasis on methods for controlling the fluxes of aqueous species to maximize uranium reduction; (3) the reductive capacity of biologically-reduced sediments (with respect to re-oxidation by convective fluxes of O2 and NO3-) and

  6. Influence of Reactive Transport on the Reduction of U(VI) in the Presence of Fe(III) and Nitrate: Implications for U(VI) Immobilization by Bioremediation/Biobarriers - Final Report

    International Nuclear Information System (INIS)

    Subsurface contamination by metals and radionuclides represent some of the most challenging remediation problems confronting the Department of Energy (DOE) complex. In situ remediation of these contaminants by dissimilatory metal reducing bacteria (DMRB) has been proposed as a potential cost effective remediation strategy. The primary focus of this research is to determine the mechanisms by which the fluxes of electron acceptors, electron donors, and other species can be controlled to maximize the transfer of reductive equivalents to the aqueous and solid phases. The proposed research is unique in the NABIR portfolio in that it focuses on (i) the role of flow and transport in the initiation of biostimulation and the successful sequestration of metals and radionuclides [specifically U(VI)], (ii) the subsequent reductive capacity and stability of the reduced sediments produced by the biostimulation process, and (iii) the potential for altering the growth of biomass in the subsurface by the addition of specific metabolic uncoupling compounds. A scientifically-based understanding of these phenomena are critical to the ability to design successful bioremediation schemes. The laboratory research will employ Shewanella putrefaciens (CN32), a facultative DMRB that can use Fe(III) oxides as a terminal electron acceptor. Sediment-packed columns will be inoculated with this organism, and the reduction of U(VI) by the DMRB will be stimulated by the addition of a carbon and energy source in the presence of Fe(III). Separate column experiments will be conducted to independently examine: (1) the importance of the abiotic reduction of U(VI) by biogenic Fe(II); (2) the influence of the transport process on Fe(III) reduction and U(VI) immobilization, with emphasis on methods for controlling the fluxes of aqueous species to maximize uranium reduction; (3) the reductive capacity of biologically-reduced sediments (with respect to re-oxidation by convective fluxes of O2 and NO3-) and

  7. Metal-Based Antibacterial and Antifungal Agents: Synthesis, Characterization, and In Vitro Biological Evaluation of Co(II, Cu(II, Ni(II, and Zn(II Complexes with Amino Acid-Derived Compounds

    Directory of Open Access Journals (Sweden)

    Zahid H. Chohan

    2006-01-01

    Full Text Available A series of antibacterial and antifungal amino acid-derived compounds and their cobalt(II, copper(II, nickel(II, and zinc(II metal complexes have been synthesized and characterized by their elemental analyses, molar conductances, magnetic moments, and IR, and electronic spectral measurements. Ligands (L1–(L5 were derived by condensation of β-diketones with glycine, phenylalanine, valine, and histidine and act as bidentate towards metal ions (cobalt, copper, nickel, and zinc via the azomethine-N and deprotonated-O of the respective amino acid. The stoichiometric reaction between the metal(II ion and synthesized ligands in molar ratio of M: L (1: 1 resulted in the formation of the metal complexes of type [M(L(H2O4]Cl (where M = Co(II, Cu(II, and Zn(II and of M: L (1: 2 of type [M(L2(H2O2] (where M = Co(II, Cu(II, Ni(II, and Zn(II. The magnetic moment data suggested for the complexes to have an octahedral geometry around the central metal atom. The electronic spectral data also supported the same octahedral geometry of the complexes. Elemental analyses and NMR spectral data of the ligands and their metal(II complexes agree with their proposed structures. The synthesized ligands, along with their metal(II complexes, were screened for their in vitro antibacterial activity against four Gram-negative (Escherichia coli, Shigella flexeneri, Pseudomonas aeruginosa, and Salmonella typhi and two Gram-positive (Bacillus subtilis and Staphylococcus aureus bacterial strains and for in vitro antifungal activity against Trichophyton longifusus, Candida albicans, Aspergillus flavus, Microsporum canis, Fusarium solani, and Candida glaberata. The results of these studies show the metal(II complexes to be more antibacterial/antifungal against one or more species as compared to the uncomplexed ligands. The brine shrimp bioassay was also carried out to study their in vitro cytotoxic properties. Five compounds, (3, (7, (10, (11, and (22, displayed potent cytotoxic

  8. Metal-Based Antibacterial and Antifungal Agents: Synthesis, Characterization, and In Vitro Biological Evaluation of Co(II), Cu(II), Ni(II), and Zn(II) Complexes With Amino Acid-Derived Compounds.

    Science.gov (United States)

    Chohan, Zahid H; Arif, M; Akhtar, Muhammad A; Supuran, Claudiu T

    2006-01-01

    A series of antibacterial and antifungal amino acid-derived compounds and their cobalt(II), copper(II), nickel(II), and zinc(II) metal complexes have been synthesized and characterized by their elemental analyses, molar conductances, magnetic moments, and IR, and electronic spectral measurements. Ligands (L(1))-(L(5)) were derived by condensation of beta-diketones with glycine, phenylalanine, valine, and histidine and act as bidentate towards metal ions (cobalt, copper, nickel, and zinc) via the azomethine-N and deprotonated-O of the respective amino acid. The stoichiometric reaction between the metal(II) ion and synthesized ligands in molar ratio of M : L (1 : 1) resulted in the formation of the metal complexes of type [M(L)(H(2)O)(4)]Cl (where M = Co(II), Cu(II), and Zn(II)) and of M : L (1 : 2) of type [M(L)(2)(H(2)O)(2)] (where M = Co(II), Cu(II), Ni(II), and Zn(II)). The magnetic moment data suggested for the complexes to have an octahedral geometry around the central metal atom. The electronic spectral data also supported the same octahedral geometry of the complexes. Elemental analyses and NMR spectral data of the ligands and their metal(II) complexes agree with their proposed structures. The synthesized ligands, along with their metal(II) complexes, were screened for their in vitro antibacterial activity against four Gram-negative (Escherichia coli, Shigella flexeneri, Pseudomonas aeruginosa, and Salmonella typhi) and two Gram-positive (Bacillus subtilis and Staphylococcus aureus) bacterial strains and for in vitro antifungal activity against Trichophyton longifusus, Candida albicans, Aspergillus flavus, Microsporum canis, Fusarium solani, and Candida glaberata. The results of these studies show the metal(II) complexes to be more antibacterial/antifungal against one or more species as compared to the uncomplexed ligands. The brine shrimp bioassay was also carried out to study their in vitro cytotoxic properties. Five compounds, (3), (7), (10), (11), and (22

  9. A new synthesis, characterization and application chelating resin for determination of some trace metals in honey samples by FAAS.

    Science.gov (United States)

    Daşbaşı, Teslima; Saçmacı, Şerife; Çankaya, Nevin; Soykan, Cengiz

    2016-07-15

    In this study, we developed a simple and rapid solid phase extraction (SPE) method for the separation/preconcentration and determination of some trace metals by flame atomic absorption spectrometry (FAAS). A new chelating resin, poly [2-(4-methoxyphenylamino)-2-oxoethyl methacrylate-co-divinylbenzene-co-2-acrylamido-2-methyl-1-propanesulfonic acid] (MPAEMA-co-DVB-co-AMPS), was synthesized and characterized. This chelating resin was used as a new adsorbent material for determination of Cd(II), Co(II), Cr(III), Cu(II), Fe(III), Mn(II), Pb(II), and Zn(II) ions. The parameters influential on the determination of this trace metals were examined. Under the optimum conditions, the detection limits (DL) of the method for trace metals were found to be (3s) in the range of 0.9-2.2 μg L(-1) (n=21), the preconcentration factor was calculated as 200 and the relative standard deviation was obtained achieved as ⩽2% for n=11. The method was performed for the determination of trace metals in some honey samples and standard reference materials. PMID:26948616

  10. Ion flotation behaviour of thirty-one metal ions in mixed hydrochloric/nitric acid solutions.

    Science.gov (United States)

    Hualing, D; Zhide, H

    1989-06-01

    The ion flotation of 31 metal ions in hydrochloric/nitric acid solution with the cationic surfactant cetylpyridinium chloride was investigated. A 25-ml portion of 0.27-2.87 x 10(-4)M metal ion and 1.8-6.0 x 10(-4)M cetylpyridinium chloride solution in 0.17-3.4M acid mixture ([HCl]:[HNO(3)] = 2.4:1) was subjected to flotation in a cell, 22.5 cm high and 4.0 cm in diameter, for 5 min, with nitrogen bubbles. Ir(IV), Pt(IV), Ge(IV), Sn(IV), Bi(III), Au(III), Tl(III), Pd(II) and Sn(II) were floated from solution in 95-100% yield; Ru(III), Rh(III), Ir(III), Hg(II), Ag(I) and Tl(I) were partly floated, while Cr(VI), Ti(IV), Zr(IV), Ga(III), In(III), Fe(III), Sb(III), Al(III), Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II), CD(II) and Pb(II) were floated with less than 20% yield. The flotation behaviour of these metal ions in the mixed acid system was compared with that in hydrochloric acid. The flotation is more efficient in the mixed acid system. PMID:18964771

  11. Reactive polymers: part I - Novel polystyrene-anchored copper (II), nickel (II), cobalt (II), iron (III), zinc (II), cadmium (II), molybdenum (VI) and uranium (VI) complexes of the chelating resin containing thiosemicarbazone

    International Nuclear Information System (INIS)

    A new chelating resin containing thiosemicarbazone has been synthesized by the reaction of aldehydopolystyrene and thiosemicarbazide. The polystyrene bound thiosemicarbazone reacts with salicylaldehyde leading to the formation of a new Schiff base chelating resin which reacts with sodium monochloroacetate and gives the polymer bound S-acetatothiosemicarbazone. The new chelating resin forms complexes of the types PS-LCuX·S, PS-LNiX·3S, PS-LHNi(acac)2, PS-LCoX·3S, PS-LFeX2·2S, PS-LZnX·S, PS-LCdX·S, PS-LMoO2(acac) and PS-LUO2X·S (where PS-LH = polymeranchored ligand; S = DMF or CH3OH; X=Cl or CH3COO- and acacH = acetylacetone). The chelating resins and complexes have been characterized by elemental analysis, IR and electronic spectra and magnetic measurements. The Cu(II), Ni(II), Co(II), and Fe(III) complexes are paramagnetic while the Zn(II), Cd(II), Mo(VI) and U(VI) complexes are diamagnetic. The IR data indicate the thioenolization of the ligand in the complexes (except in PS-LHNi(acac)2 where it behaves as a neutral bidentate ligand). (author). 24 refs., 2 tabs

  12. Thermal properties of some pyrimidine, purine, amino-acid and mixed ligand complexes

    Energy Technology Data Exchange (ETDEWEB)

    Masoud, Mamdouh S. [Department of Chemistry, Faculty of Science, Alexandria University, Alexandria (Egypt); Ramadan, Ahmed M., E-mail: dramramadan@yahoo.com [Department of Chemistry, Faculty of Science, Alexandria University, Alexandria (Egypt); Chemistry Department, Faculty of Science, King Khalid University (Saudi Arabia); El-Ashry, Ghada M. [Central Laboratory for Food and Feed, Agriculture Research Centre, Ministry of Agriculture (Egypt)

    2013-01-10

    Highlights: Black-Right-Pointing-Pointer Synthesis of novel complexes from barbital, thiouracil, adenine, amino acids. Black-Right-Pointing-Pointer We examine their thermal stability using DTA and TG techniques. Black-Right-Pointing-Pointer The thermodynamic parameters of the decomposition reaction were evaluated. Black-Right-Pointing-Pointer We proposed mechanisms for the decomposition processes. - Abstract: Mn(II), Fe(III), Co(II), Ni(II), Zn(II) and Cd(II) complexes of barbital, thiouracil, adenine, amino acids, beside mixed metals and mixed ligands were prepared. The structures of the complexes are of Oh, distorted Oh, Td and distorted Td geometries. Differential thermal (DTA) and thermogravimetric analysis (TG) of the complexes pointed to their stability. The change of entropy values, {Delta}S{sup numbersign}, showed that the transition states are more ordered than the reacting complexes. The fractions appeared in the calculated order of the thermal reactions, n, confirmed that the thermal reactions proceed in complicated mechanisms where the bond between the central metal ion and the ligands dissociates after losing small molecules such as H{sub 2}O. In most cases, the free radical species of the ligands are assigned to exist through decomposition mechanisms.

  13. Analytical applications of some macro-schiff's bases for spectrophotometric determination of some metal ions

    International Nuclear Information System (INIS)

    In this research three schiff's bases PAD, N, NBPAD and N, NBHPAD were synthesized by condensation of o-phenylenediamine with p-aminoacetophenone, to give an intermediate which then further condensed with benzil, and 2,5 hexanedione, respectively, in ethanol to give macro schiff's bases. These schiff's bases were identified using I.R spectra, UV/VIS spectrophotometer, elemental analyzer, and melting point. Their applications as analytical reagents were studied using UV/VIS spectrophotometer with Pb(II), Cr(VI), Cu(II), Cd(II), V(V), Ni(II), Hg(II), Zn(II), Co(II), Fe(II) and Fe(III). Various parameters were investigated in order to find their optimum conditions for the analytical application of these schiff's bases. These include the effect of solvent, the effect of micelle as well as the presence of foreign metal ions. Good results were obtained for determination of Cr(VI), and V(V) with N, NBPAD in terms of linearity detection limit, and interference, and for the determination of Fe(II) with N, NBHPAD. The stoichiometry of some these complexes was determined. The study also showed a good results for the determination of Hg(II), and Pb(II) (two serious environmental pollutants) if interference is removed.(Author)

  14. Synthesis, characterization and application of a new chelating resin for solid phase extraction, preconcentration and determination of trace metals in some dairy samples by flame atomic absorption spectrometry.

    Science.gov (United States)

    Daşbaşı, Teslima; Saçmacı, Şerife; Çankaya, Nevin; Soykan, Cengiz

    2016-11-15

    In this study, a simple and rapid solid phase extraction/preconcentration procedure was developed for determination of Cd(II), Co(II), Cr(III), Cu(II), Fe(III), Mn(II), Pb(II), and Zn(II) trace metals by flame atomic absorption spectrometry (FAAS). A new chelating resin, poly(N-cyclohexylacrylamide-co-divinylbenzene-co-2-acrylamido-2-methyl-1-propanesulfonic acid) (NCA-co-DVB-co-AMPS) (hereafter CDAP) was synthesized and characterized. The influences of the analytical parameters such as pH of the sample solution, type and concentration of eluent, flow rates of the sample and eluent, volume of the sample and eluent, amount of chelating resin, and interference of ions were examined. The limit of detection (LOD) of analytes were found (3s) to be in the range of 0.65-1.90μgL(-1). Preconcentration factor (PF) of 200 and the relative standard deviation (RSD) of ⩽2% were achieved (n=11). The developed method was applied for determination of analytes in some dairy samples and certified reference materials. PMID:27283608

  15. Synthesis, spectral characterization, molecular modeling and antimicrobial activity of new potentially N2O2 Schiff base complexes

    Science.gov (United States)

    Adly, Omima M. I.; Taha, Ali; Fahmy, Shery A.

    2013-12-01

    Metal complexes of a new potentially tetradentate symmetrical Schiff base ligand (H2L) with Cu(II), Ni(II), Co(II), VO(IV), Zn(II), Cd(II), Ce(III), Fe(III) and UO2(VI) metal ions have been synthesized and characterized based on their elemental analyses, spectral (IR, UV-Vis, 1H NMR and mass spectra), magnetic and molar conductance studies as well as thermal gravimetric analysis (TGA). The synthesized complexes have the general formula [MHxL(H2O)yXn]: x = 0-1, y = 0-4 and n = 0-1; where: L = dianion of 6-hydroxy-5-[N-(2-{[(1E)-1-(6-hydroxy-2,4-dioxo-3,4-dihydro-2H-1,3-thiazin-5-yl)ethylidene]amino}ethyl) ethanimidoyl]-2H-1,3-thiazine-2,4(3H)-dione and X = nitrate or sulphate anion. The ligand behaves as diabasic tetradentate N2O2 sites, except in cases of Co(II), VO(IV) and UO2(VI) metal ions, it behaves as monobasic tetradentate Schiff base ligand. The metal complexes exhibited square planar, square-pyramidal and octahedral geometrical arrangements except for Ce(III) and UO2(VI) complexes, they are octa-coordinated. The Coats-Redfern equation was used to calculate the kinetic and thermodynamic parameters for the different thermal decomposition stages of some complexes. Structural parameters of the ligand and its metal complexes have been theoretically computed on the basis of semiemperical PM3 level, and the results were correlated with their experimental data. The antimicrobial activities of the ligand and its metal complexes were tested against some Gram-positive and Gram-negative bacteria; and fungus strain and the results were discussed.

  16. Indole-7-carbaldehyde thiosemicarbazone as a flexidentate ligand toward ZnII, CdII, PdII and PtII ions: cytotoxic and apoptosis-inducing properties of the PtII complex.

    Science.gov (United States)

    Ibrahim, Abeer A; Khaledi, Hamid; Hassandarvish, Pouya; Mohd Ali, Hapipah; Karimian, Hamed

    2014-03-14

    A new thiosemicarbazone (LH2) derived from indole-7-carbaldehyde was synthesized and reacted with Zn(II), Cd(II), Pd(II) and Pt(II) salts. The reactions with zinc and cadmium salts in 2 : 1 (ligand-metal) molar ratio afforded complexes of the type MX2(LH2)2, (X = Cl, Br or OAc), in which the thiosemicarbazone acts as a neutral S-monodentate ligand. In the presence of potassium hydroxide, the reaction of LH2 with ZnBr2 resulted in deprotonation of the thiosemicarbazone at the hydrazine and indole nitrogens to form Zn(L)(CH3OH). The reaction of LH2 with K2PdCl4 in the presence of triethylamine, afforded Pd(L)(LH2) which contains two thiosemicarbazone ligands: one being dianionic N,N,S-tridentate while the other one is neutral S-monodentate. When PdCl2(PPh3)2 was used as the Pd(II) ion source, Pd(L)(PPh3) was obtained. In a similar manner, the analogous platinum complex, Pt(L)(PPh3), was synthesized. The thiosemicarbazone in the latter two complexes behaves in a dianionic N,N,S-tridentate fashion. The platinum complex was found to have significant cytotoxicity toward four cancer cells lines, namely MDA-MB-231, MCF-7, HT-29, and HCT-116 but not toward the normal liver WRL-68 cell line. The apoptosis-inducing properties of the Pt complex was explored through fluorescence microscopy visualization, DNA fragmentation analysis and propidium iodide flow cytometry. PMID:24442181

  17. Synthesis of high-surface-area {gamma}-Al{sub 2}O{sub 3} from aluminum scrap and its use for the adsorption of metals: Pb(II), Cd(II) and Zn(II)

    Energy Technology Data Exchange (ETDEWEB)

    Asencios, Yvan J.O., E-mail: yvan@iqsc.usp.br [Instituto de Quimica de Sao Carlos, Universidade de Sao Paulo, Av. Trabalhador Saocarlense, 400, 13560-970, Sao Carlos, SP (Brazil); Sun-Kou, Maria R., E-mail: msun@pucp.edu.pe [Seccion Quimica, Departamento de Ciencias, Pontificia Universidad Catolica del Peru, Av. Universitaria 1801, Lima 32 (Peru)

    2012-10-01

    Highlights: Black-Right-Pointing-Pointer Aluminum hydroxide obtained from aluminum scrap led to the formation of gamma alumina. Black-Right-Pointing-Pointer Acidic pH of precipitation favored the formation of small particles of high surface areas. Black-Right-Pointing-Pointer Higher aging temperature favored the formation of large structures of large pore sizes. Black-Right-Pointing-Pointer Higher aging temperature generated symmetrical solids of regular hexagonal prism forms. Black-Right-Pointing-Pointer Aluminas of large pores adsorbed metals as following: Pb (1.75 Angstrom-Sign ) > Cd (1.54 Angstrom-Sign ) > Zn (1.38 Angstrom-Sign ). - Abstract: Several types of alumina were synthesized from sodium aluminate (NaAlO{sub 2}) by precipitation with sulfuric acid (H{sub 2}SO{sub 4}) and subsequently calcination at 500 Degree-Sign C to obtain {gamma}-Al{sub 2}O{sub 3}. The precursor aluminate was derived from aluminum scrap. The various {gamma}-Al{sub 2}O{sub 3} synthesized were characterized by Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), adsorption-desorption of N{sub 2} (S{sub BET}) and scanning electron microscopy (SEM). XRD revealed that distinct phases of Al{sub 2}O{sub 3} were formed during thermal treatment. Moreover, it was observed that conditions of synthesis (pH, aging time and temperature) strongly affect the physicochemical properties of the alumina. A high-surface-area alumina (371 m{sup 2} g{sup -1}) was synthesized under mild conditions, from inexpensive raw materials. These aluminas were tested for the adsorption of Cd(II), Zn(II) and Pb(II) from aqueous solution at toxic metal concentrations, and isotherms were determined.

