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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).

    PubMed

    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. Calix receptor edifice; scrupulous turn off fluorescent sensor for Fe(III), Co(II) and Cu(II).

    PubMed

    Bhatt, Keyur D; Gupte, Hrishikesh S; Makwana, Bharat A; Vyas, Disha J; Maity, Debdeep; Jain, Vinod K

    2012-11-01

    Novel Supramolecular fluorescence receptor derived from calix-system i.e. calix[4]resorcinarene bearing dansylchloride as fluorophore was designed and synthesized. The compound was purified by column chromatography and characterized by elemental analysis, NMR and Mass spectroscopy. Tetradansylated calix[4] resorcinarene (TDCR) shows a boat conformation with C(2)v symmetry. The complexation behaviour of metal cations [Ag(I), Cd(II), Co(II), Fe(III), Hg(II), Cu(II), Pb(II), Zn(II), U(VI) (1 × 10(-4) M)] with tetra dansylated calix[4]resorcinarene (1 × 10(-6) M) was studied by spectophotometry and spectrofluorometry. Red shift in the absorption spectra led us to conclude that there is strong complexation Fe(III), Co(II) and Cu(II) with TDCR. These metal cations also produce quenching with red shifts in the emission spectra. The maximum quenching in emission intensity was observed in the case of Fe(III) and its binding constant was also found to be significantly higher than that of Co(II) and Cu(II). Quantum yield of metal complexes of Fe(III) was found to be lower in comparison with Co(II) and Cu(II) complexes. Stern Volmer analysis indicates that the mechanism of fluorescence quenching is either purely dynamic, or purely static. PMID:22739703

  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

    NASA Astrophysics Data System (ADS)

    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. 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.

    PubMed

    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

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

    PubMed Central

    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

  6. Chelating agent free-solid phase extraction (CAF-SPE) of Co(II), Cu(II) and Cd(II) by new nano hybrid material (ZrO2/B2O3).

    PubMed

    Yalçinkaya, Ozcan; Kalfa, Orhan Murat; Türker, Ali Rehber

    2011-11-15

    New nano hybrid material (ZrO(2)/B(2)O(3)) was synthesized and applied as a sorbent for the separation and/or preconcentration of Co(II), Cu(II) and Cd(II) in water and tea leaves prior to their determination by flame atomic absorption spectrometry. Synthesized nano material was characterized by scanning electron microscope, transmission electron microscope and X-ray diffraction. The optimum conditions for the quantitative recovery of the analytes, including pH, eluent type and volume, flow rate of sample solution were examined. The effect of interfering ions was also investigated. Under the optimum conditions, adsorption isotherms and adsorption capacities have been examined. The recoveries of Co(II), Cu(II) and Cd(II) were 96 ± 3%, 95 ± 3%, 98 ± 4% at 95% confidence level, respectively. The analytical detection limits for Co(II), Cu(II), and Cd(II) were 3.8, 3.3, and 3.1 μg L(-1), respectively. The reusability and adsorption capacities (32.2 mg g(-1) for Co, 46.5 mg g(-1) for Cu and 109.9 mg g(-1) for Cd) of the sorbent were found as satisfactory. The accuracy of the method was confirmed by analyzing certified reference material (GBW-07605 Tea leaves) and spiked real samples. The method was applied for the determination of analytes in tap water and tea leaves. PMID:21889841

  7. Synthesis, magnetism and spectral studies of six defective dicubane tetranuclear {M4O6} (M = Ni(II), Co(II), Zn(II)) and three trinuclear Cd(II) complexes with polydentate Schiff base ligands.

    PubMed

    Jiang, Lin; Zhang, Dong-Yan; Suo, Jing-Jing; Gu, Wen; Tian, Jin-Lei; Liu, Xin; Yan, Shi-Ping

    2016-06-21

    A series of Ni(II), Co(II), Zn(II) and Cd(II) complexes with polytopic Schiff base ligands have been synthesized. The single-crystal X-ray crystallography results show that tetranuclear complexes have common face-shared defective dicubane cores, whereas trinuclear Cd(II) complexes are almost linear entities. Synthesis methods (solvent evaporation and hydrothermal synthesis), reaction conditions (pH, solvents and dosage) and coligands (azide, methanol, chloride and acetate) play vital roles in determining the final structure of the complexes and therefore their magnetic properties. In complexes , the terminal and central M(2+) ions are connected through mixed bridges, μ-phenoxido/μ1,1,1-X and μ-Oalphatic/μ1,1,1-X, while central two M(2+) ions are linked by double bridges, μ1,1,1-X (X = azido and methoxido groups for and respectively). For complex , two central Ni(II) ions are connected through two μ1,1,1-N3(-) which is relatively less reported. For complexes , there are two kinds of Cd(II), the centre Cd(II) ions are eight-coordinated with triangle dodecahedral geometries, while the two side Cd(II) ions are six-coordinated with trigonal prism geometries using chlorides or acetates as terminal ligands. Magnetic susceptibility measurements (χM) for compounds have been performed, and they reveal predominant ferromagnetic exchange interactions in Co(II) and Ni(II) tetramers. The photoluminescence studies show that the Zn(II) complex and three Cd(II) complexes have strong fluorescence, and the lifetimes are measured to be in the 10(2) nanosecond timescale. PMID:27230103

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

    NASA Astrophysics Data System (ADS)

    Xin, Ling-Yun; Liu, Guang-Zhen; Ma, Lu-Fang; Wang, Li-Ya

    2013-10-01

    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.

  9. Synthesis, characterization and in vitro anticancer activity of 18-membered octaazamacrocyclic complexes of Co(II), Ni(II), Cd(II) and Sn(II)

    NASA Astrophysics Data System (ADS)

    Kareem, Abdul; Zafar, Hina; Sherwani, Asif; Mohammad, Owais; Khan, Tahir Ali

    2014-10-01

    An effective series of 18 membered octaazamacrocyclic complexes of the type [MLX2], where X = Cl or NO3 have been synthesized by template condensation reaction of oxalyl dihydrazide with dibenzoylmethane and metal salt in 2:2:1 molar ratio. The formation of macrocyclic framework, stereochemistry and their overall geometry have been characterized by various physico-chemical studies viz., elemental analysis, electron spray ionization-mass spectrometry (ESI-MS), I.R, UV-Vis, 1H NMR, 13C NMR spectroscopy, X-ray diffraction (XRD) and TGA/DTA studies. These studies suggest formation of octahedral macrocyclic complexes of Co(II), Ni(II), Cd(II) and Sn(II). The molar conductance values suggest nonelectrolytic nature for all the complexes. Thermogravimatric analysis shows that all the complexes are stable up to 600 °C. All these complexes have been tested against different human cancer cell lines i.e. human hepatocellular carcinoma (Hep3B), human cervical carcinoma (HeLa), human breast adenocarcinoma (MCF7) and normal cells (PBMC). The newly synthesized 18-membered octaazamacrocyclic complexes during in vitro anticancer evaluation, displayed moderate to good cytotoxicity on liver (Hep3B), cervical (HeLa) and breast (MCF7) cancer cell lines, respectively. The most effective anticancer cadmium complex (C34H28N10CdO10) was found to be active with IC50 values, 2.44 ± 1.500, 3.55 ± 1.600 and 4.82 ± 1.400 in micro-molar on liver, cervical and breast cancer cell lines, respectively.

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

    SciTech Connect

    Xin, Ling-Yun; Liu, Guang-Zhen; Ma, Lu-Fang; Wang, Li-Ya

    2013-10-15

    A non-coplanar dicarboxylate ndca (H{sub 2}ndca=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)(H{sub 2}O)]{sub n} (1), ([Co(ndca)(bpe)(H{sub 2}O)]·H{sub 2}O){sub n} (2), [Co(ndca)(bpa){sub 0.5}(H{sub 2}O)]{sub n} (3), [Cd(ndca)(bpe)(H{sub 2}O)]{sub n} (4), ([Cd(ndca)(bpa)(H{sub 2}O)]·0.5H{sub 2}O){sub n} (5), and ([Cd(ndca)(bpp) (H{sub 2}O)]·H{sub 2}O){sub 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.

  11. 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

    NASA Astrophysics Data System (ADS)

    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.

  12. 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

    NASA Astrophysics Data System (ADS)

    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.

  13. 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.

    PubMed

    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

  14. Co(II), Cd(II), Hg(II) and U(VI)O2 complexes of o-hydroxyacetophenone[N-(3-hydroxy-2-naphthoyl)] hydrazone: Physicochemical study, thermal studies and antimicrobial activity

    NASA Astrophysics Data System (ADS)

    Zaky, R. R.; Yousef, T. A.; Ibrahim, K. M.

    2012-11-01

    The o-Hydroxy acetophenone [N-(3-hydroxy-2-naphthoyl)] hydrazone (H2o-HAHNH) has been prepared and its structure is confirmed by elemental analysis, IR, 1H NMR and 13C NMR spectroscopy. It has been used to produce diverse complexes with Co(II), Cd(II), Hg(II) and U(VI)O2 ions. The isolated complexes have been investigated by elemental analysis, magnetic measurements, molar conductivity, thermal (TG, DTG) and spectral (1H NMR, 13C NMR, IR, UV-visible, MS) studies. Infrared spectra suggested H2o-HAHNH acts as a bidentate and/or tridentate ligand. The electronic spectrum of [Co(Ho-HAHNH)2] complex as well as its magnetic moments suggesting octahedral geometry around Co(II) center. The TG analyses suggest high stability for most complexes followed by thermal decomposition in different steps. Moreover, the kinetic and thermodynamic parameters (Ea, A, ΔH∗, ΔS∗ and ΔG∗) for the different decomposition steps of the [Co(Ho-HAHNH)2] and [Cd(Ho-HAHNH)2] complexes were calculated using the Coats-Redfern and Horowitz-Metzger methods. Moreover, the antibacterial and antifungal activities of the isolated compounds were studied using a wide spectrum of bacterial and fungal strains.

  15. 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

    NASA Astrophysics Data System (ADS)

    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.

  16. Synthesis, magnetic, spectral, and antimicrobial studies of Cu(II), Ni(II) Co(II), Fe(III), and UO 2(II) complexes of a new Schiff base hydrazone derived from 7-chloro-4-hydrazinoquinoline

    NASA Astrophysics Data System (ADS)

    El-Behery, Mostafa; El-Twigry, Haifaa

    2007-01-01

    A new hydrazone ligand, HL, was prepared by the reaction of 7-chloro-4-hydrazinoquinoline with o-hydroxybenzaldehyde. The ligand behaves as monoprotic bidentate. This was accounted for as the ligand contains a phenolic group and its hydrogen atom is reluctant to be replaced by a metal ion. The ligand reacted with Cu(II), Ni(II), Co(II), Fe(III), and UO 2(II) ions to yield mononuclear complexes. In the case of Fe(III) ion two complexes, mono- and binuclear complexes, were obtained in the absence and presence of LiOH, respectively. Also, mixed ligand complexes were obtained from the reaction of the metal cations Cu(II), Ni(II) and Fe(III) with the ligand (HL) and 8-hydroxyquinoline (8-OHqu) in the presence of LiOH, in the molar ratio 1:1:1:1. It is clear that 8-OHqu behaves as monoprotic bidentate ligand in such mixed ligand complexes. The ligand, HL, and its metal complexes were characterized by elemental analyses, IR, UV-vis, mass, and 1H NMR spectra, as well as magnetic moment, conductance measurements, and thermal analyses. All complexes have octahedral configurations except Cu(II) complex which has an extra square-planar geometry, while Ni(II) mixed complex has also formed a tetrahedral configuration and UO 2(II) complex which formed a favorable pentagonal biprymidial geometry. Magnetic moment of the binuclear Fe(III) complex is quite low compared to calculated value for two iron ions complex and thus shows antiferromagnetic interactions between the two adjacent ferric ions. The HL and metal complexes were tested against one stain Gram positive bacteria ( Staphylococcus aureus), Gram negative bacteria ( Escherichia coli), and fungi ( Candida albicans). The tested compounds exhibited higher antibacterial acivities.

  17. A novel cellulose-dioctyl phthate-baker's yeast biosorbent for removal of Co(II), Cu(II), Cd(II), Hg(II) and Pb(II).

    PubMed

    Mahmoud, Mohamed E; Yakout, Amr A; Abed El Aziz, Marwa T; Osman, Maher M; Abdel-Fattah, Tarek M

    2015-01-01

    In this work, dioctyl phthalate (Dop) was used as a highly plasticizing material to coat and link the surface of basic cellulose (Cel) with baker's yeast for the formation of a novel modified cellulose biosorbent (Cel-Dop-Yst). Characterization was accomplished by Fourier Transform Infrared Spectroscopy (FT-IR), Thermogravimetric analysis (TGA) and Scanning Electron Microscope (SEM) measurements. The feasibility of using Cel-Dop-Yst biosorbent as an efficient material for removal of Co(II), Cu(II), Cd(II), Hg(II) and Pb(II) ions was explored using the batch equilibrium technique along with various experimental controlling parameters. The optimum pH values for removal of these metal ions were characterized in the range of 5.0-7.0. Cel-Dop-Yst was identified as a highly selective biosorbent for removal of the selected divalent metal ions. The Cel-Dop-Yst biosorbent was successfully implemented in treatment and removal of these divalent metal ions from industrial wastewater, sea water and drinking water samples using a multistage microcolumn technique. PMID:26121022

  18. 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

    NASA Astrophysics Data System (ADS)

    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.

  19. Unusual Recognition and Separation of Hydrated Metal Sulfates [M2(μ-SO4)2(H2O)n, M = Zn(II), Cd(II), Co(II), Mn(II)] by a Ditopic Receptor.

    PubMed

    Ghosh, Tamal Kanti; Dutta, Ranjan; Ghosh, Pradyut

    2016-04-01

    A ditopic receptor L1, having metal binding bis(2-picolyl) donor and anion binding urea group, is synthesized and explored toward metal sulfate recognition via formation of dinuclear assembly, (L1)2M2(SO4)2. Mass spectrometric analysis, (1)H-DOSY NMR, and crystal structure analysis reveal the existence of a dinuclear assembly of MSO4 with two units of L1. (1)H NMR study reveals significant downfield chemical shift of -NH protons of urea moiety of L1 selectively with metal sulfates (e.g., ZnSO4, CdSO4) due to second-sphere interactions of sulfate with the urea moiety. Variable-temperature (1)H NMR studies suggest the presence of intramolecular hydrogen bonding interaction toward metal sulfate recognition in solution state, whereas intermolecular H-bonding interactions are observed in solid state. In contrast, anions in their tetrabutylammonium salts fail to interact with the urea -NH probably due to poor acidity of the tertiary butyl urea group of L1. Metal sulfate binding selectivity in solution is further supported by isothermal titration calorimetric studies of L1 with different Zn salts in dimethyl sulfoxide (DMSO), where a binding affinity is observed for ZnSO4 (Ka = 1.23 × 10(6)), which is 30- to 50-fold higher than other Zn salts having other counteranions in DMSO. Sulfate salts of Cd(II)/Co(II) also exhibit binding constants in the order of ∼1 × 10(6) as in the case of ZnSO4. Positive role of the urea unit in the selectivity is confirmed by studying a model ligand L2, which is devoid of anion recognition urea unit. Structural characterization of four MSO4 [M = Zn(II), Cd(II), Co(II), Mn(II)] complexes of L1, that is, complex 1, [(L1)2(Zn)2(μ-SO4)2]; complex 2, [(L1)2(H2O)2(Cd)2(μ-SO4)2]; complex 3, [(L1)2(H2O)2(Co)2(μ-SO4)2]; and complex 4, [(L1)2(H2O)2(Mn)2(μ-SO4)2], reveal the formation of sulfate-bridged eight-membered crownlike binuclear complexes, similar to one of the concentration-dependent dimeric forms of MSO4 as observed in solid state

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

    NASA Astrophysics Data System (ADS)

    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

  1. Synthesis, spectral characterization, structural investigation and antimicrobial studies of mononuclear Cu(II), Ni(II), Co(II), Zn(II) and Cd(II) complexes of a new potentially hexadentate N2O4 Schiff base ligand derived from salicylaldehyde

    NASA Astrophysics Data System (ADS)

    Keypour, Hassan; Shayesteh, Maryam; Rezaeivala, Majid; Chalabian, Firoozeh; Elerman, Yalcin; Buyukgungor, Orhan

    2013-01-01

    A new potentially hexadentate N2O4 Schiff base ligand, H2L derived from condensation reaction of an aromatic diamine and salicylaldehyde, and its metal complexes were characterized by elemental analyses, IR, UV-Vis, EI-MS, 1H and 13C NMR spectra, as well as conductance measurements. It has been originated that the Schiff base ligand with Cu(II), Ni(II), Co(II), Cd(II) and Zn(II) ions form mononuclear complexes on 1:1 (metal:ligand) stoichiometry. The conductivity data confirm the non-electrolytic nature of the complexes. Also the crystal structures of the complexes [ZnL] and [CoL] have also been determined by using X-ray crystallographic technique. The Zn(II) and Co(II) complexes show a tetrahedral configuration. Electronic absorption spectra of the Cu(II) and Ni(II) complexes suggest a square-planar geometry around the central metal ion. The synthesized compounds have antibacterial activity against the three Gram-positive bacteria: Bacillus cereus, Enterococcus faecalis and Listeria monocytogenes and also against the three Gram-negative bacteria: Salmonella paraB, Citrobacter freundii and Enterobacter aerogenes. The results showed that in some cases the antibacterial activity of complexes were more than nalidixic acid and amoxicillin as standards.

  2. Highly stable water dispersible calix[4]pyrrole octa-hydrazide protected gold nanoparticles as colorimetric and fluorometric chemosensors for selective signaling of Co(II) ions

    NASA Astrophysics Data System (ADS)

    Bhatt, Keyur D.; Vyas, Disha J.; Makwana, Bharat A.; Darjee, Savan M.; Jain, Vinod K.

    2014-03-01

    Water dispersible stable gold nanoparticles (AuNps) have been synthesized by using calix[4]pyrrole octa-hydrazide (CPOH) as a reducing as well as stabilizing agent. CPOH-AuNps have been characterized by surface plasmon resonance, particle size analyzer and transmission electron microscopy. CPOH-AuNps are water dispersible, highly stable for more than 150 days at neutral pH with a size of less than 10 nm and zeta potential of 15 ± 2 MeV. Ion sensing property of CPOH-AuNps has been investigated for various metal ions Pb(II), Cd(II), Mn(II), Fe(III), Ni(II), Zn(II), Hg(II), Co(II) and Cu(II) by colorimetry and spectrofluorimetry. Among all the metal ions investigated, only Co(II) ions gives sharp colour change from ruby red to blue and is easily detectable by naked-eye. CPOH-AuNps being fluorescent in nature also shows great sensitivity and selectivity for Co(II) ions. Co(II) ions can be selectively detected at very low concentration level of 1 nM in a facile way of fluorescence quenching.

  3. 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

    NASA Astrophysics Data System (ADS)

    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.

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

    NASA Astrophysics Data System (ADS)

    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.

  5. 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.

    PubMed

    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

  6. Ligational behaviour of lomefloxacin drug towards Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Th(IV) and UO 2(VI) ions: Synthesis, structural characterization and biological activity studies

    NASA Astrophysics Data System (ADS)

    El-Halim, Hanan F. Abd; Mohamed, Gehad G.; El-Dessouky, Maher M. I.; Mahmoud, Walaa H.

    2011-11-01

    Nine new mononuclear Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Th(IV) and UO 2(VI) complexes of lomefloxacin drug were synthesized. The structures of these complexes were elucidated by elemental analyses, IR, XRD, UV-vis, 1H NMR as well as conductivity and magnetic susceptibility measurements and thermal analyses. The dissociation constants of lomefloxacin and stability constants of its binary complexes have been determined spectrophotometrically in aqueous solution at 25 ± 1 °C and at 0.1 M KNO 3 ionic strength. The discussion of the outcome data of the prepared complexes indicate that the lomefloxacin ligand behaves as a neutral bidentate ligand through OO coordination sites and coordinated to the metal ions via the carbonyl oxygen and protonated carboxylic oxygen with 1:1 (metal:ligand) stoichiometry for all complexes. The molar conductance measurements proved that the complexes are electrolytes. The powder XRD study reflects the crystalline nature for the investigated ligand and its complexes except Mn(II), Zn(II) and UO 2(II). The geometrical structures of these complexes are found to be octahedral. The thermal behaviour of these chelates is studied where the hydrated complexes lose water molecules of hydration in the first steps followed by decomposition of the anions, coordinated water and ligand molecules in the subsequent steps. The activation thermodynamic parameters are calculated using Coats-Redfern and Horowitz-Metzger methods. A comparative study of the inhibition zones of the ligand and its metal complexes indicates that metal complexes exhibit higher antibacterial effect against one or more bacterial species than the free LFX ligand. The antifungal and anticancer activities were also tested. The antifungal effect of almost metal complexes is higher than the free ligand. LFX, [Co(LFX)(H 2O) 4]·Cl 2 and [Zn(LFX)(H 2O) 4]·Cl 2 were found to be very active with IC50 values 14, 11.2 and 43.1, respectively. While, other complexes had

  7. Ten metal complexes of vitamin B3/niacin: Spectroscopic, thermal, antibacterial, antifungal, cytotoxicity and antitumor studies of Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Pd(II), Cd(II), Pt(IV) and Au(III) complexes

    NASA Astrophysics Data System (ADS)

    Al-Saif, Foziah A.; Refat, Moamen S.

    2012-08-01

    Ten coordination compounds, namely Mn(NA)2Cl2·4H2O (1), Fe(NA)Cl3(H2O)2 (2), Co(NA)2(NO3)2·6H2O (3), Ni(NA)Cl2·5H2O (4), Cu(NA)Cl2·3H2O (5), Zn(NA)(NO3)2·H2O (6), Pd(NA)2Cl2·H2O (7), Cd(NA)Cl2·H2O (8), Pt(NA)2Cl4·5H2O (9) and Au(NA)Cl3 (10) were obtained by the reactions of the corresponding transition metal salts with vitamin B3/niacin (NA) in the presence of 1:4 (v:v) distilled water: methanol solvent at 70 °C for about 30 min, and their suggested structures were determined by elemental analyses, molar conductivity, (infrared, UV-vis) spectra, effective magnetic moment in Bohr magnetons, electron spin resonance (ESR), thermal analysis (TG), X-ray powder diffraction (XRD) as well as scanning electron microscopy (SEM). The results revealed that in complexes 1, 3, 7, and 9 both of two NA ligand coordinates one metal ion to form four or six coordinated structures, while in compound 10, one NA ligand coordinate to Au+++ ion to form a square-planar geometry with N-bonded pyridine ligand is suggested, and (2, 4, 5, 6 and, 8) complexes have 1:1 structures. Antimicrobial and antitumor activities were assessment against some kind of (G+ and G-) bacteria, fungi and breast carcinoma cells (MCF-7-cell line).

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

    PubMed

    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

    USGS Publications Warehouse

    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

  10. Reduction of Fe(III), Mn(IV), and Toxic Metals at 100°C by Pyrobaculum islandicum

    PubMed Central

    Kashefi, Kazem; Lovley, Derek R.

    2000-01-01

    It has recently been noted that a diversity of hyperthermophilic microorganisms have the ability to reduce Fe(III) with hydrogen as the electron donor, but the reduction of Fe(III) or other metals by these organisms has not been previously examined in detail. When Pyrobaculum islandicum was grown at 100°C in a medium with hydrogen as the electron donor and Fe(III)-citrate as the electron acceptor, the increase in cell numbers of P. islandicum per mole of Fe(III) reduced was found to be ca. 10-fold higher than previously reported. Poorly crystalline Fe(III) oxide could also serve as the electron acceptor for growth on hydrogen. The stoichiometry of hydrogen uptake and Fe(III) oxide reduction was consistent with the oxidation of 1 mol of hydrogen resulting in the reduction of 2 mol of Fe(III). The poorly crystalline Fe(III) oxide was reduced to extracellular magnetite. P. islandicum could not effectively reduce the crystalline Fe(III) oxide minerals goethite and hematite. In addition to using hydrogen as an electron donor for Fe(III) reduction, P. islandicum grew via Fe(III) reduction in media in which peptone and yeast extract served as potential electron donors. The closely related species P. aerophilum grew via Fe(III) reduction in a similar complex medium. Cell suspensions of P. islandicum reduced the following metals with hydrogen as the electron donor: U(VI), Tc(VII), Cr(VI), Co(III), and Mn(IV). The reduction of these metals was dependent upon the presence of cells and hydrogen. The metalloids arsenate and selenate were not reduced. U(VI) was reduced to the insoluble U(IV) mineral uraninite, which was extracellular. Tc(VII) was reduced to insoluble Tc(IV) or Tc(V). Cr(VI) was reduced to the less toxic, less soluble Cr(III). Co(III) was reduced to Co(II). Mn(IV) was reduced to Mn(II) with the formation of manganese carbonate. These results demonstrate that biological reduction may contribute to the speciation of metals in hydrothermal environments and could

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

    PubMed

    Ruecha, Nipapan; Rodthongkum, Nadnudda; Cate, David M; Volckens, John; Chailapakul, Orawon; Henry, Charles S

    2015-05-18

    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 standard addition method. PMID:25910444

  12. Highly efficient removal of heavy metals by polymer-supported nanosized hydrated Fe(III) oxides: behavior and XPS study.

    PubMed

    Pan, Bingjun; Qiu, Hui; Pan, Bingcai; Nie, Guangze; Xiao, Lili; Lv, Lu; Zhang, Weiming; Zhang, Quanxing; Zheng, Shourong

    2010-02-01

    The present study developed a polymer-based hybrid sorbent (HFO-001) for highly efficient removal of heavy metals [e.g., Pb(II), Cd(II), and Cu(II)] by irreversibly impregnating hydrated Fe(III) oxide (HFO) nanoparticles within a cation-exchange resin D-001 (R-SO(3)Na), and revealed the underlying mechanism based on X-ray photoelectron spectroscopy (XPS) study. HFO-001 combines the excellent handling, flow characteristics, and attrition resistance of conventional cation-exchange resins with the specific affinity of HFOs toward heavy metal cations. As compared to D-001, sorption selectivity of HFO-001 toward Pb(II), Cu(II), and Cd(II) was greatly improved from the Ca(II) competition at greater concentration. Column sorption results indicated that the working capacity of HFO-001 was about 4-6 times more than D-001 with respect to removal of three heavy metals from simulated electroplating water (pH approximately 4.0). Also, HFO-001 is particularly effective in removing trace Pb(II) and Cd(II) from simulated natural waters to meet the drinking water standard, with treatment volume orders of magnitude higher than D-001. The superior performance of HFO-001 was attributed to the Donnan membrane effect exerted by the host D-001 as well as to the impregnated HFO nanoparticles of specific interaction toward heavy metal cations, as further confirmed by XPS study on lead sorption. More attractively, the exhausted HFO-001 beads can be effectively regenerated by HCl-NaCl solution (pH 3) for repeated use without any significant capacity loss. PMID:19906397

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

    SciTech Connect

    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

  14. Microbial and geochemical controls on dissimilatory Fe(III) reduction

    SciTech Connect

    Urrutia, M.M.; Roden, E.E.; Zachara, J.M.

    1995-12-31

    This study investigates the influence of coating bacterial oxide surfaces with Fe(II) on the rate and extent of Fe(III) reduction. Limitations imposed by the microorganisms themselves on the rate and extent of reduction of solid phase Fe(III) were also examined. Shewanella alga (strain BrY) cells were coated with Fe(II) and used as inocula for Fe(III) reduction experiments. The coating considerably slowed down the initial rate of Fe(III) reduction in comparison with uncoated cells, proceeding at a rate similar to that exhibited by uncoated cells at the latest stages of growth. Furthermore, the presence of chelators (EDTA and NTA) with a high affinity for Fe(II) was related to further reduction of medium surface area Goethite (MSA Gt) by BrY, which supports the idea of cessation of reduction by occlusion of the active surfaces. Reinoculation experiments, in which fresh cells were added after completion of a whole cell cycle, showed further reduction of Fe(III) with either MSA Gt, or hematite, high surface area and MSA Gt. Together, findings support the hypothesis that the binding, and eventual coating, of Fe(III) oxide and bacterial surfaces with Fe(II) is involved in the slowdown and eventual cessation of Fe(III) reduction within a cell growth cycle.

  15. Dissimilatory Fe(III) and Mn(IV) reduction.

    PubMed Central

    Lovley, D R

    1991-01-01

    The oxidation of organic matter coupled to the reduction of Fe(III) or Mn(IV) is one of the most important biogeochemical reactions in aquatic sediments, soils, and groundwater. This process, which may have been the first globally significant mechanism for the oxidation of organic matter to carbon dioxide, plays an important role in the oxidation of natural and contaminant organic compounds in a variety of environments and contributes to other phenomena of widespread significance such as the release of metals and nutrients into water supplies, the magnetization of sediments, and the corrosion of metal. Until recently, much of the Fe(III) and Mn(IV) reduction in sedimentary environments was considered to be the result of nonenzymatic processes. However, microorganisms which can effectively couple the oxidation of organic compounds to the reduction of Fe(III) or Mn(IV) have recently been discovered. With Fe(III) or Mn(IV) as the sole electron acceptor, these organisms can completely oxidize fatty acids, hydrogen, or a variety of monoaromatic compounds. This metabolism provides energy to support growth. Sugars and amino acids can be completely oxidized by the cooperative activity of fermentative microorganisms and hydrogen- and fatty-acid-oxidizing Fe(III) and Mn(IV) reducers. This provides a microbial mechanism for the oxidation of the complex assemblage of sedimentary organic matter in Fe(III)- or Mn(IV)-reducing environments. The available evidence indicates that this enzymatic reduction of Fe(III) or Mn(IV) accounts for most of the oxidation of organic matter coupled to reduction of Fe(III) and Mn(IV) in sedimentary environments. Little is known about the diversity and ecology of the microorganisms responsible for Fe(III) and Mn(IV) reduction, and only preliminary studies have been conducted on the physiology and biochemistry of this process. PMID:1886521

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

    NASA Astrophysics Data System (ADS)

    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

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

    PubMed

    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

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

    NASA Astrophysics Data System (ADS)

    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. A comparative study for the sorption of Cd(II) by soils with different clay contents and mineralogy and the recovery of Cd(II) using rhamnolipid biosurfactant.

    PubMed

    Aşçi, Y; Nurbaş, M; Açikel, Y Sağ

    2008-06-15

    Recent research has demonstrated that biosurfactants, especially rhamnolipids, can enhance recovery of soil-bound metals. To propose the success of remediation process of soils by rhamnolipids, both sorption and desorption characteristics of soils having different clay mineralogy should be known exactly. To assess sorption of Cd(II), batch equilibrium experiments were performed using three soils characterized with different proportions of clay minerals from Eskişehir region of Turkey. Soil pH, initial metal concentration and clay mineralogy affected the sorption process. For comparisons between soils, the sorption process was characterized using the Langmuir, Freundlich, Redlich-Peterson, Koble-Corrigan sorption models. The Freundlich model showed the best fit for the Cd(II) sorption data by the soils, while the Langmuir-type models generally failed to describe the sorption data. Soils with higher clay content characterized by having smectite as a dominant component had the greatest sorption capacity and intensity estimated by the KF and n parameters of the Freundlich model. The soil C has the highest sorption efficiency of 83.9%, followed by soils B and A with sorption efficiencies of 76.7% and 57.9%, respectively. After the soils were loaded by different doses of Cd(II), batch washing experiments were used to evaluate the feasibility of using rhamnolipid biosurfactant for the recovery of Cd(II) from the soils. The Cd(II) recovery of the soils were investigated as a function of pH, amount of Cd(II) loaded to the soils, and rhamnolipid concentration. Cd(II) recovery efficiencies from the soils using rhamnolipid biosurfactant decreased in the order of soil A>soil B>soil C. This order was the reverse of the Cd(II) sorption efficiency order on the soils. When 80 mM rhamnolipid was used, the recovery efficiencies of Cd(II) from the soils A, B, and C was found to be 52.9%, 47.7%, 45.5% of the sorbed Cd(II), respectively. Rhamnolipid sorption capacity of the soils in

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

    NASA Astrophysics Data System (ADS)

    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.

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

    NASA Astrophysics Data System (ADS)

    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

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

    NASA Astrophysics Data System (ADS)

    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. A kinetic model for bacterial Fe(III) oxide reduction in batch cultures

    NASA Astrophysics Data System (ADS)

    Hacherl, Eric L.; Kosson, David S.; Cowan, Robert M.

    2003-04-01

    A model has been developed describing the microbial reduction of solid-phase electron acceptors (Fe(III) oxides) as well as dissolved electron acceptors (chelated Fe(III) or organic electron shuttles) in Shewanella alga BrY. The model utilized a multiple-substrate, Monod kinetics formulation. The Monod description of solid Fe(III) reduction requires a normalization of surface Fe concentration to biomass concentration in order to describe the "bioavailable" Fe(III) concentration. The model also contains provisions for irreversible sorption of Fe(II) to Fe(III) oxide surfaces and for the precipitation of Fe(III) carbonates. The loss of bioavailable Fe(III) due to sorption of Fe(II) was found to be minor, even for highly sorptive amorphous Fe(III) oxyhydroxides. However, the final extent of microbial reduction is very sensitive to the rate of siderite precipitation, assuming that siderite precipitation could partially occlude Fe(III) surface sites. The use of a multisubstrate Monod kinetics model enabled an evaluation of the effects of electron shuttles on solid Fe(III) reduction. Because the electron shuttle is recycled, very small additions can greatly increase the overall rate of solid Fe(III) reduction.

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

    PubMed

    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) on jatropha fruit coat and seed coat.

    PubMed

    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

  6. Sequence change and phylogenetic signal in muscoid COII DNA sequences.

    PubMed

    Szalanski, Allen L; Owens, Carrie B

    2003-08-01

    The complete DNA sequence of the mtDNA cytochrome oxidase II gene from house fly, Musca domestica, face fly, Musca autumnalis, stable fly, Stomoxys calcitrans, horn fly, Haematobia irritans, and black garbage fly, Hydrotaea aenescens, are reported. The nucleotide sequence codes for a 229 amino acid peptide. The COII sequence is A + T rich (74.1%), with up to 12.3% nucleotide and 8.4% amino acid divergence among the five taxa. Of the 688 nucleotides encoding for the gene, 135 nucleotide sites (19.6%) are variable, and 55 (8.0%) are phylogenetically informative. A phylogenetic analysis using three calliphorids as the outgroup taxa, indicates that the two haematophagus species, horn fly and stable fly, form a sister group. PMID:14631656

  7. Synthesis, characterization and biological activities of Cu(II), Co(II), Mn(II), Fe(II), and UO2(VI) complexes with a new Schiff Base hydrazone: O-hydroxyacetophenone-7-chloro-4-quinoline hydrazone.

    PubMed

    Al-Shaalan, Nora H

    2011-01-01

    The Schiff base hydrazone ligand HL was prepared by the condensation reaction of 7-chloro-4-quinoline with o-hydroxyacetophenone. The ligand behaves either as monobasic bidentate or dibasic tridentate and contain ONN coordination sites. This was accounted for be the presence in the ligand of a phenolic azomethine and imine groups. It reacts with Cu(II), Ni(II), Co(II), Mn(II), UO(2) (VI) and Fe(II) to form either mono- or binuclear complexes. The ligand and its metal complexes were characterized by elemental analyses, IR, NMR, Mass, and UV-Visible spectra. The magnetic moments and electrical conductance of the complexes were also determined. The Co(II), Ni(II) and UO(2) (VI) complexes are mononuclear and coordinated to NO sites of two ligand molecules. The Cu(II) complex has a square-planar geometry distorted towards tetrahedral, the Ni(II) complex is octahedral while the UO(2) (VI) complex has its favoured heptacoordination. The Co(II), Mn(II) complexes and also other Ni(II) and Fe(III) complexes, which were obtained in the presence of Li(OH) as deprotonating agent, are binuclear and coordinated via the NNNO sites of two ligand molecules. All the binuclear complexes have octahedral geometries and their magnetic moments are quite low compared to the calculated value for two metal ions complexes and thus antiferromagnetic interactions between the two adjacent metal ions. The ligand HL and metal complexes were tested against a strain of Gram +ve bacteria (Staphylococcus aureus), Gram -ve bacteria (Escherichia coli), and fungi (Candida albicans). The tested compounds exhibited high antibacterial activities. PMID:21996717

  8. Rapid anaerobic benzene oxidation with a variety of chelated Fe(III) forms

    USGS Publications Warehouse

    Lovley, D.R.; Woodward, J.C.; Chapelle, F.H.

    1996-01-01

    Fe(III) chelated to such compounds as EDTA, N-methyliminodiacetie acid, ethanol diglycine, humic acids, and phosphates stimulated benzene oxidation coupled to Fe(III) reduction in anaerobic sediments from a petroleum- contaminated aquifer as effectively as or more effectively than nitrilotriacetic acid did in a previously demonstrated stimulation experiment. These results indicate that many forms of chelated Fe(III) might be applicable to aquifer remediation.

  9. Amylopectin-g-poly(methylacrylate-co-sodium acrylate): An efficient Cd(II) binder.

    PubMed

    Sasmal, Dinabandhu; Kolya, Haradhan; Tripathy, Tridib

    2016-10-01

    Synthesis, characterization and Cd(II) adsorption studies of a novel biodegradable graft copolymer based on partially hydrolysed polymethylacrylate (PMA) grafted amylopectin was reported, which was prepared by first grafting of PMA chains onto the amylopectin backbone followed by partial alkaline hydrolysis. The hydrolysed graft copolymer (PHAP) was characterized by measuring saponification equivalent (SE), FTIR, (1)H NMR and (13)C NMR spectroscopy and thermal analysis (TG/DTG). The graft copolymer was biodegradable. Various operating variables affecting the metal sorption such as, amount of adsorbent, solution pH, contact time, temperature and Cd(II) solution concentration were studied which showed that the maximum adsorption of Cd(II) was found at pH 5.5, temperature 90°C, time 120min, polymer dose, 0.02g/L and initial Cd(II) concentration, 50mg/L. The adsorption data were well described by the pseudo-second-order and Langmuir isotherm model. Metal complexation studies were carried out experimentally using UV-visible, FTIR spectroscopy and theoretically using Density Functional Theory by Gaussian 09 and Gauss view 5.0 programmes which confirms a square planer geometry involving Cd(II) and COO(-) groups. Calculation of the various thermodynamic parameters was also done. The negative value of free energy change indicates the spontaneous nature of the adsorption. PMID:27316770

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

    NASA Astrophysics Data System (ADS)

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

    SciTech Connect

    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 pattern

  12. Esterified coir pith as an adsorbent for the removal of Co(II) from aqueous solution.

    PubMed

    Parab, Harshala; Joshi, Shreeram; Shenoy, Niyoti; Lali, Arvind; Sarma, U S; Sudersanan, M

    2008-04-01

    Coir pith was chemically modified for the adsorption of cobalt(II) ions from aqueous solution. Chemical modification was done by esterification using succinic anhydride followed by activation with NaHCO(3) in order to improve the adsorption of Co(II). Adsorptive removal of Co(II) from aqueous solution onto modified coir pith was evaluated in batch studies under varying conditions of agitation time and metal ion concentration to assess the kinetic and equilibrium parameters. A pseudo-second-order kinetic model fitted well for the sorption of Co(II) onto modified coir pith. Sorption kinetics showed that the loading of Co(II) by this material was quite fast under ambient conditions. The Langmuir and Freundlich equilibrium isotherm models provided excellent fits for the adsorption data, with R(2) of 0.99 and 0.98, respectively. After esterification, the maximum Co(II) sorption loading Q(0); was greatly improved. It is evident that chemically modified adsorbent exhibits better Co(II) removal capability than raw adsorbent suggesting that surface modification of the adsorbent generates more adsorption sites on its solid surface for metal adsorption. A complete recovery of the adsorbed metal ions from the spent adsorbent was achieved by using 1.0N HCl. PMID:17611104

  13. Highly selective and stable florescent sensor for Cd(II) based on poly (azomethine-urethane).

    PubMed

    Kaya, İsmet; Kamacı, Musa

    2013-01-01

    In this study a kind of poly(azomethine-urethane); (E)-4-((2 hydroxyphenylimino) methyl)-2-methoxyphenyl 6-acetamidohexylcarbamate (HDI-co-3-DHB-2-AP) was prepared as in the literature and employed as a new fluorescent probe for detection of Cd(II) concentration. The photoluminescence (PL) measurements were carried out in the presence of several kinds of heavy metals. HDI-co-3-DHB-2-AP gave a linearly and highly stable response against Cd(II) as decreasing a new emission peak at 562 nm. Possible interferences of other ions were found too low. Detection limit of the sensor was found as 8.86 × 10(-4) mol L(-1). Resultantly, HDI-co-3- DHB-2-AP could be effectively used as an optical Cd(II) sensor. PMID:22941725

  14. Advanced experimental analysis of controls on microbial Fe(III) oxide reduction. 1998 annual progress report

    SciTech Connect

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

    1998-06-01

    'Understanding factors which control the long-term survival and activity of Fe(III)-reducing bacteria (FeRB) in subsurface sedimentary environments is important for predicting their ability to serve as agents for bioremediation of organic and inorganic contaminants. This project seeks to refine the authors quantitative understanding of microbiological and geochemical controls on bacterial Fe(III) oxide reduction and growth of FeRB, using laboratory reactor systems which mimic to varying degrees the physical and chemical conditions of subsurface sedimentary environments. Methods for studying microbial Fe(III) oxide reduction and FeRB growth in experimental systems which incorporate advective aqueous phase flux are being developed for this purpose. These methodologies, together with an accumulating database on the kinetics of Fe(III) reduction and bacterial growth with various synthetic and natural Fe(III) oxide minerals, will be applicable to experimental and modeling studies of subsurface contaminant transformations directly coupled to or influenced by bacterial Fe(III) oxide reduction and FeRB activity. This report summarizes research accomplished after approximately 1.5 yr of a 3-yr project. A central hypothesis of the research is that advective elimination of the primary end-product of Fe(III) oxide reduction, Fe(II), will enhance the rate and extent of microbial Fe(III) oxide reduction in open experimental systems. This hypothesis is based on previous studies in the laboratory which demonstrated that association of evolved Fe(II) with oxide and FeRB cell surfaces (via adsorption or surface precipitation) is a primary cause for cessation of Fe(III) oxide reduction activity in batch culture experiments. Semicontinuous culturing was adopted as a first approach to test this basic hypothesis. Synthetic goethite or natural Fe(III) oxide-rich subsoils were used as Fe(III) sources, with the Fe(III)-reducing bacterium Shewanella alga as the test organism.'

  15. Reaction-based reactive transport modeling of Fe(III)

    SciTech Connect

    Kemner, K.M.; Kelly, S.D.; Burgos, Bill; Roden, Eric

    2006-06-01

    This research project (started Fall 2004) was funded by a grant to Argonne National Laboratory, The Pennsylvania State University, and The University of Alabama in the Integrative Studies Element of the NABIR Program (DE-FG04-ER63914/63915/63196). Dr. Eric Roden, formerly at The University of Alabama, is now at the University of Wisconsin, Madison. Our project focuses on the development of a mechanistic understanding and quantitative models of coupled Fe(III)/U(VI) reduction in FRC Area 2 sediments. This work builds on our previous studies of microbial Fe(III) and U(VI) reduction, and is directly aligned with the Scheibe et al. NABIR FRC Field Project at Area 2.

  16. Crosslinked Electro-Spun Chitosan Nanofiber Mats with Cd(II) as Template Ions for Adsorption Applications.

    PubMed

    Li, Yan; Xu, Cong; Qiu, Tianbao; Xu, Xiaoyan

    2015-06-01

    The Cd(II) ion imprinting electro-spun crosslinked chitosan nanofiber mats were successfully prepared using Cd(II) as template ions and glutaraldehyde (GA) as crosslinker to investigate the adsorption of Cd(II) and Pb(II) ions in aqueous solutions. The Cd(II) ion imprinting electro-spun crosslinked chitosan nanofiber mats were characterized by the Fourier Transform Infrared Spectrometer (FTIR), Scanning Electron Microscope (SEM), Thermal Gravimetric Analysis (TGA), elemental analysis and solubility tests. The prepared chitosan nanofiber mats exhibited a higher adsorption capacity for both Cd(II) (364.3 mg/g) and Pb(II) (272.0 mg/g) ions. The dynamic study demonstrated that the adsorption process followed the second-order kinetic equation. Langmuir and Freundlich adsorption models were used to analyze the equilibrium isotherm data. The results showed that the Langmuir model was best suitable for predicting the adsorption isotherm of the studied system. The as prepared Cd(II) ion imprinting electro-spun crosslinked chitosan nanofiber mats might be used as an effective adsorbent for Cd(II) and Pb(II) removal from heavy metal wastewater. PMID:26369036

  17. Magnetic and low temperature phonon studies of CoCr{sub 2}O{sub 4} powders doped with Fe(III) and Ni(II) ions

    SciTech Connect

    Ptak, M. Mączka, M.; Pikul, A.; Tomaszewski, P.E.; Hanuza, J.

    2014-04-01

    Extensive temperature-dependent phonon studies and low-temperature magnetic measurements of CoCr{sub 2−x}Fe{sub x}O{sub 4} (for x=0.5, 1 and 2) and Co{sub 0.9}Ni{sub 0.1}Cr{sub 2}O{sub 4} 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 CoCr{sub 2}O{sub 4} 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 Co{sub 0.9}Ni{sub 0.1}Cr{sub 2}O{sub 4} sample are similar to those reported for pure CoCr{sub 2}O{sub 4}, i.e., partial substitution of Ni(II) for Co(II) leads to slight shift of the ferrimagnetic phase transition at T{sub C} and spiral spin order transition at T{sub S} 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 T{sub C} and decrease of T{sub S}. The latter transition disappears completely for higher concentrations of Fe(III). The performed temperature-dependent IR studies revealed interesting anomalous behavior of phonons below T{sub C} for CoCr{sub 1.5}Fe{sub 0.5}O{sub 4} and Co{sub 0.9}Ni{sub 0.1}Cr{sub 2}O{sub 4}, which was attributed to spin–phonon coupling. - Graphical abstract: Visualization of normal spinel-type AB{sub 2}O{sub 4} structure, where blue octahedrons denote BO{sub 6} and red tetrahedrons AO{sub 4} units as well as IR and Raman spectra of Co{sub 0.9}Ni{sub 0.1}Cr{sub 2}O{sub 4} powder. - Highlights: • T{sub C} (T{sub S}) increases (decreases) with increasing Fe(III) concentration.

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

    NASA Astrophysics Data System (ADS)

    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.

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

    NASA Astrophysics Data System (ADS)

    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.

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

    PubMed

    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

  1. Isolation and microbial reduction of Fe(III) phyllosilicates from subsurface sediments

    SciTech Connect

    Wu, Tao; Shelobolina, Evgenya S.; Xu, Huifang; Konishi, Hiromi; Kukkadapu, Ravi K.; Roden, Eric E.

    2012-10-12

    Fe(III)-bearing phyllosilicates can be important sources of Fe(III) for dissimilatory microbial iron reduction in clay-rich anoxic soils and sediments. The goal of this research was to isolate Fe(III) phyllosilicate phases, and if possible, Fe(III) oxide phases, from a weathered shale saprolite sediment in order to permit experimentation with each phase in isolation. Physical partitioning by density gradient centrifugation did not adequately separate phyllosilicate and Fe(III) oxide phases (primarily nanoparticulate goethite). Hence we examined the ability of chemical extraction methods to remove Fe(III) oxides without significantly altering the properties of the phyllosilicates. XRD analysis showed that extraction with oxalate alone or oxalate in the presence of added Fe(II) altered the structure of Fe-bearing phyllosilicates in the saprolite. In contrast, citrate-bicarbonate-dithionite (CBD) extraction at room temperature and 80C led to minimal alteration of phyllosilicate structures. Reoxidation of CDB-extracted sediment with H2O2 restored phyllosilicate structure (i.e. d-spacing) and redox speciation to conditions similar to that in the pristine sediment. The extent of microbial (Geobacter sulfurreducens) reduction of Fe(III) phyllosilicates isolated by CDB extraction (ca. 16 %) was comparable to what took place in pristine sediments as determined by Mossbauer spectroscopy (ca. 18 % reduction). These results suggest that materials isolated by CDB extraction and H2O2 reoxidation are appropriate targets for detailed studies of natural soil/sediment Fe(III) phyllosilicate reduction.

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

    USGS Publications Warehouse

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

    1998-01-01

    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 NO-3, Mn(IV), U(VI), fumarate, malate, S2O32-, 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.

  3. Dissimilatory Fe(III) reduction by the marine microorganism Desulfuromonas acetoxidans

    USGS Publications Warehouse

    Roden, E.E.; Lovley, D.R.

    1993-01-01

    The ability of the marine microorganism Desulfuromonas acetoxidans to reduce Fe(III) was investigated because of its close phylogenetic relationship with the freshwater dissimilatory Fe(III) reducer Geobacter metallireducens. Washed cell suspensions of the type strain of D. acetoxidans reduced soluble Fe(III)-citrate and Fe(III) complexed with nitriloacetic acid. The c-type cytochrome(s) of D. acetoxidans was oxidized by Fe(III)- citrate and Mn(IV)-oxalate, as well as by two electron acceptors known to support growth, colloidal sulfur and malate. D. acetoxidans grew in defined anoxic, bicarbonate-buffered medium with acetate as the sole electron donor and poorly crystalline Fe(III) or Mn(IV) as the sole electron acceptor. Magnetite (Fe3O4) and siderite (FeCO3) were the major end products of Fe(III) reduction, whereas rhodochrosite (MnCO3) was the end product of Mn(IV) reduction. Ethanol, propanol, pyruvate, and butanol also served as electron donors for Fe(III) reduction. In contrast to D. acetoxidans, G. metallireducens could only grow in freshwater medium and it did not conserve energy to support growth from colloidal S0 reduction. D. acetoxidans is the first marine microorganism shown to conserve energy to support growth by coupling the complete oxidation of organic compounds to the reduction of Fe(III) or Mn(IV). Thus, D. acetoxidans provides a model enzymatic mechanism for Fe(III) or Mn(IV) oxidation of organic compounds in marine and estuarine sediments. These findings demonstrate that 16S rRNA phylogenetic analyses can suggest previously unrecognized metabolic capabilities of microorganisms.

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

    PubMed

    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

  5. Effects of Fe(III) and organic matter additions on methanogenic activity and Fe(III) reduction in boreal lake and wetland sediments

    NASA Astrophysics Data System (ADS)

    Karvinen, Anu; Lehtinen, Lotta; Kankaala, Paula

    2013-04-01

    We studied potential methane production and Fe(III) reduction activity in lake sediments and wetland peat sampled from 14 sites in southern and eastern Finland. The concentration of total iron in the sediments and peat varied between 0.5 and 1200 ppm and their organic matter content (loss of ignition) varied between 1-98% of dry weight. Also the effects of added amorphous Fe(III) oxyhydroxide and organic matter (ammoniumacetate and/or sodiumacetate) on methanogenic and Fe(III) reduction activities were studied in anaerobic laboratory incubations (in vitro) lasting 5-20 days at 15 °C in darkness. Potential methane production and the effects of iron and acetate additions were highly variable between lake and peatland sites. The highest methanogenic potential was generally measured in productive littoral sites, especially in those dominated by Phragmites australis vegetation stands. In these sediments the total iron concentrations were high and acetate additions clearly increased methane production whereas Fe(III) additions decreased it. Our results demonstrate that microbial Fe(III) reduction plays an important role in the anaerobic organic matter decomposition in many boreal lakes.

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

    SciTech Connect

    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 shows

  7. Mitochondrial intergenic COII/tRNA(Lys) 9-bp deletion, a biomarker for hepatocellular carcinoma?

    PubMed

    Ren, Weihua; Li, Yawei; Li, Rui; Feng, Hongbo; Wu, Shuangting; Mao, Yuhui; Huang, Lei

    2016-07-01

    The COII/tRNA(Lys) intergenic 9-bp deletion is one of the most commonly studied human mitochondrial DNA (mtDNA) polymorphisms. It consists of the loss of one of two tandemly repeated copies of the sequence CCCCCTCTA from a non-coding region located between cytochrome oxidase II (COII) and tRNA(Lys) gene. Most recently, case-control studies have shown a positive association between this deletion with hepatocellular cancer. In this study, we first performed a detailed analysis between this deletion and clinical diseases; moreover, we took the phylogenetic approach to examine the pathogenicity status of 9-bp deletion. PMID:26017042

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

    SciTech Connect

    Bae, Youn-Sang; Spokoyny, Alexander M.; Farha, Omar K.; Snurr, Randall Q.; Hupp, Joseph T.; Mirkin, Chad A.

    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.

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

    PubMed

    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

  10. Release of 226Ra from uranium mill tailings by microbial Fe(III) reduction

    USGS Publications Warehouse

    Landa, E.R.; Phillips, E.J.P.; Lovley, D.R.

    1991-01-01

    Uranium mill tailings were anaerobically incubated in the presence of H2 with Alteromonas putrefaciens, a bacterium known to couple the oxidation of H2 and organic compounds to the reduction of Fe(III) oxides. There was a direct correlation between the extent of Fe(III) reduction and the accumulation of dissolved 226Ra. In sterile tailings in which Fe(III) was not reduced, there was negligible leaching of 226Ra. The behavior of Ba was similar to that of Ra in inoculated and sterile systems. These results demonstrate that under anaerobic conditions, microbial reduction of Fe(III) may result in the release of dissolved 226Ra from uranium mill tailings. ?? 1991.

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

    PubMed

    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. Dissimilatory Fe(III) Reduction by the Marine Microorganism Desulfuromonas acetoxidans

    PubMed Central

    Roden, Eric E.; Lovley, Derek R.

    1993-01-01

    The ability of the marine microorganism Desulfuromonas acetoxidans to reduce Fe(III) was investigated because of its close phylogenetic relationship with the freshwater dissimilatory Fe(III) reducer Geobacter metallireducens. Washed cell suspensions of the type strain of D. acetoxidans reduced soluble Fe(III)-citrate and Fe(III) complexed with nitriloacetic acid. The c-type cytochrome(s) of D. acetoxidans was oxidized by Fe(III)-citrate and Mn(IV)-oxalate, as well as by two electron acceptors known to support growth, colloidal sulfur and malate. D. acetoxidans grew in defined anoxic, bicarbonate-buffered medium with acetate as the sole electron donor and poorly crystalline Fe(III) or Mn(IV) as the sole electron acceptor. Magnetite (Fe3O4) and siderite (FeCO3) were the major end products of Fe(III) reduction, whereas rhodochrosite (MnCO3) was the end product of Mn(IV) reduction. Ethanol, propanol, pyruvate, and butanol also served as electron donors for Fe(III) reduction. In contrast to D. acetoxidans, G. metallireducens could only grow in freshwater medium and it did not conserve energy to support growth from colloidal S0 reduction. D. acetoxidans is the first marine microorganism shown to conserve energy to support growth by coupling the complete oxidation of organic compounds to the reduction of Fe(III) or Mn(IV). Thus, D. acetoxidans provides a model enzymatic mechanism for Fe(III) or Mn(IV) oxidation of organic compounds in marine and estuarine sediments. These findings demonstrate that 16S rRNA phylogenetic analyses can suggest previously unrecognized metabolic capabilities of microorganisms. Images PMID:16348888

  13. Crystal structure and magnetic properties of a linear tetranuclear Co(II) cluster.

    PubMed

    Wang, Yingying; Wen, Meixia; Gao, Zhongjun; Sheng, Ning

    2016-09-01

    Polynuclear complexes are an important class of inorganic functional materials and are of interest particularly for their applications in molecular magnets. Multidentate chelating ligands play an important role in the design and syntheses of polynuclear metal clusters. A novel linear tetranuclear Co(II) cluster, namely bis{μ3-(E)-2-[(2-oxidobenzylidene)amino]phenolato}bis{μ2-(E)-2-[(2-oxidobenzylidene)amino]phenolato}bis(1,10-phenanthroline)tetracobalt(II), [Co4(C14H11NO2)4(C12H8N2)2], was prepared under solvothermal conditions through a mixed-ligand synthetic strategy. The structure was determined by X-ray single-crystal diffraction and bulk purity was confirmed by powder X-ray diffraction. The complex molecule has a centrosymmetric tetranuclear chain-like structure and the four Co(II) ions are located in two different coordination environments. The Co(II) ions at the ends of the chain are in a slightly distorted octahedral geometry, while the two inner Co(II) ions are in five-coordinate distorted trigonal bipyramidal environments. A magnetic study reveals ferromagnetic Co(II)...Co(II) exchange interactions for the complex. PMID:27585934

  14. Adsorption of Co(II) by a carboxylate-functionalized polyacrylamide grafted lignocellulosics.

    PubMed

    Shibi, I G; Anirudhan, T S

    2005-02-01

    A new adsorbent (PGBS-COOH) having carboxylate functional group at the chain end was synthesized by graft copolymerization of acrylamide onto banana stalk, BS (Musa Paradisiaca) using ferrous ammonium sulphate/H2O2 redox initiator system. The efficiency of the adsorbent in the removal of cobalt [Co(II)] from water was investigated using batch adsorption technique. The adsorbent exhibits very high adsorption potential for Co(II) and under optimum conditions more than 99% removal was achieved. The maximum adsorption capacity was observed at the pH range 6.5-9.0. The equilibrium isotherm data were analysed using three isotherm models, Langmuir, Freundlich and Scatchard, to determine the best fit equation for the sorption of Co(II) on the PGBS-COOH. A comparative study with a commercial cation exchanger, Ceralite IRC-50, having carboxylate functional group showed that PGBS-COOH is 2.8 times more effective compared to Ceralite IRC-50 at 30 degrees C. Synthetic nuclear power plant coolant water samples were also treated by the adsorbent to demonstrate its efficiency in removing Co(II) from water in the presence of other metal ions. Acid regeneration was tried for several cycles to recover the adsorbed metal ions and also to restore the sorbent to its original state. PMID:15664619

  15. From discrete molecule, to polymer, to MOF: mapping the coordination chemistry of Cd(II) using (113)Cd solid-state NMR.

