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Sample records for cobalt ii oxinate

  1. Gravimetric determination of beryllium with sodium oxinate.

    PubMed

    Hundekar, A M; Umapathy, P; Sen, D N

    1978-04-01

    Sodium oxinate is found to precipitate Be(II) quantitatively in the pH range 7.5-8.2. The complex has the composition Be(2)O(C(9)H(6)NO)(2).2H(2)O, is stable and can be weighed directly after drying at 105-110 degrees . A method for the estimation of Be(II) and its separation from interfering elements is described. The monohydrate has been prepared from the dihydrate and characterized. The results show the presence of hydroxyl bridges in the monohydrate. Methods using various organic reagents for the direct estimation of beryllium in ores and alloys have been examined and it is found that 4-chloro-2,5-dimethoxyacetoacetanilide gives the best results. A method for the determination of be(II) in beryl without prior separation of Fe(III) and Al(III) is described.

  2. Cobalt(II) and Cobalt(III) Coordination Compounds.

    ERIC Educational Resources Information Center

    Thomas, Nicholas C.; And Others

    1989-01-01

    Presents a laboratory experiment which illustrates the formation of tris(phenanthroline)cobalt complexes in the 2+ and 3+ oxidation states, the effect of coordination on reactions of the ligand, and the use of a ligand displacement reaction in recovering the transformed ligand. Uses IR, UV-VIS, conductivity, and NMR. (MVL)

  3. Cobalt(II) and Cobalt(III) Coordination Compounds.

    ERIC Educational Resources Information Center

    Thomas, Nicholas C.; And Others

    1989-01-01

    Presents a laboratory experiment which illustrates the formation of tris(phenanthroline)cobalt complexes in the 2+ and 3+ oxidation states, the effect of coordination on reactions of the ligand, and the use of a ligand displacement reaction in recovering the transformed ligand. Uses IR, UV-VIS, conductivity, and NMR. (MVL)

  4. Cobalt(II) complexes with hydroxypyridines and halogenides

    NASA Astrophysics Data System (ADS)

    Dojer, Brina; Pevec, Andrej; Jagličić, Zvonko; Kristl, Matjaž

    2017-01-01

    We have synthesized and characterized two new cobalt(II) complexes: difluoridotetrakis(3-hydroxypyridine-κN)cobalt(II), [CoF2(C5H5NO)4] (1) and hexa(2-pyridone-κO)cobalt(II) tetrachloridocobaltate(II), [Co(C5H5NO)6][CoCl4] (2). The complexes were prepared by solvothermal synthesis. A methanol solution of hydroxypyridine was added to water solution of cobalt(II) acetate dihydrate followed by a few drops of concentrated hydrofluoric or hydrochloric acid into the mixture. The crystals of the compounds 1 and 2 are stable on air. The compounds were characterized structurally by single-crystal X-ray diffraction analysis, spectrally by FT-IR spectroscopy and thermally. Thermal analysis showed that the final product of both complexes after heating to 900 °C is elemental cobalt. The interactions between building units in the crystal structures include intra- and intermolecular hydrogen bonds in both compounds and π-π interactions in compound 2.

  5. [Spectral evidences for aggregation of sulfonated naphthalocyanine zinc (II) and cobalt (II)].

    PubMed

    Liu, Ying; Liu, Yue; Zuo, Xia; Wu, Yi-qun

    2004-06-01

    When the naphthalocyanines were sulfonated to give sulfonated naphthalocyanine cobalt (II) and sulfonated naphthalocyanine zinc (II), enhanced aggregation tendency was observed. The Q band of the fluorescence emission spectra and electronic absorption spectra for sulfonated naphthalocyanine zinc (II) and sulfonated naphthalocyanine cobalt (II) in the solutions of DMF and ethanol showed that the excimer or the aggregation form coexists with the monomer, that the aggregation form dissociates into its monomer when the excimer releases a photon or the ground aggregation form absorbs a photon, and that mirror symmetry exists between the fluorescence emission spectrum of the excimer and the electronic absorption spectrum of the corresponding ground aggregation form. There is a red shift for the excimer in the fluorescence emission spectrum and a blue shift for the aggregation form in the electronic absorption spectrum of the Q band. The quenching effect in fluorescence emission spectrum is large when the concentration of sulfonated naphthalocyanine cobalt (II) is high.

  6. Analysis of cobalt(II) in 2-(5-cyanotetrazolato)pentaammine cobalt(III) perchlorate

    SciTech Connect

    Schumacher, R.J.; Brown, N.E.; Deutsch, E.A.

    1985-10-30

    A new method of analysis is described for cobalt(II) complexes in 2-(5-cyanotetrazolato)pentaammine cobalt(III) perchlorate. The color reagent is 2,2'-dipyridyl-2-pyridyl hydrazone (DPPH), which complexes with the Co(II) and is oxidized to a substitution inert Co(III) (DPPH)/sub 2/ complex. Interferences from other ions is not a problem because the complex is stable at pH 2 - where complexes formed between DPPH and other ions are not stable. The usual air oxidant in this type of analysis has been replaced with ammonium peroxydisulfate improving both the precision and accuracy. The Sandell sensitivity is 0.0015 ..mu..g Co(II)/cm/sup 2/. The system obeys Beer's Law up to 4 ..mu..g in Co(II)mL of solution and has a molar absorptivity of 3.9 x 10/sup 4/ L/mole cm at 514 nm. The procedure was used to determine the degree of decomposition in samples that had undergone partial thermal decomposition. 11 refs., 4 figs., 6 tabs.

  7. Cobalt(II) selective membrane electrode based on palladium(II) dichloro acetylthiophene fenchone azine.

    PubMed

    Isa, I M; Mustafar, S; Ahmad, M; Hashim, N; Ghani, S A

    2011-12-15

    A new cobalt(II) ion selective electrode based on palladium(II) dichloro acetylthiophene fenchone azine(I) has been developed. The best membrane composition is found to be 10:60:10:21.1 (I)/PVC/NaTPB/DOP (w/w). The electrode exhibits a Nerstian response in the range of 1.0 × 10(-1)-1.0 × 10(-6)M with a detection limit and slope of 8.0 × 10(-7)M and 29.6 ± 0.2 mV per decade respectively. The response time is within the range of 20-25s and can be used for a period of up to 4 months. The electrode developed reveals good selectivity for cobalt(II) and could be used in pH range of 3-7. The electrode has been successfully used in the determination of cobalt(II) in water samples.

  8. Spectroelectrochemical studies of cobalt(II) porphyrins with paracyclophanyl, pyridinium and nucleoside substituents

    NASA Astrophysics Data System (ADS)

    Malinski, T.; Kubaszewski, E.; Bennett, J.; Fish, J.; Niedbala, H.; Wheeler, D. E.; Czuchajowski, L.

    1992-07-01

    This work describes the synthesis of novel cobalt complexes of porphyrins: ( meso-tetrakis [2.2]paracyclophanylporphyrinato)cobalt(II) (T(PCP)PCo(II)); ( meso-mono[2.2]paracyclophanyltriphenylporphyrinato)cobalt(II) (PCPPCo(II)); ( meso-tetrakis(5'-0- p-phenylene-2',3'-0-isopropylideneuridine)porphyrinato)cobalt(II) (TPUPCo(II)), and ( meso-5'-0- p-phenylene-2',3'-0-isopropylideneuridinetri( N-methyl-4-pyridinium)porphyrinato)cobalt(II) (PUPCo(II)). The redox properties of these complexes were characterized by voltammetry and UV—visible spectroelectrochemistry. The effects of the electron-donating and electron-withdrawing properties of the substituents on the electrochemical and spectroscopic data obtained are described and discussed. These compounds are the first examples of a linkage of a biomolecule, such as uridine, with the porphyrin system. These porphyrins also undergo electrochemical polymerization with the formation of conductive films.

  9. Preparation and Spectroscopic Studies of Cobalt(II)-Stellacyanin

    PubMed Central

    McMillin, David R.; Holwerda, Robert A.; Gray, Harry B.

    1974-01-01

    The cobalt(II) derivative of the “blue” copper protein stellacyanin has been prepared, and its visible-ultraviolet spectrum is reported. Tryptophan fluorescence quenching and p-mercuribenzoate titration results strongly suggest that Co(II) and Cu(II) compete for the same stellacyanin binding site and that a cysteine sulfur atom is coordinated in both cases. This interpretation is supported by the finding of an intense band at 355 nm in Co(II)-stellacyanin attributable to a charge transfer transition of the RS- → Co(II) type. The visible absorption spectrum of Co(II)-stellacyanin exhibits band maxima at 540, 625, and 655 nm. These bands are attributable to d-d transitions originating in a high-spin Co(II) center. It is suggested that a correspondence exists between charge transfer bands observed at 355 and 300 nm in the Co(II) derivative to those found at 604 and 450 nm in the native protein. It is concluded that the intense 604-nm peak in Cu(II)-stellacyanin is attributable to a cys-S → Cu(II) charge transfer transition. PMID:4275396

  10. Preparation and spectroscopic studies of cobalt(II)-stellacyanin.

    PubMed

    McMillin, D R; Holwerda, R A; Gray, H B

    1974-04-01

    The cobalt(II) derivative of the "blue" copper protein stellacyanin has been prepared, and its visible-ultraviolet spectrum is reported. Tryptophan fluorescence quenching and p-mercuribenzoate titration results strongly suggest that Co(II) and Cu(II) compete for the same stellacyanin binding site and that a cysteine sulfur atom is coordinated in both cases. This interpretation is supported by the finding of an intense band at 355 nm in Co(II)-stellacyanin attributable to a charge transfer transition of the RS(-) --> Co(II) type. The visible absorption spectrum of Co(II)-stellacyanin exhibits band maxima at 540, 625, and 655 nm. These bands are attributable to d-d transitions originating in a high-spin Co(II) center. It is suggested that a correspondence exists between charge transfer bands observed at 355 and 300 nm in the Co(II) derivative to those found at 604 and 450 nm in the native protein. It is concluded that the intense 604-nm peak in Cu(II)-stellacyanin is attributable to a cys-S --> Cu(II) charge transfer transition.

  11. Cobalt.

    PubMed

    Fowler, Joseph F

    2016-01-01

    Cobalt has been a recognized allergen capable of causing contact dermatitis for decades. Why, therefore, has it been named 2016 "Allergen of the Year"? Simply put, new information has come to light in the last few years regarding potential sources of exposure to this metallic substance. In addition to reviewing some background on our previous understanding of cobalt exposures, this article will highlight the recently recognized need to consider leather as a major site of cobalt and the visual cues suggesting the presence of cobalt in jewelry. In addition, a chemical spot test for cobalt now allows us to better identify its presence in suspect materials.

  12. Cobalt

    SciTech Connect

    1993-02-01

    Cobalt is typical a by- or co-product with copper or nickel. The average crustal abundance of cobalt is 23 pans per million. Cobalt-containing minerals include cobaltite, skutterudite, and linnaeite. Due to the diversity of cobalt deposits, several techniques are used to extract the ore. The copper/cobalt-bearing ores of Zaire are extracted by open pit and underground methods. In Zambia, similar deposits are mined using modified sublevel, and cut-and-fill underground stoping methods. The sulfide and oxide ore concentrates mined in Zaire are roasted and leached in sulfuric acid. Copper is subsequently recovered by electrolysis, and cobalt is precipitated in the form of a hydrate. Finally, the hydrate is dissolved in acid and cobalt is recovered by electrolysis.

  13. Metal thiolate clusters in cobalt(II)-metallothionein.

    PubMed

    Vasák, M; Kägi, J H

    1981-11-01

    Rabbit liver metallothionein-1 in which all seven metal-binding sites are occupied by cobalt(II) exhibits spectral features typical of tetrathiolate coordination with approximate Td microsymmetry [Vasák, M. (1980) J. Am. Chem. Soc. 102, 3953-3955]. With a total of 20 cysteine residues per molecule, this mode of metal binding implies that some of the thiolate ligands are shared by neighboring Co(II) ions, resulting in clustered structures. In this study, evidence for the existence of thiolate-linked Co(II) clusters is presented and their mode of formation is explored by comparing the optical and magnetic properties of forms of Co(II)-metallothionein containing 1-7 equivalents of Co(II). Preparations with up to 4 Co(II) equivalents display electronic spectra in the d-d and charge-transfer regions that resemble those of isolated tetrahedral Co(II)-tetrathiolate complexes. Upon binding of more than four Co(II) ions, however, the spectrum changes progressively and approaches in the fully saturated Co(II)-metallothionein an absorption profile similar to that of crystallographically defined model (Co)II-tetrathiolate clusters [Dance, I. G. (1979) J. Am. Chem. Soc. 101, 6264-6273]. These effects are closely paralleled by changes in the ESR spectrum. Above 4 Co(II) equivalents per thionein, the ESR signal at gx approximately 5.9 measured at 4 K decreases progressively in intensity, until in the fully occupied protein the complex is nearly diamagnetic. These changes, which were confirmed by measurements of paramagnetic susceptibility, establish the existence of Co(II) thiolate clusters in Co(II)-metallothionein. The loss of paramagnetism reflects most likely antiferromagnetic coupling of neighboring Co(II) ions brought about by a superexchange mechanism via the thiolate bridging ligands.