  18. M(II) transfer across a liquid-liquid microinterface facilitated by a complex formation with 8-Hydroxyquinoline: Application to quantification of Pb(II), Cd(II) and Zn(II) alone or in mixture in effluents

    International Nuclear Information System (INIS)

    Highlights: • Study of assisted transfer of lead ions by 8-HQ at water/1,2-DCE for the first time. • Formation of a monocharged specie in good agreement with the solution chemistry. • Possible quantification by cyclic and square wave voltammetry measurements. • Quantification of Pb(II) ions until 0.2 ppm lower than the limit fixed in industrial effluents. • Highlighting of the interesting overall quantification of heavy metals: Lead, Cadmium and Zinc. - Abstract: For the first time, the assisted transfer of Pb(II) across a water/1,2-Dichloroethane (DCE) microinterface was investigated in the presence of 8-Hydroxyquinoline (named also oxine or 8-HQ) in the organic phase. A monocharged complex was formed in the aqueous phase and then transferred in the organic phase. A good relationship was obtained between currents and Pb(II) concentrations in the 10−4 to 5 10−3 M range and 10−5 to 6 10−5 M range using cyclic voltammetry and square wave voltammetry respectively. In presence of other heavy metals such as Cd(II) and Zn(II), only one electrochemical process is observed regardless of the mixture. Moreover, stationary currents increase in direct linear relation with the sum of M(II) concentrations added in water, allowing an overall detection of heavy metals. This result indicates that this method can be very interesting for monitoring all toxic metals in effluents. The limit of detection was found equal to 0.2 ppm for lead. This value allows us to reach levels significant for industrial effluents, in comparison to the limits fixed by the French ministry of ecology for lead, cadmium and zinc to 0.5 ppm, 0.2 ppm and 2.0 ppm respectively. This study highlights the real interest of devices based on a liquid-liquid microinterface

  19. Influence of Ni(II) and Fe(III) complexes of 1,2 dihydroxy 9,10 anthraquinone on the modification in calf thymus DNA upon gamma irradiation

    International Nuclear Information System (INIS)

    Ionizing radiation when allowed to fall upon cells or DNA, the radicals produced modify the base-pair region of the double strands. Radiation-induced double-strand modifications in calf thymus DNA were detected using Ni(II) and Fe(III) complexes of 1,2 dihydroxy 9,10 anthraquinone (DHA). 60Co was used as the source for γ-radiation and ethidium bromide (EB) as the fluorescent dye for detecting double-strand modifications caused in DNA. Results show that the Fe(III)-DHA complex is more efficient in modifying the base-pair region in double-stranded DNA in comparison to DHA or the Ni(II)-DHA complex

  20. Comportamento do ácido fítico na presença de Fe(II) e Fe(III) Behaviour of phytic acid in the presence of iron(II) and iron(III)

    OpenAIRE

    Hanna Raquel Quirrenbach; Francieli Kanumfre; Neiva Deliberali Rosso; Marco Aurélio Carvalho Filho

    2009-01-01

    O ácido fítico, dependendo do valor de pH, apresenta alto potencial quelante, complexando íons metálicos, inibindo, assim, a produção de espécies reativas de oxigênio, responsáveis pela destruição oxidativa em sistemas biológicos. Esse potencial quelante tem fundamentado diversos estudos aplicados à ação antioxidante em produtos alimentícios. O objetivo deste trabalho foi estudar o grau de interação do ácido fítico com os íons metálicos Fe(II) e Fe(III), de importância biológica, em condições...

  1. Metal ion influences distortion of the ligand in the structure of [M{2-MeO(O)CC6H4NHC(S)NP(S)(OiPr)2}2] (M = Zn(II), Cd(II)) complexes: a driving force for intermolecular aggregation.

    Science.gov (United States)

    Safin, Damir A; Babashkina, Maria G; Bolte, Michael; Mitoraj, Mariusz P; Klein, Axel

    2015-08-21

    Reaction of the in situ deprotonated N-thiophosphorylated thiourea 2-MeO(O)CC6H4NHC(S)NHP(S)(OiPr)2 () with MCl2 (M = Zn(II), Cd(II)) in aqueous ethanol leads to complexes of the formula . Both compounds crystallise in the triclinic space group P1[combining macron] with Z = 2 and the metal cations are found in a tetrahedral S2S coordination environment formed by the C-S and P-S sulfur atoms. The crystal structures reveal intramolecular N-HO[double bond, length as m-dash]C hydrogen bonds formed within the 2-MeO(O)CC6H4NH fragments. Both structures are further stabilised by intermolecular ππ stacking interactions, which are more efficient in . Here, a pronounced dimeric intermolecular aggregate is observed which goes along with a pronounced distortion of the chelate [(S)CNP(S)](-) backbone of the ligand upon coordination to Cd(II) as well as a significantly distorted coordination tetrahedron CdS2S. The aggregation is also reflected in the positive electrospray ionisation (ESI) mass spectrum of the Cd(II) complex, which exhibits peaks for the dimeric cations [Cd2L3](+), [Cd2L4 + H](+) and [Cd2L4 + Na](+), while for the Zn(II) analogue only monomeric species were observed. Quantum chemical ETS-NOCV (ADF) calculations confirm the higher stability of dimers in compared with . The ππ stacking interactions are prodominantly due to dispersion contributions, though the electrostatic and orbital interaction components are also important. QTAIM (ADF) type calculations additionally quantify the covalent and non-covalent interactions in the momomers. PMID:26172266

  2. Ligational behavior of clioquinol antifungal drug towards Ag(I), Hg(II), Cr(III) and Fe(III) metal ions: Synthesis, spectroscopic, thermal, morphological and antimicrobial studies

    Science.gov (United States)

    El-Megharbel, Samy M.; Refat, Moamen S.

    2015-04-01

    This article presents a synthesis, characterization, theoretical and biological (anti-bacterial, and anti-fugal) evaluation studies of Ag(I), Hg(II), Cr(III) and Fe(III) complexes of clioquinol (CQ) drug ligand. Structures of the titled complexes cited herein were discussed using elemental analyses and spectral measurements e.g., IR, 1H NMR, and electronic studies. The results confirmed the formation of the clioquinol complexes by three molar ratios (1:1) for Ag(I), (1:2) for Hg(II) and (1:3) for both Cr(III) and Fe(III) metal ions. The clioquinol reacts as a bidentate chelate bound to all respected metal ions through the oxygen and nitrogen of quinoline-8-ol. The metal(II) ions coordinated to clioquinol ligand through deprotonation of sbnd OH terminal group. Infrared and 1H NMR spectral data confirm that coordination is via the oxygen of phenolic group and nitrogen atom of quinoline moiety. The molar conductance measurements of the CQ complexes in DMSO correspond to be non-electrolyte nature. Thus, these complexes may be formulated as [Ag(CQ)(H2O)2] H2O, [Hg(CQ)2]ṡ2H2O, [Cr(CQ)3] and [Fe(CQ)3]H2O. The Coats-Redfern method, the kinetic thermodynamic parameters like activation energies (E∗), entropies (ΔS∗), enthalpies (ΔH∗), and Gibbs free energies (ΔG∗) of the thermal decomposition reactions have been deduced from thermogravimetric curves (TG) with helpful of differential thermo gravimetric (DTG) curves. The narrow size distribution in nano-scale range for the clioquinol complexes have been discussed using X-ray powder diffraction (XRD), scanning electron microscope (SEM), and X-ray energy dispersive spectrometer (EDX) analyzer.

  3. Determination of kinetic and equilibrium parameters of the batch adsorption of Mn(II), Co(II), Ni(II) and Cu(II) from aqueous solution by black carrot (Daucus carota L.) residues

    International Nuclear Information System (INIS)

    In this study, the effect of temperature on the adsorption of Mn(II), Ni(II), Co(II) and Cu(II) from aqueous solution by modified carrot residues (MCR) was investigated. The equilibrium contact times of adsorption process for each heavy metals-MCR systems were determined. Kinetic data obtained for each heavy metal by MCR at different temperatures were applied to the Lagergren equation, and adsorption rate constants (kads) at these temperatures were determined. These rate constants related to the adsorption of heavy metal by MCR were applied to the Arrhenius equation, and activation energies (Ea) were determined. In addition, the isotherms for adsorption of each heavy metal by MCR at different temperatures were also determined. These isothermal data were applied to linear forms of isotherm equations that they fit the Langmuir adsorption isotherm, and the Langmuir constants (qm and b) were calculated. b constants determined at different temperatures were applied to thermodynamic equations, and thermodynamic parameters such as enthalpy (ΔH), free energy (ΔG), and entropy (ΔS) were calculated and these values show that adsorption of heavy metal on MCR was an endothermic process and process of adsorption was favoured at high temperatures

  4. Determination of kinetic and equilibrium parameters of the batch adsorption of Mn(II), Co(II), Ni(II) and Cu(II) from aqueous solution by black carrot (Daucus carota L.) residues

    Energy Technology Data Exchange (ETDEWEB)

    Guezel, Fuat [Department of Chemistry, Faculty of Education, Dicle University, 21280 Diyarbakir (Turkey)], E-mail: fguzel@dicle.edu.tr; Yakut, Hakan; Topal, Giray [Department of Chemistry, Faculty of Education, Dicle University, 21280 Diyarbakir (Turkey)

    2008-05-30

    In this study, the effect of temperature on the adsorption of Mn(II), Ni(II), Co(II) and Cu(II) from aqueous solution by modified carrot residues (MCR) was investigated. The equilibrium contact times of adsorption process for each heavy metals-MCR systems were determined. Kinetic data obtained for each heavy metal by MCR at different temperatures were applied to the Lagergren equation, and adsorption rate constants (k{sub ads}) at these temperatures were determined. These rate constants related to the adsorption of heavy metal by MCR were applied to the Arrhenius equation, and activation energies (E{sub a}) were determined. In addition, the isotherms for adsorption of each heavy metal by MCR at different temperatures were also determined. These isothermal data were applied to linear forms of isotherm equations that they fit the Langmuir adsorption isotherm, and the Langmuir constants (q{sub m} and b) were calculated. b constants determined at different temperatures were applied to thermodynamic equations, and thermodynamic parameters such as enthalpy ({delta}H), free energy ({delta}G), and entropy ({delta}S) were calculated and these values show that adsorption of heavy metal on MCR was an endothermic process and process of adsorption was favoured at high temperatures.

  5. Models for association of metal ions with heterogeneous environmental sorbents. 1. Complexation of Co(II) by leonardite humic acid as a function of pH and NaClO{sub 4} concentration

    Energy Technology Data Exchange (ETDEWEB)

    Westall, J.C.; Jones, J.D. [Oregon State Univ., Corvallis, OR (United States); Turner, G.D. [Oregon State Univ., Corvallis, OR (United States)]|[Pacific Northwest Lab., Richland, WA (United States); Zachara, J.M. [Pacific Northwest Lab., Richland, WA (United States)

    1995-04-01

    A discrete log K spectrum model has been developed to represent the binding of protons and Co(II) to leonardite humic acid (LHA) over a wide variation of solution composition: pH 4.5-9.5, [NaClO{sub 4}] 0.01-0.1 M, T{sub Co} 200 nM-500 $mu@M. The model is internally self-consistent over the range indicated without an explicit electrostatic term. The LHA was represented by four acid sites (HL{sub i} = H{sup +} + L{sub i}{sup -}) with a fixed pK{sub a} spectrum: pK{sub a} = 4, 6, 8, and 10. From the acid-base titration data, total concentrations of these sites and Na{sup +} binding constants (L{sub i}{sup -} + Na{sup +} = NaL{sub i}) were obtained. From Co{sup 21} binding as a function of pH, constants for the reaction L{sub i}{sup -} + Co{sup 21} = CoL{sub i}{sup +} were obtained. Total concentrations of sites and binding constants were similar to those expected from other studies. This discrete log K approach has been selected as the easiest way to parameterize multidimensional data (i.e., data with variations in many solution chemistry parameters) for subsequent application in transport models. 37 refs., 3 figs., 6 tabs.

  6. Reversible thermally induced phase transition in ordered domains of Co(II)-5,10,15,20-tetrakis-(3,5-di-tert-butylphenyl)-porphyrin on Cu(111)

    Science.gov (United States)

    Stark, Michael; Ditze, Stefanie; Thomann, Michael; Lungerich, Dominik; Jux, Norbert; Steinrück, Hans-Peter; Marbach, Hubertus

    2016-08-01

    We investigated the adsorption behavior of Co(II)-5,10,15,20-tetrakis-(3,5-di-tert-butylphenyl)-porphyrin (CoTTBPP) on Cu(111) by scanning tunneling microscopy (STM). At room temperature (RT), the coverage dependent adsorption behavior follows an expected scheme: at low coverage step decoration is found, which evolves into supramolecular domains with a hexagonal order at higher coverage. Interestingly, upon cooling the sample to 180 K the occurrence of a clearly distinguishable coexisting herringbone phase is observed. Upon heating to RT again, the herringbone phase vanishes. Thus a temperature dependent, fully reversible phase transition was observed. High resolution STM micrographs allow for the determination of the intramolecular conformations which are different for the two supramolecular arrangements. In addition, we studied the bias voltage dependent appearance of the molecule in STM and assigned a dominant contribution of the central Co at negative bias voltages close to the Fermi edge to the occupied dz2 orbital. Interestingly, the herringbone phase, which dominates at 180 K, exhibits a significantly higher molecular density than the monomodal hexagonal arrangement at RT, which is in line with the "normal" behavior of freezing substances.

  7. Synthesis, spectroscopic characterization, DNA interaction and biological activities of Mn(II), Co(II), Ni(II) and Cu(II) complexes with [(1H-1,2,4-triazole-3-ylimino)methyl]naphthalene-2-ol

    Science.gov (United States)

    Gaber, Mohamed; El-Wakiel, Nadia A.; El-Ghamry, Hoda; Fathalla, Shaimaa K.

    2014-11-01

    Manganese(II), cobalt(II), nickel(II) and copper(II) complexes of [(1H-1,2,4-triazole-3-ylimino)methyl]naphthalene-2-ol have been synthesized. The structure of complexes have been characterized by elemental analysis, molar conductance, magnetic moment measurements and spectral (IR, 1H NMR, EI-mass, UV-Vis and ESR), and thermal studies. The results showed that the chloro and nitrato Cu(II) complexes have octahedral geometry while Ni(II), Co(II) and Mn(II) complexes in addition to acetato Cu(II) complex have tetrahedral geometry. The possible structures of the metal complexes have been computed using the molecular mechanic calculations using the hyper chem. 8.03 molecular modeling program to confirm the proposed structures. The kinetic and thermodynamic parameters of the thermal decomposition steps were calculated from the TG curves. The binding modes of the complexes with DNA have been investigated by UV-Vis absorption titration. The results showed that the mode of binding of the complexes to DNA is intercalative or non-intercalative binding modes. Schiff base and its metal complexes have been screened for their in vitro antimicrobial activities against Gram positive bacteria (Staphylococcus aureus), Gram negative bacteria (Escherichia coli and Pesudomonas aeruginosa), fungi (Asperigllus flavus and Mucer) and yeast (Candida albicans and Malassezia furfur).

  8. Sulphate radical generation through interaction of peroxymonosulphate with Co(II) for in-line sample preparation aiming at spectrophotometric flow-based determination of phosphate and phosphite in fertilizers.

    Science.gov (United States)

    Crispino, Carla C; Kamogawa, Marcos Y; Ferreira, José R; Zagatto, Elias A G

    2016-09-01

    An advanced oxidative process relying on the interaction of peroxymonosulphate and cobalt(II) was implemented for generating the sulphate radicals in flow analysis, in order to accomplish in-line sample preparation thus improving the spectrophotometric determination of phosphate and phosphite in liquid foliar fertilizers. To this end, a flow-batch system with a heated chamber was designed. The sample was handled twice, with and without the step of phosphite oxidation to phosphate, and the formed orthophosphate was quantified after interaction with the vanadate-molybdate reagent. Phosphite was determined as the difference in analytical signals corresponding to sample handling with and without the oxidation step. Influence of Co(II) on the peroxymonosulphate activation, reagent concentrations and added volumes, acidity, temperature and heating time were investigated like aiming at to improve analytical recovery and measurement repeatability, as well as the and system ruggedness. The 6.6-20.0mgL(-1) P2O5 standards were in-line prepared from a single stock solution. Detection limits were estimated as 0.8 and 0.1mgL(-1) for P2O5 and P-PO4. Twenty-four samples are were run per hour, and results are were in agreement with those obtained by the official procedure. PMID:27343605

  9. Synthesis, characterization, thermal study and biological evaluation of Cu(II), Co(II), Ni(II) and Zn(II) complexes of Schiff base ligand containing thiazole moiety

    Science.gov (United States)

    Nagesh, G. Y.; Mahendra Raj, K.; Mruthyunjayaswamy, B. H. M.

    2015-01-01

    The novel Schiff base ligand 2-(4-(dimethylamino)benzylidene)-N-(4-phenylthiazol-2-yl)hydrazinecarboxamide (L) obtained by the condensation of N-(4-phenylthiazol-2-yl)hydrazinecarboxamide with 4-dimethylaminobenzaldehyde and its newly synthesized Cu(II), Co(II), Ni(II) and Zn(II) complexes have been characterized by microanalysis, magnetic susceptibility, molar conductance, thermal analysis, FT-IR, 1H NMR, ESI mass, UV-Visible, ESR spectroscopy and powder X-ray diffraction data. The newly synthesized ligand behaves as a bidentate ON donor. The IR results confirmed the bidentate binding of the ligand involving oxygen atom of amide carbonyl and azomethine nitrogen. 1H NMR spectral data of the ligand (L) and its Zn(II) complex agreed well with the proposed structures. In order to evaluate the effect of antimicrobial activity of metal ions upon chelation, the newly synthesized ligand and its metal complexes were screened for their antibacterial and antifungal activities by minimum inhibitory concentration (MIC) method. The DNA cleavage activities were studied using plasmid DNA pBR322 as a target molecule by agarose gel electrophoresis method. The brine shrimp bioassay was also carried out to study the in vitro cytotoxicity properties of all the compounds against Artemia salina. Furthermore, the antioxidant activity of the ligand (L) and its metal complexes were determined in vitro by reduction of 1,1-diphenyl-2-picryl hydrazyl (DPPH), the ligand exhibited potent in vitro - antioxidant activity than its metal complexes.

  10. Synthesis, characterization, and antioxidant/cytotoxic activity of new chromone Schiff base nano-complexes of Zn(II), Cu(II), Ni(II) and Co(II)

    Science.gov (United States)

    Saif, M.; El-Shafiy, Hoda F.; Mashaly, Mahmoud M.; Eid, Mohamed F.; Nabeel, A. I.; Fouad, R.

    2016-08-01

    A chromone Schiff base complexes of Zn(II) (1), Cu(II) (2), Ni(II) (3) and Co(II) (4) were successfully prepared in nano domain with crystalline or amorphous structures. The spectroscopic data revealed that the Schiff base ligand behaves as a monoanionic tridentate ligand. The metal complexes exhibited octahedral geometry. Transmission electron microscope (TEM) analysis showed that Cu(II) complex have aggregated nanospheres morphology. The obtained nano-complexes were tested as antioxidant and antitumor agents. The H2L and its Cu(II) complex (2) were found to be more potent antioxidant (IC50(H2L) = 0.93 μM; IC50(Cu(II) complex) = 1.1 μM than standard ascorbic acid (IC50 = 2.1 μM) as evaluated by DPPH• method. The H2L and its complexes (1-4) were tested for their in vitro cytotoxicity against Ehrlich Ascites Carcinoma cell line (EAC). The Cu(II) nano-complex (2) effectively inhibited EAC growth with IC50 value of 47 μM in comparison with its parent compound and other prepared complexes. The high antioxidant activity and antitumor activity of Cu(II) nano-complex (2) were attributed to their chemical structure, Cu(II) reducing capacity, and nanosize property. The toxicity test on mice showed that Zn(II) (1) and Cu(II) (2) nano-complex have lower toxicity than the standard cis-platin.

  11. Solution behaviour of myo-inositol hexakisphosphate in the presence of multivalent cations. Prediction of a neutral pentamagnesium species under cytosolic/nuclear conditions.