    PubMed

    Frost, Jamie M; Kobera, Libor; Pialat, Amélie; Zhang, Yixin; Southern, Scott A; Gabidullin, Bulat; Bryce, David L; Murugesu, Muralee

    2016-08-23

    Studies of three related Cd(II) systems (a discrete [Cd(II)2] unit, a one-dimensional [Cd(II)2]n coordination polymer and a Cd(II)-based MOF) all derived from the ligand 2,4,6-tris(2-pyrimidyl)-1,3,5-triazine, reveal an exceptionally rare example of (113)Cd-(113)Cd J coupling in the polymer that is detectable by solid-state NMR ((2)JCd-Cd = ∼65 Hz). PMID:27507123

  16. Sorption mechanism of Cd(II) from water solution onto chicken eggshell

    NASA Astrophysics Data System (ADS)

    Flores-Cano, Jose Valente; Leyva-Ramos, Roberto; Mendoza-Barron, Jovita; Guerrero-Coronado, Rosa María; Aragón-Piña, Antonio; Labrada-Delgado, Gladis Judith

    2013-07-01

    The mechanism and capacity of eggshell for sorbing Cd(II) from aqueous solution was examined in detail. The eggshell was characterized by several techniques. The eggshell was mainly composed of Calcite (CaCO3). The surface charge distribution was determined by acid-base titration and the point of zero charge (PZC) of the eggshell was found to be 11.4. The sorption equilibrium data were obtained in a batch adsorber, and the adsorption isotherm of Langmuir fitted the data quite well. The sorption capacity of eggshell increased while raising the pH from 4 to 6, this tendency was attributed to the electrostatic interaction between the Cd2+ in solution and the surface of the eggshell. Furthermore, the sorption capacity was augmented by increasing the temperature from 15 to 35 °C because the sorption was endothermic. The sorption of Cd(II) occurred mainly onto the calcareous layer of the eggshell, but slightly on the membrane layer. It was demonstrated that the sorption of Cd(II) was not reversible, and the main sorption mechanisms were precipitation and ion exchange. The precipitation of (Cd,Ca)CO3 on the surface of the eggshell was corroborated by SEM and XRD analysis.

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

    NASA Astrophysics Data System (ADS)

    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.

  18. Impaired ergosterol biosynthesis mediated fungicidal activity of Co(II) complex with ligand derived from cinnamaldehyde.

    PubMed

    Shreaz, Sheikh; Shiekh, Rayees A; Raja, Vaseem; Wani, Waseem A; Behbehani, Jawad M

    2016-03-01

    In this study, we have used aldehyde function of cinnamaldehyde to synthesize N, N'-Bis (cinnamaldehyde) ethylenediimine [C20H20N2] and Co(II) complex of the type [Co(C40H40N4)Cl2]. The structures of the synthesized compounds were determined on the basis of physiochemical analysis and spectroscopic data ((1)H NMR, FTIR, UV-visible and mass spectra) along with molar conductivity measurements. Anticandidal activity of cinnamaldehyde its ligand [L] and Co(II) complex was investigated by determining MIC80, time-kill kinetics, disc diffusion assay and ergosterol extraction and estimation assay. Ligand [L] and Co(II) complex are found to be 4.55 and 21.0 folds more efficient than cinnamaldehyde in a liquid medium. MIC80 of Co(II) complex correlated well with ergosterol inhibition suggesting ergosterol biosynthesis to be the primary site of action. In comparison to fluconazole, the test compounds showed limited toxicity against H9c2 rat cardiac myoblasts. In confocal microscopy propidium iodide (PI) penetrates the yeast cells when treated with MIC of metal complex, indicating a disruption of cell membrane that results in imbibition of dye. TEM analysis of metal complex treated cells exhibited notable alterations or damage to the cell membrane and the cell wall. The structural disorganization within the cell cytoplasm was noted. It was concluded that fungicidal activity of Co(II) complex originated from loss of membrane integrity and a decrease in ergosterol content is only one consequence of this. PMID:26806515

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

    PubMed

    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

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

    NASA Astrophysics Data System (ADS)

    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).

  1. Bacterial reductive dissolution of crystalline Fe(III) oxide in continuous-flow column reactors

    SciTech Connect

    Roden, E.E.; Urrutia, M.M.; Mann, C.J.

    2000-03-01

    Bacterial reductive dissolution of synthetic crystalline Fe(III) oxide-coated sand was studied in continuous-flow column reactors in comparison with parallel batch cultures. The cumulative amount of aqueous Fe(II) exported from the columns over a 6-month incubation period corresponded to (95.0 {+-} 3.7)% (n = 3) of their original Fe(III) content. Wet-chemical analysis revealed that only (6.5 {+-} 3.2)% of the initial Fe(III) content remained in the columns at the end of the experiment. The near-quantitative removal of Fe was visibly evidenced by extensive bleaching of color from the sand in the columns. In contrast to the column reactors, Fe(II) production quickly reached an asymptote in batch cultures, and only (13.0 {+-} 2.2)% (n = 3) of the Fe(III) oxide content was reduced. Sustained bacterial-cell growth occurred in the column reactors, leading to the production and export of a quantity of cells 100-fold greater than that added during inoculation. Indirect estimates of cell growth, based on the quantity of Fe(III) reduced, suggest that only an approximate doubling of initial cell abundance was likely to have occurred in the batch cultures. Their results indicate that removal of biogenic Fe(II) via aqueous-phase transport in the column reactors decreased the passivating influence of surface-bound Fe(II) on oxide reduction activity, thereby allowing a dramatic increase in the extent of Fe(III) oxide reduction and associated bacterial growth. These findings have important implications for understanding the fate of organic and inorganic contaminants whose geochemical behavior is linked to Fe(III) oxide reduction.

  2. Effects of background electrolytes and ionic strength on enrichment of Cd(II) ions with magnetic graphene oxide-supported sulfanilic acid.

    PubMed

    Hu, Xin-jiang; Liu, Yun-guo; Zeng, Guang-ming; You, Shao-hong; Wang, Hui; Hu, Xi; Guo, Yi-ming; Tan, Xiao-fei; Guo, Fang-ying

    2014-12-01

    To elucidate the influence mechanisms of background electrolytes and ionic strength on Cd(II) removal, the adsorption of Cd(II) onto magnetic graphene oxide-supported sulfanilic acid (MGO-SA) in aqueous solutions containing different types and concentrations of background electrolytes was studied. The results indicate that Cd(II) adsorption was strongly dependent on pH and could be strongly affected by background electrolytes and ionic strength. The Cd(II) removal was decreased with the presence of background electrolyte cations (Na(+), K(+), Ca(2+), Mg(2+), Mn(2+), Zn(2+), and Ni(2+)), and the divalent cations exerted more obvious influences on the Cd(II) uptake than the monovalent cations at pH 6. Both Cl(-) and NO3(-) had negative effects on Cd(II) adsorption because they can form water-soluble metal-anion complexes with Cd(II) ions. The presence of 0.01molL(-1) Na3PO4 reduced the removal percentage of Cd(II) at pH<5 but extremely enhanced the Cd(II) removal when the pH>5. The Cd(II) adsorption was sensitive to changes in the concentration of NaCl, NaNO3, NaClO4, and Na3PO4. Besides, the adsorption isotherm of Cd(II) onto MGO-SA could be well described by the Freundlich model and was also influenced by the type of background electrolyte ions and the ionic strength. PMID:25238326

  3. Role of Humic-Bound Iron as an Electron Transfer Agent in Dissimilatory Fe(III) Reduction

    PubMed Central

    Lovley, Derek R.; Blunt-Harris, Elizabeth L.

    1999-01-01

    The dissimilatory Fe(III) reducer Geobacter metallireducens reduced Fe(III) bound in humic substances, but the concentrations of Fe(III) in a wide range of highly purified humic substances were too low to account for a significant portion of the electron-accepting capacities of the humic substances. Furthermore, once reduced, the iron in humic substances could not transfer electrons to Fe(III) oxide. These results suggest that other electron-accepting moieties in humic substances, such as quinones, are the important electron-accepting and shuttling agents under Fe(III)-reducing conditions. PMID:10473447

  4. Iron Isotope Fractionations Reveal a Finite Bioavailable Fe Pool for Structural Fe(III) Reduction in Nontronite.

    PubMed

    Shi, Bingjie; Liu, Kai; Wu, Lingling; Li, Weiqiang; Smeaton, Christina M; Beard, Brian L; Johnson, Clark M; Roden, Eric E; Van Cappellen, Philippe

    2016-08-16

    We report on stable Fe isotope fractionation during microbial and chemical reduction of structural Fe(III) in nontronite NAu-1. (56)Fe/(54)Fe fractionation factors between aqueous Fe(II) and structural Fe(III) ranged from -1.2 to +0.8‰. Microbial (Shewanella oneidensis and Geobacter sulfurreducens) and chemical (dithionite) reduction experiments revealed a two-stage process. Stage 1 was characterized by rapid reduction of a finite Fe(III) pool along the edges of the clay particles, accompanied by a limited release to solution of Fe(II), which partially adsorbed onto basal planes. Stable Fe isotope compositions revealed that electron transfer and atom exchange (ETAE) occurred between edge-bound Fe(II) and octahedral (structural) Fe(III) within the clay lattice, as well as between aqueous Fe(II) and structural Fe(III) via a transient sorbed phase. The isotopic fractionation factors decreased with increasing extent of reduction as a result of the depletion of the finite bioavailable Fe(III) pool. During stage 2, microbial reduction was inhibited while chemical reduction continued. However, further ETAE between aqueous Fe(II) and structural Fe(III) was not observed. Our results imply that the pool of bioavailable Fe(III) is restricted to structural Fe sites located near the edges of the clay particles. Blockage of ETAE distinguishes Fe(III) reduction of layered clay minerals from that of Fe oxyhydroxides, where accumulation of structural Fe(II) is much more limited. PMID:27291525

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

    NASA Astrophysics Data System (ADS)

    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.

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

    PubMed

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

    2015-02-25

    Four Co(II) coordination polymers, [Co(suc)]n 1, [Co(pdc)]n 2, {[Co7(suc)4(OH)6(H2O)3]·8H2O}n 3, {[Co(bdc)(phen)(H2O)]·H2O}n 4 (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 suc(2-) and pdc(2-) anions bridging Co(II) ions, respectively. Polymer 3 exhibits a 2D structure with suc(2-) anions bridging seven-nuclear [Co7(OH)6(H2O)3](3-) unit and polymer 4 is a 1D structure bridged by bdc(2-) 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. PMID:25280332

  7. Advanced Experiment Analysis of controls on Microbial FE(III) Oxide Reduction

    SciTech Connect

    Roden, Eric E.; Urrutia, Matilde M.

    1999-06-01

    Understanding factors which control the long-term survival and activity of Fe(III)-reducing bacteria (FeRB) in subsurface sedimentary environments is important for predicting the ability of these organisms to serve as agents for bioremediation of organic and inorganic contaminants. This project seeks to refine our quantitative understanding of microbiological and geochemical controls on bacterial Fe(III) oxide reduction and growth of FeRB, using laboratory reactor systems which mimic to varying degrees the physical and chemical conditions of subsurface sedimentary environments. Methods for studying microbial Fe(III) oxide reduction and FeRB growth in experimental systems which incorporate advective aqueous phase flux are being developed for this purpose. These methodologies, together with an accumulating database on the kinetics of Fe(III) reduction and bacterial growth with various synthetic and natural Fe(III) oxide minerals, will be applicable to experimental and modeling studies of subsurface contaminant transformations directly coupled to or influenced by bacterial Fe(III) oxide reduction activity.

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

    SciTech Connect

    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.

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

    PubMed

    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

  10. Amino-functionalized core-shell magnetic mesoporous composite microspheres for Pb(II) and Cd(II) removal.

    PubMed

    Tang, Yulin; Liang, Song; Wang, Juntao; Yu, Shuili; Wang, Yilong

    2013-04-01

    Amino-functionalized Fe3O4@mesoporous SiO2 core-shell composite microspheres NH2-MS in created in multiple synthesis steps have been investigated for Pb(II) and Cd(II) adsorption. The microspheres were characterized by transmission electron microscope (TEM), scanning electron microscope (SEM), N2 adsorption-desorption, zeta potential measurements and vibrating sample magnetometer. Batch adsorption tests indicated that NH2-MS exhibited higher adsorption affinity toward Pb(II) and Cd(II) than MS did. The Langmuir model could fit the adsorption isotherm very well with maximum adsorption capacity of 128.21 and 51.81 mg/g for Pb(II) and Cd(II), respectively, implying that adsorption processes involved monolayer adsorption. Pb(II) and Cd(II) adsorption could be well described by the pseudo second-order kinetics model, and was found to be strongly dependent on pH and humic acid. The Pb(II)- and Cd(II)-loaded microspheres were effectively desorbed using 0.01 mol/L HCl or EDTA solution. NH2-MS have promise for use as adsorbents in the removal of Pb(II) and Cd(II) in wastewater treatment processes. PMID:23923794

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

    PubMed

    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

  12. Polarized Neutron Diffraction as a Tool for Mapping Molecular Magnetic Anisotropy: Local Susceptibility Tensors in Co(II) Complexes.

    PubMed

    Ridier, Karl; Gillon, Béatrice; Gukasov, Arsen; Chaboussant, Grégory; Cousson, Alain; Luneau, Dominique; Borta, Ana; Jacquot, Jean-François; Checa, Ruben; Chiba, Yukako; Sakiyama, Hiroshi; Mikuriya, Masahiro

    2016-01-11

    Polarized neutron diffraction (PND) experiments were carried out at low temperature to characterize with high precision the local magnetic anisotropy in two paramagnetic high-spin cobalt(II) complexes, namely [Co(II) (dmf)6 ](BPh4 )2 (1) and [Co(II) 2 (sym-hmp)2 ](BPh4 )2 (2), in which dmf=N,N-dimethylformamide; sym-hmp=2,6-bis[(2-hydroxyethyl)methylaminomethyl]-4-methylphenolate, and BPh4 (-) =tetraphenylborate. This allowed a unique and direct determination of the local magnetic susceptibility tensor on each individual Co(II) site. In compound 1, this approach reveals the correlation between the single-ion easy magnetization direction and a trigonal elongation axis of the Co(II) coordination octahedron. In exchange-coupled dimer 2, the determination of the individual Co(II) magnetic susceptibility tensors provides a clear outlook of how the local magnetic properties on both Co(II) sites deviate from the single-ion behavior because of antiferromagnetic exchange coupling. PMID:26728231

  13. Tuning the Ising-type anisotropy in trigonal bipyramidal Co(II) complexes.

    PubMed

    Shao, Feng; Cahier, Benjamin; Guihéry, Nathalie; Rivière, Eric; Guillot, Régis; Barra, Anne-Laure; Lan, Yanhua; Wernsdorfer, Wolfgang; Campbell, Victoria E; Mallah, Talal

    2015-11-28

    This paper demonstrates the engineering and tuning of Ising-type magnetic anisotropy in trigonal bipyramidal Co(II) complexes. Here, we predict that employing a ligand that forces a trigonal bipyramidal arrangement and has weak equatorial σ-donating atoms, increases (in absolute value) the negative zero field splitting parameter D. With these considerations in mind, we used a sulfur containing ligand (NS3(iPr)), which imposes a trigonal bipyramidal geometry to the central Co(II) ion with long equatorial Co-S bonds. The resulting complex exhibits a larger anisotropy barrier and a longer relaxation time in comparison to the complex prepared with a nitrogen containing ligand (Me6tren). PMID:26440770

  14. Microbial reduction of Fe(III) under alkaline conditions relevant to geological disposal.

    PubMed

    Williamson, Adam J; Morris, Katherine; Shaw, Sam; Byrne, James M; Boothman, Christopher; Lloyd, Jonathan R

    2013-06-01

    To determine whether biologically mediated Fe(III) reduction is possible under alkaline conditions in systems of relevance to geological disposal of radioactive wastes, a series of microcosm experiments was set up using hyperalkaline sediments (pH ~11.8) surrounding a legacy lime working site in Buxton, United Kingdom. The microcosms were incubated for 28 days and held at pH 10. There was clear evidence for anoxic microbial activity, with consumption of lactate (added as an electron donor) concomitant with the reduction of Fe(III) as ferrihydrite (added as the electron acceptor). The products of microbial Fe(III) reduction were black and magnetic, and a range of analyses, including X-ray diffraction, transmission electron microscopy, X-ray absorption spectroscopy, and X-ray magnetic circular dichroism confirmed the extensive formation of biomagnetite in this system. The addition of soluble exogenous and endogenous electron shuttles such as the humic analogue anthraquinone-2,6-disulfonate and riboflavin increased both the initial rate and the final extent of Fe(III) reduction in comparison to the nonamended experiments. In addition, a soluble humic acid (Aldrich) also increased both the rate and the extent of Fe(III) reduction. These results show that microbial Fe(III) reduction can occur in conditions relevant to a geological disposal facility containing cement-based wasteforms that has evolved into a high pH environment over prolonged periods of time (>100,000 years). The potential impact of such processes on the biogeochemistry of a geological disposal facility is discussed, including possible coupling to the redox conditions and solubility of key radionuclides. PMID:23524677

  15. Microbial Reduction of Fe(III) under Alkaline Conditions Relevant to Geological Disposal

    PubMed Central

    Williamson, Adam J.; Morris, Katherine; Shaw, Sam; Byrne, James M.; Boothman, Christopher

    2013-01-01

    To determine whether biologically mediated Fe(III) reduction is possible under alkaline conditions in systems of relevance to geological disposal of radioactive wastes, a series of microcosm experiments was set up using hyperalkaline sediments (pH ∼11.8) surrounding a legacy lime working site in Buxton, United Kingdom. The microcosms were incubated for 28 days and held at pH 10. There was clear evidence for anoxic microbial activity, with consumption of lactate (added as an electron donor) concomitant with the reduction of Fe(III) as ferrihydrite (added as the electron acceptor). The products of microbial Fe(III) reduction were black and magnetic, and a range of analyses, including X-ray diffraction, transmission electron microscopy, X-ray absorption spectroscopy, and X-ray magnetic circular dichroism confirmed the extensive formation of biomagnetite in this system. The addition of soluble exogenous and endogenous electron shuttles such as the humic analogue anthraquinone-2,6-disulfonate and riboflavin increased both the initial rate and the final extent of Fe(III) reduction in comparison to the nonamended experiments. In addition, a soluble humic acid (Aldrich) also increased both the rate and the extent of Fe(III) reduction. These results show that microbial Fe(III) reduction can occur in conditions relevant to a geological disposal facility containing cement-based wasteforms that has evolved into a high pH environment over prolonged periods of time (>100,000 years). The potential impact of such processes on the biogeochemistry of a geological disposal facility is discussed, including possible coupling to the redox conditions and solubility of key radionuclides. PMID:23524677

  16. New Approaches to Characterizing Fe(III) Bioreduction by Hyperthermophiles: Combining Physiological Potential with Mineral Spectroscopies

    NASA Astrophysics Data System (ADS)

    Kashyap, S.; Sklute, E.; Dyar, M. D.; Holden, J. F.

    2015-12-01

    Fe(III) is a widely available electron acceptor in many mildly-reducing deep-sea hydrothermal vents and terrestrial hot springs. Dissimilatory iron reduction, or the extracellular reduction of Fe(III) to Fe(II), is an integral biogeochemical process at these sites. Most of what is known about microbial Fe(III) reduction, however, has been established for mesophiles rather than the hyperthermophiles that are ubiquitous in hot environments. Our study examines the rates and constraints of Fe(III) bioreduction by hyperthermophilic archaea in order to address the types of Fe(III) (oxyhydr)oxides that are favored for growth of hyperthermophiles, the rates of growth and Fe(II) production for these organisms, and the mineralogy of Fe(III) bioreduction and possible variations with electron acceptor. We synthesized a range of nanophase Fe(III) (oxyhydr)oxides (2-line-ferrihydrite, 6-line-ferrihydrite, lepidocrocite, hematite, goethite, maghemite and akaganéite) and examined cell growth and Fe(II) production rates of Pyrodictium sp. Su06 and Pyrobaculum islandicum on the different Fe(III) (oxyhydr)oxides at 90°C and 95°C, respectively. Two different aggregate sizes of 2-line ferrihydrite and one of 6-line ferrihydrite were used to understand the effect of mineral aggregate size and shape on bioreduction. Direct cell counts and ferrozine assays were used to monitor cell growth and Fe(II) production respectively. Transformed mineral products were characterized using Mössbauer and attenuated total reflectance (ATR) spectroscopies. Preliminary results suggest that Pyrodictium sp. Su06 can only utilize 2-line ferrihydrite, producing up to 35 mM Fe(II) for smaller aggregates, and 10 mM Fe(II) for larger aggregates. P. islandicum on the other hand, can reduce 2-line-ferrihydrite, goethite, and lepidocrocite, producing up to 8 mM Fe(II) with ferrihydrite, 7 mM with lepidocrocite, and 2 mM with goethite as an electron acceptor. Initial results from Mössbauer and ATR spectra

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

    PubMed

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

    2016-05-17

    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 spectroscopy, and Mössbauer spectroscopy confirm the relationship between the model and authentic samples. These studies settle controversy in the cultural heritage field, where an alternative structure for Fe(III) gallate has been commonly cited. PMID:27058399

  18. Fe Isotope Fractionation During Fe(III) Reduction to Fe(II)

    NASA Astrophysics Data System (ADS)

    Baker, E. A.; Greene, S.; Hardin, E. E.; Hodierne, C. E.; Rosenberg, A.; John, S.

    2014-12-01

    The redox chemistry of Fe(III) and Fe(II) is tied to a variety of earth processes, including biological, chemical, or photochemical reduction of Fe(III) to Fe(II). Each process may fractionate Fe isotopes, but the magnitudes of the kinetic isotope effects have not been greatly explored in laboratory conditions. Here, we present the isotopic fractionation of Fe during reduction experiments under a variety of experimental conditions including photochemical reduction of Fe(III) bound to EDTA or glucaric acid, and chemical reduction of Fe-EDTA by sodium dithionite, hydroxylamine hydrochloride, Mn(II), and ascorbic acid. A variety of temperatures and pHs were tested. In all experiments, Fe(III) bound to an organic ligand was reduced in the presence of ferrozine. Ferrozine binds with Fe(II), forming a purple complex which allows us to measure the extent of reaction. The absorbance of the experimental solutions was measured over time to determine the Fe(II)-ferrozine concentration and thus the reduction rate. After about 5% of the Fe(III) was reduced, Fe(III)-EDTA and Fe(II)-ferrozine were separated using a C-18 column to which Fe(II)-ferrozine binds. The Fe(II) was eluted and purified through anion exchange chromatography for analysis of δ56Fe by MC-ICPMS. Preliminary results show that temperature and pH both affect reduction rate. All chemical reductants tested reduce Fe(III) at a greater rate as temperature increases. The photochemical reductant EDTA reduces Fe(III) at a greater rate under more acidic conditions. Comparison of the two photochemical reductants shows that glucaric acid reduces Fe(III) significantly faster than EDTA. For chemical reduction, the magnitude of isotopic fractionation depends on the reductant used. Temperature and pH also affect the isotopic fractionation of Fe. Experiments using chemical reductants show that an increase in temperature at low temperatures produces lighter 56Fe ratios, while at high temperatures some reductants produce heavier

  19. Molecular Underpinnings of Fe(III) Oxide Reduction by Shewanella Oneidensis MR-1

    PubMed Central

    Shi, Liang; Rosso, Kevin M.; Clarke, Tomas A.; Richardson, David J.; Zachara, John M.; Fredrickson, James K.

    2012-01-01

    In the absence of O2 and other electron acceptors, the Gram-negative bacterium Shewanella oneidensis MR-1 can use ferric [Fe(III)] (oxy)(hydr)oxide minerals as the terminal electron acceptors for anaerobic respiration. At circumneutral pH and in the absence of strong complexing ligands, Fe(III) oxides are relatively insoluble and thus are external to the bacterial cells. S. oneidensis MR-1 and related strains of metal-reducing Shewanella have evolved machinery (i.e., metal-reducing or Mtr pathway) for transferring electrons from the inner-membrane, through the periplasm and across the outer-membrane to the surface of extracellular Fe(III) oxides. The protein components identified to date for the Mtr pathway include CymA, MtrA, MtrB, MtrC, and OmcA. CymA is an inner-membrane tetraheme c-type cytochrome (c-Cyt) that belongs to the NapC/NrfH family of quinol dehydrogenases. It is proposed that CymA oxidizes the quinol in the inner-membrane and transfers the released electrons to MtrA either directly or indirectly through other periplasmic proteins. A decaheme c-Cyt, MtrA is thought to be embedded in the trans outer-membrane and porin-like protein MtrB. Together, MtrAB deliver the electrons through the outer-membrane to the MtrC and OmcA on the outmost bacterial surface. MtrC and OmcA are the outer-membrane decaheme c-Cyts that are translocated across the outer-membrane by the bacterial type II secretion system. Functioning as terminal reductases, MtrC and OmcA can bind the surface of Fe(III) oxides and transfer electrons directly to these minerals via their solvent-exposed hemes. To increase their reaction rates, MtrC and OmcA can use the flavins secreted by S. oneidensis MR-1 cells as diffusible co-factors for reduction of Fe(III) oxides. Because of their extracellular location and broad redox potentials, MtrC and OmcA can also serve as the terminal reductases for soluble forms of Fe(III). In addition to Fe(III) oxides, Mtr pathway is also involved in reduction of

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

    SciTech Connect

    Xu, Cai-Xia; Zhang, Jian-Guo 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.

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

    PubMed

    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

  2. Indirect Oxidation of Co(II) in the Presence of the Marine Mn(II)-Oxidizing Bacterium Bacillus Sp. Strain SG-1

    SciTech Connect

    Murray, K.J.; Webb, S.M.; Bargar, J.R.; Tebo, B.M.; /Scripps Inst. Oceanography /SLAC, SSRL /Oregon Health Sci. U.

    2009-04-29

    Cobalt(II) oxidation in aquatic environments has been shown to be linked to Mn(II) oxidation, a process primarily mediated by bacteria. This work examines the oxidation of Co(II) by the spore-forming marine Mn(II)-oxidizing bacterium Bacillus sp. strain SG-1, which enzymatically catalyzes the formation of reactive nanoparticulate Mn(IV) oxides. Preparations of these spores were incubated with radiotracers and various amounts of Co(II) and Mn(II), and the rates of Mn(II) and Co(II) oxidation were measured. Inhibition of Mn(II) oxidation by Co(II) and inhibition of Co(II) oxidation by Mn(II) were both found to be competitive. However, from both radiotracer experiments and X-ray spectroscopic measurements, no Co(II) oxidation occurred in the complete absence of Mn(II), suggesting that the Co(II) oxidation observed in these cultures is indirect and that a previous report of enzymatic Co(II) oxidation may have been due to very low levels of contaminating Mn. Our results indicate that the mechanism by which SG-1 oxidizes Co(II) is through the production of the reactive nanoparticulate Mn oxide.

  3. Evaluation of a biomarker of Cd(II) exposure on Limnoperna fortunei.

    PubMed

    Mariano, Belaich; Cristian, Oliver; Marcela, Pilloff; Porta, Andrés

    2006-11-01

    The use of organisms to monitor contamination allows the access to information that cannot be acquired by chemical methods. Limnoperna fortunei, mussel frequently found in Río de la Plata estuary, fulfils the requirements to be used as a biomonitoring organism. In this work we report that a polypeptide of 22 kDa of molecular weight (LF22) is induced when L. fortunei is exposed to Cd (II), Cu(II) and Hg(II) sublethal levels. To characterize LF22, mussels were sampled from a non-polluted region and whole soft tissue was homogenized, with and without previous exposure to 100 microg/L of Cd(II). The cytosolic proteins were evaluated by mono and bidimensional SDS-PAGE, and size exclusion chromatography. All the methods showed that LF22 triples its concentration in presence of Cd(II). Purification of LF22 was achieved by fractioned precipitation, salting-out, ionic exchange and size exclusion chromatography. We conclude that LF22 is a useful biomarker of heavy metal exposure. PMID:16603290

  4. Extracellular Electron Transfer to Fe(III) Oxides by the Hyperthermophilic Archaeon Geoglobus ahangari via a Direct Contact Mechanism

    PubMed Central

    Manzella, Michael P.; Reguera, Gemma

    2013-01-01

    The microbial reduction of Fe(III) plays an important role in the geochemistry of hydrothermal systems, yet it is poorly understood at the mechanistic level. Here we show that the obligate Fe(III)-reducing archaeon Geoglobus ahangari uses a direct-contact mechanism for the reduction of Fe(III) oxides to magnetite at 85°C. Alleviating the need to directly contact the mineral with the addition of a chelator or the electron shuttle anthraquinone-2,6-disulfonate (AQDS) stimulated Fe(III) reduction. In contrast, entrapment of the oxides within alginate beads to prevent cell contact with the electron acceptor prevented Fe(III) reduction and cell growth unless AQDS was provided. Furthermore, filtered culture supernatant fluids had no effect on Fe(III) reduction, ruling out the secretion of an endogenous mediator too large to permeate the alginate beads. Consistent with a direct contact mechanism, electron micrographs showed cells in intimate association with the Fe(III) mineral particles, which once dissolved revealed abundant curled appendages. The cells also produced several heme-containing proteins. Some of them were detected among proteins sheared from the cell's outer surface and were required for the reduction of insoluble Fe(III) oxides but not for the reduction of the soluble electron acceptor Fe(III) citrate. The results thus support a mechanism in which the cells directly attach and transfer electrons to the Fe(III) oxides using redox-active proteins exposed on the cell surface. This strategy confers on G. ahangari a competitive advantage for accessing and reducing Fe(III) oxides under the extreme physical and chemical conditions of hot ecosystems. PMID:23728807

  5. Solubility of Fe(III) and Al in AMD by modelling and experimtn

    SciTech Connect

    Mitchell, K.G.; Wildeman, T.R.

    1995-12-01

    Studies of Fe(III) and Al species in acid mine drainage (AMD) alone and in contact with limestone were conducted by MINTEQA2 and by experiments. Using Fe(OH){sub 3} as the primary species and the standard values for MINTEQ, Fe(III) precipitates at pH 2.90 when the concentration is 453 mg/L. Al precipitates at a pH of 4.00 when the concentration is 108 mg/L. Experiments found that over 90 % of Fe(III) and 45 % of Al were precipitated at these pH`s. Experimental verification of Fe(III) concentrations at pH`s from 2.90 to 4.0 found that modelling agreed with experiment when ferrihydrite is the primary solid and the log Ksp is -38.9. For Al, gibbsite would be the primary solid and log Ksp is -34.1. For AMD in contact with CaCO{sub 3} when CO{sub 2} is conserved, final alkalinity is higher when mineral acidity is higher even though pH of the final solution is lower. This modelling result was confirmed by experiment. Higher mineral acidity causes generation of more CO{sub 2} that reacts with CaCO{sub 3} to generate more dissolved HCO{sub 3-}.

  6. ADVANCED EXPERIMENTAL ANALYSIS OF CONTROLS ON MICROBIAL FE(III) OXIDE REDUCTION

    EPA Science Inventory

    Fe(III) oxides are ubiquitous components of soils, sediments, and subsurface materials, and are one of the most important sorbents for heavy metals, radionuclides, organic contaminants and organic/metal co-contaminants in the subsurface. These compounds can serve as electron sink...

  7. FINAL REPORT. ADVANCED EXPERIMENTAL ANALYSIS OF CONTROLS ON MICROBIAL FE(III) OXIDE REDUCTION

    EPA Science Inventory

    The objectives of this research project were to refine existing models of microbiological and geochemical controls on Fe(III) oxide reduction, using laboratory reactor systems which mimic to varying degrees the physical and chemical conditions of the subsurface. Novel experimenta...

  8. Rapid electron exchange between surface-exposed bacterial cytochromes and Fe(III) minerals

    NASA Astrophysics Data System (ADS)

    White, Gaye F.; Shi, Zhi; Shi, Liang; Wang, Zheming; Dohnalkova, Alice C.; Marshall, Matthew J.; Fredrickson, James K.; Zachara, John M.; Butt, Julea N.; Richardson, David J.; Clarke, Thomas A.

    2013-04-01

    The mineral-respiring bacterium Shewanella oneidensis uses a protein complex, MtrCAB, composed of two decaheme cytochromes, MtrC and MtrA, brought together inside a transmembrane porin, MtrB, to transport electrons across the outer membrane to a variety of mineral-based electron acceptors. A proteoliposome system containing a pool of internalized electron carriers was used to investigate how the topology of the MtrCAB complex relates to its ability to transport electrons across a lipid bilayer to externally located Fe(III) oxides. With MtrA facing the interior and MtrC exposed on the outer surface of the phospholipid bilayer, the established in vivo orientation, electron transfer from the interior electron carrier pool through MtrCAB to solid-phase Fe(III) oxides was demonstrated. The rates were 103 times higher than those reported for reduction of goethite, hematite, and lepidocrocite by S. oneidensis, and the order of the reaction rates was consistent with those observed in S. oneidensis cultures. In contrast, established rates for single turnover reactions between purified MtrC and Fe(III) oxides were 103 times lower. By providing a continuous flow of electrons, the proteoliposome experiments demonstrate that conduction through MtrCAB directly to Fe(III) oxides is sufficient to support in vivo, anaerobic, solid-phase iron respiration.

  9. Rapid electron exchange between surface-exposed bacterial cytochromes and Fe(III) minerals

    PubMed Central

    White, Gaye F.; Shi, Zhi; Shi, Liang; Wang, Zheming; Dohnalkova, Alice C.; Marshall, Matthew J.; Fredrickson, James K.; Zachara, John M.; Butt, Julea N.; Richardson, David J.; Clarke, Thomas A.

    2013-01-01

    The mineral-respiring bacterium Shewanella oneidensis uses a protein complex, MtrCAB, composed of two decaheme cytochromes, MtrC and MtrA, brought together inside a transmembrane porin, MtrB, to transport electrons across the outer membrane to a variety of mineral-based electron acceptors. A proteoliposome system containing a pool of internalized electron carriers was used to investigate how the topology of the MtrCAB complex relates to its ability to transport electrons across a lipid bilayer to externally located Fe(III) oxides. With MtrA facing the interior and MtrC exposed on the outer surface of the phospholipid bilayer, the established in vivo orientation, electron transfer from the interior electron carrier pool through MtrCAB to solid-phase Fe(III) oxides was demonstrated. The rates were 103 times higher than those reported for reduction of goethite, hematite, and lepidocrocite by S. oneidensis, and the order of the reaction rates was consistent with those observed in S. oneidensis cultures. In contrast, established rates for single turnover reactions between purified MtrC and Fe(III) oxides were 103 times lower. By providing a continuous flow of electrons, the proteoliposome experiments demonstrate that conduction through MtrCAB directly to Fe(III) oxides is sufficient to support in vivo, anaerobic, solid-phase iron respiration. PMID:23538304

  10. Reduction of structural Fe(III) in nontronite by methanogen Methanosarcina barkeri

    NASA Astrophysics Data System (ADS)

    Liu, Deng; Dong, Hailiang; Bishop, Michael E.; Wang, Hongmei; Agrawal, Abinash; Tritschler, Sarah; Eberl, Dennis D.; Xie, Shucheng

    2011-02-01

    Clay minerals and methanogens are ubiquitous and co-exist in anoxic environments, yet it is unclear whether methanogens are able to reduce structural Fe(III) in clay minerals. In this study, the ability of methanogen Methanosarcina barkeri to reduce structural Fe(III) in iron-rich smectite (nontronite NAu-2) and the relationship between iron reduction and methanogenesis were investigated. Bioreduction experiments were conducted in growth medium using three types of substrate: H 2/CO 2, methanol, and acetate. Time course methane production and hydrogen consumption were measured by gas chromatography. M. barkeri was able to reduce structural Fe(III) in NAu-2 with H 2/CO 2 and methanol as substrate, but not with acetate. The extent of bioreduction, as measured by the 1,10-phenanthroline method, was 7-13% with H 2/CO 2 as substrate, depending on nontronite concentration (5-10 g/L). The extent was higher when methanol was used as a substrate, reaching 25-33%. Methanogenesis was inhibited by Fe(III) reduction in the H 2/CO 2 culture, but enhanced when methanol was used. High charge smectite and biogenic silica formed as a result of bioreduction. Our results suggest that methanogens may play an important role in biogeochemical cycling of iron in clay minerals and may have important implications for the global methane budget.

  11. Anaerobic Microbial-Mineral Processes with Fe(III) Oxides: Experimental Considerations and Approaches

    SciTech Connect

    Zachara, John M.; Fredrickson, Jim K.; Kukkadapu, Ravi K.; Gorby, Yuri A.

    2007-07-01

    The biogeochemical cycle of Fe is a one of the dominant redox cycles operative in surface waters and sediments, soils and vadose zones, and groundwater systems. In this cycle which is pronounced at oxic-anoxic boundaries, Fe compounds and microorganisms couple to mediate the oxidation of organic matter by molecular oxygen. The cycle includes: i.) the reductive dissolution of Fe(III) oxides by biogenic organic acids and organic matter oxidizing-metal reducing bacteria yielding Fe2+(aq) and ferrous containing minerals as products, and ii.) the oxidation of dissolved and solid-phase ferrous iron by molecular oxygen and microaerophilic Fe(II)-oxidizing bacteria with subsequent precipitation of poorly crystalline Fe(III) oxides (e.g., ferrihydrite). These Fe(III) oxides; that may recrystallize slowly with time to goethite, hematite, and lepidocrocite; represent a primary redox buffering agent (in terms of electron equivalents) in soils, sediments, and subsurface materials. Manganese (III/IV) oxides are also important in this regard. Because of the high surface area and surface chemical reactivity of Fe(III) oxides and Fe(II) containing mineral phases, the Fe biogeochemical cycle is closely linked to those of the trace metals, phosphorous, and various organic and inorganic anthropogenic contaminants.

  12. Reaction-Based Reactive Transport Modeling of Fe(III) and U(V) Reduction

    SciTech Connect

    Burgos, William D.; Roden, Eric E.; Yeh, Gour-Tsyh

    2005-06-01

    Our new research project (started Fall 2004) was funded by a grant to The Pennsylvania State University, University of Central Florida, and The University of Alabama in the Integrative Studies Element of the NABIR Program (DE-FG04-ER63914/63915/63196). Our previous NABIR project (DE-FG02-01ER63180/63181/63182, funded within the Biotransformation Element) focused on (1) microbial reduction of Fe(III) and U(VI) individually, and concomitantly in natural sediments, (2) Fe(III) oxide surface chemistry, specifically with respect to reactions with Fe(II) and U(VI), (3) the influence of humic substances on Fe(III) and U(VI) bioreduction, and on U(VI) complexation, and (4) the development of reaction-based reactive transport biogeochemical models to numerically simulate our experimental results. The new project focuses on the development of a mechanistic understanding and quantitative models of coupled Fe(III)/U(VI) reduction in FRC Area 2 sediments. This work builds on our previous studies of microbial Fe(III) and U(VI) reduction, and is directly aligned with the Scheibe et al. NABIR FRC Field Project at Area 2.

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

    NASA Astrophysics Data System (ADS)

    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

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

    SciTech Connect

    Kieft, T. L.; Fredrickson, J. K.; Onstott, T. C.; Gorby, Y. A.; Kostandarithes, H. M.; Bailey, T. J.; Kennedy, D. W.; Li, S. W.; Plymale, A. E.; Spadoni, C. M.; Gray, M. S.

    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.

  15. Rapid photooxidation of Sb(III) in the presence of different Fe(III) species

    NASA Astrophysics Data System (ADS)

    Kong, Linghao; He, Mengchang; Hu, Xingyun

    2016-05-01

    The toxicity and mobility of antimony (Sb) are strongly influenced by the redox processes associated with Sb. Dissolved iron (Fe) is widely distributed in the environment as different species and plays a significant role in Sb speciation. However, the mechanisms of Sb(III) oxidation in the presence of Fe have remained unclear because of the complexity of Fe and Sb speciation. In this study, the mechanisms of Sb(III) photooxidation in the presence of different Fe species were investigated systematically. The photooxidation of Sb(III) occurred over a wide pH range, from 1 to 10. Oxygen was not a predominant or crucial factor in the Sb(III) oxidation process. The mechanism of Sb(III) photooxidation varied depending on the Fe(III) species. In acidic solution (pH 1-3), dichloro radicals (radCl2-) and hydroxyl radicals (radOH) generated by the photocatalysis of FeCl2+ and FeOH2+ were the main oxidants for Sb(III) oxidation. Fe(III) gradually transformed into the colloid ferric hydroxide (CFH) and ferrihydrite in circumneutral and alkaline solutions (pH 4-10). Photooxidation of Sb(III) occurred through electron transfer from Sb(III) to Fe(III) along with the reduction of Fe(III) to Fe(II) through a ligand-to-metal charge-transfer (LMCT) process. The photocatalysis of different Fe(III) species may play an important role in the geochemical cycle of Sb(III) in surface soil and aquatic environments.

  16. Solubility of Fe(III) Al in AMD by modelling and experiment

    SciTech Connect

    Mitchell, K.G.; Wildeman, T.R.

    1996-12-31

    Studies of Fe(III) and Al species in acid mine drainage (AMD) alone and in contact with limestone were conducted by MINTEQA2 modelling and by experiments. The objectives of these studies were to: (1) determine at what pH Fe(III) and Al would be in solution in AMD such that the water would be harmful to an anoxic limestone drain (ALD), and (2) evaluate the theoretical limits to the amount of alkalinity that could be generated by an ALD. Using Fe(OH){sub 3} as the primary species and the standard values for MINTEQA2, Fe(III) precipitates at pH 2.90 when the concentration is over 453 mg/L. Al precipitates at a pH of 4.00 when the concentration is over 108 mg/L. Experiments found that over 90 % of Fe(III) and 45% of Al were precipitated at these pH`s. Experimental verification of Fe(III) concentrations of pH`s from 2.90 to 4.0 found that modelling agreed with experiment when ferrihydrite is the primary solid and the log Ksp (solubility product) is -38.9. For Al, gibbsite would be the primary solid and log Ksp is -34.1. For AMD in contact with CaCO{sub 3} when CO{sub 2} is conserved, final alkalinity is higher when mineral acidity is higher even though pH of the final solution is lower. This modelling result was confirmed by experiment. Higher mineral acidity causes generation of more CO{sub 2} that reacts with CaCO{sub 3} to generate more dissolved HCO{sub -3}.

  17. Photodegradation of 4-tert octylphenol in aqueous solution promoted by Fe(III).

    PubMed

    Wu, Yanlin; Yuan, Haixia; Wei, Guanran; Zhang, Shanduan; Li, Hongjing; Dong, Wenbo

    2013-01-01

    4-Tert-octylphenol (4-t-OP), a kind of endocrine-disrupting compounds, is widely distributed in natural water surroundings but can hardly be biodegraded. The advanced oxidation processes (AOPs) have been proved to be an efficient method to degrade 4-t-OP. In this study, the photodegradation of 4-t-OP in aqueous solution promoted by Fe(III) and the photooxidation mechanism were investigated. The ferric perchlorate was added into the aqueous solution for the production of hydroxyl radical. The efficiency of mineralization was monitored by total organic carbon analyzer, and photooxidation products were determined by high-performance liquid chromatography and liquid chromatography-mass spectrometer. 4-t-OP (2.4 × 10(-5) M) in aqueous solution was completely degraded after 45 min in the presence of Fe(III) (1.2 × 10(-3) M) under UV irradiation (λ = 365 nm). The optimal pH was 3.5. Higher Fe(III) concentration or lower initial 4-t-OP concentration led to increased photodegradation efficiency of 4-t-OP. The reaction was almost completely inhibited in the presence of 2-propanol. About 70 % mineralization of the solution was obtained after 50 h. The photooxidation product was supposed to be 4-tert-octyl catechol. 4-t-OP in aqueous solution can be degraded in the presence of Fe(III) under the solar irradiation. The photoinduced degradation is due to the reaction with hydroxyl radicals. It shows that the 4-t-OP is mineralized by the inducement of Fe(III) aquacomplexes, which exposes to solar light. Therefore, the results would provide useful information for the potential application of the AOPs to remove 4-t-OP in water surroundings. PMID:22814959

  18. Aluminum affects heterogeneous Fe(III) (Hydr)oxide nucleation, growth, and ostwald ripening.

    PubMed

    Hu, Yandi; Li, Qingyun; Lee, Byeongdu; Jun, Young-Shin

    2014-01-01

    Heterogeneous coprecipitation of iron and aluminum oxides is an important process for pollutant immobilization and removal in natural and engineered aqueous environments. Here, using a synchrotron-based small-angle X-ray scattering technique, we studied heterogeneous nucleation and growth of Fe(III) (hydr)oxide on quartz under conditions found in acid mine drainage (at pH = 3.7 ± 0.2, [Fe(3+)] = 10(-4) M) with different initial aqueous Al/Fe ratios (0:1, 1:1, and 5:1). Interestingly, although the atomic ratios of Al/Fe in the newly formed Fe(III) (hydr)oxide precipitates were less than 1%, the in situ particle size and volume evolutions of the precipitates on quartz were significantly influenced by aqueous Al/Fe ratios. At the end of the 3 h experiments, with aqueous Al/Fe ratios of 0:1, 1:1, and 5:1, the average radii of gyration of particles on quartz were 5.7 ± 0.3, 4.6 ± 0.1, and 3.7 ± 0.3 nm, respectively, and the ratio of total particle volumes on quartz was 1.7:3.4:1.0. The Fe(III) (hydr)oxide precipitates were poorly crystallized, and were positively charged in all solutions. In the presence of Al(3+), Al(3+) adsorption onto quartz changed the surface charge of quartz from negative to positive, which caused the slower heterogeneous growth of Fe(III) (hydr)oxide on quartz. Furthermore, Al affected the amount of water included in the Fe(III) (hydr)oxides, which can influence their adsorption capacity. This study yielded important information usable for pollutant removal not only in natural environments, but also in engineered water treatment processes. PMID:24289329

  19. Removal of Pb(II) and Cd(II) ions from aqueous solution by thiosemicarbazide modified chitosan.

    PubMed

    Li, Manlin; Zhang, Zengqiang; Li, Ronghua; Wang, Jim J; Ali, Amjad

    2016-05-01

    The removal of Pb(II) and Cd(II) ions from aqueous solution by thiosemicarbazide modified chitosan (TCS) was studied in this article. The synthesized TCS was characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), element analysis, N2 adsorption-desorption, scanning electron microscopy (SEM) and X-ray photoelectron spectrophotometer (XPS). Moreover, the influence of solution pH, contact time, initial heavy metal concentration, and solution temperature on the adsorption process was examined, and the adsorbent reusability and adsorption mechanisms were also studied. The results showed that TCS adsorbed greater amount of Pb(II) and Cd(II) ions than the raw chitosan. The adsorption amounts of Pb(II) and Cd(II) ions were affected by increasing solution pH and temperature. The maximum adsorption capacities of the TCS for Pb(II) and Cd(II) ions were found to be 325.2 and 257.2 mg/g, respectively. The endothermic adsorption fitted the pseudo-second-order kinetics equation and the adsorption isotherms could be well described by Langmuir model. The metal ions adsorption mechanism was concluded to be mainly dominated by complexation reaction process. The desorption study indicated that the target adsorbent was easy to be regenerated. PMID:26879912

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

    NASA Astrophysics Data System (ADS)

    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.

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

    PubMed

    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

  2. Structures and stabilities of Cd(II) and Cd(II)-phthalate complexes at the goethite/water interface

    NASA Astrophysics Data System (ADS)

    Boily, Jean-François; Sjöberg, Staffan; Persson, Per

    2005-07-01

    The complexation of Cd(II) and Cd(II)-phthalate at the goethite/water interface were investigated by EXAFS and IR spectroscopy, by batch adsorption experiments and by potentiometric titrations at 298.15 K. The EXAFS spectra showed Cd(II) to form only inner-sphere corner-sharing complexes with the goethite surface sites in the presence and absence of phthalate. EXAFS spectra also showed the presence of Cd(II)-chloride complexes in 0.1 mol/L NaCl. IR spectra also showed phthalate to form (1) an inner-sphere complex with adsorbed corner-sharing Cd(II) surface complexes in the pH 3.5 to 9.5 and (2) an outer-sphere complex with the same type of corner-sharing Cd(II) complex however at pH > 6, in addition to the inner- and outer-sphere complexes of phthalate reported in a previous study. The potentiometric titration and the batch adsorption data were used to constrain the formation constants of the different Cd(II)-phthalate surface complexes on the dominant {110} and the {001} planes of the goethite. The models were carried out with the Charge Distribution Multisite Complexation model coupled to the Three Plane Model and can predict the molecular-scale speciation of cadmium and phthalate in the presence of goethite. Cd(II) adsorption models calibrated on a 90 m 2/g goethite also could accurately predict experimental data for a 37 m 2/g goethite of slightly different basic charging properties.

  3. Structures and stabilities of Cd(II) and Cd(II)-phthalate complexes at the goethite/water interface

    SciTech Connect

    Boily, Jean F.; Sjoberg, Staffan; Persson, Per

    2005-01-01

    The complexation of Cd(II) and Cd(II)-phthalate at the goethite/water interface were investigated by EXAFS and IR spectroscopy, by batch adsorption experiments and by potentiometric titrations at 298.15 K. The EXAFS spectra showed Cd(II) to form only inner-sphere corner-sharing complexes with the goethite surface sites in the presence and absence of phthalate. EXAFS spectra also showed the presence of Cd(II)-chloride complexes in 0.1 mol/L NaCl. IR spectra also showed phthalate to form (1) an inner-sphere complex with adsorbed corner-sharing Cd(II) surface complexes in the pH 3.5 to 9.5 and (2) an outer-sphere complex with the same type of corner-sharing Cd(II) complex however at pH > 6, in addition to the inner- and outer-sphere complexes of phthalate reported in a previous study. The potentiometric titration and the batch adsorption data were used to constrain the formation constants of the different Cd(II)-phthalate surface complexes on the dominant {110} and the {001} planes of the goethite. The models were carried out with the Charge Distribution Multisite Complexation model coupled to the Three Plane Model and can predict the molecular-scale speciation of cadmium and phthalate in the presence of goethite. Cd(II) adsorption models calibrated on a 90 m2/g goethite also could accurately predict experimental data for a 37 m2/g goethite of slightly different basic charging properties.

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

    PubMed

    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

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

    PubMed

    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

  6. Coordination Behavior of 3-Ethoxycarbonyltetronic Acid towards Cu(II) and Co(II) Metal Ions

    PubMed Central

    Athanasellis, Giorgos; Zahariou, Georgia; Kikionis, Stefanos; Igglessi-Markopoulou, Olga; Markopoulos, John

    2008-01-01

    Tetronic acids, 4-hydroxy-5H-furan-2-ones, constitute a class of heterocyclic compounds with potent biological and pharmacological activity. The β, β′-tricarbonyl moiety plays an integral role in biological systems and forms a variety of metal complexes. In this report, we present the complexation reactions of 3-ethoxycarbonyl tetronic acids with acetates and chlorides of Cu(II) and Co(II). These complexes have been studied by means of EPR spectroscopy and magnetic susceptibility measurements. From the obtained results, a preliminary complexation mode of the ligand is proposed. PMID:19197392

  7. Separation and extraction of Co(II) using magnetic chitosan nanoparticles grafted with β-cyclodextrin and determination by FAAS

    NASA Astrophysics Data System (ADS)

    Moghimi, Ali

    2014-12-01

    A novel and selective method for the fast determination of trace amounts of Co(II) ions in water samples has been developed. The procedure is based on the selective sorption of Co(II) ions using magnetic chitosan nanoparticles grafted with β-cyclodextrin at different pH followed by elution with organic eluents and determination by atomic absorption spectrometry The preconcentration factor was 100 (1 mL elution volume) for a 100 mL sample volume. The limit of detection of the proposed method is 1.0 ng mL-1. The maximum sorption capacity of sorbent under optimum conditions has been found to be 5 mg of Co per gram of sorbent. The relative standard deviation under optimum conditions was 3.0% ( n = 10). Accuracy and applicability of the method was estimated using test samples of natural and model water with different amounts of Co(II).

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

    PubMed Central

    Kieft, T. L.; Fredrickson, J. K.; Onstott, T. C.; Gorby, Y. A.; Kostandarithes, H. M.; Bailey, T. J.; Kennedy, D. W.; Li, S. W.; Plymale, A. E.; Spadoni, C. M.; Gray, M. S.

    1999-01-01

    A thermophilic bacterium that can use O2, NO3−, Fe(III), and S0 as terminal electron acceptors for growth was isolated from groundwater sampled at a 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 rRNA gene (rDNA) 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. Neither SA-01 nor NMX2 A.1 grew fermentatively, i.e., addition of an external electron acceptor was required for anaerobic growth. Thermus strain SA-01 reduced soluble Fe(III) complexed with citrate or nitrilotriacetic acid (NTA); however, it could reduce only relatively small quantities (0.5 mM) of hydrous ferric oxide except when the humic acid analog 2,6-anthraquinone disulfonate was added as an electron shuttle, in which case 10 mM Fe(III) was reduced. Fe(III)-NTA was reduced quantitatively to Fe(II); reduction of Fe(III)-NTA was coupled to the oxidation of lactate and supported growth through three consecutive transfers. Suspensions of Thermus strain SA-01 cells also reduced Mn(IV), Co(III)-EDTA, Cr(VI), and U(VI). Mn(IV)-oxide was reduced in the presence of either lactate or H2. Both strains were also able to mineralize NTA to CO2 and to couple its oxidation to Fe(III) reduction and growth. The optimum temperature for growth and Fe(III) reduction by Thermus strains SA-01 and NMX2 A.1 is approximately 65°C; their 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. PMID:10049886

  9. Luminescent properties, internal hydrogen bonds and π-π interactions of Cd(II), Zn(II), Co(II) complexes based on 2,8-di(pyridin-4-yl)dibenzothiophene and dicarboxylate ligands

    NASA Astrophysics Data System (ADS)

    Huang, Cheng-Yan; Wang, Jie; Ding, Zhi-Yuan; Cui, Kai

    2015-04-01

    Based on a V-shaped N-containing ligand [2,8-di(pyridin-4-yl)dibenzothiophene, DPDBT], three new coordination polymers with different dimensionality, namely, {[Cd2(DPDBT)2(DCPS)2(H2O)](H2O)}n (1), {[Zn(DPDBT)2(5-OH-bdc)]}n (2) and {[Co(DPDBT)2(H2O)4](hfipbb)}n (3), [H2DCPS = 4,4‧-dicarboxydiphenyl sulfone, 5-OH-H2bdc = 5-hydroxyisophthalic acid, H2hfipbb = 4,4‧-(Hexafluoroisopropylidene)bis(benzoic acid)], have been synthesized under solvothermal conditions. Complex 1 exhibits a 2D structure with two different kinds of binuclear cadmium cluster units. The formation from 0D, 1D, 2D → 3D structures with hydrogen bonds and π-π interactions in 1-3 were investigated in details. In addition, luminescent properties of 1, 2 and related free ligands in the solid state have also been studied.

  10. Molecular Underpinnings of Fe(III) Oxide Reduction by Shewanella oneidensis MR-1

    SciTech Connect

    Shi, Liang; Rosso, Kevin M.; Clarke, Thomas A.; Richardson, David J.; Zachara, John M.; Fredrickson, Jim K.

    2012-02-15

    In the absence of O2 and other electron acceptors, the Gram-negative bacterium Shewanella oneidensis MR-1 can use ferric [Fe(III)] (oxy)(hydr)oxide minerals as the terminal electron acceptors for anaerobic respiration. At circumneutral pH and in the absence of strong complexing ligands, Fe(III) oxides are relatively insoluble and thus are external to the bacterial cells. S. oneidensis MR-1 and related strains of metal-reducing Shewanella have evolved the machinery (i.e., metal-reducing or Mtr pathway) for transferring electrons from the inner-membrane, through the periplasm and across the outer-membrane to the surface of extracellular Fe(III) oxides. The protein components identified to date for the Mtr pathway include CymA, MtrA, MtrB, MtrC and OmcA. CymA is an inner-membrane tetraheme c-type cytochrome (c-Cyt) that belongs to the NapC/NrfH family of quinol dehydrogenases. It is proposed that CymA oxidizes the quinol in the inner-membrane and transfers the released electrons to redox proteins in the periplasm. Although the periplasmic proteins receiving electrons from CymA during Fe(III) oxidation have not been identified, they are believed to relay the electrons in the periplasm to MtrA. A decaheme c-Cyt, MtrA is thought to be embedded in the trans outer-membrane and porin-like protein MtrB. Together, MtrAB deliver the electrons through the outer-membrane to the MtrC and OmcA on the outmost bacterial surface. MtrC and OmcA are the outer-membrane decaheme c-Cyts that are translocated across the outer-membrane by the bacterial type II secretion system. Functioning as terminal reductases, MtrC and OmcA can bind the surface of Fe(III) oxides and transfer electrons directly to these minerals via their solvent-exposed hemes. To increase their reaction rates, MtrC and OmcA can use the flavins secreted by S. oneidensis MR-1 cells as diffusible co-factors for reduction of Fe(III) oxides. Because of their extracellular location and broad redox potentials, MtrC and OmcA can

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

    NASA Astrophysics Data System (ADS)

    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. Requirement for a microbial consortium to completely oxidize glucose in Fe(III)- reducing sediments

    USGS Publications Warehouse

    Lovley, D.R.; Phillips, E.J.P.

    1989-01-01

    In various sediments in which Fe(III) reduction was the terminal electron-accepting process, [14C]glucose was fermented to 14C-fatty acids in a manner similar to that observed in methanogenic sediments. These results are consistent with the hypothesis that, in Fe(III)-reducing sediments, fermentable substrates are oxidized to carbon dioxide by the combined activity of fermentative bacteria and fatty acid-oxidizing, Fe(III)-reducing bacteria.

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

    PubMed

    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

  14. Rapid electron exchange between surface-exposed bacterial cytochromes and Fe(III) minerals

    SciTech Connect

    White, Gaye F.; Shi, Zhi; Shi, Liang; Wang, Zheming; Dohnalkova, Alice; Marshall, Matthew J.; Fredrickson, Jim K.; Zachara, John M.; Butt, Julea N.; Richardson, David; Clarke, Thomas A.

    2013-04-16

    The mineral respiring bacterium Shewanella oneidensis uses a protein complex, MtrCAB, composed of two decaheme cytochromes brought together inside a transmembrane porin to transport electrons across the outer membrane to a variety of mineral-based electron acceptors. A proteoliposome system that contains methyl viologen as an internalised electron carrier has been used to investigate how the topology of the MtrCAB complex relates to its ability to transport electrons across a lipid bilayer to externally-located Fe(III) oxides. With MtrA facing the interior and MtrC exposed on the outer surface of the phospholipid bilayer, direct electron transfer from the interior through MtrCAB to solid-phase Fe(III) oxides was demonstrated. The observed rates of conduction through the protein complex were 2 to 3 orders of magnitude higher than that observed in whole cells, demonstrating that direct electron exchange between MtrCAB and Fe(III) oxides is efficient enough to support in-vivo, anaerobic, solid phase iron respiration.

  15. Microbial Reductive Transformation of Phyllosilicate Fe(III) and U(VI) in Fluvial Subsurface Sediments

    SciTech Connect

    Lee, Ji-Hoon; Fredrickson, Jim K.; Kukkadapu, Ravi K.; Boyanov, Maxim I.; Kemner, Kenneth M.; Lin, Xueju; Kennedy, David W.; Bjornstad, Bruce N.; Konopka, Allan; Moore, Dean A.; Resch, Charles T.; Phillips, Jerry L.