  14. Metal thiolate clusters in cobalt(II)-metallothionein.

    PubMed Central

    Vasák, M; Kägi, J H

    1981-01-01

    Rabbit liver metallothionein-1 in which all seven metal-binding sites are occupied by cobalt(II) exhibits spectral features typical of tetrathiolate coordination with approximate Td microsymmetry [Vasák, M. (1980) J. Am. Chem. Soc. 102, 3953-3955]. With a total of 20 cysteine residues per molecule, this mode of metal binding implies that some of the thiolate ligands are shared by neighboring Co(II) ions, resulting in clustered structures. In this study, evidence for the existence of thiolate-linked Co(II) clusters is presented and their mode of formation is explored by comparing the optical and magnetic properties of forms of Co(II)-metallothionein containing 1-7 equivalents of Co(II). Preparations with up to 4 Co(II) equivalents display electronic spectra in the d-d and charge-transfer regions that resemble those of isolated tetrahedral Co(II)-tetrathiolate complexes. Upon binding of more than four Co(II) ions, however, the spectrum changes progressively and approaches in the fully saturated Co(II)-metallothionein an absorption profile similar to that of crystallographically defined model (Co)II-tetrathiolate clusters [Dance, I. G. (1979) J. Am. Chem. Soc. 101, 6264-6273]. These effects are closely paralleled by changes in the ESR spectrum. Above 4 Co(II) equivalents per thionein, the ESR signal at gx approximately 5.9 measured at 4 K decreases progressively in intensity, until in the fully occupied protein the complex is nearly diamagnetic. These changes, which were confirmed by measurements of paramagnetic susceptibility, establish the existence of Co(II) thiolate clusters in Co(II)-metallothionein. The loss of paramagnetism reflects most likely antiferromagnetic coupling of neighboring Co(II) ions brought about by a superexchange mechanism via the thiolate bridging ligands. PMID:6273885

  15. [Study on the thermodynamical molar absorptivity of the interaction of cobalt(II) and the histidine].

    PubMed

    Chen, L; Zhang, D; Yang, D; He, Z; Wang, Y

    1999-02-01

    In this paper UV-Vis absorption spectrum of Cobalt(II) with the histidine and the thermodynamical molar absorptivity of the complex reaction were determined and the complexes of Cobalt(II) with the histidine were compared in terms of stability.

  16. Cobalt

    SciTech Connect

    Fox, G.J.

    1994-12-01

    Traditionally, cobalt has been well-known for its chemical uses, including pigments used in ceramic glazes that create the popular cobalt blue color derived from cobalt aluminate. Because of its diverse physical properties, the element is linked to many other applications, including superalloys, permanent magnets, and chemical catalysts. Cobalt 60, a radioisotope of cobalt, continues to be a contributor to the success of high-technology advancements, including innovations in medical treatments. Typically a by-product of copper and nickel production, significant cobalt reserves are found in only a few countries. The African countries of Zaire and Zambia, as well as Canada, are leading cobalt producers. Although the USA is the world's largest consumer, accounting for about one-third of total consumption, it has no domestic production and relies solely upon foreign imports to satisfy demand. The world market has been plagued with the effects of economic and political factors throughout the years, and consequently, price instability has been common. Presently, supply and demand are moving toward a closer balance, and lower market prices are expected within the next year.

  17. Biosorption of copper(II) and cobalt(II) from aqueous solutions by crab shell particles.

    PubMed

    Vijayaraghavan, K; Palanivelu, K; Velan, M

    2006-08-01

    Biosorption of each of the heavy metals, copper(II) and cobalt(II) by crab shell was investigated in this study. The biosorption capacities of crab shell for copper and cobalt were studied at different particle sizes (0.456-1.117 mm), biosorbent dosages (1-10 g/l), initial metal concentrations (500-2000 mg/l) and solution pH values (3.5-6) in batch mode. At optimum particle size (0.767 mm), biosorbent dosage (5 g/l) and initial solution pH (pH 6); crab shell recorded maximum copper and cobalt uptakes of 243.9 and 322.6 mg/g, respectively, according to Langmuir model. The kinetic data obtained at different initial metal concentrations indicated that biosorption rate was fast and most of the process was completed within 2h, followed by slow attainment of equilibrium. Pseudo-second order model fitted the data well with very high correlation coefficients (>0.998). The presence of light and heavy metal ions influenced the copper and cobalt uptake potential of crab shell. Among several eluting agents, EDTA (pH 3.5, in HCl) performed well and also caused low biosorbent damage. The biosorbent was successfully regenerated and reused for five cycles.

  18. Determination of cobalt(II)-EDTA, cobalt(III)-EDTA, and cobalt(II) in an aqueous solution

    SciTech Connect

    Ayres, D.M.; Davis, A.P.

    1996-11-01

    The determination of Co-EDTA species is critical to the understanding of radionuclide migration in the environment, as well as determining efficiencies of various complexed-Co treatment technologies. A new, simple column-oxidation separation methodology was devised to determine the fraction of uncomplexed Co(II), Co(II)-EDTA, and Co(III)-EDTA in an aqueous mixture. A Dowex 50W (H{sup +}) ion-exchange resin, and the oxidative conversion of residual Co(II)-EDTA to Co(III)-EDTA using H{sub 2}O{sub 2}, allowed the separation of species fractions. Only atomic absorption spectrophotometric measurements were required after separation of the fractions. Analysis of individual Co species separated from mixtures ranging in concentration from 3 {times} 10{sup {minus}5} to 3 {times} 10{sup {minus}3} M total Co resulted in average recoveries of 97 {plus_minus} 4%. 15 refs., 2 tabs.

  19. Spectroscopic studies of cobalt(II) binding to Escherichia coli bacterioferritin.

    PubMed

    Keech, A M; Le Brun, N E; Wilson, M T; Andrews, S C; Moore, G R; Thomson, A J

    1997-01-03

    The iron storage protein bacterioferritin (BFR) consists of 24 identical subunits, each containing a dinuclear metal binding site called the ferroxidase center, which is essential for fast iron core formation. Cobalt(II) binding to wild-type and site-directed variants of Escherichia coli BFR was studied by optical and magnetic techniques. Data from absorption spectroscopy demonstrate the binding of two cobalt(II) ions per subunit of wild-type and heme-free BFR, each with a pseudotetrahedral or pentacoordinate geometry, and EPR studies show that the two cobalt(II) ions are weakly magnetically coupled. Studies of variants of BFR in which a single glutamic acid residue at the ferroxidase center is replaced by alanine confirm that this is the site of cobalt(II) binding, since the altered centers bind only one cobalt(II) ion. This work shows that the electroneutrality of the ferroxidase center is preserved on binding a pair of divalent metal ions. Optical and EPR data show that cobalt(II) binding to BFR exhibits positive cooperativity, with an average Kd of approximately 1 x 10(-5) M. The favored filling of the ferroxidase center with pairs of metal ions may have mechanistic implications for the iron(II) binding process. Discrimination against oxidation of single iron(II) ions avoids odd electron reduction products of oxygen.

  20. Leukemic cell labeling with indium-111-oxine

    SciTech Connect

    Uchida, T.; Takagi, Y.; Matsuda, S.; Yui, T.; Ishibashi, T.; Kimura, H.; Kariyone, S.

    1984-01-01

    Leukemic cells were labeled with In-111-oxine in patients with acute leukemia. In vitro labeling studies revealed that labeling efficiency reached maximum 80.8 +- 3.6% (mean +- 1SD) by 2 times washes after 20 minutes incubation time. Cell viability was assessed by trypan blue exclusion test and in vitro culture of leukemic cells, which showed no cellular damage during labeling procedure. Elution of In-111 from the labeled cells was 10.0 +- 1.2% at 12 hours after labeling. For in vivo leukemic cell kinetic studies, more than 10/sup 8/ leukemic cells separated from Ficoll-Hypacque sedimentation were labeled by 30 minutes of In-111-oxine incubation and two times washes at 37/sup 0/C. In vivo studies were performed in 7 patients with acute myeloblastic, lymphoblastic leukemia and blastic crisis of chronic myelocytic leukemia. Labeled leukemic cells disappeared in single exponential fashion with half life of 9.6 to 31.8 hours. Total leukemic cell pool in peripheral circulation was calculated, which correlated well with peripheral leukemic cell counts (r=0.99). No relationship was observed between total leukemic cell pool and leukemic cell turnover rate. Migration patterns of labeled leukemic cells showed that pulmonary uptake was evident within 15 minutes after the infusion and returned to base-line. Splenic and hepatic uptake showed gradual increase up to 24 hours. Bone marrow accumulation was shown only in 2 cases. Presently, there are no suitable radionuclides for leukemic cell labeling. In-111-oxine labeled leukemic cells would overcome this difficulty.

  1. Synthesis, Characterization, and Use of a Cobalt(II) Complex as an NMR Shift Reagent.

    ERIC Educational Resources Information Center

    Goff, Harold M.; And Others

    1982-01-01

    Describes procedures for preparing acetylacetonate complex of cobalt(II), followed by spectrophotometric analysis to characterize the material, with additional characterization methods supplied by students to provide open-ended dimension for the experiment. (SK)

  2. Structure of catabolite activator protein with cobalt(II) and sulfate

    SciTech Connect

    Rao, Ramya R.; Lawson, Catherine L.

    2014-04-15

    The crystal structure of E. coli catabolite activator protein with bound cobalt(II) and sulfate ions at 1.97 Å resolution is reported. The crystal structure of cyclic AMP–catabolite activator protein (CAP) from Escherichia coli containing cobalt(II) chloride and ammonium sulfate is reported at 1.97 Å resolution. Each of the two CAP subunits in the asymmetric unit binds one cobalt(II) ion, in each case coordinated by N-terminal domain residues His19, His21 and Glu96 plus an additional acidic residue contributed via a crystal contact. The three identified N-terminal domain cobalt-binding residues are part of a region of CAP that is important for transcription activation at class II CAP-dependent promoters. Sulfate anions mediate additional crystal lattice contacts and occupy sites corresponding to DNA backbone phosphate positions in CAP–DNA complex structures.

  3. Synthesis, Characterization, and Use of a Cobalt(II) Complex as an NMR Shift Reagent.

    ERIC Educational Resources Information Center

    Goff, Harold M.; And Others

    1982-01-01

    Describes procedures for preparing acetylacetonate complex of cobalt(II), followed by spectrophotometric analysis to characterize the material, with additional characterization methods supplied by students to provide open-ended dimension for the experiment. (SK)

  4. [Study on the interaction of cobalt (II) polyamidomine dendrimer with DNA by spectrometry techniques].

    PubMed

    Li, Jin-Huan; Ai, Shi-Yun; Shi, Wei-Jie; Yin, Huan-Shun; Du, Hong-Xia

    2009-03-01

    Cobalt (II) polyamidomine dendrimer was prepared by the reaction of cobalt chloride, glyoxal and polyamidomine dendrimer of 5.0 generation. The interaction of cobalt (II) polyamidomine dendrimer complex with herring sperm (hsDNA) was carried out using methylene blue (MB) as the probe molecule by absorption and fluorescence spectroscopy and synchronous fluorescence spectroscopy. The results showed that the intensity of absorption peaks and fluorescence peaks increased when the complex interacted with hsDNA. The effect of sodium chloride showed that sodium ion can significantly constrain the interaction of cobalt(II) polyamidomine dendrimer with hsDNA. The curves indicated the competitive inhibition of MB binding to hsDNA in the presence of cobalt (II) polyamidomine dendrimer complexes, also MB could insert into interior of cobalt (II) polyamidomine dendrimer complexes. The results suggested that the complex mainly interacted with negatively charged phosphate moieties on hsDNA through electrostatic attraction and stacked on the surface of double stranded hsDNA, which may reduce the binding affinity of MB to hsDNA in the surrounding site. It was indicated that sodium ion might neutralize the negatively charged phosphate backbone of hsDNA, and then weaken the electrostatic attraction between complexes and hsDNA.

  5. Aggregation of Cobalt (II) Tetrasulfonated Phthalocyanine in Methanol- Water Solutions

    DTIC Science & Technology

    1983-06-01

    10 2.1 Preparation of [29H, 31H- phthalocyanine -2,9, 16,23-tetra- sulfonate (2-) -N2’,N 3,N , ,N3 2] Cobalt (CoTSPC) ........... 10 2.2...INTRODUCTION In 1971 Abel and coworkers’ discovered that the cobalt (11) tetra- sulfonated phthalocyanine (TSPC), figure 1, binds oxygen reversibly as do oth...G.V. The Catalytic Properties of Sulfonated Cobalt Phthalocyanines with Oxidation of Cysteine and Hydrogen Sulphide. Kinetics and Catalysis, 14, 864

  6. Fabrication of nanosized cobalt powder from Cobalt(II) hydroxide of spent lithium ion battery

    NASA Astrophysics Data System (ADS)

    Yun, Jung-Yeul; Park, Dahee; Jung, Sung-Sik; Wang, Jei-Pil

    2017-09-01

    This study was investigated to fabricate nanosized cobalt (Co) powder from cobalt hydroxide Co(OH)2 recovered from spent lithium ion battery. Direct process newly proposed was attempted to transform phases as follow: Co(OH)2 → Co3O4 → Co. The variation of weight with time of the sample was measured using thermogravimetric analysis (TGA) and it was found that weight loss was observed over 500 °C. Thermal treatment was conducted to determine proper operating time for phase transformation of Co3O4 at 500 °C. Subsequently, hydrogen reduction was carried out on the effect of temperature, reaction time and flowrate. In the long run, nanosized cobalt powder was successfully fabricated with a mean particle size of 100-500 nm as well as purity of 99.21 wt.%.

  7. Synthesis, characterization, and photoactivated DNA cleavage by copper (II)/cobalt (II) mediated macrocyclic complexes.

    PubMed

    Naik, H R Prakash; Naik, H S Bhojya; Aravinda, T; Lamani, D S

    2010-01-01

    We report the synthesis of new photonuclease consisting of two Co(II)/Cu(II) complexes of macrocyclic fused quinoline. Metal complexes are [MLX(2)], type where M = Co(II) (5), Cu(II) (6), and X = Cl, and are well characterized by elemental analysis, Fourier transform infrared spectroscopy, (1)H-NMR and electronic spectra. We have shown that photocleavage of plasmid DNA is markedly enhanced when this ligand is irradiated in the presence of Cu(II), and more so than that of cobalt. The chemistry of ternary and binary Co(II) complexes showing efficient light induced (360 nm) DNA cleavage activity is summarized. The role of the metal in photoinduced DNA cleavage reactions is explored by designing complex molecules having macrocyclic structure. The mechanistic pathways are found to be concentration dependent on Co(II)/Cu(II) complexes and the photoexcitation energy photoredox chemistry. Highly effective DNA cleavage ability of 6 is attributed to the effective cooperation of the metal moiety.