    Science.gov (United States)

    Torres, Julia; Domínguez, Sixto; Cerdá, M Fernanda; Obal, Gonzalo; Mederos, Alfredo; Irvine, Robin F; Díaz, Alvaro; Kremer, Carlos

    2005-03-01

    myo-Inositol hexakisphosphate (InsP6) is an ubiquitous and abundant molecule in the cytosol and nucleus of eukaryotic cells whose biological functions are incompletely known. A major hurdle for studying the biology of InsP6 has been a deficiency of a full understanding of the chemistry of its interaction with divalent and trivalent cations. This deficiency has limited our appreciation of how it remains in solution within cells, and the likely degree to which it might interact in vivo with physiologically important cations such as Ca2+ and Fe3+. We report here the initial part of the description of the InsP6-multivalent cation chemistry, including its solution equilibria studied by high resolution potentiometry and (for the Fe(III)/Fe(II) couple) cyclic voltammetry. InsP6 forms anionic complexes of high affinities and 1:1 stoichiometry with Mg(II), Ca(II), Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II). Of particular importance is the observation that, in the exceptional case of Mg(II), InsP6 forms the species [Mg5(H2L)] (L representing fully deprotonated InsP6); this soluble neutral species is predicted to be the predominant form of InsP6 under nuclear or cytosolic conditions in animal cells. Contrary to previous suggestions, InsP6 is predicted not to interact with cytosolic calcium even when calcium is increased during signalling events. In vitro, InsP6 also forms high affinity 1:1 complexes with Fe(III) and Al(III). However, our data predict that in the biological context of excess free Mg(II), neither Fe(III) nor Fe(II) are complexed by InsP6. PMID:15708805

  12. Microencapsulated Aliivibrio fischeri in Alginate Microspheres for Monitoring Heavy Metal Toxicity in Environmental Waters

    Directory of Open Access Journals (Sweden)

    Dedi Futra

    2014-12-01

    Full Text Available In this article a luminescence fiber optic biosensor for the microdetection of heavy metal toxicity in waters based on the marine bacterium Aliivibrio fischeri (A. fischeri encapsulated in alginate microspheres is described. Cu(II, Cd(II, Pb(II, Zn(II, Cr(VI, Co(II, Ni(II, Ag(I and Fe(II were selected as sample toxic heavy metal ions for evaluation of the performance of this toxicity microbiosensor. The loss of bioluminescence response from immobilized A. fischeri bacterial cells corresponds to changes in the toxicity levels. The inhibition of the luminescent biosensor response collected at excitation and emission wavelengths of 287 ± 2 nm and 487 ± 2 nm, respectively, was found to be reproducible and repeatable within the relative standard deviation (RSD range of 2.4–5.7% (n = 8. The toxicity biosensor based on alginate micropsheres exhibited a lower limit of detection (LOD for Cu(II (6.40 μg/L, Cd(II (1.56 μg/L, Pb(II (47 μg/L, Ag(I (18 μg/L than Zn(II (320 μg/L, Cr(VI (1,000 μg/L, Co(II (1700 μg/L, Ni(II (2800 μg/L, and Fe(III (3100 μg/L. Such LOD values are lower when compared with other previous reported whole cell toxicity biosensors using agar gel, agarose gel and cellulose membrane biomatrices used for the immobilization of bacterial cells. The A. fischeri bacteria microencapsulated in alginate biopolymer could maintain their metabolic activity for a prolonged period of up to six weeks without any noticeable changes in the bioluminescence response. The bioluminescent biosensor could also be used for the determination of antagonistic toxicity levels for toxicant mixtures. A comparison of the results obtained by atomic absorption spectroscopy (AAS and using the proposed luminescent A. fischeri-based biosensor suggests that the optical toxicity biosensor can be used for quantitative microdetermination of heavy metal toxicity in environmental water samples.

  13. Five new Zn(II) and Cd(II) coordination polymers constructed by 3,5-bis-oxyacetate-benzoic acid: Syntheses, crystal structures, network topologies and luminescent properties

    International Nuclear Information System (INIS)

    Five Zn(II) and Cd(II) coordination polymers, [Zn2(BOABA)(bpp)(OH)]·0.5H2O (1), [Cd3(BOABA)2(bpp)2(H2O)6]·2H2O (2), [Cd3(BOABA)2(2,2′-bipy)3(H2O)4]·5.5H2O (3), [CdNa(BOABA)(H2O)]2·H2O (4) and [Cd2(BOABA)(bimb)Cl(H2O)2]·H2O (5) (H3BOABA=3,5-bis-oxyacetate-benzoic acid, bpp=1,3-bi(4-pyridyl)propane, 2,2′-bipy=2,2′-bipyridine, bimb=1,4-bis(imidazol-1′-yl)butane), have been solvothermally synthesized and characterized by single-crystal X-ray diffraction, elemental analyses, IR spectra and TG analyses. 1 is an uninodal 4-connected 2D square grid network based on binuclear zinc clusters. 2 is 2D wavelike layer structure and further linked by hydrogen bonds into the final 3D (5,6,6)-connected topology network. 3 is 3-connected 2D topology network and the 2,2′-bipy ligands decorate in two different types. 4 is a (4,8)-connected 2D topology network with heterocaryotic {Cd2Na2} clusters and BOABA3– ligands. 5 can be rationalized as a (3,10)-connected 3D topology network with tetranuclear {Cd4Cl2} clusters and BOABA3– ligands. Meanwhile, photoluminescence studies revealed that these five coordination polymers display strong fluorescent emission bands in the solid state at room temperature. - Graphical abstract: Five new d10 metal(II) coordination polymers based on H3BOABA ligand were obtained and characterized. They display different topological structures and luminescent properties. Highlights: ► Five d10 metal(II) polymers based on 3,5-bis-oxyacetate-benzoic acid were obtained. ► The polymers were structurally characterized by single-crystal X-ray diffraction. ► Polymers 1–5 display different topological structures. ► They show strong fluorescent emission bands in the solid state.

  14. Synthesis and characterization of binary and ternary complexes of Co(II), Ni(II), Cu(II) and Zn(II) ions based on 4-aminotoluene-3-sulfonic acid

    Science.gov (United States)

    Faheim, Abeer A.; Abdou, Safaa N.; Abd El-Wahab, Zeinab H.

    2013-03-01

    Salicylidene (4-aminotoluene-3-sulfonic acid) Schiff base ligand H2L, and its binary and ternary Co(II), Ni(II), Cu(II) and Zn(II) complexes using 8-hydroxyquinoline (8-HOqu) and 2-aminopyridine (2-Ampy) as secondary ligands have been synthesised and characterized via elemental analysis, spectral data (IR, 1H NMR, mass and solid reflectance), molar conductance, magnetic moment, TG-DSC measurements and XRPD analysis. Correlation of all spectroscopic data suggest that H2L ligand acts as monoanionic terdentate ligand with ONO sites coordinating to the metal ions via deprotonated phenolic-O, azomethine-N and sulfonate-O while 2-Ampy behaves as a neutral monodentate ligand via amino group-N and 8-HOqu behaves as a monoanionic bidentate ligand through the ring-N and deprotonated phenolic-O. The thermal behavior of these complexes shows that the coordinated water molecules were eliminated from the complexes at relatively higher temperatures than the hydrated water and there are two routes in removal of coordinated water molecules. All complexes have mononuclear structure and the tetrahedral, square planar or an octahedral geometry have been proposed. The ligand and its complexes have been screened for their antimicrobial activity against Staphylococcus aureus, Bacillus subtilis, Escherichia coli, Salmonella typhimurium, Candida albicans and Aspergillus fumigatus. Among the synthesised compounds, the binary and ternary Ni(II) complexes, (2, 8 and 10) and ternary Zn(II) complex, (12) were found to be very effective against Candida albicans and Bacillus subtilis than all other complexes with MICs of 2 and 8 μg/mL, respectively.

  15. Importance of reduced sulfur for the equilibrium chemistry and kinetics of Fe(II), Co(II) and Ni(II) supplemented to semi-continuous stirred tank biogas reactors fed with stillage

    International Nuclear Information System (INIS)

    Highlights: • Thermodynamics and kinetics of Fe, Co and Ni added to biogas reactors were studied. • Formation of Fe-sulfide and Fe-thiol aqueous complexes controlled the Fe solubility. • Cobalt solubility was controlled by processes independent of Co-sulfide interaction. • Iron added to the biogas reactors effected the Ni speciation and solubility. - Abstract: The objective of the present study was to assess major chemical reactions and chemical forms contributing to solubility and speciation of Fe(II), Co(II), and Ni(II) during anaerobic digestion of sulfur (S)-rich stillage in semi-continuous stirred tank biogas reactors (SCSTR). These metals are essential supplements for efficient and stable performance of stillage-fed SCSTR. In particular, the influence of reduced inorganic and organic S species on kinetics and thermodynamics of the metals and their partitioning between aqueous and solid phases were investigated. Solid phase S speciation was determined by use of S K-edge X-ray absorption near-edge spectroscopy. Results demonstrated that the solubility and speciation of supplemented Fe were controlled by precipitation of FeS(s) and formation of the aqueous complexes of Fe-sulfide and Fe-thiol. The relatively high solubility of Co (∼20% of total Co content) was attributed to the formation of compounds other than Co-sulfide and Co-thiol, presumably of microbial origin. Nickel had lower solubility than Co and its speciation was regulated by interactions with FeS(s) (e.g. co-precipitation, adsorption, and ion substitution) in addition to precipitation/dissolution of discrete NiS(s) phase and formation of aqueous Ni-sulfide complexes

  16. Theoretical and experimental studies of two Co(II) and Ni(II) coordination complex with N,O donor 2-chloro-6-{[(4-hydroxy-3-methoxyphenyl)methylidene]amino}-4 nitrophenol ligand

    Science.gov (United States)

    Kusmariya, Brajendra S.; Tiwari, Sandeep; Tiwari, Anjali; Mishra, A. P.; Naikoo, Gowhar Ahmad; Pandit, Umar J.

    2016-07-01

    Here we report two mononuclear Co(II) and Ni(II) complexes of general formula [M(L)2(H2O)].2H2O; {M = CoII & NiII} derived from bidentate 2-chloro-6-{[(4-hydroxy-3-methoxyphenyl)methylidene]amino}-4 nitrophenol ligand (HL). These compounds were characterized by elemental analysis, spectral (FT-IR, electronic and 1H-NMR), molar conductance, thermal, PXRD, SEM and electrochemical studies. Distorted octahedral geometry was proposed around the metal center with ligand (HL). The PXRD and SEM analysis shows the crystalline nature of complexes. The broadening of diffraction peaks were explained in terms of domain size and the lattice strain according to Scherrer and Williamson-Hall method. TG of the synthesized complexes illustrates their general decomposition pattern and thermal stability. The kinetic and thermodynamic parameters viz. activation energy (E∗), pre-exponential factor (Z), entropy of activation (ΔS∗), enthalpy of activation (ΔH∗) and free energy of activation (ΔG∗) of degradation process were also evaluated using Coats-Redfern (C-R), Piloyan-Novikova (P-N) and Horowitz-Metzger (H-M) methods for both complexes assuming first order degradation. The optical band gap values of complexes were found to be in good agreement with calculated HOMO-LUMO energy gap (ΔE) and lie in semiconducting range. The cyclic voltammetric studies of synthesized compounds were carried out in order to examine their electrochemical behavior. In addition theoretical calculations by means of DFT at B3LYP level were incorporated to support the experimental findings.

  17. Some new nano-sized Cr(III), Fe(II), Co(II), and Ni(II) complexes incorporating 2-((E)-(pyridine-2-ylimino)methyl)napthalen-1-ol ligand: Structural characterization, electrochemical, antioxidant, antimicrobial, antiviral assessment and DNA interaction.

    Science.gov (United States)

    Abdel-Rahman, Laila H; Abu-Dief, Ahmed M; Newair, Emad F; Hamdan, Samar Kamel

    2016-07-01

    To estimate the biological preference of synthetic small drugs towards DNA target, new metal based chemotherapeutic agents of nano-sized Cr(III), Fe(II), Co(II) and Ni(II) Schiff base complexes having N,N,O donor system were synthesized and thoroughly characterized by physic-chemical techniques. The redox behavior of the Cr(III), Fe(II) and Co(II) complex was investigated by electrochemical method using cyclic voltammetry. IR results proven that the tridentate binding of Schiff base ligand with metal center during complexation reflects the proposed structure. Magnetic and spectroscopic data give support to octahedral geometry for Cr(III) and Fe(II) complexes and tetrahedral geometry for Ni(II) and Co(II) complexes. The activation thermodynamic parameters, such as, E(⁎), ΔH(⁎), ΔS(⁎) and ΔG(⁎) are calculated using Coats-Redfern method by analyzing the TGA data. The particle size of the investigated metal complexes was estimated by TEM. In addition to, the interaction of the nanosized complexes with CT-DNA was estimated by electronic absorption, viscosity and gel electrophoresis. These techniques revealed that the complexes could bind to CT-DNA through intercalation mode. Moreover, the in vitro cytotoxic and antiviral activities of the nanosized complexes were checked against Herpes Simplex virus and Tobacco Mosaic viruses. Moreover, investigation of antioxidant activities of the new nanosized compounds was done by ABTS assay. Among the compounds tested, Fe(II) complex showed the strongest potent radical scavenging activity with percent of 58.60%. Furthermore, the antimicrobial bustle of the prepared compounds was screened against different types of bacteria and fungi and the results show that all metal complexes have superior activity than its free ligand. PMID:27088506

  18. Synthesis, spectral studies and antibacterial activity of Cu(II), Co(II) and Ni(II) complexes of 1-(2-hydroxyphenyl)-3-phenyl-2-propen-1-one, N2-[(3,5-dimethyl-1H-pyrazol-1-yl)methyl]hydrazone

    OpenAIRE

    PAULMONY THARMARAJ; DEIVASIGAMANI KODIMUNTHIRI; CLARENCE D. SHEELA; CHAPPANI S. SHANMUGA PRIYA

    2009-01-01

    A new series of Cu(II), Co(II) and Ni(II) complexes with the 1-(2-hydroxyphenyl)-3-phenyl-2-propen-1-one, N2-[(3,5-dimethyl-1H-pyrazol-1-yl)methyl]hydrazone ligand, C21H22N4O (LH), were synthesized by the reaction of 1-(2-hydroxyphenyl)-3-phenyl-2-propen-1-one, hydrazone with (3,5-dimethyl-1H-pyrazol-1-yl)methanol and characterized. The nature of the bonding and geometry of the complexes were deduced from elemental analysis, IR, electronic and 1H-NMR spectroscopy, and magnetic susceptibility ...

  19. Liquid-liquid extraction (LLE) of Fe(III) and Ti(IV) by bis-(2-ethyl-hexyl) phosphoric acid (D2EHPA) in sulfuric acid medium; Extracao liquido-liquido de ferro (III) e titanio (IV) pelo acido bis-(2-etil-hexil) fosforico (D2EHPA) em meio de acido sulfurico

    Energy Technology Data Exchange (ETDEWEB)

    Silva, Glauco Correa da; Cunha, Jose Waldemar Silva Dias da [Instituto de Engenharia Nuclear (IEN), Rio de Janeiro, RJ (Brazil). Dept. de Quimica e Materiais Nucleares; Dweck, Jo [Universidade Federal do Rio de Janeiro (UFRJ), RJ (Brazil). Escola de Quimica. Dept. de Processos Inorganicos; Afonso, Julio Carlos [Universidade Federal do Rio de Janeiro (UFRJ), RJ (Brazil). Inst. de Quimica. Dept. de Quimica Analitica]. E-mail: julio@iq.ufrj.br

    2008-07-01

    This work presents a study on the separation of Fe(III) and Ti(IV) from sulfuric acid leaching solutions of ilmenite (FeTiO{sub 3}) using liquid-liquid extraction with D2EHPA in n-dodecane as extracting agent. The distribution coefficients (K{sub D}) of the elements related to free acidity and concentration of Fe(III) and Ti(IV) were determined. Free acidity was changed from 3x10{sup -2} to 11.88 mol L{sup -1} and D2EHPA concentration was fixed at 1.5 mol L{sup 1}. Recovery of final products as well as recycling of wastes generated in the process were also investigated. The LLE process as a feasible alternative to obtain high-purity TiO{sub 2}. (author)

  20. Comparative ligational, optical band gap and biological studies on Cr(III) and Fe(III) complexes of hydrazones derived from 2-hydrazinyl-2-oxo-N-phenylacetamide with both vanillin and O-vanillin

    Science.gov (United States)

    Yousef, T. A.; Abu El-Reash, G. M.; Attia, M. I.; El-Tabai, M. N.

    2015-09-01

    The Cr(III) and Fe(III) complexes of hydrazones derived from the condensation of 2-hydrazinyl-2-oxo-N-phenylacetamide with both vanillin and o-vanillin synthesized and characterized by different conventional physicochemical techniques. The kinetic and thermodynamic parameters for the different decomposition steps were calculated using Coats-Redfern and Horowitz-Metzger equations. The bond lengths, bond angles, HOMO, LUMO, dipole moment and binding energy calculated by DFT calculations. The optical band gap (Eg) values equal 3.28, 3.03, 3.58 and 3.57 eV for [Cr(HL1)Cl2(H2O)2](0.75H2O), [Cr(HL2)Cl2(H2O)](H2O), [Fe(HL1)Cl2(H2O)2](0.5H2O) and [Fe(HL2)2Cl(H2O)](3H2O) complexes, respectively. The antibacterial activities tested against Bacillus subtilis and Escherichia coli bacteria.

  1. Formation of a metalloporphyrin-based nanoreactor by postsynthetic metal-ion exchange of a polyhedral-cage containing a metal-metalloporphyrin framework.

    Science.gov (United States)

    Wang, Xi-Sen; Chrzanowski, Matthew; Wojtas, Lukasz; Chen, Yu-Sheng; Ma, Shengqian

    2013-03-01

    A change for the better: Exchange of Cd(II) in the catalytically inactive framework MMPF-5 (see scheme) with Co(II) afforded a metalloporphyrin-based nanoreactor, MMPF-5(Co). This framework, consisting of small cubicuboctahedral cages, demonstrated interesting performances in the catalytic epoxidation of trans-stilbene with tBuOOH. PMID:23386517

  2. Cobalt(II), nickel(II), copper(II), zinc(II), cadmium(II) and dioxouranium(II) complexes of thiophene-2-aldehyde-4-phenyl-thiosemicarbazone

    International Nuclear Information System (INIS)

    The present paper describes the synthesis and characterisation of thiophene-2-aldehyde-4-phenylthiosemicarbazone (TAPTSC) and its metal complexes with Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and UO(II). (author). 30 refs., 1 table

  3. Farklı İran bal arısı (A. mellifera meda) populasyonlarında COI-COII mitokondriyel dna lokusları arasında yer alan bölgedeki genetik varyasyonun PCR- RFLP yöntemi ile belirlenmesi

    OpenAIRE

    FAKHRI, Bahman

    2008-01-01

    Bu çalışmada, PCR-RFLP ve DNA dizi analizi yöntemlerinden yararlanılarak farklı İran bal arısı (Apis mellifera meda ) populasyonları arasındaki genetik varyasyonun mtDNA COI-COII arasındaki bölge bakımından DraI ve HinfI enzimleri kullanılarak belirlenmesi amaçlanmıştır. İran’ın 15 farklı yöresini temsil eden toplam 92 işçi arı örneği materyal olarak kullanılmıştır.Çalışılan örneklerin tamamında mitokondriyel DNA COI-COII arasındaki bölgenin DraI enzim kesimi sonucunda genetik varyasyon tespi...

  4. Metal based drugs: design, synthesis and in-vitro antimicrobial screening of Co(II), Ni(II), Cu(II) and Zn(II) complexes with some new carboxamide derived compounds: crystal structures of N-[ethyl(propan-2-yl)carbamothioyl]thiophene-2-carboxamide and its copper(II) complex.

    Science.gov (United States)

    Sumrra, Sajjad H; Hanif, Muhammad; Chohan, Zahid H; Akram, Muhammad Safwan; Akhtar, Javeed; Al-Shehri, Saad M

    2016-08-01

    A new series of compounds derived from thiophene-2-carboxamide were synthesized and characterized by IR, (1)H-NMR and (13)C-NMR, mass spectrometry and elemental analysis. These compounds were further used to prepare their Co(II), Ni(II), Cu(II) and Zn(II) metal complexes. All metal(II) complexes were air and moisture stable. Physical, spectral and analytical data have shown the Ni(II) and Cu(II) complexes to exhibit distorted square-planar and Co(II) and Zn(II) complexes tetrahedral geometries. The ligand (L(1)) and its Cu(II) complex were characterized by the single-crystal X-ray diffraction method. All the ligands and their metal(II) complexes were screened for their in-vitro antimicrobial activity. The antibacterial and antifungal bioactivity data showed that the metal(II) complexes were found to be more potent than the parent ligands against one or more bacterial and fungal strains. PMID:26067080

  5. Design, spectral characterization, thermal, DFT studies and anticancer cell line activities of Co(II), Ni(II) and Cu(II) complexes of Schiff bases derived from 4-amino-5-(pyridin-4-yl)-4H-1,2,4-triazole-3-thiol

    Science.gov (United States)

    Tyagi, Prateek; Chandra, Sulekh; Saraswat, B. S.; Yadav, Deepak

    2015-06-01

    A series of two biologically active Schiff base ligands L1, L2 have been synthesized in equimolar reaction of 4-amino-5-(pyridin-4-yl)-4H-1,2,4-triazole-3-thiol with thiophene-2-carbaldehyde and furan-2-carbaldehyde. The synthesized Schiff bases were used for complexation with different metal ions like Co(II), Ni(II) and Cu(II) by using a molar ratio of ligand: metal as 1:1 and 2:1. The characterization of Schiff bases and metal complexes was done by 1H NMR, UV-Vis, TGA, IR, mass spectrometry and molar conductivity studies. The in DFT studies the geometries of Schiff bases and metal complexes were fully optimized with respect to the energy using the 6-31+g(d,p) basis set. On the basis of the spectral studies an octahedral geometry has been assigned for Co(II), Ni(II) and Cu(II) complexes. The effect of these complexes on proliferation of human breast cancer cell line (MCF-7) and human hepatocellular liver carcinoma cell line (Hep-G2) were studied and compared with those of free ligand. The anticancer cell line results reveal that all metal complexes show moderate to significant % cytotoxicity on cell line HepG2 and MCF-7.