    2012-03-14

    The microbial reduction of Fe(III) and U(VI) were investigated in shallow aquifer sediments collected from subsurface Pleistocene flood deposits near the Hanford Reach of the Columbia River in Washington State. Increases in 0.5 N HCl-extractable Fe(II) were observed in incubated sediments and 57Fe Mössbauer spectroscopy revealed that Fe(III) associated with phyllosilicates and pyroxene was reduced to Fe(II). Aqueous uranium(VI) concentrations decreased in incubated Hanford sediments with the rate and extent being greater in sediment amended with organic carbon. X-ray absorption spectroscopy of bioreduced sediments indicated that 67-77% of the U signal was U(VI), probably as an adsorbed species associated with a new or modified reactive mineral phase. Phylotypes within the Deltaproteobacteria were more common in Hanford sediments incubated with U(VI) than without and in U(VI)-free incubations, members of the Clostridiales were dominant with sulfate-reducing phylotypes more common in the sulfate-amended sediments. These results demonstrate the potential for anaerobic reduction phyllosilicate Fe(III) and sulfate in Hanford unconfined aquifer sediments and biotransformations involving reduction and adsorption leading to decreased aqueous U concentrations.

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

    PubMed Central

    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. Evidence for the aquatic binding of arsenate by natural organic matter-suspended Fe(III)

    USGS Publications Warehouse

    Ritter, K.; Aiken, G.R.; Ranville, J.F.; Bauer, M. E.; Macalady, D.L.

    2006-01-01

    Dialysis experiments with arsenate and three different NOM samples amended with Fe(III) showed evidence confirming the formation of aquatic arsenate-Fe(III)-NOM associations. A linear relationship was observed between the amount of complexed arsenate and the Fe(III) content of the NOM. The dialysis results were consistent with complex formation through ferric iron cations acting as bridges between the negatively charged arsenate and NOM functional groups and/or a more colloidal association, in which the arsenate is bound by suspended Fe(III)-NOM colloids. Sequential filtration experiments confirmed that a significant proportion of the iron present at all Fe/C ratios used in the dialysis experiments was colloidal in nature. These colloids may include larger NOM species that are coagulated by the presence of chelated Fe(III) and/or NOM-stabilized ferric (oxy)hydroxide colloids, and thus, the solution-phase arsenate-Fe(III)-NOM associations are at least partially colloidal in nature. ?? 2006 American Chemical Society.

  18. Applying the Fe(III) binding property of a chemical transferrin mimetic to Ti(IV) anticancer drug design.

    PubMed

    Parks, Timothy B; Cruz, Yahaira M; Tinoco, Arthur D

    2014-02-01

    As an endogenous serum protein binder of Ti(IV), transferrin (Tf) serves as an excellent vehicle to stabilize the hydrolysis prone metal ion and successfully transport it into cells. This transporting role is thought to be central to Ti(IV)'s anticancer function, but efforts to synthesize Ti(IV) compounds targeting transferrin have not produced a drug. Nonetheless, the Ti(IV) transferrin complex (Ti2Tf) greatly informs on a new Ti(IV)-based anticancer drug design strategy. Ti2Tf interferes with cellular uptake of Fe(III), which is particularly detrimental to cancer cells because of their higher requirement for iron. Ti(IV) compounds of chemical transferrin mimetic (cTfm) ligands were designed to facilitate Ti(IV) activity by attenuating Fe(III) intracellular levels. In having a higher affinity for Fe(III) than Ti(IV), these ligands feature the appropriate balance between stability and lability to effectively transport Ti(IV) into cancer cells, release Ti(IV) via displacement by Fe(III), and deplete the intracellular Fe(III) levels. The cTfm ligand N,N'-di(o-hydroxybenzyl)ethylenediamine-N,N'-diacetic acid (HBED) was selected to explore the feasibility of the design strategy. Kinetic studies on the Fe(III) displacement process revealed that Ti(IV) can be transported and released into cells by HBED on a physiologically relevant time scale. Cell viability studies using A549 cancerous and MRC5 normal human lung cells and testing the cytotoxicity of HBED and its Ti(IV), Fe(III), and Ga(III) compounds demonstrate the importance of Fe(III) depletion in the proposed drug design strategy and the specificity of the strategy for Ti(IV) activity. The readily derivatized cTfm ligands demonstrate great promise for improved Ti(IV) anticancer drugs. PMID:24422475

  19. Effects of dissimilatory sulfate reduction on FeIII (hydr)oxide reduction and microbial community development

    NASA Astrophysics Data System (ADS)

    Kwon, Man Jae; Boyanov, Maxim I.; Antonopoulos, Dionysios A.; Brulc, Jennifer M.; Johnston, Eric R.; Skinner, Kelly A.; Kemner, Kenneth M.; O'Loughlin, Edward J.

    2014-03-01

    Although dissimilatory iron and sulfate reduction (DIR and DSR) profoundly affect the biogeochemical cycling of C, Fe, and S in subsurface systems, the dynamics of DIR and DSR in the presence of both FeIII (hydr)oxides and sulfate have not been well-studied with mixed microbial populations. This study examined the response of native microbial communities in subsurface sediment from the U.S. Department of Energy’s Integrated Field Research Challenge site in Rifle, CO to the availability of sulfate and specific FeIII (hydr)oxide minerals in experimental systems containing lactate as the electron donor, with ferrihydrite, goethite, or lepidocrocite and high (10.2 mM) or low (0.2 mM) sulfate as electron acceptors. We observed rapid fermentation of lactate to acetate and propionate. FeIII reduction was slow and limited in the presence of low-sulfate, but the extent of FeIII reduction increased more than 10 times with high-sulfate amendments. Furthermore, the extent of FeIII reduction was higher in ferrihydrite or lepidocrocite incubations than in goethite incubations. Propionate produced during fermentation of lactate was used as the electron donor for DSR. The concurrence of sulfate reduction and FeII production suggests that FeII production was driven primarily by reduction of FeIII by biogenic sulfide. X-ray absorption fine-structure analysis confirmed the formation of ferrous sulfide and the presence of O-coordinated ferrous species. 16S rRNA-based microbial community analysis revealed the development of distinct communities with different FeIII (hydr)oxides. These results highlight the highly coupled nature of C, Fe, and S biogeochemical cycles during DIR and DSR and provide new insight into the effects of electron donor utilization, sulfate concentration, and the presence of specific FeIII (hydr)oxide phases on microbial community development.

  20. Simultaneous Adsorption and Degradation of Cr(VI) and Cd(II) Ions from Aqueous Solution by Silica-Coated Fe0 Nanoparticles

    PubMed Central

    Ma, Hongpu; Ren, Bozhi; Li, Tielong

    2013-01-01

    Core-shell silica-coated Fe0 nanoparticles (Fe@SiO2) were prepared in one-step synthesis by aqueous reduction combined with modified Stöber method. The as-prepared Fe@SiO2 were then used for simultaneous removal of Cr(VI) and Cd(II) from aqueous solution. Batch tests indicated that Fe@SiO2 exhibited high removal capacity toward Cr(VI) and Cd(II). Cr(VI) was removed by Fe@SiO2 through reduction rather than adsorption, while Cd(II) removal was mainly through adsorption. The removal rate increased with increasing initial Fe NPs dose and decreased with increasing initial Cr(VI) and Cd(II) concentrations. Cd(II) adsorption was also strengthened by Cr(VI) reduction with the release of OH−. The removals of Cr(VI) and Cd(II) were weakened in the presence of cations or humic acid, as a result of aggregation and less active site of Fe@SiO2. Overall, the simply prepared Fe@SiO2 were potential material for the heavy metals removed from water. PMID:24455425

  1. Online spectrophotometric determination of Fe(II) and Fe(III) by flow injection combined with low pressure ion chromatography.

    PubMed

    Chen, Shujuan; Li, Nan; Zhang, Xinshen; Yang, Dongjing; Jiang, Heimei

    2015-03-01

    A simple and new low pressure ion chromatography combined with flow injection spectrophotometric procedure for determining Fe(II) and Fe(III) was established. It is based on the selective adsorption of low pressure ion chromatography column to Fe(II) and Fe(III), the online reduction reaction of Fe(III) and the reaction of Fe(II) in sodium acetate with phenanthroline, resulting in an intense orange complex with a suitable absorption at 515nm. Various chemical (such as the concentration of colour reagent, eluant and reductive agent) and instrumental parameters (reaction coil length, reductive coil length and wavelength) were studied and were optimized. Under the optimum conditions calibration graph of Fe(II)/Fe(III) was linear in the Fe(II)/Fe(III) range of 0.040-1.0mg/L. The detection limit of Fe(III) and Fe(II) was respectively 3.09 and 1.55μg/L, the relative standard deviation (n=10) of Fe(II) and Fe(III) 1.89% and 1.90% for 0.5mg/L of Fe(II) and Fe(III) respectively. About 2.5 samples in 1h can be analyzed. The interfering effects of various chemical species were studied. The method was successfully applied in the determination of water samples. PMID:25523043

  2. Online spectrophotometric determination of Fe(II) and Fe(III) by flow injection combined with low pressure ion chromatography

    NASA Astrophysics Data System (ADS)

    Chen, Shujuan; Li, Nan; Zhang, Xinshen; Yang, Dongjing; Jiang, Heimei

    2015-03-01

    A simple and new low pressure ion chromatography combined with flow injection spectrophotometric procedure for determining Fe(II) and Fe(III) was established. It is based on the selective adsorption of low pressure ion chromatography column to Fe(II) and Fe(III), the online reduction reaction of Fe(III) and the reaction of Fe(II) in sodium acetate with phenanthroline, resulting in an intense orange complex with a suitable absorption at 515 nm. Various chemical (such as the concentration of colour reagent, eluant and reductive agent) and instrumental parameters (reaction coil length, reductive coil length and wavelength) were studied and were optimized. Under the optimum conditions calibration graph of Fe(II)/Fe(III) was linear in the Fe(II)/Fe(III) range of 0.040-1.0 mg/L. The detection limit of Fe(III) and Fe(II) was respectively 3.09 and 1.55 μg/L, the relative standard deviation (n = 10) of Fe(II) and Fe(III) 1.89% and 1.90% for 0.5 mg/L of Fe(II) and Fe(III) respectively. About 2.5 samples in 1 h can be analyzed. The interfering effects of various chemical species were studied. The method was successfully applied in the determination of water samples.

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

    SciTech Connect

    Lovley, Derek R.

    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

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

    NASA Astrophysics Data System (ADS)

    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

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

    NASA Astrophysics Data System (ADS)

    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

  6. Thermal and kinetic studies on solid complexes of 2-(2-benzimidazolylazo)-4-acetamidophenol with some transition metals.

    PubMed

    Mohamed, G G; Zayed, M A; El-Gamel, Nadia E A

    2002-12-01

    The preparation and characterization of 2-(2-benzimidazolylazo)-4-acetamidophenol (BIAAP) complexes are reported. Different physico-chemical methods like IR, Magnetic, solid reflectance spectra and molar conductance, were used to investigate the structure of BIAAP complexes. In particular, the thermal decomposition of Fe(III), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) complexes of BIAAP is studied in nitrogen atmosphere. All the complexes do not contain coordinated water molecules but contain (2-4) water molecules of crystallization. The water molecules were removed in a single step. The complexes of Co(II) and Ni(II) ions exhibited a phase transition and the decomposition or combustion of BIAAP occurred in the second and subsequent steps. The final decomposition products were identified by mass spectrometry as the corresponding metal oxides or carbonate. The activation thermodynamic parameters, such as, energy of activation, enthalpy, entropy and free energy change of the complexes were evaluated and the stabilities of the thermal decomposition of the complexes are discussed. From the kinetic point of view, it is found that the thermal stability of the complexes follows the order Ni(II) > Cu(II) > Zn(II) > Fe(III) > Co(II) > Cd(II). PMID:12511101

  7. Moessbauer spectroscopic study of the initial stages of iron-core formation in horse spleen apoferritin: Evidence for both isolated Fe(III) atoms and oxo-bridged Fe(III) dimers as early intermediates

    SciTech Connect

    Bauminger, E.R.; Nowik, I. ); Harrison, P.M.; Treffry, A. )

    1989-06-27

    Ferritin stores iron within a hollow protein shell as a polynuclear Fe(III) hydrous oxide core. Although iron uptake into ferritin has been studied previously, the early stages in the creation of the core need to be clarified. These are dealt with in this paper by using Moessbauer spectroscopy, a technique that enables several types of Fe(II) and Fe(III) to be distinguished. Systematic Moessbauer studies were performed on samples prepared by adding {sup 57}Fe(II) atoms to apoferritin as a function of pH (5.6-7.0), n (the number of Fe/molecule (4-480)), and t{sub f} (the time the samples were held at room temperature before freezing). Four different Fe(III) species were identified: solitary Fe(III) atoms giving relaxation spectra, which can be identified with the species observed before by EPR and UV difference spectroscopy; oxo-bridged dimers giving doublet spectra with large splitting, observed for the first time in ferritin; small Fe(III) clusters giving doublets of smaller splitting and larger antiferromagnetically coupled Fe(III) clusters, similar to those found previously in larger ferritin iron cores, which, for samples with n {ge} 40, gave magnetically split spectra at 4.1 K. Both solitary Fe(III) and dimers diminished with time, suggesting that they are intermediates in the formation of the iron core. Two kinds of divalent iron were distinguished for n = 480, which may correspond to bound and free Fe(II).

  8. Adsorption of Cd(II) and Cu(II) from aqueous solution by carbonate hydroxylapatite derived from eggshell waste.

    PubMed

    Zheng, Wei; Li, Xiao-ming; Yang, Qi; Zeng, Guang-ming; Shen, Xiang-xin; Zhang, Ying; Liu, Jing-jin

    2007-08-17

    Carbonate hydroxylapatite (CHAP) synthesized by using eggshell waste as raw material has been investigated as metal adsorption for Cd(II) and Cu(II) from aqueous solutions. The effect of various parameters on adsorption process such as contact time, solution pH, amount of CHAP and initial concentration of metal ions was studied at room temperature to optimize the conditions for maximum adsorption. The results showed that the removal efficiency of Cd(II) and Cu(II) by CHAP could reach 94 and 93.17%, respectively, when the initial Cd(II) concentration 80 mg/L and Cu(II) 60 mg/L and the liquid/solid ratio was 2.5 g/L. The equilibrium sorption data for single metal systems at room temperature could be described by the Langmuir and Freundlich isotherm models. The highest value of Langmuir maximum uptake, (b), was found for cadmium (111.1mg/g) and copper (142.86 mg/g). Similar Freundlich empirical constants, K, were obtained for cadmium (2.224) and copper (7.925). Ion exchange and surface adsorption might be involved in the adsorption process of cadmium and copper. Desorption experiments showed that CaCl2, NaCl, acetic acid and ultrasonic were not efficient enough to desorb substantial amount of metal ions from the CHAP. The results obtained show that CHAP has a high affinity to cadmium and copper. PMID:17368932

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

    SciTech Connect

    Cheng, Lin; Wang, Jun; Yu, Hai-Yan; Zhang, Xiu-Ying; Gou, Shao-Hua; Fang, Lei

    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.

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

    PubMed

    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

  11. Uptake, p53 Pathway Activation, and Cytotoxic Responses for Co(II) and Ni(II) in Human Lung Cells: Implications for Carcinogenicity

    PubMed Central

    Luczak, Michal W.; Zhitkovich, Anatoly

    2013-01-01

    Cobalt(II) and nickel(II) ions display similar chemical properties and act as hypoxia mimics in cells. However, only soluble Co(II) but not soluble Ni(II) is carcinogenic by inhalation. To explore potential reasons for these differences, we examined responses of human lung cells to both metals. We found that Co(II) showed almost 8 times higher accumulation than Ni(II) in H460 cells but caused a less efficient activation of the transcriptional factor p53 as measured by its accumulation, Ser15 phosphorylation, and target gene expression. Unlike Ni(II), Co(II) was ineffective in downregulating the p53 inhibitor MDM4 (HDMX). Co(II)-treated cells continued DNA replication at internal doses that caused massive apoptosis by Ni(II). Apoptosis and the overall cell death by Co(II) were delayed and weaker than by Ni(II). Inhibition of caspases but not programmed necrosis pathways suppressed Co(II)-induced cell death. Knockdown of p53 produced 50%–60% decreases in activation of caspases 3/7 and expression of 2 most highly upregulated proapoptotic genes PUMA and NOXA by Co(II). Overall, p53-mediated apoptosis accounted for 55% cell death by Co(II), p53-independent apoptosis for 20%, and p53/caspase-independent mechanisms for 25%. Similar to H460, normal human lung fibroblasts and primary human bronchial epithelial cells had several times higher accumulation of Co(II) than Ni(II) and showed a delayed and weaker caspase activation by Co(II). Thus, carcinogenicity of soluble Co(II) could be related to high survival of metal-loaded cells, which permits accumulation of genetic and epigenetic abnormalities. High cytotoxicity of soluble Ni(II) causes early elimination of damaged cells and is expected to be cancer suppressive. PMID:24068677

  12. 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

    NASA Astrophysics Data System (ADS)

    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.

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

    PubMed Central

    2011-01-01

    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(Sal)2(H2O)2] (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 farming

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

    PubMed

    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

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

    NASA Astrophysics Data System (ADS)

    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

  16. Effect of phosphate and sulfate on Ni repartitioning during Fe(II)-catalyzed Fe(III) oxide mineral recrystallization

    NASA Astrophysics Data System (ADS)

    Hinkle, Margaret A. G.; Catalano, Jeffrey G.

    2015-09-01

    Dissolved Fe(II) activates coupled oxidative growth and reductive dissolution of Fe(III) oxide minerals, causing recrystallization and the repartitioning of structurally-compatible trace metals. Phosphate and sulfate, two ligands common to natural aquatic systems, alter Fe(II) adsorption onto Fe(III) oxides and affect Fe(III) oxide dissolution and precipitation. However, the effect of these oxoanions on trace metal repartitioning during Fe(II)-catalyzed Fe(III) oxide recrystallization is unclear. The effects of phosphate and sulfate on Ni adsorption and Ni repartitioning during Fe(II)-catalyzed Fe(III) oxide recrystallization were investigated as such repartitioning may be affected by both Fe(II)-oxoanion and metal-oxoanion interactions. In most systems examined, phosphate alters Ni repartitioning during Fe(II)-catalyzed recrystallization to a larger extent than sulfate. Phosphate substantially enhances Ni adsorption onto hematite but decreases (nearly inhibiting) Fe(II)-catalyzed Ni incorporation into and release from this mineral. In the goethite system, however, phosphate suppresses Ni release but enhances Ni incorporation in the presence of aqueous Fe(II). In contrast, sulfate has little effect on macroscopic Ni adsorption and release of Ni from Fe(III) oxides, but substantially enhances Ni incorporation into goethite. This demonstrates that phosphate and sulfate have unique, mineral-specific interactions with Ni during Fe(II)-catalyzed Fe(III) oxide recrystallization. This research suggests that micronutrient bioavailability at redox interfaces in hematite-dominated systems may be especially suppressed by phosphate, while both oxoanions likely have limited effects in goethite-rich soils or sediments. Phosphate may also exert a large control on contaminant fate at redox interfaces, increasing Ni retention on iron oxide surfaces. These results further indicate that trace metal retention by iron oxides during lithification and later repartitioning during

  17. Complexes With Biologically Active Ligands. Part 101 Inhibition of Carbonic Anhydrase Isozymes I and II With Metal Complexes of Imidazo[2,1−b ]-1,3,4-Thiadiazole-2-Sulfonamide

    PubMed Central

    Scozzafava, Andrea

    1997-01-01

    The title compound was prepared by an improved variant of the literature procedure, and metal complexes containing its anion and the following metal ions: Zn(II), Cd(II), Hg(II), Co(II), Ni(II), Cu(II), V(IV), Fe(III) and Ag(I) were synthesized and characterized by standard procedures (elemental analysis; IR, electronic, NMR and EPR spectroscopy; TG, magnetic and conductimetric measurements). The parent sulfonamide and its metal complexes are potent inhibitors of two carbonic anhydrase (CA) isozymes, CA I and II, and they might possess applications as selective cerebrovasodilating agents. PMID:18475761

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

    PubMed

    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

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

    PubMed Central

    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

  20. Evaluation of cerium doped tin oxide nanoparticles as a sensitive sensor for selective detection and extraction of cobalt

    NASA Astrophysics Data System (ADS)

    Khan, Sher Bahadar; Asiri, Abdullah M.; Rahman, Mohammed M.; Marwani, Hadi M.; Alamry, Khalid A.

    2015-06-01

    Chemo-sensor technology demands to design a single, preconcentrator based sensing system having higher sensitivity, sufficient selectivity and efficient removal of metal ions with simple operating and recognition methodology. Here we effectively deliberated Ce doped SnO2 nanoparticles based sensing system which can be exploited for the recognition and extraction of Co(II) ions in a single step by strong interaction between Ce doped SnO2 nanoparticles and Co(II). The sensing ability of Ce doped SnO2 nanoparticles were deliberated for a selective removal of cobalt using inductively coupled plasma-optical emission spectrometry. The sensing ability of Ce doped SnO2 is studied for various metal ions, such as Cd(II), Co(II), Cr(III), Cu(II), Fe(III), Ni(II) and Zn(II) but the designed sensor was most selective toward Co(II) which was 5000 time more sensitive to Co(II) rather than different interfering metal ions. In addition, the desorption study for regeneration of Ce doped SnO2 nanoparticles was carried out. This novel approach provides a new route for simultaneous detection and removal of Co(II) in a single step and can be a time and cost alternative tool for environmental safety.

  1. Nanowires, Capacitors, and Other Novel Outer-Surface Components Involved in Electron Transfer to Fe(III) Oxides in Geobacter Species

    SciTech Connect

    Lovley, Derek R.

    2005-06-01

    In the past year studies have primarily focused on elucidating the role of pili in electron transport to Fe(III) oxide in Geobacter sulfurreducens. As summarized in last year's report, it was previously found that pili are specifically expressed during growth on Fe(III) oxide and that Fe(III) oxide reduction is inhibited if the gene for the structural pilin protein is deleted. However, it was also found that a pilin-deficient mutant of G. sulfurreducens could attached to Fe(III) oxide as well as wild type.

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

    PubMed

    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

  3. Biosorption of Cd(II) by live and dead cells of Bacillus cereus RC-1 isolated from cadmium-contaminated soil.

    PubMed

    Huang, Fei; Dang, Zhi; Guo, Chu-Ling; Lu, Gui-Ning; Gu, Roy R; Liu, Hong-Juan; Zhang, Hui

    2013-07-01

    The present study investigated the biosorption capacity of live and dead cells of Bacillus cereus RC-1 for Cd(II). The biosorption characteristics were investigated as a function of initial pH, contact time, and initial cadmium concentration. Equilibrium biosorption was modeled using Langmuir, Freundlich and Redlich-Peterson isotherm equations. It was found that the maximum biosorption capacities calculated from Langmuir isotherm were 31.95 mg/g and 24.01 mg/g for dead cells and live cells, respectively. The kinetics of the biosorption was better described by pseudo-second order kinetic model. Desorption efficiency of biosorbents was investigated at various pH values. These results indicated that dead cells have higher Cd(II) biosorption capacity than live cells. Furthermore, zeta potential, transmission electron microscopy (TEM), scanning electron microscopy (SEM) coupled with energy dispersive X-ray (EDX), and Fourier transform infrared spectroscopy (FTIR) studies were carried out to understand the differences in the Cd(II) biosorption behavior for the both biosorbents. The bioaccumulation of Cd(II) by B. cereus RC-1 was found to depend largely on extracellular biosorption rather than intracellular accumulation. Based on the above studies, dead biomass appears to be a more efficient biosorbent for the removal of Cd(II) from aqueous solution. PMID:23466537

  4. Adsorption of Cd(II), Cu(II) and Ni(II) ions by cross-linking chitosan/rectorite nano-hybrid composite microspheres.

    PubMed

    Zeng, Lixuan; Chen, Yufei; Zhang, Qiuyun; Guo, Xingmei; Peng, Yanni; Xiao, Huijuan; Chen, Xiaocheng; Luo, Jiwen

    2015-10-01

    Chitosan/rectorie (CTS/REC) nano-hybrid composite microsphere was prepared by changing the proportion of CTS/REC with 2:1, 3:1 and 4:1. Compared with the pure cross-linking chitosan microsphere, the nano-hybrid composite microsphere was proved to have better sorption capacity of Cd(II), Cu(II) and Ni(II), especially 2:1(CTS/REC-1). The adsorption behavior of the microsphere of Cd(II), Cu(II) and Ni(II) was investigated in single and binary metal systems. In single system, the equilibrium studies showed that the adsorption of Cd(II), Cu(II) and Ni(II) followed the Langmuir model and the pseudo-second-order kinetic model. The negative values of (ΔG) suggested that the adsorption process was spontaneous. In binary system, the combined action of the metals was found to be antagonistic and the metal sorption followed the order of Cu(II)>Cd(II)>Ni(II). The regeneration studies indicated that EDTA desorbed Cd(II), Cu(II) and Ni(II) from cross-linking microspheres better than HCl. The FT-IR and XPS spectra showed that coordination bonds were formed between Cd(II), Cu(II) and Ni(II) and the nitrogen atoms of cross-linking CTS/REC nano-hybrid composite microspheres. PMID:26076634

  5. Sputtered bismuth screen-printed electrode: a promising alternative to other bismuth modifications in the voltammetric determination of Cd(II) and Pb(II) ions in groundwater.

    PubMed

    Sosa, Velia; Serrano, Núria; Ariño, Cristina; Díaz-Cruz, José Manuel; Esteban, Miquel

    2014-02-01

    A commercially available sputtered bismuth screen-printed electrode (BispSPE) has been pioneeringly applied for the simultaneous determination of Cd(II) and Pb(II) ions in a certified groundwater sample by means of differential pulse anodic stripping voltammetry (DPASV) as an alternative to more conventional bismuth screen-printed carbon electrodes (BiSPCEs). BispSPEs can be used for a large set of measurements without any previous plating or activation. The obtained detection and quantification limits suggest that BispSPEs produce a better analytical performance as compared to In-situ BiSPCE for Pb(II) and Cd(II) determination, but also to Ex-situ BiSPCE for Cd(II) determination. The results confirm the applicability of these devices for the determination of low level concentrations of these metal ions in natural samples with very high reproducibility (0.7% and 2.5% for Pb(II) and Cd(II) respectively), and good trueness (0.3% and 2.4% for Pb(II) and Cd(II) respectively). PMID:24401424

  6. Formation of Fe(III) oxyhydroxide colloids in freshwater and brackish seawater, with incorporation of phosphate and calcium

    NASA Astrophysics Data System (ADS)

    Gunnars, Anneli; Blomqvist, Sven; Johansson, Peter; Andersson, Christian

    2002-03-01

    The formation of Fe(III) oxyhydroxide colloids by oxidation of Fe(II) and their subsequent aggregation to larger particles were studied in laboratory experiments with natural water from a freshwater lake and a brackish coastal sea. Phosphate was incorporated in the solid phase during the course of hydrolysis of iron. The resulting precipitated amorphous Fe(III) oxyhydroxide phases were of varying composition, depending primarily on the initial dissolved Fe/P molar ratio, but with little influence by salinity or concentration of calcium ions. The lower limiting Fe/P ratio found for the solid phase suggests the formation of a basic Fe(III) phosphate compound with a stoichiometric Fe/P ratio of close to two. This implies that an Fe/P stoichiometry of ≈2 ultimately limits the capacity of precipitating Fe(III) to fix dissolved phosphate at oxic/anoxic boundaries in natural waters. In contrast to phosphorus, the uptake of calcium seemed to be controlled by sorption processes at the surface of the iron-rich particles formed. This uptake was more efficient in freshwater than in brackish water, suggesting that salinity restrains the uptake of calcium by newly formed Fe(III) oxyhydroxides in natural waters. Moreover, salinity enhanced the aggregation rate of the colloids formed. The suspensions were stabilised by the presence of organic matter, although this effect was less pronounced in seawater than in freshwater. Thus, in seawater of 6 to 33 ‰S, the removal of particles was fast (removal half time < 200 h), whereas the colloidal suspensions formed in freshwater were stable (removal half time > 900 h). Overall, oxidation of Fe(II) and removal of Fe(III) oxyhydroxide particles were much faster in seawater than in freshwater. This more rapid turnover results in lower iron availability in coastal seawater than in freshwater, making iron more likely to become a limiting element for chemical scavenging and biologic production.

  7. Single peak parameters technique for simultaneous measurements: Spectrophotometric sequential injection determination of Fe(II) and Fe(III).

    PubMed

    Kozak, J; Paluch, J; Węgrzecka, A; Kozak, M; Wieczorek, M; Kochana, J; Kościelniak, P

    2016-02-01

    Spectrophotometric sequential injection system (SI) is proposed to automate the method of simultaneous determination of Fe(II) and Fe(III) on the basis of parameters of a single peak. In the developed SI system, sample and mixture of reagents (1,10-phenanthroline and sulfosalicylic acid) are introduced into a vessel, where in an acid environment (pH≅3) appropriate compounds of Fe(II) and Fe(III) with 1,10-phenanthroline and sulfosalicylic acid are formed, respectively. Then, in turn, air, sample, EDTA and sample again, are introduced into a holding coil. After the flow reversal, a segment of air is removed from the system by an additional valve and as EDTA replaces sulfosalicylic acid forming a more stable colorless compound with Fe(III), a complex signal is registered. Measurements are performed at wavelength 530 nm. The absorbance measured at minimum of the negative peak and the area or the absorbance measured at maximum of the signal can be used as measures corresponding to Fe(II) and Fe(III) concentrations, respectively. The time of the peak registration is about 2 min. Two-component calibration has been applied to analysis. Fe(II) and Fe(III) can be determined within the concentration ranges of 0.04-4.00 and 0.1-5.00 mg L(-1), with precision less than 2.8% and 1.7% (RSD), respectively and accuracy better than 7% (RE). The detection limit is 0.04 and 0.09 mg L(-1) for Fe(II) and Fe(III), respectively. The method was applied to analysis of artesian water samples. PMID:26653493

  8. Spectroscopic and mycological studies of Co(II), Ni(II) and Cu(II) complexes with 4-aminoantipyrine derivative

    NASA Astrophysics Data System (ADS)

    Sharma, Amit Kumar; Chandra, Sulekh

    2011-10-01

    Complexes of the type [M(L)X 2], where M = Co(II), Ni(II) and Cu(II), have been synthesized with novel NO-donor Schiff's base ligand, 1,4-diformylpiperazine bis(4-imino-2,3-dimethyl-1-phenyl-3-pyrazolin-5-one) which is obtained by the acid catalyzed condensation of 1,4-diformylpiperazine with 4-aminoantipyrine. The elemental analyses, molar conductance measurements, magnetic susceptibility measurements, IR, UV, NMR, mass and EPR studies of the compounds led to the conclusion that the ligand acts as tetradentate chelate. The Schiff's base ligand forms hexacoordinated complexes having octahedral geometry for Ni(II) and tetragonal geometry for Co(II) and Cu(II) complexes. The mycological studies of the compounds were examined against the several opportunistic pathogens, i.e., Alternaria brassicae, Aspergillus niger and Fusarium oxysporum. The Cu(II) complexes were found to have most fungicidal behavior.

  9. Adsorption behavior of Eu(III) on partially Fe(III)- or Ti(IV)-coated silica

    PubMed Central

    2012-01-01

    The adsorption behavior of Eu(III) onto silica surface, which was partially coated with Fe(III) or Ti(IV), was investigated to determine Fe(III) or Ti(IV) effects on the surface reaction of lanthanides on mineral surfaces in groundwater. Compared with a parallel uncoated silica, the Fe(III)-coated silica did not enhance the adsorption of Eu(III). However, enhanced adsorption of Eu(III) on the Ti(IV)-coated silica was observed by increasing the amount of Ti(IV) on the silica surface. PMID:22221407

  10. Microbial Reduction of Fe(III) in the Fifthian and Muloorina illites: Contrasting extents and rates of bioreduction

    USGS Publications Warehouse

    Seabaugh, J.L.; Dong, H.; Kukkadapu, R.K.; Eberl, D.D.; Morton, J.P.; Kim, J.

    2006-01-01

    Shewanella putrefaciens CN32 reduces Fe(III) within two illites which have different properties: the Fithian bulk fraction and the <0.2 ??m fraction of Muloorina. The Fithian illite contained 4.6% (w/w) total Fe, 81% of which was Fe(III). It was dominated by illite with some jarosite (???32% of the total Fe(III)) and goethite (11% of the total Fe(III)). The Muloorina illite was pure and contained 9.2% Fe, 93% of which was Fe(III). Illite suspensions were buffered at pH 7 and were inoculated with CN32 cells with lactate as the electron donor. Select treatments included anthraquinone-2,6-disulfonate (AQDS) as an electron shuttle. Bioproduction of Fe(II) was determined by ferrozine analysis. The unreduced and bioreduced solids were characterized by Mo??ssbauer spectroscopy, X-ray diffraction and transmission electron microscopy. The extent of Fe(III) reduction in the bulk Fithian illite was enhanced by the presence of AQDS (73%) with complete reduction of jarosite and goethite and partial reduction of illite. Mo??ssbauer spectroscopy and chemical extraction determined that 21-25% of illite-associated Fe(III) was bioreduced. The extent of bioreduction was less in the absence of AQDS (63%) and only jarosite was completely reduced with partial reduction of goethite and illite. The XRD and TEM data revealed no significant illite dissolution or biogenic minerals, suggesting that illite was reduced in the solid state and biogenic Fe(II) from jarosite and goethite was either released to aqueous solution or adsorbed onto residual solid surfaces. In contrast, only 1% of the structural Fe(III) in Muloorina illite was bioreduced. The difference in the extent and rate of bioreduction between the two illites was probably due to the difference in layer charge and the total structural Fe content between the Fithian illite (0.56 per formula) and Muloorina illite (0.87). There may be other factors contributing to the observed differences, such as expandability, surface area and the

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

    NASA Astrophysics Data System (ADS)

    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.

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

    NASA Astrophysics Data System (ADS)

    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. Structural analysis of complexes formed by ethyl 4-phenylthiocarbamoyl piperazine-1-carboxylate with Ni(II), Zn(II) and Cd(II) through spectroscopic and DFT techniques

    NASA Astrophysics Data System (ADS)

    Prakash, Om; Gautam, Priyanka; Dani, R. K.; Nandi, Abhisikta; Singh, N. K.; Singh, Ranjan K.

    2014-04-01

    A piperazine derivative, ethyl 4-phenylthiocarbamoyl piperazine-1-carboxylate and its Ni(II), Zn(II) and Cd(II) complexes have been synthesized and characterized by elemental analyses, magnetic susceptibility measurement, UV-Visible, FTIR, Raman spectroscopic and DFT methods. The Ni(II) and Zn(II) bind through the N and S sites of the two ligand Heptpc and N site of two pyridine molecules. However, the Cd(II) binds through the only N sites of the two ligand Heptpc and N site of two pyridine molecules. On the basis of various techniques used for the characterizations of the complexes, we found that the most possible geometry of the Ni(II) and Zn(II) complexes are distorted octahedral and of the Cd(II) complex is distorted tetrahedral.

  14. Ni(II) And Co(II) Sensing By Escherichia Coli RcnR

    SciTech Connect

    Iwig, J.S.; Leitch, S.; Herbst, R.W.; Maroney, M.J.; Chivers, P.T.

    2009-05-18

    Escherichia coli RcnR and Mycobacterium tuberculosis CsoR are the founding members of a recently identified, large family of bacterial metal-responsive DNA-binding proteins. RcnR controls the expression of the metal efflux protein RcnA only in response to Ni(II) and Co(II) ions. Here, the interaction of Ni(II) and Co(II) with wild-type and mutant RcnR proteins is examined to understand how these metals function as allosteric effectors. Both metals bind to RcnR with nanomolar affinity and stabilize the protein to denaturation. X-ray absorption and electron paramagnetic resonance spectroscopies reveal six-coordinate high-spin sites for each metal that contains a thiolate ligand. Experimental data support a tripartite N-terminal coordination motif (NH{sub 2}-Xaa-NH-His) that is common for both metals. However, the Ni(II)- and Co(II)-RcnR complexes are shown to differ in the remaining coordination environment. Each metal coordinates a conserved Cys ligand but with distinct M-S distances. Co(II)-thiolate coordination has not been observed previously in Ni(II)-/Co(II)-responsive metalloregulators. The ability of RcnR to recruit ligands from the N-terminal region of the protein distinguishes it from CsoR, which uses a lower coordination geometry to bind Cu(I). These studies facilitate comparisons between Ni(II)-RcnR and NikR, the other Ni(II)-responsive transcriptional regulator in E. coli, to provide a better understanding how different nickel levels are sensed in E. coli. The characterization of the Ni(II)- and Co(II)-binding sites in RcnR, in combination with bioinformatics analysis of all RcnR/CsoR family members, identified a four amino acid fingerprint that likely defines ligand-binding specificity, leading to an emerging picture of the similarities and differences between different classes of RcnR/CsoR proteins.

  15. Binuclear Cu(II) and Co(II) Complexes of Tridentate Heterocyclic Shiff Base Derived from Salicylaldehyde with 4-Aminoantipyrine

    PubMed Central

    Al-Obaidi, Omar Hamad Shihab

    2012-01-01

    New binuclear Co(II) and Co(II) complexes of ONO tridentate heterocyclic Schiff base derived from 4-aminoantipyrine with salicylaldehyde have been synthesized and characterized on the bases of elemental analysis, UV-Vis., FT-IR, and also by aid of molar conductivity measurements, magnetic measurements, and melting points. It has been found that the Schiff bases with Cu(II) or Co(II) ion forming binuclear complexes on (1 : 1) “metal : ligand” stoichiometry. The molar conductance measurements of the complexes in DMSO correspond to be nonelectrolytic nature for all prepared complexes. Distorted octahedral environment is suggested for metal complexes. A theoretical treatment of the formation of complexes in the gas phase was studied, and this was done by using the HyperChem-6 program for the molecular mechanics and semi-empirical calculations. The free ligand and its complexes have been tested for their antibacterial activities against two types of human pathogenic bacteria: the first type (Staphylococcus aureus) is Gram positive and the second type (Escherichia coli) is Gram negative (by using agar well diffusion method). Finally, it was found that compounds show different activity of inhibition on growth of the bacteria. PMID:22611346

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

    PubMed

    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

  17. Penicillamine-modified sensor for the voltammetric determination of Cd(II) and Pb(II) ions in natural samples.

    PubMed

    Pérez-Ràfols, Clara; Serrano, Núria; Díaz-Cruz, José Manuel; Ariño, Cristina; Esteban, Miquel

    2015-11-01

    A new penicillamine-GCE was developed based on the immobilization of d-penicillamine on aryl diazonium salt monolayers anchored to the glassy carbon electrode (GCE) surface and it was applied for the first time to the simultaneous determination of Cd(II) and Pb(II) ions by stripping voltammetric techniques. The detection and quantification limits at levels of µg L(-1) suggest that the penicillamine-GCE could be fully suitable for the determination of the considered ions in natural samples. PMID:26452863

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

    NASA Astrophysics Data System (ADS)

    Cheng, Lin; Wang, Jun; Yu, Hai-Yan; Zhang, Xiu-Ying; Gou, Shao-Hua; Fang, Lei

    2015-01-01

    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.

  19. Dependency of simultaneous Cr(VI), Cu(II) and Cd(II) reduction on the cathodes of microbial electrolysis cells self-driven by microbial fuel cells

    NASA Astrophysics Data System (ADS)

    Zhang, Yong; Yu, Lihua; Wu, Dan; Huang, Liping; Zhou, Peng; Quan, Xie; Chen, Guohua

    2015-01-01

    Microbial fuel cells (MFCs) using either Cr(VI) (MFCsCr) or Cu(II) (MFCsCu) as a final electron acceptor, are stacked to self-drive microbial electrolysis cells (MECs) using Cd(II) (MECsCd) as an electron acceptor for simultaneous reduction of Cr(VI) in MFCsCr, Cu(II) in MFCsCu and Cd(II) in MECsCd with no external energy consumption. Titanium sheet (TS) and carbon rod (CR) as the cathodes of MECsCd are assessed for efficient system performance. MFCsCr and MFCsCu in series is superior to the parallel configuration, and higher Cd(II) reduction along with simultaneous Cr(VI) and Cu(II) reduction supports TS function as a good cathode material. Conversely, CR can not entirely proceed Cd(II) reduction in MECsCd despite of more Cr(VI) and Cu(II) reduction in the same serial configuration than either system alone. While a decrease in cathode volume in both MFCsCr and MFCsCu with serial connection benefits to reduction of Cr(VI) in MFCsCr and Cu(II) in MFCsCu, Cd(II) reduction in MECsCd is substantially enhanced under a decrease in cathode volume in individual MFCsCr and serially connected with volume-unchanged MFCsCu. This study demonstrates simultaneous Cr(VI), Cu(II) and Cd(II) recovery from MFCsCr-MFCsCu-MECsCd self-driven system is feasible, and TS as the cathodes of MECsCd is critical for efficient system performance.

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

    PubMed

    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

  1. Bioavailability of Fe(III) in Loess Sediments: An Important Source of Electron Acceptors

    SciTech Connect

    Bishop, Michael E.; Jaisi, Deb P.; Dong, Hailiang; Kukkadapu, Ravi K.; Ji, Junfeng

    2010-08-01

    A quantitative study was conducted to understand if Fe (III) in loess sediments is available for microbial respiration by using a common metal reducing bacterium, Shewanella putrefaciens, CN32. The loess samples were collected from three different sites: St. Louis (Peoria), Missouri, USA; Huanxia (HX) and Yanchang (YCH), Shanxi Province of China. Wet chemical analyses indicated that the total Fe concentration for the three samples was 1.69%, 2.76%, and 3.29%, respectively, of which 0.48%, 0.67%, and 1.27% was Fe(III). All unreduced loess sediments contained iron oxides and phyllosilicates (smectite, illite, chlorite, vermiculite), in addition to common minerals such as quartz, feldspar, plagioclase, calcite, and dolomite. Bioreduction experiments were performed at a loess concentration of 20 mg/mL using lactate as the sole electron donor, Fe(III) in loess as the sole electron acceptor in the presence and absence of anthraquinone-2, 6-disulfonate (AQDS) as an electron shuttle. Experiments were performed in non-growth (bicarbonate buffer) and growth (M1) media with a cell concentration of ~2.8 x 107 and 2.1 x 107 cells/mL, respectively. The unreduced and bioreduced solids were analyzed by X-ray diffraction (XRD), Mössbauer spectroscopy, diffuse reflection spectroscopy (DRS), and scanning electron microscopy/energy dispersive spectroscopy (SEM/EDS) methods. Despite many similarities among the three loess samples, the extent and rate of Fe (III) reduction varied significantly. For example, in presence of AQDS the extent of reduction in the non-growth experiment was 25% in HX, 34% in Peoria, and 38% in YCH. The extent of reduction in the growth experiment was 72% in HX, 94% in Peoria, and 56% in YCH. The extent of bioreduction was lower in absence of AQDS. Overall, AQDS and the M1 growth medium significantly enhanced the rate and extent of bioreduction. Fe(III) in iron oxides and Fe(III)-containing phyllosilicates was bioreduced. Biogenic illite, siderite, and

  2. Microbial Reduction of Fe(III) in Acidic Sediments: Isolation of Acidiphilium cryptum JF-5 Capable of Coupling the Reduction of Fe(III) to the Oxidation of Glucose

    PubMed Central

    Küsel, Kirsten; Dorsch, Tanja; Acker, Georg; Stackebrandt, Erko

    1999-01-01

    To evaluate the microbial populations involved in the reduction of Fe(III) in an acidic, iron-rich sediment, the anaerobic flow of supplemental carbon and reductant was evaluated in sediment microcosms at the in situ temperature of 12°C. Supplemental glucose and cellobiose stimulated the formation of Fe(II); 42 and 21% of the reducing equivalents that were theoretically obtained from glucose and cellobiose, respectively, were recovered in Fe(II). Likewise, supplemental H2 was consumed by acidic sediments and yielded additional amounts of Fe(II) in a ratio of approximately 1:2. In contrast, supplemental lactate did not stimulate the formation of Fe(II). Supplemental acetate was not consumed and inhibited the formation of Fe(II). Most-probable-number estimates demonstrated that glucose-utilizing acidophilic Fe(III)-reducing bacteria approximated to 1% of the total direct counts of 4′,6-diamidino-2-phenylindole-stained bacteria. From the highest growth-positive dilution of the most-probable-number series at pH 2.3 supplemented with glucose, an isolate, JF-5, that could dissimilate Fe(III) was obtained. JF-5 was an acidophilic, gram-negative, facultative anaerobe that completely oxidized the following substrates via the dissimilation of Fe(III): glucose, fructose, xylose, ethanol, glycerol, malate, glutamate, fumarate, citrate, succinate, and H2. Growth and the reduction of Fe(III) did not occur in the presence of acetate. Cells of JF-5 grown under Fe(III)-reducing conditions formed blebs, i.e., protrusions that were still in contact with the cytoplasmic membrane. Analysis of the 16S rRNA gene sequence of JF-5 demonstrated that it was closely related to an Australian isolate of Acidiphilium cryptum (99.6% sequence similarity), an organism not previously shown to couple the complete oxidation of sugars to the reduction of Fe(III). These collective results indicate that the in situ reduction of Fe(III) in acidic sediments can be mediated by heterotrophic Acidiphilium

  3. Biosorption of Cr(III) and Fe(III) in single and binary systems onto pretreated orange peel.

    PubMed

    Lugo-Lugo, V; Barrera-Díaz, C; Ureña-Núñez, F; Bilyeu, B; Linares-Hernández, I

    2012-12-15

    Trivalent chromium and iron are the products of the traditional reduction of hexavalent chromium by ferrous salts in industrial wastewater. Although there have been a few studies of Cr(III) adsorption, none have considered the effect of Fe(III) on Cr(III) adsorption in a binary system representing expected products of hexavalent chromium in industrial wastewater. The biosorption of Cr(III) and Fe(III) ions onto pretreated ground orange peel in single and binary systems was studied in batch experiments using a variety of techniques. The kinetic results showed a rapid rate of biosorption of Cr(III) and Fe(III) in single and binary systems and mutual interference effects in the competitive binary Cr(III)-Fe(III) system. Second order kinetic models showed the best fit for all systems. The behavior of competitive Cr(III)-Fe(III) biosorption were successfully described by the multicomponent Langmuir model, obtaining maximum capacities for Cr(III) and Fe(III) of 9.43 and 18.19 mg/g respectively. SEM/EDS results confirmed that the metals adsorb on the surface and FTIR identified the hydroxyl groups on the carboxylic acids as the active binding sites. PMID:22892173

  4. Dietary iron depletion at weaning imprints low microbiome diversity and this is not recovered with oral nano Fe(III)

    PubMed Central

    Pereira, Dora I A; Aslam, Mohamad F; Frazer, David M; Schmidt, Annemarie; Walton, Gemma E; McCartney, Anne L; Gibson, Glenn R; Anderson, Greg J; Powell, Jonathan J

    2015-01-01

    Alterations in the gut microbiota have been recently linked to oral iron. We conducted two feeding studies including an initial diet-induced iron-depletion period followed by supplementation with nanoparticulate tartrate-modified ferrihydrite (Nano Fe(III): considered bioavailable to host but not bacteria) or soluble ferrous sulfate (FeSO4: considered bioavailable to both host and bacteria). We applied denaturing gradient gel electrophoresis and fluorescence in situ hybridization for study-1 and 454-pyrosequencing of fecal 16S rRNA in study-2. In study-1, the within-community microbial diversity increased with FeSO4 (P = 0.0009) but not with Nano Fe(III) supplementation. This was confirmed in study-2, where we also showed that iron depletion at weaning imprinted significantly lower within- and between-community microbial diversity compared to mice weaned onto the iron-sufficient reference diet (P < 0.0001). Subsequent supplementation with FeSO4 partially restored the within-community diversity (P = 0.006 in relation to the continuously iron-depleted group) but not the between-community diversity, whereas Nano Fe(III) had no effect. We conclude that (1) dietary iron depletion at weaning imprints low diversity in the microbiota that is not, subsequently, easily recovered; (2) in the absence of gastrointestinal disease iron supplementation does not negatively impact the microbiota; and (3) Nano Fe(III) is less available to the gut microbiota. PMID:25461615

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

    PubMed

    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

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

    SciTech Connect

    Rana, Vijay Kumar; Selvaraj, M.; Parambadath, Surendran; Chu, Sang-Wook; Park, Sung Soo; Mishra, Satyendra; Singh, Raj Pal; Ha, Chang-Sik

    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.

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

    SciTech Connect

    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.

  8. Mechanisms of Sb(III) Photooxidation by the Excitation of Organic Fe(III) Complexes.

    PubMed

    Kong, Linghao; He, Mengchang

    2016-07-01

    Organic Fe(III) complexes are widely distributed in the aqueous environment, which can efficiently generate free radicals under light illumination, playing a significant role in heavy metal speciation. However, the potential importance of the photooxidation of Sb(III) by organic Fe(III) complexes remains unclear. Therefore, the photooxidation mechanisms of Sb(III) were comprehensively investigated in Fe(III)-oxalate, Fe(III)-citrate and Fe(III)-fulvic acid (FA) solutions by kinetic measurements and modeling. Rapid photooxidation of Sb(III) was observed in an Fe(III)-oxalate solution over the pH range of 3 to 7. The addition of tert-butyl alcohol (TBA) as an ·OH scavenger quenched the Sb(III) oxidation, suggesting that ·OH is an important oxidant for Sb(III). However, the incomplete quenching of Sb(III) oxidation indicated the existence of other oxidants, presumably an Fe(IV) species in irradiated Fe(III)-oxalate solution. In acidic solutions, ·OH may be formed by the reaction of Fe(II)(C2O4) with H2O2, but a hypothetical Fe(IV) species may be generated by the reaction of Fe(II)(C2O4)2(2-) with H2O2 at higher pH. Kinetic modeling provides a quantitative explanation of the results. Evidence for the existence of ·OH and hypothetical Fe(IV) was also observed in an irradiated Fe(III)-citrate and Fe(III)-FA system. This study demonstrated an important pathway of Sb(III) oxidation in surface waters. PMID:27267512

  9. The Impact of Ionizing Radiation on the Microbial Reduction of Fe(III)

    NASA Astrophysics Data System (ADS)

    Brown, A.; Correa, E. S.; Xu, Y.; Vaughan, D. J.; Pimblott, S. M.; Goodacre, R.; Lloyd, J. R.

    2014-12-01

    Biogeochemical processes mediated by Fe(III)-reducing bacteria have the potential to impact on the post-closure evolution of a geological disposal facility (GDF) for radioactive waste. However, the organisms promoting these processes will likely be subject to significant radiation fluxes. Therefore, the impact of acute doses of ionizing radiation on the physiological status of the model Fe(III)-reducing bacterium Shewanella oneidensis was assessed. FT-IR spectroscopy and MALDI-TOF-MS suggested that the metabolic response to radiation is underpinned by alterations to lipids and proteins. Furthermore, the irradiated phenotype exhibits enhanced Fe(III)-reduction. The impact of radiation on the extracellular environment was also assessed. Exposure to gamma radiation caused activation of ferrihydrite and hematite for enzymatic reduction by S. oneidensis. TEM, SAED and Mössbauer spectroscopy revealed that this effect was a result of radiation induced changes to crystallinity leading to an increase in bioavailability of Fe(III) for respiration. To assess the impact of radiation on sediment microbial communities, a series of microcosm experiments were constructed and gamma irradiated over a two month period. Sediments irradiated at a dose rate of 0.5 Gy h-1 exhibited enhanced Fe(III) reduction despite receiving doses potentially lethal to indigenous microorganisms, whilst biogeochemical processes in sediments irradiated with 30 Gy h-1 were only partially restricted. Despite this, 16S rRNA gene pyrosequencing revealed significant dose-dependent shifts in the microbial communities in tandem with changes in microcosm biogeochemical profiles. Collectively, these results indicate that, despite significant total absorbed doses, biogeochemical processes will likely not be restricted by dose rates expected in a deep geological repository. Indeed, electron accepting processes in such environments may even be stimulated by radiation.

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

    USGS Publications Warehouse

    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%, P<0.05 in all cases). The percentage of poorly crystalline Fe(III) was significantly correlated with the percentage of FeRB (r=0.76), reflecting the fact that poorly crystalline Fe(III) minerals are labile with respect to microbial reduction. Abiotic reductive dissolution consumed about 75% of the rhizosphere 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. Microporous Cd(II) metal-organic framework as fluorescent sensor for nitroaromatic explosives at the sub-ppm level

    NASA Astrophysics Data System (ADS)

    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.

  12. Microbial Reduction of Fe(III) in the Fithian and Muloorina Illites : Contrasting Extents and Rates of Bioreduction

    SciTech Connect

    Seabaugh, J. L.; Dong, Hailiang; Kukkadapu, Ravi K.; Eberl, Dennis D.; Morton, John P.; Kim, Jinwook

    2006-01-01

    This study was undertaken to investigate the rate and extent of reduction of Fe(III) in two different illite samples, Muloorina and Fithian, by facultative anaerobe, Shewanella putrefaciens CN32. The Fithian illite (API reference illite from Illinois) is relatively pure with only a trace amount of goethite. The starting material contained 4% of Fe, 19% of which is Fe(II) as determined by Mössbauer spectroscopy. Mössbauer spectroscopy also confirmed the presence of two different sites for Fe(III) in the illite structure. The surface area of the Fithian illite is 85.31 m2/g. The Muloorina illite, attained from Lake Eyre, S. Australia, has a surface area of 107.68 m2/g. The <0.2 µm size fraction was separated from a rock containing the Muloorina illite and used for bioreduction experiment. This size fraction is pure with no other Fe-containing minerals. The starting material contained 9.2% Fe, 93% of which is Fe(III) as determined by chemical and Mössbauer methods. A subsurface iron-reducing bacterium, Shewenella putrefactions CN32, was used in the illite reduction experiments. For both bioreduction experiments, illite suspensions of 10 mg/mL were made in bicarbonate buffer and experimental tubes were inoculated with about 4.0 x 10-6-6.0 x 10-7 CN32 cells. In selected treatments, antraquinone-2,6-disulfonate (AQDS) was included as an electron shuttle to facilitate bioreduction while lactate was used as an electron donor. Controls were identical but no cells were added. Fe(II) production at various time points was determined by Ferrozine assay. Aqueous concentrations of major elements, Si, Al, Mg, and Fe were measured by direct current plasma emission spectroscopy. Lactate and its metabolic product acetate were measured by high performance liquid chromatography. Residual and biogenic solids were characterized by transmission electron microscopy, Mössbauer spectroscopy, and electron energy loss spectroscopy. The extent of reduction was much greater in the presence

  13. Transformation of Tetracycline Antibiotics and Fe(II) and Fe(III) Species Induced by Their Complexation.

    PubMed

    Wang, Hui; Yao, Hong; Sun, Peizhe; Li, Desheng; Huang, Ching-Hua

    2016-01-01

    Tetracycline antibiotics (TCs) are frequently detected micropollutants and are known to have a strong tendency to complex with metal ions such as Fe(II) and Fe(III) in aquatic environments. Experiments with Fe(II) and TCs showed that the complexation of Fe(II) with tetracycline (TTC), oxytetracycline (OTC), or chlorotetracycline (CTC) could lead to the accelerated oxidation of Fe(II) and the promoted degradation of TCs simultaneously. The reaction started with complexation of Fe(II) with TC followed by oxidation of the Fe(II)-TC complex by dissolved oxygen to generate a Fe(III)-TC complex and reactive oxygen species (ROS). The ROS (primarily ·OH) then degraded TC. The oxidation rate constants of Fe(II) in the Fe(II)-H2L and Fe(II)-HL complexes were 0.269 and 1.511 min(-1), respectively, at ambient conditions (pH 7, 22 °C, and PO2 of 0.21 atm), which were about 60 and 350 times of the oxidation rate of uncomplexed Fe(II). Humic acids (HA) compete with TCs for Fe(II), but the effect was negligible at moderate HA concentrations (≤10 mg·L(-1)). Experiments with Fe(III) and TCs showed that the complexation of Fe(III) with TC could generate oxidized TC and Fe(II) without the need of oxygen at a relatively slower rate compared to the reaction involving Fe(II), O2, and TCs. These findings indicate the mutually influenced environmental transformation of TCs and Fe(II) and Fe(III) induced by their complexation. These newly identified reactions could play an important role in affecting the environmental fate of TCs and cycling of Fe(II) and Fe(III) in TCs-contaminated water and soil systems. PMID:26618388

  14. Development of Wood Apple Shell (Feronia acidissima) Powder Biosorbent and Its Application for the Removal of Cd(II) from Aqueous Solution

    PubMed Central

    Suresh, Ch.; Reddy, D. Harikisore Kumar; Harinath, Yapati; Naik, B. Ramesh; Seshaiah, K.; Reddy, Annareddy V. Ramana

    2014-01-01

    A biosorbent was prepared by using wood apple shell (WAS) powder and studied its application for the removal of Cd(II) from aqueous solution by a batch method. The biosorbent was characterized by infrared spectroscopy, X-ray diffraction, scanning electron microscopy, and elemental analysis. WAS is principally made up of lignin and cellulose, containing functional groups such as alcoholic, ketonic, and carboxylic groups which can be involved in complexation reactions with Cd(II). The effect of experimental parameters like initial pH, contact time, metal ion concentration, and sorbent dose on adsorption was investigated. The optimum pH for biosorption of Cd(II) onto WAS was found to be pH 5.0 and the quantitative removal of Cd(II) ions was achieved in 30 min. The kinetic study showed that the biosorption process followed the pseudo-second-order rate. Experimental data were analyzed by Langmuir, Freundlich, and Dubinin-Radushkevich isotherm models. Desorption studies were carried out using HCl solution. PMID:24977180

  15. Cooperative cathode electrode and in situ deposited copper for subsequent enhanced Cd(II) removal and hydrogen evolution in bioelectrochemical systems.

    PubMed

    Wang, Qiang; Huang, Liping; Pan, Yuzhen; Zhou, Peng; Quan, Xie; Logan, Bruce E; Chen, Hongbo

    2016-01-01

    Bioelectrochemical systems (BESs) were first operated in microbial fuel cell mode for recovering Cu(II), and then shifted to microbial electrolysis cells for Cd(II) reduction on the same cathodes of titanium sheet (TS), nickel foam (NF) or carbon cloth (CC). Cu(II) reduction was similar to all materials (4.79-4.88mg/Lh) whereas CC exhibited the best Cd(II) reduction (5.86±0.25mg/Lh) and hydrogen evolution (0.35±0.07m(3)/m(3)d), followed by TS (5.27±0.43mg/Lh and 0.15±0.02m(3)/m(3)d) and NF (4.96±0.48mg/Lh and 0.80±0.07m(3)/m(3)d). These values were higher than no copper controls by factors of 2.0 and 5.0 (TS), 4.2 and 2.0 (NF), and 1.8 and 7.0 (CC). These results demonstrated cooperative cathode electrode and in situ deposited copper for subsequent enhanced Cd(II) reduction and hydrogen production in BESs, providing an alternative approach for efficiently remediating Cu(II) and Cd(II) co-contamination with simultaneous hydrogen production. PMID:26528907

  16. Adaptively Evolving Bacterial Communities for Complete and Selective Reduction of Cr(VI), Cu(II), and Cd(II) in Biocathode Bioelectrochemical Systems.