  8. Carbene radicals in cobalt(II)-porphyrin-catalysed carbene carbonylation reactions; a catalytic approach to ketenes.

    PubMed

    Paul, Nanda D; Chirila, Andrei; Lu, Hongjian; Zhang, X Peter; de Bruin, Bas

    2013-09-23

    One-pot radicals: Cobalt(III)-carbene radicals, generated by metallo-radical activation of diazo compounds and N-tosylhydrazone sodium salts with cobalt(II) complexes of porphyrins, readily undergo radical addition to carbon monoxide, allowing the catalytic production of ketenes. These ketenes subsequently react with various amines, alcohols and imines in one-pot tandem transformations to produce differently substituted amides, esters and β-lactams in good isolated yields.

  9. Fluorescence characteristic study of the ternary complex of fluoroquinolone antibiotics and cobalt (II) with ATP

    NASA Astrophysics Data System (ADS)

    Wu, Shuqing; Zhang, Wujuan; Chen, Xingguo; Hu, Zhide; Hooper, Martin; Hooper, Beveley; Zhao, Zhengfeng

    2001-05-01

    The results from the measurement of the fluorescence spectra of fluoroquinolone antibiotics including ofloxacin (OF), norfloxacin (NOR) and ciprofloxacin (CIP) complexed with cobalt (II) and ATP give information concerning the antibiotics-nucleotide interactions. From the fluorescence spectral data, it appears that the fluoroquinolone antibiotic cannot directly complex with ATP but indirectly complex with cobalt (II), which is playing an intermediary role. The interaction of fluoroquinolone antibiotic with the nucleotide occurs mainly through the phosphate group. The conclusion offers a more complete mechanism, which is important for understanding the interaction of these drugs with DNA.

  10. Preparation and Spectroscopic Studies of Cobalt(II) Derivatives of Blue Copper Proteins

    PubMed Central

    McMillin, David R.; Rosenberg, Robert C.; Gray, Harry B.

    1974-01-01

    Preparation of cobalt(II) derivatives of type 1 copper proteins has been extended to include bean plastocyanin and azurin from Pseudomonas aeruginosa. Fluorescence quenching data suggest that Co(II) binds to the type 1 site of both apoplastocyanin and apoazurin. Electronic absorption spectral measurements have been made for cobalt(II)-stellacyanin, cobalt(II)-plastocyanin, and cobalt(II)-azurin. In each case two visible bands with moderate intensities and two rather strong ultraviolet absorption peaks are observed. The intensity pattern and the separation of the two ultraviolet bands in the Co(II) derivatives correspond closely to the two intense, low-lying absorption peaks in the analogous, type 1 copper proteins. The evidence suggests that the intense, two-band systems represent ligand-to-metal charge transfer transitions in both Cu(II) and Co(II) derivatives. It is proposed that the transitions in each case originate in the 3pπ and 3pσ orbitals of a cysteine sulfur ligand at the type 1 site. The visible absorption bands in the Co(II) derivatives are assigned to d-d transitions. The large 4P splitting observed indicates that the type 1 Co(II) site is of low symmetry. The d-d band pattern suggests that the high-spin Co(II) center is either distorted tetrahedral or five-coordinate. The observed band intensities are in much closer accord with the values for Co(II) complexes known to have distorted tetrahedral structures. PMID:4216022

  11. What is the weighing form in gravimetric determination of antimony(III) with oxine?

    PubMed

    Hioki, Akiharu

    2004-03-01

    The gravimetric analysis of antimony(III) with oxine (8-quinolinol, Hox) was studied. The amount of antimony left in filtrate and washing solutions was corrected with the results of atomic absorption spectrometry. The weighing form, which had not been conclusive before the present study, was determined to be SbO(ox)(Hox)2. The result (purity of antimony(II) oxide: 99.84 +/- 0.05% (m/m)) of the gravimetric analysis was in good agreement with that of coulometric titration with electrogenerated iodine.

  12. Cobalt (II) β-diketonate adducts as new precursors for the growth of cobalt oxide films by liquid injection MOCVD

    NASA Astrophysics Data System (ADS)

    Pasko, S.; Abrutis, A.; Hubert-Pfalzgraf, L. G.; Kubilius, V.

    2004-02-01

    New metalorganic compounds—adducts of cobalt(II) acetylacetonate (acac) and cobalt(II) 2,2,6,6-tetramethyl-3,5-heptanedionate (thd) with N,N,N',N'-tetramethyl-1,2-diaminoethane have been synthesized and studied as potential precursors for liquid injection metalorganic chemical vapor deposition of Co 3O 4 films. The properties of the films were compared with those deposited using standard [Co(acac) 2] 4 and Co(thd) 2 precursors. Depositions were carried out at 350-600°C on LaAlO 3 (1 0 0), sapphire (R-plane), MgO (1 0 0) and Si (1 0 0) substrates. The films were characterized by X-ray diffraction, X-ray photoelectron spectroscopy and atomic force microscopy. Depending on substrate material, highly (1 1 0) or (1 0 0) textured Co 3O 4 films have been deposited; moreover, films exhibited preferential in-plane orientation. No significant difference has been found in the quality of Co 3O 4 films deposited from different precursors.

  13. Solvent effects on the stability of nifuroxazide complexes with cobalt(II), nickel(II) and copper(II) in alcohols.

    PubMed

    Khan, Mustayeen A; Ali, S Kauser; Bouet, Gilles M

    2002-05-21

    A spectrophotometric study of the complexation of nifuroxazide with cobalt(II), nickel(II) and copper(II) was carried out in different alcohols. The formation of a complex in each case is reported and their stability constants have been calculated. For a given solvent, the stability of the complexes increases from cobalt to copper. In the case of copper(II), the stability varies as an inverse function of the dielectric constant of the solvent. A possible structure of the complex is proposed.

  14. Monomeric square-planar cobalt(II) acetylacetonate: mystery or mistake?

    PubMed

    Vreshch, Volodimir D; Yang, Jen-Hsien; Zhang, Haitao; Filatov, Alexander S; Dikarev, Evgeny V

    2010-09-20

    No evidence was found for the existence of a previously reported mononuclear square-planar form of unsolvated cobalt(II) acetylacetonate, Co(acac)(2), in all samples that have been obtained by using a variety of preparative techniques and crystallization conditions. It was confirmed that the structure of tetramer Co(4)(acac)(8), reported back in 1964 by Cotton and Elder, is correct, the synthesis is reproducible, and the bulk material corresponds to single-crystal data. Additionally, the title compound can be isolated in tetranuclear form by reducing cobalt(III) acetylacetonate with cobalt metal in solvent-free conditions or by crystallization from a hexanes solution. At the same time, from noncoordinating halogenated solvents, Co(acac)(2) crystallizes as a trinuclear core molecule, in which all Co atoms also exhibit octahedral coordination. From coordinating solvents such as ethanol, cobalt(II) acetylacetonate was found to appear in the form of its bis-adduct Co(acac)(2)(EtOH)(2). On the basis of observations made in this work and the details presented in the original paper, we suggest that the reported mononuclear structure of square-planar acetylacetonate should likely contain copper instead of cobalt.

  15. Study of the influence of the bridge on the magnetic coupling in cobalt(II) complexes.

    PubMed

    Fabelo, Oscar; Cañadillas-Delgado, Laura; Pasán, Jorge; Delgado, Fernando S; Lloret, Francesc; Cano, Joan; Julve, Miguel; Ruiz-Pérez, Catalina

    2009-12-07

    Two new cobalt(II) complexes of formula [Co(2)(bta)(H(2)O)(6)](n) x 2nH(2)O (1) and [Co(phda)(H(2)O)](n) x nH(2)O (2) [H(4)bta = 1,2,4,5-benzenetetracarboxylic acid, H(2)phda = 1,4-phenylenediacetic acid] have been characterized by single crystal X-ray diffraction. Compound 1 is a one-dimensional compound where the bta(4-) ligand acts as 2-fold connector between the cobalt(II) ions through two carboxylate groups in para-conformation. Triply bridged dicobalt(II) units occur within each chain, a water molecule, a carboxylate group in the syn-syn conformation, and an oxo-carboxylate with the mu(2)O(1);kappa(2)O(1),O(2) coordination mode acting as bridges. Compound 2 is a three-dimensional compound, where the phda(2-) group acts as a bridge through its two carboxylate groups, one of them adopting the mu-O,O' coordination mode in the syn-syn conformation and the other exhibiting the single mu(2)-O'' bridging mode. As in 1, chains of cobalt(II) ions occur in 2 with a water molecule, a syn-syn carboxylate group, and an oxo-carboxylate constitute the triply intrachain bridging skeleton. Each chain is linked to other four ones through the phda(2-) ligand, giving rise to the three-dimensional structure. The values of the intrachain cobalt-cobalt separation are 3.1691(4) (1) and 3.11499(2) A (2) whereas those across the phenyl ring of the extended bta(4-) (1) and phda(2-) (2) groups are 10.1120(6) and 11.4805(69 A, respectively. The magnetic properties of 1 and 2 have been investigated in the temperature range 1.9-300 K, and their analysis has revealed the occurrence of moderate intrachain ferromagnetic couplings [J = +5.4 (1) and +2.16 cm(-1) (2), J being the isotropic magnetic coupling parameter], the magnetic coupling through the extended bta(4-) and phda(2-) with cobalt-cobalt separations larger than 10 A being negligible. The nature and magnitude of the magnetic interactions between the high-spin cobalt(II) ions in 1 and 2 are compared to those of related systems and

  16. Cobalt(II) Oxidation by the Marine Manganese(II)-Oxidizing Bacillus sp. Strain SG-1

    PubMed Central

    Lee, Yoon; Tebo, Bradley M.

    1994-01-01

    The geochemical cycling of cobalt (Co) has often been considered to be controlled by the scavenging and oxidation of Co(II) on the surface of manganese [Mn(III,IV)] oxides or manganates. Because Mn(II) oxidation in the environment is often catalyzed by bacteria, we have investigated the ability of Mn(II)-oxidizing bacteria to bind and oxidize Co(II) in the absence of Mn(II) to determine whether some Mn(II)-oxidizing bacteria also oxidize Co(II) independently of Mn oxidation. We used the marine Bacillus sp. strain SG-1, which produces mature spores that oxidize Mn(II), apparently due to a protein in their spore coats (R.A. Rosson and K. H. Nealson, J. Bacteriol. 151:1027-1034, 1982; J. P. M. de Vrind et al., Appl. Environ. Microbiol. 52:1096-1100, 1986). A method to measure Co(II) oxidation using radioactive 57Co as a tracer and treatments with nonradioactive (cold) Co(II) and ascorbate to discriminate bound Co from oxidized Co was developed. SG-1 spores were found to oxidize Co(II) over a wide range of pH, temperature, and Co(II) concentration. Leucoberbelin blue, a reagent that reacts with Mn(III,IV) oxides forming a blue color, was found to also react with Co(III) oxides and was used to verify the presence of oxidized Co in the absence of added Mn(II). Co(II) oxidation occurred optimally around pH 8 and between 55 and 65°C. SG-1 spores oxidized Co(II) at all Co(II) concentrations tested from the trace levels found in seawater to 100 mM. Co(II) oxidation was found to follow Michaelis-Menten kinetics. An Eadie-Hofstee plot of the data suggests that SG-1 spores have two oxidation systems, a high-affinity-low-rate system (Km, 3.3 × 10-8 M; Vmax, 1.7 × 10-15 M · spore-1 · h-1) and a low-affinity-high-rate system (Km, 5.2 × 10-6 M; Vmax, 8.9 × 10-15 M · spore-1 · h-1). SG-1 spores did not oxidize Co(II) in the absence of oxygen, also indicating that oxidation was not due to abiological Co(II) oxidation on the surface of preformed Mn(III,IV) oxides. These

  17. Structure, antimicrobial activity and DNA-binding properties of the cobalt(II)-sparfloxacin complex.

    PubMed

    Efthimiadou, Eleni K; Karaliota, Alexandra; Psomas, George

    2008-07-15

    The neutral mononuclear cobalt(II) complex with sparfloxacin has been prepared and characterized with physicochemical, spectroscopic and electrochemical techniques, and molecular mechanics calculations. The interaction of the complex with calf-thymus DNA has been investigated with UV spectroscopy, cyclic voltammetry, and competitive studies with ethidium bromide. The antimicrobial activity of the complex has been tested against three microorganisms.

  18. Method for labelling leucocytes with indium In-111 oxine

    SciTech Connect

    Kaminsky, D.

    1992-03-03

    This patent describes an improved method for radio-labelling leucocytes with Indium In-111 oxine. It comprises separating the leucocytes from whole blood for obtaining separated leucocytes mixed with residual red blood cells; and then labelling the separated leucocytes with Indium In-111 oxine; wherein the improvement comprises the following further step: depleting residual red blood cells from the separated leucocytes by resuspending the leucocytes in an isotonic saline solution, then rocking the resuspended leucocytes for causing the leucocytes to preferentially settle out, and then removing residual red blood cells which remain suspended within the supernatant isotonic saline solution.