  6. Determination of Cd(II, Zn(II and Ag(Iin different matrixes after solid phase extraction on sodium dodecyl sulfate(SDS-coated alumina as their 2,3 Di Hydro 2,3 paratolylQinazoline (1 H- 4 one (DPTQO by Flame atomic absorption spectrometric

    Directory of Open Access Journals (Sweden)

    Farveh Raoufi

    2016-03-01

    Full Text Available A sensitive and selective solid phase extraction procedure for the determination of traces of Cd(II, Zn(II and Ag(I ions has been developed. An alumina-sodium dodecyl sulfate (SDS coated on with 2,3 Di Hydro 2,3 paratolylQinazoline (1 H- 4 one (DPTQO. The influences of the analytical parameters including pH and sample volume were investigated.Common coexisting ions did not interfere on the separation and determination of analytes under study. The adsorbed analytes were desorbed by using 6mL of 4 mol L−1 nitric acid. The responses are linear 0.02–0.85 µg mL-1 for Cd2+ ion0.01–0.90 µg mL-1 for Zn2+and0.02–0.92µg mL-1for Ag+ detection limit for Cd(II, Zn(II and Ag(I ions were found to be 1.4, 1.3 and1.12(ng mL-1, respectively.It was found that the recovery for Cd2+, Zn2+and Ag+ ions were 97.7, 98.2 and 98.0 with RSD of 1.9, 1.8 and 1.7. It was also observed that recovery for repeated recovery on the same solid phase not varies more than 3%. The presented procedurewas successfully applied for determination of analytes in radiology wastewater, amalgam, natural water and blood samples.

  7. Ligand-controlled assembly of Cd(II) coordination polymers based on mixed ligands of naphthalene-dicarboxylate and dipyrido[3,2-d:2',3'-f]quinoxaline: From 0D+1D cocrystal, 2D rectangular network (4,4), to 3D PtS-type architecture

    International Nuclear Information System (INIS)

    Three novel Cd(II) coordination polymers, namely, [Cd(Dpq)(1,8-NDC)(H2O)2][Cd(Dpq)(1,8-NDC)].2H2O (1), [Cd(Dpq)(1,4-NDC)(H2O)] (2), and [Cd(Dpq)(2,6-NDC)] (3) have been obtained from hydrothermal reactions of cadmium(II) nitrate with the mixed ligands dipyrido [3,2-d:2',3'-f]quinoxaline (Dpq) and three structurally related naphthalene-dicarboxylate ligands [1,8-naphthalene-dicarboxylic acid (1,8-H2NDC), 1,4-naphthalene-dicarboxylic acid (1,4-H2NDC), and 2,6-naphthalene-dicarboxylic acid (2,6-H2NDC)]. Single-crystal X-ray diffraction analysis reveals that the three polymers exhibit novel structures due to different naphthalene-dicarboxylic acid. Compound 1 is a novel cocrystal of left- and right-handed helical chains and binuclear complexes and ultimately packed into a 3D supramolecular structure through hydrogen bonds and π-π stacking interactions. Compound 2 shows a 2D rectangular network (4,4) bridged by 1,4-NDC with two kinds of coordination modes and ultimately packed into a 3D supramolecular structure through inter-layer π-π stacking interactions. Compound 3 is a new 3D coordination polymer with distorted PtS-type network. In addition, the title compounds exhibit blue/green emission in solid state at room temperature. - Graphical abstract: Three novel Cd(II) compounds have been synthesized under hydrothermal conditions exhibiting a systematic variation of architecture by the employment of three structurally related naphthalene-dicarboxylate ligands

  8. Decontamination of a radioactive process waste water by adsorbing colloid flotation

    International Nuclear Information System (INIS)

    As a part of a research programme on the treatment of a radioactive process waste water by foam separation techniques, adsorbing colloid flotation was tested to remove 144Ce, 60Co, 65Zn and 89Sr from the waste water. Potassium oleate was used as the collector, and Fe(III) hydroxide, Al(III) hydroxide or Co(II) hydroxide as the coprecipitant. Under the optimal conditions; removals exceeding 99% could be achieved for 65Zn with any of the tested coprecipitants, for 144Ce with Fe(III) and Co(II) hydroxides and for 60Co with only Co(II) hydroxide. For 89Sr removals > 90% could be achieved with only Fe(III) hydroxide. The adsorbing colloid flotation process was compared with both chemical precipitation and ion exchange, and advantages of adsorbing colloid flotation were enumerated. (author)

  9. Decontamination of radioactive process waste water by adsorbing colloid flotation

    International Nuclear Information System (INIS)

    Adsorbing colloid flotation was tested to remove 144Ce, 60Co, 65Zn, and 89Sr from radioactive process waste water. Potassium oleate was used as the collector, and Fe(III) hydroxide, Al(III) hydroxide or Co(II) hydroxide as the coprecipitant. Under optimal conditions, removals exceeding 99% could be achieved for 65Zn with any of the tested coprecipitants, for 144Ce with Fe(III) and Co(II) hydroxides and for 60Co with only Co(II) hydroxide. For 89Sr removals of 90% could be achieved only with Fe(III) hydroxide. The adsorbing colloid flotation process was compared with both chemical precipitation and ion exchange. Advantages of adsorbing colloid flotation are discussed. (author)

  10. Bioalteration of synthetic Fe(III)-, Fe(II)-bearing basaltic glasses and Fe-free glass in the presence of the heterotrophic bacteria strain Pseudomonas aeruginosa: Impact of siderophores

    Science.gov (United States)

    Perez, Anne; Rossano, Stéphanie; Trcera, Nicolas; Huguenot, David; Fourdrin, Chloé; Verney-Carron, Aurélie; van Hullebusch, Eric D.; Guyot, François

    2016-09-01

    This study aims to evaluate the role of micro-organisms and their siderophores in the first steps of the alteration processes of basaltic glasses in aqueous media. In this regard, three different types of glasses - with or without iron, in the reduced Fe(II) or oxidized Fe(III) states - were prepared on the basis of a simplified basaltic glass composition. Control and Pseudomonas aeruginosa inoculated experiments were performed in a buffered (pH 6.5) nutrient depleted medium to stimulate the production of the pyoverdine siderophore. Results show that the presence of P. aeruginosa has an effect on the dissolution kinetics of all glasses as most of the calculated elemental release rates are increased compared to sterile conditions. Reciprocally, the composition of the glass in contact with P. aeruginosa has an impact on the bacterial growth and siderophore production. As an essential nutrient for this microbial strain, Fe notably appears to play a central role during biotic experiments. Its presence in the glass stimulates the bacterial growth and minimizes the synthesis of pyoverdine. Moreover the initial Fe2+/Fe3+ ratio in the glasses modulates this synthesis, as pyoverdine is not detected at all in the system in contact with Fe(III)-bearing glass. Finally, the dissolution rates appear to be correlated to siderophore concentrations as they increase with respect to sterile experiments in the order Fe(III)-bearing glass bacteria, as initial dissolution rates are increased by a factor of 3. This study attests to the essential role of siderophores in the P. aeruginosa-promoted dissolution processes of basaltic glasses as well as to the complex relationships between the nutritional potential of the glass and its dissolution rates.

  11. Selective Iron(III ion uptake using CuO-TiO2 nanostructure by inductively coupled plasma-optical emission spectrometry

    Directory of Open Access Journals (Sweden)

    Rahman Mohammed M

    2012-12-01

    Full Text Available Abstract Background CuO-TiO2 nanosheets (NSs, a kind of nanomaterials is one of the most attracting class of transition doped semiconductor materials due to its interesting and important optical, electrical, and structural properties and has many technical applications, such as in metal ions detection, photocatalysis, Chemi-sensors, bio-sensors, solar cells and so on. In this paper the synthesis of CuO-TiO2 nanosheets by the wet-chemically technique is reported. Methods CuO-TiO2 NSs were prepared by a wet-chemical process using reducing agents in alkaline medium and characterized by UV/vis., FT-IR spectroscopy, X-ray photoelectron spectroscopy (XPS, powder X-ray diffraction (XRD, and field-emission scanning electron microscopy (FE-SEM etc. Results The structural and optical evaluation of synthesized NSs were measured by XRD pattern, Fourier transform infrared (FT-IR and UV–vis spectroscopy, respectively which confirmed that the obtained NSs are well-crystalline CuO-TiO2 and possessing good optical properties. The morphological analysis of CuO-TiO2 NSs was executed by FE-SEM, which confirmed that the doped products were sheet-shaped and growth in large quantity. Here, the analytical efficiency of the NSs was applied for a selective adsorption of iron(III ion prior to detection by inductively coupled plasma-optical emission spectrometry (ICP-OES. The selectivity of NSs towards various metal ions, including Au(III, Cd(II, Co(II, Cr(III, Fe(III, Pd(II, and Zn(II was analyzed. Conclusions Based on the selectivity study, it was confirmed that the selectivity of doped NSs phase was the most towards Fe(III ion. The static adsorption capacity for Fe(III was calculated to be 110.06 mgg−1. Results from adsorption isotherm also verified that the adsorption process was mainly monolayer-adsorption onto a surface containing a finite number of CuO-TiO2 NSs adsorption sites.

  12. Layered hybrid organic-inorganic Co(II) alkylphosphonates. Synthesis, crystal structure and magnetism of the first two members of the series: Co[(CH3PO3)(H2O)] and Co[(C2H5PO3)(H2O)

    International Nuclear Information System (INIS)

    Co[(CH3PO3)(H2O)] (1) and Co[(C2H5PO3)(H2O)] (2) were prepared by the hydrothermal method and isolated as blue-violet platelet crystals. They were characterized by X-ray diffraction, FT-IR, TGA-DSC techniques and their magnetic properties studied by a dc-SQUID magnetometer. Compound (1) shows an hybrid layered structure, made of alternating inorganic and organic layers along the a-direction of the unit cell. The inorganic layers contain Co(II) ions six-coordinated by five phosphonate oxygen atoms and one from the water molecule. These layers are separated by bi-layers of methyl groups and van der Waals contacts are established between them. In compound (2), the layered hybrid structure is rather similar to that described for compound (1), but the alternation of the inorganic and organic layers is along the b-direction of the unit cell. The magnetic behavior of (1) and (2) as function of temperature and magnetic field was studied. The compounds obey the Curie-Weiss law at temperatures above 100K, the Curie C, and Weiss θ constants for the methyl derivative being C=3.36cm3Kmol-1 and θ=-53K and for the ethyl derivative C=3.62cm3Kmol-1 and θ=-75K, respectively. The observed magnetic moments for Co atom at room temperature (i.e. μeff=5.18 and 5.38 BM, respectively) are higher than those expected for a spin-only value for high spin Co(II) (S=3/2), revealing a substantial orbital contribution to the magnetic moment. The negative values of θ are an indication of the presence of antiferromagnetic exchange couplings between the near-neighbors Co(II) ions, within the layers. [Co(CnH2n+1PO3)(H2O)] (n=1,2) are 2D Ising antiferromagnets at low temperatures

  13. Bioalteration of synthetic Fe(III)-, Fe(II)-bearing basaltic glasses and Fe-free glass in the presence of the heterotrophic bacteria strain Pseudomonas aeruginosa: Impact of siderophores

    Science.gov (United States)

    Perez, Anne; Rossano, Stéphanie; Trcera, Nicolas; Huguenot, David; Fourdrin, Chloé; Verney-Carron, Aurélie; van Hullebusch, Eric D.; Guyot, François

    2016-09-01

    This study aims to evaluate the role of micro-organisms and their siderophores in the first steps of the alteration processes of basaltic glasses in aqueous media. In this regard, three different types of glasses - with or without iron, in the reduced Fe(II) or oxidized Fe(III) states - were prepared on the basis of a simplified basaltic glass composition. Control and Pseudomonas aeruginosa inoculated experiments were performed in a buffered (pH 6.5) nutrient depleted medium to stimulate the production of the pyoverdine siderophore. Results show that the presence of P. aeruginosa has an effect on the dissolution kinetics of all glasses as most of the calculated elemental release rates are increased compared to sterile conditions. Reciprocally, the composition of the glass in contact with P. aeruginosa has an impact on the bacterial growth and siderophore production. As an essential nutrient for this microbial strain, Fe notably appears to play a central role during biotic experiments. Its presence in the glass stimulates the bacterial growth and minimizes the synthesis of pyoverdine. Moreover the initial Fe2+/Fe3+ ratio in the glasses modulates this synthesis, as pyoverdine is not detected at all in the system in contact with Fe(III)-bearing glass. Finally, the dissolution rates appear to be correlated to siderophore concentrations as they increase with respect to sterile experiments in the order Fe(III)-bearing glass < Fe(II)-bearing glass < Fe-free glass. This increase is attributed to complexation reactions between siderophores and Fe or Al for Fe(II)-bearing glass or Fe-free glass, respectively. The dissolution of an Fe-free glass is significantly improved in the presence of bacteria, as initial dissolution rates are increased by a factor of 3. This study attests to the essential role of siderophores in the P. aeruginosa-promoted dissolution processes of basaltic glasses as well as to the complex relationships between the nutritional potential of the glass and

  14. Schiff base ligand derived from (±trans-1,2-cyclohexanediamine and its Cu(II, Co(II, Zn(II and Mn(II complexes: Synthesis, characterization, styrene oxidation and hydrolysis study of the imine bond in Cu(II Schiff base complex

    Directory of Open Access Journals (Sweden)

    Sarkheil Marzieh

    2016-01-01

    Full Text Available A Schiff base ligand (H2L derived from 2´-hydroxypropiophenone and (±trans-1,2-cyclohexanediamine was synthesized. The reactions of MCl2.xH2O (M =Cu(II, Co(II, Zn(II and Mn(IIwith the di-Schiff base ligand (H2L were studied. This ligand when stirred with 1 equivalent of CuCl2.2H2O in the solution of ethanol and chloroform undergoes partial hydrolysis of the imino bond and the resultant tridentate ligand (HL′immediately forms complex[CuL´Cl]∙3/2CHCl3(1with N2O coordination sphere. Under the same condition, the reaction of H2L with MCl2.xH2O (M = Co(II (3, Zn(II (4 and Mn(II (5 gave complexes[ML]•1/2CHCl3∙3/2H2O (3-5with N2O2 coordination sphere and no hydrolytic cleavage was occurred. Also, the reaction of H2L with CuCl2.2H2O in THF gave the complex CuL (2with N2O2 coordination sphere. The ligand and complexes were characterized by FTIR, UV-Vis, 1H NMRand elemental analysis. The homogeneous catalytic activity of the complexes1, 3 and 5wasevaluated for the oxidation of styrene using tert-butyl hydroperoxide (TBHP as oxidant. Finally, the copper(II complex(1encapsulated in the nanopores of zeolite-Y by flexible ligand method (CuL´-Yand its encapsulation was ensured by different studies. The catalytic performance of heterogeneous catalyst in the styrene oxidation with TBHP was investigated. The catalytic tests showed that the homogenous and heterogeneous catalysts were active in the oxidation of styrene.

  15. New solid phase extractors for selective separation and preconcentration of mercury (II) based on silica gel immobilized aliphatic amines 2-thiophenecarboxaldehyde Schiff's bases

    Energy Technology Data Exchange (ETDEWEB)

    Soliman, Ezzat M. [Chemistry Department, Faculty of Science, El-Minia University, El-Minia 61519 (Egypt)]. E-mail: ezzat_soliman@yahoo.com; Saleh, Mohamed B. [Chemistry Department, Faculty of Science, El-Minia University, El-Minia 61519 (Egypt); Ahmed, Salwa A. [Chemistry Department, Faculty of Science, El-Minia University, El-Minia 61519 (Egypt)

    2004-10-04

    2-Thiophenecarboxaldhyde is chemically bonded to silica gel surface immobilized monoamine, ethylenediamine and diethylenetriamine by a simple Schiff's base reaction to produce three new SP-extractors, phases (I-III). The selectivity properties of these phases toward Hg(II) uptake as well as eight other metal ions: Ca(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Pb(II) were extensively studied and evaluated as a function of pH of metal ion solution and equilibrium shaking time by the batch equilibrium technique. The data obtained clearly indicate that the new SP-extractors have the highest affinity for retention of Hg(II) ion. Their Hg(II) uptake in mmol g{sup -1} and distribution coefficient as log K{sub d} values are always higher than the uptake of any other metal ion along the range of pH used (pH 1.0-10.0). The uptake of Hg(II) using phase I was 2.0 mmol g{sup -1} (log K{sub d} 6.6) at pH 1.0 and 2.0. 1.8 mmol g{sup -1} (log K{sub d} 4.25), 1.6 mmol g{sup -1} (log K{sub d} 3.90) and 1.08 mmol g{sup -1} (log K{sub d} 3.37) at pH 3.0, 5.0 and 8.0, respectively. Selective separation of Hg(II) from the other eight coexisting metal ions under investigation was achieved successfully using phase I at pH 2.0 either under static or dynamic conditions. Hg(II) was completely retained while Ca(II), Co(II) and Cd(II) ions were not retained. Ni(II), Cu(II), Zn(II), Pb(II) and Fe(III) showed very low percentage retention values to be 0.74, 0.97, 3.5 and 6.3%, respectively. Moreover, the high recovery values (95.5 {+-} 0.5, 95.8 {+-} 0.5 and 99.0% {+-} 1.0) of percolating two liters of doubly distilled water, drinking tap water and Nile river water spiked with 5 ng/l of Hg(II) over 100 mg of phase I packed in a minicolumn and used as a thin layer enrichment bed demonstrate the accuracy and validity of the new SP-extractors for preconcentration of the ultratrace amount of spiked Hg(II) prior to the determination by borohydride generation atomic absorption

  16. New solid phase extractors for selective separation and preconcentration of mercury (II) based on silica gel immobilized aliphatic amines 2-thiophenecarboxaldehyde Schiff's bases

    International Nuclear Information System (INIS)

    2-Thiophenecarboxaldhyde is chemically bonded to silica gel surface immobilized monoamine, ethylenediamine and diethylenetriamine by a simple Schiff's base reaction to produce three new SP-extractors, phases (I-III). The selectivity properties of these phases toward Hg(II) uptake as well as eight other metal ions: Ca(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Pb(II) were extensively studied and evaluated as a function of pH of metal ion solution and equilibrium shaking time by the batch equilibrium technique. The data obtained clearly indicate that the new SP-extractors have the highest affinity for retention of Hg(II) ion. Their Hg(II) uptake in mmol g-1 and distribution coefficient as log Kd values are always higher than the uptake of any other metal ion along the range of pH used (pH 1.0-10.0). The uptake of Hg(II) using phase I was 2.0 mmol g-1 (log Kd 6.6) at pH 1.0 and 2.0. 1.8 mmol g-1 (log Kd 4.25), 1.6 mmol g-1 (log Kd 3.90) and 1.08 mmol g-1 (log Kd 3.37) at pH 3.0, 5.0 and 8.0, respectively. Selective separation of Hg(II) from the other eight coexisting metal ions under investigation was achieved successfully using phase I at pH 2.0 either under static or dynamic conditions. Hg(II) was completely retained while Ca(II), Co(II) and Cd(II) ions were not retained. Ni(II), Cu(II), Zn(II), Pb(II) and Fe(III) showed very low percentage retention values to be 0.74, 0.97, 3.5 and 6.3%, respectively. Moreover, the high recovery values (95.5 ± 0.5, 95.8 ± 0.5 and 99.0% ± 1.0) of percolating two liters of doubly distilled water, drinking tap water and Nile river water spiked with 5 ng/l of Hg(II) over 100 mg of phase I packed in a minicolumn and used as a thin layer enrichment bed demonstrate the accuracy and validity of the new SP-extractors for preconcentration of the ultratrace amount of spiked Hg(II) prior to the determination by borohydride generation atomic absorption spectrometry (AAS) with no matrix interference. The detection limit (3

  17. Energy transfer--room temperature phosphorescence for the optosensing of transition metal ions

    Energy Technology Data Exchange (ETDEWEB)

    Diaz-Garcia, Juan; Costa-Fernandez, Jose M.; Bordel, Nerea; Pereiro, Rosario; Sanz-Medel, Alfredo

    2003-06-11

    A room temperature phosphorescence (RTP) method for the optosensing of environmentally important transition metals (Hg(II), Cd(II), Pb(II), Zn(II), Cu(II), Ni(II), Co(II) and Fe(III)) in waters is described. The measurement principle is based on the radiationless energy transfer (ET) from the Al-ferron chelate immobilised on Dowex 1X2-200, and acting as the phosphorescent donor, to dithizone dye acting as the acceptor. Dithizone presents an absorption spectrum exhibiting adequate spectral overlap with the RTP emission spectrum of the donor and so giving rise to useful analytical RTP signals. The method has been developed by means of a flow injection system, where the immobilised Al-ferron chelate is packed into a conventional flow cell placed inside the cell holder of a phosphorimeter. After measurement, the sensing phase can be regenerated using ethanol. Working under optimized experimental conditions, including 0.1 M sodium acetate/acetic acid, pH 5.0, and an acceptor concentration of 5x10{sup -5} M, the selected metal ions form metal-dithizone complexes. The increase of the RTP signal observed can be related to the increase of the concentrations of the analytes (i.e. to the decrease of the free dithizone concentration). Both RTP intensity and triplet lifetime measurements can be used as analytical signals in the proposed method. Detection limits (3{sigma}) of 15-33 {mu}g l{sup -1} were found for the metal ions under study using RTP intensity measurements. The precision (R.S.D.) at 0.5 mg l{sup -1} for all analytes was <1.8% (n=5) and the calibration graphs were linear up to 1.5 mg l{sup -1} (maximum concentration assayed)