    PubMed

    Huang, Liping; Wang, Qiang; Jiang, Linjie; Zhou, Peng; Quan, Xie; Logan, Bruce E

    2015-08-18

    Bioelectrochemical systems (BESs) have been shown to be useful in removing individual metals from solutions, but effective treatment of electroplating and mining wastewaters requires simultaneous removal of several metals in a single system. To develop multiple-reactor BESs for metals removal, biocathodes were first individually acclimated to three different metals using microbial fuel cells with Cr(VI) or Cu(II) as these metals have relatively high redox potentials, and microbial electrolysis cells for reducing Cd(II) as this metal has a more negative redox potential. The BESs were then acclimated to low concentrations of a mixture of metals, followed by more elevated concentrations. This procedure resulted in complete and selective metal reduction at rates of 1.24 ± 0.01 mg/L-h for Cr(VI), 1.07 ± 0.01 mg/L-h for Cu(II), and 0.98 ± 0.01 mg/L-h for Cd(II). These reduction rates were larger than the no adaptive controls by factors of 2.5 for Cr(VI), 2.9 for Cu(II), and 3.6 for Cd(II). This adaptive procedure produced less diverse microbial communities and changes in the microbial communities at the phylum and genus levels. These results demonstrated that bacterial communities can adaptively evolve to utilize solutions containing mixtures of metals, providing a strategy for remediating wastewaters containing Cr(VI), Cu(II), and Cd(II). PMID:26175284

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

    PubMed

    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

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

    PubMed

    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

  19. A double network gel as low cost and easy recycle adsorbent: Highly efficient removal of Cd(II) and Pb(II) pollutants from wastewater.

    PubMed

    Chu, Lin; Liu, Chengbin; Zhou, Guiyin; Xu, Rui; Tang, Yanhong; Zeng, Zebing; Luo, Shenglian

    2015-12-30

    A high strength of polyving alcohol/polyacrylic acid double network gel (PVA/PAA gel) adsorbent was successfully prepared by a simple two-step method in this study. The gel adsorbent possessed the advantages of low cost and high adsorptivity for heavy metals in solution. The maximum uptake capacities of PVA/PAA gel were 194.99 mg/g for Pb(II) and 115.88 mg/g for Cd(II) inferred from the Langmuir model at 303 K. At the concentration levels of Pb(II)<150 mg/L and Cd(II)<100mg/L, the Pb(II) and Cd(II) could be completely adsorbed, showing a great potential of removing heavy metals from wastewater. Simultaneously, the PVA/PAA gel adsorbent exhibited an excellent reusability. Even in the fifth cycle, the removal efficiencies of both Pb(II) and Cd(II) remained nearly 100%. Significantly, the gel adsorbent displayed a satisfactory performance of removing heavy metals in actual industrial effluent. The results reveal that the double network gel can be considered as a potential candidate for practical application. PMID:26177491

  20. The structural and functional effects of Hg(II) and Cd(II) on lipid model systems and human erythrocytes: A review.

    PubMed

    Payliss, Brandon J; Hassanin, Mohamed; Prenner, Elmar J

    2015-12-01

    The anthropogenic mobilization of mercury and cadmium into the biosphere has led to an increased and ineludible entry of these metals into biological systems. Here we discuss the impact of Hg(II) and Cd(II) on lipid model systems and human erythrocytes from a biophysical perspective. After a brief introduction to their implications on human health, studies that have investigated the effects of Hg(II) and Cd(II) on lipid model systems and human erythrocytes are discussed. In terms of lipids as toxicological target sites, predominantly variations in lipid head groups have been the source of investigation. However, as research in this field progresses, the effects of Hg(II) and Cd(II) on other structural features, such as acyl chain length and unsaturation, and other important lipid components and complex biomimetic lipid mixtures, will require further examinations. This review provides an analysis of what has been learned collectively from the diverse methodologies and experimental conditions used thus far. Consequently, there is a need for more comprehensive and thorough investigations into the effects of Hg(II) and Cd(II) on lipid membranes under consistent experimental conditions such as pH, ionic strength, temperature, and choice of lipid model system. PMID:26455331

  1. Poly(methacrylic acid)-grafted chitosan microspheres via surface-initiated ATRP for enhanced removal of Cd(II) ions from aqueous solution.

    PubMed

    Huang, Liqiang; Yuan, Shaojun; Lv, Li; Tan, Guangqun; Liang, Bin; Pehkonen, S O

    2013-09-01

    Cross-linked chitosan (CCS) microspheres tethered with pH-sensitive poly(methacrylic acid) (PMAA) brushes were developed for the efficient removal of Cd(II) ions from aqueous solutions. Functional PMAA brushes containing dense and active carboxyl groups (COOH) were grafted onto the CCS microsphere surface via surface-initiated atom transfer radical polymerization (ATRP). Batch adsorption results showed that solution pH values had a major impact on cadmium adsorption by the PMAA-grafted CCS microspheres with the optimal removal observed above pH 5. The CCS-g-PMAA microsphere was found to achieve the adsorption equilibrium of Cd(II) within 1 h, much faster than about 7 h on the CCS microsphere. At pH 5 and with an initial concentration 0.089-2.49 mmol dm(-3), the maximum adsorption capacity of Cd(II), derived from the Langmuir fitting on the PMAA-grafted microspheres was around 1.3 mmol g(-1). Desorption and adsorption cycle experimental results revealed that the PMAA-grafted CCS microspheres loaded with Cd(II) can be effectively regenerated in a dilute HNO3 solution, and the adsorption capacity remained almost unchanged upon five cycle reuse. PMID:23755995

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

    PubMed

    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

  3. Energy-level matching of Fe(III) ions grafted at surface and doped in bulk for efficient visible-light photocatalysts.

    PubMed

    Liu, Min; Qiu, Xiaoqing; Miyauchi, Masahiro; Hashimoto, Kazuhito

    2013-07-10

    Photocatalytic reaction rate (R) is determined by the multiplication of light absorption capability (α) and quantum efficiency (QE); however, these two parameters generally have trade-off relations. Thus, increasing α without decreasing QE remains a challenging issue for developing efficient photocatalysts with high R. Herein, using Fe(III) ions grafted Fe(III) doped TiO2 as a model system, we present a novel method for developing visible-light photocatalysts with efficient R, utilizing the concept of energy level matching between surface-grafted Fe(III) ions as co-catalysts and bulk-doped Fe(III) ions as visible-light absorbers. Photogenerated electrons in the doped Fe(III) states under visible-light efficiently transfer to the surface grafted Fe(III) ions co-catalysts, as the doped Fe(III) ions in bulk produced energy levels below the conduction band of TiO2, which match well with the potential of Fe(3+)/Fe(2+) redox couple in the surface grafted Fe(III) ions. Electrons in the surface grafted Fe(III) ions efficiently cause multielectron reduction of adsorbed oxygen molecules to achieve high QE value. Consequently, the present Fe(III)-FexTi1-xO2 nanocomposites exhibited the highest visible-light R among the previously reported photocatalysts for decomposition of gaseous organic compounds. The high R can proceed even under commercial white-light emission diode irradiation and is very stable for long-term use, making it practically useful. Further, this efficient method could be applied in other wide-band gap semiconductors, including ZnO or SrTiO3, and may be potentially applicable for other photocatalysis systems, such as water splitting, CO2 reduction, NOx removal, and dye decomposition. Thus, this method represents a strategic approach to develop new visible-light active photocatalysts for practical uses. PMID:23768256

  4. An Optical Biosensor from Green Fluorescent Escherichia coli for the Evaluation of Single and Combined Heavy Metal Toxicities

    PubMed Central

    Futra, Dedi; Heng, Lee Yook; Ahmad, Asmat; Surif, Salmijah; Ling, Tan Ling

    2015-01-01

    A fluorescence-based fiber optic toxicity biosensor based on genetically modified Escherichia coli (E. coli) with green fluorescent protein (GFP) was developed for the evaluation of the toxicity of several hazardous heavy metal ions. The toxic metals include Cu(II), Cd(II), Pb(II), Zn(II), Cr(VI), Co(II), Ni(II), Ag(I) and Fe(III). The optimum fluorescence excitation and emission wavelengths of the optical biosensor were 400 ± 2 nm and 485 ± 2 nm, respectively. Based on the toxicity observed under optimal conditions, the detection limits of Cu(II), Cd(II), Pb(II), Zn(II), Cr(VI), Co(II), Ni(II), Ag(I) and Fe(III) that can be detected using the toxicity biosensor were at 0.04, 0.32, 0.46, 2.80, 100, 250, 400, 720 and 2600 μg/L, respectively. The repeatability and reproducibility of the proposed biosensor were 3.5%–4.8% RSD (relative standard deviation) and 3.6%–5.1% RSD (n = 8), respectively. The biosensor response was stable for at least five weeks, and demonstrated higher sensitivity towards metal toxicity evaluation when compared to a conventional Microtox assay. PMID:26029952

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

    NASA Astrophysics Data System (ADS)

    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.

  6. Structure of Fe(III) precipitates generated by the electrolytic dissolution of Fe(0) in the presence of groundwater ions

    NASA Astrophysics Data System (ADS)

    van Genuchten, Case M.; Peña, Jasquelin; Amrose, Susan E.; Gadgil, Ashok J.

    2014-02-01

    We apply Fe K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy and pair distribution function (PDF) analysis of high-energy X-ray scattering to investigate the effects of bivalent cation-oxyanion pairs on the structure of Fe(III) precipitates formed from the oxidation of Fe(II) generated by the electrolytic dissolution of Fe(0) electrodes. We found that Fe(II) oxidation in the presence of weakly adsorbing electrolytes (NaCl, CaCl2, MgCl2) leads to pseudo-lepidocrocite (Lp; γ-FeOOH), a poorly crystalline version of Lp with low sheet-stacking coherence. In the absence of bivalent cations, P and As(V) have similar uptake behavior, but different effects on the average Fe(III) precipitate structure: pseudo-Lp dominates in the presence of P, whereas a disordered ferrihydrite-like precipitate akin to hydrous ferric oxide (HFO) is the dominant phase that forms in the presence of As(V). Despite its lower affinity for Fe(III) precipitates, Si leads to Si-HFO in all conditions tested. The presence of 1 mM Ca2+ or Mg2+ enhances oxyanion uptake, destabilizes the colloidally stable oxyanion-bearing particle suspensions and, in some P and As(V) electrolytes, results in more crystalline precipitates. The trends in oxyanion uptake and Fe(III) precipitate structure in the presence of Ca2+/Mg2+ suggest a systematic decrease in the strength of bivalent cation:oxyanion interaction in the order of Ca2+ > Mg2+ and P > As(V) ≫ Si. Using the PDF technique, we identify the polyhedral linkages that contribute to the intermediate structures (>6 Å) of disordered, nanoscale oxyanion-bearing Fe(III) precipitate samples. Our results suggest that oxyanions present during Fe(III) polymerization bind to corner-sharing Fe surface sites leading to a precipitate surface deficient in corner-sharing Fe, whereas the edge- and corner-sharing Fe sites in the precipitate core likely remain intact.

  7. Coordination chemistry and hydrolysis of Fe(III) in a peat humic acid studied by X-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Karlsson, Torbjörn; Persson, Per

    2010-01-01

    The speciation of iron (Fe) in soils, sediments and surface waters is highly dependent on chemical interactions with natural organic matter (NOM). However, the molecular structure and hydrolysis of the Fe species formed in association with NOM is still poorly described. In this study extended X-ray absorption fine structure (EXAFS) spectroscopy was used to determine the coordination chemistry and hydrolysis of Fe(III) in solution of a peat humic acid (5010-49,200 μg Fe g -1 dry weight, pH 3.0-7.2). Data were analyzed by both conventional EXAFS data fitting and by wavelet transforms in order to facilitate the identification of the nature of backscattering atoms. Our results show that Fe occurs predominantly in the oxidized form as ferric ions and that the speciation varies with pH and Fe concentration. At low Fe concentrations (5010-9920 μg g -1; pH 3.0-7.2) mononuclear Fe(III)-NOM complexes completely dominates the speciation. The determined bond distances for the Fe(III)-NOM complexes are similar to distances obtained for Fe(III) complexed by desferrioxamine B and oxalate indicating the formation of a five-membered chelate ring structure. At higher Fe concentrations (49,200 μg g -1; pH 4.2-6.9) we detect a mixture of mononuclear Fe(III)-NOM complexes and polymeric Fe(III) (hydr)oxides with an increasing amount of Fe(III) (hydr)oxides at higher pH. However, even at pH 6.9 and a Fe concentration of 49,200 μg g -1 our data indicates that a substantial amount of the total Fe (>50%) is in the form of organic complexes. Thus, in environments with significant amounts of organic matter organic Fe complexes will be of great importance for the geochemistry of Fe. Furthermore, the formation of five-membered chelate ring structures is in line with the strong complexation and limited hydrolytic polymerization of Fe(III) in our samples and also agrees with EXAFS derived structures of Fe(III) in organic soils.

  8. Co(II) PCP Pincer Complexes as Catalysts for the Alkylation of Aromatic Amines with Primary Alcohols.

    PubMed

    Mastalir, Matthias; Tomsu, Gerald; Pittenauer, Ernst; Allmaier, Günter; Kirchner, Karl

    2016-07-15

    Efficient alkylations of amines by alcohols catalyzed by well-defined Co(II) complexes are described that are stabilized by a PCP ligand (N,N'-bis(diisopropylphosphino)-N,N'-dimethyl-1,3-diaminobenzene) based on the 1,3-diaminobenzene scaffold. This reaction is an environmentally benign process implementing inexpensive, earth-abundant nonprecious metal catalysts and is based on the acceptorless alcohol dehydrogenation concept. A range of primary alcohols and aromatic amines were efficiently converted into mono-N-alkylated amines in good to excellent isolated yields. PMID:27356282

  9. Structural, DFT and biological studies on Co(II) complexes of semi and thiosemicarbazide ligands derived from diketo hydrazide

    NASA Astrophysics Data System (ADS)

    Yousef, T. A.; El-Gammal, O. A.; Ahmed, Sara F.; Abu El-Reash, G. M.

    2014-11-01

    Three ligands have been prepared by addition ethanolic suspension of 2-hydrazino-2-oxo-N-phenyl-acetamide to phenyl isocyanate (H2PAPS), phenyl isothiocyanate (H2PAPT) and benzoyl isothiocyanate (H2PABT). The Co(II) chloride complexes were prepared and characterized by conventional techniques. The isolated complexes were assigned the formulaes, [Co(HPAPS)Cl(H2O)2]H2O, [Co(HPAPT)Cl]H2O and [Co(H2PABT)Cl2], respectively. The IR spectra of complexes shows that H2PAPS behaves as a mononegative tridentate via CO of hydrazide moiety and enolized CO of hydrazide moiety and CN (azomethine) group due to enolization of CO isocyanate moiety. H2PAPT behaves as mononegative tridentate via one CO of hydrazide moiety and thiol CS and NH groups and finally H2PABT behaves as neutral tetradentate via one CO of hydrazide moiety, CO of benzoyl moiety, Cdbnd S due to enolization of the second CO of hydrazide moiety and new CN (azomethine) groups. The vibrational frequencies of the IR spectra of ligands which were determined experimentally are compared with those obtained theoretically from DFT calculations. Also, the bond lengths, bond angles, HOMO, LUMO and dipole moments have been calculated. The calculated HOMO-LUMO energy gap reveals that charge transfer occurs within the ligand molecules. The calculated values of binding energies indicates the stability of metal complexes is higher that of ligand. Also, the kinetic and thermodynamic parameters for the different thermal degradation steps of the complexes were determined by Coats-Redfern and Horowitz-Metzger methods. The antibacterial activities were also tested against Bacillus subtilis and Escherichia coli bacteria. The free ligands showed a higher antibacterial effect than their Co(II) complexes except [Co(HPAPS)Cl(H2O)2]H2O which shows higher activity than corresponding ligand. The antitumor activities of the Ligands and their Co(II) complexes have been evaluated against liver (HePG2) and breast (MCF-7) cancer cells. All ligands

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

    NASA Astrophysics Data System (ADS)

    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.

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

    NASA Astrophysics Data System (ADS)

    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.

  12. Catalysts of Cu(II) and Co(II) ions adsorbed in chitosan used in transesterification of soy bean and babassu oils - a new route for biodiesel syntheses.

    PubMed

    da Silva, Rondinelly Brandão; Lima Neto, Alcides Fernandes; Soares Dos Santos, Lucas Samuel; de Oliveira Lima, José Renato; Chaves, Mariana Helena; Dos Santos, José Ribeiro; de Lima, Geraldo Magela; de Moura, Edmilson Miranda; de Moura, Carla Verônica Rodarte

    2008-10-01

    Catalysts of Cu(II) and Co(II) adsorbed in chitosan was used in transesterification of soy bean and babassu oils. The catalysts were characterized by infrared, atomic absorption and TG, and biodiesels was characterized by infrared, NMR, CG, TG, physic chemistry analysis. The maximum adsorption values found for copper and cobalt cations were 1.584 and 1.260mgg(-1), respectively, in 180min. However, conversion of oils in biodiesel was better when used Co(II) adsorbed in chitosan. PMID:18440802

  13. Single-ion-magnet behavior in a two-dimensional coordination polymer constructed from Co(II) nodes and a pyridylhydrazone derivative.

    PubMed

    Liu, Xiangyu; Sun, Lin; Zhou, Huiliang; Cen, Peipei; Jin, Xiaoyong; Xie, Gang; Chen, Sanping; Hu, Qilin

    2015-09-21

    A novel two-dimensional (2D) coordination polymer, [Co(ppad)2]n (1), resulted from the assembly of Co(II) ions based on a versatile ligand termed N(3)-(3-pyridoyl)-3-pyridinecarboxamidrazone. Alternating/direct-current magnetic studies of compound 1 indicate that the spatially separated high-spin Co(II) ions act as single-ion magnets (SIMs). The present work represents the first case of a 2D Co(II)-based SIM composed of a monocomponent organic spacer. PMID:26347189

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

    NASA Astrophysics Data System (ADS)

    Rana, Vijay Kumar; Selvaraj, M.; Parambadath, Surendran; Chu, Sang-Wook; Park, Sung Soo; Mishra, Satyendra; Singh, Raj Pal; Ha, Chang-Sik

    2012-10-01

    To achieve a high level of heavy metal adsorption, 1,1',1″-(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.

  15. SERS Activity of Silver Nanoparticles Functionalized with A Desferrioxamine B Derived Ligand for FE(III) Binding and Sensing

    NASA Astrophysics Data System (ADS)

    Galinetto, P.; Taglietti, A.; Pasotti, L.; Pallavicini, P.; Dacarro, G.; Giulotto, E.; Grandi, M. S.

    2016-01-01

    We report the SERS activity of colloidal silver nanoparticles functionalized with a ligand, derived from the siderophore desferrioxamine B (desferal, DFO), an iron chelator widely used in biological and medical applications. The ligand was equipped with a sulfur-containing moiety to ensure optimal binding with silver surfaces. By means of Raman and SERS effects we monitored the route of material preparation from the modified DFO-S molecule to the colloidal aggregates. The results indicate that the functionalization of the chelating agent does not affect its binding ability towards Fe(III). The resulting functionalized silver nanoparticles are a promising SERS tag for operation in biological environments. The Fe-O stretching signature, arising when DFO-S grafted to silver nanoparticles binds Fe(III), could provide a tool for cation sensing in solution.

  16. Polarized Neutron Diffraction to Probe Local Magnetic Anisotropy of a Low-Spin Fe(III) Complex.

    PubMed

    Ridier, Karl; Mondal, Abhishake; Boilleau, Corentin; Cador, Olivier; Gillon, Béatrice; Chaboussant, Grégory; Le Guennic, Boris; Costuas, Karine; Lescouëzec, Rodrigue

    2016-03-14

    We have determined by polarized neutron diffraction (PND) the low-temperature molecular magnetic susceptibility tensor of the anisotropic low-spin complex PPh4 [Fe(III) (Tp)(CN)3 ]⋅H2 O. We found the existence of a pronounced molecular easy magnetization axis, almost parallel to the C3 pseudo-axis of the molecule, which also corresponds to a trigonal elongation direction of the octahedral coordination sphere of the Fe(III) ion. The PND results are coherent with electron paramagnetic resonance (EPR) spectroscopy, magnetometry, and ab initio investigations. Through this particular example, we demonstrate the capabilities of PND to provide a unique, direct, and straightforward picture of the magnetic anisotropy and susceptibility tensors, offering a clear-cut way to establish magneto-structural correlations in paramagnetic molecular complexes. PMID:26890339

  17. Enzymatic versus nonenzymatic conversions during the reduction of EDTA-chelated Fe(III) in BioDeNOx reactors.

    PubMed

    Van Der Maas, Peter; Peng, Shen; Klapwijk, Bram; Lens, Piet

    2005-04-15

    Reduction of EDTA-chelated Fe(III) is one of the core processes in the BioDeNOx process, a chemically enhanced technique for biological NOx removal from industrial flue gases. The capacity of Escherichia coli, three mixed cultures from full scale methanogenic granular sludge reactors, one denitrifying sludge, and a BioDeNOx sludge to reduce Fe(III)EDTA- (25 mM) was determined at 37 and 55 degrees C using batch experiments. Addition of catalytic amounts of sulfide greatly accelerated Fe(III)EDTA- reduction, indicating that biological Fe(III)EDTA- reduction is not a direct, enzymatic conversion but an indirect reduction with involvement of an electron-mediating compound, presumably polysulfides. It is suggested that not thermophilic dissimilatory iron-reducing bacteria but reducers of elemental sulfur or polysulfides are primarily involved in the reduction of EDTA-chelated Fe(III) in BioDeNOx reactors. PMID:15884357

  18. Synthesis, Structure, and Reactivity of Co(II) and Ni(II) PCP Pincer Borohydride Complexes

    PubMed Central

    2015-01-01

    The 15e square-planar complexes [Co(PCPMe-iPr)Cl] (2a) and [Co(PCP-tBu)Cl] (2b), respectively, react readily with NaBH4 to afford complexes [Co(PCPMe-iPr)(η2-BH4)] (4a) and [Co(PCP-tBu)(η2-BH4)] (4b) in high yields, as confirmed by IR spectroscopy, X-ray crystallography, and elemental analysis. The borohydride ligand is symmetrically bound to the cobalt center in η2-fashion. These compounds are paramagnetic with effective magnetic moments of 2.0(1) and 2.1(1) μB consistent with a d7 low-spin system corresponding to one unpaired electron. None of these complexes reacted with CO2 to give formate complexes. For structural and reactivity comparisons, we prepared the analogous Ni(II) borohydride complex [Ni(PCPMe-iPr)(η2-BH4)] (5) via two different synthetic routes. One utilizes [Ni(PCPMe-iPr)Cl] (3) and NaBH4, the second one makes use of the hydride complex [Ni(PCPMe-iPr)H] (6) and BH3·THF. In both cases, 5 is obtained in high yields. In contrast to 4a and 4b, the borohydride ligand is asymmetrically bound to the nickel center but still in an η2-mode. [Ni(PCPMe-iPr)(η2-BH4)] (5) loses readily BH3 at elevated temperatures in the presence of NEt3 to form 6. Complexes 5 and 6 are both diamagnetic and were characterized by a combination of 1H, 13C{1H}, and 31P{1H} NMR, IR spectroscopy, and elemental analysis. Additionally, the structure of these compounds was established by X-ray crystallography. Complexes 5 and 6 react with CO2 to give the formate complex [Ni(PCPMe-iPr)(OC(C=O)H] (7). The extrusion of BH3 from [Co(PCPMe-iPr)(η2-BH4)] (4a) and [Ni(PCPMe-iPr)(η2-BH4)] (5) with the aid of NH3 to yield the respective hydride complexes [Co(PCPMe-iPr)H] and [Ni(PCPMe-iPr)H] (6) and BH3NH3 was investigated by DFT calculations showing that formation of the Ni hydride is thermodynamically favorable, whereas the formation of the Co(II) hydride, in agreement with the experiment, is unfavorable. The electronic structures and the bonding of the borohydride ligand in [Co

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

    NASA Astrophysics Data System (ADS)

    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

  20. Antioxidant, tautomerism and antibacterial studies of Fe(III)-1,2,4-triazole based complexes

    NASA Astrophysics Data System (ADS)

    Kharadi, G. J.

    2013-06-01

    New Fe(III) complexes have been synthesized by the reactions of ferric nitrate with Schiff base derived from 3-substituted phenyl-4-amino-5-hydrazino-1,2,4-triazole and indoline-2,3-dione. All these complexes are soluble in DMF and DMSO; low molar conductance values indicate that they are non-electrolytes. Elemental analyses suggest that the complexes have 1:1 stoichiometry of the type [FeLn(H2O)(OH)]·xH2O. Structural and spectroscopic properties have been studied on the basis of elemental analyses, infrared spectra, 1H and 13H NMR spectra, electronic spectra, magnetic measurements and FAB mass spectra. FT-IR, 1H and 13H NMR studies reveal that the ligand (Ln) exists in the tautomeric enol form in both the states with intramolecular hydrogen bonding. Magnetic moment and reflectance spectral studies reveal that an octahedral geometry has been assigned to all the prepared complexes. FRAP values indicate that all the compounds have a ferric reducing antioxidant power. The compounds 2 and 3 showed relatively high antioxidant activity while compound 1 and 4 shows poor antioxidant power. Also good antimicrobial activities of the complexes against Staphylococcus aureus, Bacillus subtilis, Serratia marcescens, Pseudomonas aeruginosa and Escherichia coli have been found compared to its free ligands.

  1. Investigating Pseudomonas putida-Candida humicola interactions as affected by chelate Fe(III) in soil.

    PubMed

    Wang, Fei; Yao, Jun; Yu, Chan; Chen, Huilun; Yi, Zhengji

    2014-03-01

    Microcalorimetric technique was applied to assess the toxic effect of EDTA-chelated trivalent iron on Pseudomonas putida (P. putida) (bacterium), Candida humicola (C. humicola) (fungus) and their mixture in sterilized soil. Microbial growth rate constant k, total heat evolution Q T, metabolic enthalpy ∆H met, mass specific heat rate J Q/S, microbial biomass C and inhibitory ratio I were calculated. Results showed that microcalorimetric indexes decreased with the increasing Fe(III)-EDTA complex concentration. Comparing the single and mixed strains, the effect of Fe(III) on bacterium-fungus interaction was dominant at lower dose, whereas, the metal toxicity at high dose of Fe was the main factor affecting P. putida and C. humicola activity. Thus, the mixture had moderate tolerance to the iron overload, and exhibit synergistic interaction in exponential growth phase (0-0.3 mg g(-1)). The results of glucose degradation showed that glucose was consumed totally at the end of exponential phase of microbial growth. PMID:24270965

  2. Solution thermodynamics and structures of biscatecholamide complexes of Fe(III) and U(VI)

    SciTech Connect

    Gohdes, J.W.; Reilly, S.D.; Pecha, A.W.; Neu, M.P.

    1996-12-31

    We have studied the solution and solid-state complexes of a bis-catecholamide ligand, 2-LICAMS, with Fe(III) and U(VI). The first protonation constant was found to be pK{sub al} = 14.2(3) using {sup 1}H NMR titrations. Subsequent protonation constants were determined by potentiometric titration in 0.1 M TMAOTf at 25{degrees}C to be pK{sub a2} = 11.2(1), pK{sub 13} =6.5(1), pK{sub a4}= 5.9(1). Ligand-metal formation constants, {Beta}{sub mlh}, were found to be log {beta}{sub 110} = 31.4(2), log {beta}{sub 111} = 31.7(2), log {beta}{sub 112} = 34.9(2), and log {beta}11.1 = 18.0(1) for uranium(VI). To discriminate between monomeric or dimeric species models which both fit the potentiometric titration data, we isolated the hydroxide species and determined its single-crystal X-ray structure and EXAFS. The structure consists of a dimeric, bis-hydroxide bridged iron core which is spanned by two ligands. This study of solution equilibria indicates a higher stability for iron complexes of 2-LICAMS relative to uranyl complexes.

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

    NASA Astrophysics Data System (ADS)

    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.

  4. Probing bistability in Fe(II) and Co(II) complexes with an unsymmetrically substituted quinonoid ligand.

    PubMed

    van der Meer, Margarethe; Rechkemmer, Yvonne; Breitgoff, Frauke D; Dechert, Sebastian; Marx, Raphael; Dörfel, María; Neugebauer, Petr; van Slageren, Joris; Sarkar, Biprajit

    2016-05-28

    The generation of molecular platforms, the properties of which can be influenced by a variety of external perturbations, is an important goal in the field of functional molecular materials. We present here the synthesis of a new quinonoid ligand platform containing an [O,O,O,N] donor set. The ligand is derived from a chloranilic acid core by using the [NR] (nitrogen atom with a substituent R) for [O] isoelectronic substitution. Mononuclear Fe(II) and Co(II) complexes have been synthesized with this new ligand. Results obtained from single crystal X-ray crystallography, NMR spectroscopy, (spectro)electrochemistry, SQUID magnetometry, multi-frequency EPR spectroscopy and FIR spectroscopy are used to elucidate the electronic and geometric structures of the complexes. Furthermore, we show here that the spin state of the Fe(II) complex can be influenced by temperature, pressure and light and the Co(II) complex displays redox-induced spin-state switching. Bistability is observed in the solid-state as well as in solution for the Fe(II) complex. The new ligand presented here, owing to the [NR] group present in it, will likely have more adaptability while investigating switching phenomena compared to its [O,O,O,O] analogues. Thus, such classes of ligands as well as the results obtained on the reversible changes in physical properties of the metal complexes are likely to contribute to the generation of multifunctional molecular materials. PMID:27109712

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

    NASA Astrophysics Data System (ADS)

    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.

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

    PubMed Central

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

    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 analysis it was found that hydroxyl, methoxy, and carbonyl groups are responsible for Co(II) biosorption. The kinetic data obtained for both biosorbents was well fitted with pseudo-second-order kinetic model. The equilibrium data was in tune with the Langmuir and Freundlich isotherm models. The thermodynamic studies were also carried and it was observed that sorption process was endothermic at 298–328 K. These studies demonstrated that both biosorbents were promising, efficient, economic, and biodegradable sorbents. PMID:24324384

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

    PubMed Central

    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 sequences of His residues have been introduced by protein engineering. The His residues could be either consecutive or spaced with other amino acids in between. The cleavage reaction required the presence of low concentrations of ascorbate and in the case of Cu(II) also hydrogen peroxide. The amount of metal ions required for cleavage was very low; in the case of Cu(II) only one to two molar equivalents of Cu(II) to protein was required. In the case of Co(II), 10 molar equivalents gave optimal cleavage. The reaction occurred within minutes, at a wide pH range, and efficiently at temperatures ranging from 0°C to 70°C. The work described here can also have implications for understanding protein stability in vitro and in vivo. PMID:17600148

  8. A genetic system for Geobacter metallireducens: role of the flagellin and pilin in the reduction of Fe(III) oxide

    SciTech Connect

    Tremblay, PL; Aklujkar, M; Leang, C; Nevin, KP; Lovley, D

    2011-11-27

    Geobacter metallireducens is an important model organism for many novel aspects of extracellular electron exchange and the anaerobic degradation of aromatic compounds, but studies of its physiology have been limited by a lack of techniques for gene deletion and replacement. Therefore, a genetic system was developed for G. metallireducens by making a number of modifications in the previously described approach for homologous recombination in Geobacter sulfurreducens. Critical modifications included, among others, a 3.5-fold increased in the quantity of electrotransformed linear DNA and the harvesting of cells at early-log. The Cre-lox recombination system was used to remove an antibiotic resistance cassette from the G. metallireducens chromosome permitting the generation of multiple mutations in the same strain. Deletion of the gene fliC, which encodes the flagellin protein, resulted in a strain that did not produce flagella, was non-motile, and was defective for the reduction of insoluble Fe(III). Deletion of pilA, which encodes the structural protein of the type IV pili, inhibited the production of lateral pili as well as Fe(III) oxide reduction and electron transfer to an electrode. These results demonstrate the importance of flagella and pili in the reduction of insoluble Fe(III) by G. metallireducens and provide methods for additional genetic-based approaches for the study of G. metallireducens.

  9. A Simple Small Size and Low Cost Sensor Based on Surface Plasmon Resonance for Selective Detection of Fe(III)

    PubMed Central

    Cennamo, Nunzio; Alberti, Giancarla; Pesavento, Maria; D'Agostino, Girolamo; Quattrini, Federico; Biesuz, Raffaela; Zeni, Luigi

    2014-01-01

    A simple, small size, and low cost sensor based on a Deferoxamine Self Assembled Monolayer (DFO-SAM) and Surface Plasmon Resonance (SPR) transduction, in connection with a Plastic Optical Fiber (POF), has been developed for the selective detection of Fe(III). DFO-SAM sensors based on appropriate electrochemical techniques can be frequently found in the scientific literature. In this work, we present the first example of a DFO-SAM sensor based on SPR in an optical fiber. The SPR sensing platform was realized by removing the cladding of a plastic optical fiber along half the circumference, spin coating a buffer of Microposit S1813 photoresist on the exposed core, and finally sputtering a thin gold film. The hydroxamate siderophore deferoxamine (DFO), having high binding affinity for Fe(III), is then used in its immobilized form, as self-assembled monolayer on the gold layer surface of the POF sensor. The results showed that the DFO-SAM-POF-sensor was able to sense the formation of the Fe(III)/DFO complex in the range of concentrations between 1 μm and 50 μm with a linearity range from 0 to 30 μm of Fe(III). The selectivity of the sensor was also proved by interference tests. PMID:24608007

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

    PubMed

    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

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

    PubMed

    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

  12. Fe(III) doped and grafted PbTiO{sub 3} film photocathode with enhanced photoactivity for hydrogen production

    SciTech Connect

    Hu, Yuxiang; Dong, Wen; Zheng, Fengang; Fang, Liang; Shen, Mingrong

    2014-08-25

    The photoelectrochemical activity of the PbTiO{sub 3} film photocathode deposited on indium tin oxide-coated quartz substrate was significantly improved through modifying the film surface by both the Fe(III) doping and grafting. Doping the PbTiO{sub 3} with Fe(III) ions narrows its band gap thus increases the visible light utilization, while the surface-grafted Fe(III) ions on the doped PbTiO{sub 3} surface are helpful to improve the charge transfer on the photocathode/electrolyte interface. Consequently, the photocurrent was increased from 38 μA/cm{sup 2} to 220 μA/cm{sup 2} under the irradiation of 100 mW/cm{sup 2} Xe lamp by using 0.1M Na{sub 2}SO{sub 4} as an electrolyte and zero-potential versus saturated calomel as a reference electrode. The corresponding increase in open circuit voltage was 0.95–1.11 V.

  13. 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.

    PubMed

    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

  14. Proteins involved in electron transfer to Fe(III) and Mn(IV) oxides by Geobacter sulfurreducens and Geobacter uraniireducens.

    PubMed

    Aklujkar, M; Coppi, M V; Leang, C; Kim, B C; Chavan, M A; Perpetua, L A; Giloteaux, L; Liu, A; Holmes, D E

    2013-03-01

    Whole-genome microarray analysis of Geobacter sulfurreducens grown on insoluble Fe(III) oxide or Mn(IV) oxide versus soluble Fe(III) citrate revealed significantly different expression patterns. The most upregulated genes, omcS and omcT, encode cell-surface c-type cytochromes, OmcS being required for Fe(III) and Mn(IV) oxide reduction. Other electron transport genes upregulated on both metal oxides included genes encoding putative menaquinol : ferricytochrome c oxidoreductase complexes Cbc4 and Cbc5, periplasmic c-type cytochromes Dhc2 and PccF, outer membrane c-type cytochromes OmcC, OmcG and OmcV, multicopper oxidase OmpB, the structural components of electrically conductive pili, PilA-N and PilA-C, and enzymes that detoxify reactive oxygen/nitrogen species. Genes upregulated on Fe(III) oxide encode putative menaquinol : ferricytochrome c oxidoreductase complexes Cbc3 and Cbc6, periplasmic c-type cytochromes, including PccG and PccJ, and outer membrane c-type cytochromes, including OmcA, OmcE, OmcH, OmcL, OmcN, OmcO and OmcP. Electron transport genes upregulated on Mn(IV) oxide encode periplasmic c-type cytochromes PccR, PgcA, PpcA and PpcD, outer membrane c-type cytochromes OmaB/OmaC, OmcB and OmcZ, multicopper oxidase OmpC and menaquinone-reducing enzymes. Genetic studies indicated that MacA, OmcB, OmcF, OmcG, OmcH, OmcI, OmcJ, OmcM, OmcV and PccH, the putative Cbc5 complex subunit CbcC and the putative Cbc3 complex subunit CbcV are important for reduction of Fe(III) oxide but not essential for Mn(IV) oxide reduction. Gene expression patterns for Geobacter uraniireducens were similar. These results demonstrate that the physiology of Fe(III)-reducing bacteria differs significantly during growth on different insoluble and soluble electron acceptors and emphasize the importance of c-type cytochromes for extracellular electron transfer in G. sulfurreducens. PMID:23306674

  15. DNA binding, photoactivated DNA cleavage and cytotoxic activity of Cu(II) and Co(II) based Schiff-base azo photosensitizers

    NASA Astrophysics Data System (ADS)

    Pradeepa, S. M.; Bhojya Naik, H. S.; Vinay Kumar, B.; Indira Priyadarsini, K.; Barik, Atanu; Prabhakara, M. C.

    2015-04-01

    A new class of Cu(II) and Co(II) complexes of azo-containing Schiff base of the type [Cu(L1)2] and [Co(L1)2], where L1 = 4-[(E)-{2-hydroxy-3-[(E)-(4-bromophenyl)diazenyl]benzylidene}amino]benzoic acid have been synthesized and characterized. Extension of conjugation and the presence of free carboxylic acid group of the ligand L1 increased the wavelength of the complexes from visible region to the near IR region (620-850 nm). The Cu(II) and Co(II) complexes interacted with CT-DNA via intercalative mode with the respective Kb value of 3.2 × 104 M-1 and 2.9 × 104 M-1 and acted as proficient photocleavers of SC pUC19 DNA in UV-A light, forming 1O2 as the reactive oxygen species with the quantum yield of 0.38 and 0.36, respectively. Furthermore, the Cu(II) and Co(II) complexes showed photocytotoxicity toward two selected tumor cell lines MCF-7 and A549 by 3-(4,5-Dimethylthiazol-2-yl)-2,5-diphenyltetrazoliumbromide (MTT) method, and the Cu(II) complex exhibits higher photocytotoxicity than Co(II) complex against each of the selected cell lines, this result is identical with their DNA binding ability order.

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

    NASA Astrophysics Data System (ADS)

    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.

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

    SciTech Connect

    Bao, Qi; Hui, K.N.; Hui, K.S.; Wang, Yi; Hong, Xiaoting

    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.

  18. H-point standard addition method for simultaneous spectrophotometric determination of Co(II) and Ni(II) by 1-(2-pyridylazo)2-naphthol in micellar media.

    PubMed

    Afkhami, Abbas; Bahram, Morteza

    2004-01-01

    A very simple and selective spectrophotometric method for simultaneous determination of Co(II) and Ni(II) by 1-(2-pyridylazo) 2-naphthol (PAN), in micellar media, using H-point standard addition method (HPSAM) is described. The ligand and its metal complexes (Co(II)-PAN and Ni(II)-PAN) were made water-soluble by the neutral surfactant Triton X-100, and therefore, no extraction with organic solvents was required. Formation of both the complexes was complete within 10 min at pH 9 (adjusted by ammonia buffer). The linear range was 0.10-2.00 microg ml(-1) for Co(II) and 0.05-1.50 microg ml(-1) for Ni(II). The relative standard deviation (R.S.D.) for the simultaneous determination of 0.50 microg ml(-1) each of Co(II) and Ni(II) was 2.32 and 3.13%, respectively. Interference effects of common anions and cations were studied and the method was applied to simultaneous determination of Co(II) and Ni(II) in alloy samples. The method was compared with derivative spectrophotometric method. PMID:14670476

  19. Ferromagnetic coupling mediated by Coπ non-covalent contacts in a pentacoordinate Co(ii) compound showing field-induced slow relaxation of magnetization.

    PubMed

    Nemec, I; Herchel, R; Trávníček, Z

    2016-08-01

    [Co(II)(dpt)(NCS)2], where dpt = bis(3-aminopropyl)amine, was identified as a pentacoordinate Co(II) compound showing field-induced slow relaxation of magnetization. Furthermore, intermolecular ferromagnetic coupling mediated by Coπ non-covalent contacts, where π orbitals originate from the thiocyanato ligand, is reported for the first time. PMID:27435418

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

    NASA Astrophysics Data System (ADS)

    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

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

    PubMed

    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

  2. Infrared and Raman spectra of ethylene trithiocarbonate complexes of some Zn(II), Cd(II) and Hg(II) halides

    NASA Astrophysics Data System (ADS)

    Contreras, J. Guillermo; Gnecco, Juan A.

    Coordination compounds of ethylene trithiocarbonate (ETTC) with some Zn(II), Cd(II) and Hg(II) halides have been prepared, characterized and their infrared and Raman spectra recorded. The i.r. spectra in the range 4000-400 cm -1 suggest that the organic ligand is bonded to the metal ions through its exocyclic sulphur atom, whereas the far-i.r. and Raman spectra show that the complexes of the type HgX 2(ETTC) (X = Cl, Br or I) possess a trans dimeric halogen-bridged structure. The Cd(II) and Zn(II) species are of the type MX 2(ETTC) 2 and they possess a pseudotetrahedral structure of C2υ symmetry.

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

    SciTech Connect

    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 [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.

  4. Seizure modeling of Pb(II) and Cd(II) from aqueous solution by chemically modified sugarcane bagasse fly ash: isotherms, kinetics, and column study.

    PubMed

    Shah, Bhavna; Mistry, Chirag; Shah, Ajay

    2013-04-01

    Heavy metal pollution is a common environmental problem all over the world. The purpose of the research is to examine the applicability of bagasse fly ash (BFA)-an agricultural waste of sugar industry used for the synthesis of zeolitic material. The zeolitic material are used for the uptake of Pb(II) and Cd(II) heavy metal. Bagasse fly ash is used as a native material for the synthesis of zeolitic materials by conventional hydrothermal treatment without (conventional zeolitic bagasse fly ash (CZBFA)) and with electrolyte (conventional zeolitic bagasse fly ash in electrolyte media (ECZBFA)) media. Heavy metal ions Pb(II) and Cd(II) were successfully seized from aqueous media using these synthesized zeolitic materials. In this study, the zeolitic materials were well characterized by different instrumental methods such as Brunauer-Emmett-Teller, XRF, Fourier transform infrared spectroscopy, powder X-ray diffraction, and scanning electron microscopic microphotographs. The presence of analcime, phillipsite, and zeolite P in adsorbents confirms successful conversion of native BFA into zeolitic materials. Seizure modeling of Pb(II) and Cd(II) was achieved by batch sorption experiments, isotherms, and kinetic studies. These data were used to compare and evaluate the zeolitic materials as potential sorbents for the uptake of heavy metal ions from an aqueous media. The Langmuir isotherm correlation coefficient parameters best fit the equilibrium data which indicate the physical sorption. Pseudo-second-order and intra-particle diffusion model matches best which indicates that the rate of sorption was controlled by film diffusion. The column studies were performed for the practical function of sorbents, and breakthrough curves were obtained, which revealed higher sorption capacity as compared to batch method. Synthesized zeolitic material (CZBFA and ECZBFA), a low-cost sorbent, was proven as potential sorbent for the uptake of Pb(II) and Cd(II) heavy metal ions. PMID:22739768

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

    PubMed Central

    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

  6. Multilayer adsorption of Cu(II) and Cd(II) over Brazilian Orchid Tree (Pata-de-vaca) and its adsorptive properties

    NASA Astrophysics Data System (ADS)

    Jorgetto, Alexandre de O.; da Silva, Adrielli C. P.; Wondracek, Marcos H. P.; Silva, Rafael I. V.; Velini, Edivaldo D.; Saeki, Margarida J.; Pedrosa, Valber A.; Castro, Gustavo R.

    2015-08-01

    Through very simple and inexpensive processes, pata-de-vaca leaves were turned into a powder and applied as an adsorbent for the uptake of Cu(II) and Cd(II) from water. The material was characterized through SEM, EDX, FTIR and surface area measurement. The material had its point of zero charge determined (5.24), and its adsorption capacity was evaluated as a function of time, pH and metal concentration. The material presented fast adsorption kinetics, reaching adsorption equilibrium in less than 5 min and it had a good correlation with the pseudo-second order kinetic model. Optimum pH for the adsorption of Cu(II) and Cd(II) were found to be in the range from 4 to 5, approximately. In the experiment as a function of the analyte concentration, analogously to gas adsorption, the material presented a type II isotherm, indicating the formation of multilayers for both species. Such behavior was explained with basis in the alternation between cations and anions over the material's surface, and the maximum adsorption capacity, considering the formation of the multilayers were found to be 0.238 mmol L-1 for Cu(II) and 0.113 mmol L-1 for Cd(II).

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

    PubMed

    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

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

    PubMed

    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

  9. Synthesis, characterization, DFT and biological studies of isatinpicolinohydrazone and its Zn(II), Cd(II) and Hg(II) complexes

    NASA Astrophysics Data System (ADS)

    El-Gammal, O. A.; Rakha, T. H.; Metwally, H. M.; Abu El-Reash, G. M.

    2014-06-01

    Isatinpicolinohydrazone (H2IPH) and its Zn(II), Cd(II) and Hg(II) complexes have been synthesized and investigated using physicochemical techniques viz. IR, 1H NMR, 13C NMR, UV-Vis spectrometric methods and magnetic moment measurements. The investigation revealed that H2IPH acts as binegative tetradentate in Zn(II), neutral tridentate in Cd(II) and as neutral bidentate towards Hg(II) complex. Octahedral geometry is proposed for all complexes. The bond length, bond angle, chemical reactivity, energy components (kcal/mol), binding energy (kcal/mol) and dipole moment (Debyes) for all the title compounds were evaluated by DFT and also MEP for the ligand is shown. Theoretical infrared intensities of H2IPH and also the theoretical electronic spectra of the ligand and its complexes were calculated. The thermal behavior and the kinetic parameters of degradation were determined using Coats-Redfern and Horowitz-Metzger methods. The in vitro antibacterial studies of the complexes proved them as growth inhibiting agents. The DDPH antioxidant of the compounds have been screened. Antitumor activity, carried out in vitro on human mammary gland (breast) MCF7, have shown that Hg(II) complex exhibited potent activity followed by Zn(II), Cd(II) complexes and the ligand.

  10. Mononuclear, dinuclear and 1-D polymeric complexes of Cd(II) of a pyridyl pyrazole ligand: Syntheses, crystal structures and photoluminescence studies

    NASA Astrophysics Data System (ADS)

    Das, Kinsuk; Konar, Saugata; Jana, Atanu; Barik, Anil Kumar; Roy, Sangita; Kar, Susanta Kumar

    2013-03-01

    The syntheses, crystal structures and photoluminescence properties of four new Cd(II) complexes are reported using strongly coordinating ligand 3,5-dimethyl-1-(2'-pyridyl) pyrazole (L) in presence of anionic ancillary bridging ligands as nitrite, chloride and dicyanamide. Among the complexes two (1 and 2) are monomeric, 3 is μ2 - chloro bridged dimer and the last one (4) is a mixed alternate chloro - end to end (EE) dicyanamide bridged 1D polymer. All the four complexes have been X-ray crystallographically characterized. The ligand L behaves as a potent bidentate neutral N, N donor. Geometrical diversity of Cd(II) complexes is due to no loss or gain of crystal field stability with the variation of geometry. Consequently the stability of a structure depends on steric requirements. The ligand L shows considerable fluorescence and all four complexes in methanol exhibit interesting photoluminescence properties with different emission intensities. The band maxima and fluorescence efficiency (in methanol) are found to be dependent on the coordination chromophore and structural rigidity induced by the incorporated Cd(II) ion. Among the synthesized complexes 1 exhibits the highest fluorescence intensity in methanol.

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

    NASA Astrophysics Data System (ADS)

    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.

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

    PubMed

    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 (<800 Oe) and only one process under a high dc field (≥800 Oe), which was an unusually discovery for 3d metal ions. On the basis of the ac 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

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

    NASA Astrophysics Data System (ADS)

    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.

  14. Detection of Mitochondrial COII DNA Sequences in Ant Guts as a Method for Assessing Termite Predation by Ants

    PubMed Central

    Fayle, Tom M.; Scholtz, Olivia; Dumbrell, Alex J.; Russell, Stephen; Segar, Simon T.; Eggleton, Paul

    2015-01-01

    Termites and ants contribute more to animal biomass in tropical rain forests than any other single group and perform vital ecosystem functions. Although ants prey on termites, at the community level the linkage between these groups is poorly understood. Thus, assessing the distribution and specificity of ant termitophagy is of considerable interest. We describe an approach for quantifying ant-termite food webs by sequencing termite DNA (cytochrome c oxidase subunit II, COII) from ant guts and apply this to a soil-dwelling ant community from tropical rain forest in Gabon. We extracted DNA from 215 ants from 15 species. Of these, 17.2 % of individuals had termite DNA in their guts, with BLAST analysis confirming the identity of 34.1 % of these termites to family level or better. Although ant species varied in detection of termite DNA, ranging from 63 % (5/7; Camponotus sp. 1) to 0 % (0/7; Ponera sp. 1), there was no evidence (with small sample sizes) for heterogeneity in termite consumption across ant taxa, and no evidence for species-specific ant-termite predation. In all three ant species with identifiable termite DNA in multiple individuals, multiple termite species were represented. Furthermore, the two termite species that were detected on multiple occasions in ant guts were in both cases found in multiple ant species, suggesting that ant-termite food webs are not strongly compartmentalised. However, two ant species were found to consume only Anoplotermes-group termites, indicating possible predatory specialisation at a higher taxonomic level. Using a laboratory feeding test, we were able to detect termite COII sequences in ant guts up to 2 h after feeding, indicating that our method only detects recent feeding events. Our data provide tentative support for the hypothesis that unspecialised termite predation by ants is widespread and highlight the use of molecular approaches for future studies of ant-termite food webs. PMID:25853549

  15. Evolutionary history of the COII/tRNALys intergenic 9 base pair deletion in human mitochondrial DNAs from the Pacific.

    PubMed

    Redd, A J; Takezaki, N; Sherry, S T; McGarvey, S T; Sofro, A S; Stoneking, M

    1995-07-01

    Length changes in human mitochondrial DNA (mtDNA) are potentially useful markers for inferring the evolutionary history of populations. One such length change is a nine base pair (9-bp) deletion that is located in the intergenic region between the COII gene and the Lysine tRNA gene (COII/tRNALys intergenic region). This deletion has been used as a genetic marker to trace descent from peoples of East Asian origin. A geographic cline of the deletion frequency across modern Pacific Islander populations suggests that the deletion may be useful for tracing prehistoric Polynesian origins and affinities. Mitochondrial DNA sequence variation within two variable segments of the control region (CR) permits a number of inferences regarding the evolutionary history of the 9-bp deletion that cannot be determined from frequency data alone. We obtained CR sequences from 74 mtDNAs with the 9-bp deletion from Indonesia, coastal Papua New Guinea (PNG), and American Samoa. Phylogenetic and pairwise distribution analysis of these CR sequences pooled with previously published CR sequences reveals that the deletion arose independently in Africa and Asia and suggests possible multiple origins of the deletion in Asia. A clinal increase of the frequency of the 9-bp deletion across the three Pacific populations is associated with a decrease in CR sequence diversity, consistent with founder events. Furthermore, analysis of pairwise difference distributions indicates an expansion time of proto-Polynesians that began 5,500 yr ago from Southeast Asia. These results are consistent with the express train model of Polynesian origins. PMID:7659016

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

    NASA Astrophysics Data System (ADS)

    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

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

    PubMed Central

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

    2000-01-01

    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 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. PMID:10788374

  18. Heterogeneous reduction of PuO₂ with Fe(II): importance of the Fe(III) reaction product.

    PubMed

    Felmy, Andrew R; Moore, Dean A; Rosso, Kevin M; Qafoku, Odeta; Rai, Dhanpat; Buck, Edgar C; Ilton, Eugene S

    2011-05-01

    Heterogeneous reduction of actinides in higher, more soluble oxidation states to lower, more insoluble oxidation states by reductants such as Fe(II) has been the subject of intensive study for more than two decades. However, Fe(II)-induced reduction of sparingly soluble Pu(IV) to the more soluble lower oxidation state Pu(III) has been much less studied, even though such reactions can potentially increase the mobility of Pu in the subsurface. Thermodynamic calculations are presented that show how differences in the free energy of various possible solid-phase Fe(III) reaction products can greatly influence aqueous Pu(III) concentrations resulting from reduction of PuO₂(am) by Fe(II). We present the first experimental evidence that reduction of PuO₂(am) to Pu(III) by Fe(II) was enhanced when the Fe(III) mineral goethite was spiked into the reaction. The effect of goethite on reduction of Pu(IV) was demonstrated by measuring the time dependence of total aqueous Pu concentration, its oxidation state, and system pe/pH. We also re-evaluated established protocols for determining Pu(III) {[Pu(III) + Pu(IV)] - Pu(IV)} by using thenoyltrifluoroacetone (TTA) in toluene extractions; the study showed that it is important to eliminate dissolved oxygen from the TTA solutions for accurate determinations. More broadly, this study highlights the importance of the Fe(III) reaction product in actinide reduction rate and extent by Fe(II). PMID:21469710

  19. Heterogeneous Reduction of PuO2 with Fe(II): Importance of the Fe(III) Reaction Product

    SciTech Connect

    Felmy, Andrew R.; Moore, Dean A.; Rosso, Kevin M.; Qafoku, Odeta; Rai, Dhanpat; Buck, Edgar C.; Ilton, Eugene S.

    2011-05-01

    Abstract Heterogeneous reduction of actinides in higher and more soluble oxidation states to lower more insoluble oxidation states by reductants such as Fe(II) has been the subject of intensive study for more than two decades. However, Fe(II)-induced reduction of sparingly soluble Pu(IV) to the more soluble lower oxidation state Pu(III) has been much less studied even though such reactions can potentially increase the mobility of Pu in the subsurface. Thermodynamic calculations are presented that show how differences in the free energy of various possible solid-phase Fe(III) reaction products can greatly influence aqueous Pu(III) concentrations resulting from reduction of PuO2(am) by Fe(II). We present the first experimental evidence that reduction of PuO2(am) to Pu(III) by Fe(II) was enhanced when the Fe(III) mineral goethite was spiked into the reaction. The effect of goethite on reduction of Pu(IV) was demonstrated by measuring the time-dependence of total aqueous Pu concentration, its oxidation state, and system pe/pH. We also re-evaluated established protocols for determining Pu(III) [(Pu(III) + Pu(IV)) - Pu(IV)] by using thenoyltrifluoroacetone (TTA) in toluene extractions; the study showed that it is important to eliminate dissolved oxygen from the TTA solutions for accurate determinations. More broadly, this study highlights the importance of the Fe(III) reaction product in actinide reduction rate and extent by Fe(II).

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

    SciTech Connect

    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.

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

    PubMed

    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

  2. Oxidation of Orange G by persulfate activated by Fe(II), Fe(III) and zero valent iron (ZVI).

    PubMed

    Rodriguez, S; Vasquez, L; Costa, D; Romero, A; Santos, A

    2014-04-01

    Persulfate (PS) was employed in the oxidation of Orange G (OG), an azo dye commonly found in textile wastewaters. Activation of PS was conducted with iron to generate sulfate free radicals (SO4(-)) with high redox potential capable to oxidize most of the organics in water. Identification of oxidation intermediates was carried out by analyzing at different times organic by-products generated from treatment of a concentrate dye solution (11.6 mM) with 153 mM of PS and 20 mM of Fe(II) at 20 °C. Intermediate reaction products (mainly phenol (PH) and benzoquinone (BQ), and in less extent aniline, phenolic compounds and naphthalene type compounds with quinone groups) were identified by GC/MS and HPLC, and an oxidation pathway was proposed for the oxidation of OG with iron activated PS. The effect of iron valence (0, II and III) in the oxidation of an aqueous solution of OG (containing 0.1 mM) was studied in a 0.5 L batch reactor at 20 °C. Initial activator and PS concentrations employed were both 1 mM. Complete pollutant removal was achieved within the first 30 min when iron II or III were employed as activators. Quinone intermediates generated during pollutant oxidation may act as electron shuttles, allowing the reduction of Fe(III) into Fe(II) in the redox cycling of iron. Therefore, activation of PS by Fe(III) allowed complete OG removal. When zero valent iron (ZVI) was employed (particle diameter size 0.74 mm) the limiting step in SO4(-) generation was the surface reaction between ZVI and the oxidant yielding a lower oxidation rate of the dye. An increase in the oxidant dosage (0.2 mM OG, 2 mM Fe(III) and 6 mM PS) allowed complete pollutant and ecotoxicity removal, as well as mineralization close to 75%. PMID:24439838

  3. Kinetic spectrophotometric determination of Fe(II) in the presence of Fe(III) by H-point standard addition method in mixed micellar medium.

    PubMed

    Hasani, Masoumeh; Rezaei, Alireza; Abdollahi, Hamid

    2007-11-01

    The H-point standard addition method was applied to kinetic data for simultaneous determination of Fe(II) and Fe(III) or selective determination of Fe(II) in the presence of Fe(III). The method is based on the difference in the rate of complex formation between iron in two different oxidation states and methylthymol blue (MTB) at pH 3.5 in mixed cetyltrimethylammonium bromide (CTAB) and Triton X-100 micellar medium. Fe(II) can be determined in the range 0.25-2.5 microg ml(-1) with satisfactory accuracy and precision in the presence of excess Fe(III) and other metal ions that rapidly form complexes with MTB under working condition. The proposed method was successfully applied to the simultaneous determination of Fe(II) and Fe(III) or selective determination of Fe(II) in the presence of Fe(III) in spiked real environmental and synthetic samples with complex composition. PMID:17329160

  4. Removal of Cd(II) ions from aqueous solution and industrial effluent using reverse osmosis and nanofiltration membranes.