  19. Equilibrium studies of cobalt(II) extraction with 2-pyridineketoxime from mixed sulphate/chloride solution.

    PubMed

    Wieszczycka, Karolina; Krupa, Marta; Wojciechowska, Aleksandra; Wojciechowska, Irmina; Olszanowski, Andrzej

    In present paper the equilibrium of cobalt extraction with 1-(2-pyridyl)tridecan-1-one oxime from the chloride/sulphate solutions was studied. The presented results indicated that extraction depends on a number of process variables, including the pH, metal and Cl(-) concentration in the aqueous feed, and concentration of the oxime in the organic phase. The created cobalt-complexes with the 2-pyridine ketoxime were stable and only concentrated HCl was found to be a suitable stripping agent for coordinated metal. The separation of Co(II) from Zn(II), Ni(II) and Cu(II) was also studied, but the selective recovery of the metals was possible using the multi-stage stripping process.

  20. Cobalt(II)-substituted class III alcohol and sorbitol dehydrogenases from human liver.

    PubMed

    Maret, W

    1989-12-26

    The catalytic zinc atoms in class III (chi) alcohol dehydrogenase (ADH) and sorbitol dehydrogenase (SDH) from human liver have been specifically removed and replaced by cobalt(II) with a new ultrafiltration technique. The electronic absorption spectrum of class III cobalt ADH (epsiolon 638 = 870 M-1 cm-1) is nearly identical with those of active site substituted horse EE and human class I (beta 1 beta 1) cobalt ADH. Thus, the coordination environment of the catalytic metal is strictly conserved in these enzymes. However, significant differences are noted when the spectra of class III ADH-coenzyme complexes are compared to the corresponding spectra of the horse enzyme. The spectrum of class III ADH.NADH is split into three bands, centered at 680, 638, and 562 nm. The class III ADH.NAD+ species resembles the alkaline form of the corresponding horse enzyme complex but without exhibiting the pH dependence of the latter. These spectral changes underscore the role of the coenzymes in differentially fine tuning the catalytic metal for its particular function in each ADH. The noncatalytic zinc of class III ADH exchanges with cobalt at pH 7.0. While 9 residues out of 15 in the loop surrounding the noncatalytic zinc of class III ADH differ from those of the class I ADH, the electronic absorption spectra of cobalt in the noncatalytic metal site of class III ADH establish that the coordination environment of this site is conserved as well. The spectrum of cobalt SDH differs significantly from those of cobalt ADHs.(ABSTRACT TRUNCATED AT 250 WORDS)

  1. Characterization of cobalt(II) chloride-modified condensation polyimide films

    NASA Technical Reports Server (NTRS)

    Rancourt, J. D.; Taylor, L. T.

    1988-01-01

    The effect of solvent extraction on the properties of cobalt(II) chloride-modified polyimide films was investigated. Solvent-cast films were prepared from solutions of cobalt chloride in poly(amide acid)/N,N-dimethylacetamide (DMAc) and were subsequently dried and cured in static air, forced air, or inert gas ovens with controlled humidity. The films were extracted by either of the three processes (1) soaking in a tray with distilled water at room temperature, (2) soxhlett extraction with distilled water, or (3) soxhell extraction with DMAc. Extraction with DMAc was found to remove both cobalt and chlorine from the films and to slightly increase bulk thermal stability and both surface resistivity and electrical resistivity.

  2. Characterization of cobalt(II) chloride-modified condensation polyimide films

    NASA Technical Reports Server (NTRS)

    Rancourt, J. D.; Taylor, L. T.

    1988-01-01

    The effect of solvent extraction on the properties of cobalt(II) chloride-modified polyimide films was investigated. Solvent-cast films were prepared from solutions of cobalt chloride in poly(amide acid)/N,N-dimethylacetamide (DMAc) and were subsequently dried and cured in static air, forced air, or inert gas ovens with controlled humidity. The films were extracted by either of the three processes (1) soaking in a tray with distilled water at room temperature, (2) soxhlett extraction with distilled water, or (3) soxhell extraction with DMAc. Extraction with DMAc was found to remove both cobalt and chlorine from the films and to slightly increase bulk thermal stability and both surface resistivity and electrical resistivity.

  3. Synthesis, crystal structure and magnetic property of a new cobalt(II) vanadate

    SciTech Connect

    Zhang, Su-Yun; Guo, Wen-Bin; Yang, Ming; Tang, Ying-Ying; Wang, Nan-Nan; Huang, Rong-Rong; Cui, Mei-Yan; He, Zhang-Zhen

    2015-05-15

    A new cobalt(II) vanadate has been synthesized by hydrothermal reaction. It exhibits 3D cobalt(II) oxide architecture with Co{sub 12} member ring (MR) and Co{sub 6} MR tunnels along c-axis. V(2)O{sub 4} tetrahedra are located at the center of Co{sub 6}-MR tunnels whereas V(1)O{sub 4} tetrahedra and ‘isolated’ 1D Co(1)O{sub 6} octahedral chains are located at the Co{sub 12}-MR tunnels. The 3D cobalt(II) oxide architecture is constructed on irregular ladder chains formed by edge- and face-sharing of Co(2)O{sub 6} octahedra whereas the ‘isolated’ 1D Co(1)O{sub 6} octahedral chain in the tunnels are formed by face-sharing of Co(1)O{sub 6} octahedra. Magnetic property is investigated by means of magnetic susceptibility, magnetization and heat capacity measurement. Magnetic susceptibility and heat capacity measurement indicate a typical long-range spin-canting antiferromagnetic ordering below ~71 K; metamagnetic behavior was detected in the isothermal magnetization measurement at 2 K. - Graphical abstract: A cobalt(II) vanadate, Co{sub 7}V{sub 4}O{sub 16}(OH){sub 2}(H{sub 2}O) has been synthesized and structurally characterized. It exhibits antiferromagnetic interaction with weak spin-canting below ~71 K; metamagnetic behavior was detected in isothermal magnetization at 2 K. - Highlights: • Hydrothermal reaction of CoCl{sub 2}·6H{sub 2}O and Na{sub 3}VO{sub 4} yielded a new cobalt(||) vanadate. • It shows novel structure since its large Co/V ratio. • It shows long-range spin-canting antiferromagnetic ordering below ~71 K. • Metamagnetic behavior was detected in the isothermal magnetization at 2 K.

  4. Spectrophotometric determination of cobalt(II) and cyanocobalamin with vanillilfluorone and its applications.

    PubMed

    Hoshino, Mitsuru; Matsushita, Momoka; Samma, Megumi; Asano, Mamiko; Yamaguchi, Takako; Fujita, Yoshikazu

    2011-01-01

    Spectrophotometric determination of cobalt(II) was accomplished with vanillilfluorone (VF) in the presence of dimethylbenzyltetradecylammonium chloride (Zephiramine, Zep). In the determination of cobalt(II), Beer's law was obeyed in the range of 24-470 ng/ml, with an effective molar absorption coefficient (at 575 nm) and relative standard deviation of 1.35×10(5) l mol(-1) cm(-1) and 0.66% (n=5), respectively. The composition ratio of the colored complex was determined by the mole ratio and continuous variation methods, and it was found to be Co(II) : VF : Zep=1 : 2 : 4. Analysis of cyanocobalamin by the same procedure showed that cyanocobalamin could be determined in the concentration range of 0.5-0.11 µg/ml using the proposed method.

  5. Sol-gel synthesized adsorbents for mercury(II), chromium(III) and cobalt(II) separations

    NASA Astrophysics Data System (ADS)

    Nam, Kwan-Hyun

    Novel organo-ceramic adsorbents are synthesized and characterized for mercury(II), chromium(III) and cobalt(II) separations from aqueous streams. Mercury(II) adsorption on thiol functional adsorbents (SOL-AD-IV) is studied for two systems: (1) coal-fired utility plant scrubber water, and (2) acidic nuclear wastes. To exemplify the removal of mercury from these systems, simulants are prepared and used. Results show that the mercury adsorption capacity is higher than reported in the literature. In addition, the adsorbent exhibits high adsorption capacity even at 4 M HNO3. In column operation, flow rates as high as 1100 BV/h could be employed with effluent concentrations reaching below 0.06 mug/L. This adsorbent is found to exhibit superior mercury adsorption characteristics with a demonstrated long life cycle. Chromium(III) and cobalt(II) adsorption is evaluated using phosphonic acid (SOL-PHONIC) and phosphinic acid (SOL-PHINIC) functional adsorbents synthesized via sol-gel processing by co-condensation of clusters of functional precursor (FPS) and cross-linking (CA) silanes. Nuclear magnetic resonance (NMR) spectroscopy is used to examine the evolution of oligomeric species with hydrolysis and condensation reaction times. The effects of both the FPS and CA oligomeric species on the physicochemical properties of the resulting adsorbent materials are evaluated and explained in terms of structural and adsorption capacity characteristics. The adsorbents are further characterized by solid-state NMR spectroscopy to elucidate the incorporation of the FPS and the nature of the functional groups in the adsorbent matrix. SOL-PHONIC is employed for the removal of chromium, and both SOL-PHONIC and SOL-PHINIC are employed for the removal of cobalt. Results show that chromium and cobalt adsorptions are solution pH dependent. Cobalt adsorption tests evaluated using the two adsorbents show that SOL-PHONIC exhibits a higher selectivity towards cobalt over nickel. The adsorption

  6. A bio-inspired switch based on cobalt(II) disulfide/cobalt(III) thiolate interconversion.

    PubMed

    Gennari, Marcello; Gerey, Bertrand; Hall, Nikita; Pécaut, Jacques; Collomb, Marie-Noëlle; Rouzières, Mathieu; Clérac, Rodolphe; Orio, Maylis; Duboc, Carole

    2014-05-19

    Disulfide/thiolate interconversion supported by transition-metal ions is proposed to be implicated in fundamental biological processes, such as the transport of metal ions or the regulation of the production of reactive oxygen species. We report herein a mononuclear dithiolate Co(III) complex, [Co(III)LS(Cl)] (1; LS=sulfur containing ligand), that undergoes a clean, fast, quantitative and reversible Co(II) disulfide/Co(III) thiolate interconversion mediated by a chloride anion. The removal of Cl(-) from the Co(III) complex leads to the formation of a bis(μ-thiolato) μ-disulfido dicobalt(II) complex, [Co2(II,II)LSSL](2+) (2(2+)). The structures of both complexes have been resolved by single-crystal X-ray diffraction; their magnetic, spectroscopic, and redox properties investigated together with DFT calculations. This system is a unique example of metal-based switchable M(n)2-RSSR/2 M((n+1))-SR (M=metal ion, n=oxidation state) system that does not contain copper, acts under aerobic conditions, and involves systems with different nuclearities.

  7. Copper(II)-8-hydroxquinoline coprecipitation system for preconcentration and separation of cobalt(II) and manganese(II) in real samples.

    PubMed

    Soylak, Mustafa; Kaya, Betul; Tuzen, Mustafa

    2007-08-25

    A separation-preconcentration procedure based on the coprecipitation of cobalt(II) and manganese(II) ions with copper(II)-8-hydroxquinoline system has been developed. The analytical parameters including pH, amount of copper(II) as carrier element, amount of 8-hydroxquinoline, sample volume, etc., was investigated for the quantitative recoveries of Co(II) and Mn(II). No interferic effects were observed from the concomitant ions which are present in real samples. The detection limits for analyte ions by three sigma criteria were 0.86microgL(-1) for cobalt and 0.98microgL(-1) for manganese. The validation of the presented preconcentration procedure was performed by the analysis of NIST SRM 2711 Montana soil and GBW 07605 Tea certified reference materials. The procedure presented was applied to the analyte contents of real samples including natural waters and some food samples with successfully analytical results.

  8. Local structure studies of some cobalt (II) complexes using extended X-ray absorption fine structure

    NASA Astrophysics Data System (ADS)

    Mishra, Ashutosh; Ninama, Samrath; Trivedi, Apurva

    2014-09-01

    Extended X-ray Absorption Fine Structure (EXAFS) analysis of Cobalt (II) complex as a ligand of 2 -methyl-3-[(bis-aniline(R) phenyl]-3H-l,5 benzodiazepine for finding local structure using conventional method .The Co(II) complexes were prepared by chemical root method. The EXAFS spectra were recorded at Cobalt K-edge i.e.; 7709 eV using Dispersive EXFAS beam line at 2.5GeV Indus-2 Synchrotron Radiation Source(SRS) at RRCAT, Indore, India. The recorded EXAFS data were analysed using the computer software Athena for determine the nearest neighbouring distances (bond lengths) of these complexes with conventional methods and it compared with Fourier transform(FT) analysis. The Fourier Transform convert EXAFS data signal into r-space or k-space. This is useful for visualizing the major contributions to the EXAFS spectrum.

  9. Synthesis, crystal structures and spectroscopic properties of cobalt(II) complexes with chelating sulfonylamidophosphate ligands

    NASA Astrophysics Data System (ADS)

    Znovjyak, Kateryna O.; Seredyuk, Maksym; Kusz, Joachim; Nowak, Maria; Moroz, Olesia V.; Sliva, Tetiana Yu; Amirkhanov, Vladimir M.

    2015-11-01

    Two new cobalt(II) complexes with general formula Co(L1)2Phen (1) and Co(L2)2Phen (2), in which HL1 = dimethyl phenylsulfonylphosphoramidate and HL2 = dimethyl tosylphosphoramidate, were prepared in one-step synthesis and characterized by IR, UV-VIS spectroscopy, TGA-DTA and elemental analysis. Moreover, the single crystal structures of 1 and 2 were determined by single crystal X-ray diffractometry. Complexes consist of mononuclear units comprising two L1-(or L2-) and phenanthroline ligands bidentatly linked to metal ion. The UV-VIS spectra of complexes in the solid state show broad asymmetric band at 530 nm attributed to the d-d transition of the metal ion. Comparing of these spectra with the absorption spectra in acetone, octahedral environment of the cobalt(II) ion in solution were considered. The structural similarity of 1 and 2 leads to a similar thermal decomposition profile.