  18. Synthesis and characterization of a chelating resin containing ONO donor tridentate Schiff base and its coordination compounds with copper(II), nickel(II), cobalt(II), iron(III), zinc(II), cadmium(II), manganese(II), molybdenum(VI), zirconium(IV) and uranium(VI)

    International Nuclear Information System (INIS)

    New polystyrene supported coordination compounds have been synthesized by the reaction of metal salt/metal coordination compound with the polystyrene supported Schiff base (PS-LH2) (obtained by the reaction of chloromethylated polystyrene, 3-formylsalicylic acid and ethanolamine). The compounds have the formulae: PS-LCu.DMF, PS-LNi-3DMF, PS-LCo.3DMF, PS-LFeCl.2DMF, PS-LZn.DMF, PS-LCd.DMF, PS-LMn.3DMF, PS-LMoO2.DMF, PS-LZr(OH)2.2DMF and PS-LUO2.DMF (DMF = dimethylformamide). The compounds have been characterized by elemental analyses, IR, electronic, ESR spectral and magnetic susceptibility measurements. The Cu(II), Ni(II), Co(II), Fe(III) and Mn(II) compounds are paramagnetic while the Zn(II), Cd(II), Zr(IV), Mo(VI) and U(VI) compounds are diamagnetic. The magnetic and ESR data indicate the magnetically dilute nature of the metal centres. The shifts of the v(C=N)(azomethine), v(C-O)(phenolic) and v(C-O)(alcoholic) stretches have been monitored to find out the donor sites of PS-LH2. A square planar structure for PS-LCu.DMF; a tetrahedral structure for PS-LZn.DMF and PS-LCd.DMF; an octahedral structure for PS-LNi.3DMF, PS-LCo.3DMF, PS-LFeCl.2DMF, PS-LMn.3DMF, PS-LMoO2.DMF and PS-LUO2.DMF have been suggested for the compounds. PS-LZr(OH)2.2DMF is pentagonal bipyramidal. (author)

  19. Assessment of heavy metal tolerance and hexavalent chromium reducing potential of Corynebacterium paurometabolum SKPD 1204 isolated from chromite mine seepage

    Directory of Open Access Journals (Sweden)

    Satarupa Dey

    2016-07-01

    Full Text Available Corynebacterium paurometabolum SKPD 1204 (MTCC 8730, a heavy metal tolerant and chromate reducing bacterium isolated from chromite mine seepage of Odisha, India has been evaluated for chromate reduction under batch culture. The isolate was found to tolerate metals like Co(II, Cu(II, Ni(II, Mn(II, Zn(II, Fe(III and Hg(II along with Cr(VI and was resistant to different antibiotics as evaluated by disc-diffusion method. The isolate, SKPD 1204 was found to reduce 62.5% of 2 mM Cr(VI in Vogel Bonner broth within 8 days of incubation. Chromate reduction capability of SKPD 1204 decreased with increase in Cr(VI concentration, but increased with increase in cell density and attained its maximum at 1010 cells/mL. Chromate reducing efficiency of SKPD 1204 was promoted in the presence of glycerol and glucose, while the highest reduction was recorded at pH 7.0 and 35 °C. The reduction process was inhibited by divalent cations Zn(II, Cd(II, Cu(II, and Ni(II, but not by Mn(II. Anions like nitrate, phosphate, sulphate and sulphite was found to be inhibitory to the process of Cr(VI reduction. Similarly, sodium fluoride, carbonyl cyanide m-chlorophenylhydrazone, sodium azide and N, N,-Di cyclohexyl carboiimide were inhibitory to chromate reduction, while 2,4-dinitrophenol appeared to be neither promotive nor inhibitory to the process.

  20. New non-toxic transition metal nanocomplexes and Zn complex-silica xerogel nanohybrid: Synthesis, spectral studies, antibacterial, and antitumor activities

    Science.gov (United States)

    Shebl, Magdy; Saif, M.; Nabeel, Asmaa I.; Shokry, R.

    2016-08-01

    A new chromone Schiff base and its complexes of Cu(II), Ni(II), Co(II), Fe(III), Zn(II), Cd(II), and UO2(VI) as well as Zn(II) complex-silica xerogel nanohybrid were successfully prepared in a nano domain with crystalline or amorphous structures. Structures of the Schiff base and its complexes were investigated by elemental and thermal analyses, IR, 1H NMR, electronic, ESR, mass spectra, XRD, and TEM, as well as conductivity and magnetic susceptibility measurements. The spectroscopic data revealed that the Schiff base ligand behaves as a monobasic tridentate ligand. The coordination sites with metal ions are γ-pyrone oxygen, azomethine nitrogen, and oxygen of the carboxylic group. The metal complexes exhibited octahedral geometry, except Cu(II) complex, which has a square planar geometry and UO2(VI) complex, in which uranium ion is hepta-coordinated. Transmission electron microscope (TEM) analysis showed that Ni(II) and Zn(II) complexes have aggregated spheres and rod morphologies, respectively. TEM images of Zn(II) complex-silica xerogel nanohybrid showed a nanosheet morphology with 46 nm average size and confirmed that the complex was uniformly distributed into the silica pores. The obtained nanocomplexes were tested as antimicrobial and antitumor agents. The results showed that Zn(II) nanocomplex and Zn(II) complex-silica xerogel nanohybrid have high activity. The toxicity test on mice showed that Zn(II) complex and Zn(II) complex-silica xerogel nanohybrid have lower toxicity than cisplatin.

  1. The separation of trace elements in manganese dioxide

    International Nuclear Information System (INIS)

    Separations from manganese are discribed for (a)Al(III), Mo(VI), V(V), and Ti(IV), and (b)trace elements in general. In the first separation, a combined anion-cation exchange, the oxalate complexes are absorbed onto the anionic BIO.RAD 1-X8 resin. V(V) and Al(III) are then eluted into a cation-exchange column from which they are eluted successively, Mo(VI) and Ti(IV) then being eluted from the anionic resin. In the second separation, up to 2g of manganese is absorbed onto BIO.RAD AG 50W-X8 resin, from which V(V) is eluted with dilute hydrochloric acid prior to the elution of Co(II), Cu(II), Zn(II), Cd(II), Fe(III), As(III), Sb(III), Mo(VI), W(VI), and Sn(II) with a mixture of 1 M hydrochloric acid, 80 per cent acetone, and 0,1 per cent hydrogen peroxide. Mn(11) is eluted next with a mixture of 0,75M hydrochloric acid and 90 per cent acetone, after which the remaining cations are eluted with 4M hydrochloric acid. Satisfactory recoveries ranging from 0,8 to 60 mg/l were obtained for 18 of the 21 elements tested. After concentration by evaporation, final measurements were made by the use of atomic-absorption spectrophotometry, or direct-reading spectrometry with excitation from an inductively coupled plasma source. Comparative results were obtained with atomic-absorption procedures where the manganese was not separated. However, the separation procedure can reduce the time required for analysis by the direct method because it limits the number of dilutions necessary and eliminates the need for the use of the method of additions to compensate for interferences from manganese

  2. Ultraviolet spectroscopy and metal ions detection

    International Nuclear Information System (INIS)

    The spectrochemical analysis is based on the interaction of radiation with the chemical species and depends on their nature, having pi, sigma or electrons, or d and f electrons, UV. Visible spectrophotometry has been used extensively in the detection and determination of both organics and inorganics. In UV detection the sensitivity is proportional to the bath length and the excitation coefficient of the given sample. It may be insensitive to many species unless these are converted to UV, absorbing derivatives. The technique has been applied for the monitoring of the effluents from HPLC, as chlorides or other complexes of various elements in this article the utility of HCl as reagent for the spectrophotometric determination of the metal ions like Al(III), As(III,IV), Ba(II), Cd(II), Ca(II) Ce(III), Cs(i), Cr(III,VI), Co(II), Cu(II), Dy(III), Eu(III), Gd(III), Au(III), Hf(IV), Ho(III), In(III), Fe(III), La(III), Pb(II), Lu (III), Mg(II), Mn(II), Hg(II), Mo(VI), Ni(II), Pd(II), Pt(IV), K(I), Pr(III), Re(VII), Ru(IV), Sm(III), Sc(III), Ag(I), Sr(II) Te(III), Th(IV), Sn(II,IV), Ti(III,IV), W(VI), U(VI), V(IV,V), Yb(III), Zn(II) AND Zr(IV) Ions i.e. for meta ions from d of the most of these metal ions has been found sufficient permit their detection in HPLC. Their molar absorptive have also been reported. Reference has also been provided to post column derivatization of some metal ions from d and f block elements for their detection in HPLC. (author) 12 figs.; 6 tabs.; 27 refs

  3. Development of flow injection method for indirect copper determination with amperometric detection in drinking water samples

    Directory of Open Access Journals (Sweden)

    Nikolić-Mandić Snežana

    2012-01-01

    Full Text Available A gas-diffusion flow injection method with amperometric detection for indirect copper determination on a silver electrode is developed. The flow through system is equipped with two injection valves and a gas-diffusion unit. In the first step, a signal of cyanide solution was recorded. In the following step a signal of cyanide in the presence of copper was measured. Interferences (Cd(II, Co(II, Ag(I, Ni(II, Fe(III, Hg(II and Zn(II were investigated and successfully removed. The calibration graph is linear in the range 1-90 μmol dm-3 of copper, correlation coefficient is 0.993, the regression equation is I = (0.0455±0.0015c + (0.4611±0.0671, I is relative signal decrease in μA and c is concentration in μmol dm-3. Relative standard deviation for six consecutive injections of 30 μmol dm-3 copper(II was 1.47 % and for 1 μmol dm-3 copper(II was 3.40 %. The detection limit, calculated as 3 s/m (where s is a standard deviation of nine measurement of a reagent blank and m is the slope of the calibration curve, was 0.32 μmol dm-3, which corresponds to 2.44 ng of copper(II (loop volume was 0.12 cm3. The method enables 60 analyses per hour and it was successfully applied on determination of copper in drinking water samples. [Acknowledgements. The authors acknowledge the grant from the Ministry of Education and Science of the Republic of Serbia, Project number 172051

  4. Sorption of cobalt and lead on modified silica gel matrices (Dissertation submitted for fulfillment of the scientific degree 'Philosophiae doctor' (PhD.))

    International Nuclear Information System (INIS)

    Most organo-functional groups attached on silica gel surfaces with the aim of adsorbing metal ions from aqueous and nonaqueous solutions have often nitrogen, sulfur or oxygen as a donor atom. Preparation, characterization and use of silica gel sorbents with immobilized organo-functional group (imidazole, crown ethers) is described. Various silica gel materials (spherical SILIKASPHER, amorphous SILASORB and mesoporous MCM-41) were chemically modified with imidazole, diaza-18-crown-6 (DA18C6) and dibenzo-18-crown-6 (DB18C6). The degree of functionalization depends on the reflux time and silica gel matrix used. Experimental sorption capacity ranged between 0.038 and 0.228 mmol/g (for sorbents with imidazole) and between 0.019 and 0.05 mmol/g (for sorbents with DA18C6 and DB18C6). Synthesized hexagonal mesoporous silica matrix MCM-41 with uniform pore diameter -1 (for imidazole), 85 and 120 mL/g (for DB18C6) and between 230 and 500 mL/g (for DA18C6) according to silica gel matrix used and according to the method of sorbent preparation. pH plays important role in the sorption of cobalt on prepared sorbents with immobilized crown ethers due to protonization of crown ethers. The influence of the presence of heavy or toxic metals (Hg(II), CD(II), Mn(II), Zn(II), Cu(II), Fe(III), Cr(III), Al(III) and the influence of sodium and potassium on sorption Co(II) from aqueous solutions was studied. (author)

  5. Synthesis, characterization and thermal studies of binary and/or mixed ligand complexes of Cd(II), Cu(II), Ni(II) and Co(III) based on 2-(Hydroxybenzylidene) thiosemicarbazone: DNA binding affinity of binary Cu(II) complex

    Science.gov (United States)

    Saif, M.; Mashaly, Mahmoud M.; Eid, Mohamed F.; Fouad, R.

    A new series of metal complexes of Cd(II), Cu(II), Ni(II) and Co(III) with Schiff base ligand, H2L, 2-(Hydroxybenzylidene) thiosemicarbazone were synthesized. The mixed ligand complexes were prepared by using glycine (Gly), 2-aminopyridine (2-Ampy) and 1,10-phenanthroline (Phen) as secondary ligands. The structure of these complexes was identified and confirmed by elemental analysis, molar conductivity, UV-Vis, FT-IR and 1H NMR spectroscopy and magnetic moment measurements as well as TG-DSC technique. The discussions of the prepared complexes indicate that the ligand behaves as a monoanionic tridentate ligand through ONS donor sites. Thermal studies suggested a mechanism for the degradation of the metal complexes as a function of temperature supporting the chelation modes and showed the possibility of obtaining new complexes pyrolytically in the solid state which cannot be synthesized from the solution. The absorption studies support that the binary Cu(II) complex exhibits a significant binding affinity to HS-DNA through intercalative mode.

  6. Co-extraction and stripping behaviour of various elements present in simulated high-level liquid waste in unsymmetrical diglycolamide

    International Nuclear Information System (INIS)

    High-level liquid waste (HLLW) is a complex mixture of several metal ions such as actinides, lanthanides, transition group elements and alkali and alkaline earth metals present in 3-4 M nitric acid medium. These metal ions generally interfere in partitioning of minor actinides from HLLW and complicate the subsequent transmutation. Therefore, it is necessary to understand the co-extraction and stripping behaviour of these unwanted metal ions during partitioning of minor actinides. However, the estimation of unwanted metal ions present in the waste is a challenging task of determining various metal ions in a complex mixture of multi-elemental matrix. Nevertheless, methods, based on ICP-OES, have been developed in our laboratory for determining these elements present in simulated high-level liquid waste (SHLLW). In the recent past, we developed a solvent composed of 0.1 M N,N-di-2-ethylhexyl- N',N'-di-octyl-3-oxa-1,5-diamide (DEHDODGA)-0.5 M N,N-dihexyIoctanamide (DHOA) in n-dodecane and proposed for partitioning of minor actinides from HLLW. In this paper, the distribution ratio of various metal ions present in SHLLW was measured as a faction of the concentration of nitric acid and interfering ions. The concentrations of various elements were analysed by inductively-coupled plasma optical emission spectroscopy (ICP-OES), atomic absorption spectroscopy (AAS) and gamma spectroscopy. The extraction of metal ions decreased in the order M4+≥M3+ ≫ M2+ ∼ MO22+ ≫ M+. The extraction of Am(III), Eu(III), Y(III), and Zr(IV) was quantitative. However, the distribution ratio of unwanted metal ions such as Fe(III), Co(II), Sb(III), Mn(VI), and Cs(1) was negligible. The distribution ratios of Cd(II), Ru(III), Pd(II), Mo(VI), Cr(VI), Ba(II), Ni(II), and Sr(II) were not insignificant, but were quite low. The extraction and stripping of Zr(IV), Sr(II), Cs(I), Mn(VI), Co(II) was compared by estimating their concentrations by ICP-OES, AAS, gamma spectroscopy, and Nal

  7. Evaluation of dispersive liquid-liquid microextraction for the determination of cobalt and cadmium by flame atomic absorption spectrometry: application in water and food samples

    OpenAIRE

    Bosch Ojeda C.; Sánchez Rojas F.

    2014-01-01

    Dispersive liquid-liquid microextraction (DLLME) was applied to the separation and preconcentration of Cd(II) and Co(II) from water and food samples. The influence of the following analytical parameters on the quantitative recoveries of cadmium and cobalt were investigated: pH, extraction solvent volume, dispersing solvent volume and type, and concentration of chelating agent. Under the optimized conditions, the detection limits were 2 μg L-1 and 13 μg L-1 for Cd(II) a...

  8. Metal complexes as antibacterial agents: Synthesis, characterization and antibacterial activity of some 3d metal complexes of sulphadimidine

    Directory of Open Access Journals (Sweden)

    Adedibu Clement Tella

    2010-06-01

    Full Text Available Metal complexes of Sulphadimidine(SAD were synthesized.The complexes were formulated as [Co(SAD2Cl2], [Cu(SAD2 (H2O2], [Ni (SAD2 Cl2 H2O], [Cd (SAD2 Br2], [Fe (SAD3](H­2O­3 and [Mn (SAD2Cl2] characterized by elemental Analysis, conductivity, IR , UV-Vis, Magnet moment and 1H-NMR and Mass spectroscopies. Co(II, Mn (II,  and Ni(II sulphadimidine complexes consist of metal ion which coordinates through amino nitrogen of the terminal NH2 group and oxygen of sulfonamidic group of the two molecules of sulphadimidine ligand and two halide ions to form octahedral structure while Cd(II coordinates with sulphadimidine through amino nitrogen of the terminal NH2 group with two bromine ions to complete tetrahedral structure. In Cu(II sulphadimidine complex, copper ion coordinates through both pyrimidinic nitrogen (heterocyclic nitrogen and sulfonamidic nitrogen of the two molecules of sulphadimidine. Fe(III coordinates to three molecules of sulphadimidine through heterocyclic nitrogen (pyrimidinic nitrogen and sulfonamidic nitrogen,with three molecules of water outside the coordination sphere. Both Fe(III and Cu(II complexes exhibit octahedral geometry. The antibacterial activity of the complexes and the ligands was investigated against Esherichia coli,  Staphylococcus aureus and Klebsiella pneumonia .  The data obtained revealed that the complexes showed greater activity against the three micro-organisms when compared to parent compound. Stability constant of the complexes were evaluated for the metal salts, the order of stability constant b was found to be Cu (II > Fe (III >Ni(II> Co (II > Cd (II.The values of stability constant (b was found to be log 6.31, 5.93, 5.29, 4.63 and 3.92, respectively. The stability constant data revealed that this ligand may be used as antidote or chelating agent for medical treatment of metals overload or poisoning.

  9. Chromium(III, VI) speciation analysis with preconcentration on a maleic acid-functionalized XAD sorbent

    International Nuclear Information System (INIS)

    Chromium may exist in environmental waters as Cr(III) and Cr(IV), the latter being the toxic and carcinogenic form. Since atomic absorption spectrometry (AAS) and inductively coupled plasma atomic emission spectrometry can only yield information on total Cr concentration, a polymer resin bearing O,O-donor chelating groups such as the maleic acid-functionalized XAD-(CO)CH-CH-COOH resin was synthesized to selectively retain Cr(III) at pH 4.0-5.5. The dynamic breakthrough capacity of the resin for Cr(III) at pH 5.0 was 7.52 mg g-1, and the preconcentration factor extended to 250-300. Chromium(III) in the presence of 250-fold Cr(VI)--which was not retained--could be effectively preconcentrated on the NH4+-form of the resin and determined by AAS or diphenylcarbazide (DPC) spectrophotometry. When Cr(VI) was reduced to Cr(III) with Na2SO3 solution brought to pH 1 by the addition of 1 M H2SO4, and preconcentrated on the resin, total Cr could be determined. The developed method was validated with a blended coal sample CRM-1632. Since the adsorption behavior as a function of pH of possible interferent metal ions, e.g. Ni(II), Co(II), Cu(II), Cd(II), Zn(II), Pb(II) and Fe(III), was similar to that of Cr(III), selective elution of Cr(III) from the resin was realized using a mixture of 1 wt.% H2O2+1 M NH3. The eluate containing Cr as chromate could be directly analyzed by diphenyl carbazide spectrophotometry without any adverse effect from the common interferents of this method, i.e. Fe(III), Cu(II) Hg(II), VO3-, MoO42- and WO42-. Various synthetic waste solutions typical of electroplating bath effluents containing Cr, Cu, Ni, Zn, Na, Ca, cyanide (and chemical oxidation demand (COD), achieved by glucose addition) were subjected to pretreatment procedures such as hypochlorite oxidation (of cyanide) and catalytic oxidation (of COD) with peroxodisulfate. Chromium determination gave satisfactory results. The combined column preconcentration--selective elution

  10. Non-bonding interactions and non-covalent delocalization effects play a critical role in the relative stability of group 12 complexes arising from interaction of diethanoldithiocarbamate with the cations of transition metals Zn(II), Cd(II), and Hg(II): a theoretical study.