    PubMed

    Kheriji, Jamel; Tabassi, Dorra; Hamrouni, Béchir

    2015-01-01

    Industrial effluents loaded with cadmium have contributed to the pollution of the environment and health troubles for humans. Therefore, these effluents need treatment to reduce cadmium concentration before releasing them to public sewage. The purpose of the research is to study the major role of reverse osmosis (RO) and nanofiltration (NF) processes, which can contribute to the removal of cadmium ions from model water and wastewater from the battery industry. For this reason, two RO and two nanofiltration membranes have been used. The effects of feed pressure, concentration, ionic strength, nature of anion associated with cadmium and pH on the retention of Cd(II) were studied with model solutions. Thereafter, NF and RO membranes were used to reduce cadmium ions and total salinity of battery industry effluent. Among these membranes, there are only three which eliminate more than 95% of cadmium. This was found to depend on operating conditions. It is worth noting that the Spiegler-Kedem model was applied to fit the experimental results. PMID:26398037

  5. A series of Cd(II) supramolecular architectures based on polycarboxylate and 2-amino-benzimidazole mixed-ligands

    NASA Astrophysics Data System (ADS)

    Wang, Xiu-Guang; Li, Jian; Ding, Bin; Yang, En-Cui; Zhao, Xiao-Jun

    2008-03-01

    By reaction of Cd(II) salts, different aromatic/aliphatic carboxylic acid and 2-amino-benzimidazole (Abm), four crystalline supramolecular coordination polymers, {[Cd 2(tma) 2(Abm) 4]·2(HAbm)·5.5(H 2O)} n ( 1), {[Cd(tp)(Abm) 2]·(DMF)} n ( 2), {[Cd(ip) 2]·2(HAbm)} n ( 3), and {[Cd(ga) 2]·2(HAbm)} n ( 4) (H 3tma = trimesic acid; H 2tp = terephalatic acid; H 2ip = isophthalic acid; H 2ga = glutaric acid), have been successfully synthesized. In 1 pairs of 1D right- and left-hand helical structure and in 2 1D zigzag chains can be found, which are further extended into 3D hydrogen bonded frameworks via strong intra- and inter-chain N-H···O interactions. In contrast, 3 and 4 with 2D layer structure are stacked together in the ABAB way, where protonated HAbm cations are located between 2D layers and further stabilized by cooperative N-H···O, π···π and C-H···π interactions. Interestingly, single crystal 3 can reversibly transform into single crystal of its hydrated compound 3a, indicating small guest water molecules can be effectively absorbed in the host framework of 3. The FT-IR spectra of 1- 4 have also been discussed briefly.

  6. Syntheses, crystal structure, and luminescence properties of three new Cd(II) polymers based on different conformational carboxylates

    NASA Astrophysics Data System (ADS)

    Liu, Jian-Qiang; Jia, Zhen-Bin; Wang, Yao-Yu

    2011-02-01

    Three new coordination polymers, namely, {[Cd 3(L 1) 2(IP) 2(H 2O) 4]} n ( 1), {[Cd 2(L 2) 2(IP) 2]·(CH 3OH)(DMF)} n ( 2) and [Cd(L 3)(IP)] n ( 3) (H 3L 1 = benzene-1,2,4-tricarboxylic acid, H 2L 2 = 2,2-bis(4-carboxyphenyl)hexafluoropropane, H 2L 3 = 1,3-phenylenediacetic acid and IP = 1H-imidazo[4,5-f][1,10]-phenanthroline), were prepared via self-assembly of pharmaceutical agent IP with cadmium sulfate in the presence of the different backbones of carboxylate linkers under mild conditions. All the polymers possess 2D structural motifs. The rigid tricarboxylate ligand links the metal centers to form a tetranuclear core in 1. In 2, the 2D network with trinuclear cores is further extended into 3D supramolecular arrays through aromatic stacking interactions. Interestingly, IP ligand acts in a tridentate mode via the two N atoms of pyridyl rings and the third N atom of imidazole ring and connects metal atoms into 1D zigzag chain in 3. The structural analysis reveals that the backbones of carboxylates have critical effect on the construction of the complexes. Solid-state luminescent spectra of the Cd(II) complexes indicate intense fluorescent emissions.

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

    NASA Astrophysics Data System (ADS)

    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. Paramagnetic centers in particulate formed from the oxidative pyrolysis of 1-methylnaphthalene in the presence of Fe(III)2O3 nanoparticles

    PubMed Central

    Herring, Paul; Khachatryan, Lavrent; Lomnicki, Slawomir; Dellinger, Barry

    2015-01-01

    The identity of radical species associated with particulate formed from the oxidative pyrolysis of 1-methylnaphthalene (1-MN) was investigated using low temperature matrix isolation electron paramagnetic resonance spectroscopy (LTMI-EPR), a specialized technique that provided a method of sampling and analysis of the gas-phase paramagnetic components. A superimposed EPR signal was identified to be a mixture of organic radicals (carbon and oxygen-centered) and soot. The carbon-centered radicals were identified as a mixture of the resonance-stabilized indenyl, cyclopentadienyl, and naphthalene 1-methylene radicals through the theoretical simulation of the radical’s hyperfine structure. Formation of these radical species was promoted by the addition of Fe(III)2O3 nanoparticles. Enhanced formation of resonance stabilized radicals from the addition of Fe(III)2O3 nanoparticles can account for the observed increased sooting tendency associated with Fe(III)2O3 nanoparticle addition. PMID:25673882

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

    PubMed

    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

  10. Synthesis of Imine-Naphthol Tripodal Ligand and Study of Its Coordination Behaviour towards Fe(III), Al(III), and Cr(III) Metal Ions

    PubMed Central

    Kaur, Kirandeep

    2014-01-01

    A hexadentate Schiff base tripodal ligand is synthesized by the condensation of tris (2-aminoethyl) amine with 2-hydroxy-1-naphthaldehyde and characterized by various spectroscopic techniques like UV-VIS, IR, NMR, MASS, and elemental analysis. The solution studies by potentiometric and spectrophotometric methods are done at 25 ± 1°C, µ = 0.1 M KCl, to calculate the protonation constants of the ligand and formation constants of metal complexes formed by the ligand with Fe(III), Al(III), and Cr(III) metal ions. The affinity of the ligand towards Fe(III) is compared with deferiprone (a drug applied for iron intoxication) and transferrin (the main Fe(III) binding protein in plasma). Structural analysis of the ligand and the metal complexes was done using semiempirical PM6 method. Electronic and IR spectra are calculated by semiempirical methods and compared with experimental one. PMID:25294978

  11. Influence of Biogenic Fe(II) on the Extent of Microbial Reduction of Fe(III) in Clay Minerals Nontronite, Illite, and Chlorite

    SciTech Connect

    Jaisi, Deb P.; Dong, Hailiang; Liu, Chongxuan

    2007-03-01

    Microbial reduction of Fe(III) in clay minerals is an important process that affects properties of clay-rich materials and iron biogeochemical cycling in natural environments. Microbial reduction often ceases before all Fe(III) in clay minerals is exhausted. The factors causing the cessation are, however, not well understood. The objective of this study was to assess the role of biogenic Fe(II) in microbial reduction of Fe(III) in various clay minerals. Bioreduction experiments were performed in a batch system, where lactate was used as the sole electron donor, Fe(III) in clay minerals as the sole electron acceptor, and Shewanella putrefaciens CN32 as the mediator with and without an electron shuttle AQDS. Our results showed that bioreduction activity ceased within two weeks with variable extents of bioreduction of structural Fe(III) in clay minerals. When fresh CN32 cells were added to the old cultures (6 months), bioreduction resumed and extents increased. This result indicated that the previous cessation of Fe(III) bioreduction was not necessarily due to the exhaustion of bioavailable Fe(III) in the mineral structure, and suggested that the changes of cell physiology or solution chemistry, such as Fe(II) production during microbial reduction, affected the extent of bioreduction. To investigate the effect of Fe(II) production on Fe(III) bioreduction, a typical bioreduction process (consisting of lactate, clay, cells and AQDS) was separated into two steps: 1. AQDS was reduced by cells in the absence of clay but in the presence of variable Fe(II) concentrations; 2. reduction of Fe(III) in clays by biogenic AH2DS in the absence of cells. The inhibitory effect of Fe(II) on CN32 activity was confirmed. TEM analysis revealed a thick electron dense halo surrounding the cell surfaces that most likely resulted from Fe(II) sorption/precipitation. Such electron dense materials might have blocked or interfered electron transfers on cell surfaces. The inhibitory effect of Fe

  12. Synthesis of a novel heptacoordinated Fe(III) dinuclear complex: experimental and theoretical study of the magnetic properties.

    PubMed

    Craig, Gavin A; Barrios, Leoní A; Sánchez Costa, José; Roubeau, Olivier; Ruiz, Eliseo; Teat, Simon J; Wilson, Chick C; Thomas, Lynne; Aromí, Guillem

    2010-05-28

    A new functionalized bis-pyrazol-pyridine ligand has been prepared by reaction with hydrazine of the corresponding bis-β-diketone precursor, also unprecedented. The aerobic reaction of this ligand with ferrous thiocyanate in the presence of ascorbic or oxalic acid affords the dinuclear complex of seven-coordinate Fe(III), [Fe₂(H₄L2)₂(ox)(NCS)₄] (1), as revealed by single crystal X-ray diffraction. This may represent an entry into a new family of [Fe₂] compounds with heptacoordinate metal centres. The capacity of this unusual chromophore to undergo magnetic super-exchange was investigated by means of bulk magnetization and DFT calculations. Both approaches confirmed the presence of antiferromagnetic interactions within the molecule. The theoretical investigation has served to describe the magnetic orbitals of Fe(III) in this unusual coordination geometry, as well as the exchange mechanism. A brief review of the scarce number of iron heptacoordinate complexes reported in the literature is also included and discussed. PMID:21491658

  13. Pro-oxidant activity of aluminum: promoting the Fenton reaction by reducing Fe(III) to Fe(II).

    PubMed

    Ruipérez, F; Mujika, J I; Ugalde, J M; Exley, C; Lopez, X

    2012-12-01

    The possibility for an Al-superoxide complex to reduce Fe(III) to Fe(II), promoting oxidative damage through the Fenton reaction, is investigated using highly accurate ab initio methods and density functional theory in conjunction with solvation continuum methods to simulate bulk solvent effects. It is found that the redox reaction between Al-superoxide and Fe(III) to produce Fe(II) is exothermic. Moreover, the loss of an electron from the superoxide radical ion in the Al-superoxide complex leads to a spontaneous dissociation of molecular oxygen from aluminum, recovering therefore an Al(3+) hexahydrated complex. As demonstrated in previous studies, this complex is again prone to stabilize another superoxide molecule, suggesting a catalytic cycle that augments the concentration of Fe(II) in the presence of Al(III). Similar results are found for Al(OH)(2+) and Al(OH)(2)(+) hydrolytic species. Our work reinforces the idea that the presence of aluminum in biological systems could lead to an important pro-oxidant activity through a superoxide formation mechanism. PMID:23085591

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

    PubMed

    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

  15. Simultaneous spectrophotometric determination of Fe(III) and Al(III) using orthogonal signal correction-partial least squares calibration method after solidified floating organic drop microextraction.

    PubMed

    Rohani Moghadam, Masoud; Haji Shabani, Ali Mohammad; Dadfarnia, Shayessteh

    2015-01-25

    A solidified floating organic drop microextraction (SFODME) procedure was developed for the simultaneous extraction and preconcentration of Fe(III) and Al(III) from water samples. The method was based on the formation of cationic complexes between Fe(III) and Al(III) and 3,5,7,2',4'-pentahydroxyflavone (morin) which were extracted into 1-undecanol as ion pairs with perchlorate ions. The absorbance of the extracted complexes was then measured in the wavelength range of 300-450 nm. Finally, the concentration of each metal ion was determined by the use of the orthogonal signal correction-partial least squares (OSC-PLS) calibration method. Several experimental parameters that may be affected on the extraction process such as the type and volume of extraction solvent, pH of the aqueous solution, morin and perchlorate concentration and extraction time were optimized. Under the optimum conditions, Fe(III) and Al(III) were determined in the ranges of 0.83-27.00 μg L(-1) (R(2)=0.9985) and 1.00-32.00 μg L(-1) (R(2)=0.9979) of Fe(III) and Al(III), respectively. The relative standard deviations (n=6) at 12.80 μg L(-1) of Fe(III) and 17.00 μg L(-)(1) of Al(III) were 3.2% and 3.5%, respectively. An enhancement factors of 102 and 96 were obtained for Fe(III) and Al(III) ions, respectively. The procedure was successfully applied to determination of iron and aluminum in steam and water samples of thermal power plant; and the accuracy was assessed through the recovery experiments and independent analysis by electrothermal atomic absorption spectroscopy (ETAAS). PMID:25168229

  16. Simultaneous spectrophotometric determination of Fe(III) and Al(III) using orthogonal signal correction-partial least squares calibration method after solidified floating organic drop microextraction

    NASA Astrophysics Data System (ADS)

    Rohani Moghadam, Masoud; Haji Shabani, Ali Mohammad; Dadfarnia, Shayessteh

    2015-01-01

    A solidified floating organic drop microextraction (SFODME) procedure was developed for the simultaneous extraction and preconcentration of Fe(III) and Al(III) from water samples. The method was based on the formation of cationic complexes between Fe(III) and Al(III) and 3,5,7,2‧,4‧-pentahydroxyflavone (morin) which were extracted into 1-undecanol as ion pairs with perchlorate ions. The absorbance of the extracted complexes was then measured in the wavelength range of 300-450 nm. Finally, the concentration of each metal ion was determined by the use of the orthogonal signal correction-partial least squares (OSC-PLS) calibration method. Several experimental parameters that may be affected on the extraction process such as the type and volume of extraction solvent, pH of the aqueous solution, morin and perchlorate concentration and extraction time were optimized. Under the optimum conditions, Fe(III) and Al(III) were determined in the ranges of 0.83-27.00 μg L-1 (R2 = 0.9985) and 1.00-32.00 μg L-1 (R2 = 0.9979) of Fe(III) and Al(III), respectively. The relative standard deviations (n = 6) at 12.80 μg L-1 of Fe(III) and 17.00 μg L-1 of Al(III) were 3.2% and 3.5%, respectively. An enhancement factors of 102 and 96 were obtained for Fe(III) and Al(III) ions, respectively. The procedure was successfully applied to determination of iron and aluminum in steam and water samples of thermal power plant; and the accuracy was assessed through the recovery experiments and independent analysis by electrothermal atomic absorption spectroscopy (ETAAS).

  17. Humic substance-mediated Fe(III) reduction by a fermenting Bacillus strain from the alkaline gut of a humus-feeding scarab beetle larva.

    PubMed

    Hobbie, Sven N; Li, Xiangzhen; Basen, Mirko; Stingl, Ulrich; Brune, Andreas

    2012-06-01

    Humus-feeding macroinvertebrates play an important role in the transformation of soil organic matter. Their diet contains significant amounts of redox-active components such as iron minerals and humic substances. In soil-feeding termites, acid-soluble Fe(III) and humic acids are almost completely reduced during gut passage. Here, we show that the reduction of Fe(III) and humic acids takes place also in the alkaline guts of scarab beetle larvae. Sterilized gut homogenates of Pachnoda ephippiata no longer converted Fe(III) to Fe(II), indicating an essential role of the gut microbiota in the process. From Fe(III)-reducing enrichment cultures inoculated with highly diluted gut homogenates, we isolated several facultatively anaerobic, alkali-tolerant bacteria that were closely related to metal-reducing isolates in the Bacillus thioparans group. Strain PeC11 showed a remarkable capacity for dissimilatory Fe(III) reduction, both at pH 7 and 10. Rates were strongly stimulated by the addition of the redox mediator 2,6-antraquinone disulfonate and by redox-active components in the fulvic-acid fraction of humus. Although the contribution of strain PeC11 to intestinal Fe(III) reduction in P. ephippiata remains to be further elucidated, our results corroborate the hypothesis that the lack of oxygen and the solubilization of humic substances in the extremely alkaline guts of humivorous soil fauna provide favorable conditions for the efficient reduction of Fe(III) and humic substances by a primarily fermentative microbiota. PMID:22525666

  18. Use of Fe(III) as an electron acceptor to recover previously uncultured hyperthermophiles: isolation and characterization of Geothermobacterium ferrireducens gen. nov., sp. nov.

    PubMed

    Kashefi, Kazem; Holmes, Dawn E; Reysenbach, Anna-Louise; Lovley, Derek R

    2002-04-01

    It has recently been recognized that the ability to use Fe(III) as a terminal electron acceptor is a highly conserved characteristic in hyperthermophilic microorganisms. This suggests that it may be possible to recover as-yet-uncultured hyperthermophiles in pure culture if Fe(III) is used as an electron acceptor. As part of a study of the microbial diversity of the Obsidian Pool area in Yellowstone National Park, Wyo., hot sediment samples were used as the inoculum for enrichment cultures in media containing hydrogen as the sole electron donor and poorly crystalline Fe(III) oxide as the electron acceptor. A pure culture was recovered on solidified, Fe(III) oxide medium. The isolate, designated FW-1a, is a hyperthermophilic anaerobe that grows exclusively by coupling hydrogen oxidation to the reduction of poorly crystalline Fe(III) oxide. Organic carbon is not required for growth. Magnetite is the end product of Fe(III) oxide reduction under the culture conditions evaluated. The cells are rod shaped, about 0.5 microm by 1.0 to 1.2 microm, and motile and have a single flagellum. Strain FW-1a grows at circumneutral pH, at freshwater salinities, and at temperatures of between 65 and 100 degrees C with an optimum of 85 to 90 degrees C. To our knowledge this is the highest temperature optimum of any organism in the Bacteria. Analysis of the 16S ribosomal DNA (rDNA) sequence of strain FW-1a places it within the Bacteria, most closely related to abundant but uncultured microorganisms whose 16S rDNA sequences have been previously recovered from Obsidian Pool and a terrestrial hot spring in Iceland. While previous studies inferred that the uncultured microorganisms with these 16S rDNA sequences were sulfate-reducing organisms, the physiology of the strain FW-1a, which does not reduce sulfate, indicates that these organisms are just as likely to be Fe(III) reducers. These results further demonstrate that Fe(III) may be helpful for recovering as-yet-uncultured microorganisms

  19. Use of Fe(III) as an Electron Acceptor To Recover Previously Uncultured Hyperthermophiles: Isolation and Characterization of Geothermobacterium ferrireducens gen. nov., sp. nov.

    PubMed Central

    Kashefi, Kazem; Holmes, Dawn E.; Reysenbach, Anna-Louise; Lovley, Derek R.

    2002-01-01

    It has recently been recognized that the ability to use Fe(III) as a terminal electron acceptor is a highly conserved characteristic in hyperthermophilic microorganisms. This suggests that it may be possible to recover as-yet-uncultured hyperthermophiles in pure culture if Fe(III) is used as an electron acceptor. As part of a study of the microbial diversity of the Obsidian Pool area in Yellowstone National Park, Wyo., hot sediment samples were used as the inoculum for enrichment cultures in media containing hydrogen as the sole electron donor and poorly crystalline Fe(III) oxide as the electron acceptor. A pure culture was recovered on solidified, Fe(III) oxide medium. The isolate, designated FW-1a, is a hyperthermophilic anaerobe that grows exclusively by coupling hydrogen oxidation to the reduction of poorly crystalline Fe(III) oxide. Organic carbon is not required for growth. Magnetite is the end product of Fe(III) oxide reduction under the culture conditions evaluated. The cells are rod shaped, about 0.5 μm by 1.0 to 1.2 μm, and motile and have a single flagellum. Strain FW-1a grows at circumneutral pH, at freshwater salinities, and at temperatures of between 65 and 100°C with an optimum of 85 to 90°C. To our knowledge this is the highest temperature optimum of any organism in the Bacteria. Analysis of the 16S ribosomal DNA (rDNA) sequence of strain FW-1a places it within the Bacteria, most closely related to abundant but uncultured microorganisms whose 16S rDNA sequences have been previously recovered from Obsidian Pool and a terrestrial hot spring in Iceland. While previous studies inferred that the uncultured microorganisms with these 16S rDNA sequences were sulfate-reducing organisms, the physiology of the strain FW-1a, which does not reduce sulfate, indicates that these organisms are just as likely to be Fe(III) reducers. These results further demonstrate that Fe(III) may be helpful for recovering as-yet-uncultured microorganisms from hydrothermal

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

    NASA Astrophysics Data System (ADS)

    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.

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

    NASA Astrophysics Data System (ADS)

    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.

  2. Synthesis, Characterization and Biological Evaluation of Co(II), Cu(II), Ni(II) and Zn(II) Complexes With Cephradine

    PubMed Central

    Jaffery, Maimoon F.

    2000-01-01

    Some Co(II), Cu(II), Ni(II) and Zn(II) complexes of antibacterial drug cephradine have been prepared and characterized by their physical, spectral and analytical data. Cephradine acts as bidentate and the complexes have compositions, [M(L)2X2] where [M = Co(II), Ni(II) and Zn(II), L = cephradine and X = Cl2] showing octahedral geometry, and [M(L)2] where [M = Cu(II), L = cephradine] showing square planar geometry. In order to evaluate the effect of metal ions upon chelation, eephradine and its complexes have been screened for their antibacterial activity against bacterial strains, Escherichia coli, Staphylococcus aureus, and Pseudomonas aeruginosa. PMID:18475955

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

    PubMed

    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

  4. Spectroscopic investigation of the structure of complex compounds of Cu(II), Co(II), and Ni(II) with. cap alpha. - and. beta. -diketone

    SciTech Connect

    Krymova, N.M.; Ivanov, V.E.; Ostapkevich, N.A.

    1986-11-10

    In the reactions of Cu(II), Co(II), and Ni(II) chlorides with 2,3-butanedione and 2,4-pentanedione isonicotinoylhydrazones in neutral and weakly acid media complex compounds of the addition-product type are formed, but in an alkaline medium inner-complex compounds are formed. By methods of electronic and ESR spectroscopy it was shown that the Cu(II) complex compounds have a planar-square structure, the Ni(II) complexes are octrahedral, but the Co(II) complexes have a tetrahedral or distorted tetrahedral structure. In the spectrochemical series 2,3-butanedione and 2,4-pentanedione isonicotinoylhydrazones occupy positions between water and ammonia.

  5. Co(II), Mn(II), and Cr(III) iminodiacetate complexes heterogenized on silica gel in the liquid-phase oxidation of cyclohexene

    SciTech Connect

    Berentsveig, V.V.; Barinova, T.V.; Lisichkin, G.V.; Nga, C.B.

    1985-06-01

    A study was carried out on the catalytic properties of Co(II), Mn(II), and Cr(III) iminodiacetate complexes heterogenized on silica gel. The liquid-phase oxidation of cyclohexene in the presence of these catalysts proceeds mainly by a heterogeneous-homogeneous radical chain methanism. Variation in the selectivity of this liquid-phase reaction is possible by changing the nature of the transition metal ion.

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

    PubMed Central

    2012-01-01

    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). PMID:23369255

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

    PubMed

    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

  8. Characterization and biological studies on Co(II), Ni(II) and Cu(II) complexes of carbohydrazones ending by pyridyl ring

    NASA Astrophysics Data System (ADS)

    Abu El-Reash, G. M.; El-Gammal, O. A.; Ghazy, S. E.; Radwan, A. H.

    2013-03-01

    The chelating behavior of ligands based on carbohydrazone core modified with pyridine end towards Co(II), Ni(II) and Cu(II) ions have been examined. The ligands derived from the condensation of carbohydrazide with 2-acetylpyridine (H2APC) and 4-acetylpyridine (H2APEC). The 1H NMR, IR data and the binding energy calculations of H2APC revealed the presence of two stereoisomers syn and anti in the solid state and in the solution. The 1H NMR, IR data and the binding energy calculations confirmed the presence of H2APEC in one keto form only in the solid state and in the solution. The spectroscopic data confirmed that H2APC behaves as a monobasic pentadentate in Co(II) and Cu(II) complexes and as mononegative tetradentate in Ni(II) complex. On the other hand, H2APEC acts as a mononegative tridentate in Co(II) complex, neutral tridentate in Ni(II) complex and neutral bidentate in Cu(II) complex. The electronic spectra and the magnetic measurements of complexes as well as the ESR of the copper complexes suggested the octahedral geometry. The bond length and bond angles were evaluated by DFT method using material studio program. The thermal behavior and the kinetic parameters of degradation were determined using Coats-Redfern and Horowitz-Metzger methods. The antioxidant (DDPH and ABTS methods), anti-hemolytic and in vitro Ehrlich ascites of the compounds have been screened.

  9. Selective Divalent Cobalt Ions Detection Using Ag2O3-ZnO Nanocones by ICP-OES Method for Environmental Remediation

    PubMed Central

    Rahman, Mohammed M.; Khan, Sher Bahadar; Marwani, Hadi M.; Asiri, Abdullah M.

    2014-01-01

    Here, we have synthesized Ag2O3-ZnO nanocones (NCs) by a wet-chemical route using reducing agents at low temperature. The structural, optical and morphological properties of Ag2O3-ZnO NCs were investigated by several conventional techniques such as powder XRD, XPS, FESEM, XEDS, FTIR and UV/vis. spectroscopy. The analytical parameters of prepared NCs were also calculated for a selective detection of divalent cobalt [Co(II)] prior to its determination by inductively coupled plasma-optical emission spectrometry (ICP-OES). The selectivity of NCs toward various metal ions, including Cd(II), Co(II), Cr(III), Cu(II), Fe(III), Ni(II), and Zn(II) was studied. Results of the selectivity study demonstrated that Ag2O3-ZnO NC phase was the most selective towards Co(II) ion. The uptake capacity for Co(II) ion was experimentally calculated to be ∼76.69 mgg−1. Moreover, adsorption isotherm data provided that the adsorption process was mainly monolayer on homogeneous adsorbent surfaces of Ag2O3-ZnO NCs. Kinetic study revealed that the adsorption of Co(II) on Ag2O3-ZnO NCs phase followed the pseudo-second-order kinetic model. In addition, thermodynamic results provided that the adsorption mechanism of Co(II) ions on Ag2O3-ZnO NCs was a spontaneous process and thermodynamically favorable. Finally, the proposed method was validated by applying it to real environmental water samples with reasonable results. PMID:25464507

  10. Evidence for ligand hydrolysis and Fe(III) reduction in the dissolution of goethite by desferrioxamine-B

    NASA Astrophysics Data System (ADS)

    Simanova, Anna A.; Persson, Per; Loring, John S.

    2010-12-01

    Desferrioxamine-B (DFOB) is a bacterial trihydroxamate siderophore and probably the most studied to date. However, the manner in which DFOB adsorbs at mineral surfaces and promotes dissolution is still under discussion. Here we investigated the adsorption and dissolution reactions in the goethite-DFOB system using both in situ infrared spectroscopic and quantitative analytical methods. Experiments were carried out at a total DFOB concentration of 1 μmol/m 2, at pH 6, and in the absence of visible light. Our infrared spectroscopic results indicated that the adsorption of DFOB was nearly complete after a 4-h reaction time. In an attempt to determine the coordination mode at the goethite surface, we compared the spectrum of adsorbed DFOB after a 4-h reaction time to the spectra of model aqueous species. However, this approach proved too simplistic in the case of such a complex ligand as DFOB, and we suggest that a more detailed investigation (IR in D 2O, EXAFS of adsorbed model complexes) is needed to elucidate the structure of the adsorbed siderophore. Between a 4-h and 4-day reaction time, we observed the growth of carboxylate stretching bands at 1548 and 1404 cm -1, which are indicators of DFOB hydrolysis. Acetate, a product of DFOB hydrolysis at its terminal hydroxamate group, was quantified by ion chromatography. Its rate of formation was linear and nearly the same as the rate of Fe(III) dissolution. The larger hydrolysis product, a hydroxylamine fragment, was not detected by LC-MS. However, a signal due to the oxidized form of this fragment, a nitroso compound, was found to increase linearly with time, which is an indirect indication for Fe(III) reduction. Based on these findings, we propose that DFOB undergoes metal-enhanced hydrolysis at the mineral surface followed by the reduction of surface Fe(III). While Fe(II) was not detected in solution, this is likely because it remains adsorbed at the goethite surface or becomes buried in the goethite crystal by

  11. Thermal studies and vibrational analyses of m-methylaniline complexes of Zn(II), Cd(II) and Hg(II) bromides

    NASA Astrophysics Data System (ADS)

    Golcuk, K.; Altun, A.; Kumru, M.

    2003-06-01

    The complexes having the MBr2L2 (M: Zn, Cd and Hg; L: m-methylaniline) formulae have been prepared and characterized by their elemental analyses, thermogravimetric analyses, IR and Raman spectral studies. IR and Raman bands of the complexes have been assigned as compared with the free ligand. Coordination effects on the internal modes of m-methylaniline have been discussed. Vibrational spectra propose that the [ZnBr2(mMA)2] complex is in a tetrahedral environment around Zn(II) ion with C2v symmetry whereas Cd(II) and Hg(II) complexes have 5-coordinate polymeric bromide bridged structures.

  12. Thermal Studies of Zn(II), Cd(II) and Hg(II) Complexes of Some N-Alkyl-N-Phenyl-Dithiocarbamates

    PubMed Central

    Onwudiwe, Damian C.; Ajibade, Peter A.

    2012-01-01

    The thermal decomposition of Zn(II), Cd(II) and Hg(II) complexes of N-ethyl-N-phenyl and N-butyl-N-phenyl dithiocarbamates have been studied using thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The products of the decomposition, at two different temperatures, were further characterized by scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDX). The results show that while the zinc and cadmium complexes undergo decomposition to form metal sulphides, and further undergo oxidation forming metal oxides as final products, the mercury complexes gave unstable volatiles as the final product. PMID:22949811

  13. Synthesis and studies on Cu(II), Co(II), Ni(II) complexes of Knoevenagel β-diketone ligands

    NASA Astrophysics Data System (ADS)

    Sumathi, S.; Tharmaraj, P.; Sheela, C. D.; Anitha, C.

    2012-11-01

    Transition metal complexes of various acetylacetone based ligands of the type ML [where M = Cu(II), Ni(II), Co(II); L = 3-(aryl)-pentane-2,4-dione] have been synthesized. The structural features have been derived from their elemental analysis, magnetic susceptibility, molar conductance, IR, UV-Vis, 1H NMR, Mass and ESR spectral studies. Conductivity measurements reveal that all the complexes are non-electrolytic in nature. Spectroscopic and other analytical data of the complexes suggest octahedral geometry for other metal(II) complexes. The redox behavior of the copper(II) complexes have been studied by cyclic voltammetry. The free ligands and their metal complexes have been screened for their in vitro biological activities against the bacteria Pseudomonas aeruginosa, Escherichia coli and Staphylococcus aureus as well as the fungus Candida albicans by well diffusion method. The zone of inhibition value indicates that the most of the metal(II) complexes are found to possess increased activities compared to those of the free ligands. All synthesized compounds may serve as potential photoactive materials as indicated from their characteristic fluorescence properties. The second harmonic generation (SHG) efficiency of the ligands (L1-L3) was found to be considerable effect than that of urea and KDP (potassium dihydrogen phosphate).

  14. The precursor form of Hansenula polymorpha copper amine oxidase 1 in complex with CuI and CoII.

    PubMed

    Klema, Valerie J; Johnson, Bryan J; Klinman, Judith P; Wilmot, Carrie M

    2012-05-01

    Copper amine oxidases (CAOs) catalyze the oxidative deamination of primary amines to their corresponding aldehydes, with the concomitant reduction of O(2) to H(2)O(2). Catalysis requires two cofactors: a mononuclear copper center and the cofactor 2,4,5-trihydroxyphenylalanine quinone (TPQ). TPQ is synthesized through the post-translational modification of an endogenous tyrosine residue and requires only oxygen and copper to proceed. TPQ biogenesis in CAO can be supported by alternate metals, albeit at decreased rates. A variety of factors are thought to contribute to the degree to which a metal can support TPQ biogenesis, including Lewis acidity, redox potential and electrostatic stabilization capability. The crystal structure has been solved of one of two characterized CAOs from the yeast Hansenula polymorpha (HPAO-1) in its metal-free (apo) form, which contains an unmodified precursor tyrosine residue instead of fully processed TPQ (HPAO-1 was denoted HPAO in the literature prior to 2010). Structures of apoHPAO-1 in complex with Cu(I) and Co(II) have also been solved, providing structural insight into metal binding prior to biogenesis. PMID:22691777

  15. Sensitive spectrophotometric determination of Co(II) using dispersive liquid-liquid micro-extraction method in soil samples.

    PubMed

    Hasanpour, Foroozan; Hadadzadeh, Hassan; Taei, Masoumeh; Nekouei, Mohsen; Mozafari, Elmira

    2016-05-01

    Analytical performance of conventional spectrophotometer was developed by coupling of effective dispersive liquid-liquid micro-extraction method with spectrophotometric determination for ultra-trace determination of cobalt. The method was based on the formation of Co(II)-alpha-benzoin oxime complex and its extraction using a dispersive liquid-liquid micro-extraction technique. During the present work, several important variables such as pH, ligand concentration, amount and type of dispersive, and extracting solvent were optimized. It was found that the crucial factor for the Co(II)-alpha benzoin oxime complex formation is the pH of the alkaline alcoholic medium. Under the optimized condition, the calibration graph was linear in the ranges of 1.0-110 μg L(-1) with the detection limit (S/N = 3) of 0.5 μg L(-1). The preconcentration operation of 25 mL of sample gave enhancement factor of 75. The proposed method was applied for determination of Co(II) in soil samples. PMID:27040110

  16. The precursor form of Hansenula polymorpha copper amine oxidase 1 in complex with CuI and CoII

    PubMed Central

    Klema, Valerie J.; Johnson, Bryan J.; Klinman, Judith P.; Wilmot, Carrie M.

    2012-01-01

    Copper amine oxidases (CAOs) catalyze the oxidative deamination of primary amines to their corresponding aldehydes, with the concomitant reduction of O2 to H2O2. Catalysis requires two cofactors: a mononuclear copper center and the cofactor 2,4,5-trihydroxyphenylalanine quinone (TPQ). TPQ is synthesized through the post-translational modification of an endogenous tyrosine residue and requires only oxygen and copper to proceed. TPQ biogenesis in CAO can be supported by alternate metals, albeit at decreased rates. A variety of factors are thought to contribute to the degree to which a metal can support TPQ biogenesis, including Lewis acidity, redox potential and electrostatic stabilization capability. The crystal structure has been solved of one of two characterized CAOs from the yeast Hansenula polymorpha (HPAO-1) in its metal-free (apo) form, which contains an unmodified precursor tyrosine residue instead of fully processed TPQ (HPAO-1 was denoted HPAO in the literature prior to 2010). Structures of apoHPAO-1 in complex with CuI and CoII have also been solved, providing structural insight into metal binding prior to biogenesis. PMID:22691777

  17. 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.

    PubMed

    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

  18. Assessing bioavailability levels of metals in effluent-affected rivers: effect of Fe(III) and chelating agents on the distribution of metal speciation.

    PubMed

    Han, Shuping; Naito, Wataru; Masunaga, Shigeki

    2016-01-01

    To assess the effects of Fe(III) and anthropogenic ligands on the bioavailability of Ni, Cu, Zn, and Pb, concentrations of bioavailable metals were measured by the DGT (diffusive gradients in thin films) method in some urban rivers, and were compared with concentrations calculated by a chemical equilibrium model (WHAM 7.0). Assuming that dissolved Fe(III) (<0.45 μm membrane filtered) was in equilibrium with colloidal iron oxide, the WHAM 7.0 model estimated that bioavailable concentrations of Ni, Cu, and Zn were slightly higher than the corresponding values estimated assuming that dissolved Fe(III) was absent. In contrast, lower levels of free Pb were predicted by the WHAM 7.0 model when dissolved Fe(III) was included. Estimates showed that most of the dissolved Pb was present as colloidal iron-Pb complex. Ethylene-diamine-tetra-acetic acid (EDTA) concentrations at sampling sites were predicted from the relationship between EDTA and the calculated bioavailable concentration of Zn. When both colloidal iron and predicted EDTA concentrations were included in the WHAM 7.0 calculations, dissolved metals showed a strong tendency to form EDTA complexes, in the order Ni > Cu > Zn > Pb. With the inclusion of EDTA, bioavailable concentrations of Ni, Cu, and Zn predicted by WHAM 7.0 were different from those predicted considering only humic substances and colloidal iron. PMID:27533864

  19. Nanowires, Capacitors, and Other Novel Outer-Surface Components Involved in Electron Transfer to Fe(III) Oxides in Geobacter Species

    SciTech Connect

    Lovley, Derek, R.

    2008-12-22

    The overall goal of this project was to better understand the mechanisms by which Geobacter species transfer electrons outside the cell onto Fe(III) oxides. The rationale for this study was that Geobacter species are often the predominant microorganisms involved in in situ uranium bioremediation and the growth and activity of the Geobacter species during bioremediation is primarily supported by electron transfer to Fe(III) oxides. These studies greatly expanded the understanding of electron transfer to Fe(III). Novel concepts developed included the potential role of microbial nanowires for long range electron transfer in Geobacter species and the importance of extracytoplasmic cytochromes functioning as capacitors to permit continued electron transfer during the hunt for Fe(III) oxide. Furthermore, these studies provided target sequences that were then used in other studies to tract the activity of Geobacter species in the subsurface through monitoring the abundance of gene transcripts of the target genes. A brief summary of the major accomplishments of the project is provided.

  20. Potential for nitrate and Fe(III) additions to control indicator bacteria, retain nitrogen, and reduce odors in beef cattle feedlot soils

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A wide variety of volatile odor compounds accumulate during the anaerobic fermentation of livestock wastes. Since these compounds are easily degraded in other environments when alternate electron acceptors (compounds other than O2) are available, we evaluated the use of amending NO3- and Fe(III) in...

  1. An Analytical Chemistry Experiment in Simultaneous Spectrophotometric Determination of Fe(III) and Cu(II) with Hexacyanoruthenate(II) Reagent.

    ERIC Educational Resources Information Center

    Mehra, M. C.; Rioux, J.

    1982-01-01

    Experimental procedures, typical observations, and results for the simultaneous analysis of Fe(III) and Cu(II) in a solution are discussed. The method is based on selective interaction between the two ions and potassium hexacyanoruthenate(II) in acid solution involving no preliminary sample preparations. (Author/JN)

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

    SciTech Connect

    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.

  3. Charge-Transfer Phase Transition of a Cyanide-Bridged Fe(II) /Fe(III) Coordination Polymer.

    PubMed

    Zhang, Kuirun; Kang, Soonchul; Yao, Zi-Shuo; Nakamura, Kazusa; Yamamoto, Takashi; Einaga, Yasuaki; Azuma, Nobuaki; Miyazaki, Yuji; Nakano, Motohiro; Kanegawa, Shinji; Sato, Osamu

    2016-05-10

    Heterometallic Prussian blue analogues are known to exhibit thermally induced charge transfer, resulting in switching of optical and magnetic properties. However, charge-transfer phase transitions have not been reported for the simplest FeFe cyanide-bridged systems. A mixed-valence Fe(II) /Fe(III) cyanide-bridged coordination polymer, {[Fe(Tp)(CN)3 ]2 Fe(bpe)⋅5 H2 O}n , which demonstrates a thermally induced charge-transfer phase transition, is described. As a result of the charge transfer during this phase transition, the high-spin state of the whole system does not change to a low-spin state. This result is in contrast to FeCo cyanide-bridged systems that exhibit charge-transfer-induced spin transitions. PMID:27061860

  4. Redox cycling of Fe(II) and Fe(III) in magnetite by Fe-metabolizing bacteria.

    PubMed

    Byrne, James M; Klueglein, Nicole; Pearce, Carolyn; Rosso, Kevin M; Appel, Erwin; Kappler, Andreas

    2015-03-27

    Microorganisms are a primary control on the redox-induced cycling of iron in the environment. Despite the ability of bacteria to grow using both Fe(II) and Fe(III) bound in solid-phase iron minerals, it is currently unknown whether changing environmental conditions enable the sharing of electrons in mixed-valent iron oxides between bacteria with different metabolisms. We show through magnetic and spectroscopic measurements that the phototrophic Fe(II)-oxidizing bacterium Rhodopseudomonas palustris TIE-1 oxidizes magnetite (Fe3O4) nanoparticles using light energy. This process is reversible in co-cultures by the anaerobic Fe(III)-reducing bacterium Geobacter sulfurreducens. These results demonstrate that Fe ions bound in the highly crystalline mineral magnetite are bioavailable as electron sinks and electron sources under varying environmental conditions, effectively rendering magnetite a naturally occurring battery. PMID:25814583

  5. Structural characterization of a family of cytochromes c{sub 7} involved in Fe(III) respiration by Geobacter sulfurreducens.

    SciTech Connect

    Pokkuluri, P. R.; Londer, Y. Y.; Yang, X.; Duke, N. E. C.; Erickson, J.; Orshonsky, V.; Johnson, G.; Schiffer, M.; Biosciences Division

    2010-02-01

    Periplasmic cytochromes c{sub 7} are important in electron transfer pathway(s) in Fe(III) respiration by Geobacter sulfurreducens. The genome of G. sulfurreducens encodes a family of five 10-kDa, three-heme cytochromes c{sub 7}. The sequence identity between the five proteins (designated PpcA, PpcB, PpcC, PpcD, and PpcE) varies between 45% and 77%. Here, we report the high-resolution structures of PpcC, PpcD, and PpcE determined by X-ray diffraction. This new information made it possible to compare the sequences and structures of the entire family. The triheme cores are largely conserved but are not identical. We observed changes, due to different crystal packing, in the relative positions of the hemes between two molecules in the crystal. The overall protein fold of the cytochromes is similar. The structure of PpcD differs most from that of the other homologs, which is not obvious from the sequence comparisons of the family. Interestingly, PpcD is the only cytochrome c{sub 7} within the family that has higher abundance when G. sulfurreducens is grown on insoluble Fe(III) oxide compared to ferric citrate. The structures have the highest degree of conservation around 'heme IV'; the protein surface around this heme is positively charged in all of the proteins, and therefore all cytochromes c{sub 7} could interact with similar molecules involving this region. The structures and surface characteristics of the proteins near the other two hemes, 'heme I' and 'heme III', differ within the family. The above observations suggest that each of the five cytochromes c{sub 7} could interact with its own redox partner via an interface involving the regions of heme I and/or heme III; this provides a possible rationalization for the existence of five similar proteins in G. sulfurreducens.

  6. Electron transfer capacity dependence of quinone-mediated Fe(III) reduction and current generation by Klebsiella pneumoniae L17.

    PubMed

    Li, Xiaomin; Liu, Liang; Liu, Tongxu; Yuan, Tian; Zhang, Wei; Li, Fangbai; Zhou, Shungui; Li, Yongtao

    2013-06-01

    Quinone groups in exogenous electron shuttles can accelerate extracellular electron transfer (EET) from bacteria to insoluble terminal electron acceptors, such as Fe(III) oxides and electrodes, which are important in biogeochemical redox processes and microbial electricity generation. However, the relationship between quinone-mediated EET performance and electron-shuttling properties of the quinones remains incompletely characterized. This study investigates the effects of a series of synthetic quinones (SQs) on goethite reduction and current generation by a fermenting bacterium Klebsiella pneumoniae L17. In addition, the voltammetric behavior and electron transfer capacities (ETCs) of SQ, including electron accepting (EAC) and donating (EDC) capacities, is also examined using electrochemical methods. The results showed that SQ can significantly increase both the Fe(III) reduction rates and current outputs of L17. Each tested SQ reversibly accepted and donated electrons as indicated by the cyclic voltammograms. The EAC and EDC results showed that Carmine and Alizarin had low relative capacities of electron transfer, whereas 9,10-anthraquinone-2,6-disulfonic acid (AQDS), 2-hydroxy-1,4-naphthoquinone (2-HNQ), and 5-hydroxy-1,4-naphthoquinone (5-HNQ) showed stronger relative ETC, and 9,10-anthraquinone-2-carboxylic acid (AQC) and 9,10-anthraquinone-2-sulfonic acid (AQS) had high relative ETC. Enhancement of microbial goethite reduction kinetics and current outputs by SQ had a good linear relationship with their ETC, indicating that the effectiveness of quinone-mediated EET may be strongly dependent on the ETC of the quinones. Therefore, the presence of quinone compounds and fermenting microorganisms may increase the diversity of microbial populations that contribute to element transformation in natural environments. Moreover, ETC determination of different SQ would help to evaluate their performance for microbial EET under anoxic conditions. PMID:23461838

  7. Photoinduced electron transfer between Fe(III) and adenosine triphosphate-BODIPY conjugates: Application to alkaline-phosphatase-linked immunoassay.

    PubMed

    Lin, Jia-Hui; Yang, Ya-Chun; Shih, Ya-Chen; Hung, Szu-Ying; Lu, Chi-Yu; Tseng, Wei-Lung

    2016-03-15

    Fluorescent boron dipyrromethene (BODIPY) analogs are often used as sensors for detecting various species because of their relatively high extinction coefficients, outstanding fluorescence quantum yields, photostability, and pH-independent fluorescence. However, there is little-to-no information in the literature that describes the use of BODIPY analogs for detecting alkaline phosphatase (ALP) activity and inhibition. This study discovered that the fluorescence of BODIPY-conjugated adenosine triphosphate (BODIPY-ATP) was quenched by Fe(III) ions through photoinduced electron transfer. The ALP-catalyzed hydrolysis of BODIPY-ATP resulted in the formation of BODIPY-adenosine and phosphate ions. The fluorescence of the generated BODIPY-adenosine was insensitive to the change in the concentration of Fe(III) ions. Thus, the Fe(III)-induced fluorescence quenching of BODIPY-ATP can be paired with its ALP-mediated dephosphorylation to design a turn-on fluorescence probe for ALP sensing. A method detection limit at a signal-to-noise ratio of 3 for ALP was estimated to be 0.02 units/L (~6 pM; 1 ng/mL). This probe was used for the screening of ALP inhibitors, including Na3VO4, imidazole, and arginine. Because ALP is widely used in enzyme-linked immunosorbent assays, the probe was coupled to an ALP-linked immunosorbent assay for the sensitive and selective detection of immunoglobulin G (IgG). The lowest detectable concentration for IgG in this system was 5 ng/mL. Compared with the use of 3,6-fluorescein diphosphate as a signal reporter in an ALP-linked immunosorbent assay, the proposed system provided comparable sensitivity, large linear range, and high stability over temperature and pH changes. PMID:26409025

  8. Heterogeneous oxidation of Fe(II) on iron oxides in aqueous systems: Identification and controls of Fe(III) product formation

    NASA Astrophysics Data System (ADS)

    Larese-Casanova, Philip; Kappler, Andreas; Haderlein, Stefan B.

    2012-08-01

    The aqueous Fe(II)-oxide Fe(III) system is a reactant for many classes of redox sensitive compounds via an interfacial Fe(II) sorption and electron transfer process. The poorly soluble Fe(III) products formed as a result of contaminant reduction and Fe(II) oxidation on iron oxides may be capable of modifying iron oxide surfaces and affecting subsequent reduction rates of contaminants such as halogenated ethenes or nitroaromatic compounds. The scope of this study was to identify the secondary Fe(III) mineral phases formed after Fe(II) oxidation on common iron oxides during heterogeneous contaminant reduction by directly targeting the secondary minerals using Mössbauer-active isotopes. Fe(III) mineral characterization was performed using 57Fe-Mössbauer spectroscopy, μ-X-ray diffraction, and electron microscopy after oxidation of dissolved 57Fe(II) using nitrobenzenes as a model oxidant in pH-buffered suspensions of 56hematite, 56goethite, 56magnetite, and 56maghemite. Mössbauer spectra confirmed sorbed 57Fe(II) becomes oxidized by the parent 56Fe(III)-oxide sorbent and assimilated as the sorbent oxide prior to any nitrobenzene reduction, consistent with several reports in the literature. In addition to oxide sorbent growth, Fe(II) sorption and oxidation by nitrobenzene result also in the formation of secondary Fe(III) minerals. Goethite formed on three hematite morphologies (rhombohedra, needles, and hexagonal platelets), and acicular needle shapes typical of goethite appeared on the micron-sized hexagonal platelets, at times aligned in 60° orientations on (0 0 1) faces. The proportion of goethite formation on the three hematites was linked to number of surface sites. Only goethite was observed to form on a goethite sorbent. In contrast, lepidocrocite was observed to form on magnetite and maghemite sorbents (consistent with homogeneous Fe(II) oxidation by O2) and assumed spherulite morphologies. All secondary Fe(III) phases were confirmed within

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

    NASA Astrophysics Data System (ADS)

    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

  10. Binding of α-Synuclein with Fe(III) and with Fe(II) and Biological Implications of the Resultant Complexes

    PubMed Central

    Peng, Yong; Wang, Chengshan; Xu, Howard; Liu, You-Nian; Zhou, Feimeng

    2009-01-01

    Parkinson's disease (PD) is hallmarked by the abnormal intracellular inclusions (Lewy bodies or LBs) in dopaminergic cells. Amyloidogenic protein α-synuclein (α-syn) and iron (including both Fe(III) and Fe(II)) are both found to be present in LBs. The interaction between iron and α-syn might have important biological relevance to PD etiology. Previously, a moderate binding affinity between α-syn and Fe(II) (5.8 × 103 M-1) has been measured, but studies on the binding between α-syn and Fe(III) have not been reported. In this work, electrospray mass spectrometry (ES–MS), cyclic voltammetry (CV), and fluorescence spectroscopy were used to study the binding between α-syn and Fe(II) and the redox property of the resultant α-syn-Fe(II) complex. The complex is of a 1:1 stoichiometry and can be readily oxidized electrochemically and chemically (by O2) to the putative α-syn-Fe(III) complex, with H2O2 as a co-product. The reduction potential was estimated to be 0.025 V vs. Ag/AgCl, which represents a shift by −0.550 V vs. the standard reduction potential of the free Fe(III)/Fe(II) couple. Such a shift allows a binding constant between α-syn and Fe(III), 1.2 × 1013 M-1, to be deduced. Despite the relatively high binding affinity, α-syn-Fe(III) generated from the oxidation of α-syn-Fe(II) still dissociates due to the stronger tendency of Fe(III) to hydrolyze to Fe(OH)3 and/or ferrihydrite gel. The roles of α-syn and its interaction with Fe(III) and/or Fe(II) are discussed in the context of oxidative stress, metal-catalyzed α-syn aggregation, and iron transfer processes. PMID:20005574

  11. Fate of a stilbene-type fluorescent whitening agent (DSBP) in the presence of Fe(III) aquacomplexes: from the redox process to the photodegradation.

    PubMed

    Wong-Wah-Chung, Pascal; Mailhot, Gilles; Aguer, Jean-Pierre; Bolte, Michèle

    2006-12-01

    The behaviour of 4,4'-bis(2-sulfostyryl)biphenyl (DSBP), a fluorescent whitening agent, was investigated in the presence of Fe(III) aquacomplexes at room temperature. In the dark, a two-step reaction was observed when adding Fe(III) to a solution of DSBP: an initial fast redox reaction between DSBP and the monomeric species Fe(OH)(2+) and a slower reaction leading to the coagulation of oxidised DSBP and iron. This phenomenon is due to the formation of a complex or an ion-pair between Fe(II) and/or Fe(III) with oxidised DSBP and it probably occurs by charge neutralisation in our experimental conditions. The precipitation of DSBP depends on the initial concentration in Fe(OH)(2+) and is achieved for a ratio [Fe(OH) (2+)]/[DSBP] of 5 approximately. Under irradiation at 365 nm, a complicated behaviour was observed: a complexation of iron by oxidised DSBP favoured by irradiation and a degradation of DSBP induced by an intramolecular electron transfer in the complex or by a photoredox of Fe(OH)(2+) species generating .OH radicals in the supernatant. The complete degradation of DSBP is reached four times faster in the presence of Fe(III) with respect to the direct photolysis of DSBP alone. Moreover, the total mineralization of DSBP obtained in less than 120 h upon irradiation at 365 nm is only observed in the presence of the ferric ions, enlightening the efficiency of the method involving Fe(III) and UV irradiation. PMID:16860369

  12. The Geoglobus acetivorans Genome: Fe(III) Reduction, Acetate Utilization, Autotrophic Growth, and Degradation of Aromatic Compounds in a Hyperthermophilic Archaeon

    PubMed Central

    Mardanov, Andrey V.; Slododkina, Galina B.; Slobodkin, Alexander I.; Beletsky, Alexey V.; Gavrilov, Sergey N.; Kublanov, Ilya V.; Bonch-Osmolovskaya, Elizaveta A.; Skryabin, Konstantin G.

    2014-01-01

    Geoglobus acetivorans is a hyperthermophilic anaerobic euryarchaeon of the order Archaeoglobales isolated from deep-sea hydrothermal vents. A unique physiological feature of the members of the genus Geoglobus is their obligate dependence on Fe(III) reduction, which plays an important role in the geochemistry of hydrothermal systems. The features of this organism and its complete 1,860,815-bp genome sequence are described in this report. Genome analysis revealed pathways enabling oxidation of molecular hydrogen, proteinaceous substrates, fatty acids, aromatic compounds, n-alkanes, and organic acids, including acetate, through anaerobic respiration linked to Fe(III) reduction. Consistent with the inability of G. acetivorans to grow on carbohydrates, the modified Embden-Meyerhof pathway encoded by the genome is incomplete. Autotrophic CO2 fixation is enabled by the Wood-Ljungdahl pathway. Reduction of insoluble poorly crystalline Fe(III) oxide depends on the transfer of electrons from the quinone pool to multiheme c-type cytochromes exposed on the cell surface. Direct contact of the cells and Fe(III) oxide particles could be facilitated by pilus-like appendages. Genome analysis indicated the presence of metabolic pathways for anaerobic degradation of aromatic compounds and n-alkanes, although an ability of G. acetivorans to grow on these substrates was not observed in laboratory experiments. Overall, our results suggest that Geoglobus species could play an important role in microbial communities of deep-sea hydrothermal vents as lithoautotrophic producers. An additional role as decomposers would close the biogeochemical cycle of carbon through complete mineralization of various organic compounds via Fe(III) respiration. PMID:25416759

  13. Crown ether-modified electrodes for the simultaneous stripping voltammetric determination of Cd(II), Pb(II) and Cu(II).

    PubMed

    Serrano, Núria; González-Calabuig, Andreu; del Valle, Manel

    2015-06-01

    This work describes the immobilization of 4-carboxybenzo-18-crown-6 (CB-18-crown-6) and 4-carboxybenzo-15-crown-5 (CB-15-crown-5) assisted by lysine on aryl diazonium salt monolayers anchored to the surface of graphite-epoxy composite electrodes (GEC), and their use for the simultaneous determination of Cd(II), Pb(II) and Cu(II) by differential pulse anodic stripping voltammetry (DPASV). These modified electrodes display a good repeatability and reproducibility with detection and quantification limits at levels of µg L(-1) (ppb), confirming their suitability for the determination of Cd(II), Pb(II) and Cu(II) ions in environmental samples. The overlapped nature of the multimetal stripping measurements was resolved by employing the two-sensor array CB-15-crown-5-GEC and CB-18-crown-6-GEC, since the metal complex selectivity exhibited by the considered ligands could add some discrimination power. For the processing of the voltammograms, Discrete Wavelet Transform and Causal Index were selected as preprocessing tools for data compression coupled with an artificial neural network for the modeling of the obtained responses, allowing the resolution of mixtures of these metals with good prediction of their concentrations (correlation with expected values for an external test subset better than 0.942). PMID:25863381

  14. Competitive adsorption of Cd(II), Zn(II) and Ni(II) from their binary and ternary acidic systems using tourmaline.

    PubMed

    Liu, Haibin; Wang, Cuiping; Liu, Jingting; Wang, Baolin; Sun, Hongwen

    2013-10-15

    The adsorption of Cd(II), Zn(II) and Ni(II) from aqueous solutions in binary and ternary component systems by tourmaline was investigated. Kinetic data were accurately fitted to pseudo-second order and internal diffusion models, which indicated that the adsorption of heavy metals occurred on the interior surface of the sorbent and internal diffusion was the controlling mechanism during heavy metal ion adsorption but was not the only rate-controlling step. Additionally, tourmaline had a very good adsorption capacity for Cd(II), Zn(II) and Ni(II) in multi-component aqueous solutions at strongly acidic pH values (in contrast to industrial wastewater pH values). This good adsorption capacity is attributed to the fact that tourmaline can automatically adjust the pH values of acidic (except pH 2.0 and 3.0), neutral or alkaline aqueous solutions to 6.0. Adsorption isotherms and separation factors showed that tourmaline displays a high selectivity toward one metal in a two-component or a three-component system with an affinity order of Cd(II) > Zn(II) > Ni(II). Thermodynamic parameters indicated that heavy metal adsorption was feasible, spontaneous, and endothermic. Therefore, tourmaline should be explored as a material for removing pollutants from the strongly acidic wastewater. PMID:23851318

  15. A Biphenol-Based Chemosensor for Zn(II) and Cd(II) Metal Ions: Synthesis, Potentiometric Studies, and Crystal Structures.

    PubMed

    Ambrosi, Gianluca; Formica, Mauro; Fusi, Vieri; Giorgi, Luca; Macedi, Eleonora; Micheloni, Mauro; Paoli, Paola; Rossi, Patrizia

    2016-08-01

    We synthesized and characterized the ligand N,N'-bis[(2,2'-dihydroxybiphen-3-yl)methyl]-N,N'-dimethylethylenediamine (L), which contains two biphenol moieties linked as side arms to an N,N'-dimethylethylenediamine scaffold. The ligand is highly soluble in a 50/50 (v/v) water/ethanol mixture and, in its deprotonated form H-2L(2-), is able to coordinate transition-metal ions such as Ni(II), Zn(II), Cu(II), Cd(II), and Pd(II). The crystal structures of [Ni(H-2L)·2n-BuOH], [Ni(H-2L)·2MeOH], [Cd(H-2L)·2DMF], [Cu(H-2L)(DMF)], and [Pd(H-2L)(DMF)] were also determined and described. Potentiometric titrations were carried out in a mixed solvent with Zn(II), Cu(II), and Ni(II) metal ions to determine the acid-base and stability constants. L was highly fluorescent in the visible range (400 nm). Moreover, its emission intensity increased upon the addition of Zn(II) or Cd(II) ions in an ethanol/water solution and behaved as a chemosensor for the presence of these ions in the solution. PMID:27439670

  16. Poly(itaconic acid)-grafted chitosan adsorbents with different cross-linking for Pb(II) and Cd(II) uptake.

    PubMed

    Kyzas, George Z; Siafaka, Panoraia I; Lambropoulou, Dimitra A; Lazaridis, Nikolaos K; Bikiaris, Dimitrios N

    2014-01-14

    Two novel chitosan (CS) adsorbents were prepared in powder form, after modification with the grafting of itaconic acid (CS-g-IA) and cross-linking with either glutaraldehyde (CS-g-IA(G)) or epichlorohydrin (CS-g-IA(E)). Their adsorption properties were evaluated in batch experiments for Cd(II) or Pb(II) uptake. Characterization techniques were applied to the prepared adsorbents as swelling experiments, TGA, SEM, XRD, and FTIR. Adsorption mechanisms were suggested for different pH conditions. Various adsorption parameters were determined as the effect of pH, contact time, and temperature. The maximum adsorption capacities for Cd(II) uptake were 405 and 331 mg/g for CS-g-IA(G) and CS-g-IA(E), respectively, revealing the capacity enhancement after grafting (124 and 92 mg/g were the respective values before grafting, respectively). A similar grafting effect was observed for Pb(II) uptake, proving its adsorption effectiveness on the CS backbone. The reuse of adsorbents was tested with 20 adsorption-desorption cycles. PMID:24011255

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

    PubMed

    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

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

    PubMed

    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

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

    PubMed

    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

  20. 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

    NASA Astrophysics Data System (ADS)

    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.

  1. Crystal structure and photoluminescence properties of a new Cd(II) coordination polymer catena-poly[bis[4-bromo-2-({[2-(pyrrolidin-1-yl)ethyl]imino}methyl)phenolato-κ(3)N,N',O]di-μ3-chlorido-di-μ2-chlorido-bis(methanol-κO)tricadmium(II)].