  10. Nitrous oxide activation by a cobalt(ii) complex for aldehyde oxidation under mild conditions.

    PubMed

    Corona, Teresa; Company, Anna

    2016-10-07

    Nitrous oxide (N2O) is a waste gas produced in many industrial processes with an important environmental impact. Thus, its application as an oxidant is highly desirable because it produces innocuous N2 as a by-product. In this work we report a new cobalt(ii) complex that reacts with N2O under mild conditions and the catalytic application of this system to carry out the oxidation of aldehydes.

  11. Poly[(μ4-decanedio-ato)cobalt(II)].

    PubMed

    Giuseppe, Bruno; Francesco, Nicolò; Giovanni, Grassi; Alessandro, Saccà; Mollica Nardo, Viviana

    2014-05-01

    In the title compound, [Co(C10H16O4)] n , the Co(II) atom is bonded in a slightly distorted tetra-hedral environment by four O atoms from the bridging sebacate dications, comprising two separate half-ligands which lie across crystallographic inversion centres. In the three-dimensional network coordination polymer, there are two different spatial extensions of Co(II) atoms, one with the Co(II) atoms lying parallel to (100) [Co⋯Co = 4.653 (1) Å], the other lying parallel to (010) [Co⋯Co = 4.764 (1) Å].

  12. Structural and magnetic properties of cobalt(II) complexes with pyridinecarboxamide ligands

    NASA Astrophysics Data System (ADS)

    Dojer, Brina; Pevec, Andrej; Belaj, Ferdinand; Jagličić, Zvonko; Kristl, Matjaž; Drofenik, Miha

    2014-11-01

    The synthesis and characterization of two new cobalt(II) coordination compounds with nicotinamide (nia) and isonicotinamide (isn) are reported. The products were characterized magnetically, structurally by single-crystal X-ray diffraction analysis and spectrally by FT-IR spectroscopy. Using the reaction of cobalt(II) acetate tetrahydrate and nicotinamide in methanol we obtained light-red crystals of the mononuclear complex [Co(nia)2(H2O)4](CH3COO)2·2H2O (1). The synthesis in a system cobalt(II) acetate dihydrathe, isonicotinamide and dimethylformamide-methanol mixture gave a new dinuclear coordination compound with the formula [Co2(CH3COO)4(isn)4]·2C3H7NO (2). In both compounds a trans arrangement of pyridinecarboxamide ligands was found. Intermolecular hydrogen bonds in the crystal structures of both complexes are discussed. The magnetic properties were studied between 2 K and 300 K giving the result μeff = 4.6 BM for 1 and μeff = 4.7 BM for 2 in the paramagnetic region.

  13. A highly selective and sensitive fluorescence assay for determination of copper(II) and cobalt(II) ions in environmental water and toner samples.

    PubMed

    Tsai, Chia-Yi; Lin, Yang-Wei

    2013-02-21

    In this study, a highly selective and sensitive fluorescence assay has been proposed for the determination of copper(II) and cobalt(II) ions in environmental water and toner samples. In the presence of hydrogen peroxide, copper(II) reacted with a new fluorescence reagent Amplex® UltraRed (AUR), forming a fluorescence product only at pH 7.0, while the fluorescence product of cobalt(II) with AUR formed only at pH 9.0. The fluorescence signal obtained was linear with respect to the copper(II) concentration over the range of 1.6-12.0 μM (R(2) = 0.988) and was linear with respect to the cobalt(II) concentration over the range of 45.0 nM to 1.0 μM (R(2) = 0.992). The limits of detection (at a signal-to-noise ratio of 3) for copper(II) and cobalt(II) were 0.17 μM and 14.0 nM, respectively. Our present approach is simpler, faster, and more cost-effective than other techniques for the detection of copper(II) and cobalt(II) ions in environmental water samples and that of copper(II) ions in toner samples.

  14. 13C NMR studies of carboxylate inhibitor binding to cobalt(II) carboxypeptidase A.

    PubMed

    Bertini, I; Monnanni, R; Pellacani, G C; Sola, M; Vallee, B L; Auld, D S

    1988-01-01

    Both 13C NMR and electronic absorption spectral studies on cobalt(II) carboxypeptidase A in the presence of acetate and phenylacetate provide evidence for two binding sites for each of these agents. The transverse relaxation rate T2-1 for the 13C-enriched carboxyl groups of the inhibitors is significantly increased when bound to the paramagnetic cobalt carboxypeptidase as compared to the diamagnetic zinc enzyme. The acetate concentration dependence of T2p-1 shows two inflections indicative of sequential binding of two inhibitor molecules. The cobalt-13C distances, calculated by means of the Solomon equation, indicate that the second acetate molecule binds directly to the metal ion while the first acetate molecule binds to a protein group at a distance 0.5-0.8 nm for the metal ion, consistent with it binding to one or more of the arginyl residues (Arg-145, Arg-127, or Arg-71). In the case of phenylacetate, perturbation of the cobalt electronic absorption spectrum shows that binding occurs stepwise. 13C NMR distance measurements indicate that one of the two phenylacetates is bound to the metal in the EI2 complex. These binding sites may correspond to those identified previously by kinetic means (one of which is competitive, the other noncompetitive) with peptide binding. The studies further indicate that it should be possible to map the protein interactions of the carbonyl groups of both substrate and noncompetitive inhibitors during catalysis by means of 13C NMR studies with suitably labeled substrates and inhibitors.

  15. Synthesis, magnetic properties, and STM spectroscopy of cobalt(II) Cubanes [Co(II) (4)(Cl)(4)(HL)(4)].

    PubMed

    Scheurer, Andreas; Ako, Ayuk M; Saalfrank, Rolf W; Heinemann, Frank W; Hampel, Frank; Petukhov, Konstantin; Gieb, Klaus; Stocker, Michael; Müller, Paul

    2010-04-26

    Reaction of cobalt(II) chloride hexahydrate with N-substituted diethanolamines H(2)L(2-4) (3) in the presence of LiH in anhydrous THF leads under anaerobic conditions to the formation of three isostructural tetranuclear cobalt(II) complexes [Co(II) (4)(Cl)(4)(HL(2-4))(4)] (4) with a [Co(4)(mu(3)-O)(4)](4+) cubane core. According to X-ray structural analyses, the complexes 4 a,c crystallize in the tetragonal space group I4(1)/a, whereas for complex 4 b the tetragonal space group P$\\bar 4$ was found. In the solid state the orientation of the cubane cores and the formation of a 3D framework were controlled by the ligand substituents of the cobalt(II) cubanes 4. This also allowed detailed magnetic investigations on single crystals. The analysis of the SQUID magnetic susceptibility data for 4 a gave intramolecular ferromagnetic couplings of the cobalt(II) ions (J(1) approximately 20.4 K, J(2) approximately 7.6 K), resulting in an S=6 ground-state multiplet. The anisotropy was found to be of the easy-axis type (D=-1.55 K) with a resulting anisotropy barrier of Delta approximately 55.8 K. Two-dimensional electron-gas (2DEG) Hall magnetization measurements revealed that complex 4 a is a single-molecule magnet and shows hysteretic magnetization characteristics with typical temperature and sweep-rate dependencies below a blocking temperature of about 4.4 K. The hysteresis loops collapse at zero field owing to fast quantum tunneling of the magnetization (QTM). The structural and electronic properties of cobalt(II) cubane 4 a, deposited on a highly oriented pyrolytic graphite (HOPG) surface, were investigated by means of STM and current imaging tunneling spectroscopy (CITS) at RT and standard atmospheric pressure. In CITS measurements the rather large contrast found at the expected locations of the metal centers of the molecules indicated the presence of a strongly localized LUMO.

  16. Synthesis and DNA cleavage activities of mononuclear macrocyclic polyamine zinc(II), copper(II), cobalt(II) complexes which linked with uracil.

    PubMed

    Wang, Xiao-Yan; Zhang, Ji; Li, Kun; Jiang, Ning; Chen, Shan-Yong; Lin, Hong-Hui; Huang, Yu; Ma, Li-Jian; Yu, Xiao-Qi

    2006-10-01

    Mononuclear macrocyclic polyamine zinc(II), copper(II), cobalt(II) complexes, which could attach to peptide nucleic acid (PNA), were synthesized as DNA cleavage agents. The structures of these new mononuclear complexes were identified by MS and (1)H NMR spectroscopy. The catalytic activities on DNA cleavage of these mononuclear complexes with different central metals were subsequently studied, which showed that copper complex was better catalyst in the DNA cleavage process than zinc and cobalt complexes. The effects of reaction time, concentration of complexes were also investigated. The results indicated that the copper(II) complexes could catalyze the cleavage of supercoiled DNA (pUC 19 plasmid DNA) (Form I) under physiological conditions to produce selectively nicked DNA (Form II, no Form III produced) with high yields. The mechanism of the cleavage process was also studied.

  17. Crystal structures of salicylideneguanylhydrazinium chloride and its copper(II) and cobalt(III) chloride complexes

    SciTech Connect

    Chumakov, Yu. M. Tsapkov, V. I.; Bocelli, G.; Antosyak, B. Ya.; Shova, S. G.; Gulea, A. P.

    2006-01-15

    The crystal structures of salicylideneguanylhydrazinium chloride hydrate hemiethanol solvate (I), salicylideneguanylhydrazinium trichloroaquacuprate(II) (II), and bis(salicylideneguanylhydrazino)cobalt(III) chloride trihydrate (III) are determined using X-ray diffraction. The structures of compounds I, II, and III are solved by direct methods and refined using the least-squares procedure in the anisotropic approximation for the non-hydrogen atoms to the final factors R = 0.0597, 0.0212, and 0.0283, respectively. In the structure of compound I, the monoprotonated molecules and chlorine ions linked by hydrogen bonds form layers aligned parallel to the (010) plane. In the structure of compound II, the salicylaldehyde guanylhydrazone cations and polymer chains consisting of trichloroaquacuprate(II) anions are joined by an extended three-dimensional network of hydrogen bonds. In the structure of compound III, the [Co(LH){sub 2}]{sup +} cations, chloride ions, and molecules of crystallization water are linked together by a similar network.

  18. Neutral (bis-beta-diketonato) iron(III), cobalt(II), nickel(II), copper(II) and zinc(II) metallocycles: structural, electrochemical and solvent extraction studies.

    PubMed

    Clegg, Jack K; Bray, David J; Gloe, Kerstin; Gloe, Karsten; Hayter, Michael J; Jolliffe, Katrina A; Lawrance, Geoffrey A; Meehan, George V; McMurtrie, John C; Lindoy, Leonard F; Wenzel, Marco

    2007-05-07

    Neutral dimeric metallocyclic complexes of type [M(2)(L(1))(2)B(n)] (where M = cobalt(II), nickel(II) and zinc(II), L(1) is the doubly deprotonated form of a 1,3-aryl linked bis-beta-diketone ligand of type 1,3-bis(RC(O)CH(2)C(O))C(6)H(4) (R=Me, n-Pr, t-Bu) and B is pyridine (Py) or 4-ethylpyridine (EtPy)) have been synthesised, adding to similar complexes already reported for copper(II). New lipophilic ligand derivatives with R = octyl or nonyl were also prepared for use in solvent extraction experiments. Structural, electrochemical and solvent extraction investigations of selected metal complex systems from the above series are reported, with the X-ray structures of [Co(2)(L(1))(2)(Py)(4)] x 2.25CHCl(3) x 0.5H(2)O (R=Pr), [Co(2)(L(1))(2)(EtPy)(4)] (R=t-Bu), [Ni(2)(L(1))(2)(EtPy)(4)] (R=t-Bu), [Zn(2)(L(1))(2)(EtPy)(2)] (R=Me) and [Zn(2)(L(1))(2)(EtPy)(4)] (R=t-Bu) being presented. The electrochemistry of H(2)L(1) (R=t-Bu) and of [Fe(2)(L(1))(3)], [Co(2)(L(1))(2)(Py)(4)], [Ni(2)(L(1))(2)(Py)(4)], [Cu(2)(L(1))(2)] and [Zn(2)(L(1))(2)(Py)(2)] has been examined. Oxidative processes for the complexes are dominantly irreversible, but several examples of quasireversible behaviour were observed and support the assignment of an anodic process, seen between +1.0 and +1.6 V, as a metal-centred oxidation. The reduction processes for the respective metal complexes are not simple, and irreversible in most cases. Solvent extraction studies (water/chloroform) involving variable concentrations of metal, bis-beta-diketone and heterocyclic base have been performed for cobalt(II) and zinc(II) using a radiotracer technique to probe the stoichiometries of the extracted species in each case. Synergism was observed when 4-ethylpyridine was added to the bis-beta-diketone ligand in the chloroform phase. Competitive extraction studies show a clear uptake preference for copper(II) over cobalt(II), nickel(II), zinc(II) and cadmium(II).

  19. Preparation and spectroscopic characterization of a coupled binuclear center in cobalt(II)-substituted hemocyanin.

    PubMed

    Bubacco, L; Magliozzo, R S; Beltramini, M; Salvato, B; Peisach, J

    1992-09-29

    A binuclear cobalt derivative of arthropod hemocyanin (Hc) has been prepared by the reaction of apo-Hc with Co(II) in the presence of thiocyanate. The crude product of the reaction contains specifically and adventitiously bound metal, the latter being removable by EDTA treatment. The specifically bound Co(II) constitutes a binuclear metal center that exhibits optical and CD spectra typical in their absorption maxima and extinction coefficients of Co(II) complexes with near-tetrahedral geometry. The EPR spectrum of the binuclear Co(II) derivative contains a resonance at g approximately 13, which is characteristic of integer spin systems and indicates coupled metal ions; the excess Co(II) bound to crude products exhibits an EPR signal at g approximately 4. The time course of derivative formation was followed by EPR, optical and atomic absorption techniques, and by fluorimetry. The intensity of the optical absorption in the visible region due to Co(II) increases with increasing stoichiometry of specifically bound metal [up to 2 Co(II) per protein monomer], but the intensity of the Co(II) EPR signal increases only during the formation of a mononuclear derivative. As the reaction proceeds over approximately 100 h to the formation of the binuclear derivative, the EPR signal intensity decreases to 10% of the value expected for 2 mol of EPR-active Co(II)/mol of protein. The binuclear cobalt derivative cannot be reconstituted to native Hc with Cu(I), indicating the stable loading of Co(II) in the active site. EPR and optical spectroscopic evidence is presented showing that the binuclear derivative does not bind oxygen.