    Science.gov (United States)

    Bahrami, Homayoon; Farhadi, Saeed; Siadatnasab, Firouzeh

    2016-07-01

    The chelating properties of diethanoldithiocarbamate (DEDC) and π-electron flow from the nitrogen atom to the sulfur atom via a plane-delocalized π-orbital system (quasi ring) was studied using a density functional theory method. The molecular structure of DEDC and its complexes with Zn(II), Cd(II), and Hg(II) were also considered. First, the geometries of this ligand and DEDC-Zn(II), DEDC-Cd(II), and DEDC-Hg(II) were optimized, and the formation energies of these complexes were then calculated based on the electronic energy, or sum of electronic energies, with the zero point energy of each species. Formation energies indicated the DEDC-Zn(II) complex as the most stable complex, and DEDC-Cd(II) as the least stable. Structural data showed that the N1-C2 π-bond was localized in the complexes rather than the ligand, and a delocalized π-bond over S7-C2-S8 was also present. The stability of DEDC-Zn(II), DEDC-Cd(II), and DEDC-Hg(II) complexes increased in the presence of the non-specific effects of the solvent (PCM model), and their relative stability did not change. There was π-electron flow or resonance along N1-C2-S7 and along S7-C2-S8 in the ligand. The π-electron flow or resonance along N1-C2-S7 was abolished when the metal interacted with sulfur atoms. Energy belonging to van der Waals interactions and non-covalent delocalization effects between the metal and sulfur atoms of the ligand was calculated for each complex. The results of nucleus-independent chemical shift (NICS) indicated a decreasing trend as Zn(II) electronic cloud localized on Hg(II) in the Hg(II)-DEDC complex. PMID:27299888

  11. Co(II)1-xCo(0)x/3Mn(III)2x/3S Nanoparticles Supported on B/N-Codoped Mesoporous Nanocarbon as a Bifunctional Electrocatalyst of Oxygen Reduction/Evolution for High-Performance Zinc-Air Batteries.

    Science.gov (United States)

    Wang, Zilong; Xiao, Shuang; An, Yiming; Long, Xia; Zheng, Xiaoli; Lu, Xihong; Tong, Yexiang; Yang, Shihe

    2016-06-01

    Rechargeable Zn-air battery is an ideal type of energy storage device due to its high energy and power density, high safety, and economic viability. Its large-scale application rests upon the availability of active, durable, low-cost electrocatalysts for the oxygen reduction reaction (ORR) in the discharge process and oxygen evolution reaction (OER) in the charge process. Herein we developed a novel ORR/OER bifunctional electrocatalyst for rechargeable Zn-air batteries based on the codoping and hybridization strategies. The B/N-codoped mesoporous nanocarbon supported Co(II)1-xCo(0)x/3Mn(III)2x/3S nanoparticles exhibit a superior OER performance compared to that of IrO2 catalyst and comparable Zn-air battery performance to that of the Pt-based battery. The rechargeable Zn-air battery shows high discharge peak power density (over 250 mW cm(-2)) and current density (180 mA cm(-2) at 1 V), specific capacity (∼550 mAh g(-1)), small charge-discharge voltage gap of ∼0.72 V at 20 mA cm(-2) and even higher stability than the Pt-based battery. The advanced performance of the bifunctional catalysts highlights the beneficial role of the simultaneous formation of Mn(III) and Co(0) as well as the dispersed hybridization with the codoped nanocarbon support. PMID:27163673

  12. Co(II, Ni(II, Cu(II, and Zn(II complexes derived from 4-[{3-(4-bromophenyl-1-phenyl-1H-pyrazol-4-ylmethylene}-amino]-3-mercapto-6-methyl-5-oxo-1,2,4-triazine

    Directory of Open Access Journals (Sweden)

    Kiran Singh

    2016-03-01

    Full Text Available A new series of Co(II, Ni(II, Cu(II and Zn(II complexes were prepared with bidentate ligand derived by condensation of 4-amino-3-mercapto-6-methyl-5-oxo-1,2,4-triazine with 3-(p-bromophenyl-1-phenyl-1H-pyrazolecarboxaldehyde. The Schiff base and its metal complexes were characterized on the basis of various spectroscopic investigation like IR, NMR, fluorescence and thermal analyses. The coordinated water molecules were confirmed by IR and thermal data, while the geometry of the complexes was confirmed by electronic spectra, magnetic moment measurements and ESR analysis. Cyclic voltammetry shows the redox behavior of copper complexes. All the complexes were colored, stable in air and non-electrolytic in nature. Schiff base and its metal complexes were screened for in vitro antimicrobial activity and it was observed that metal complexes show enhanced biological activity as compared to ligand or metal salts. In addition, Zn(II complexes show enhanced biological activity against most of the microbial strains as compared to ligand and other metal complexes.

  13. Synthesis, characterization and 3D molecular modeling of some ternary complexes of Cu(II), Ni(II), Co(II), Zn(II), Sm(III), Th(IV) and UO2(VI) with Schiff base derived from the sulfa drug sulfabenzamide and 1,10-phenanthroline

    International Nuclear Information System (INIS)

    Some new mixed-ligand ternary complexes of Cu(II), Ni(Il), Co(Il), Zn(Il), Sm(III), Th(IV) and UO2(VI) with the Schiff base derived from salicylaldehyde and the sulfa drug sulfabenzamide, (N-(salicylidene)sulfabenzamide) (LH) and the heterocyclic base 1,10-phenanthroline (phen) have been synthesized and characterized by IR, NMR, diffuse reflectance spectra, and thermal, magnetic and molar conductance measurements. Thermal analyses indicate the presence of lattice and coordinated water molecules in the complexes, which is also supported by the IR spectral data. The coordination by the azomethine nitrogen is inferred by the upfield shifting of the -CH=N- signal in the NMR spectra and the shift of v(C=N) to lower wave numbers in the IR spectra upon complexation. The Schiff base ligand (LH) acts as a monobasic bidentate ligand in complex formation. The presence of anion, viz., CH3COO- or NO3- in the coordination sphere is also inferred by the IR spectral data and conductance measurements. The general compositions of the complexes are found to be (M(L)(phen)(OAc)(H2O)), where M = Cu(II), Ni(II), Co(II), Zn(II) or UO2(VI), (Sm(L)(phen)(OAc)2(H2O)2).H2O and (Th(L)(phen)(NO3)3(H2O)).4H2O, where AcOH = acetic acid and LH (N-(salicylidene)sulfabenzamide). (author)

  14. Synthesis and structural characterization of nickel(II), cobalt(II), Zinc(II), manganese(II), cadmium(II) and uranium(VI) complexes of α-oximinoacetoacet-o/p-anisidide thiosemicarbazone

    International Nuclear Information System (INIS)

    A few metal complexes of α-oximinoacetoacet-o/p-anisidide thiosemicarbazones (OAOATS)/(OAPATS) with Ni(II), Co(II), Zn(II), Mn(II), Hg(II), Cd(II) and UO2(II) have been prepared and characterized by elemental analyses, conductivity, differential scanning calorimetry study, thermogravimetric analyses and infrared and electronic spectral measurements in conjunction with magnetic susceptibility measurements at room temperature. They have also been tested for their antimicrobial activities. (author). 24 refs., 2 tabs

  15. Molecular tectonics: heterometallic coordination networks based on a Pt(II) organometallic metallatecton.

    Science.gov (United States)

    Zigon, Nicolas; Kyritsakas, Nathalie; Hosseini, Mir Wais

    2015-08-28

    Combinations of a neutral organometallic tecton based on a square planar Pt(ii) complex bearing two triphenylphosphine groups and two 4-ethynylpyridyl coordinating moieties in trans positions, with various metal halides (MX2, M = Co(ii), Ni(ii), Cd(ii), X = Cl(-) or Br(-)) lead to the formation of 2D grid type heterobimetallic coordination networks in the crystalline phase. PMID:26204438

  16. Pharmacologically significant complexes of Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) of novel Schiff base ligand, (E)-N-(furan-2-yl methylene) quinolin-8-amine: Synthesis, spectral, XRD, SEM, antimicrobial, antioxidant and in vitro cytotoxic studies

    Science.gov (United States)

    Shakir, M.; Hanif, Summaiya; Sherwani, Mohd. Asif; Mohammad, Owais; Al-Resayes, Saud I.

    2015-07-01

    A novel series of metal complexes of the types, [ML2(H2O)2]Cl2 and [ML2]Cl2 [M = Mn(II), 1; Co(II), 2; Ni(II), 3; Cu(II), 4; and Zn(II), 5] were synthesized by the interaction of ligand, L (E)-N-(furan-2-yl methylene) quinolin-8-amine, derived from the condensation of 2-furaldehyde and 8-aminoquinoline. The synthesized ligand and its metal complexes were characterized on the basis of results obtained from elemental analysis, ESI-MS, XRD, SEM, TGA/DTA, FT-IR, UV-Vis, magnetic moment and 1H and 13C NMR spectroscopic studies. EPR parameters were recorded in case of complex 4. The comparative in-vitro antimicrobial activities against various pathogens with reference to known antibiotics and antioxidant activity against standard control at variable concentrations revealed that the metal complexes show enhanced antimicrobial and free radical scavenging activities in general as compared to free ligand. However, the complexes 1 and 5 have shown best antioxidant activity among all the metal complexes. Furthermore, comparative in-vitro antiproliferative activity on ligand and its metal chelates performed on MDA-MB-231 (breast carcinoma), KCL22 (blood lymphoid carcinoma), HeLa (cervical carcinoma) cell lines and normal cells (PBMC) revealed that metal chelates show moderate to good activity as compared to ligand where as complex 1 seems to be the most promising one possessing a broad spectrum of activity against all the selected cancer cell lines with IC50 < 2.10 μM.

  17. Two fumarato-bridged Co(II) coordination polymers: syntheses, crystal structures and properties of Co(H2O)4L and [Co3(H2O)4(OH)2L2]·2H2O with H2L-HOOCCH-CHCOOH

    International Nuclear Information System (INIS)

    Two fumarato-bridged Co(II) coordination polymers Co(H2O)4L 1 and [Co3(H2O)4(OH)2L2]·2H2O 2 with H2L-HOOCCH-CHCOOH were prepared. Complex 1 consists of polymeric chains ∞1[Co(H2O)4(C4H2O4)2/2], which result from octahedrally coordinated Co atoms bridged by bis-monodentate fumarate anions and are assembled by interchain hydrogen bonds. Within 2, the edge-shared Co2O10 bi-octahedra are connected to the CoO6 octahedra to form 1D cobalt oxide chains and 3D open framework generated from the chains inter-linked by bis-bidentate fumarate anions displays rhombic tunnels, which are filled with the lattice H2O molecules. Thermal and magnetic behaviors of both the title coordination polymers are discussed. Crystal data: (1) monoclinic, P21/c, Z=4, a=7.493(1) A, b=14.377(1) A, c=7.708(1) A, β=99.54(1) deg., V=818.9(2) A3, R1=0.0304, and wR2=0.0669 for 1487 observed reflections (I≥2σ(I)) out of 1877 unique reflections; (2) monoclinic, P21/c, Z=2, a=6.618(1) A, b=8.172(2) A, c=15.578(3) A, β=96.30(3) deg., V=837.4(3) A3, R1=0.0360 and wR2=0.0663 for 1442 observed reflections (I≥2σ(I)) out of 1927 unique reflections

  18. Simultaneous removal of heavy-metal ions in wastewater samples using nano-alumina modified with 2,4-dinitrophenylhydrazine.

    Science.gov (United States)

    Afkhami, Abbas; Saber-Tehrani, Mohammad; Bagheri, Hasan

    2010-09-15

    2,4-Dinitrophenylhydrazine (DNPH) immobilized on sodium dodecyl sulfate coated nano-alumina was developed for the removal of metal cations Pb(II), Cd(II), Cr(III), Co(II), Ni(II) and Mn(II) from water samples. The research results displayed that adsorbent has the highest adsorption capacity for Pb(II), Cr(III) and Cd(II) in ions mixture system. Optimal experimental conditions including pH, adsorbent dosage and contact time have been established. Langmuir and Freundlich isotherm models were applied to analyze the experimental data. The best interpretation for the experimental data was given by the Freundlich adsorption isotherm equation for Mn(II), Pb(II), Cr(III) and Cd(II) ions and by Langmuir isotherm equation for Ni(II) and Co(II) ions. Desorption experiments by elution of the adsorbent with a mixture of nitric acid and methanol show that the modified alumina nanoparticles could be reused without significant losses of its initial properties even after three adsorption-desorption cycles. Thus, modified nano-alumina with DNPH is favorable and useful for the removal of these metal ions, and the high adsorption capacity makes it a good promising candidate material for Pb(II),Cr(III) and Cd(II) removal. PMID:20542378

  19. Metallic complexes with glyphosate: a review; Complexos metalicos com o herbicida glifosato: revisao

    Energy Technology Data Exchange (ETDEWEB)

    Coutinho, Claudia F.B.; Mazo, Luiz Henrique [Sao Paulo Univ., Sao Carlos, SP (Brazil). Inst. de Quimica]. E-mail: claudiabreda@iqsc.usp.br

    2005-11-15

    We present studies involving metallic ions and the herbicide glyphosate. The metallic complexes of Cu(II), Zn(II), Mn(II), Ni(II), Cd(II), Pb(II), Cr(III), Fe(III), Co(III), ammonium, sodium, Ag(I), alkaline earth metals and of some lanthanides ions are described. The complexes are discussed in terms of their synthesis, identification, stability and structural properties, based on data from the current literature. (author)

  20. Metallic complexes with glyphosate: a review

    International Nuclear Information System (INIS)

    We present studies involving metallic ions and the herbicide glyphosate. The metallic complexes of Cu(II), Zn(II), Mn(II), Ni(II), Cd(II), Pb(II), Cr(III), Fe(III), Co(III), ammonium, sodium, Ag(I), alkaline earth metals and of some lanthanides ions are described. The complexes are discussed in terms of their synthesis, identification, stability and structural properties, based on data from the current literature. (author)

  1. Radiometric stuides on the reaction of some metals with potassium pentacyanonitrosyl manganate

    International Nuclear Information System (INIS)

    The nature and composition of complexes formed by the reaction of Fe/III/, Cr/III/ Zn/II/, and Co/II/ with potassium pentacyanonitrosyl manganate K3(Mn/CN/5NO) has been investigated by radiometric method. The metals form 1:1 complexes with K3 (Mn/CN/5NO) the optimum pH for maximum precipitation being 3.6 for Fe/III/, 7.3 for Cr/III/, 5.4 for Zn/II/ and 8.3 for Co/II/. The solubility of the complexes as computed from activity at maximum precipitation point follows the order: chromium complex< iron complex< cobalt complex< zinc complex. The radiometric titration curves also show the formation of colloidal precipitates with dilute Zn/II/ solutions. (T.G.)

  2. Alumina physically loaded by thiosemicarbazide for selective preconcentration of mercury(II) ion from natural water samples

    Energy Technology Data Exchange (ETDEWEB)

    Ahmed, Salwa A. [Chemistry Department, Faculty of Science, El-Minia University, El-Minia (Egypt)], E-mail: salwa_kasem2003@yahoo.com

    2008-08-15

    The multifunctional ligand, thiosemicarbazide, was physically loaded on neutral alumina. The produced alumina-modified solid phase (SP) extractor named, alumina-modified thiosemicarbazide (AM-TSC), experienced high thermal and medium stability. This new phase was identified based on surface coverage determination by thermal desorption method to be 0.437 {+-} 0.1 mmol g{sup -1}. The selectivity of AM-TSC phase towards the uptake of different nine metal ions was checked using simple, fast and direct batch equilibration technique. AM-TSC was found to have the highest capacity in selective extraction of Hg(II) from aqueous solutions all over the range of pH used (1.0-7.0), compared to the other eight tested metal ions. So, Hg(II) uptake was 1.82 mmol g{sup -1} (distribution coefficient log K{sub d} = 5.658) at pH 1.0 or 2.0 and 1.78, 1.73, 1.48, 1.28 and 1.28 mmol g{sup -1} (log K{sub d} = 4.607, 4.265, 3.634, 3.372 and 3.372), at pH 3.0, 4.0, 5.0, 6.0 and 7.0, respectively. On the other hand, the metal ions Ca(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Pb(II) showed low uptake values in range 0.009-0.720 mmol g{sup -1} (log K{sub d} < 3.0) at their optimum pH values. A mechanism was suggested to explain the unique uptake of Hg(II) ions based on their binding as neutral and chloroanionic species predominate at pH values {<=}3.0 of a medium rich in chloride ions. Application of the new phase for the preconcentration of ultratrace amounts of Hg(II) ions spiked natural water samples: doubly distilled water (DDW), drinking tap water (DTW) and Nile river water (NRW) using cold vapor atomic absorption spectroscopy (CV-AAS) was studied. The high recovery values obtained using AM-TSC (98.5 {+-} 0.5, 98.0 {+-} 0.5 and 103.0 {+-} 1.0) for DDW, DTW and NRW samples, respectively based on excellent enrichment factor 1000, along with a good precision (R.S.D.% 0.51-0.97%, n 3) demonstrate the accuracy and validity of the new modified alumina sorbent for preconcentrating

  3. Alumina physically loaded by thiosemicarbazide for selective preconcentration of mercury(II) ion from natural water samples

    International Nuclear Information System (INIS)

    The multifunctional ligand, thiosemicarbazide, was physically loaded on neutral alumina. The produced alumina-modified solid phase (SP) extractor named, alumina-modified thiosemicarbazide (AM-TSC), experienced high thermal and medium stability. This new phase was identified based on surface coverage determination by thermal desorption method to be 0.437 ± 0.1 mmol g-1. The selectivity of AM-TSC phase towards the uptake of different nine metal ions was checked using simple, fast and direct batch equilibration technique. AM-TSC was found to have the highest capacity in selective extraction of Hg(II) from aqueous solutions all over the range of pH used (1.0-7.0), compared to the other eight tested metal ions. So, Hg(II) uptake was 1.82 mmol g-1 (distribution coefficient log Kd = 5.658) at pH 1.0 or 2.0 and 1.78, 1.73, 1.48, 1.28 and 1.28 mmol g-1 (log Kd = 4.607, 4.265, 3.634, 3.372 and 3.372), at pH 3.0, 4.0, 5.0, 6.0 and 7.0, respectively. On the other hand, the metal ions Ca(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Pb(II) showed low uptake values in range 0.009-0.720 mmol g-1 (log Kd < 3.0) at their optimum pH values. A mechanism was suggested to explain the unique uptake of Hg(II) ions based on their binding as neutral and chloroanionic species predominate at pH values ≤3.0 of a medium rich in chloride ions. Application of the new phase for the preconcentration of ultratrace amounts of Hg(II) ions spiked natural water samples: doubly distilled water (DDW), drinking tap water (DTW) and Nile river water (NRW) using cold vapor atomic absorption spectroscopy (CV-AAS) was studied. The high recovery values obtained using AM-TSC (98.5 ± 0.5, 98.0 ± 0.5 and 103.0 ± 1.0) for DDW, DTW and NRW samples, respectively based on excellent enrichment factor 1000, along with a good precision (R.S.D.% 0.51-0.97%, n 3) demonstrate the accuracy and validity of the new modified alumina sorbent for preconcentrating ultratrace amounts of Hg(II) with no matrix

  4. Fixation of metallic sulfosalicylate complexes on an anionic exchange resin

    International Nuclear Information System (INIS)

    Since sulfosalicylate ions have acid-base properties, sulfosalicylate complexes have an apparent stability which varies with the ph. As a result, the fixation of sulfo-salicylates on an anionic exchange resin depends on the ph of the solution in equilibrium with the resin. This research has been aimed at studying the influence of the ph on the fixation on an anionic exchange resin (Dowex 1 x 4) of sulfosalicylate anions on the one hand, and of metallic sulfosalicylate complexes on the other hand. In the first part of this work, a determination has been made, by frontal analysis of the distribution of sulfosalicylate ions in the resin according to the total sulfosalicylate I concentration in the aqueous solution in equilibrium with the resin. The exchange constants of these ions between the resin and the solution have been calculated. In the second part, a study has been made of the fixation of anionic sulfosalicylate complexes of Fe(III), Al(III), Cr(III), Cu(II), Ni(II), Co(II), Zn(II), Mn(II), Cd(II), Fe(II) and UO22+. By measuring the partition coefficients of these different elements between the resin and the solution it has been possible to give interpretation for the modes of fixation of the metallic ions, and to calculate their exchange constant between the resin and the solution. The relationship has been established for each metallic element studied, between its partition coefficient, the ph and the total concentration of the complexing agent in solution. Such a relationship makes it possible to predict, for given conditions, the nature of the species in solution and in the resin, as well as the partition coefficient of a metallic, element. Finally, in the third part of the work, use has been made of results obtained previously, to carry out some separations (Ni2+ - Co2+; Ni2+ - Co2+ - Cu2+; UO22+ - Fe3+; UO22+ - Cr3+; UO22+ - Cu2+; UO22+ - Ni2+; UO22+ - Co2+; UO22+ - Mn2+ and UO22+ - Cd2+), as well as the purification of a uranyl sulfosalicylate solution

  5. Development of fluorescent FeIII sensor based on chalcone

    Energy Technology Data Exchange (ETDEWEB)

    Wei Yanli, E-mail: weiyanli@sxu.edu.cn [Research Center of Environmental Science and Engineering, Shanxi University, Taiyuan 030006 (China); Qin Guojie [Institute of Horticulture, Shanxi Academy of Agriculture Science, Taiyuan 030031 (China); Wang Wenyan; Bian Wei; Shuang Shaomin [Research Center of Environmental Science and Engineering, Shanxi University, Taiyuan 030006 (China); Dong Chuan, E-mail: dc@sxu.edu.cn [Research Center of Environmental Science and Engineering, Shanxi University, Taiyuan 030006 (China)

    2011-08-15

    In this paper, 4-dimethylamino 2,5-dihydroxy chalcone (DMADHC), which exhibits excited state intramolecular charge transfer (ICT) characteristics, was synthesized and characterized. A sensitive optochemical sensor for Fe{sup 3+} ion was developed using DMADHC as fluorescence receptor. The fluorescence of DMADHC was gradually quenched with the addition of Fe{sup 3+} ion, which attributed to the formation of 1:1 complex between DMADHC and Fe{sup 3+} ion. The sensor exhibited excellent selectivity for Fe{sup 3+} ion over a large number of cation ions such as alkali, alkaline earth and transitional metal ions with a linear range of 3.984x10{sup -7}-1.135x10{sup -5} and a limit of detection of 8.223x10{sup -8} mol/L. On this basis, the sensor was preliminary applied to the determination of the content of iron ions in multi-vitamin tablet with satisfied results and the recoveries were in the 95-100% interval, and precision (n=5) was better than 5%. - Highlights: > A fluorescence receptor, 4-dimethylamino 2,5-dihydroxy chalcone was synthesis by one-step reaction. > Its intramolecular charge transfer fluorescence characteristics could be blocked by Fe{sup 3+} ion. > Based on this, an optochemical sensor for Fe{sup 3+} ion was developed. > Importantly, our proposed method is particularly useful for determination of Fe{sup 3+} ion in real sample.