    PubMed

    Yahsi, Yasemin; Ozbek, Hatice; Aygun, Muhittin; Kara, Hulya

    2016-05-01

    Schiff base-metal complexes have been used widely as catalysts for many organic reactions, such as ring-opening polymerization and oxidation. In view of the importance of Cd(II) coordination polymers and in an effort to enlarge the library of such complexes, the title novel polymeric Cd(II) tridentate Schiff base complex, [Cd3(C13H16BrN2O)2Cl4(CH4O)2]n, has been synthesized and characterized by elemental analyses, UV and IR spectroscopies, and single-crystal X-ray diffraction. The complex crystallizes in the triclinic P-1 space group with two symmetry-independent Cd(II) atoms, one of which lies on an inversion centre, and analysis of the crystal structure shows that both Cd(II) atoms are six-coordinated; the environment around one Cd(II) atom can be described as distorted octahedral, while that around the second Cd(II) atom is octahedral. The Cd(II) atoms are linked by chloride ligands to form a one-dimensional coordination polymer. The nonbonding intermolecular Cd...Cd distances are 3.7009 (4) and 4.3563 (5) Å. Furthermore, the photoluminescence properties of the complex have been investigated and it displays a strong red emission in the solid state at room temperature. PMID:27146573

  2. Characterization and Properties of Activated Carbon Prepared from Tamarind Seeds by KOH Activation for Fe(III) Adsorption from Aqueous Solution

    PubMed Central

    Mopoung, Sumrit; Moonsri, Phansiri; Palas, Wanwimon; Khumpai, Sataporn

    2015-01-01

    This research studies the characterization of activated carbon from tamarind seed with KOH activation. The effects of 0.5 : 1–1.5 : 1 KOH : tamarind seed charcoal ratios and 500–700°C activation temperatures were studied. FTIR, SEM-EDS, XRD, and BET were used to characterize tamarind seed and the activated carbon prepared from them. Proximate analysis, percent yield, iodine number, methylene blue number, and preliminary test of Fe(III) adsorption were also studied. Fe(III) adsorption was carried out by 30 mL column with 5–20 ppm Fe(III) initial concentrations. The percent yield of activated carbon prepared from tamarind seed with KOH activation decreased with increasing activation temperature and impregnation ratios, which were in the range from 54.09 to 82.03 wt%. The surface functional groups of activated carbon are O–H, C=O, C–O, –CO3, C–H, and Si–H. The XRD result showed high crystallinity coming from a potassium compound in the activated carbon. The main elements found in the activated carbon by EDS are C, O, Si, and K. The results of iodine and methylene blue adsorption indicate that the pore size of the activated carbon is mostly in the range of mesopore and macropore. The average BET pore size and BET surface area of activated carbon are 67.9764 Å and 2.7167 m2/g, respectively. Finally, the tamarind seed based activated carbon produced with 500°C activation temperature and 1.0 : 1 KOH : tamarind seed charcoal ratio was used for Fe(III) adsorption test. It was shown that Fe(III) was adsorbed in alkaline conditions and adsorption increased with increasing Fe(III) initial concentration from 5 to 20 ppm with capacity adsorption of 0.0069–0.019 mg/g. PMID:26689357

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

    PubMed

    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

  4. Synthesis, magnetic, thermal and structural properties of Co(II), Ni(II) and Cu(II) complexes containing isophthalato ligands

    NASA Astrophysics Data System (ADS)

    Rogan, Jelena; Poleti, Dejan; Karanović, Ljiljana; Jagličić, Zvonko

    2011-01-01

    A series of novel ternary Co(II), Ni(II) and Cu(II) complexes containing 2,2'-dipyridylamine (dipya), 2,2'-bipyridine (bipy), and 1,10-phenanthroline (phen), as aromatic diamine ligands, and dianion of isophthalic acid (ipht) have been prepared by ligand exchange reactions from diluted H 2O/EtOH solutions. The complexes were characterized by elemental analysis, IR spectroscopy, magnetic susceptibility measurements and TG and DSC analysis. Three complexes, Cu(dipya)(ipht)·H 2O ( 1), Co(dipya)(ipht)·2H 2O ( 2) and Cu(ipht)(phen)·2H 2O ( 5) are polymeric with bis-monodentate ipht, while the other two complexes M(bipy)(ipht)·4H 2O, M dbnd Co(II) ( 3) and Ni(II) ( 4), contain ipht as a counter ion. All Co(II) and Ni(II) complexes are (pseudo)octahedral, while Cu(II) complexes have square-pyramidal or distorted octahedral geometry. The variable temperature magnetic susceptibility measurements showed very weak antiferromagnetic behaviour for all complexes. Dehydration processes, decomposition mechanisms and thermal stability of 1- 5 are assumed. One complex from the above series, [Ni(bipy)(H 2O) 4](ipht) ( 4), and one additional complex, [Co(bipy)(ipht)] n ( 6), are obtained as single-crystals and their structures are determined from X-ray diffraction data. In both structures M(II) centers are in deformed octahedral environment and they are linked by hemi-ipht ligands ( 4) and two different bridging ipht ligands ( 6). Three-dimensional networks in 4 and 6 are governed by strong noncovalent interactions. The cations and ipht anions in 4 are connected by hydrogen bonds building double layers parallel to ab-plane that are further packed by π- π interactions. In 6 double chains extending along b-axis are strengthened by interchain π- π interactions constructing a three-dimensional framework.

  5. Adsorption studies of Cd(II) onto Al 2O 3/Nb 2O 5 mixed oxide dispersed on silica matrix and its on-line preconcentration and determination by flame atomic absorption spectrometry

    NASA Astrophysics Data System (ADS)

    Mendonça Costa, Lucimara; Ribeiro, Emerson Schwingel; Segatelli, Mariana Gava; do Nascimento, Danielle Raphael; de Oliveira, Fernanda Midori; Tarley, César Ricardo Teixeira

    2011-05-01

    The present study describes the adsorption characteristic of Cd(II) onto Nb 2O 5/Al 2O 3 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 SiO 2/Al 2O 3/Nb 2O 5 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 2 4 full factorial design and Doehlert matrix. The effect of SO 42-, Cu 2+, Zn 2+ and Ni 2+ 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).

  6. Rapid coprecipitation technique using yttrium hydroxide for the preconcentration and separation of trace elements in saline water prior to their ICP-AES determination.

    PubMed

    Kagaya, Shigehiro; Miwa, Satoshi; Mizuno, Toshiyuki; Tohda, Koji

    2007-08-01

    Yttrium hydroxide quantitatively coprecipitated Be(II), Ti(IV), Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Cd(II), and Pb(II) at pH 9.6 - 10.0 for seawater and pH 10.5 - 11.4 for a table-salt solution. The coprecipitated elements could be determined by inductively coupled plasma atomic emission spectrometry; yttrium was used as an internal standard element. The detection limits ranged from 0.001(6) microg (Mn(II)) to 0.22 microg (Zn(II)) in 100 mL of sample solutions. The operation time required to separate 11 elements was approximately 30 min. PMID:17690440

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

    PubMed

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

    2016-05-15

    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. PMID:26945123

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

    NASA Astrophysics Data System (ADS)

    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).

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

    NASA Astrophysics Data System (ADS)

    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.

  10. Synthesis, characterization, antibacterial, antifungal and immunomodulating activities of gatifloxacin-metal complexes

    NASA Astrophysics Data System (ADS)

    Sultana, Najma; Naz, Asia; Arayne, M. Saeed; Mesaik, M. Ahmed

    2010-04-01

    Gatifloxacin is a potent fluoroquinolone antibacterial agent. It is reported and our previous work has also proved that availability of gatifloxacin is reduced by co-administration of metallic supplements. For better understanding of these interactions, complexes of gatifloxacin were synthesized with Mg(II), Ca(II), Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) (usually present in human body) and their structures were established with the help of spectroscopic studies like IR, UV, and NMR. The IR spectra of the complexes suggest that the gatifloxacin behaves as a monoanionic bidentate ligand. In vitro antibacterial, antifungal, anti-inflammatory and immunosuppressive activities of the gatifloxacin and the complexes were tested. GTX-Ni and GTX-Cu has excellent anti-inflammatory activity.

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

    NASA Astrophysics Data System (ADS)

    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.

  12. The transformation of ferrihydrite in the presence of trace Fe(II): The effect of the ammonia, amine and the coordination ions of Fe(III)

    NASA Astrophysics Data System (ADS)

    Liu, Hui; Yang, Lijuan; Ma, Miaorui; Li, Ping; Wei, Yu

    2010-03-01

    This work examined Fe(II)-induced transformation of ferrihydrite in the presence of ammonia, amine and the coordination ions of Fe(III). Our earlier results showed that ferrihydrite transformed into the mixture of lepidocrocite, goethite and/or hematite in the presence of trace Fe(II) and absence of ammonia and similar species. However, the formation of lepidocrocite was restrained when using ammonia as precipitants. When introducing some amines (e.g. ethanolamine and diethanolamine) and some coordination ions (e.g. F - and CO42- ions) into the reaction system, a similar effect on the transformation of ferrihydrite was found. Probably, the complexes formed between Fe(III) and those additives favor the formation of goethite. At the same time, the introduction of these additives hinders Fe(II) from interacting with ferrihydrite, which makes the catalytic dissolution of ferrihydrite be limited, thus, the formation of lepidocrocite be restrained.

  13. To Transfer or Not to Transfer? Development of a Dinitrosyl Iron Complex as a Nitroxyl Donor for the Nitroxylation of an Fe(III) -Porphyrin Center.

    PubMed

    Tseng, Yu-Ting; Chen, Chien-Hong; Lin, Jing-Yu; Li, Bing-Han; Lu, Yu-Huan; Lin, Chia-Her; Chen, Hsin-Tsung; Weng, Tsu-Chien; Sokaras, Dimosthenes; Chen, Huang-Yeh; Soo, Yun-Liang; Lu, Tsai-Te

    2015-12-01

    A positive myocardial inotropic effect achieved using HNO/NO(-) , compared with NO⋅, triggered attempts to explore novel nitroxyl donors for use in clinical applications in vascular and myocardial pharmacology. To develop M-NO complexes for nitroxyl chemistry and biology, modulation of direct nitroxyl-transfer reactivity of dinitrosyl iron complexes (DNICs) is investigated in this study using a Fe(III) -porphyrin complex and proteins as a specific probe. Stable dinuclear {Fe(NO)2 }(9) DNIC [Fe(μ-(Me) Pyr)(NO)2 ]2 was discovered as a potent nitroxyl donor for nitroxylation of Fe(III) -heme centers through an associative mechanism. Beyond the efficient nitroxyl transfer, transformation of DNICs into a chemical biology probe for nitroxyl and for pharmaceutical applications demands further efforts using in vitro/in vivo studies. PMID:26437878

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

    PubMed

    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

  15. Depth-dependent geochemical and microbiological gradients in Fe(III) deposits resulting from coal mine-derived acid mine drainage

    PubMed Central

    Brantner, Justin S.; Haake, Zachary J.; Burwick, John E.; Menge, Christopher M.; Hotchkiss, Shane T.; Senko, John M.

    2014-01-01

    We evaluated the depth-dependent geochemistry and microbiology of sediments that have developed via the microbially-mediated oxidation of Fe(II) dissolved in acid mine drainage (AMD), giving rise to a 8–10 cm deep “iron mound” that is composed primarily of Fe(III) (hydr)oxide phases. Chemical analyses of iron mound sediments indicated a zone of maximal Fe(III) reducing bacterial activity at a depth of approximately 2.5 cm despite the availability of dissolved O2 at this depth. Subsequently, Fe(II) was depleted at depths within the iron mound sediments that did not contain abundant O2. Evaluations of microbial communities at 1 cm depth intervals within the iron mound sediments using “next generation” nucleic acid sequencing approaches revealed an abundance of phylotypes attributable to acidophilic Fe(II) oxidizing Betaproteobacteria and the chloroplasts of photosynthetic microeukaryotic organisms in the upper 4 cm of the iron mound sediments. While we observed a depth-dependent transition in microbial community structure within the iron mound sediments, phylotypes attributable to Gammaproteobacterial lineages capable of both Fe(II) oxidation and Fe(III) reduction were abundant in sequence libraries (comprising ≥20% of sequences) from all depths. Similarly, abundances of total cells and culturable Fe(II) oxidizing bacteria were uniform throughout the iron mound sediments. Our results indicate that O2 and Fe(III) reduction co-occur in AMD-induced iron mound sediments, but that Fe(II)-oxidizing activity may be sustained in regions of the sediments that are depleted in O2. PMID:24860562

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

    NASA Astrophysics Data System (ADS)

    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.

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

    PubMed Central

    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

  18. Depth-dependent geochemical and microbiological gradients in Fe(III) deposits resulting from coal mine-derived acid mine drainage.

    PubMed

    Brantner, Justin S; Haake, Zachary J; Burwick, John E; Menge, Christopher M; Hotchkiss, Shane T; Senko, John M

    2014-01-01

    We evaluated the depth-dependent geochemistry and microbiology of sediments that have developed via the microbially-mediated oxidation of Fe(II) dissolved in acid mine drainage (AMD), giving rise to a 8-10 cm deep "iron mound" that is composed primarily of Fe(III) (hydr)oxide phases. Chemical analyses of iron mound sediments indicated a zone of maximal Fe(III) reducing bacterial activity at a depth of approximately 2.5 cm despite the availability of dissolved O2 at this depth. Subsequently, Fe(II) was depleted at depths within the iron mound sediments that did not contain abundant O2. Evaluations of microbial communities at 1 cm depth intervals within the iron mound sediments using "next generation" nucleic acid sequencing approaches revealed an abundance of phylotypes attributable to acidophilic Fe(II) oxidizing Betaproteobacteria and the chloroplasts of photosynthetic microeukaryotic organisms in the upper 4 cm of the iron mound sediments. While we observed a depth-dependent transition in microbial community structure within the iron mound sediments, phylotypes attributable to Gammaproteobacterial lineages capable of both Fe(II) oxidation and Fe(III) reduction were abundant in sequence libraries (comprising ≥20% of sequences) from all depths. Similarly, abundances of total cells and culturable Fe(II) oxidizing bacteria were uniform throughout the iron mound sediments. Our results indicate that O2 and Fe(III) reduction co-occur in AMD-induced iron mound sediments, but that Fe(II)-oxidizing activity may be sustained in regions of the sediments that are depleted in O2. PMID:24860562

  19. Pyrobaculum ferrireducens sp. nov., a hyperthermophilic Fe(III)-, selenate- and arsenate-reducing crenarchaeon isolated from a hot spring.

    PubMed

    Slobodkina, G B; Lebedinsky, A V; Chernyh, N A; Bonch-Osmolovskaya, E A; Slobodkin, A I

    2015-03-01

    A novel hyperthermophilic, anaerobic, archaeon was isolated from a terrestrial hot spring at Uzon Caldera, Kronotsky Nature Reserve, Kamchatka, Russia. The isolate, strain 1860(T), grew optimally at 90-95 °C and pH 6.0-7.0. The cells were non-motile straight rods, 1.5-5.0 µm in length, covered with surface-layer lattice. Strain 1860(T) utilized complex proteinaceous compounds as electron donors and ferrihydrite, Fe(III) citrate, nitrate, thiosulfate, selenite, selenate and arsenate as electron acceptors for growth. The sequence of the 16S rRNA gene of strain 1860(T) had 97.9-98.7 % similarity with those of members of the genus Pyrobaculum. On the basis of its physiological properties and phylogenetic analyses including in silico genome to genome hybridization, the isolate is considered to represent a novel species, for which the name Pyrobaculum ferrireducens sp. nov. is proposed. The type strain is 1860(T) ( = DSM 28942(T) = VKM B-2856(T)). PMID:25510975

  20. Characterization of solid-phase extraction of Fe(III) by unloaded polyurethane foam as thiocyanate complex.

    PubMed

    de Almeida, Gil Nunes; de Sousa, Leandro M; Pereira Netto, Annibal D; Cassella, Ricardo J

    2007-11-01

    This work presents a detailed study about the adsorption of iron(III)-thiocyanate complexes onto unloaded polyether-type polyurethane foam (PUF). A novel strategy was employed for this purpose, utilizing the adjustment of the plug cylinder of PUF to the arm of an overhead stirrer. The system was characterized in relation to equilibrium and kinetic aspects and it was modeled by applying Langmuir and Freundlich isotherms. The results obtained showed that adsorption occurs on a monolayer and that external transport of the solute from solution to adsorbent was the rate-determining mechanism. A maximum adsorption capacity of 2.06 x 10(-4) mol Fe g(-1) was obtained under established experimental conditions (0.5 mol L(-1) SCN(-) and 0.005 mol L(-1) HCl). Sequential extraction experiments were carried out by changing PUF in time intervals previously defined (5, 20, and 40 min), and the obtained results showed that it is possible to remove around 95% of the Fe(III) in solution through five consecutive extractions of 5 min with five 200 mg PUF cylinders. PMID:17662992

  1. Heterometallic Fe(III) /K Coordination Polymer with a Wide Thermal Hysteretic Spin Transition at Room Temperature.

    PubMed

    Kang, Soonchul; Shiota, Yoshihito; Kariyazaki, Akira; Kanegawa, Shinji; Yoshizawa, Kazunari; Sato, Osamu

    2016-01-11

    The anionic Fe(III) complex exhibiting cooperative spin transition with a wide thermal hysteresis near room temperature, K[Fe(5-Brthsa)2 ] (5-Brthsa-H2 =5-bromosalicylaldehyde thiosemicarbazone), is reported. The hysteresis (Δ=69 K in the first cycle) shows a one-step transition in heating mode and a two-step transition in cooling mode. X-ray structure analysis showed that the coexistence of hydrogen bond and cation-π interactions, as well as alkali metal coordination bonds, to give 2D coordination polymer structure. This result is contrary to previous reports of broad thermal hysteresis induced by coordination bonds of Fe(II) spin crossover coordination polymers (with 1D/3D structures), and by strong intermolecular interactions in the molecular packing through π-π stacking or hydrogen-bond networks. As a consequence, the importance, or the very good suitability of alkali metal-based coordination bonds and cation-π interactions for communicating cooperative interactions in spin-crossover (SCO) compounds must be reconsidered. PMID:26564335

  2. New Light on NO Bonding in Fe(III) Heme Proteins from Resonance Raman Spectroscopy and DFT Modeling

    PubMed Central

    Soldatova, Alexandra V.; Ibrahim, Mohammed; Olson, John S.; Czernuszewicz, Roman S.; Spiro, Thomas G.

    2010-01-01

    Visible and ultraviolet resonance Raman (RR) spectra are reported for FeIII(NO) adducts of myoglobin variants with altered polarity in the distal heme pockets. The stretching frequencies of the FeIII–NO and N–O bonds, νFeN and νNO, are negatively correlated, consistent with backbonding. However, the correlation shifts to lower νNO for variants lacking a distal histidine. DFT modeling reproduces the shifted correlations, and shows the shift to be associated with the loss of a lone-pair donor interaction from the distal histidine that selectively strengthens the N–O bond. However, when the model contains strongly electron-withdrawing substituents at the heme β-positions, νFeN and νNO become positively correlated. This effect results from FeIII–N–O bending, which is induced by lone pair donation to the NNO atom. Other mechanisms for bending are discussed, which likewise lead to a positive νFeN/νNO correlation, including thiolate ligation in heme proteins and electron-donating meso-substituents in heme models. The νFeN/νNO data for the Fe(III) complexes are reporters of heme pocket polarity and the accessibility of lone pair, Lewis base donors. Implications for biologically important processes, including NO binding, reductive nitrosylation and NO reduction, are discussed. PMID:20218710

  3. Organic carboxylate ligands tuned structural variations of two new Cd(II) coordination polymers: From 2D layer to 3D framework

    NASA Astrophysics Data System (ADS)

    Lv, Chang-Wei; Li, Jing; Liu, Yan-Wu; Li, Xia; Yuan, Zhi

    2015-11-01

    Two new Cd(II) coordination polymers, namely [Cd(4,4‧-sdb) (biimpy)]n·1.5n(H2O) (1) and [Cd2(Htci)2(biimpy)2]n (2) (4,4‧-H2sdb = 4,4‧-sulfonyldibenzoate, H3tci = tri(2-carboxyethyl)isocyanurate and biimpy = 2,6-bis(1-imdazoly)pyridine), have been synthesized by the hydrothermal reactions of Cd(NO3)2 and the mixed ligands of 4,4‧-H2sdb and biimpy or H3tci and biimpy. Single crystal X-ray structural analyses reveal that compound 1 features a 2D layered structure with 3-connected topology, and compound 2 features a 3D framework with 6-connected 6T8 topology. In addition, the thermal stabilities and luminescent properties of compounds 1 and 2 were also investigated.

  4. Isostructural 1D coordination polymers of Zn(II), Cd(II) and Cu(II) with phenylpropynoic acid and DABCO as organic linkers

    NASA Astrophysics Data System (ADS)

    Saravanakumar, Rajendran; Varghese, Babu; Sankararaman, Sethuraman

    2014-11-01

    Using phenylpropynoic acid (PPA) and 1,4-diazabicyclo[2.2.2]octane (DABCO) as organic spacers, isostructural coordination polymers of Zn(II), Cd(II) and Cu(II) were synthesized by solvothermal method and structurally characterized using single crystal XRD, powder XRD, 13C CP-MAS NMR spectroscopy. Single crystal XRD data revealed four PPA units coordinating with two metal ions forming a paddle wheel secondary building unit (SBU). The paddle wheel units are connected through coordination of DABCO nitrogen to the metal centers from the axial positions leading to the formation of the 1D coordination polymers along the c axis. Intermolecular π stacking and Csbnd H…π interactions between the adjacent polymer chains convert the 1D coordination polymer into an interesting 3D network with the Csbnd H…π bonds running along the crystallographic a and b axes. Thermal and nitrogen adsorption studies of these coordination polymers are reported.

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

    NASA Astrophysics Data System (ADS)

    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.

  6. Spectroscopic studies on Fe(II) and Fe(III) complexes of 5-aryl azo substituted lH-pyrimidine-2,4-dione

    NASA Astrophysics Data System (ADS)

    Vidya, G. V.; Meena, S. S.; Bhatt, Pramod; Sadasivan, V.; Mini, S.

    2013-06-01

    The Fe(II) and Fe(III) complexes of an azo dye [UAAPJderived from 4-amino-2, 3-dimethyl-l-phenyl-3-pyrazoline-5-one and lH-pyrimidine-2, 4-dione have been prepared. The ligand and metal complexes were characterized by elemental analysis, magnetic measurement, molar conductance, FTIR, UV-Vis spectra, 1H NMR, and Mössbauer spectroscopic studies and thermo gravimetric analysis. Analytical data suggests molecular formula [Fe(UAAP)2]Cl3 for Fe(III) complex and [Fe(UAAP)2SO4] for Fe(II) complex. The IR spectral data suggest that [UAAP] is acting as a neutral tridentate ligand towards Fe(III) and as a neutral bidentate ligand towards Fe(II) in their complexes. Mossbauer and electronic spectral data and magnetic moment value agree with the high spin octahedral geometry for both complexes. The ligand and complexes were screened for antibacterial and antifungal studies. The metal complexes exhibit increased antimicrobial activity than ligand.

  7. Fluorescent Sensing of both Fe(III) and pH Based on 4-Phenyl-2-(2-Pyridyl)Thiazole and Construction of OR Logic Function.

    PubMed

    Yang, Ming-Yang; Zhao, Xiao-Long; Zheng, Ming-Hua; Wang, Yue; Jin, Jing-Yi

    2016-09-01

    In the presented paper we investigated a 2-pyridylthiazole derivative, 4-phenyl-2-(2-pyridyl)thiazole (2-PTP), as the molecular fluorescent switches. It was firstly found that 2-PTP could perform a "turn-on" fluorescent sensing for Fe(III) with selectivity and reversibility. A 2:1 stoichiometry between 2-PTP and Fe(III) was determined according to the molar ratio method. The binding constant was evaluated as (1.90 ± 0.05) × 10(5) (L/mol)(2). The detection limit was found as 2.2 × 10(-7) M (S/N = 3). Secondly, 2-PTP also exhibited a pH-dependent dual-emission. The pK a(2-PTP-H(+)/2-PTP) value was then estimated as 2.0. To explain the identical emission at 479 nm of both the Fe(III) coordinated form and the protonated form of the ligand, we proposed a "locked" conformation. Finally, combining the two external stimuli as inputs, an OR logic gate was constructed using the fluorescent emission at 479 nm as the output channel. PMID:27465707

  8. Natural input of arsenic into a coral-reef ecosystem by hydrothermal fluids and its removal by Fe(III) oxyhydroxides

    SciTech Connect

    Pichler, T.; Veizer, J.; Hall, G.E.M.

    1999-05-01

    The coral reef that circles Ambitle Island, Papua New Guinea, is exposed to the discharge of a hot, mineralized hydrothermal fluid. The hydrothermal fluids have a pH of {approximately}6 and are slightly reducing and rich in As. Seven individual vents discharge an estimated 1500 g of As per day into an area of approximately 50 x 100 m that has an average depth of 6 m. Despite the amount of As released into the bay, corals, clams, and fish do not show a response to the elevated values. The authors analyzed hydrothermal precipitates for their chemical and mineralogical composition in order to determine As sinks. Two mechanisms efficiently control and buffer the As concentration: (1) dilution by seawater and (2) incorporation in and adsorption on Fe(III) oxyhydroxides that precipitate when the hydrothermal fluids mix with ambient seawater. Fe(III) oxyhydroxides contain up to 76,000 ppm As, by an order of magnitude the highest As values found in a natural marine environment. Following adsorption, As is successfully retained in the Fe(III) oxyhydroxide deposits because oxidizing conditions prevail and high As activity allows for the formation of discrete As minerals, such as claudetite, arsenic oxide, and scorodite.

  9. The transformation of ferrihydrite in the presence of trace Fe(II): The effect of the ammonia, amine and the coordination ions of Fe(III)

    SciTech Connect

    Liu Hui; Yang Lijuan; Ma Miaorui; Li Ping; Wei Yu

    2010-03-15

    This work examined Fe(II)-induced transformation of ferrihydrite in the presence of ammonia, amine and the coordination ions of Fe(III). Our earlier results showed that ferrihydrite transformed into the mixture of lepidocrocite, goethite and/or hematite in the presence of trace Fe(II) and absence of ammonia and similar species. However, the formation of lepidocrocite was restrained when using ammonia as precipitants. When introducing some amines (e.g. ethanolamine and diethanolamine) and some coordination ions (e.g. F{sup -} and C{sub 2}O{sub 4}{sup 2-} ions) into the reaction system, a similar effect on the transformation of ferrihydrite was found. Probably, the complexes formed between Fe(III) and those additives favor the formation of goethite. At the same time, the introduction of these additives hinders Fe(II) from interacting with ferrihydrite, which makes the catalytic dissolution of ferrihydrite be limited, thus, the formation of lepidocrocite be restrained. - Graphical Abstract: Fe(II)-induced transformation of ferrihydrite in the presence of ammonia, amine and coordination ions of Fe(III) was studied. The introduction of the additives favors the formation of goethite.

  10. Biostimulation of Iron Reduction and Subsequent Oxidation of Sediment Containing Fe-silicates and Fe-oxides: Effect of Redox Cycling on Fe(III) Bioreduction

    SciTech Connect

    Komlos, John; Kukkadapu, Ravi K.; Zachara, John M.; Jaffe, Peter R.

    2007-07-01

    Microbial reduction of iron has been shown to be important in the transformation and remediation of contaminated sediments. Re-oxidation of microbially reduced iron may occur in sediments that experience oxidation-reduction cycling and can thus impact the extent of contaminant remediation. The purpose of this research was to quantify iron oxidation in a flow-through column filled with biologically-reduced sediment and to compare the iron phases in the re-oxidized sediment to both the pristine and biologically-reduced sediment. The sediment contained both Fe(III)-oxides (primarily goethite) and silicate Fe (illite/vermiculite) and was biologically reduced in phosphate buffered (PB) medium during a 497 day column experiment with acetate supplied as the electron donor. Long-term iron reduction resulted in partial reduction of silicate Fe(III) without any goethite reduction, based on Mössbauer spectroscopy measurements. This reduced sediment was treated with an oxygenated PB solution in a flow-through column resulting in the oxidation of 38% of the biogenic Fe(II). Additional batch experiments showed that the Fe(III) in the oxidized sediment was more quickly reduced compared to the pristine sediment, indicating that oxidation of the sediment not only regenerated Fe(III) but also enhanced iron reduction compared to the pristine sediment. Oxidation-reduction cycling may be a viable method to extend iron-reducing conditions during in-situ bioremediation.

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

    PubMed

    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

  12. Polyacrylonitrile-based fiber modified with thiosemicarbazide by microwave irradiation and its adsorption behavior for Cd(II) and Pb(II).

    PubMed

    Deng, Sheng; Wang, Peng; Zhang, Guangshan; Dou, Yuan

    2016-04-15

    A novel thiosemicarbazide modified adsorbent (PAN(MW)-TSC) based on polyacrylonitrile fiber was successfully synthesized under microwave irradiation, which was applied for the uptake of Cd(II) and Pb(II) from aqueous solution subsequently. Microwave irradiation method is a new approach to achieve the modification and it turns out that just a 30min process is enough for the anchoring of functional groups in the fiber matrix. The surface characterization was performed by fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM) elemental analysis (EA) and thermogravimetric analysis (TGA), indicating that the modification was successfully accomplished. Batch adsorption experiments including equilibrium isotherms, kinetics and the effects of pH and temperature on the adsorption of Cd(II) and Pb(II) were systematically studied. Among three kinetic models, the pseudo-second-order kinetic model provides the best correlation for the process. The nonlinear resolution of the Langmuir isotherm equation has been found to show the closest fit to the equilibrium date. Thermodynamic parameters, involving △G, △H and △S were also calculated from graphical interpretation of the experimental data, which suggest that metal ions adsorption onto PAN(MW)-TSC fibers is spontaneous and exothermic. Regeneration of PAN(MW)-TSC fibers loaded with metal ions was efficiently done with 0.5M HNO3, by which the investigated adsorbent could be used reproductively for five times with a small decrease in sorption capacity. The feasible preparation of PAN(MW)-TSC fibers with high adsorption capacities opens a new perspective in the potential application for wastewater treatment. PMID:26775107

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

    PubMed

    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

  14. Assembly multi-dimensional CdII coordination architectures based on flexible bis(benzimidazole) ligands: Diversity of their coordination geometries and fluorescent properties

    NASA Astrophysics Data System (ADS)

    Jiao, Cui-huan; Geng, Jian-chen; He, Cui-hong; Cui, Guang-hua

    2012-08-01

    Based on three structurally related flexible bis(5,6-dimethylbenzimidazole) ligand, five novel metal-organic CdII coordination architectures: from 0D to 3D structures CdII complexes have been hydrothermally synthesized and structurally characterized, namely, Cd2I4(L1)2 (1), [CdCl2(L1)]n (2), [CdCl2(L2)]n (3), {[Cd(chdc)(L2)0.5]·H2O}n (4), {[Cd(pydca)(L3)0.5(H2O)2]·H2O}n (5) (where L1 = 1,2-bis(5,6-dimethylbenzimidazole)ethane, L2 = 1,3-bis(5,6-dimethylbenzimidazole)propane, L3 = 1,4-bis(5,6-dimethylbenzimidazole)butane, H2chdc = 1,4-cyclohexanedicarboxylic acid, H2pydca = pyridine-2,6-dicarboxylic acid). A discrete binuclear [2 + 2] metallomacrocycles cadmium(II) complex of 1 is 0D, 3 and 5 exhibit one-dimensional helical and zigzag chain structures, respectively. 4 Forms a 2D layer with sql net topology bridged by carboxylate anion and L2, while 2 is an overall 3D array with the diamond topology (dia). In these complexes, the influences of anions coordination on the framework formation were observed and discussed. These results indicate the spacer length of the ligands and anions play important roles in controlling the diversity structural topologies of such metal-organic coordination architectures. The thermogravimetric analyses, X-ray powder diffraction and solid-state luminescent properties of the complexes have also been investigated.

  15. Permeation of iridium(IV) and metal impurity chlorocomplexes through a supported liquid membrane designed for rhodium separation

    SciTech Connect

    Ashrafizadeh, S.N.; Demopoulos, G.P.; Rovira, M.; Sastre, A.M.

    1998-06-01

    A supported liquid membrane (SLM) system previously designed for Rh separation has been examined for its capability to reject the metal impurities which are commonly encountered in industrial Rh chloride solutions. Special attention was paid to Ir(IV) chlorocomplexes and their extraction/transport behavior against both conventional solvent extraction and supported liquid membrane systems of Kelex 100. A lab-scale SLM cell with an effective membrane area of 44 cm{sup 2} was used to conduct the SLM permeation tests. The SLM was composed of a Gore-Tex polymer substrate impregnated with an organic solution of Kelex 100, tridecanol, and kerosene. The impurities tested [in addition to Ir(IV)] were AG(I), As(V), Bi(III), Cd(II), Co(II), Cu(II), Fe(III), Ni(II), Pb(II), Pd(II), Pt(IV), Se(IV), Te(IV), and Zn(II). These impurities, based on their response against the SLM, were classified into three groups, i.e., those permeated through [Zn(II), Pb(II), Cd(II), Bi(III), Te(IV), and Ir(IV)], those nonpermeated at all [Ni(II), Co(II), As(V), Se(IV), Cu(II), and Fe(III)], and those blocking the membrane [Pt(IV), Pd(II), Ag(I), Pb(II), and Bi(III)]. The SLM was not capable of discriminating between Rh(III) and Ir(IV) transport at the optimum operating conditions. Complementary upstream and downstream processes are required to separate the impurities from the feed and the product solutions, respectively. Overall, this work revealed the great limitations of SLMs as effective and potentially useful separation media for the extraction of metals from industrial-like multicomponent aqueous feed solutions.

  16. Spectroscopic and structural studies of new mononucleating tetradentate Schiff base metal chelates derived from 5-acetyl-4-hydroxy-2H-1,3-thiazine-2,6(3H)-dione and 1,3-diaminopropane

    NASA Astrophysics Data System (ADS)

    Adly, Omima M. I.; Taha, Ali; Fahmy, Shery A.

    2015-08-01

    Metal complexes with the general formula Some newly transition metal complexes, [ML(H2O)x(NO3)y], x = 1-2 and y = 0-1, [M = Cr(III), Fe(III), Co(II), Ni(II), Cu(II), Ce(III), Cd(II), Zn(II) or UO2(VI)], L= of the Schiff base (H2L) derived from the reaction of 5-acetyl-4-hydroxy-2H-1,3-thiazine-2,6(3H)-dione with 1,3-diaminopropane have been prepared and characterized by physical, spectral and analytical data. The structure of the Schiff - base acts as dibasic tetradentate N2O2 for the complexation reaction with Cr(III), Fe(III), Co(II), Cu(II), Ni(II), Ce(III), Cd(II), and UO2(II) ions via phenolates oxygen and nitrogen of azomethine groups. Based on spectral data and magnetic moments, an octahedral geometry may be proposed for the synthesized complexes except cerium(III) complex which has pentagonal bipyramidal arrangement. The low values of the molar conductance indicate non-electrolyte nature of complexes, while 1:1 electrolyte for cerium(III)- and chromium(III)-complexes. The Coats-Redfern equation was used to calculate the kinetic and thermodynamic parameters for the different thermal decomposition steps of some complexes. All the synthesized compounds were tested for in vitro antibacterial activity against some Gram-positive and Gram-negative bacteria, yeast and fungus. Molecular structure of the Schiff base ligand and its complexes were optimized for the proposed structures on the basis of semiempirical PM3 method.

  17. Study on column SPE with synthesized graphene oxide and FAAS for determination of trace amount of Co(II) and Ni(II) ions in real samples.

    PubMed

    Pourjavid, Mohammad Reza; Arabieh, Masoud; Yousefi, Seyed Reza; Jamali, Mohammad Reza; Rezaee, Mohammad; Hosseini, Majid Haji; Sehat, Ali Akbari

    2015-02-01

    A selective method for the preconcentration and separation of trace amounts of Co(II) and Ni(II) by column solid phase extraction has been developed. The method is based on the adsorption of metal ions as N-(5-methyl-2-hydroxyacetophenone)-N'-(2-hydroxyacetophenone) ethylene diamine (MHE) complex on synthesized graphene oxide. Computational modeling based on PM6 semi-empirical potential energy surface was utilized to investigate the interaction of metallic complexes with graphene oxide sheet. The adsorption was achieved quantitatively on graphene oxide at pH6.0 and then the retained analyte contents on the column were quantitatively eluted with 3.0 mol L(-1) HNO3. Experimental conditions for effective separation of trace levels of the analyte ions such as pH, flow rate, concentration of eluent, sample volume and interference ions were investigated. A preconcentration factor of 250 was achieved by passing 1250 mL of sample through the solid phase, while the limit of detection of Co(II) and Ni(II) ions were found to be 0.25 and 0.18 ng mL(-1), respectively. The method was applied to the determination of analyte ions in water, black tea and tomato samples. PMID:25492179

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

    PubMed

    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

  19. Spectroscopic and fluorescence studies on Mn(II), Co(II), Ni(II) and Cu(II) complexes with NO donor fluorescence dyes.

    PubMed

    Refat, Moamen S; el-Metwaly, Nashwa M

    2011-10-15

    The reactions of the two common dyes [2TMPACT and 4PENI] with Mn(II), Co(II), Ni(II) and Cu(II) ions were done. All the isolated complexes have been characterized by physicochemical and spectroscopic techniques. The IR data reflect the bidentate mode of 2TMPACT towards the mononuclear complex [Mn(II)] even its tetradentate in binuclear complexes [Co(II) and Cu(II)]. However, the bidentate mode is the only behavior of 4PENI ligand towards each metal ion in its mononuclear complexes. The UV-vis spectral analysis beside the magnetic moment measurements are proposed different geometries concerning each metal ions with the two ligands under investigation, as the Mn(II)-2TMPACT complex is an octahedral but Mn(II)-4PENI is a tetrahedral geometry. All the synthesized compounds are thermogravimetrically investigated. The proposed thermal decomposition was discussed for each compound with each step as well as, the kinetic parameters were calculated for all preferrible decomposition steps. The mass spectroscopy tool was used to emphasis on the suitable molecular formula proposed and the fragmentation patterns were displayed. The fluorescence properties of the synthesized ligands and their complexes were studied in DMSO at room temperature. PMID:21763185

  20. DNA cleavage, antibacterial, antifungal and anthelmintic studies of Co(II), Ni(II) and Cu(II) complexes of coumarin Schiff bases: Synthesis and spectral approach

    NASA Astrophysics Data System (ADS)

    Patil, Sangamesh A.; Prabhakara, Chetan T.; Halasangi, Bhimashankar M.; Toragalmath, Shivakumar S.; Badami, Prema S.

    2015-02-01

    The metal complexes of Co(II), Ni(II) and Cu(II) have been synthesized from 6-formyl-7,8-dihydroxy-4-methylcoumarin with o-toluidine/3-aminobenzotrifluoride. The synthesized Schiff bases and their metal complexes were structurally characterized based on IR, 1H NMR, 13C NMR, UV-visible, ESR, magnetic, thermal, fluorescence, mass and ESI-MS studies. The molar conductance values indicate that complexes are non-electrolytic in nature. Elemental analysis reveals ML2·2H2O [M = Co(II), Ni(II) and Cu(II)] stoichiometry, where 'L' stands for a singly deprotonated ligand. The presence of co-ordinated water molecules were confirmed by thermal studies. The spectroscopic studies suggest the octahedral geometry. Redox behavior of the complexes were confirmed by cyclic voltammetry. All the synthesized compounds were screened for their antibacterial (Escherichia coli, Pseudomonas auregenosa, klebsiella, Proteus, Staphylococcus aureus and salmonella) antifungal (Candida, Aspergillus niger and Rhizopus), anthelmintic (Pheretima posthuma) and DNA cleavage (Calf Thymus DNA) activity.

  1. Synthesis, structural characterization, thermal and electrochemical studies of Mn(II), Co(II), Ni(II) and Cu(II) complexes containing thiazolylazo ligands

    NASA Astrophysics Data System (ADS)

    Chavan, S. S.; Sawant, V. A.

    2010-02-01

    Some thiazolylazo derivatives and their metal complexes of the type [M(L)(H 2O)Cl]; M = Mn(II), Co(II), Ni(II), Cu(II) and L = 6-(2'-thiazolylazo)-2-mercapto-quinazolin-4-one (HL 1), 6-(4'-phenyl-2'-thiazolylazo)-2-mercapto-quinazolin-4-one (HL 2), 6-(2'-thiazolylazo)-2-mercapto-3-( m-tolyl)-quinazolin-4-one (HL 3) and 6-(4'-phenyl-2'-thiazolylazo)-2-mercapto-3-( m-tolyl)-quinazolin-4-one (HL 4) have been prepared. All the complexes were characterized on the basis of elemental analysis, molar conductance, magnetic moment, IR, UV-vis, ESR, TG-DTA and powder X-ray diffraction studies. IR spectra of these complexes reveal that the complex formation occurred through thiazole nitrogen, azo nitrogen, imino nitrogen and sulfur atom of the ligands. On the basis of electronic spectral data and magnetic susceptibility measurement octahedral geometry has been proposed for the Mn(II), Co(II) and Ni(II) complexes and distorted octahedral geometry for the Cu(II) complexes. Electrochemical behavior of Ni(II) complexes exhibit quasireversible oxidation corresponding to Ni(III)/Ni(II) couple along with ligand reduction. X-ray diffraction study is used to elucidate the crystal structure of the complexes.

  2. Spectroscopic and fluorescence studies on Mn(II), Co(II), Ni(II) and Cu(II) complexes with NO donor fluorescence dyes

    NASA Astrophysics Data System (ADS)

    Refat, Moamen S.; El-Metwaly, Nashwa M.

    2011-10-01

    The reactions of the two common dyes [2TMPACT and 4PENI] with Mn(II), Co(II), Ni(II) and Cu(II) ions were done. All the isolated complexes have been characterized by physicochemical and spectroscopic techniques. The IR data reflect the bidentate mode of 2TMPACT towards the mononuclear complex [Mn(II)] even its tetradentate in binuclear complexes [Co(II) and Cu(II)]. However, the bidentate mode is the only behavior of 4PENI ligand towards each metal ion in its mononuclear complexes. The UV-vis spectral analysis beside the magnetic moment measurements are proposed different geometries concerning each metal ions with the two ligands under investigation, as the Mn(II)-2TMPACT complex is an octahedral but Mn(II)-4PENI is a tetrahedral geometry. All the synthesized compounds are thermogravimetrically investigated. The proposed thermal decomposition was discussed for each compound with each step as well as, the kinetic parameters were calculated for all preferrible decomposition steps. The mass spectroscopy tool was used to emphasis on the suitable molecular formula proposed and the fragmentation patterns were displayed. The fluorescence properties of the synthesized ligands and their complexes were studied in DMSO at room temperature.

  3. Crystal structure, DFT, spectroscopic and biological activity evaluation of analgin complexes with Co(ii), Ni(ii) and Cu(ii).

    PubMed

    Mansour, Ahmed M

    2014-11-14

    Reaction of analgin (NaL) with Co(ii), Ni(ii) and Cu(ii) salts in ethanol affords complexes of the type [ML2], which were characterized by elemental analysis, FT IR, UV-Vis, EPR, TG/DTA, magnetic susceptibility and conductance measurements. The copper(ii) complex crystallizes in the orthorhombic Pbca space group. Analgin behaves as a mono-negatively tridentate ligand via pyrazolone O, sulfonate O and tertiary amino groups. The interaction of the tertiary nitrogen with M(n+) ions is the main factor which determines the stability of complexes as revealed from natural bond orbital analysis data, where the binding energy of [ML2] decreases with an increase in the bond length of the M-N bond. Time-dependent density functional theory calculations were applied in order to realize the electronic structures and to explain the related experimental observations. The anti-bacterial activity was studied on Staphylococcus aureus and Escherichia coli. Coordination of analgin to Ni(ii) and Cu(ii) leads to a significant increase in its antibacterial activity as compared with the Co(ii) complex. PMID:25231028

  4. N-donor co-ligands driven two new Co(II)- coordination polymers with bi- and trinuclear units: Crystal structures, and magnetic properties

    NASA Astrophysics Data System (ADS)

    Zhou, Zhi-Hang; Han, Min-Le; Wu, Ya-Pan; Dong, Wen-Wen; Li, Dong-Sheng; Lu, Jack Y.

    2016-10-01

    Two new Co(II) coordination polymers(CPs), namely [Co2(bpe)2(Hbppc)]n (1) and [Co3(μ3-OH)(bppc)(bpm)(H2O)]·3H2O (2) (H5bppc=biphenyl-2,4,6,3‧,5‧-pentacarboxylic acid, bpe=1,2-bis(4-pyridyl)ethene, bpm=bis(4-pyridyl)amine), have been obtained and characterized by elemental analysis, single-crystal X-ray diffraction, powder X-ray diffraction (PXRD), IR spectra and thermogravimetric analysis (TGA). 1 shows a binodal (4,6)-connected fsc net with a (44·610·8)(44·62) topology, while 2 shows a binodal (5,7)-connected 3D network based on trinuclear [Co3(μ3-OH)]5+ units with unusual (3.46.52.6)(32.46.57.65.7) topology. Variable-temperature magnetic susceptibility measurements reveals that complex 1 shows ferromagnetic interactions between the adjacent Co(II) ions, whereas 2 is a antiferromagnetic system.

  5. Synthesis, X-ray crystal structure and spectroscopy of a Werner-type host Co(II) complex, trans-bisisothiocyanatotetrakis( trans-4-styrylpyridine)cobalt(II)

    NASA Astrophysics Data System (ADS)

    Karunakaran, C.; Thomas, K. R. J.; Shunmugasundaram, A.; Murugesan, R.

    2000-05-01

    Single crystals of the title Co(II) complex, [Co(stpy) 4(NCS) 2] [stpy= trans-4-styrylpyridine] are prepared and characterized by elemental analysis, IR, and UV-visible spectroscopy and X-ray crystal structure determination. The complex crystallizes in the orthorhombic space group Pna2 1 with unit-cell parameters, a=32.058(3), b=15.362(5), c=9.818(5) Å, and Z=4. The structure consists of discrete monomeric units of [Co(stpy) 4(NCS) 2]. The equatorial positions of the Co(II) polyhedron are occupied by nitrogen atoms of the four stpy ligands and the axial positions are occupied by the nitrogen atoms of the two thiocyanate ions. The unit cell packing reveals interpenetration of styryl groups owing to conformational flexibility of phenyl and pyridyl rings in stpy ligands. Thus, it leads to efficient packing of the crystal lattice leaving no space available for guest inclusion. IR spectra reveal nitrogen coordination from stpy and terminal -NCS coordination of the thiocyanate group. The optical reflectance bands 475, 540 (shoulder) and 1022 nm suggest octahedral geometry in accordance with the X-ray data. However, the optical spectrum of acetonitrile solution shows an intense band at 615 nm and a weak shoulder at 570 nm suggesting participation of the solvent molecules in the coordination sphere. These bands indicate the presence of both tetrahedral and octahedral species in solution.

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

    SciTech Connect

    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.

  7. Direct involvement of ombB, omaB, and omcB genes in extracellular reduction of Fe(III) by Geobacter sulfurreducens PCA

    SciTech Connect

    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.

  8. Direct involvement of ombB, omaB, and omcB genes in extracellular reduction of Fe(III) by Geobacter sulfurreducens PCA

    DOE PAGESBeta

    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 nomore » 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.« less

  9. Evidence for microbial Fe(III) reduction in anoxic, mining-impacted lake sediments (Lake Coeur d'Alene, Idaho).

    PubMed

    Cummings, D E; March, A W; Bostick, B; Spring, S; Caccavo, F; 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(-1), suggesting that iron reduction has occurred recently. The maximum concentrations of dissolved Fe(II) in interstitial water (41 mg liter(-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(3)O(4)), a common product of bacterial Fe(III) hydroxide reduction, was as much as 15.5 g kg(-1). Most-probable-number enrichment cultures revealed that the mean density of Fe(III)-reducing bacteria was 8.3 x 10(5) cells g (dry weight) of sediment(-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. PMID:10618217

  10. Evidence for Microbial Fe(III) Reduction in Anoxic, Mining-Impacted Lake Sediments (Lake Coeur d'Alene, Idaho)

    PubMed Central

    Cummings, David E.; March, Anthony W.; Bostick, Benjamin; Spring, Stefan; Caccavo, Frank; Fendorf, Scott; Rosenzweig, R. Frank

    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−1, suggesting that iron reduction has occurred recently. The maximum concentrations of dissolved Fe(II) in interstitial water (41 mg liter−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 (Fe3O4), a common product of bacterial Fe(III) hydroxide reduction, was as much as 15.5 g kg−1. Most-probable-number enrichment cultures revealed that the mean density of Fe(III)-reducing bacteria was 8.3 × 105 cells g (dry weight) of sediment−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. PMID:10618217

  11. 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

    NASA Astrophysics Data System (ADS)

    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.

  12. Synthesis, characterization and in vitro antimicrobial studies of Co(II), Ni(II) and Cu(II) complexes derived from macrocyclic compartmental ligand

    NASA Astrophysics Data System (ADS)

    El-Gammal, O. A.; Bekheit, M. M.; El-Brashy, S. A.

    2015-02-01

    New Co(II), Ni(II) and Cu(II) complexes derived from tetradentate macrocyclic nitrogen ligand, (1E,4E,8E,12E)-5,8,13,16-tetramethyl-1,4,9,12-tetrazacyclohexadeca-4,8,12,16-tetraene (EDHDH) have been synthesized. The complexes have been characterized by elemental analysis, spectral (IR, UV-Vis, 1H NMR and ESR (for Cu(II) complex)) mass, and magnetic as well as thermal analysis measurements. The complexes afforded the formulae: [Cu(EDHDH)Cl2]·2EtOH and [M(EDHDH)X2]·nH2O where M = Co(II) and Ni(II), X = Cl- or OH-, n = 1,0, respectively. The data revealed an octahedral arrangement with N4 tetradentate donor sites in addition to two Cl atoms occupying the other two sites. ESR spectrum of Cu2+ complex confirmed the suggested geometry with values of a α2and β2 indicating that the in-plane σ-bonding and in-plane π-bonding are appreciably covalent, and are consistent with very strong σ-in-plane bonding in the complexes. The molecular modeling is drawn and showed the bond length, bond angle, chemical reactivity, energy components (kcal/mol) and binding energy (kcal/mol) for all the title compounds using DFT method. Also, the thermal behavior and the kinetic parameters of degradation were determined using Coats-Redfern and Horowitz-Metzger methods. Moreover, the in vitro antibacterial studies of all compounds screened against pathogenic bacteria (two Gram +ve and two Gram -ve) to assess their inhibiting potential. The assay indicated that the inhibition potential is metal ion dependent. The ligand, EDHDH, Co(II) and Cu(II) complexes exhibited a remarkable antibacterial activity against Streptococcus Pyogenes as Gram +ve and Proteus vulgaris as Gram -ve bacterial strains. On the other hand, Ni(II) complex revealed a moderate antibacterial activity against both Gram +ve organisms and no activity against Gram -ve bacterial strain.

  13. Characterization of Cu(II) and Cd(II) resistance mechanisms in Sphingobium sp. PHE-SPH and Ochrobactrum sp. PHE-OCH and their potential application in the bioremediation of heavy metal-phenanthrene co-contaminated sites.

    PubMed

    Chen, Chen; Lei, Wenrui; Lu, Min; Zhang, Jianan; Zhang, Zhou; Luo, Chunling; Chen, Yahua; Hong, Qing; Shen, Zhenguo

    2016-04-01

    Soil that is co-contaminated with heavy metals (HMs) and polycyclic aromatic hydrocarbons (PAHs) is difficult to bioremediate due to the ability of toxic metals to inhibit PAH degradation by bacteria. We demonstrated the resistance mechanisms to Cu(II) and Cd(II) of two newly isolated strains of Sphingobium sp. PHE-SPH and Ochrobactrum sp. PHE-OCH and further tested their potential application in the bioremediation of HM-phenanthrene (PhA) co-contaminated sites. The PHE-SPH and PHE-OCH strains tolerated 4.63 and 4.34 mM Cu(II) and also showed tolerance to 0.48 and 1.52 mM Cd(II), respectively. Diverse resistance patterns were detected between the two strains. In PHE-OCH cells, the maximum accumulation of Cu(II) occurred in the cell wall, while the maximum accumulation was in the cytoplasm of PHE-SPH cells. This resulted in a sudden suppression of growth in PHE-OCH and a gradual inhibition in PHE-SPH as the concentration of Cu(II) increased. Organic acid production was markedly higher in PHE-OCH than in PHE-SPH, which may also have a role in the resistance mechanisms, and contributes to the higher Cd(II) tolerance of PHE-OCH. The factors involved in the absorption of Cu(II) or Cd(II) in PHE-SPH and PHE-OCH were identified as proteins and carbohydrates by Fourier transform infrared (FT-IR) spectroscopy. Furthermore, both strains showed the ability to efficiently degrade PhA and maintained this high degradation efficiency under HM stress. The high tolerance to HMs and the PhA degradation capacity make Sphingobium sp. PHE-SPH and Ochrobactrum sp. PHE-OCH excellent candidate organisms for the bioremediation of HM-PhA co-contaminated sites. PMID:26670028

  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.

    PubMed

    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

    NASA Astrophysics Data System (ADS)

    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. Incorporation of dithiooxamide as a complexing agent into cellulose for the removal and pre-concentration of Cu(II) and Cd(II) ions from natural water samples

    NASA Astrophysics Data System (ADS)

    Jorgetto, A. O.; Silva, R. I. V.; Longo, M. M.; Saeki, M. J.; Padilha, P. M.; Martines, M. A. U.; Rocha, B. P.; Castro, G. R.

    2013-01-01

    The present study describes the incorporation of a complexing agent, dithiooxamide, into microcrystalline cellulose for use in the pre-concentration of Cu(II) and Cd(II) ions from aqueous samples. The FTIR spectrum of the adsorbent exhibited an absorption band in the region of 800 cm-1, which confirmed the binding of the silylating agent to the matrix. Elemental analysis indicated the amount of 0.150 mmol g-1 of the complexing agent. The adsorption data were fit to the modified Langmuir equation, and the maximum amount of metal species extracted from the solution, Ns, was determined to be 0.058 and 0.072 mmol g-1 for Cu(II) and Cd(II), respectively. The covering fraction ϕ, which was 0.39 and 0.48 for Cu(II) and Cd(II), respectively, was used to estimate a 1:2 (metal:ligand) ratio in the formed complex, and a binding model was proposed based on this information. The adsorbent was applied in the pre-concentration of natural water samples and exhibited an enrichment factor of approximately 50-fold for the species studied, which enabled its use in the analysis of trace metals in aqueous samples. The system was validated by the analysis of certified standard (1643e), and the adsorbent was stable for more than 20 cycles, thus enabling its safe reutilization.

  17. Structural, spectroscopic and redox properties of a mononuclear Co(II) thiolate complex--the reactivity toward S-alkylation: an experimental and theoretical study.

    PubMed

    Gennari, Marcello; Gerey, Bertrand; Hall, Nikita; Pécaut, Jacques; Vezin, Hervé; Collomb, Marie-Noëlle; Orio, Maylis; Duboc, Carole

    2012-10-28

    The structural, spectroscopic, redox properties and also the reactivity toward S-alkylation of a new mononuclear N2S2 dithiolate Co(II) complex [CoL] (1), with H(2)L = 2,2'-(2,2'-bipyridine-6,6'-diyl)bis(1,1-diphenylethanethiol), have been investigated. The X-ray structure of 1 has revealed an unusual distorted square planar geometry for a Co(II) ion within a thiolate environment. The X-band EPR spectrum of displays a rhombic S = 1/2 signal consistent with a low spin configuration for the d(7) Co(II) ion with a large g-anisotropy (g(x) = 2.94, g(y) = 2.32 and g(z) = 2.01). By pulsed EPR experiments (HYSCORE), two weak hyperfine couplings (hfc) of 3.2 and 2.2 MHz have been measured and attributed respectively to protons and nitrogen nuclei of the bipyridine unit. In addition, another hyperfine coupling (hfc) of 7.5 MHz has been attributed to the cobalt ion. DFT calculations have successfully reproduced the (59)Co and (14)N hfc parameters. However, multiconfigurational ab initio calculations were required to predict the g-tensor of 1. The cyclic voltammogram (CV) displays two one-electron metal based processes: a quasi-reversible Co(III)/Co(II) oxidation wave at E(1/2) = -0.5 V vs. Fc(+)/Fc and a quasi-reversible Co(II)/Co(I) reduction wave at E(1/2) = -1.7 V. 1 reacts with CH(3)I, generating the mono S-methylated complex, [CoL(Me)I] (1(Me)). The X-band EPR spectrum of 1(Me) displays a typical signal of a high spin (S = 3/2) Co(II) species. An optimized structure of 1(Me), calculated by DFT, is consistent with its EPR and UV-visible spectra. Time dependent density functional theory (TD-DFT) calculations attribute the most prominent features observed in the electronic absorption spectra of 1 and 1(Me). The singly occupied MO (SOMO) of 1 shows a notable delocalization of the unpaired electron over the metal (85%) and the ligand, especially over the sulphur atoms (10.5%), indicating a certain degree of covalency for the Co-S bonds. In 1(Me), for two of the three SOMOs

  18. Synthesis, spectral characterization and catalytic activity of Co(II) complexes of drugs: Crystal structure of Co(II)-trimethoprim complex

    NASA Astrophysics Data System (ADS)

    Madhupriya, Selvaraj; Elango, Kuppanagounder P.

    2014-01-01

    New Co(II) complexes with drugs such as trimethoprim (TMP), cimetidine (CTD), niacinamide (NAM) and ofloxacin (OFL) as ligands were synthesized. The complexes were characterized by analytical analysis, various spectral techniques such as FT-IR, UV-Vis, magnetic measurements and molar conductivity. The magnetic susceptibility results coupled with the electronic spectra suggested a tetrahedral geometry for the complexes. The coordination mode of trimethoprim ligand and geometry of the complex were confirmed by single crystal X-ray studies. In this complex the metal ion possesses a tetrahedral geometry with two nitrogen atom from two TMP ligands and two chloride ions coordinated to it. The catalytic activity of the complexes in aryl-aryl coupling reaction was screened and the results indicated that among the four complexes [Co(OFL)Cl(H2O)] exhibited excellent catalytic activity.

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

    NASA Astrophysics Data System (ADS)

    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.

  20. Synthesis, characterization, equilibrium study and biological activity of Cu(II), Ni(II) and Co(II) complexes of polydentate Schiff base ligand

    NASA Astrophysics Data System (ADS)

    El-Sherif, Ahmed A.; Shehata, Mohamed R.; Shoukry, Mohamed M.; Barakat, Mohammad H.