  20. Synthesis, Crystal Structure, and Thermal Decomposition of the Cobalt(II) Complex with 2-Picolinic Acid

    PubMed Central

    Li, Di

    2014-01-01

    The cobalt(II) complex of 2-picolinic acid (Hpic), namely, [Co(pic)2(H2O)2] · 2H2O, was synthesized with the reaction of cobalt acetate and 2-picolinic acid as the reactants by solid-solid reaction at room temperature. The composition and structure of the complex were characterized by elemental analysis, infrared spectroscopy, single crystal X-ray diffraction, and thermogravimetry-differential scanning calorimetry (TG-DSC). The crystal structure of the complex belongs to monoclinic system and space group P2(1)/n, with cell parameters of a = 9.8468(7) Å, b = 5.2013(4) Å, c = 14.6041(15) Å, β = 111.745(6)°, V = 747.96(11) Å3, Z = 2, D c = 1.666 g cm−3, R 1 = 0.0297, and wR 2 = 0.0831. In the title complex, the Co(II) ion is six-coordinated by two pyridine N atoms and two carboxyl O atoms from two 2-picolinic acid anions, and two O atoms from two H2O molecules, and forming a slightly distorted octahedral geometry. The thermal decomposition processes of the complex under nitrogen include dehydration and pyrolysis of the ligand, and the final residue is cobalt oxalate at about 450°C. PMID:24578654

  1. Diaqua-bis-(hydrogen tartrato)cobalt(II) dihydrate.

    PubMed

    Du, Chao-Jun; Zhang, Qun-An; Wang, Li-Sheng; Du, Chao-Ling

    2012-02-01

    The title complex, [Co(C(4)H(5)O(6))(2)(H(2)O)(2)]·2H(2)O, contains a Co(II) ion, two single deprotonated tartrate anions, two coordinated water mol-ecules and two lattice water mol-ecules. The coordination geometry of the Co(II) ion is a distorted octa-hedron with two O atoms from two coordinated water mol-ecules occupying cis positions in the equatorial plane and four O atoms from two hydrogen tartrate ions occupying the remaining positions. In the crystal, inter-molecular O-H⋯O hydrogen bonds link the mol-ecules into a three-dimensional network.

  2. Selective, Tunable O2 Binding in Cobalt(II)-Triazolate/Pyrazolate Metal-Organic Frameworks.

    PubMed

    Xiao, Dianne J; Gonzalez, Miguel I; Darago, Lucy E; Vogiatzis, Konstantinos D; Haldoupis, Emmanuel; Gagliardi, Laura; Long, Jeffrey R

    2016-06-08

    The air-free reaction of CoCl2 with 1,3,5-tri(1H-1,2,3-triazol-5-yl)benzene (H3BTTri) in N,N-dimethylformamide (DMF) and methanol leads to the formation of Co-BTTri (Co3[(Co4Cl)3(BTTri)8]2·DMF), a sodalite-type metal-organic framework. Desolvation of this material generates coordinatively unsaturated low-spin cobalt(II) centers that exhibit a strong preference for binding O2 over N2, with isosteric heats of adsorption (Qst) of -34(1) and -12(1) kJ/mol, respectively. The low-spin (S = 1/2) electronic configuration of the metal centers in the desolvated framework is supported by structural, magnetic susceptibility, and computational studies. A single-crystal X-ray structure determination reveals that O2 binds end-on to each framework cobalt center in a 1:1 ratio with a Co-O2 bond distance of 1.973(6) Å. Replacement of one of the triazolate linkers with a more electron-donating pyrazolate group leads to the isostructural framework Co-BDTriP (Co3[(Co4Cl)3(BDTriP)8]2·DMF; H3BDTriP = 5,5'-(5-(1H-pyrazol-4-yl)-1,3-phenylene)bis(1H-1,2,3-triazole)), which demonstrates markedly higher yet still fully reversible O2 affinities (Qst = -47(1) kJ/mol at low loadings). Electronic structure calculations suggest that the O2 adducts in Co-BTTri are best described as cobalt(II)-dioxygen species with partial electron transfer, while the stronger binding sites in Co-BDTriP form cobalt(III)-superoxo moieties. The stability, selectivity, and high O2 adsorption capacity of these materials render them promising new adsorbents for air separation processes.

  3. Octahedral-tetrahedral equilibrium and solvent exchange of cobalt(II) ions in primary alkylamines.

    PubMed

    Aizawa, Sen-ichi; Funahashi, Shigenobu

    2002-08-26

    The enthalpy differences (Delta H degrees ) of the equilibrium between the octahedral and tetrahedral solvated cobalt(II) complexes were obtained in some primary alkylamines such as propylamine (pa, 36.1 +/- 2.3 kJ mol(-1)), n-hexylamine (ha, 34.9 +/- 1.0 kJ mol(-1)), 2-methoxyethylamine (meea, 44.8 +/- 3.1 kJ mol(-1)), and benzylamine (ba, 50.1 +/- 3.6 kJ mol(-1)) by the spectrophotometric method. The differences in the energy levels between the two geometries of the cobalt(II) complexes in the spherically symmetric field (Delta E(spher)) were estimated from the values of Delta H degrees by offsetting the ligand field stabilization energies. It was indicated that the value of Delta E(spher) is the decisive factor in determining the value of Delta H degrees and is largely dependent on the electronic repulsion between the d-electrons and the donor atoms and the interelectronic repulsion in the d orbitals. The comparison between activation enthalpies (Delta H(++)) for the solvent exchange reactions of octahedral cobalt(II) ions in pa and meea revealed that the unexpectedly large rate constant and small Delta H(++) in pa are attributed to the strong electronic repulsion in the ground state and removal of the electronic repulsion in the dissociative transition state, which can give the small Delta E(spher) between the ground and transition states. Differences in the solvent exchange rates and the DeltaH(++) values of the octahedral metal(II) ions in some other solvents are discussed in connection with the electronic repulsive factors.

  4. Dinuclear cobalt(II) and copper(II) complexes with a Py2N4S2 macrocyclic ligand.

    PubMed

    Núñez, Cristina; Bastida, Rufina; Lezama, Luis; Macías, Alejandro; Pérez-Lourido, Paulo; Valencia, Laura

    2011-06-20

    The interaction between Co(II) and Cu(II) ions with a Py(2)N(4)S(2)-coordinating octadentate macrocyclic ligand (L) to afford dinuclear compounds has been investigated. The complexes were characterized by microanalysis, conductivity measurements, IR spectroscopy and liquid secondary ion mass spectrometry. The crystal structure of the compounds [H(4)L](NO(3))(4), [Cu(2)LCl(2)](NO(3))(2) (5), [Cu(2)L(NO(3))(2)](NO(3))(2) (6), and [Cu(2)L(μ-OH)](ClO(4))(3)·H(2)O (7) was also determined by single-crystal X-ray diffraction. The [H(4)L](4+) cation crystal structure presents two different conformations, planar and step, with intermolecular face-to-face π,π-stacking interactions between the pyridinic rings. Complexes 5 and 6 show the metal ions in a slightly distorted square-pyramidal coordination geometry. In the case of complex 7, the crystal structure presents the two metal ions joined by a μ-hydroxo bridge and the Cu(II) centers in a slightly distorted square plane or a tetragonally distorted octahedral geometry, taking into account weak interactions in axial positions. Electron paramagnetic resonance spectroscopy is in accordance with the dinuclear nature of the complexes, with an octahedral environment for the cobalt(II) compounds and square-pyramidal or tetragonally elongated octahedral geometries for the copper(II) compounds. The magnetic behavior is consistent with the existence of antiferromagnetic interactions between the ions for cobalt(II) and copper(II) complexes, while for the Co(II) ones, this behavior could also be explained by spin-orbit coupling.

  5. Solvent extraction separation of nickel and cobalt from a sulfate solution containing iron(II) and magnesium using versatic 10

    NASA Astrophysics Data System (ADS)

    Ichlas, Zela Tanlega; Purwadaria, Sunara

    2017-01-01

    The separation of nickel and cobalt from a synthetic sulfate solution that contains iron(II) and magnesium via solvent extraction techniques using a neodecanoic acid, Versatic 10, as extractant was explored. The extraction behavior of the metals was investigated by varying the operating pH while the stripping behavior was investigated by varying the acidity of the stripping agent which was sulfuric acid. The experimental results demonstrate that nickel, cobalt and iron(II) can be separated easily from magnesium via selective extraction using 20% Versatic 10 as extractant and 5% tri-n-butyl phosphate (TBP) as phase modifier at pH 7.0, while the nickel and cobalt in the loaded organic phase can be separated from iron(II) by selective stripping of the two metals using 0.1 mol/L sulfuric acid solution leaving iron(II) in the organic phase. Attempts to optimize the extraction and stripping processes were reported.

  6. Management of Stage II glottic cancer. [Cobalt 60

    SciTech Connect

    Jose, B.,; Mohammed, A.; Calhoun, D.L.

    1981-08-01

    A detailed retrospective analysis was done of 55 patients with Stage II (TsNqMq) glottic cancer, treated at the University of Louisville Radiation Center from October 1953 to December 1975. Ninety-one percent of the patients were male. Eight-five percent of the patients had squamous cell carcinoma. The five year adjusted survival rate was 81% with a standard error of 5%. Twenty-seven percent of the patients had local failure and 58% of them were salvaged by further surgery. The median time to recurrence was eleven months. There was no case of laryngeal necrosis, and good function of the larynx was achieved in the majority of the patients. Eight second cancers were diagnosed during the continued follow-up of these patients. A brief review of the literature is included.

  7. Synthesis, structure and properties of {M4O4} cubanes containing nickel(II) and cobalt(II).

    PubMed

    Isele, Katharina; Gigon, Fabienne; Williams, Alan F; Bernardinelli, Gérald; Franz, Patrick; Decurtins, Silvio

    2007-01-21

    A survey of the crystal structures containing simple {M4O4} cubane units is reported. It shows that the average M-M distance in these complexes is relatively constant for a given metal ion M. The structures are all distorted from the idealised cube to a T(d) structure, and most show a further distortion which, however, usually maintains some elements of symmetry. A system for classifying the different types of ligand in these complexes is proposed. Two new cubanes of cobalt(II) and nickel(II) with the ligand (R,R)-bis-1,2-(1-methylbenzimidazol-2-yl)ethane-1,2-diol, (R,R)- or its enantiomer have been isolated and the crystal structure of the cobalt(II) complex confirms the cubane structure. Electronic, CD and (1)H NMR spectra and magnetic susceptibility data are reported. The magnetic data for these and other compounds in the literature are discussed in terms of the structural parameters.

  8. Part I. Cobalt thiolate complexes modeling the active site of cobalt nitrile hydratase. Part II. Formation of inorganic nanoparticles on protein scaffolding in Escherichia coli glutamine synthetase

    NASA Astrophysics Data System (ADS)

    Kung, Irene Yuk Man

    Part I. A series of novel cobalt dithiolate complexes with mixed imine/amine ligand systems is presented here as electronic and structural models for the active site in the bacterial enzyme class, nitrile hydratase (NHase). Pentadentate cobalt(II) complexes with S2N 3 ligand environments are first studied as precursors to the more relevant cobalt(III) complexes. Adjustment of the backbone length by removal of a methylene group increases the reactivity of the system; whereas reduction of the two backbone imine bonds to allow free rotation about those bonds may decrease reactivity. Reactivity change due to the replacement of the backbone amine proton with a more sterically challenging methyl group is not yet clear. Upon oxidation, the monocationic pentadentate cobalt(III) complex, 1b, shows promising reactivity similar to that of NHase. The metal's open coordination site allows reversible binding of the endogenous, monoanionic ligands, N 3- and NCS-. Oxygenation of the thiolate sulfur atoms by exposure to O2 and H2O 2 produces sulfenate and sulfinate ligands in complex 8, which resembles the crystal structure of "deactivated" Fe NHase. However, its lack of reactivity argues against the oxygenated enzyme structure as the active form. Six-coordinate cobalt(III) complexes with S2N4 amine/amine ligand systems are also presented as analogues of previously reported iron(III) compounds, which mimic the spectroscopic properties of Fe NHase. The cobalt complexes do not seem to similarly model Co NHase. However, the S = 0 cobalt(III) center can be spectroscopically silent and difficult to detect, making comparison with synthetic models using common techniques hard. Part II. Dodecameric Escherichia coli glutamine synthetase mutant, E165C, stacks along its six-fold axis to produce tubular nanostructures in the presence of some divalent metal ions, as does the wild type enzyme. The centrally located, engineered Cys-165 residues appear to bind to various species and may serve as

  9. Bis[bis-(penta-methyl-cyclo-penta-dien-yl)cobalt(III)] tetra-chlorido-cobaltate(II) di-chloro-methane disolvate.

    PubMed

    Merola, Joseph S; Ngo, Mai; Karpin, George W

    2013-01-01

    The title compound, [Co(C10H15)2]2[CoCl4]·2CH2Cl2, was isolated as a dichloromethane solvate and was formed in the reaction between lithium penta-methyl-cyclo-penta-dienide and anyhydrous cobalt(II) chloride in tetra-hydro-furan. There are two deca-methyl-cobaltocenium cations, one tetrachloridocobaltate(II) anion and two di-chloro-methane solvent mol-ecules in the formula unit. There is a slight disorder of the di-chloro-methane solvent which was treated with a two-site model [occupancy rates = 0.765 (4) and 0.235 (4)]. The di-chloro-methane mol-ecules display significant C-H⋯Cl inter-actions with the tetrachloridocobaltate(II) dianion. The cobalt atom of the deca-methyl-cobaltocenium cation sits on a twofold rotation axis, with only one penta-methyl-cyclo-penta-diene ligand being unique and the second generated by symmetry. The cobalt atom of the [CoCl4](-2) ion sits on a special site with -4 symmetry, with one unique chloride ligand and the others generated by the fourfold inversion axis.