  6. Lead hexamethylenedithiocarbamate as a chelate matrix for preconcentration and subsequent neutron-activation determination of trace elements in natural waters

    International Nuclear Information System (INIS)

    The authors studied the coprecipitation of trace elements with lead hexamethylenedithiocarbamate. The following elements were found to quantitatively preconcentrate at pH 5-7: Au(III), Ag(I), Co(II), Cr(III), Fe(III), Zn(II), Sb(III), and Hg(II). The preconcentration method developed was used for the neutron-activation analysis of waters from the central part of the Indian Ocean

  7. Synthesis, characterization and thermal study of some transition metal complexes of an asymmetrical tetradentate Schiff base ligand

    Directory of Open Access Journals (Sweden)

    ACHUT S. MUNDE

    2010-03-01

    Full Text Available Complexes of Cu(II, Ni(II, Co(II, Mn(II and Fe(III with an asymmetric tetradentate Schiff base ligand derived from dehydroacetic acid, 4-methyl-o-phenylenediamine and salicylic aldehyde were synthesized and characterized by elemental analysis, conductometry, magnetic susceptibility, UV–Vis, IR, 1H-NMR spectroscopy, X-ray diffraction analysis of powdered samples and thermal analysis, and screened for antimicrobial activity. The IR spectral data suggested that the ligand behaves as a dibasic tetadentate ligand towards the central metal ion with an ONNO donor atoms sequence. From the microanalytical data, the stoichiometry of the complexes 1:1 (metal:ligand was found. The physico-chemical data suggested square planar geometry for the Cu(II and Ni(II complexes and octahedral geometry for the Co(II, Mn(II and Fe(III complexes. The thermal behaviour (TGA/DTA of the complexes was studied and kinetic parameters were determined by Horowitz–Metzger and Coats–Redfern methods. The powder X-ray diffraction data suggested a monoclinic crystal system for the Co(II, Mn(II and Fe(III complexes. The ligand and their metal complexes were screened for antibacterial activity against Staphylococcus aureus and Escherichia coli and fungicidal activity against Aspergillus niger and Trichoderma viride.

  8. Studies on the Use of Supported Liquid Membrane Technique for Removal of Heavy Metals from Water Effluents

    International Nuclear Information System (INIS)

    The present work is directed to develop, assess and establish different systems for the removal and recovery of Co, Ni, Zn and Cd from aqueous solutions using supported liquid membrane (SLM) technique. The individual permeation of Co(II) and Ni(II) from aqueous chloride solutions through SLM using CYANEX 301 in kerosene supported on cellulose acetate membrane was studied based on the optimum conditions for separation obtained by liquid-liquid extraction experiments. Application studies of the investigated system were carried out on the permeation of four heavy elements (Co(II), Ni(II), Zn(II) and Cd(II) ) of equal concentrations when mixed together in real water samples from different origins. For this purpose, samples from Ismailia canal, El-Manzala lake, sea water and drinking water were selected for these experiments. The results obtained show that complete removal of Zn(II) from aqueous chloride medium of ph 3 from El-Manzala lake water is obtained at different temperature degrees and the removal of a large amounts of Co(II), Cd(II) and Ni(II) from drinking water is also possible.

  9. Extractive properties of benzohydroxamic and N-benzoyl-benzohydroxamic acids as analytical reagents towards six transition metal ions

    International Nuclear Information System (INIS)

    Two hydroxamic acids were prepared: benzohydroxamic and N-benzoyl benzohydroxamic acids. The former was prepared by coupling the free hydrox amine with benzoyl chloride with the ratio 1:1 in alkaline medium, where as the latter by the same procedure with the ratio 1:2 respectively, they were identified by their melting points, elemental analysis of their nitrogen contents. infra-red spectrophotometry, as well as their nitrogen using elevation of boiling point and the titration method to determine their molecular weights. The two hydroxamic acids were used as analytical reagents for the extraction of the metals Cr(vi), Fe(III), Ti(iv), Co(II) and U(vi). Benzohydroxamic acid has a maximum extraction 99.55% for Cr.(vi) 3M H2SO4, of 90.16% for Ti(iv) at pH 2.0,of 80.56% for Co(II) at pH 8.0 and 98.01% for U(vi) at pH 6.0. N-benzoyl benzohydroxamic acid has a maximum extraction of 96.45% for Cr(vi) at 3M H2So4, of 90.82% for Fe(III) at pH 4.0, of 97.02% for V(v) at 3M H2So4, of 83.56% for Ti(iv) at pH 2.0, of 89.82% for Co(II) at pH 8.0 and of 97.16% for U(vi) at pH 6.0. at the same pH of maximum extraction using heavy matrix, synthetic sea-water, benzohydroxamic acid has maximum values of 91.08%, of 77.99%, of 91.39%, of 87.50 and of 93.17% for Cr(vi), Fe(III), V(v), Ti(iv), Co9II) and U(vi) respectively whereas n-benzoyl benzohydroxamic acid has maximum values of 86.17%, of 77.78%, of 89.61%, of 75.66%, of 79.63% and of 91.18% for Cr(vi), Fe(III), V(v), Ti(iv), Co(II) and U(vi) respectively. The ratio of metal to ligand was determined utilizing the continuous variation method. It was 1 :2, 1: 1, 1 : 1, 1 : 2, 1: 2 and 1 : 2 with respect to Cr(vi), fe(III), Ti(iv), Co(II) and U(vi) respectively.(Author)

  10. Cobalt(II), nickel(II), copper(II), zinc(II), cadmium(II), dioxouranium(VI) and oxovanadium(IV) complexes with 2-(N-α-benzyl-2-hydroxybenzylidineimino)-ethane sulphonic acid

    International Nuclear Information System (INIS)

    The dissociation constants of 2-(N-αbenzyl-2-hydroxbenzylidineimino) ethane sulphonic acid (H2BE) and stability constants of its chelates with CoII, NiII, CuII, ZnII, CdII, UVIO2 and VIVO have been determined in aqueous medium (μ-0.1 M) at 25, 35 and 45deg using Calvin's extension of Bjerrum's method. Values of ΔGo, ΔHo and ΔSo of the chelates have been evaluated. Elemental analysis, molecular weight, electronic and ir spectra, magnetic moments and conductance of the solid complexes indicate an octahedral stereochemistry for these chelates except those of the ZnII and CdII which possesses a tetrahedral geometry. (author)

  11. Bivalent transition metal complexes of ONO donor hydrazone ligand: Synthesis, structural characterization and antimicrobial activity.

    Science.gov (United States)

    Bhaskar, Ravindra; Salunkhe, Nilesh; Yaul, Amit; Aswar, Anand

    2015-12-01

    Mononuclear transition metal complexes of Mn(II), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) with a new hydrazone ligand derived from pyrazine-2-carbohydrazide and 2-hydroxyacetophenone have been synthesized. The isolated complexes were characterized by elemental analysis, spectral and analytical methods including elemental analyses, IR, diffuse reflectance, (1)H-NMR, mass spectra, molar conductance, magnetic moment, ESR, XRD, TG and SEM analysis. From the elemental analyses data, the stoichiometry of the complexes was found to be 1:1 (metal:ligand) having the general formulae [M(HL)(Cl)(H2O)2], [M=Mn(II), Co(II), Ni(II) and Cu(II)] and [M(L)(H2O)], [M=Zn(II) and Cd(II)]. The molar conductance values indicate the nonelectrolytic nature of metal complexes. The IR spectral data suggest that the ligand behaves as tridentate moiety with ONO donor atoms sequence towards central metal ion. The Mn(II), Co(II), Ni(II) and Cu(II) complexes have been assigned a monomeric octahedral geometry whereas tetrahedral to Zn(II) and Cd(II) complexes. The antibacterial and antifungal activities of the ligand and its metal complexes were studied against bacterial species Escherichia coli, Pseudomonas aeruginosa, Staphylococcus aureus, Bacillus subtilis, Enterococcus faecalis and Streptococcus pyogenes and fungi Candida albicans, Aspergillus niger and Aspergillus clavatus. The activity data show that the metal complexes have a promising biological activity comparable with the parent ligand against all bacterial and fungal species. PMID:26163785

  12. SYNTHESIS AND BIOLOGICAL ACTIVITY OF BUTANONE THIOSEMICARBAZONE AND THEIR METALLIC COMPLEXES

    OpenAIRE

    Sandeep Kumar; Nitin Kumar

    2013-01-01

    In present work, Ligand butanone thiosemicarbazone and their 11 complexes of the type ML2X2, ML2X’, where M = Cu(II), Cd(II), Co(II), Zn(II), Hg(II); L = butanone thiosemicarbazone; X = Cl, NO3 or CH3COO; X’ = SO4 have been synthesized and characterized with the help of infra-red and ultra-violet spectroscopy. The spectral data revealed that the thiosemicarbazone act as bidentate ligand, making use of thionic sulphur and the azomethine nitrogen atom for co-ordination to the central metal a...

  13. CNDO/2 calculations for α-oximino-acetoacetanilide thiosemicarbazone and synthesis and characterization of some metal chelates derived from it

    International Nuclear Information System (INIS)

    Solid complexes of α-oximinoacetoacetanilide thiosemicarbazone (OAATS) with Ni(II), Co(II), Zn(II), Mn(II), Cd(II), Hg(II) and UO2(II) have been prepared and characterized on the basis of their elemental analyses, conductivity, differential scanning calorimetry, thermogravimetric analysis, infrared and electronic spectral measurements, in conjunction with magnetic susceptibility measurements. Molecular orbital calculations employing the CNDO/2 method have been made for a number of conformations of the ligand molecule to ascertain the most stable one. (author). 24 refs., 3 figs., 2 tabs

  14. Synthesis and characterization of nickel(II), chromium(III), cobalt(II), copper(II), zinc(II), and cadmium(II) complexes with isatin- isonicotinoylhydrazone

    International Nuclear Information System (INIS)

    A few metal complexes of isatin-isonicotinoylhydrazone with Ni(II), Cr(III), Co(II), Cu(II), Zn(II) and Cd(II) have been prepared and characterized on the basis of elemental analyses, infrared and electronic spectra as well as 1H NMR spectra, conductivity and magnetic measurements. In view of the results obtained, it has been found that two molecules of isatin-isonicotinoylhydrazone are chelated to the central metal ion as bis-uninegative ONO tridentate ligand forming non-electrolytic octahedral metal complexes. (author)

  15. Metal adsorption by agricultural biosorbents: Adsorption isotherm, kinetic and biosorbents chemical structures.

    Science.gov (United States)

    Sadeek, Sadeek A; Negm, Nabel A; Hefni, Hassan H H; Wahab, Mostafa M Abdel

    2015-11-01

    Biosorption of Cu(II), Co(II) and Fe(III) ions from aqueous solutions by rice husk, palm leaf and water hyacinth was investigated as a function of initial pH, initial heavy metal ions concentration and treatment time. The adsorption process was examined by two adsorption isotherms: Langmuir and Freundlich isotherms. The experimental data of biosorption process were analyzed using pseudo-first order, pseudo-second order kinetic models. The equilibrium biosorption isotherms showed that the three studied biosorbents possess high affinity and sorption capacity for Cu(II), Co(II) and Fe(III) ions. Rice husk showed more efficiency than palm leaf and water hyacinth. Adsorption of Cu(II) and Co(II) was more efficient in alkaline medium (pH 9) than neutral medium due to the high solubility of metal ion complexes. The metal removal efficiency of each biosorbent was correlated to its chemical structure. DTA studies showed formation of metal complex between the biosorbents and the metal ions. The obtained results showed that the tested biosorbents are efficient and alternate low-cost biosorbent for removal of heavy metal ions from aqueous media. PMID:26282929

  16. Physicochemical properties of cloned nucleocapsid parotein from HIV. Interactions with metal ions

    International Nuclear Information System (INIS)

    The nucleocapsid (NC) protein (p15) of the human immunodeficiency virus (HIV) has been cloned and overproduced (under the control of a phage T7 promoter) in soluble form in an Escherichia coli host. The soluble NC protein is a fusion protein containing 15 amino acids from the T7 gene 10 and 7 amino acids from the HIV p24 protein at the N-terminus to make a protein of 171 amino acids. The plasmid containing the fusion gene is designated p15DF. A homogeneous product has been isolated from the induced cells and, when isolated under aerobic conditions, contains 0.3-0.5 mol of Zn/mol of protein and has only 2 titratable SH groups. Reduction and refolding in the presence of Zn(II) yields a protein containing 2.0 mol of Zn/mol of protein and 6 titratable SH groups. On the other hand, if the cells are sonicated in 2 mM CdCl2 and purified at pH 5.0, an unoxidized protein containing 2 mol of Cd/mol of protein is obtained. The Cd(II) ions can be exchanged with Zn(II), Co(II), or 113Cd(II). 113CdNMR of the 113Cd(II)2NC protein shows two 113Cd NMR signals at 659 and 640 ppm, respectively, each integrating to ∼ Cd(II) ion. The downfield chemical shifts suggest coordination of each 113Cd(II) ion to 3 sulfur donor atoms. The spectroscopic data fully support the prediction that the NC protein binds metal ions to each of the tandem repeats of the -Cys-X2-Cys-X4-His-X4-Cys-sequence contained in the N-terminal half of the molecule. 113Cd NMR shows, however, that the sites are not identical

  17. Dispersive liquid-liquid microextraction for simultaneous determination of cadmium, cobalt, lead and nickel in water samples by inductively coupled plasma optical emission spectrometry

    International Nuclear Information System (INIS)

    We report on a new method for the dispersive liquid-liquid microextraction of Cd(II), Co(II), Pb(II) and Ni (II) from water samples prior to their simultaneous determination by inductively coupled plasma optical emission spectrometry (ICP-OES). The procedure is based on the injection of a ternary solvent system composed of appropriate quantities of extraction solvent (trichloroethylene), dispersive solvent (ethanol), and the chelating reagent 2-(2'-benzothiazolylazo)-p-cresol into the sample solution. The solution turns turbid immediately after injection, and the analytes are extracted into the droplets of the organic phase which was dried and dissolved in a mixture of Triton X-114, nitric acid, and ethanol. The metal ions in this mixture were quantified by ICP-OES. The detection limits under optimized conditions are 0.2, 0.3, 0.2 and 0.7 μg L-1 for Cd(II), Co(II), Pb(II) and Ni(II), respectively. The enrichment factors were also calculated for Cd (13), Co (11), Pb (11) and Ni (8). The procedure was applied to the determination of cadmium, cobalt, lead and nickel in certified reference material (waterway sediment) and water samples. (author)

  18. Separation Of Cadmium(II, Cobalt(II And Nickel(II By Transport Through Polymer Inclusion Membranes With Phosphonium Ionic Liquid As Ion Carrier / Separacja Jonów Kadmu(II, Kobaltu(II I Niklu(II W Procesie Transportu Przez Polimerowe Membrany Inkluzyjne Zawierające Fosfoniową Ciecz Jonową W Roli Przenośnika

    Directory of Open Access Journals (Sweden)

    Pospiech B.

    2015-12-01

    Full Text Available This paper presents study on the facilitated transport of cadmium(II, cobalt(II and nickel(II ions from aqueous chloride solutions through polymer inclusion membranes (PIMs with phosphonium ionic liquid. Cyphos IL 101 (trihexyl(tetradecyl phosphonium chloride was used as a selective carrier for synthesis of cellulose triacetate membranes containing o-nitrophenyl pentyl ether (ONPPE as a plasticizer. Effect of different parameters such as hydrochloric acid concentration in the source phase as well as ion carrier concentration in the polymer membrane on metal ions transport has been investigated. Cd(II was transported preferably from hydrochloric acid solutions containing Co(II and Ni(II through PIM containing 18.8 wt.% CTA and 26.0 wt.% Cyphos 101 and 55.1 wt.% ONPPE into 0.5 M HNO3 as the receiving phase. The obtained results suggest that there is a possibility of application of this membrane with Cyphos IL 101 as ion carrier for separation of Cd(II over Co(II and Ni(II from hydrochloric acid solutions.

  19. Synthesis and Characterization of Dinuclear Metal Complexes Stabilized by Tetradentate Schiff Base Ligands

    Directory of Open Access Journals (Sweden)

    Eid A. Abdalrazaq

    2010-01-01

    Full Text Available Problem statement: The synthesis, spectroscopic properties and theoretical calculations of acetylacetonimine and acetylacetanilidimine Schiff-base ligands, L1H and L2H, respectively and their dinuclear complexes of the type [M2LnCl2(H2O2], where n = 1 or 2, M = Co(II, Ni(II, Cu(II, Zn(II and Cd(II are described. Approach: The new tetradentate dianion Schiff base ligand which was used as stabilizers for the complexes were prepared by condensation of hydrazine with acetylacetone or acetylacetanilide. The dinuclear complexes of theses ligands were synthesized by treating an ethanolic solution of the prepared ligand with hydrated metal salts in molar ratio of 1:2 (L:M. Results: The ligand and their dinuclear metal complexes were characterized by CHN elemental analysis, FT-IR, UV-Vis, 1HNMR (for the ligands, conductivity, magnetic susceptibility and theoretical calculation by using MM2 modeling program. Conclusion: The reaction of these ligands in a 1:2 (L:M afford dinuclear M(II metal complexes with tetrahedral arrangement around Co(II, Zn(II and Cd(II and square planar around Ni(II and Cu(II.

  20. Removal of Industrial Pollutants From Wastewater's By Graft Copolymers

    International Nuclear Information System (INIS)

    Graft copolymers that obtained by radiation grafting of acrylic acid and acrylamide onto LDPE film were converted to N-hydroxy ethyl amide and hydroxamic acid derivatives respectively. The possible application for the different prepared chemical derivatives of LDPE graft copolymers in metal adsorption from solutions containing a single cation or simulated medium active waste has been investigated. The results showed that the adsorption of Cu(II) metal by different chemical derivatives was greatly affected by different factors such as graft yield, ph value, concentration of metal in the feed solution, immersion time and treatment temperature. The affinity of N-hydroxy ethyl amide derivative toward the different metals was found to be in the order of; Cu(II) >Pd(II) > Cd(II)> Co(II). However, for hydroxamic acid derivative , the affinity order was: Cd(II) > Cu(II) > Co(II). The ESR and IR analysis revealed that the metal ions are chelated through the lone pair of electrons on the -OH and -NH- groups forming a ring structure. The measured metal ion uptake from simulated medium active waste mixture by N-hydroxy ethyl amide derivative was found to follow the following order: Fe> U> Ni> Zr> Zn> Cr. On the other hand, the measured metal uptake by hydroxamic acid derivative was found to follow: Fe>U> Zr> Ca. It is concluded that the prepared grafted copolymers are of interest for metal chelation and could be applied in the field of waste treatment

  1. Synthesis, Characterization, Antimicrobial, DNA Cleavage, and Antioxidant Studies of Some Metal Complexes Derived from Schiff Base Containing Indole and Quinoline Moieties

    Directory of Open Access Journals (Sweden)

    Mahendra Raj Karekal

    2013-01-01

    Full Text Available A new Schiff base of 5-chloro-3-phenyl-1H-indole-2-carboxyhydrazide and 3-formyl-2-hydroxy-1H-quinoline (HL, and its Cu(II, Co(II, Ni(II, Zn(II, Cd(II, and Hg(II complexes have been synthesized and characterized in the light of microanalytical, IR, H1 NMR, UV-Vis, FAB-mass, ESR, XRD, and TGA spectral studies. The magnetic susceptibility measurements and low conductivity data provide evidence for monomeric and neutral nature of the complexes. On the basis of spectral studies and analytical data, it is evident that the Schiff base acts as tridentate ligand. The Cu(II, Co(II, and Ni(II complexes were octahedral, whereas Zn(II, Cd(II, and Hg(II complexes were tetrahedral in nature. The redox behavior of the Cu(II complex was investigated by electrochemical method using cyclic voltammetry. In order to evaluate the effect of metal ions upon chelation, both the ligand and its metal complexes were screened for their antibacterial and antifungal activities by minimum inhibitory concentration (MIC method. The DNA cleavage experiment performed using agarose gel electrophoresis method showed the cleavage of DNA by all the metal complexes. The free radical scavenging activity of newly synthesized compounds has been determined at a different concentration range by means of their interaction with the stable free radical 1,1-diphenyl-2-picrylhydrazyl (DPPH.