    2012-10-01

    Schiff base ligand, 1,4-bis[(2-hydroxybenzaldehyde)propyl]piperazine (BHPP), and its Cu(II), Ni(II) and Co(II) metal complexes were synthesized and characterized by elemental analysis, magnetic susceptibility, molar conductance and spectral (IR and UV-vis) studies. The ground state of BHPP ligand was investigated using the BUILDER module of MOE. Metal complexes are formed in the 1:1 (M:L) ratio as found from the elemental analysis and found to have the general formula [ML]·nH2O, where M = Co(II), Ni(II) and Cu(II), L = BHPP. In all the studied complexes, the (BHPP) ligand behaves as a hexadentate divalent anion with coordination involving the two azomethine nitrogen's, the two nitrogen atoms of piperazine ring and the two deprotonated phenolic OH-groups. The magnetic and spectral data indicates octahedral geometry of metal(II) complexes. The ligand and their metal chelates have been screened for their antimicrobial activities using the disc diffusion method against the selected bacteria and fungi. They were found to be more active against Gram-positive than Gram-negative bacteria. Protonation constants of (BHPP) ligand and stability constants of its Cu2+, Co2+ and Ni2+ complexes were determined by potentiometric titration method in 50% DMSO-water solution at ionic strength of 0.1 M sodium nitrate. It has been observed that the protonated Schiff base ligand (BHPP) have four protonation constants. The divalent metal ions Cu2+, Ni2+ and Co2+ form 1:1 complexes.

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

    PubMed

    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

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

    NASA Astrophysics Data System (ADS)

    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.

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

    SciTech Connect

    Liu, Dong-Sheng; College of Chemistry and Chemical Engineering, Fuzhou University, Fuzhou, Fujian 350108 ; Sui, Yan; Chen, Weng-Tong; Huang, Jian-Gen; Chen, Jian-Zhong; Huang, Chang-Cang

    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.

  4. A solid phase extraction procedure for the determination of Cd(II) and Pb(II) ions in food and water samples by flame atomic absorption spectrometry.

    PubMed

    Daşbaşı, Teslima; Saçmacı, Şerife; Ülgen, Ahmet; Kartal, Şenol

    2015-05-01

    A relatively rapid, accurate and precise solid phase extraction method is presented for the determination of cadmium(II) and lead(II) in various food and water samples. Quantitation is carried out by flame atomic absorption spectrometry (FAAS). The method is based on the retention of the trace metal ions on Dowex Marathon C, a strong acid cation exchange resin. Some important parameters affecting the analytical performance of the method such as pH, flow rate and volume of the sample solution; type, concentration, volume, flow rate of the eluent; and matrix effects on the retention of the metal ions were investigated. Common coexisting ions did not interfere on the separation and determination of the analytes. The detection limits (3 σb) for Cd(II) and Pb(II) were found as 0.13 and 0.18 μg L(-1), respectively, while the limit of quantification values (10 σb) were computed as 0.43 and 0.60 μg L(-1) for the same sequence of the analytes. The precision (as relative standard deviation was lower than 4% at 5 μg L(-1) Cd(II) and 10 μg L(-1) Pb(II) levels, and the preconcentration factor was found to be 250. The accuracy of the proposed procedure was verified by analysing the certified reference materials, SPS-WW2 Batch 108 wastewater level 2 and INCT-TL-1 tea leaves, with the satisfactory results. In addition, for the accuracy of the method the recovery studies (⩾ 95%) were carried out. The method was applied to the determination of the analytes in the various natural waters (lake water, tap water, waste water with boric acid, waste water with H2SO4) and food samples (pomegranate flower, organic pear, radish leaf, lamb meat, etc.), and good results were obtained. While the food samples almost do not contain cadmium, they have included lead at low levels of 0.13-1.12 μg g(-1). PMID:25529724

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

    USGS Publications Warehouse

    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

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

    PubMed

    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

  7. Synthesis of some novel CoII and CoIII complexes by tribochemical reactions using KI with some derivatives of thiosemicarbazide complexes derived from Girard's T and P.

    PubMed

    Al-Ashqar, S M; Mostafa, M M

    2008-12-15

    The starting Co(II) complexes of the general formulae, [Co(L1)2]Cl4.4H2O, [Co(L1)Cl2]Cl (L1=N-([(allyl amino)thioxomethyl]hydrazinocarbonylmethyl) trimethylammonium chloride; ATHTC), [Co(L2)Cl]Cl.2H2O.(1/2)EtOH (L2=N-([(ethylamine)thioxomethyl]hydrazinocarbonylmethyl)trimethylammonium chloride; ETHTC) and [Co(L3)Cl2]Cl.2EtOH (L3=N-([(phenylaminomethyl)thioxomethyl]hydrazinocarbonylmethyl)pyridinium chloride; PTHPC), were synthesized by the conventional chemical methods. Tribochemical reactions of the above mentioned CoII complexes obtained by chemical methods with KI afford novel CoII and CoIII complexes with the general formulae [Co(L1')I3.(1/2)EtOH]I, [Co2(L1')I4]I.EtOH, [Co(L2')I2.(3/2)EtOH]I, [Co2(L2')I4(OEt)2(H2O)2]I.(1/2)EtOH and [Co(L3')I2.H2O]I.3H2O. The ligands (L1', L2' and L3') formed by tribochemical reactions are quite similar to these of L1, L2 and L3, except that the ionizable chloride ions in case of L1, L2 and L3 are substituted by iodide ions in (L1', L2' and L3'). The isolated solid CoII and CoIII complexes have been characterized by elemental analyses, conductivities, spectral (IR, UV-vis, 1H NMR) and magnetic measurements. The IR spectra of the starting CoII complexes indicate that both L1 and L3 behave in bidentate manner coordinating via the carbonyl oxygen and NH2 groups, but L2 behaves as a tridentate fashion coordinating via the carbonyl oxygen, azomethine (C=N2) and SH groups with displacement of a hydrogen atom from the latter group. On the other hand, the IR spectra of the iodide CoII and CoIII complexes, synthesized by tribochemical reactions, suggest that L1' behaves only in a bidentate fashion via NH1 and CS groups. L2' behaves either as bidentate ligand through NH1 and CSH with deprotonation from the latter group or as a tetradentate ligand towards two cobalt ions via OH, C=N2, C=N1 and C-SH with displacement of a hydrogen atom from the latter group. Moreover, L3' behaves in a tetradentate ligand, toward two cobalt ions via the

  8. Adsorption of Pb(II), Cr(III), Cu(II), Cd(II) and Ni(II) onto a vanadium mine tailing from aqueous solution.

    PubMed

    Shi, Taihong; Jia, Shiguo; Chen, Ying; Wen, Yinghong; Du, Changming; Guo, Huilin; Wang, Zhuochao

    2009-09-30

    The adsorption of heavy metal cations Pb(II), Cr(III), Cu(II), Cd(II) and Ni(II) from aqueous solution by a mine tailing which mainly contains muscovite was investigated. The property of the mineral was investigated by using SEM, FT-IR, XRD and BET analysis. pH(pzc) was measured by an titration technique to give a value of 5.4+/-0.1. Kinetics experiments indicated that the processes can be simulated by pseudo-second-order model. Total adsorption amounts of the heavy metal increased, while the adsorption density decreased when the solid-to-liquid ratio (S/L) increased. Grain size did not affect the adsorption capacity significantly. The resulting isotherms can be described by Frendlich relationship. And the maximum adsorption capacity (molar basis) followed the order of Cr(III)>Pb(II)>Cu(II)>Ni(II)>Cd(II). Thermodynamic analysis showed that the adsorption processed were endothermic and may be chemical in nature with positive DeltaH(0). The positive DeltaS(0) suggested that dissociative processed were involved. Small positive DeltaG(0) suggested that the adsorption processes required a small amount of energy. Adsorption processes were slightly affected by electrolyte ion concentration but strongly dependent on pH value. The most possible mechanism of the adsorption processes involve the inner-sphere-complexions by the aluminol or silanol groups on the surface of the mineral. PMID:19427115

  9. Synthesis, structure and characterization of two new Zn(II) and Cd(II) complexes with the bidentate ligand 2-[(2-aminoethyl)amino]ethanaminium (AEEA)

    NASA Astrophysics Data System (ADS)

    Nbili, Wijdene; Zeller, Matthias; Lefebvre, Frédéric; Ben Nasr, Cherif

    2015-04-01

    Two new Zn(II) and Cd(II) complexes with the bidentate ligand 2-[(2-aminoethyl)amino]ethanaminium (AEEA), [ZnCl2(C4H14N3)]ClO4 (1) and [CdCl2(C4H14N3)]ClO4 (2), have been prepared and were characterized by single crystal X-ray diffraction, elemental analysis, CP-MAS-NMR and IR spectroscopies. The basic coordination patterns of the AEEA coordinated metal cations is highly distorted tetrahedral in (1) and distorted octahedral in (2). The crystal structure of (1) is characterized by ZnCl2N2 tetrahedra interconnected via N-H⋯Cl hydrogen bonds to form layers parallel to the (b, a + c) plane. In (2), the CdN2Cl4 entities form polymeric chains of edge-sharing octahedra extending along the a-axis direction. The crystal structures are stabilized by sets of hydrogen bonds, some of which are bi or trifurcated. The 13C and 15N CP-MAS NMR spectra are discussed and the vibrational absorption bands were identified by infrared spectroscopy.

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

    PubMed

    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

  11. Photo-transformation of pedogenic humic acid and consequences for Cd(II), Cu(II) and Pb(II) speciation and bioavailability to green microalga.

    PubMed

    Worms, Isabelle A M; Adenmatten, David; Miéville, Pascal; Traber, Jacqueline; Slaveykova, Vera I

    2015-11-01

    Humic substances (HS) play key role in toxic metal binding and protecting aquatic microorganisms from metal-induced stress. Any environmental changes that could alter HS concentration and reactivity can be expected to modify metal complexation and thus affect metal speciation and bioavailability to microalgae. The present study explores the influence of increased solar irradiance on the chemical structures and molecular weight of Elliott soil humic acid (EHA) and the associated consequences for Cd(II), Cu(II) and Pb(II) complexation and intracellular metal content in microalga. The results demonstrate that high radiance doses induce an oxidation of EHA with a formation of low molecular weight acids, an increase of -OH and -COOH group abundance, and a drop in EHA hydrodynamic size and molecular weight. The photo-induced structural changes are accompanied with a release of metal from M-EHA complexes and narrowing their size distribution, which in turn results in an increase of the intracellular Cd, Cu and Pb contents in microalga Chlamydomonas reinhardtii in agreement with the measured free metal ions concentrations. PMID:25563161

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

    NASA Astrophysics Data System (ADS)

    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.

  13. Determination of the complexation constants of Pb(II) and Cd(II) with thymol blue using spectrophotometry, SQUAD and the HSAB principle.

    PubMed

    Balderas-Hernández, P; Rojas-Hernández, A; Galván, M; Romo, M Romero; Palomar-Pardavé, M; Ramírez-Silva, M T

    2007-01-01

    This paper presents the results concerning the determination of the formation constants of the complexes between thymol blue, TB, and the metal ions Pb(II) or Cd(II). The experimental procedure was carried out in the presence of a nitrogen atmosphere at 25 degrees C. The spectrophotometry data obtained were processed through the software SQUAD to calculate the complexation constants of the metal-indicator and to establish an adequate base of the models which considered the structure of the indicator, and the actual metal species in the aqueous solutions. For the Pb(II)-TB-H2O system the logK value calculated for the PbTB complex was 5.591+/-0.057 while for the Cd(II)-TB-H2O system, the logK value of the CdTB complex was 5.099+/-0.008. Also, supporting theoretical chemistry results on the chemical hardness of TB molecule were performed to enable establishment of a relative prediction scale of the TB complexation constants ranking in the framework of the Principle of Hard and Soft Acids and Bases or HSAB Principle. PMID:16829173

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

    PubMed

    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. PMID:25311520

  15. Synthesis and characterization of an azo dibenzoic acid Schiff base and its Ni(II), Pb(II), Zn(II) and Cd(II) complexes

    NASA Astrophysics Data System (ADS)

    Kakanejadifard, Ali; Esna-ashari, Fatemeh; Hashemi, Payman; Zabardasti, Abedin

    2013-04-01

    The new Schiff base 4,4'-(1E,1'E)-(3,3'-(1E,1'E)-(pyridine-2,6-diylbis(azan-1-yl-1-ylid ene))bis(methan-1-yl-1-ylidene)bis(4-hydroxy-3,1-phenylene))bis(diazene-2,1-diyl)dibenzoic acid (1) was prepared from the condensation reaction of 2,6-diaminopyridine with 4-((3-formyl-4-hydroxyphenyl)diazenyl)benzoic acid in methanol. The compound 1 is potentially an N, O multidentate chelating ligand which could form stable complexes with metal ions in 1:1 up to 1:3 mol ratio of metal to ligand. The 1:1 complexes of Schiff base 1 with Ni(II), Pb(II), Zn(II) and Cd(II) have been synthesized by its condensation reaction with appropriate salts of metal ions. Structures of Schiff base (1) as well as its complexes with abovementioned metal ions were characterized by elemental analysis, mass, IR, UV-vis., 1H and 13С NMR spectroscopy.

  16. Determination of the complexation constants of Pb(II) and Cd(II) with thymol blue using spectrophotometry, SQUAD and the HSAB principle

    NASA Astrophysics Data System (ADS)

    Balderas-Hernández, P.; Rojas-Hernández, A.; Galván, M.; Romo, M. Romero; Palomar-Pardavé, M.; Ramírez-Silva, M. T.

    2007-01-01

    This paper presents the results concerning the determination of the formation constants of the complexes between thymol blue, TB, and the metal ions Pb(II) or Cd(II). The experimental procedure was carried out in the presence of a nitrogen atmosphere at 25 °C. The spectrophotometry data obtained were processed through the software SQUAD to calculate the complexation constants of the metal-indicator and to establish an adequate base of the models which considered the structure of the indicator, and the actual metal species in the aqueous solutions. For the Pb(II)-TB-H 2O system the log K value calculated for the PbTB complex was 5.591 ± 0.057 while for the Cd(II)-TB-H 2O system, the log K value of the CdTB complex was 5.099 ± 0.008. Also, supporting theoretical chemistry results on the chemical hardness of TB molecule were performed to enable establishment of a relative prediction scale of the TB complexation constants ranking in the framework of the Principle of Hard and Soft Acids and Bases or HSAB Principle.

  17. Comparison of Cd(II), Cu(II), and Pb(II) biouptake by green algae in the presence of humic acid.

    PubMed

    Lamelas, Cristina; Slaveykova, Vera I

    2007-06-01

    The present study examines the role of humic acid, as a representative of dissolved organic matter, in Cd(II), Cu(II), and Pb(II) speciation and biouptake by green microalgae. Cellular and intracellular metal fractions were compared in the presence of citric and humic acids. The results demonstrated that Cd and Cu uptake in the presence of 10 mg L(-1) humic acid was consistent with that predicted from measured free metal concentrations, while Pb biouptake was higher. By comparing Cd, Cu, and Pb cellular concentrations in the absence and presence of humic acid, it was found that the influence of the increased negative algal surface charge, resulting from humic acid adsorption, on cellular metal was negligible. Moreover, the experimental results for all three metals were in good agreement with the ternary complex hypothesis. Given that metal has much higher affinity with algal sites than humic acid adsorbed to algae, the contribution of the ternary complex to metal bioavailability was negligible in the case of Cd (II) and Cu (II). In contrast, the ternary complex contributed to over 90% of total cellular metal for Pb(II), due to the comparable affinity of Pb to algal sites in comparison with humic acid adsorbed to algae. Therefore, the extension of the biotic ligand model by including the formation of the ternary complex between the metal, humic acid, and algal surface would help to avoid underestimation of Pb biouptake in the presence of humic substances by green algae Chlorella kesslerii. PMID:17612207

  18. 4,4‧-Bipyridine-aided synthesis and characterization of Zn(II) and Cd(II) 2-sulfoterephthalate complexes

    NASA Astrophysics Data System (ADS)

    Xiao, Shan-Shan; Li, Xin-Xin; Zheng, Xiang-Jun; Jia, Tian-Jing; Jin, Lin-Pei

    2013-09-01

    Six d10 complexes, [Zn1.5(stp)(bpy)0.5(H2O)2]·0.5H2O (1), Cd1.5(stp)(bpy)0.5(H2O)2 (2), [Cd1.5(stp)(bpy)(H2O)]·H2O (3), [Zn0.5(bpy)0.5(H2O)2][Zn(stp)(bpy)(H2O)]·0.5H2O (4), Cd3(stp)2(bpy)3(H2O)3 (5), Hbpy·[Zn0.5(bpy)(H2O)2][Zn0.5(stp)(H2O)]·H2O (6) based on 2-sulfoterephthalate (stp3-) and 4,4'-bipyridine (bpy) have been synthesized under hydro/solvo-thermal conditions and structurally characterized. Complex 1 exhibits a three-fold interpenetrated 3D porous architecture. Complexes 2 and 3 possess helices with different chirality arranging alternately. 4 and 6 are addition compounds, which compose of complex cation and complex anion. Complex 5 features a 3D layer-pillar framework in which a (4, 4) grid layer is constructed by stp3- ligands and Cd(II) ions, and the layers are further connected by bpy pillars. The solid-state luminescent properties of the coordination polymers have also been investigated.

  19. Complexation of trivalent cations (Al(III), Cr(III), Fe(III)) with two phosphonic acids in the pH range of fresh waters.

    PubMed

    Lacour, S; Deluchat, V; Bollinger, J C; Bernard Serpaud

    1998-08-01

    The complex formation constants of two phosphonic acids, HEDP and ATMP, with three trivalent metallic cations, Al(III), Cr(III) and Fe(III), have been determined by acid-base titration at 25 degrees C and constant ionic strength (0.1 mol l(-1), KNO(3)), using Martell and Motekaitis' computer programs. Species distribution curves showed that all three cations are in complex form in the pH range of fresh waters (5-9). The study of different cation/ligand ratios proved that both ligands mainly form anionic soluble complexes for systems having an excess of ligand-as protonated and unprotonated forms and especially ternary complexes with HEDP. For higher metal concentrations (excess of cation), weakly soluble species of HEDP and ATMP were formed with Al(III) and Cr(III). Two insoluble complexes with ATMP have been identified by SEM/EDAX as AlH(3)X((s)) and Cr(2)X((s)). Regarding Fe(III) species, Fe(OH)(3(s)) precipitate seems to predominate in solution. PMID:18967224

  20. Synthesis, spectroscopic, thermal and anticancer studies of metal-antibiotic chelations: Ca(II), Fe(III), Pd(II) and Au(III) chloramphenicol complexes

    NASA Astrophysics Data System (ADS)

    Al-Khodir, Fatima A. I.; Refat, Moamen S.

    2016-09-01

    Four Ca(II), Fe(III), Pd(II) and Au(III) complexes of chloramphenicol drug have been synthesized and well characterized using elemental analyses, (infrared, electronic, and 1H-NMR) spectra, magnetic susceptibility measurement, and thermal analyses. Infrared spectral data show that the chloramphenicol drug coordinated to Ca(II), Pd(II) and Au(III) metal ions through two hydroxyl groups with 1:1 or 1:2 M ratios, but Fe(III) ions chelated towards chloramphenicol drug via the oxygen and nitrogen atoms of amide group with 1:2 ratio based on presence of keto↔enol form. The X-ray powder diffraction (XRD), scanning electron microscope (SEM) and transmission electron microscopy (TEM) techniques were used to identify the nano-size particles of both iron(III) and gold(III) chloramphenicol complexes. The antimicrobial assessments of the chloramphenicol complexes were scanned and collected the results against of some kind of bacteria and fungi. The cytotoxic activity of the gold(III) complex was tested against the human colon carcinoma (HCT-116) and human hepatocellular carcinoma (HepG-2) tumor cell lines.

  1. Fe(III) Reduction and U(VI) Immobilization by Paenibacillus sp. Strain 300A, Isolated from Hanford 300A Subsurface Sediments

    PubMed Central

    Ahmed, Bulbul; Cao, Bin; McLean, Jeffrey S.; Ica, Tuba; Dohnalkova, Alice; Istanbullu, Ozlem; Paksoy, Akin; Fredrickson, Jim K.

    2012-01-01

    A facultative iron-reducing [Fe(III)-reducing] Paenibacillus sp. strain was isolated from Hanford 300A subsurface sediment biofilms that was capable of reducing soluble Fe(III) complexes [Fe(III)-nitrilotriacetic acid and Fe(III)-citrate] but unable to reduce poorly crystalline ferrihydrite (Fh). However, Paenibacillus sp. 300A was capable of reducing Fh in the presence of low concentrations (2 μM) of either of the electron transfer mediators (ETMs) flavin mononucleotide (FMN) or anthraquinone-2,6-disulfonate (AQDS). Maximum initial Fh reduction rates were observed at catalytic concentrations (<10 μM) of either FMN or AQDS. Higher FMN concentrations inhibited Fh reduction, while increased AQDS concentrations did not. We also found that Paenibacillus sp. 300A could reduce Fh in the presence of natural ETMs from Hanford 300A subsurface sediments. In the absence of ETMs, Paenibacillus sp. 300A was capable of immobilizing U(VI) through both reduction and adsorption. The relative contributions of adsorption and microbial reduction to U(VI) removal from the aqueous phase were ∼7:3 in PIPES [piperazine-N,N′-bis(2-ethanesulfonic acid)] and ∼1:4 in bicarbonate buffer. Our study demonstrated that Paenibacillus sp. 300A catalyzes Fe(III) reduction and U(VI) immobilization and that these reactions benefit from externally added or naturally existing ETMs in 300A subsurface sediments. PMID:22961903

  2. Fe(III) reduction and U(VI) immobilization by Paenibacillus sp. strain 300A, isolated from Hanford 300A subsurface sediments.

    PubMed

    Ahmed, Bulbul; Cao, Bin; McLean, Jeffrey S; Ica, Tuba; Dohnalkova, Alice; Istanbullu, Ozlem; Paksoy, Akin; Fredrickson, Jim K; Beyenal, Haluk

    2012-11-01

    A facultative iron-reducing [Fe(III)-reducing] Paenibacillus sp. strain was isolated from Hanford 300A subsurface sediment biofilms that was capable of reducing soluble Fe(III) complexes [Fe(III)-nitrilotriacetic acid and Fe(III)-citrate] but unable to reduce poorly crystalline ferrihydrite (Fh). However, Paenibacillus sp. 300A was capable of reducing Fh in the presence of low concentrations (2 μM) of either of the electron transfer mediators (ETMs) flavin mononucleotide (FMN) or anthraquinone-2,6-disulfonate (AQDS). Maximum initial Fh reduction rates were observed at catalytic concentrations (<10 μM) of either FMN or AQDS. Higher FMN concentrations inhibited Fh reduction, while increased AQDS concentrations did not. We also found that Paenibacillus sp. 300A could reduce Fh in the presence of natural ETMs from Hanford 300A subsurface sediments. In the absence of ETMs, Paenibacillus sp. 300A was capable of immobilizing U(VI) through both reduction and adsorption. The relative contributions of adsorption and microbial reduction to U(VI) removal from the aqueous phase were ∼7:3 in PIPES [piperazine-N,N'-bis(2-ethanesulfonic acid)] and ∼1:4 in bicarbonate buffer. Our study demonstrated that Paenibacillus sp. 300A catalyzes Fe(III) reduction and U(VI) immobilization and that these reactions benefit from externally added or naturally existing ETMs in 300A subsurface sediments. PMID:22961903

  3. New calcareous soil-alginate composites for efficient uptake of Fe(III), Mn(II) and As(V) from water.

    PubMed

    El-Sherbiny, Ibrahim M; Abdel-Hamid, Mohammed I; Rashad, Mohamed; Ali, Abdelnaser S M; Azab, Yehia A

    2013-07-25

    In the present study, various grades of sodium alginates were extracted from different brown macro-algae and their characteristics were investigated using FTIR, UV-vis and EA. The alginates were used in combination with different proportions of calcareous soil to develop new composite microparticles as potential sorbents for efficient uptake of Fe(III), Mn(II) and As(V) from water. Under the investigated conditions (1g of composite equilibrated in 100ml of standard metal ion solution), the composites have removed almost 100% of Fe(III) in the concentration range of 0.5-16.0 mg l(-1). Soil, alginate and composites exhibited the highest removal (about 89%) of Mn(II) at 0.5 mg l(-1). Reasonable removal efficiency (50-60%) was recorded at 0.5 mg l(-1) of As(V) whereas, increasing the initial As(V) concentration resulted in marked decrease in removal efficiency. The collected equilibrium data were also fitted to both Langmuir and Freundlich isotherms for all the developed composites. PMID:23768586

  4. K 3 Fe(CN) 6 under External Pressure: Dimerization of CN Coupled with Electron Transfer to Fe(III)

    SciTech Connect

    Li, Kuo; Zheng, Haiyan; Wang, Lijuan; Tulk, Christopher A.; Molaison, Jamie J.; Feygenson, Mikhail; Yang, Wenge; Guthrie, Malcolm; Mao, Hokwang

    2015-09-14

    The addition polymerization of charged monomers like C≡C2– and C≡N– is scarcely seen at ambient conditions but can progress under external pressure with their conductivity significantly enhanced, which expands the research field of polymer science to inorganic salts. Moreover, the reaction pressures of transition metal cyanides like Prussian blue and K3Fe(CN)6 are much lower than that of alkali cyanides. To figure out the effect of the transition metal on the reaction, the crystal structure and electronic structure of K3Fe(CN)6 under external pressure are investigated by in situ neutron diffraction, in situ X-ray absorption fine structure (XAFS), and neutron pair distribution functions (PDF) up to ~15 GPa. The cyanide anions react following a sequence of approaching–bonding–stabilizing. The Fe(III) brings the cyanides closer which makes the bonding progress at a low pressure (2–4 GPa). At ~8 GPa, an electron transfers from the CN to Fe(III), reduces the charge density on cyanide ions, and stabilizes the reaction product of cyanide. Finally, from this study we can conclude that bringing the monomers closer and reducing their charge density are two effective routes to decrease the reaction pressure, which is important for designing novel pressure induced conductor and excellent electrode materials.

  5. K 3 Fe(CN) 6 under External Pressure: Dimerization of CN – Coupled with Electron Transfer to Fe(III)

    DOE PAGESBeta

    Li, Kuo; Zheng, Haiyan; Wang, Lijuan; Tulk, Christopher A.; Molaison, Jamie J.; Feygenson, Mikhail; Yang, Wenge; Guthrie, Malcolm; Mao, Hokwang

    2015-09-14

    The addition polymerization of charged monomers like C≡C2– and C≡N– is scarcely seen at ambient conditions but can progress under external pressure with their conductivity significantly enhanced, which expands the research field of polymer science to inorganic salts. Moreover, the reaction pressures of transition metal cyanides like Prussian blue and K3Fe(CN)6 are much lower than that of alkali cyanides. To figure out the effect of the transition metal on the reaction, the crystal structure and electronic structure of K3Fe(CN)6 under external pressure are investigated by in situ neutron diffraction, in situ X-ray absorption fine structure (XAFS), and neutron pair distributionmore » functions (PDF) up to ~15 GPa. The cyanide anions react following a sequence of approaching–bonding–stabilizing. The Fe(III) brings the cyanides closer which makes the bonding progress at a low pressure (2–4 GPa). At ~8 GPa, an electron transfers from the CN to Fe(III), reduces the charge density on cyanide ions, and stabilizes the reaction product of cyanide. Finally, from this study we can conclude that bringing the monomers closer and reducing their charge density are two effective routes to decrease the reaction pressure, which is important for designing novel pressure induced conductor and excellent electrode materials.« less

  6. Fe(III) Reduction and U(VI) Immobilization by Paenibacillus sp. Strain 300A, Isolated from Hanford 300A Subsurface Sediments

    SciTech Connect

    Ahmed, B.; Cao, B.; McLean, Jeffrey S.; Ica, Tuba; Dohnalkova, Alice; Istanbullu, Ozlem; Paksoy, Akin; Fredrickson, Jim K.; Beyenal, Haluk

    2012-11-07

    A facultative iron-reducing (Fe(III)-reducing) Paenibacillus sp. strain was isolated from Hanford 300A subsurface sediment biofilms that was capable of reducing soluble Fe(III) complexes (Fe(III)-NTA and Fe(III)-citrate) but unable to reduce poorly crystalline ferrihydrite (Fh). However, Paenibacillus sp. 300A was capable of reducing Fh in the presence of low concentrations (2 µM) of either of electron transfer mediators (ETMs) flavin mononucleotide (FMN) or anthraquinone-2,6-disulfonate (AQDS). Maximum initial Fh reduction rates were observed at catalytic concentrations (<10 µM) of either FMN or AQDS. Higher FMN concentrations inhibited Fh reduction, while increased AQDS concentrations did not. We found that Paenibacillus sp. 300A also could reduce Fh in the presence of natural ETMs from Hanford 300A subsurface sediments. In the absence of ETMs, Paenibacillus sp. 300A was capable of immobilizing U(VI) through both reduction and adsorption. The relative contributions of adsorption and microbial reduction to U(VI) removal from the aqueous phase were ~7:3 in PIPES and ~1:4 in bicarbonate buffer. Our study demonstrated that Paenibacillus sp. 300A catalyzes Fe(III) reduction and U(VI) immobilization and that these reactions benefit from externally added or naturally existing ETMs in 300A subsurface sediments.

  7. Chemometrics-assisted spectrophotometric methods for simultaneous determination and complexation study of Fe(III), Al(III) and V(V) with morin in micellar media.

    PubMed

    Ghavami, Raoof; Najafi, Amir; Hemmateenejad, Bahram

    2008-09-01

    Evolutionary factor analysis (EFA) and rank annihilation factor analysis (RAFA) were applied to resolve the two-way equilibrium spectrophotometric data belonging to the complexes of Fe(III), Al(III) and V(V) with morin (3,5,7,20,40-penta hydroxy flavone) as chelating agent in triton X-100 micellar media. Then, partial least square regression combined with genetic algorithm for wavelength selection (GA-PLS) was used for simultaneous determination of the metal ions. The parameters controlling behavior of the system were investigated and optimum conditions were selected. The predictive abilities of partial least squares regression (PLS) and genetic algorithm-partial least squares regression (GA-PLS) were examined in simultaneous determination of ternary mixtures of metal ions over the concentration range of 17.0-170.0ngml(-1), 25.0-180.0ngml(-1) and 40.0-325.0ngml(-1) for Fe(III), Al(III) and V(V), respectively. The relative standard errors for prediction of the ions in synthetic mixtures were lower than 5% and the mean recoveries in the tap water spiked samples were 104.2 and 101.7% for PLS and GA-PLS, respectively. PMID:18055249

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

    SciTech Connect

    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.

  9. Effect of Fe(III) on 1,1,2,2-tetrachloroethane degradation and vinyl chloride accumulation in wetland sediments of the Aberdeen proving ground

    USGS Publications Warehouse

    Jones, E.J.P.; Voytek, M.A.; Lorah, M.M.

    2004-01-01

    1,1,2,2-Tetrachloroethane (TeCA) contaminated groundwater at the Aberdeen Proving Ground discharges through an anaerobic wetland in West Branch Canal Creek, MD, where dechlorination occurred. Two microbially mediated pathways, dichloroelimination and hydrogenolysis, account for most of the TeCA degradation at this site. The dichloroelimination pathways led to the formation of vinyl chloride (VC), a recalcitrant carcinogen of great concern. The effect of adding Fe(III) to TeCA-amended microcosms of wetland sediment was studied. Differences were identified in the TeCA degradation pathway between microcosms treated with amorphous ferric oxyhydroxide (AFO-treated) and untreated (no AFO) microcosms. TeCA degradation was accompanied by a lower accumulation of VC in AFO-treated microcosms than no AFO microcosms. The microcosm incubations and subsequent experiments with the microcosm materials showed that AFO treatment resulted in lower production of VC by shifting TeCA degradation from dichloroelimination pathways to production of a greater proportion of chlorinated ethane products, and decreasing the microbial capability to produce VC from 1,2-dichloroethylene. VC degradation was not stimulated in the presence of Fe(III). Rather, VC degradation occurred readily under methanogenic conditions and was inhibited under Fe(III)-reducing conditions.

  10. Synthesis, spectral characterization, thermal analysis, molecular modeling and antimicrobial activity of new potentially N2O2 azo-dye Schiff base complexes

    NASA Astrophysics Data System (ADS)

    Alaghaz, Abdel-Nasser M. A.; Ammar, Yousry A.; Bayoumi, Hoda A.; Aldhlmani, Sharah A.

    2014-09-01

    The azo-dye Schiff's base of N2O2 dibasic ligand, H2L [N,N‧-bis(5-(4-sulfanilamidophenylazosalicylidene)ethylenediamine] was prepared by the condensation of ethylenediamine with [5-(4-sulfanilamidophenylazo-salicylaldehyde] in ethanol. New complexes of with metal ions Cu(II), Ni(II), Co(II), Mn(II), Zn(II), Cd(II), Pt(IV), Fe(III) and Cr(III) are synthesized. Elemental, spectroscopic and thermal analyses as well as conductivity and magnetic susceptibility measurements are used to elucidate the structure of the newly prepared metal complexes. The azo-dye Schiff's base behaves as a di-negative N2O2 tetradentate ligand. The metal complexes exhibited square planar, tetrahedral and octahedral geometrical arrangements, the molar conductivity data indicates that all complexes are neutral. The thermogravimetry (TG) and differential thermoanalysis (DTA) of the Cu(II), Mn(II), Cr(III) and Co(II) complexes were carried out in the range of 30-800 °C. The complexes were decomposed in one and two stages of the Cu(II), Mn(II), Cr(III) and Co(II) complexes, respectively. Also, decomposition of the synthesized complexes is related to the Schiff's base characteristics. The thermal decomposition of the studied reactions was first order. The kinetic parameters for the decomposition steps in Cu(II), Mn(II), Cr(III) and Co(II) complexes thermograms have been calculated using Broido's method. In molecular modeling the geometries of azo-dye Schiff base ligand H2L and its metal(II/III/IV) complexes were fully optimized with respect to the energy using the 6-31G basis set. Antimicrobial activities of the azo-dye Schiff's base ligand and its corresponding metal complexes were screened against various organisms. The azo-dye Schiff's base ligand and some of its complexes were found to be biologically inactive.

  11. Molecular-level modes of As binding to Fe(III) (oxyhydr)oxides precipitated by the anaerobic nitrate-reducing Fe(II)-oxidizing Acidovorax sp. strain BoFeN1

    NASA Astrophysics Data System (ADS)

    Hohmann, Claudia; Morin, Guillaume; Ona-Nguema, Georges; Guigner, Jean-Michel; Brown, Gordon E.; Kappler, Andreas

    2011-09-01

    Sorption of contaminants such as arsenic (As) to natural Fe(III) (oxyhydr)oxides is very common and has been demonstrated to occur during abiotic and biotic Fe(II) oxidation. The molecular mechanism of adsorption- and co-precipitation of As has been studied extensively for synthetic Fe(III) (oxyhydr)oxide minerals but is less documented for biogenic ones. In the present study, we used Fe and As K-edge X-ray Absorption Near Edge Structure (XANES), extended X-ray Absorption Fine Structure (EXAFS) spectroscopy, Mössbauer spectroscopy, XRD, and TEM in order to investigate the interactions of As(V) and As(III) with biogenic Fe(III) (oxyhydr)oxide minerals formed by the nitrate-reducing Fe(II)-oxidizing bacterium Acidovorax sp. strain BoFeN1. The present results show the As immobilization potential of strain BoFeN1 as well as the influence of As(III) and As(V) on biogenic Fe(III) (oxyhydr)oxide formation. In the absence of As, and at low As loading (As:Fe ≤ 0.008 mol/mol), goethite (Gt) formed exclusively. In contrast, at higher As/Fe ratios (As:Fe = 0.020-0.067), a ferrihydrite (Fh) phase also formed, and its relative amount systematically increased with increasing As:Fe ratio, this effect being stronger for As(V) than for As(III). Therefore, we conclude that the presence of As influences the type of biogenic Fe(III) (oxyhydr)oxide minerals formed during microbial Fe(II) oxidation. Arsenic-K-edge EXAFS analysis of biogenic As-Fe-mineral co-precipitates indicates that both As(V) and As(III) form inner-sphere surface complexes at the surface of the biogenic Fe(III) (oxyhydr)oxides. Differences observed between As-surface complexes in BoFeN1-produced Fe(III) (oxyhydr)oxide samples and in abiotic model compounds suggest that associated organic exopolymers in our biogenic samples may compete with As oxoanions for sorption on Fe(III) (oxyhydr)oxides surfaces. In addition HRTEM-EDXS analysis suggests that As(V) preferentially binds to poorly crystalline phases, such as

  12. On the Importance of Noncovalent Carbon-Bonding Interactions in the Stabilization of a 1D Co(II) Polymeric Chain as a Precursor of a Novel 2D Coordination Polymer.

    PubMed

    Pal, Pampi; Konar, Saugata; Lama, Prem; Das, Kinsuk; Bauzá, Antonio; Frontera, Antonio; Mukhopadhyay, Subrata

    2016-07-14

    A new cobalt(II) coordination polymer 2 with μ1,5 dicyanamide (dca) and a bidentate ligand 3,5-dimethyl-1-(2'-pyridyl)pyrazole (pypz) is prepared in a stepwise manner using the newly synthesized one-dimensional linear Co(II) coordination polymer 1 as a precursor. The structural and thermal characterizations elucidate that the more stable complex 2 shows a two-dimensional layer structural feature. Here, Co(II) atoms with μ1,5 dicyanamido bridges are linked by the ligand pypz forming a macrocyclic chain that runs along the crystallographic 'c' axis having 'sql' (Shubnikov notation) net topology with a 4-connected uninodal node having point symbol {4(4).6(2)}. The remarkable noncovalent carbon-bonding contacts detected in the X-ray structure of compound 1 are analyzed and characterized by density functional theory calculations and the analysis of electron charge density (atoms in molecules). PMID:27295490

  13. 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

    NASA Astrophysics Data System (ADS)

    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.

  14. Antibacterial Co(II) and Ni(II) Complexes of N-(2-Furanylmethylene)-2-Aminothiadiazole and Role of SO42−, NO3−, C2O42− and CH3CO2− anions on Biological Properties

    PubMed Central

    Rauf, Abdul; Supuran, Claudiu T.

    2002-01-01

    Co(II) and Ni(II) complexes with a Schiff base, N-(2-furanylmethylene)-2-aminothiadiazole have been prepared and characterized by their physical, spectral and analytical data. The synthesized Schiff-bases act as tridentate ligands during the complexation reaction with Co(II) and Ni(II. metal ions. They possess the composition [M(L)2]Xn (where M=Co(II) or Ni(II), L=, X=NO3−, SO42−, C2O42− or CH3CO2− and n=1 or 2) and show an octahedral geometry. In order to evaluate the effect of anions upon chelation, the Schiff-base and its complexes have been screened for antibacterial activity against bacterial strains e.g., Escherichia coli, Staphylococcus aureus, and Pseudomonas aeruginosa. PMID:18476008

  15. 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

    SciTech Connect

    Nasr-Esfahani, M.

    2009-12-15

    The title binuclear complex, tris[N,N-bis(3-methoxysalicylidene)-1,4-diaminobutane] dicobalt(II), C{sub 60}H{sub 70}Co{sub 2}N{sub 6}O{sub 15}, was prepared by the reaction of the tetradentate Schiff base ligand bis(3-methoxysalicylidene)-1,4-diaminobutane and Co(CH{sub 3}COO){sub 2} . 4H{sub 2}O 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 N{sup 0},N'-bis(3-methoxysalicylidene)-1,4-diaminobutane. The two Co(II) ions, have two distorted octahedral coordination involving two O and two N atoms.

  16. Synthesis, antimicrobial activity, structural and spectral characterization and DFT calculations of Co(II), Ni(II), Cu(II) and Pd(II) complexes of 4-amino-5-pyrimidinecarbonitrile

    NASA Astrophysics Data System (ADS)

    Mohamed, Tarek A.; Shaaban, Ibrahim A.; Farag, Rabei S.; Zoghaib, Wajdi M.; Afifi, Mahmoud S.

    2015-01-01

    Co(II), Ni(II), Cu(II) and Pd(II) complexes of 4-amino-5-pyrimidinecarbonitrile (APC) have been synthesized and characterized using elemental analysis, magnetic susceptibility, mass spectrometry, infrared (4000-200 cm-1), UV-Visible (200-1100 nm), 1H NMR and ESR spectroscopy as well as TGA analysis. The molar conductance measurements in DMSO imply non-electrolytic complexes, formulated as [M(APC)2Cl2] where M = Co(II), Ni(II), Cu(II) and Pd(II). The infrared spectra of Co(II), Ni(II) and Cu(II) complexes indicate a bidentate type of bonding for APC through the exocyclic amino and adjacent pyrimidine nitrogen as donors whereas APC coordinated to Pd(II) ion as a monodentated ligand via a pyrimidine nitrogen donor. The magnetic measurements and the electronic absorption spectra support distorted octahedral geometries for Co(II), Ni(II) and Cu(II) complexes however a square planar complex was favored for the Pd(II) complex (C2h skeleton symmetry). In addition, we carried out B3LYP and ω-B97XD geometry optimization at 6-31G(d) basis set except for Pd(II) where we implemented LanL2DZ/6-31G(d) combined basis set. The computational results favor all trans geometrical isomers where amino N, pyrimidine N and Cl are trans to each other (structure 1). Finally, APC and its divalent metal ion complexes were screened for their antibacterial activity, and the synthesized complexes were found to be more potent antimicrobial agents than APC against one or more microbial species.

  17. Synthesis, structure, magnetic and biological activity studies of bis-hydrazone derived Cu(ii) and Co(ii) coordination compounds.

    PubMed

    Golla, Upendarrao; Adhikary, Amit; Mondal, Amit Kumar; Tomar, Raghuvir Singh; Konar, Sanjit

    2016-08-01

    Four coordination compounds of formulae [Cu(II)2(H2L(1))(HL(1))](ClO4)3·H2O (1), [Cu(II)2(H2L(2))(CH3OH)2](ClO4)2·2CH3OH (2), [Co(II)2(H2L(1))2](ClO4)4 (3) and [Co(II)2(H2L(2))2]·2H2O (4) were synthesized via self-assembly of succinohydrazone derived ligands (H2L(1) = N',N'-4-bis(2-pyridyl)succinohydrazide, H4L(2) = N',N'-4-bis(2-hydroxybenzylidene)succinohydrazide) and Cu(2+) and Co(2+) ions, respectively. The compounds were characterized by crystal structure determination, magnetic measurements and biological activities. Compounds 1, 3 and 4 have discrete double helicate structures, whereas compound 2 is a one-dimensional chain. Magnetic studies show antiferromagnetic exchange interactions in 2 with a J value of -67.1 cm(-1) and antiferromagnetic spin-canting in compound 3 originates through supramolecular H-bonding. For compound 3, a clear bifurcation was observed in zero field cooled (ZFC) and field cooled (FC) measurement at a temperature of 3.5 K and field of 0.1 T, implying long range magnetic ordering below this temperature. Interestingly, all of compounds 1-4 show significant changes in their absorption (hypo- and hyperchromism) in the presence of SS-DNA, inferring interaction between the compounds and DNA. In addition, compounds 1-4 significantly exhibited nuclease activities on both RNA and pUC19 plasmid DNA. Moreover, the nuclease activity was further enhanced in the presence of oxidant (H2O2) and suggests the possible role of reactive oxygen species in DNA nicking ability of compounds 1-4. Furthermore, compounds 1, 2 and 4 exhibited significant cytotoxicity against mammalian cancer cell lines (HeLa, A549 and MDAMB-231). In addition, our results from Annexin/PI staining and DNA fragmentation assays revealed that these compounds are capable of inducing apoptosis and have potential to act as anticancer drugs. PMID:27377047

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

    PubMed

    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

  19. Synthesis, characterization and in vitro antimicrobial studies of Co(II), Ni(II) and Cu(II) complexes derived from macrocyclic compartmental ligand.

    PubMed

    El-Gammal, O A; Bekheit, M M; El-Brashy, S A

    2015-02-25

    New Co(II), Ni(II) and Cu(II) complexes derived from tetradentate macrocyclic nitrogen ligand, (1E,4E,8E,12E)-5,8,13,16-tetramethyl-1,4,9,12-tetrazacyclohexadeca-4,8,12,16-tetraene (EDHDH) have been synthesized. The complexes have been characterized by elemental analysis, spectral (IR, UV-Vis, (1)H NMR and ESR (for Cu(II) complex)) mass, and magnetic as well as thermal analysis measurements. The complexes afforded the formulae: [Cu(EDHDH)Cl2]·2EtOH and [M(EDHDH)X2]·nH2O where M=Co(II) and Ni(II), X=Cl(-) or OH(-), n=1,0, respectively. The data revealed an octahedral arrangement with N4 tetradentate donor sites in addition to two Cl atoms occupying the other two sites. ESR spectrum of Cu(2+) complex confirmed the suggested geometry with values of a α(2)and β(2) indicating that the in-plane σ-bonding and in-plane π-bonding are appreciably covalent, and are consistent with very strong σ-in-plane bonding in the complexes. The molecular modeling is drawn and showed the bond length, bond angle, chemical reactivity, energy components (kcal/mol) and binding energy (kcal/mol) for all the title compounds using DFT method. Also, the thermal behavior and the kinetic parameters of degradation were determined using Coats-Redfern and Horowitz-Metzger methods. Moreover, the in vitro antibacterial studies of all compounds screened against pathogenic bacteria (two Gram +ve and two Gram -ve) to assess their inhibiting potential. The assay indicated that the inhibition potential is metal ion dependent. The ligand, EDHDH, Co(II) and Cu(II) complexes exhibited a remarkable antibacterial activity against Streptococcus Pyogenes as Gram +ve and Proteus vulgaris as Gram -ve bacterial strains. On the other hand, Ni(II) complex revealed a moderate antibacterial activity against both Gram +ve organisms and no activity against Gram -ve bacterial strain. PMID:25218230

  20. Theoretical and experimental studies on three new coordination complexes of Co(II), Ni(II), and Cu(II) with 2,4-dichloro-6-{(E)-[(5-chloro-2 sulfanylphenyl)imino]methyl}phenol Schiff base ligand.

    PubMed

    Kusmariya, Brajendra S; Mishra, A P

    2015-11-01

    Three mononuclear coordination complexes of Co(II), Ni(II), and Cu(II) have been synthesized from 2,4-dichloro-6-{(E)-[(5-chloro-2-sulfanylphenyl)imino]methyl}phenol ligand (H 2 L) obtained by simple condensation reaction of 3,5-dichloro-2-hydroxybenzaldehyde and 2-amino-4-chlorobenzenethiol and characterized by elemental analysis, spectral (FT-IR, electronic, and (1)H-NMR), molar conductance, thermal, SEM, PXRD, and fluorescence studies. The PXRD analysis and SEM-EDX micrographs show the crystalline nature of complexes. The domain size and the lattice strain of synthesized compounds have been determined according to Williamson-Hall plot. TG of the synthesized complexes illustrates the general decomposition pattern of the complexes. The ligand exhibits an interesting fluorescence property which is suppressed after complex formation. The Co(II) complex adopted a distorted octahedral configuration while Ni(II) and Cu(II) complexes showed square planar geometry around metal center. The geometry optimization, HOMO-LUMO, molecular electrostatic potential map (MEP), and spin density of synthesized compounds have been performed by density functional theory (DFT) method using B3LYP/6-31G and B3LYP/LANL2DZ as basis set. Graphical abstract Three new coordination complexes of Co(II), Ni(II) and Cu(II) with 2,4-dichloro-6-{(E)-[(5-chloro-2 sulfanylphenyl)imino]methyl}phenol Schiff base ligand. PMID:26438445

  1. Reductive Biotransformation of Fe in Shale-Limestone Saprolite Containing Fe(III) Oxides and Fe(II)/Fe(III) Phyllosilicates

    SciTech Connect

    Kukkadapu, Ravi K.; Zachara, John M.; Fredrickson, Jim K.; McKinley, James P.; Kennedy, David W.; Smith, Steven C.; Dong, Hailiang

    2006-07-15

    A <2.0-mm fraction of a mineralogically complex subsurface sediment containing goethite and Fe(II)/Fe(III) phyllosilicates was incubated with Shewanella putrefaciens (strain CN32) and lactate at circumneutral pH under anoxic conditions to investigate electron acceptor preference and the nature of the resulting biogenic Fe(II) fraction. Anthraquinone-2,6-disulfonate (AQDS), an electron shuttle, was included in select treatments to enhance bioreduction and subsequent biomineralization. The sediment was highly aggregated and contained two distinct clast populations: i) a highly weathered one with “sponge-like” internal porosity, large mineral crystallites, and Fe-containing micas, and ii) a dense, compact one with fine-textured Fe-containing illite and nano-sized goethite, as revealed by various forms of electron microscopic analyses. Approximately 10 to 15% of the Fe(III)TOT was bioreduced by CN32 over 60 d in media without AQDS, whereas 24% and 35% of the Fe(III)TOT was bioreduced by CN32 after 40 and 95 d in media with AQDS. Little or no Fe2+, Mn, Si, Al, and Mg were evident in aqueous filtrates after reductive incubation. Mössbauer measurements on the bioreduced sediments indicated that both goethite and phyllosilicate Fe(III) were partly reduced without bacterial preference. Goethite was more extensively reduced in the presence of AQDS whereas phyllosilicate Fe(III) reduction was not influenced by AQDS. Biogenic Fe(II) resulting from phyllosilicate Fe(III) reduction remained in a layer-silicate environment that displayed enhanced solubility in weak acid. The mineralogic nature of the goethite biotransformation product was not determined. Chemical and cryogenic Mössbauer measurements, however, indicated that the transformation product was not siderite, green rust, magnetite, Fe(OH)2, or Fe(II) adsorbed on phyllosilicate or bacterial surfaces. Several lines of evidence suggested that biogenic Fe(II) existed as surface associated phase on the residual goethite

  2. Coexistence of Microaerophilic, Nitrate-Reducing, and Phototrophic Fe(II) Oxidizers and Fe(III) Reducers in Coastal Marine Sediment

    PubMed Central

    Laufer, Katja; Nordhoff, Mark; Røy, Hans; Schmidt, Caroline; Behrens, Sebastian; Jørgensen, Bo Barker

    2015-01-01

    Iron is abundant in sediments, where it can be biogeochemically cycled between its divalent and trivalent redox states. The neutrophilic microbiological Fe cycle involves Fe(III)-reducing and three different physiological groups of Fe(II)-oxidizing microorganisms, i.e., microaerophilic, anoxygenic phototrophic, and nitrate-reducing Fe(II) oxidizers. However, it is unknown whether all three groups coexist in one habitat and how they are spatially distributed in relation to gradients of O2, light, nitrate, and Fe(II). We examined two coastal marine sediments in Aarhus Bay, Denmark, by cultivation and most probable number (MPN) studies for Fe(II) oxidizers and Fe(III) reducers and by quantitative-PCR (qPCR) assays for microaerophilic Fe(II) oxidizers. Our results demonstrate the coexistence of all three metabolic types of Fe(II) oxidizers and Fe(III) reducers. In qPCR, microaerophilic Fe(II) oxidizers (Zetaproteobacteria) were present with up to 3.2 × 106 cells g dry sediment−1. In MPNs, nitrate-reducing Fe(II) oxidizers, anoxygenic phototrophic Fe(II) oxidizers, and Fe(III) reducers reached cell numbers of up to 3.5 × 104, 3.1 × 102, and 4.4 × 104 g dry sediment−1, respectively. O2 and light penetrated only a few millimeters, but the depth distribution of the different iron metabolizers did not correlate with the profile of O2, Fe(II), or light. Instead, abundances were homogeneous within the upper 3 cm of the sediment, probably due to wave-induced sediment reworking and bioturbation. In microaerophilic Fe(II)-oxidizing enrichment cultures, strains belonging to the Zetaproteobacteria were identified. Photoferrotrophic enrichments contained strains related to Chlorobium and Rhodobacter; the nitrate-reducing Fe(II) enrichments contained strains related to Hoeflea and Denitromonas. This study shows the coexistence of all three types of Fe(II) oxidizers in two near-shore marine environments and the potential for competition and interrelationships between them

  3. Coexistence of Microaerophilic, Nitrate-Reducing, and Phototrophic Fe(II) Oxidizers and Fe(III) Reducers in Coastal Marine Sediment.

    PubMed

    Laufer, Katja; Nordhoff, Mark; Røy, Hans; Schmidt, Caroline; Behrens, Sebastian; Jørgensen, Bo Barker; Kappler, Andreas

    2015-01-01

    Iron is abundant in sediments, where it can be biogeochemically cycled between its divalent and trivalent redox states. The neutrophilic microbiological Fe cycle involves Fe(III)-reducing and three different physiological groups of Fe(II)-oxidizing microorganisms, i.e., microaerophilic, anoxygenic phototrophic, and nitrate-reducing Fe(II) oxidizers. However, it is unknown whether all three groups coexist in one habitat and how they are spatially distributed in relation to gradients of O2, light, nitrate, and Fe(II). We examined two coastal marine sediments in Aarhus Bay, Denmark, by cultivation and most probable number (MPN) studies for Fe(II) oxidizers and Fe(III) reducers and by quantitative-PCR (qPCR) assays for microaerophilic Fe(II) oxidizers. Our results demonstrate the coexistence of all three metabolic types of Fe(II) oxidizers and Fe(III) reducers. In qPCR, microaerophilic Fe(II) oxidizers (Zetaproteobacteria) were present with up to 3.2 × 10(6) cells g dry sediment(-1). In MPNs, nitrate-reducing Fe(II) oxidizers, anoxygenic phototrophic Fe(II) oxidizers, and Fe(III) reducers reached cell numbers of up to 3.5 × 10(4), 3.1 × 10(2), and 4.4 × 10(4) g dry sediment(-1), respectively. O2 and light penetrated only a few millimeters, but the depth distribution of the different iron metabolizers did not correlate with the profile of O2, Fe(II), or light. Instead, abundances were homogeneous within the upper 3 cm of the sediment, probably due to wave-induced sediment reworking and bioturbation. In microaerophilic Fe(II)-oxidizing enrichment cultures, strains belonging to the Zetaproteobacteria were identified. Photoferrotrophic enrichments contained strains related to Chlorobium and Rhodobacter; the nitrate-reducing Fe(II) enrichments contained strains related to Hoeflea and Denitromonas. This study shows the coexistence of all three types of Fe(II) oxidizers in two near-shore marine environments and the potential for competition and interrelationships between

  4. A series of Cd(II) complexes with {pi}-{pi} stacking and hydrogen bonding interactions: Structural diversities by varying the ligands

    SciTech Connect

    Wang Xiuli; Zhang Jinxia; Liu Guocheng; Lin Hongyan

    2011-02-15

    Seven new Cd(II) complexes consisting of different phenanthroline derivatives and organic acid ligands, formulated as [Cd(PIP){sub 2}(dnba){sub 2}] (1), [Cd(PIP)(ox)].H{sub 2}O (2), [Cd(PIP)(1,4-bdc)(H{sub 2}O)].4H{sub 2}O (3), [Cd(3-PIP){sub 2}(H{sub 2}O){sub 2}].4H{sub 2}O (4), [Cd{sub 2}(3-PIP){sub 4}(4,4'-bpdc)(H{sub 2}O){sub 2}].5H{sub 2}O (5), [Cd(3-PIP)(nip)(H{sub 2}O)].H{sub 2}O (6), [Cd{sub 2}(TIP){sub 4}(4,4'-bpdc)(H{sub 2}O){sub 2}].3H{sub 2}O (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, H{sub 2}ox=oxalic acid, 1,4-H{sub 2}bdc=benzene-1,4-dicarboxylic acid, 4,4'-H{sub 2}bpdc=biphenyl-4,4'-dicarboxylic acid, H{sub 2}nip=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 {pi}-{pi} stacking and hydrogen bonding interactions. The N-donor ligands with extended {pi}-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: {yields} Complexes 1-7 are 0D or 1D polymeric structure, the {pi}-{pi} stacking and H-bonding interactions extend the complexes into 3D supramolecular network. To our knowledge, systematic study on {pi}-{pi} stacking and H-bonding interactions in cadmium(II) complexes are still limited. {yields} The structural

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

    NASA Astrophysics Data System (ADS)

    Wang, Xiuli; Zhang, Jinxia; Liu, Guocheng; Lin, Hongyan

    2011-02-01

    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)]·H 2O ( 2), [Cd(PIP)(1,4-bdc)(H 2O)]·4H 2O ( 3), [Cd(3-PIP) 2(H 2O) 2]·4H 2O ( 4), [Cd 2(3-PIP) 4(4,4'-bpdc)(H 2O) 2]·5H 2O ( 5), [Cd(3-PIP)(nip)(H 2O)]·H 2O ( 6), [Cd 2(TIP) 4(4,4'-bpdc)(H 2O) 2]·3H 2O ( 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, H 2ox=oxalic acid, 1,4-H 2bdc=benzene-1,4-dicarboxylic acid, 4,4'-H 2bpdc=biphenyl-4,4'-dicarboxylic acid, H 2nip=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.

  6. Diverse Cd(II) compounds based on N-benzoyl-L-glutamic acid and N-donor ligands: Structures and photoluminescent properties

    NASA Astrophysics Data System (ADS)

    Ma, Ning; Guo, Wei-Ying; Song, Hui-Hua; Yu, Hai-Tao

    2016-01-01

    Five new Cd(II) coordination polymers with N-benzoyl-L-glutamic acid (H2bzgluO) and different N-donor ligands, [Cd(bzgluO)(2,2‧-bipy)(H2O)]n (1), [Cd(bzgluO)(2,4‧-bipy)2(H2O)·3H2O]n (2), [Cd(bzgluO)(phen)·H2O]n (3), [Cd(bzgluO)(4,4‧-bipy)(H2O)]n (4), [Cd(bzgluO)(bpp)(H2O)·2H2O]n (5) were synthesized (2,2‧-bipy=2,2‧-bipyridine, 2,4‧-bipy=2,4‧-bipyridine, phen=1,10-phenanthroline, 4,4‧-bipy=4,4‧-bipyridine, bpp=1,3-di(4-pyridyl)propane). Compounds 1-2 exhibit a 1D single-chain structure. Compound 1 generates a 2D supramolecular structure via π-π stacking and hydrogen bonding, 3D architecture of compound 2 is formed by hydrogen bonding. Compound 3 features a 1D double-chain structure, which are linked by π-π interactions into a 2D supramolecular layer. Compounds 4-5 display a 2D network structure. Neighboring layers of 4 are extended into a 3D supramolecular architecture through hydrogen bonding. The structural diversity of these compounds is attributed to the effect of ancillary N-donor ligands and coordination modes of H2bzgluO. Luminescent properties of 1-5 were studied at room temperature. Circular dichroism of compounds 1, 2 and 5 were investigated.