  10. Fluorescence reaction of 5-(p-methoxyphenylazo)-8-(p-tolylsulfonamido)quinoline with cobalt(II) and its analytical application

    SciTech Connect

    Zeng Zuotao ) Xu Qiheng )

    1992-08-01

    5-(p-Methoxyphenylazo)-8-(p-tolylsulfonamido)quinoline(MTAQ) has been synthesized. The product was checked by IR, thermogravimetry, NMR and elemental analysis. A highly sensitive spectrofluorimetric method has been developed for the determination of cobalt(II) based on the formation of a complex with MTAQ in slightly basic medium aqueous solution and in the presence of nonionic surfactant, tween-80. The complex shows two excitation maxima at 304 nm and 338 nm, its emission maximum is centered at 402nm. The fluorescence intensity is proportional to cobalt(II) concentration in the range of 0-85 ppb. The method has good selectivity and has been applied to the direct fluorimetric determination of trace cobalt(II) in pig's liver, Dianchi shrimp and celery.

  11. Cytotoxic activity, X-ray crystal structures and spectroscopic characterization of cobalt(II), copper(II) and zinc(II) coordination compounds with 2-substituted benzimidazoles.

    PubMed

    Sánchez-Guadarrama, Obdulia; López-Sandoval, Horacio; Sánchez-Bartéz, Francisco; Gracia-Mora, Isabel; Höpfl, Herbert; Barba-Behrens, Noráh

    2009-09-01

    Herein we present the synthesis, structural and spectroscopic characterization of coordination compounds of cobalt(II), copper(II) and zinc(II) with 2-methylbenzimidazole (2mbz), 2-phenylbenzimidazole (2phbz), 2-chlorobenzimidazole (2cbz), 2-benzimidazolecarbamate (2cmbz) and 2-guanidinobenzimidazole (2gbz). Their cytotoxic activity was evaluated using human cancer cell lines, PC3 (prostate), MCF-7 (breast), HCT-15 (colon), HeLa (cervic-uterine), SKLU-1 (lung) and U373 (glioblastoma), showing that the zinc(II) and copper(II) compounds [Zn(2mbz)(2)Cl(2)].0.5H(2)O, [Zn(2cmbz)(2)Cl(2)].EtOH, [Cu(2cmbz)Br(2)].0.7H(2)O and [Cu(2gbz)Br(2)] had significant cytotoxic activity. The isostructural cobalt(II) complexes showed not significant activity. The cytotoxic activity is related to the presence of halides in the coordination sphere of the metal ion. Recuperation experiments with HeLa cells, showed that the cells recuperated after removing the copper(II) compounds and, on the contrary, the cells treated with the zinc(II) compounds did not. These results indicate that the mode of action of the coordination compounds is different.

  12. Simultaneous Determination of Cobalt(II) and Nickel(II) by Fourth-Order Derivative Spectrophotometric Method Using 2-Hydroxy-3-Methoxy Benzaldehyde Thiosemicarbazone

    PubMed Central

    Kumar, A. Praveen; Reddy, P. Raveendra; Reddy, V. Krishna

    2007-01-01

    A simple and new simultaneous fourth derivative spectrophotometric method is proposed for the analysis of a two-component system containing cobalt(II) and nickel(II) without separation using 2-hydroxy-3-methoxy benzaldehyde thiosemicarbazone (HMBATSC) as a chromophoric reagent. The reagent reacts with cobalt(II) and nickel(II) at pH 6.0, forming soluble brown and yellow colored species, respectively. Cobalt(II) and nickel(II) present in themixture are simultaneously determined without solving the simultaneous equations bymeasuring the fourth derivative amplitudes at 468.5 nm and 474.5 nm, respectively. The derivative amplitudes obey Beer's law at 468.5 nm and 474.5 nm for Co(II) and Ni(II) in the range 0.059–3.299 μg mL−1 and 0.058–3.285 μg mL−1 respectively. A large number of foreign ions do not interfere in the present method. The present simultaneous method is used for the determination of micro amounts of cobalt in biological samples, nickel in plant samples, and in some alloy steels and soil sample. PMID:17671609

  13. Spin Crossover in Double Salts Containing Six- and Four-Coordinate Cobalt(II) Ions.

    PubMed

    Palion-Gazda, Joanna; Machura, Barbara; Kruszynski, Rafal; Grancha, Thais; Moliner, Nicolás; Lloret, Francesc; Julve, Miguel

    2017-06-05

    The preparation and spectroscopic and structural characterization of three cobalt(II) complexes of formulas [Co(tppz)2](dca)2 (1), [Co(tppz)2][Co(NCS)4]·MeOH (2), and [Co(tppz)2][Co(NCO)4]·2H2O (3) [tppz = 2,3,5,6-tetrakis(2-pyridyl)pyrazine and dca = dicyanamide] are reported here. Compounds 1-3 have in common the presence of the cationic [Co(tppz)2](2+) entity where each mer-tridentate tppz ligand coordinates to the cobalt(II) ion equatorially through two pyridyl donors and axially via the pyrazine, completing the six-coordination. The electroneutrality is achieved by the organic dca group (1) and the anionic tetrakis(thiocyanato-κN)cobaltate(II) (2) and tetrakis(cyanato-κN)cobaltate(II) (3) complexes. Direct current (dc) magnetic susceptibility measurements of 1 in the temperature range 1.9-400 K show the occurrence of a thermally induced spin crossover behavior of the [Co(tppz)2](2+) unit from a high spin (S = 3/2) at higher temperatures to a low-spin (S = 1/2) at lower temperatures, with the low spin phase being reached at T ≤ 200 K. X-band electron paramagnetic resonance (EPR) measurements in solution at low temperatures were used to characterize the low spin state. An analytical expression based on the combination of the spin-orbit coupling and both first- and second-order Zeeman effects for a d(7) electronic configuration was used to fit the magnetic data of 1, the values of the best-fit parameters being Cvib = 0.1367(9), λ = -168(2) cm(-1), α = 1.12(1), Δ = 1626(15) cm(-1), and gLS = 2.12(1). The magnetic behavior of the four-coordinate cobalt(II) ions [Co(NCS)4](2-) (2) and [Co(NCO)4](2-) (3) with a (4)A2 ground state overlaps with the spin crossover of the [Co(tppz)2]2+ entity, the abrupt decrease of the χMT product below 15.0 K being due to zero-field splitting effects between the spin components |±1/2> and |±3/2>. The combined analysis of the dc magnetic data and the Q-band EPR spectra in the solid state of 2 and 3 led to the following sets

  14. Correlation of reactivity with structural factors in a series of Fe(II) substituted cobalt ferrites

    SciTech Connect

    Sileo, Elsa E.; Garcia Rodenas, Luis; Paiva-Santos, Carlos O.; Stephens, Peter W.; Morando, Pedro J. . E-mail: morando@cnea.gov.ar; Blesa, Miguel A.

    2006-07-15

    A series of powdered cobalt ferrites, Co {sub x} Fe{sub 3-} {sub x} O{sub 4} with 0.66{<=}x<1.00 containing different amounts of Fe{sup II}, were synthesized by a mild procedure, and their Fe and Co site occupancies and structural characteristics were explored using X-ray anomalous scattering and the Rietveld refinement method. The dissolution kinetics, measured in 0.1 M oxalic acid aqueous solution at 70 deg. C, indicate in all cases the operation of a contracting volume rate law. The specific rates increased with the Fe{sup II} content following approximately a second-order polynomial expression. This result suggests that the transfer of Fe{sup III} controls the dissolution rate, and that the leaching of a first layer of ions Co{sup II} and Fe{sup II} leaves exposed a surface enriched in slower dissolving octahedral Fe{sup III} ions. Within this model, inner vicinal lattice Fe{sup II} accelerates the rate of Fe{sup III} transfer via internal electron hopping. A chain mechanism, involving successive electron transfers, fits the data very well. - Graphical abstract: The electron exchange between octahedral Fe{sup II} and Fe{sup III} ions has important consequences on the specific dissolution rates. Display Omitted.

  15. Spectrophotometric Study of the Complex Formation of Anionic Chelates of Cobalt(II) with Monotetrazolium Cations

    NASA Astrophysics Data System (ADS)

    Divarova, V. V.; Stojnova, K. T.; Racheva, P. V.; Lekova, V. D.

    2017-05-01

    The complex formation and extraction of anionic chelates of Co(II)-4-(2-thiazolylazo)resorcinol (TAR) with cations of monotetrazolium salts (TS) — (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl-2H-tetrazolium bromide (MTT) and 3-(2-naphthyl)-2,5-diphenyl-2H-tetrazolium chloride (TV) — in the liquid-liquid extraction system Co(II)-TAR-TS-H2O-CHCl3 were studied by spectrophotometric methods. The optimum conditions for the extraction of Co(II) were found. The molar ratio of the components and the form of the anionic chelates of Co(II) in the extracted compounds were determined by independent methods. The association process in the aqueous phase and the extraction process were investigated and quantitatively characterized. The following key constants were calculated: association constant, distribution constant, extraction constant, and recovery factor. The validity of the Beer's law was checked, and some analytical characteristics were calculated. Based on the obtained results and the lower price of the monotetrazolium salt MTT compared with that of TV, the ion-associated complex of Co(II)-TAR-MTT can be implemented for determination of cobalt(II) traces in alloys and biological, medical, and pharmaceutical samples.

  16. Selective, tunable O2 binding in cobalt(II)–triazolate/pyrazolate metal–organic frameworks

    DOE PAGES

    Xiao, Dianne J.; Gonzalez, Miguel I.; Darago, Lucy E.; ...

    2016-05-16

    Here, the air-free reaction of CoCl2 with 1,3,5-tri(1H- 1,2,3-triazol-5-yl)benzene (H3BTTri) in N,N-dimethylformamide (DMF) and methanol leads to the formation of Co- BTTri (Co3[(Co4Cl)3(BTTri)8]2·DMF), a sodalite-type metal-organic framework. Desolvation of this material generates coordinatively unsaturated low-spin cobalt(II) centers that exhibit a strong preference for binding O2 over N2, with isosteric heats of adsorption (Qst) of -34(1) and -12(1) kJ/ mol, respectively. The low-spin (S = 1/2) electronic configuration of the metal centers in the desolvated framework is supported by structural, magnetic susceptibility, and computational studies. A single-crystal X-ray structure determination reveals that O2 binds end-on to each framework cobalt center inmore » a 1:1 ratio with a Co-O2 bond distance of 1.973(6) Å. Replacement of one of the triazolate linkers with a more electron-donating pyrazolate group leads to the isostructural framework Co-BDTriP (Co3[(Co4Cl)3(BDTriP)8]2·DMF; H3BDTriP = 5,5'-(5-(1H-pyrazol-4-yl)-1,3-phenylene)bis(1H-1,2,3-triazole)), which demonstrates markedly higher yet still fully reversible O2 affinities (Qst = -47(1) kJ/mol at low loadings). Electronic structure calculations suggest that the O2 adducts in Co-BTTri are best described as cobalt(II)-dioxygen species with partial electron transfer, while the stronger binding sites in Co-BDTriP form cobalt(III)-superoxo moieties. The stability, selectivity, and high O2 adsorption capacity of these materials render them promising new adsorbents for air separation processes.« less

  17. Selective, Tunable O2 Binding in Cobalt(II)–Triazolate/Pyrazolate Metal–Organic Frameworks

    PubMed Central

    2016-01-01

    The air-free reaction of CoCl2 with 1,3,5-tri(1H-1,2,3-triazol-5-yl)benzene (H3BTTri) in N,N-dimethylformamide (DMF) and methanol leads to the formation of Co-BTTri (Co3[(Co4Cl)3(BTTri)8]2·DMF), a sodalite-type metal–organic framework. Desolvation of this material generates coordinatively unsaturated low-spin cobalt(II) centers that exhibit a strong preference for binding O2 over N2, with isosteric heats of adsorption (Qst) of −34(1) and −12(1) kJ/mol, respectively. The low-spin (S = 1/2) electronic configuration of the metal centers in the desolvated framework is supported by structural, magnetic susceptibility, and computational studies. A single-crystal X-ray structure determination reveals that O2 binds end-on to each framework cobalt center in a 1:1 ratio with a Co–O2 bond distance of 1.973(6) Å. Replacement of one of the triazolate linkers with a more electron-donating pyrazolate group leads to the isostructural framework Co-BDTriP (Co3[(Co4Cl)3(BDTriP)8]2·DMF; H3BDTriP = 5,5′-(5-(1H-pyrazol-4-yl)-1,3-phenylene)bis(1H-1,2,3-triazole)), which demonstrates markedly higher yet still fully reversible O2 affinities (Qst = −47(1) kJ/mol at low loadings). Electronic structure calculations suggest that the O2 adducts in Co-BTTri are best described as cobalt(II)–dioxygen species with partial electron transfer, while the stronger binding sites in Co-BDTriP form cobalt(III)–superoxo moieties. The stability, selectivity, and high O2 adsorption capacity of these materials render them promising new adsorbents for air separation processes. PMID:27180991

  18. Uptake of {sup 64}Cu-oxine by marine phytoplankton

    SciTech Connect

    Croot, P.L.; Karson, B.; Elteren, J.T. van; Kroon, J.J.