  2. Optimization of a new cloud point extraction procedure for the selective determination of trace amounts of total iron in some environmental samples

    OpenAIRE

    Duran, Celal; ÖZDEŞ, Duygu; KAYA, Elif ÇELENK; KANTEKİN, Halit

    2012-01-01

    A new, simple, and rapid cloud point extraction (CPE) procedure system, combined with flame atomic absorption spectrometry (FAAS), was developed for selective separation, preconcentration, and determination of trace amounts of total iron in some environmental samples. The complexing agent, N,N'-(2,2'-(ethane-1,2-diylbis(oxy)) bis(ethane-2,1-diyl))bis(2-chloroacetamide) (EDBOCA), is selective at pH 5.0 for only Fe(II) and Fe(III) ions in the presence of Cu(II), Pb(II), Cd(II)...

  3. Some derivatives of mesoionic 1,2,3,4-thiatriazolo-5-aminide interaction with metal ions

    International Nuclear Information System (INIS)

    Derivatives of mesoionic 1,2,3,4-thiatriazolo-5-aminides, 1 and 2, interact strongly with metal cations. The interactions with Pb(II), Fe(II), Fe(III), Cu(II) and Cd(II) were studied by means of UV-VIS spectroscopy, 1H' 113Cd NMR. The stoichiometry of the complex was determined by Job's method. Few species, being in equilibrium in the solution, are found in most cases. Some cations form insoluble materials with thiatriazoles 1 and 2. Ligand 2 interacts with cadmium acetate giving a 2:1 complex with a stability constant (4.3±0.5)x107 mol-2. (author)

  4. Structural, photophysical and magnetic properties of transition metal complexes based on the dipicolylamino-chloro-1,2,4,5-tetrazine ligand.

    Science.gov (United States)

    Nazarenko, Iuliia; Pop, Flavia; Sun, Qinchao; Hauser, Andreas; Lloret, Francesc; Julve, Miguel; El-Ghayoury, Abdelkrim; Avarvari, Narcis

    2015-05-21

    The ligand 3-chloro-6-dipicolylamino-1,2,4,5-tetrazine (Cl-TTZ-dipica) , prepared by the direct reaction between 3,6-dichloro-1,2,4,5-tetrazine and di(2-picolyl)-amine, afforded a series of four neutral transition metal complexes formulated as [Cl-TTZ-dipica-MCl2]2, with M = Zn(II), Cd(II), Mn(II) and Co(II), when reacted with the corresponding metal chlorides. The dinuclear structure of the isostructural complexes was disclosed by single crystal X-ray analysis, clearly indicating the formation of [M(II)-(μ-Cl)2M(II)] motifs and the involvement of the amino nitrogen atom in semi-coordination with the metal centers, thus leading to distorted octahedral coordination geometries. Moreover, the chlorine atoms, either coordinated to the metal or as a substituent on the tetrazine ring, engage respectively in specific anion-π intramolecular and intermolecular interactions with the electron-poor tetrazine units in the solid state, thus controlling the supramolecular architecture. Modulation of the emission properties is observed in the case of the Zn(II) and Cd(II) complexes when compared to the free ligand. A striking difference is observed in the magnetic properties of the Mn(II) and Co(II) complexes. An antiferromagnetic coupling takes place in the dimanganese(II) compound (J = -1.25 cm(-1)) while the Co(II) centers are ferromagnetically coupled in the corresponding complex (J = +0.55 cm(-1)), the spin Hamiltonian being defined as H = -JSA·SB. PMID:25868861

  5. Selective recognition by novel calix system: ICT based chemosensor for metal ions

    International Nuclear Information System (INIS)

    A new calix[4]pyrrole derivative bearing four dansyl groups through hydroxyl groups has been synthesized and duly characterized by FT-IR, NMR and ESI-MS. Tetra dansylated calix[4]pyrrole (TDCP) shows selective behavior for U(VI), Th(IV) and Fe(III) ions among all other metal ions, e.g. Li(I), Na(I), K(I), Ca(II), Ni(II), Cd(II), Cu(II), Zn(II), Pb(II), Hg(II) and Ag(I), in the absorption spectra as well as in the emission spectra. The absorption spectra show a bathochromic shift while the emission spectra along with red-shift exhibit quenching for U(VI), Th(IV) and Fe(III) ions. The binding constants, stoichiometry and quantum yields have been determined. The mechanism of quenching by Stern–Vohmer equation has also been discussed. -- highlights: • A new selective turn-off fluorescent sensor i.e. tetra dansylated calix[4]pyrrole (TDCP) was synthesized and characterized. • The sensor shows selective behavior for U(VI), Th(IV) and Fe(III) ions among various other metal ions. • The absorption spectra show a bathochromic shift while the emission spectra along with red-shift exhibit quenching for U(VI), Th(IV) and Fe(III) ions. • The sensor binds metal ions in 1:1 stoichiometry with good binding constant

  6. Metalloporphyrin intercalation in liposome membranes: ESR study

    OpenAIRE

    Man, Dariusz; Słota, Rudolf; Małgorzata A. Broda; Mele, Giuseppe; Li, Jun

    2010-01-01

    Liposomes characterized by membranes featuring diverse fluidity (liquid-crystalline and/or gel phase), prepared from egg yolk lecithin (EYL) and dipalmitoylphosphatidylcholine (DPPC), were doped with selected metalloporphyrins and the time-related structural and dynamic changes within the lipid double layer were investigated. Porphyrin complexes of Mg(II), Mn(III), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), and the metal-free base were embedded into the particular liposome systems and tested fo...

  7. Transient photo-induced phenomena in vacancy-controlled Co-Fe cyanides

    International Nuclear Information System (INIS)

    Time-resolved absorption spectra have been investigated for vacancy-controlled films of Na1.23Co[Fe(CN)6]0.92.9H2O and Na0.46Co[Fe(CN)6]0.713.8H2O, whose electronic configuration is CoIII - FeII and CoII - FeIII, respectively. In both the films, we observed absorption saturation at 2.3 eV, and ascribed it to formation of anti-state. We found that the charge dynamics is qualitatively different between two films.

  8. 2 : 2 Fe(III): ligand and "adamantane core" 4 : 2 Fe(III): ligand (hydr)oxo complexes of an acyclic ditopic ligand

    DEFF Research Database (Denmark)

    Ghiladi, Morten; Larsen, Frank B.; McKenzie, Christine J.; Søtofte, Inger; Tuchagues, Jean-Pierre

    -ray structure of the dinuclear complex [{( Hbpbp) Fe(mu-OH)}(2)](ClO4)(4) center dot 2C(3)H(6)O ( 1 center dot 2C(3)H(6)O) shows that only one of the metal-binding cavities of each ligand is occupied by an iron( III) atom and two [Fe(Hbpbp)](3+) units are linked together by two hydroxo bridging groups to form a......A bis-hydroxo-bridged diiron(III) complex and a bis-mu-oxo-bis-mu-hydroxo-bridged tetrairon( III) complex are isolated from the reaction of 2,6-bis((N, N'-bis-(2-picolyl) amino) methyl)-4-tert-butylphenol (Hbpbp) with iron perchlorate in acidic and neutral solutions respectively. The X...... bond lengths of the two different octahedral iron sites: Fe -mu-OH, 1.953( 5), 2.013( 5) angstrom and Fe-mu-O, 1.803( 5), 1.802( 5) angstrom. The difference in ligand environment is too small for allowing Mossbauer spectroscopy to distinguish between the two crystallographically independent Fe sites...

  9. Synthesis, structure, and properties of Cd(II) complexes generated from 2-phenylquinoline derivatives

    Science.gov (United States)

    Lei, Na; Ren, Qing-Ling; Liu, Ya-Ping; Li, Ji; Cong, Peng; Qin, Jie; Zhu, Hai-Liang

    2014-06-01

    Carboxyl functionalized 2-phenylquinoline derivatives, 2-(4-fluorophenyl)quinoline-4-carboxylic acid (HL1) and 2-(4-methoxyphenyl)quinoline-4-carboxylic acid (HL2) were synthesized. Further reaction of these ligands with Cd(CH3COO)2 afforded new cadmium complexes, [Cd2(L1)4(CH3OH)4]ṡ1.5H2O (1) and [Cd2(L2)4(CH3OH)4] (2), respectively. These complexes were characterized by elemental analysis, infrared spectra, and single-crystal X-ray diffraction. The fluorescent behavior and antibacterial (Escherichia coli, Pseudomonas aeruginosa, Bacillus subtilis and Staphylococcus aureus) activities of these compounds have been studied.

  10. Selective Solid-Phase Extraction of Cd(II) Using Double Imprinting Strategy

    OpenAIRE

    Birlik ÖZKÜTÜK, Ebru; Elif ÖZALP; Gülgün İŞLER; EMİR, Sibel DİLTEMİZ; ERSÖZ, Arzu

    2010-01-01

    Molecular imprinting technology is a strategy for producing chemically selective binding sites, which recognize a particular molecule, in a macroporous polymer matrix. Molecular recognition-based separation techniques have received much attention in various fields because of their high selectivity for target molecules. In this study, we have used a molecular imprinting approach to achieve specific metal binding utilizing 3-aminopropyltrimethoxysilane (APTS) as a metal-complexing ligand. In th...

  11. Sintesis dan Karakterisasi Ion Cd(II) Imprinted Polymer (Cd-IIP)

    OpenAIRE

    Taba, Paulina; Liong, Syarifuddin; Asmawati; Nur Basir, Djabal

    2013-01-01

    Ion Imprinted Polimer (IIP) dan Non Imprinted Polimer (NIP) telah disintesis melalui dua tahap. Tahap pertama adalah pengkompleksan Cd(NO3)2 dengan asam kuinaldat dengan rasio mol 1:1. Tahap kedua adalah pencampuran kompleks dengan asam salisilat-formaldehida (1:3) dengan HCl 2 M sebagai katalis. Polimerisasi dilakukan dengan menggunakan microwave pada suhu 140 oC selama 15 menit. Hasil dicuci dengan akuades dan dikeringkan dalam oven pada suhu 50 oC. Polimer dihaluskan (60???100 mesh), di...

  12. A zeolitic Cd(II) boron imidazolate framework with sensing and catalytic properties

    Science.gov (United States)

    Liu, Liyang; Wen, Tian; Chen, Shumei; Zhang, Jian

    2015-11-01

    A zeolitic Cd(II)-boron-imidazolate-framework (BIF-51) with ABW topology has been successfully synthesized by using pre-synthesized B(im)4 - ligands (im=imidazole) and [Cd(CH3COO)]- building units. Ag nanoparticles (NPs) were loaded in BIF-51 by the pore confinement effect of BIFs. Sensing property of nitrobenzene on BIF-51 and catalytic property of 4-nitrophenol (4-NP) on Ag@BIF-51 were also investigated.

  13. Syntheses and characterization of copper (II), nickel (II), iron (III), zinc (II), cadmium (II), zirconium (IV), molybdenum (V and VI) and uranium (VI) complexes of polystyrene supported resin containing the Schiff base derived from 3-formylsalicylic acid and O-aminophenol

    International Nuclear Information System (INIS)

    A new series of polystyrene supported metal complexes of the formulae PS-LCu.DMF, PS-LNi.3DMF, PS-LFeCl.2DMF, PS-LZn.DMF, Ps-Lcd.DMF, PS-LMoOCl.DMF, PS-LMoO2.DMF,PS-LZr(OH)2.2DMF and PS-LUO2.DMF (where Ps-L deprotonated polymer-anchored Schiff base) have been synthesized by the reaction of metal salt/metal complex with the chelating resin containing the Schiff base derived from 3-formylsalicylic acid and o-aminophenol. The polymer supported metal complexes have been characterized by elemental analysis, IR, electronic and ESR spectra and magnetic susceptibility measurements. The geometry of the complexes are comparable with the corresponding metal complexes of non-anchored ligands. The polymer supported Cu(II) complex is square planar, Zn(II) and Cd(II) complexes are tetrahedral, Ni(II), Fe(III), U(VI) and Mo(V and VI) complexes are octahedral and zirconium(IV) complex is pentagonal bipyramidal. The polymer-anchored Ni(II), Cu(II), Fe(III) and Mo(V) complexes are paramagnetic while the Zn(II), Cd(II), Zr(IV), U(VI) and Mo(VI) complexes are diamagnetic. (author). 33 refs

  14. Selective separation of uranium(VI) on a chelating styrene-DVB based resin containing quinaldinic acid amide group

    International Nuclear Information System (INIS)

    A new chelating styrene-DVB based resin containing quinaldinic acid amide functional group, has been synthesised and characterised. The sorption patterns of Na(I), K(I), Be(II), Ca(II), Mg(II), Zn(II), Cd(II), Cu(II), Pb(II), Ni(II), Bi(III), Fe(III), Ti(IV) and U(VI) have been studied as a function of pH. The resin sorbs U(VI) over a wide range of pH (1.0 to 4.0) with a maximum sorption of 0.32 mmol/g at pH 3.5 to 4.0. Zn(II), Cd(II), Cu(II), Na(II), Pb(II), Fe(III) and Ti(IV) are also sorbed to different extents by the resin while Na(I), K(I), Be(II), Ca(II), Mg(II) and Bi(III) are not sorbed. Conditions for separation of U(VI) from these metal ions have been identified. The eluting agent used for U(VI) is 3 N HNO3 and the recovery recorded is about 99.9 per cent (author). 12 refs., 3 tabs

  15. Inhibition effects in the partial oxidation of cyclohexane on polymer supported Co(II catalysts

    Directory of Open Access Journals (Sweden)

    MAJA ODOVIC

    2005-02-01

    Full Text Available Polymer supported catalysts with different contents of metal ions where synthesized by wet impregnation of the degassed support from ethanolic solutions of cobalt(II nitrate. Amacroreticular copolymer of poly-4-vinylpyridine with divinylbenzene was used as the support. The prepared catalysts were tested in the partial oxidation of cyclohexane to cyclohexanol and cyclohexanone. Activity tests were performed in a stainless steel, laboratory scale, stirred autoclave, in the semi batch regime under isothermal and non-isothermal conditions. Isothermal experiments where performed at 170 °C for 120 min. In the non-isothermal conditions. isothermal experiments where performed at 170 °C for 120 min. In the non-isothermal experiments, a constant heating rate of 0.3 degree/min was used in the range between 110 °C and 170 °C. Non-linear, least-squares analysis with the simplex optimization method and numerical simulation of the reaction model in each iterative step was used for the kinetic characterization of the process in a non-stationary, semi-batch regime. Apparent rate constants were obtained as an invariant measure of the catalytic system. Anon-linear effect of the content of metal ions on the reaction rate and on the ratio of the yield of the products was observed, which is attributed to a complex interactions between the reaction medium and the heterogeneous catalyst, including a catalyst-inhibition effect.

  16. Co(II) complexes of amino acids and peptides in aqueous solution studied by 170 NMR

    International Nuclear Information System (INIS)

    Structural, dynamic and kinetic 170 NMR investigations of the complexation of metal ions with amino acids and peptides were performed in Glicine, proling cyclo(Ala '1'70-Ala), cyclo-(Gly170-Pro) and cyclo(Pro170-Gly). The 170 carboxyl and carbonylsignals of paramagnetic complexes with amino acids were observed and allowed for the determinatio, in several cases, of the stoichiometry of the ocmplexes formed and the kinetic and thermodynamic parameters characterizing ligand exchange. It was found that the paramagnetic ions bind to the oxygen of the peptide carboxyl group. (H.W.). 25 refs.; 10 figs.; 3 tabs

  17. Peculiarities of MCD C-term saturation behavior of the exchange coupled Co(II) dimers

    International Nuclear Information System (INIS)

    Graphical abstract: The change of sign of the MCD signal with temperature and magnetic field increase can take place. The origin of this peculiarity is explained by the strong orbital contribution. Highlights: → MCD C-term saturation behavior of the exchange coupled cobalt dimer. → Strong orbital contribution to the magneto-optical behavior. → Change of sign of the MCD signal with temperature and magnetic field increase. - Abstract: The MCD C-term saturation behavior of the exchange coupled octahedrally coordinated cobalt dimers is studied for different types of distortion of the local surrounding of each interacting ion. It was found that in the case of antiferromagnetic exchange interaction the change of sign of the MCD signal with temperature and magnetic field increase can take place. This signal behavior is not the result of overlapping of different electronic transitions and it is characteristic of an individual MCD line. The origin of this magneto-optical behavior is explained by the strong contribution coming from the unquenched orbital angular momenta of interacting cobalt ions. The found peculiarity is inherent to complexes composed of nonequivalent cobalt ions as well as to the dimeric complexes with the equivalent Co ions with nonparallel local axes.

  18. Tuning affinity and reversibility for O2 binding in dinuclear Co(II) complexes

    DEFF Research Database (Denmark)

    Vad, Mads Sørensen; Johansson, Frank Bartnik; Seidler-Egdal, Rune Kirk;

    2013-01-01

    The O2 binding affinity of a series of dicobalt(II) complexes can be tuned between p(O2)50% = 2.3 × 10−3 and 700 × 10−3 atm at 40 °C by varying the number of H and Cl atoms in the bridging acetato ligands of [Co2(bpbp)(CH(3−n)ClnCO2)(CH3CN)2]2+, where bpbp− = 2,6-bis(N,N-bis(2-pyridylmethyl......)aminomethyl)-4- tert-butylphenolate and n = {0, 1, 2, 3}. O2 binds most strongly to the deoxy complex containing the acetato bridge and the O2 affinity decreases linearly as the number of Cl atoms is increased from 0 to 3 in [Co2(bpbp)(O2)(CH3CO2)]2+, [Co2(bpbp)(O2)(CH2ClCO2)]2+, [Co2(bpbp)(O2)(CHCl2CO2)]2+ and...... acetato-bridged complex to 696 mV for the trichloroacetato-bridged system. Despite the clear difference in reactivity in solution, there are no clear trends which can be correlated to O2 affinity in the O–O bond lengths in the X-ray crystal structures at 180 K (1.415(4)–1.424(2) Å) or in the frequencies...

  19. Synthesis, spectroscopic, cytotoxic aspects and computational study of N-(pyridine-2-ylmethylene)benzo[d]thiazol-2-amine Schiff base and some of its transition metal complexes

    Science.gov (United States)

    Abd El-Aziz, Dina M.; Etaiw, Safaa Eldin H.; Ali, Elham A.

    2013-09-01

    N-(pyridine-2-ylmethylene)benzo[d]thiazol-2-amine Schiff base (L) and its Cu(II), Fe(III), Co(II), Ni(II) and Zn(II) complexes were synthesized and characterized by a set of chemical and spectroscopic measurements using elemental analysis, electrical conductance, mass spectra, magnetic susceptibility and spectral techniques (IR, UV-Vis, 1H NMR). Elemental and mass spectrometric data are consistent with the proposed formula. IR spectra confirm the bidentate nature of the Schiff base ligand. The octahedral geometry around Cu(II), Fe(III), Ni(II) and Zn(II) as well as tetrahedral geometry around Co(II) were suggested by UV-Vis spectra and magnetic moment data. The thermal degradation behavior of the Schiff base and its complexes was investigated by thermogravimetric analysis. The structure of the Schiff base and its transition metal complexes was also theoretically studied using molecular mechanics (MM+). The obtained structures were minimized with a semi-empirical (PM3) method. The in vitro antitumor activity of the synthesized compounds was studied. The Zn-complex exhibits significant decrease in surviving fraction of breast carcinoma (MCF 7), liver carcinoma (HEPG2), colon carcinoma (HCT116) and larynx carcinoma (HEP2) cell lines human cancer.

  20. Spectral, thermal and electrochemical investigation of carbohydrazone derived ionophore as Fe(III) ion selective electrode

    Science.gov (United States)

    Chandra, Sulekh; Deepshikha; Sarkar, Anjana

    2013-04-01

    Dibenzoylmethane bis(carbohydrazone) (BMBC) has been synthesized and structurally characterized on the basis of IR, 1H NMR, mass, UV spectra and thermogravimetric analyses. BMBC has been analysed electrochemically and explored as new N, N Schiff base. It plays the role of an excellent ion carrier in the construction of iron(III) ion selective membrane sensor. This sensor shows very good selectivity and sensitivity towards iron ion over a wide variety of cations, including alkali, alkaline earth, transition and heavy metal ions. The response mechanism was discussed in the view of UV-spectroscopy and Electrochemical Impedance Spectroscopy (EIS). The proposed sensor was successfully used for the determination of iron in different samples.