  7. Multi-component synthesis of 2-amino-6-(alkyllthio)pyridine-3,5-dicarbonitriles using Zn(II) and Cd(II) metal-organic frameworks (MOFs) under solvent-free conditions

    PubMed Central

    Thimmaiah, Muralidhara; Li, Peng; Regati, Sridhar; Chen, Banglin; Zhao, John Cong-Gui

    2012-01-01

    Multi-component synthesis 2-amino-3,5-dicarbonitrile-6-thio-pyridines has been developed by using the reaction of aldehydes, malononitrile, and thiophenols in the presence of a Zn (II) or a Cd(II) metal-organic framework (MOF) as the heterogeneous catalyst. This protocol tolerates different functional groups on the substrates and does not require the use of any organic solvent. Moreover, the Zn(II) and Cd (II) MOF catalysts can be recovered and reused for a number of runs without loss of activity. PMID:23002309

  8. Effectively simultaneous naked-eye detection of Cu(II), Pb(II), Al(III) and Fe(III) using cyanidin extracted from red cabbage as chelating agent

    NASA Astrophysics Data System (ADS)

    Khaodee, Warangkhana; Aeungmaitrepirom, Wanlapa; Tuntulani, Thawatchai

    Simultaneous determination of Cu(II), Pb(II), Al(III) and Fe(III) using cyanidin as a chelating agent was investigated in terms of both quantitative and qualitative detections. Cyanidin was extracted and purified from red cabbage which is a local plant in Thailand. The selectivity of this method was examined by regulating the pH of cyanidin solution operated together with masking agents. It was found that Cu(II), Pb(II), Al(III) and Fe(III) simultaneously responded with the color change at pH 7, pH 6, pH 5 and pH 4, respectively. KF, DMG and the mixture of KF and DMG were used as masking agents for the determination of Fe(III), Al(III) and Pb(II), respectively. Results from naked-eye detection were evaluated by comparing with those of inductively coupled plasma (ICP), and there was no significant difference noticed. Cyanidin using as a multianalyte reagent could be employed for simultaneous determination of Cu(II), Pb(II), Al(III) and Fe(III) at the lowest concentration at 50, 80, 50 and 200 μM, respectively, by slightly varying pHs. Moreover, the proposed method could be potentially applied for real water samples with simplicity, rapidity, low cost and environmental safety.

  9. Oxygen Activation by Co(II) and a Redox Non-Innocent Ligand: Spectroscopic Characterization of a Radical-Co(II)-Superoxide Complex with Divergent Catalytic Reactivity.

    PubMed

    Corcos, Amanda R; Villanueva, Omar; Walroth, Richard C; Sharma, Savita K; Bacsa, John; Lancaster, Kyle M; MacBeth, Cora E; Berry, John F

    2016-02-17

    Bimetallic (Et4N)2[Co2(L)2], (Et4N)2[1] (where (L)(3-) = (N(o-PhNC(O)(i)Pr)2)(3-)) reacts with 2 equiv of O2 to form the monometallic species (Et4N)[Co(L)O2], (Et4N)[3]. A crystallographically characterized analog (Et4N)2[Co(L)CN], (Et4N)2[2], gives insight into the structure of [3](1-). Magnetic measurements indicate [2](2-) to be an unusual high-spin Co(II)-cyano species (S = 3/2), while IR, EXAFS, and EPR spectroscopies indicate [3](1-) to be an end-on superoxide complex with an S = 1/2 ground state. By X-ray spectroscopy and calculations, [3](1-) features a high-spin Co(II) center; the net S = 1/2 spin state arises after the Co electrons couple to both the O2(•-) and the aminyl radical on redox non-innocent (L(•))(2-). Dianion [1](2-) shows both nucleophilic and electrophilic catalytic reactivity upon activation of O2 due to the presence of both a high-energy, filled O2(-) π* orbital and an empty low-lying O2(-) π* orbital in [3](1-). PMID:26799113

  10. Synthesis, DFT Calculation, and Antimicrobial Studies of Novel Zn(II), Co(II), Cu(II), and Mn(II) Heteroleptic Complexes Containing Benzoylacetone and Dithiocarbamate

    PubMed Central

    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 < Co < Cu > 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

  11. Synthesis, characterization, antibacterial activities and carbonic anhydrase enzyme inhibitor effects of new arylsulfonylhydrazone and their Ni(II), Co(II) complexes

    NASA Astrophysics Data System (ADS)

    Özdemir, Ümmühan Özmen; Arslan, Fatma; Hamurcu, Fatma

    2010-01-01

    Ethane sulfonic acide hydrazide ( esh: CH 3CH 2SO 2NHNH 2) derivatives as 5-methylsalicyl-aldehydeethanesulfonylhydrazone ( 5msalesh), 5-methyl-2-hydroxyacetophenoneethane sulfonylhydrazone ( 5mafesh) and their Ni(II), Co(II) complexes have been synthesized for the first time. The structure of these compounds has been investigated by elemental analysis, FT-IR, 1H NMR, 13C NMR, LC/MS, UV-vis spectrophotometric method, magnetic susceptibility, thermal studies and conductivity measurements. The antibacterial activities of synthesized compounds were studied against Gram positive bacteria; Staphylococcus aureus, Bacillus subtilis, Bacillus magaterium and Gram negative bacteria; Salmonella enteritidis, Escherichia coli by using the microdilution broth method. The biological activity screening showed that ligands have more activity than complexes against the tested bacteria. The inhibition activities of these compounds on carbonic anhydrase II (CA II) have been investigated by comparing IC 50 and Ki values and it has been found that 5msalesh and its complexes have more enzyme inhibition efficiency than other compounds.

  12. Co(II), Ce(III) and UO 2(VI) bis-salicylatothiosemicarbazide complexes . Binary and ternary complexes, thermal studies and antimicrobial activity

    NASA Astrophysics Data System (ADS)

    El-Wahab, Z. H. Abd; Mashaly, Mahmoud M.; Salman, A. A.; El-Shetary, B. A.; Faheim, A. A.

    2004-10-01

    A series of new metal complexes of Co(II), Ce(III) and UO 2(VI), with the Schiff base ligand, H 2L, bis-salicylatothiosemicarbazide have been prepared in presence of different molar ratios of LiOH·H 2O as a deprotonating agent. Also, the ternary complexes were prepared by using 2-aminopyridine (2-Ampy) or oxalic acid (Ox) as a secondary ligand. All synthesized compounds were identified and confirmed by elemental analyses, molar conductivities, spectral (UV-Vis, IR, 1H NMR, mass) and magnetic moment measurements as well as TG-DSC technique. The changes in the selected vibrational absorption bands in IR and NMR spectra of the Schiff base ligand upon coordination indicate that, the ligand behaves as a neutral, monoanionic and/or dianionic tetradentate manner with ONNO donor sites. Conductance measurements suggest the non-electrolytic and 1:1 electrolytic nature of the metal complexes. Thermal studies suggest a mechanism for degradation of the metal complexes as function of temperature supporting the chelation modes, moreover, show the possibility of obtaining new complexes pyrolytically in the solid state which cannot be synthesized from solution. Antimicrobial screening of the free ligand and its binary complexes showed that, the free ligand and some metal complexes possess antimicrobial activities towards four type of bacteria and five types of fungi and these results were compared with eleven type of known antibiotics.

  13. Synthesis, characterization, biological activity of binuclear Co(II), Cu(II) and mononuclear Ni(II) complexes of bulky multi-dentate thiosemicarbazide

    NASA Astrophysics Data System (ADS)

    El-Gammal, O. A.; Abd Al-Gader, I. M.; El-Asmy, A. A.

    2014-07-01

    The chelation behavior of 9,10-dihydro-9,10-ethanoanthracene-11,12-dicarbonyl) bis (N-ethylhydrazine-1-carbothioamide) (H6ETS)(1) towards Co2+, Ni2+and Cu2+ have been studied. The spectral data revealed that the ligand acts as a bi- and/or mono-negative multi-dentate. The isolated Ni(II) and Cu(II) complexes are square-planar while the Co(II) is tetrahedral. EPR spectrum of Cu(II) complex confirmed simulated an axial spin-Hamiltonian exhibiting a four-line pattern with nitrogen super-hyperfine couplings originating from imine hydrazinic nitrogen atoms and possess a significant amount of tetrahedral distortion leading to a pseudo-square-planar geometry with unpaired electron has d ground state. Also, the thermal behavior and kinetic parameters were determined. Furthermore, the title compounds were investigated for their antibacterial activity using inhibition zone diameter and for DNA degradation, superoxide-scavenging activity as well as hydroxyl radicals that generated by the oxidation of cytochrome c in L-ascorbic acid/CuSO4-cytochrome c system.

  14. Synthesis, spectroscopic and catalytic studies of Cu(II), Co(II) and Ni(II) complexes immobilized on Schiff base modified chitosan

    NASA Astrophysics Data System (ADS)

    Antony, R.; Theodore David Manickam, S.; Saravanan, K.; Karuppasamy, K.; Balakumar, S.

    2013-10-01

    A new class of bidentate (N, O) Schiff base ligand (L) has been derived from the functional biopolymer (chitosan) and 1,2-diphenylethanedione in 1:1 M ratio. This ligand has been used to synthesise the new first row transition metal complexes of Cu(II), Co(II) and Ni(II). The structural properties of the ligand and the synthesized tetra-coordinated complexes have been investigated by elemental analysis, magnetic study, molar conductance measurement and spectroscopic methods viz. FT-IR, UV-Vis., 1H NMR, 13C NMR and XRD. The spectral evidences strongly suggested the square planar geometry to the complexes. The XRD studies proved that crystallinity of chitosan has been diminished after Schiff base formation and metal complexation of L. Thermal and surface properties of the complexes have been also discussed from the investigation of their TG-DTG curves and SEM images, respectively. In addition, the catalytic efficiency of these complexes has been studied in the cyclohexane oxidation reaction using H2O2 as oxidant at 70 °C.

  15. Suppressing of slow magnetic relaxation in tetracoordinate Co(II) field-induced single-molecule magnet in hybrid material with ferromagnetic barium ferrite.

    PubMed

    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

  16. Suppressing of slow magnetic relaxation in tetracoordinate Co(II) field-induced single-molecule magnet in hybrid material with ferromagnetic barium ferrite

    PubMed Central

    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

  17. DNA Binding, Cleavage and Antibacterial Activity of Mononuclear Cu(II), Ni(II) and Co(II) Complexes Derived from Novel Benzothiazole Schiff Bases.

    PubMed

    Vamsikrishna, Narendrula; Kumar, Marri Pradeep; Tejaswi, Somapangu; Rambabu, Aveli; Shivaraj

    2016-07-01

    A series of novel bivalent metal complexes M(L1)2 and M(L2)2 where M = Cu(II), Ni(II), Co(II) and L1 = 2-((benzo [d] thiazol-6-ylimino)methyl)-4-bromophenol [BTEMBP], L2 = 1-((benzo [d] thiazol-6-ylimino)methyl) naphthalen-2-ol [BTEMNAPP] were synthesized. All the compounds have been characterized by elemental analysis, SEM, Mass, (1)H NMR, (13)C NMR, UV-Vis, IR, ESR, spectral data and magnetic susceptibility measurements. Based on the analytical and spectral data four-coordinated square planar geometry is assigned to all the complexes. DNA binding properties of these complexes have been investigated by electronic absorption spectroscopy, fluorescence and viscosity measurements. It is observed that these binary complexes strongly bind to calf thymus DNA by an intercalation mode. DNA cleavage efficacy of these complexes was tested in presence of H2O2 and UV light by gel electrophoresis and found that all the complexes showed better nuclease activity. Finally the compounds were screened for antibacterial activity against few pathogens and found that the complexes have potent biocidal activity than their free ligands. PMID:27165038

  18. 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.

    PubMed

    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

  19. MtDNA COI-COII marker and drone congregation area: an efficient method to establish and monitor honeybee (Apis mellifera L.) conservation centres.

    PubMed

    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

  20. Co(II), Ce(III) and UO2VI) bis-salicylatothiosemicarbazide complexes: binary and ternary complexes, thermal studies and antimicrobial activity.

    PubMed

    El-Wahab, Z H Abd; Mashaly, Mahmoud M; Salman, A A; El-Shetary, B A; Faheim, A A

    2004-10-01

    A series of new metal complexes of Co(II), Ce(III) and UO(2)(VI), with the Schiff base ligand, H2L, bis-salicylatothiosemicarbazide have been prepared in presence of different molar ratios of LiOH.H2O as a deprotonating agent. Also, the ternary complexes were prepared by using 2-aminopyridine (2-Ampy) or oxalic acid (Ox) as a secondary ligand. All synthesized compounds were identified and confirmed by elemental analyses, molar conductivities, spectral (UV-Vis, IR, 1H NMR, mass) and magnetic moment measurements as well as TG-DSC technique. The changes in the selected vibrational absorption bands in IR and NMR spectra of the Schiff base ligand upon coordination indicate that, the ligand behaves as a neutral, monoanionic and/or dianionic tetradentate manner with ONNO donor sites. Conductance measurements suggest the non-electrolytic and 1:1 electrolytic nature of the metal complexes. Thermal studies suggest a mechanism for degradation of the metal complexes as function of temperature supporting the chelation modes, moreover, show the possibility of obtaining new complexes pyrolytically in the solid state which cannot be synthesized from solution. Antimicrobial screening of the free ligand and its binary complexes showed that, the free ligand and some metal complexes possess antimicrobial activities towards four type of bacteria and five types of fungi and these results were compared with eleven type of known antibiotics. PMID:15350923

  1. Supramolecular complexes of Co(II), Ni(II) and Zn(II) p-hydroxybenzoates with caffeine: Synthesis, spectral characterization and crystal structure

    NASA Astrophysics Data System (ADS)

    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.

  2. Ammonia-modified Co(II) sites in zeolites: IR spectroscopy and spin-resolved charge transfer analysis of NO adsorption complexes.

    PubMed

    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

  3. DNA cleavage, antimicrobial, spectroscopic and fluorescence studies of Co(II), Ni(II) and Cu(II) complexes with SNO donor coumarin Schiff bases

    NASA Astrophysics Data System (ADS)

    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.

  4. Electrochemical Determination of Bisphenol A with Pencil Graphite Electrodes Modified with Co(II), Ni(II), Cu(II) and Fe(II) Phthalocyaninetetrasulfonates.

    PubMed

    Özcan, Levent; Altuntas, Muhammet; Büyüksagis, Aysel; Türk, Hayrettin; Yurdakal, Sedat

    2016-01-01

    Pencil graphite electrodes modified with Co(II), Ni(II), Cu(II) and Fe(II) metallophthalocyaninetetrasulfonates (MePcTSs) were investigated for an electrochemical determination of bisphenol A (BPA). The electrochemical performances of the modified electrodes for different pH values in phosphate and the Britton-Robinson buffers were determined by cyclic voltammetry; the electrode performances were better in the Britton-Robinson buffer. NiPcTS and CoPcTS modifications of the electrodes had remarkable enhancements on their performances. The differential pulse voltammetry parameters for the electrodes were optimized, and we found that the electrochemical response versus the concentration of BPA is linear from 5.0 × 10(-7) to 1.0 × 10(-5) M for the NiPcTS and CoPcTS modified electrodes. The detection limits of these modified electrodes are 2.9 × 10(-7) and 4.3 × 10(-7) M, respectively, and the effects of interfering species are less than 5%. The results show that NiPcTS and CoPcTS modified pencil graphite electrodes could be used for electrochemical determinations of BPA for analytical purposes. PMID:27506715

  5. Structural, spectral, DFT, pH-metric and biological studies on Cr(III), Mn(II) and Fe(III) complexes of dithione heterocyclic thiosemicarbazide ligand

    NASA Astrophysics Data System (ADS)

    Abu El-Reash, Gaber M.; El-Gammal, Ola A.; El-Gamil, Mohammed M.

    2013-03-01

    Cr(III), Mn(II) and Fe(III) complexes derived from the quadruple potential dithione heterocyclic thiosemicarbazide ligand (H2PET) have been prepared and characterized by conventional techniques. The isolated complexes were assigned the formulae, [Cr(HPET)(H2O)2Cl2]·3H2O, [Mn(HPET)(H2O)Cl]2 and [Fe(HPET)(H2O)2Cl2]·H2O, respectively. IR data revealed that the ligand behaves as monobasic bidentate through (Cdbnd N)py and (Csbnd S) groups in both Cr(III) and Fe(III) complexes. In the binuclear Mn(II) complex, H2PET acts as NSNS monobasic tetradente via (Cdbnd N)py, (Csbnd S), (Cdbnd S) and the new azomethine, (Ndbnd C)* groups. An octahedral geometry for all complexes was proposed. The bond lengths, bond angles, HOMO, LUMO and dipole moment have been calculated by DFT using materials studio program to confirm the geometry of H2PET and its metal complexes. The ligand association constant and the stability constants of its complexes in addition to the thermodynamic parameters were calculated from pH metrically at 298, 308 and 318°K in 50% dioxane-water mixture, respectively. Also, the kinetic and thermodynamic parameters for the different thermal degradation steps of the complexes were determined by Coats-Redfern and Horowitz-Metzger methods. Moreover, the anti-oxidant (using ABTS and DPPH methods), anti-hemolytic, and cytotoxic activities of the compounds have been tested.

  6. Development of a C3-symmetric benzohydroxamate tripod: Trimetallic complexation with Fe(III), Cr(III) and Al(III)

    NASA Astrophysics Data System (ADS)

    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.

  7. 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.

    PubMed

    Guo, Xiaoyao; Du, Bin; Wei, Qin; Yang, Jian; Hu, Lihua; Yan, Liangguo; Xu, Weiying

    2014-08-15

    In the present study, a kind of graphenes magnetic material (Fe3O4-GS) was prepared by compositing graphene sheet with ferroferric oxide, and shown to be effective 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 pHZPC value of the sorbent was estimated to be 3.5 by alkaline-titration methods. Fe3O4-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(-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. PMID:25016452

  8. 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.

    PubMed

    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

  9. Synthesis, characterization and spectroscopy studying of some metal complexes of a new Schiff base ligand; X-ray crystal structure, NMR and IR investigation of a new dodecahedron Cd(II) complex

    NASA Astrophysics Data System (ADS)

    Golbedaghi, Reza; Rezaeivala, Majid; Khalili, Maryam; Notash, Behrouz; Karimi, Javad

    2016-12-01

    Some new [Cd(H2L1)(NO3)]ClO4 (1), [Mn(H2L1)](ClO4)2 (2), [Ni(H2L1)](ClO4)2 (3) and [Cu(H2L1)](ClO4)2 (4) complexes were prepared by the reaction of a Schiff base ligand and M (II) metal ions in equimolar ratios (M = Cd, Mn, Ni and Cu). The ligand H2L1 was synthesized by reaction of 2-[2-(3-formyl phenoxy)propoxy]benzaldehyde and ethanol amine and characterized by IR, 1H,13C NMR spectroscopy and elemental analysis. The synthesized complexes were characterized with IR and elemental analysis in all cases and 1H, 13C NMR, and X-ray in the case of Cd(II) complex. The X-ray crystal structure of compound 1 showed that all nitrogen and oxygen atoms of Schiff base ligand (N2O4) and a molecule of nitrate with two donor oxygen atom have been coordinated to the metal ion and the Cd(II) ion is in an eight-coordinate environment that is best described as a distorted dodecahedron geometry.

  10. Cd(II) and Zn(II) complexes of two new hexadentate Schiff base ligands derived from different aldehydes and ethanol amine; X-ray crystal structure, IR and NMR spectroscopy studies

    NASA Astrophysics Data System (ADS)

    Golbedaghi, Reza; Rezaeivala, Majid; Albeheshti, Leila

    2014-11-01

    Four new [Cd(H2L1)(NO3)]ClO4 (1), [Zn(H2L1)](ClO4)2 (2), [Cd(H2L2)(NO3)]ClO4 (3), and [Zn(H2L2)](ClO4)2 (4), complexes were prepared by the reaction of two new Schiff base ligands and Cd(II) and Zn(II) metal ions in equimolar ratios. The ligands H2L1 and H2L2 were synthesized by reaction of 2-[2-(2-formyl phenoxy)ethoxy]benzaldehyde and/or 2-[2-(3-formyl phenoxy)propoxy]benzaldehyde and ethanol amine and characterized by IR, 1H and 13C NMR spectroscopy. All complexes were characterized by IR, 1H and 13C NMR, COSY, and elemental analysis. Also, the complex 1 was characterized by X-ray in addition to the above methods. The X-ray crystal structure of compound 1 showed that all nitrogen and oxygen atoms of ligand (N2O4) and a molecule of nitrate with two donor oxygen atom have been coordinated to the metal ion and the Cd(II) ion is in an eight-coordinate environment that is best described as a distorted dodecahedron geometry.

  11. A New Chelating Reagent: Its Synthesis/Characterization and Application for the Determination of Cd(II) and Ni(II) in Various Food and Make-Up Product Samples by FAAS Using Simultaneous Microextraction Sampling.

    PubMed

    Saçmacı, Şerife; Saçmacı, Mustafa

    2016-07-01

    A new and simple dispersive liquid-liquid simultaneous microextraction procedure was developed for the rapid separation and simultaneous extraction/preconcentration of Cd(II) and Ni(II) at ultratrace amounts. Microextraction of the analytes was carried out in the presence of 2-methyl-5-[(Z)-pyridin-4-yldiazenyl]quinolin-8-ol as the chelating reagent. Chloroform and ethanol were used as the extraction and dispersive solvents. Various parameters that influence the microextraction procedure's efficiency-such as pH, centrifugation rate and time, reagent concentration, and sampling volume on the recovery of analytes-were examined. The calibration curves were linear in the range of 0.01-1.25 and 0.075-5 mg/L with LODs of 0.25 and 0.84 μg/L, and with a preconcentration factor of 94, for Cd(II) and Ni(II), respectively. Precision was >1.0%. The accuracy of the method was confirmed by analyzing the Certified Standard Reference Material (CWW-TMD: Certified wastewater-Trace metals, wastewater). The results show that the dispersive liquid-liquid simultaneous microextraction pretreatment is a sensitive, rapid, simple, green, and safe method for the separation/preconcentration of cadmium and nickel. PMID:27301349

  12. 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

    NASA Astrophysics Data System (ADS)

    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.

  13. 4,4′-Bipyridine-aided synthesis and characterization of Zn(II) and Cd(II) 2-sulfoterephthalate complexes

    SciTech Connect

    Xiao, Shan-Shan; Li, Xin-Xin; Zheng, Xiang-Jun; Jia, Tian-Jing; Jin, Lin-Pei

    2013-09-15

    Six d{sup 10} complexes, [Zn{sub 1.5}(stp)(bpy){sub 0.5}(H{sub 2}O){sub 2}]·0.5H{sub 2}O (1), Cd{sub 1.5}(stp)(bpy){sub 0.5}(H{sub 2}O){sub 2} (2), [Cd{sub 1.5}(stp)(bpy)(H{sub 2}O)]·H{sub 2}O (3), [Zn{sub 0.5}(bpy){sub 0.5}(H{sub 2}O){sub 2}][Zn(stp)(bpy)(H{sub 2}O)]·0.5H{sub 2}O (4), Cd{sub 3}(stp){sub 2}(bpy){sub 3}(H{sub 2}O){sub 3} (5), Hbpy·[Zn{sub 0.5}(bpy)(H{sub 2}O){sub 2}][Zn{sub 0.5}(stp)(H{sub 2}O)]·H{sub 2}O (6) based on 2-sulfoterephthalate (stp{sup 3−}) and 4,4′-bipyridine (bpy) have been synthesized under hydro/solvo-thermal conditions and structurally characterized. Complex 1 exhibits a three-fold interpenetrated 3D porous architecture. Complexes 2 and 3 possess helices with different chirality arranging alternately. 4 and 6 are addition compounds, which compose of complex cation and complex anion. Complex 5 features a 3D layer-pillar framework in which a (4, 4) grid layer is constructed by stp{sup 3−} ligands and Cd(II) ions, and the layers are further connected by bpy pillars. The solid-state luminescent properties of the coordination polymers have also been investigated. - Graphical abstract: Display Omitted - Highlights: • Complexes 1–3 possess helices with different chirality arranging alternately. • The structural diversity can be attributed to various coordination modes of ligands. • The formation of helical structure is related to the adjacent carboxyl and sulfonate groups. • Bpy exhibits three roles: bridge, hydrogen bonding acceptor, and template.

  14. Interaction of a dinuclear fluorescent Cd(II) complex of calix[4]arene conjugate with phosphates and its applicability in cell imaging.

    PubMed

    Sreenivasu Mummidivarapu, V V; Hinge, Vijaya Kumar; Rao, Chebrolu Pulla

    2015-01-21

    A triazole-linked hydroxyethylimino conjugate of calix[4]arene () and its cadmium complex have been synthesized and characterized, and their structures have been established. In the complex, both the Cd(2+) centers are bound by an N2O4 core, and one of it is a distorted octahedral, whereas the other is a trigonal anti-prism. The fluorescence intensity of the di-nuclear Cd(ii) complex is quenched only in the presence of phosphates and not with other anions studied owing to their binding affinities and the nature of the interaction of the phosphates with Cd(2+). These are evident even from their absorption spectra. Different phosphates exhibit changes in both their fluorescence as well as absorption spectra to varying extents, suggesting their differential interactions. Among the six phosphates, H2PO4(-) has higher fluorescence quenching even at low equivalents of this ion, whereas P2O7(4-) shows only 50% quenching even at 10 equivalents. The fluorescence quenching is considerable even at 20 ppb (0.2 μM) of H2PO4(-), whereas all other phosphates require a concentration of 50-580 ppb to exhibit the same effect on fluorescence spectra. Thus, the interaction of H2PO4(-) is more effective by ∼30 fold as compared to that of P2O7(4-). Fluorescence quenching by phosphate is due to the release of from its original cadmium complex via the formation of a ternary species followed by the capture of Cd(2+) by the phosphate, as delineated based on the combination of spectral techniques, such as absorption, emission, (1)H NMR and ESI MS. The relative interactive abilities of the six phosphates differ from each other. The removal of Cd(2+) is demonstrated to be reversible by the repeated addition of the phosphate followed by Cd(2+). The characteristics of the ternary species formed in each of these six phosphates have been computationally modeled using molecular mechanics. The computational study revealed that the coordination between cadmium and -CH2-CH2-OH breaks and new

  15. Ternary metal complexes of guaifenesin drug: Synthesis, spectroscopic characterization and in vitro anticancer activity of the metal complexes.

    PubMed

    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

  16. COII/tRNA[sup Lys] intergenic 9-bp deletion and other mtDNA markers clearly reveal that the Tharus (Southern Nepal) have oriental affinities

    SciTech Connect

    Passarino, G.; Semino, O.; Santachiara-Benerecetti, A.S.; Modiano, G. )

    1993-09-01

    The authors searched for the East Asian mtDNA 9-bp deletion in the intergenic COII/tRNA[sup Lys] region in a sample of 107 Tharus (50 from central Terai and 57 from eastern Terai), a population whose anthropological origin has yet to be completely clarified. The deletion, detected by electrophoresis of the PCR-amplified nt 7392-8628 mtDNA fragment after digestion with HaeIII, was found in about 8% of both Tharu groups but was found in none of the 76 Hindus who were examined as a non-Oriental neighboring control population. A complete triplication of the 9-bp unit, the second case so far reported, was also observed in one eastern Tharu. All the mtDNAs with the deletion, and that with the triplication, were further characterized (by PCR amplification of the relevant mTDNA fragments and their digestion with the appropriate enzymes) to locate them in the Ballinger et al. phylogeny of East Asian mtDNA haplotypes. The deletion was found to be associated with four different haplotypes, two of which are reported for the first time. One of the deletions and especially the triplication could be best explained by the assumption of novel length-change events. Ballinger's classification of East Asian mtDNA haplotypes is mainly based on the phenotypes for the DdeI site at nt 10394 and the AluI site at nt 10397. Analysis of the entire Tharu sample revealed that more than 70% of the Tharus have both sites, the association of which has been suggested as an ancient East Asian peculiarity. These results conclusively indicate that the Tharus have a predominantly maternal Oriental ancestry. Moreover, they show at least one and perhaps two further distinct length mutations, and this suggests that the examined region is a hot spot of rearrangements. 21 refs., 5 figs., 6 tabs.

  17. Synthesis, characterization, equilibrium study and biological activity of Cu(II), Ni(II) and Co(II) complexes of polydentate Schiff base ligand.

    PubMed

    El-Sherif, Ahmed A; Shehata, Mohamed R; Shoukry, Mohamed M; Barakat, Mohammad H

    2012-10-01

    Schiff base ligand, 1,4-bis[(2-hydroxybenzaldehyde)propyl]piperazine (BHPP), and its Cu(II), Ni(II) and Co(II) metal complexes were synthesized and characterized by elemental analysis, magnetic susceptibility, molar conductance and spectral (IR and UV-vis) studies. The ground state of BHPP ligand was investigated using the BUILDER module of MOE. Metal complexes are formed in the 1:1 (M:L) ratio as found from the elemental analysis and found to have the general formula [ML]·nH(2)O, where M=Co(II), Ni(II) and Cu(II), L=BHPP. In all the studied complexes, the (BHPP) ligand behaves as a hexadentate divalent anion with coordination involving the two azomethine nitrogen's, the two nitrogen atoms of piperazine ring and the two deprotonated phenolic OH-groups. The magnetic and spectral data indicates octahedral geometry of metal(II) complexes. The ligand and their metal chelates have been screened for their antimicrobial activities using the disc diffusion method against the selected bacteria and fungi. They were found to be more active against Gram-positive than Gram-negative bacteria. Protonation constants of (BHPP) ligand and stability constants of its Cu(2+), Co(2+) and Ni(2+) complexes were determined by potentiometric titration method in 50% DMSO-water solution at ionic strength of 0.1 M sodium nitrate. It has been observed that the protonated Schiff base ligand (BHPP) have four protonation constants. The divalent metal ions Cu(2+), Ni(2+) and Co(2+) form 1:1 complexes. PMID:22935596

  18. The meloxicam complexes of Co(II) and Zn(II): Synthesis, crystal structures, photocleavage and in vitro DNA-binding

    NASA Astrophysics Data System (ADS)

    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.

  19. Simultaneous determination of Fe(III) and Al(III) by first-derivative spectrophotometry and partial least-squares (PLS-2) method - application to post-haemodialysis fluids.

    PubMed

    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

  20. Synthesis, antimicrobial activity, structural and spectral characterization and DFT calculations of Co(II), Ni(II), Cu(II) and Pd(II) complexes of 4-amino-5-pyrimidinecarbonitrile.

    PubMed

    Mohamed, Tarek A; Shaaban, Ibrahim A; Farag, Rabei S; Zoghaib, Wajdi M; Afifi, Mahmoud S

    2015-01-25

    Co(II), Ni(II), Cu(II) and Pd(II) complexes of 4-amino-5-pyrimidinecarbonitrile (APC) have been synthesized and characterized using elemental analysis, magnetic susceptibility, mass spectrometry, infrared (4000-200 cm(-1)), UV-Visible (200-1100 nm), (1)H NMR and ESR spectroscopy as well as TGA analysis. The molar conductance measurements in DMSO imply non-electrolytic complexes, formulated as [M(APC)2Cl2] where M=Co(II), Ni(II), Cu(II) and Pd(II). The infrared spectra of Co(II), Ni(II) and Cu(II) complexes indicate a bidentate type of bonding for APC through the exocyclic amino and adjacent pyrimidine nitrogen as donors whereas APC coordinated to Pd(II) ion as a monodentated ligand via a pyrimidine nitrogen donor. The magnetic measurements and the electronic absorption spectra support distorted octahedral geometries for Co(II), Ni(II) and Cu(II) complexes however a square planar complex was favored for the Pd(II) complex (C2h skeleton symmetry). In addition, we carried out B3LYP and ω-B97XD geometry optimization at 6-31G(d) basis set except for Pd(II) where we implemented LanL2DZ/6-31G(d) combined basis set. The computational results favor all trans geometrical isomers where amino N, pyrimidine N and Cl are trans to each other (structure 1). Finally, APC and its divalent metal ion complexes were screened for their antibacterial activity, and the synthesized complexes were found to be more potent antimicrobial agents than APC against one or more microbial species. PMID:25105264

  1. Synthesis, characterization, DFT and biological studies of (Z)-N‧-(2-oxoindolin-3-ylidene)picolinohydrazide and its Co(II), Ni(II) and Cu(II) complexes

    NASA Astrophysics Data System (ADS)

    Rakha, T. H.; El-Gammal, O. A.; Metwally, H. M.; Abu El-Reash, G. M.

    2014-03-01

    The picolinohydrazide derivative: (Z)-N‧-(2-oxoindolin-3-ylidene)picolinohydrazide (H2IPH) and its Co(II), Ni(II) and Cu(II) complexes have been synthesized and investigated by using the modern spectroscopic and physicochemical techniques viz. IR, 1H NMR, UV-Vis spectrometric methods and magnetic moment measurements. The investigation study revealed that the ligand acts as monobasic tri- and tetradentate in Co(II) and Ni(II) complex, respectively and as neutral tridentate in Cu(II) complex. On the basis of magnetic moment and spectral studies, a six coordinated octahedral geometry is assigned for all complexes. The molecular modeling are drawn and showed the bond length, bond angle, chemical reactivity, energy components (kcal/mol) and binding energy (kcal/mol) for all the title compounds and also NLO for the ligand is shown. The energy gap between the HOMO and LUMO for Ni(II) complex is (-7 eV) which indicates that these compound is a promising structure for photovoltaic devices such as solar cells. A comparison of the experimental and theoretical spectra can be very useful in making correct assignments and understanding the basic chemical shift. The thermal behavior and the kinetic parameters of degradation were determined using Coats-Redfern and Horowitz-Metzger methods. The in vitro antibacterial studies of these complexes screened against pathogenic bacteria proved them as growth inhibiting agents. Antitumor activity, carried out in vitro on human mammary gland (breast) MCF7, have shown that the Co(II) complex exhibited potent activity followed by the ligand, Cu(II) and Ni(II) complexes.

  2. The outer membrane protein Omp35 affects the reduction of Fe(III), nitrate, and fumarate by Shewanella oneidensis MR-1

    PubMed Central

    Maier, Tamara M; Myers, Charles R

    2004-01-01

    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), fumarate, and

  3. A new combined process for efficient removal of Cu(II) organic complexes from wastewater: Fe(III) displacement/UV degradation/alkaline precipitation.

    PubMed

    Xu, Zhe; Gao, Guandao; Pan, Bingcai; Zhang, Weiming; Lv, Lu

    2015-12-15

    Efficient removal of heavy metals complexed with organic ligands from water is still an important but challenging task now. Herein, a novel combined process, i.e., Fe(III)-displacement/UV degradation/alkaline precipitation (abbreviated as Fe(III)/UV/OH) was developed to remove copper-organic complexes from synthetic solution and real electroplating effluent, and other processes including alkaline precipitation, Fe(III)/OH, UV/OH were employed for comparison. By using the Fe(III)/UV/OH process, some typical Cu(II) complexes, such as Cu(II)-ethylenediaminetetraacetic acid (EDTA), Cu(II)-nitrilotriacetic acid (NTA), Cu(II)-citrate, Cu(II)-tartrate, and Cu(II)-sorbate, each at 19.2 mg Cu/L initially, were efficiently removed from synthetic solution with the residual Cu below 1 mg/L. Simultaneously, 30-48% of total organic carbon was eliminated with exception of Cu(II)-sorbate. Comparatively, the efficiency of other processes was much lower than the Fe(III)/UV/OH process. With Cu(II)-citrate as the model complex, the optimal conditions for the combined process were obtained as: initial pH for Fe(III) displacement, 1.8-5.4; molar ratio of [Fe]/[Cu], 4:1; UV irradiation, 10 min; precipitation pH, 6.6-13. The mechanism responsible for the process involved the liberation of Cu(II) ions from organic complexes as a result of Fe(III) displacement, decarboxylation of Fe(III)-ligand complexes subjected to UV irradiation, and final coprecipitation of Cu(II) and Fe(II)/Fe(III) ions. Up to 338.1 mg/L of Cu(II) in the electroplating effluent could be efficiently removed by the process with the residual Cu(II) below 1 mg/L and the removal efficiency of ∼99.8%, whereas direct precipitation by using NaOH could only result in total Cu(II) removal of ∼8.6%. In addition, sunlight could take the place of UV to achieve similar removal efficiency with longer irradiation time (90 min). PMID:26454633

  4. 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.

    PubMed

    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

  5. Selective solid-phase extraction and analysis of trace-level Cr(III), Fe(III), Pb(II), and Mn(II) Ions in wastewater using diethylenetriamine-functionalized carbon nanotubes dispersed in graphene oxide colloids.

    PubMed

    Zhu, Xiangbing; Cui, Yuemei; Chang, Xijun; Wang, Hua

    2016-01-01

    Multi-walled carbon nanotubes (MCNTs) were dispersed in graphene oxide (GO) colloids to be further functionalized with diethylenetriamine (DETA), resulting in GO-MCNTs-DETA nanocomposites for the solid-phase extraction and analysis of Cr(III), Fe(III), Pb(II), and Mn(II) ions at the trace levels in wastewater. Inductively coupled plasma optical emission spectrometry (ICP-OES) indicates that this new solid-phase sorbent could facilitate the maximum static adsorption capacities of 5.4, 13.8, 6.6 and 9.5 mg g(-1) for Cr(III), Fe(III), Pb(II), and Mn(II) ions, respectively, showing the adsorption capacity up to 95% within about 30 min. Moreover, the detection limits of the GO-MCNTs-DETA-based analysis method were found to be 0.16, 0.50, 0.24 and 0.38 ng mL(-1) for Cr(III), Fe(III), Pb(II), and Mn(II) ions, respectively, with the relative standard deviation of lower than 3.0% (n=5). Importantly, common coexisting ions showed no significant interference on the separation and pre-concentration of these heavy metal ions at pH 4.0. Subsequently, the GO-MCNTs-DETA sorbent was successfully employed for the separation and analysis of trace-level Cr(III), Fe(III), Pb(II), and Mn(II) ions in wastewater samples yielding 75-folds concentration factors. PMID:26695275

  6. Studies on some salicylaldehyde Schiff base derivatives and their complexes with Cr(III), Mn(II), Fe(III), Ni(II) and Cu(II).

    PubMed

    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 pK(a) values spectrophotometrically. PMID:17084104

  7. Studies on some salicylaldehyde Schiff base derivatives and their complexes with Cr(III), Mn(II), Fe(III), Ni(II) and Cu(II)

    NASA Astrophysics Data System (ADS)

    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.

  8. Sphaerotilus natans encrusted with nanoball-shaped Fe(III) oxide minerals formed by nitrate-reducing mixotrophic Fe(II) oxidation.

    PubMed

    Park, Sunhwa; Kim, Dong-Hun; Lee, Ji-Hoon; Hur, Hor-Gil

    2014-10-01

    Ferrous iron has been known to function as an electron source for iron-oxidizing microorganisms in both anoxic and oxic environments. A diversity of bacteria has been known to oxidize both soluble and solid-phase Fe(II) forms coupled to the reduction of nitrate. Here, we show for the first time Fe(II) oxidation by Sphaerotilus natans strain DSM 6575(T) under mixotrophic condition. Sphaerotilus natans has been known to form a sheath structure enclosing long chains of rod-shaped cells, resulting in a thick biofilm formation under oxic conditions. Here, we also demonstrate that strain DSM 6575(T) grows mixotrophically with pyruvate, Fe(II) as electron donors and nitrate as an electron acceptor and single cells of strain DSM 6575(T) are dominant under anoxic conditions. Furthermore, strain DSM 6575(T) forms nanoball-shaped amorphous Fe(III) oxide minerals encrusting on the cell surfaces through the mixotrophic iron oxidation reaction under anoxic conditions. We propose that cell encrustation results from the indirect Fe(II) oxidation by biogenic nitrite during nitrate reduction and that causes the bacterial morphological change to individual rod-shaped single cells from filamentous sheath structures. This study extends the group of existing microorganisms capable of mixotrophic Fe(II) oxidation by a new strain, S. natans strain DSM 6575(T) , and could contribute to biogeochemical cycles of Fe and N in the environment. PMID:24965827

  9. Role of the Chemical Environment beyond the Coordination Site: Structural Insight into Fe(III) Protoporphyrin Binding to Cysteine-Based Heme-Regulatory Protein Motifs.

    PubMed

    Brewitz, Hans Henning; Kühl, Toni; Goradia, Nishit; Galler, Kerstin; Popp, Jürgen; Neugebauer, Ute; Ohlenschläger, Oliver; Imhof, Diana

    2015-10-12

    The importance of heme as a transient regulatory molecule has become a major focus in biochemical research. However, detailed information about the molecular basis of transient heme-protein interactions is still missing. We report an in-depth structural analysis of Fe(III) heme-peptide complexes by a combination of UV/Vis, resonance Raman, and 2D-NMR spectroscopic methods. The experiments reveal insights both into the coordination to the central iron ion and into the spatial arrangement of the amino acid sequences interacting with protoporphyrin IX. Cysteine-based peptides display different heme-binding behavior as a result of the existence of ordered, partially ordered, and disordered conformations in the heme-unbound state. Thus, the heme-binding mode is clearly the consequence of the nature and flexibility of the residues surrounding the iron ion coordinating cysteine. Our analysis reveals scenarios for transient binding of heme to heme-regulatory motifs in proteins and demonstrates that a thorough structural analysis is required to unravel how heme alters the structure and function of a particular protein. PMID:26260099

  10. In situ chemical oxidation of contaminated groundwater by persulfate: decomposition by Fe(III)- and Mn(IV)-containing oxides and aquifer materials.

    PubMed

    Liu, Haizhou; Bruton, Thomas A; Doyle, Fiona M; Sedlak, David L

    2014-09-01

    Persulfate (S2O8(2-)) is being used increasingly for in situ chemical oxidation (ISCO) of organic contaminants in groundwater, despite an incomplete understanding of the mechanism through which it is converted into reactive species. In particular, the decomposition of persulfate by naturally occurring mineral surfaces has not been studied in detail. To gain insight into the reaction rates and mechanism of persulfate decomposition in the subsurface, and to identify possible approaches for improving its efficacy, the decomposition of persulfate was investigated in the presence of pure metal oxides, clays, and representative aquifer solids collected from field sites in the presence and absence of benzene. Under conditions typical of groundwater, Fe(III)- and Mn(IV)-oxides catalytically converted persulfate into sulfate radical (SO4(•-)) and hydroxyl radical (HO(•)) over time scales of several weeks at rates that were 2-20 times faster than those observed in metal-free systems. Amorphous ferrihydrite was the most reactive iron mineral with respect to persulfate decomposition, with reaction rates proportional to solid mass and surface area. As a result of radical chain reactions, the rate of persulfate decomposition increased by as much as 100 times when benzene concentrations exceeded 0.1 mM. Due to its relatively slow rate of decomposition in the subsurface, it can be advantageous to inject persulfate into groundwater, allowing it to migrate to zones of low hydraulic conductivity where clays, metal oxides, and contaminants will accelerate its conversion into reactive oxidants. PMID:25133603

  11. Sphaerotilus natans encrusted with nanoball-shaped Fe(III) oxide minerals formed by nitrate-reducing mixotrophic Fe(II) oxidation

    PubMed Central

    Park, Sunhwa; Kim, Dong-Hun; Lee, Ji-Hoon; Hur, Hor-Gil

    2014-01-01

    Ferrous iron has been known to function as an electron source for iron-oxidizing microorganisms in both anoxic and oxic environments. A diversity of bacteria has been known to oxidize both soluble and solid-phase Fe(II) forms coupled to the reduction of nitrate. Here, we show for the first time Fe(II) oxidation by Sphaerotilus natans strain DSM 6575T under mixotrophic condition. Sphaerotilus natans has been known to form a sheath structure enclosing long chains of rod-shaped cells, resulting in a thick biofilm formation under oxic conditions. Here, we also demonstrate that strain DSM 6575T grows mixotrophically with pyruvate, Fe(II) as electron donors and nitrate as an electron acceptor and single cells of strain DSM 6575T are dominant under anoxic conditions. Furthermore, strain DSM 6575T forms nanoball-shaped amorphous Fe(III) oxide minerals encrusting on the cell surfaces through the mixotrophic iron oxidation reaction under anoxic conditions. We propose that cell encrustation results from the indirect Fe(II) oxidation by biogenic nitrite during nitrate reduction and that causes the bacterial morphological change to individual rod-shaped single cells from filamentous sheath structures. This study extends the group of existing microorganisms capable of mixotrophic Fe(II) oxidation by a new strain, S. natans strain DSM 6575T, and could contribute to biogeochemical cycles of Fe and N in the environment. PMID:24965827

  12. Fe(III) hydroxide nucleation and growth on quartz in the presence of Cu(II), Pb(II), and Cr(III): metal hydrolysis and adsorption.

    PubMed

    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

  13. Highly Enantioselective Iron-Catalyzed cis-Dihydroxylation of Alkenes with Hydrogen Peroxide Oxidant via an Fe(III) -OOH Reactive Intermediate.

    PubMed

    Zang, Chao; Liu, Yungen; Xu, Zhen-Jiang; Tse, Chun-Wai; Guan, Xiangguo; Wei, Jinhu; Huang, Jie-Sheng; Che, Chi-Ming

    2016-08-22

    The development of environmentally benign catalysts for highly enantioselective asymmetric cis-dihydroxylation (AD) of alkenes with broad substrate scope remains a challenge. By employing [Fe(II) (L)(OTf)2 ] (L=N,N'-dimethyl-N,N'-bis(2-methyl-8-quinolyl)-cyclohexane-1,2-diamine) as a catalyst, cis-diols in up to 99.8 % ee with 85 % isolated yield have been achieved in AD of alkenes with H2 O2 as an oxidant and alkenes in a limiting amount. This "[Fe(II) (L)(OTf)2 ]+H2 O2 " method is applicable to both (E)-alkenes and terminal alkenes (24 examples >80 % ee, up to 1 g scale). Mechanistic studies, including (18) O-labeling, UV/Vis, EPR, ESI-MS analyses, and DFT calculations lend evidence for the involvement of chiral Fe(III) -OOH active species in enantioselective formation of the two C-O bonds. PMID:27457506

  14. Texturing a pyramid-like structure on a silicon surface via the synergetic effect of copper and Fe(III) in hydrofluoric acid solution

    NASA Astrophysics Data System (ADS)

    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 <1 0 0> 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.

  15. In Situ Chemical Oxidation of Contaminated Groundwater by Persulfate: Decomposition by Fe(III)- and Mn(IV)-Containing Oxides and Aquifer Materials

    PubMed Central

    2015-01-01

    Persulfate (S2O82–) is being used increasingly for in situ chemical oxidation (ISCO) of organic contaminants in groundwater, despite an incomplete understanding of the mechanism through which it is converted into reactive species. In particular, the decomposition of persulfate by naturally occurring mineral surfaces has not been studied in detail. To gain insight into the reaction rates and mechanism of persulfate decomposition in the subsurface, and to identify possible approaches for improving its efficacy, the decomposition of persulfate was investigated in the presence of pure metal oxides, clays, and representative aquifer solids collected from field sites in the presence and absence of benzene. Under conditions typical of groundwater, Fe(III)- and Mn(IV)-oxides catalytically converted persulfate into sulfate radical (SO4•–) and hydroxyl radical (HO•) over time scales of several weeks at rates that were 2–20 times faster than those observed in metal-free systems. Amorphous ferrihydrite was the most reactive iron mineral with respect to persulfate decomposition, with reaction rates proportional to solid mass and surface area. As a result of radical chain reactions, the rate of persulfate decomposition increased by as much as 100 times when benzene concentrations exceeded 0.1 mM. Due to its relatively slow rate of decomposition in the subsurface, it can be advantageous to inject persulfate into groundwater, allowing it to migrate to zones of low hydraulic conductivity where clays, metal oxides, and contaminants will accelerate its conversion into reactive oxidants. PMID:25133603

  16. Bioactivity of pyridine-2-thiolato-1-oxide metal complexes: Bi(III), Fe(III) and Ga(III) complexes as potent anti-Mycobacterium tuberculosis prospective agents.

    PubMed

    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

  17. Coordination polymers of Fe(iii) and Al(iii) ions with TCA ligand: distinctive fluorescence, CO2 uptake, redox-activity and oxygen evolution reaction.

    PubMed

    Dhara, Barun; Sappati, Subrahmanyam; Singh, Santosh K; Kurungot, Sreekumar; Ghosh, Prasenjit; Ballav, Nirmalya

    2016-04-28

    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

  18. Cr(III), Fe(III) and Co(III) complexes of tetradentate (ONNO) Schiff base ligands: Synthesis, characterization, properties and biological activity

    NASA Astrophysics Data System (ADS)

    Keskioğlu, Eren; Gündüzalp, Ayla Balaban; Çete, Servet; Hamurcu, Fatma; Erk, Birgül

    2008-08-01

    A series of metal complexes were synthesized from equimolar amounts of Schiff bases: 1,4-bis[3-(2-hydroxy-1-naphthaldimine)propyl]piperazine (bappnaf) and 1,8-bis[3-(2-hydroxy-1-naphthaldimine)- p-menthane (damnaf) with metal chlorides. All of synthesized compounds were characterized by elemental analyses, spectral (UV-vis, IR, 1H- 13C NMR, LC-MS) and thermal (TGA-DTA) methods, magnetic and conductance measurements. Schiff base complexes supposed in tetragonal geometry have the general formula [M(bappnaf or damnaf)]Cl· nH 2O, where M = Cr(III), Co(III) and n = 2, 3. But also Fe(III) complexes have octahedral geometry by the coordination of two water molecules and the formula is [Fe(bappnaf or damnaf)(H 2O) 2]Cl. The changes in the selected vibration bands in FT-IR indicate that Schiff bases behave as (ONNO) tetradentate ligands and coordinate to metal ions from two phenolic oxygen atoms and two azomethine nitrogen atoms. Conductance measurements suggest 1:1 electrolytic nature of the metal complexes. The synthesized compounds except bappnaf ligand have the antimicrobial activity against the bacteria: Escherichia coli (ATCC 11230), Yersinia enterocolitica (ATCC 1501), Bacillus magaterium (RSKK 5117), Bacillus subtilis (RSKK 244), Bacillus cereus (RSKK 863) and the fungi: Candida albicans (ATCC 10239). These results have been considerably interest in piperazine derivatives due to their significant applications in antimicrobial studies.

  19. In situ atomic force microscopy investigation of the [100] face of KH2PO4 in the presence of Fe(III), Al(III), and Cr(III).

    PubMed

    Thomas, Tiffany N; Land, Terry A; DeYoreo, Jim J; Casey, William H

    2004-08-31

    Here we report the effects of dissolved metal complexes of Fe(III), Al(III), and Cr(III) on the step velocities of the [100] face of KH2PO4 (KDP) as observed with atomic force microscopy. The dependence of step velocity on supersaturation (sigma) exhibits a dead zone that scales with adsorbate concentration. The observed dependence varies with the metal complex. From these data, we derive values for the characteristic adsorption time (tau) for the Al(III) and Cr(III) step-pinning adsorbates as being on the order of several hundred microseconds as compared to 10-100 s for the corresponding Fe(III) step-pinning adsorbates. The values of tau are strikingly different than rates of ligand exchange but are associated with the adsorbate-induced morphology of the surface, including elementary steps that bunch into macrosteps and supersteps. The stoichiometry of the adsorbate species is assumed to be M(HxPO4)x, where M = Fe(III), Al(III), or Cr(III). KDP crystals grown in the presence of the dissolved metals were analyzed using laser ablation inductively coupled plasma mass spectroscopy. The data revealed sectoral zoning on the [100] face, with the concentrations of the incorporated adsorbates in the sector with slower moving elementary steps being 1.7-2.0 times greater than those measured on the sector with fast moving elementary steps. PMID:15323514

  20. Structure, infrared and Raman spectroscopic studies of newly synthetic AII(SbV0.50FeIII0.50)(PO4)2 (Adbnd Ba, Sr, Pb) phosphates with yavapaiite structure

    NASA Astrophysics Data System (ADS)

    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.

  1. Supramolecular 2D/3D isomerism in a compound containing heterometallic Cu(II)2Co(II) nodes and dicyanamide bridges.

    PubMed

    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

  2. Spectroscopic (FT-IR, FT-Raman, 1H, 13C NMR, UV/VIS), thermogravimetric and antimicrobial studies of Ca(II), Mn(II), Cu(II), Zn(II) and Cd(II) complexes of ferulic acid

    NASA Astrophysics Data System (ADS)

    Kalinowska, M.; Piekut, J.; Bruss, A.; Follet, C.; Sienkiewicz-Gromiuk, J.; Świsłocka, R.; Rzączyńska, Z.; Lewandowski, W.

    2014-03-01

    The molecular structure of Mn(II), Cu(II), Zn(II), Cd(II) and Ca(II) ferulates (4-hydroxy-3-methoxycinnamates) was studied. The selected metal ferulates were synthesized. Their composition was established by means of elementary and thermogravimetric analysis. The following spectroscopic methods were used: infrared (FT-IR), Raman (FT-Raman), nuclear magnetic resonance (13C, 1H NMR) and ultraviolet-visible (UV/VIS). On the basis of obtained results the electronic charge distribution in studied metal complexes in comparison with ferulic acid molecule was discussed. The microbiological study of ferulic acid and ferulates toward Escherichia coli, Bacillus subtilis, Candida albicans, Pseudomonas aeruginosa, Staphylococcus aureus and Proteus vulgaris was done.

  3. Spectroscopic characterization and biological activity of Zn(II), Cd(II), Sn(II) and Pb(II) complexes with Schiff base derived from pyrrole-2-carboxaldehyde and 2-amino phenol

    NASA Astrophysics Data System (ADS)

    Singh, Bibhesh K.; Prakash, Anant; Rajour, Hemant K.; Bhojak, Narendar; Adhikari, Devjani

    2010-08-01

    A new Schiff base 2-aminophenol-pyrrole-2-carboxaldehyde and its Zn(II), Cd(II), Sn(II) and Pb(II) complexes have been synthesized and characterized by various physicochemical studies. Spectral studies (IR and 1H NMR) indicate deprotonation and coordination of phenolic oxygen along with binding of pyrrole nitrogen, azomethine nitrogen and anion with metal ions. The presence of lattice water molecule(s) has also been confirmed by TG/DTA studies. Mass spectrum explains the successive degradation of the molecular species in solution and justifies ML complexes. Kinetic and thermodynamic parameters were computed from the thermal data using Coats and Redfern method, which confirm first order kinetics. The bio-efficacy of the ligand and their complexes has been examined against the growth of bacteria in vitro to evaluate their antimicrobial potential. Molecular structures of the complexes have been optimized by MM2 calculations and suggest a tetrahedral geometry around metal ions.

  4. The bipyridine adducts of N-phenyldithiocarbamato complexes of Zn(II) and Cd(II); synthesis, spectral, thermal decomposition studies and use as precursors for ZnS and CdS nanoparticles

    NASA Astrophysics Data System (ADS)

    Onwudiwe, Damian C.; Strydom, Christien A.

    2015-01-01

    Bipyridine adducts of N-phenyldithiocarbamato complexes, [ML12L2] (M = Cd(II), Zn(II); L1 = N-phenyldithiocarbamate, L2 = 2,2‧ bipyridine), have been synthesized and characterised. The decomposition of these complexes to metal sulphides has been investigated by thermogravimetric analysis (TGA). The complexes were used as single-source precursors to synthesize MS (M = Zn, Cd) nanoparticles (NPs) passivated by hexadecyl amine (HDA). The growth of the nanoparticles was carried out at two different temperatures: 180 and 220 °C, and the optical and structural properties of the nanoparticles were studied using UV-Vis spectroscopy, photoluminescence spectroscopy (PL), transmission emission microscopy (TEM) and powdered X-ray diffraction (p-XRD). Nanoparticles, whose average diameters are 2.90 and 3.54 nm for ZnS, and 8.96 and 9.76 nm for CdS grown at 180 and 220 °C respectively, were obtained.

  5. New macrocyclic schiff base complexes incorporating a homopiperazine unit: Synthesis of some Co(II), Ni(II),Cu(II) and Zn(II) complexes and crystal structure and theoretical studies

    NASA Astrophysics Data System (ADS)

    Keypour, Hassan; Rezaeivala, Majid; Ramezani-Aktij, Ameneh; Bayat, Mehdi; Dilek, Nefise; Ünver, Hüseyin

    2016-07-01

    A new macrocyclic Schiff base ligand, L, was synthesized by condensation reaction of 1,4-bis(2-formylphenyl)homopiperazine and 1,4-diaminobutane in acetonitrile. The Schiff base ligand was characterized by using elemental analyses, FT-IR, 1H, 13C NMR and mass spectroscopic techniques. The metal (II) complexes [ML], were synthesized from the reaction of MCl2.nH2O (M: Co, Ni, Cu and Zn) with Schiff base ligand, L and characterized by elemental analyses and FT-IR. X-ray crystal structure of [CoLCl]+ distorted square pyramidal geometry with an N4Cl core, arising from coordination by the four donor nitrogen atoms from the macrocyclic framework and one Cl atom. It crystallizes triclinic space group, P-1 with a = 7.1777(1) Å, b = 11.0357 (2) Å, c = 15.1520(2) Å, V = 1183.14(3), Z = 2, Dc = 1.556 g cm-3, μ (MoKα) = 0.156 mm-1. Also, the bonding situation between the [MCl]+ and Ligand (L) fragments in [MLCl]ClO4 (M = Co(II), Ni(II), Cu(II), Zn(II)) complexes were carried out by energy-decomposition analysis (EDA). The results showed that there is an increasing trend in the case of ΔEelstat of the complexes by changing the M from Co(II) to Zn(II).

  6. Synthesis, characterization and biological activity of some new VO(IV), Co(II), Ni(II), Cu(II) and Zn(II) complexes of chromone based NNO Schiff base derived from 2-aminothiazole

    NASA Astrophysics Data System (ADS)

    Kalanithi, M.; Kodimunthiri, D.; Rajarajan, M.; Tharmaraj, P.

    2011-11-01

    Coordination compounds of VO(IV), Co(II), Ni(II), Cu(II) and Zn(II) with the Schiff base obtained through the condensation of 2-aminothiazole with 3-formyl chromone were synthesized. The compounds were characterized by 1H, 13C NMR, UV-Vis, IR, Mass, EPR, molar conductance and magnetic susceptibility measurements. The Cu(II) complex possesses tetrahedrally distorted square planar geometry whereas Co(II), Ni(II), and Zn(II) show distorted tetrahedral geometry. The VO(IV) complex shows square pyramidal geometry. The cyclic voltammogram of Cu (II) complex showed a well defined redox couple Cu(II)/Cu(I) with quasireversible nature. The antimicrobial activity against the species Pseudomonas aeruginosa, Escherichia coli, Staphylococcus aureus, Bacillus subtilis, Candida albigans and Aspergillus niger was screened and compared to the activity of the ligand. Emission spectrum was recorded for the ligand and the metal(II) complexes. The second harmonic generation (SHG) efficiency was measured and found to have one fourth of the activity of urea. The SEM image of the copper(II) complex implies that the size of the particles is 2 μm.

  7. 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

    NASA Astrophysics Data System (ADS)

    El-Boraey, Hanaa A.

    2012-11-01