    1999-10-15

    Short-term uptake experiments using fie phytoplankton species (Synechococcus clone DC2, Amphidinium carterae, Chrysochromulina polylepis, Ditylum brightwelli, and Prorocentrum micans) demonstrated rapid uptake of the lipophilic complex {sup 64}Cu-oxine, presumably by diffusion of the complex across the plasma membrane. This passive uptake mechanism was extremely rapid and significantly faster than facilitated uptake by the free metal ion. Measured values of the observed permeability, P{sub obs}, ranged from 0.55 to 18.6 x 10{sup {minus}4} cm s{sup {minus}1}, showing only small differences between the various algal species. Removal rate constants, k{sup bio}, varied much more widely, 0.009--570 x 10{sup {minus}9} L cell{sup {minus}1} h{sup {minus} 1}, between the algae, indicating the influence of surface area on the uptake kinetics. Maximum internal Cu levels were reached after approximately 2 h, showing that a major limiting factor in the uptake of Cu from Cu-oxine is the concentration of intracellular Cu binding sites.

  19. Spectrophotometric Determination of Iron(II) and Cobalt(II) by Direct, Derivative, and Simultaneous Methods Using 2-Hydroxy-1-Naphthaldehyde-p-Hydroxybenzoichydrazone.

    PubMed

    Devi, V S Anusuya; Reddy, V Krishna

    2012-01-01

    Optimized and validated spectrophotometric methods have been proposed for the determination of iron and cobalt individually and simultaneously. 2-hydroxy-1-naphthaldehyde-p-hydroxybenzoichydrazone (HNAHBH) reacts with iron(II) and cobalt(II) to form reddish-brown and yellow-coloured [Fe(II)-HNAHBH] and [Co(II)-HNAHBH] complexes, respectively. The maximum absorbance of these complexes was found at 405 nm and 425 nm, respectively. For [Fe(II)-HNAHBH], Beer's law is obeyed over the concentration range of 0.055-1.373 μg mL(-1) with a detection limit of 0.095 μg mL(-1) and molar absorptivity ɛ, 5.6 × 10(4) L mol(-1) cm(-1). [Co(II)-HNAHBH] complex obeys Beer's law in 0.118-3.534 μg mL(-1) range with a detection limit of 0.04 μg mL(-1) and molar absorptivity, ɛ of 2.3 × 10(4) L mol(-1) cm(-1). Highly sensitive and selective first-, second- and third-order derivative methods are described for the determination of iron and cobalt. A simultaneous second-order derivative spectrophotometric method is proposed for the determination of these metals. All the proposed methods are successfully employed in the analysis of various biological, water, and alloy samples for the determination of iron and cobalt content.

  20. Synthesis, crystal structure and antifungal activity of a divalent cobalt(II) complex with uniconazole.

    PubMed

    Zhang, Yao; Li, Jie; Ren, Guoyu; Qin, Baofu; Ma, Haixia

    2016-06-01

    Azole compounds have attracted commercial interest due to their high bactericidal and plant-growth-regulating activities. Uniconazole [or 1-(4-chlorophenyl)-4,4-dimethyl-2-(1H-1,2,4-triazol-1-yl)pent-1-en-3-ol] is a highly active 1,2,4-triazole fungicide and plant-growth regulator with low toxicity. The pharmacological and toxicological properties of many drugs are modified by the formation of their metal complexes. Therefore, there is much interest in exploiting the coordination chemistry of triazole pesticides and their potential application in agriculture. However, reports of complexes of uniconazole are rare. A new cobalt(II) complex of uniconazole, namely dichloridotetrakis[1-(4-chlorophenyl)-4,4-dimethyl-2-(1H-1,2,4-triazol-1-yl-κN(4))pent-1-en-3-ol]cobalt(II), [CoCl2(C15H18ClN3O)4], was synthesized and structurally characterized by element analysis, IR spectrometry and X-ray single-crystal diffraction. The crystal structural analysis shows that the Co(II) atom is located on the inversion centre and is coordinated by four uniconazole and two chloride ligands, forming a distorted octahedral geometry. The hydroxy groups of an uniconazole ligands of adjacent molecules form hydrogen bonds with the axial chloride ligands, resulting in one-dimensional chains parallel to the a axis. The complex was analysed for its antifungal activity by the mycelial growth rate method. It was revealed that the antifungal effect of the title complex is more pronounced than the effect of fungicide uniconazole for Botryosphaeria ribis, Wheat gibberellic and Grape anthracnose.

  1. Thermochemical study of the processes of complexation of cobalt(II) ions with L-histidine in aqueous solution

    NASA Astrophysics Data System (ADS)

    Gorboletova, G. G.; Metlin, A. A.

    2015-09-01

    Thermal effects of the complexation of cobalt(II) ions with L-histidine at 298.15 K and several values of the ionic strength against the background of KNO3 are determined by means of direct calorimetry. The standard thermodynamic characteristics of the reactions of complexation in the aqueous solution have been calculated.

  2. Ligand contributions to the electronic structures of the oxidized cobalt(II) salen complexes.

    PubMed

    Kochem, Amélie; Kanso, Hussein; Baptiste, Benoit; Arora, Himanshu; Philouze, Christian; Jarjayes, Olivier; Vezin, Hervé; Luneau, Dominique; Orio, Maylis; Thomas, Fabrice

    2012-10-15

    Square planar cobalt(II) complexes of salen ligands N,N'-bis(3-tert-butyl-5R-salicylidene)-1,2-cyclohexanediamine), where R = OMe (1) and tert-butyl (2), were prepared. 1 and 2 were electrochemically reversibly oxidized into cations [1-H(2)O](+) and [2-H(2)O](+) in CH(2)Cl(2). The chemically generated [1-H(2)O](SbF(6))·0.68 H(2)O·0.82CH(2)Cl(2) and [2-H(2)O](SbF(6))·0.3H(2)O·0.85CH(2)Cl(2) were characterized by X-ray diffraction and NIR spectroscopy. Both complexes are paramagnetic species containing a square pyramidal cobalt ion coordinated at the apical position by an exogenous water molecule. They exhibit remarkable NIR bands at 1220 (7370 M(-1) cm(-1)) and 1060 nm (5560 M(-1) cm(-1)), respectively, assigned to a CT transition. DFT calculations and magnetic measurements confirm the paramagnetic (S = 1) ground spin state of the cations. They show that more than 70% of the total spin density in [1-H(2)O](+) and [2-H(2)O](+) is localized on the metal, the remaining spin density being distributed over the aromatic rings (30% phenoxyl character). In the presence of N-methylimidazole 1 and 2 are irreversibly oxidized by air into the genuine octahedral cobalt(III) bis(phenolate) complexes [1-im(2)](+) and [2-im(2)](+), the former being structurally characterized. Neither [1-im(2)](+) nor [2-im(2)](+) exhibits a NIR feature in its electronic spectrum. 1 and 2 were electrochemically two-electron oxidized into [1](2+) and [2](2+). The cations were identified as Co(III)-phenoxyl species by their characteristic absorption band at ca. 400 nm in the UV-vis spectrum. Coordination of the phenoxyl radical to the cobalt(III) metal ion is evidenced by the EPR signal centered at g = 2.00.

  3. Synthesis and Temperature-Induced Structural Phase and Spin Transitions in Hexadecylboron-Capped Cobalt(II) Hexachloroclathrochelate and Its Diamagnetic Iron(II)-Encapsulating Analogue.

    PubMed

    Vologzhanina, Anna V; Belov, Alexander S; Novikov, Valentin V; Dolganov, Alexander V; Romanenko, Galina V; Ovcharenko, Victor I; Korlyukov, Alexander A; Buzin, Mikhail I; Voloshin, Yan Z

    2015-06-15

    Template condensation of dichloroglyoxime with n-hexadecylboronic acid on the corresponding metal ion as a matrix under vigorous reaction conditions afforded n-hexadecylboron-capped iron and cobalt(II) hexachloroclathrochelates. The complexes obtained were characterized using elemental analysis, MALDI-TOF mass spectrometry, IR, UV-vis, (1)H and (13)C{(1)H} NMR, (57)Fe Mössbauer spectroscopies, SQUID magnetometry, electron paramagnetic resonance, and cyclic voltammetry (CV) and by X-ray crystallography. The multitemperature single-crystal X-ray diffraction, SQUID magnetometry, and differential scanning calorimetry experiments were performed to study the temperature-induced spin-crossover [for the paramagnetic cobalt(II) complex] and the crystal-to-crystal phase transitions (for both of these clathrochelates) in the solid state. Analysis of their crystal packing using the molecular Voronoi polyhedra and the Hirshfeld surfaces reveals the structural rearrangements of the apical long-chain alkyl substituents resulting from such phase transitions being more pronounced for a macrobicyclic cobalt(II) complex. Its fine-crystalline sample undergoes the gradual and fully reversible spin transition centered at approximately 225 K. The density functional theory calculated parameters for an isolated molecule of this cobalt(II) hexachloroclathrochelate in its low- and high-spin states were found to be in excellent agreement with the experimental data and allowed to localize the spin density within a macrobicyclic framework. CV of the cobalt(II) complex in the cathodic range contains one reversible wave assigned to the Co(2+/+) redox couple with the reduced anionic cobalt(I)-containing species stabilized by the electronic effect of six strong electron-withdrawing chlorine substituents. The quasireversible character of the Fe(2+/+) wave suggests that the anionic iron(I)-containing macrobicyclic species undergo substantial structural changes and side chemical reactions after such

  4. Steric interaction of solvation and sterically enhanced halogeno complexation of manganese(II), cobalt(II) and nickel(II) ions in N,N-dimethylacetamide

    SciTech Connect

    Koide, Makoto; Suzuki, Honoh; Ishiguro, Shin-ichi

    1994-12-01

    The complexation of manganese(II), cobalt(II) and nickel(II) with bromide ions has been studied in N,N-dimethylacetamide (DMA) by calorimetry and spectrophotometry. The formation of [MBr]{sup +}, [MBr{sub 2}] and [MBr{sub 3}]{sup -} (M = Mn, Co, Ni) was revealed in all the metal systems. Interestingly, the complexation is significantly enhanced in DMA over N,N-dimethylformamide (DMF). This is unusual because physicochemical properties of DMA and DMF as solvent are similar. Furthermore, extracted electronic spectra of individual complexes of Ni{sup II} suggested the presence of a geometry equilibrium, [NiBr(DMA){sub 5}]{sup +} = [NiBr(DMA){sub 4}]{sup +} + DMA, in DMA. A similar geometry equilibrium is also suggested, [NiBr{sub 2}(DMA){sub 3}] = [NiBr{sub 2}(DMA){sub 2}] + DMA. Such geometry equilibria were not observed in DMF. With regard to cobalt(II), electronic spectra show the presence of the four-coordinated [CoBr(DMA){sub 3}]{sup +} complex in DMA, unlike the six-coordinated [CoBr(DMF){sub 5}]{sup +} one in DMF. These facts suggest that a specific strong steric interaction operates between coordinating solvent molecules, which plays a key role in the complexation behavior of the divalent transition metal ions in DMA.

  5. Thermochromism, stability and thermodynamics of cobalt(II) complexes in newly synthesized nitrate based ionic liquid and its photostability.

    PubMed

    Banić, Nemanja; Vraneš, Milan; Abramović, Biljana; Csanádi, János; Gadžurić, Slobodan

    2014-11-07

    In this work a 1-(2-hydroxyethyl)-3-methylimidazolium nitrate ionic liquid, [HO(CH2)2mim]NO3, has been synthesized in order to serve as a new thermochromic material upon addition of cobalt(II) ions. Spectrophotometric measurements of a series of cobalt(II) nitrate and cobalt(II) chloride solutions in [HO(CH2)2mim]NO3 at 298.15, 308.15, 318.15, 328.15, and 338.15 K, were performed. Based on the recorded spectra, the overall stability constants and thermodynamic parameters for the cobalt(II) associations with chloride and nitrate ions were calculated. The thermodynamic calculations suggest that thermochromism is not observed in the ionic medium due to a small entropy change during the replacement of nitrate with chloride ions in the co-ordination sphere of cobalt(II). The absence of the molecular solvent was also the reason for the lack of thermochromism. Thus, cobalt(II) solutions in [HO(CH2)2mim]NO3 and water mixtures were studied as a new and green medium that can be used for the auto-regulation of the light intensity and shade protection. The investigated system with water upon addition of cobalt(II) was found to be a far more efficient and responsive thermochromic medium for all of the studied systems up until now. The structure of [HO(CH2)2mim]NO3 was confirmed by both (1)H NMR and IR spectroscopy. Also, the efficiency of different advanced oxidation processes (UV-induced photolysis, UV/H2O2 photolysis, heterogeneous photocatalysis using TiO2 Degussa P25 and TiO2 with 7.24%, w/w Fe catalysts) for [HO(CH2)2mim]NO3 degradation were investigated. The reaction intermediates formed during the photo-oxidation process were identified using LC-ESI-MS/MS and (1)H NMR techniques.

  6. A Bioinspired Molecular Polyoxometalate Catalyst with Two Cobalt(II) Oxide Cores for Photocatalytic Water Oxidation.

    PubMed

    Wei, Jie; Feng, Yingying; Zhou, Panpan; Liu, Yan; Xu, Jingyin; Xiang, Rui; Ding, Yong; Zhao, Chongchao; Fan, Linyuan; Hu, Changwen

    2015-08-24

    To overcome the bottleneck of water splitting, the exploration of efficient, selective, and stable water oxidation catalysts (WOCs) is crucial. We report an all-inorganic, oxidatively and hydrolytically stable WOC based on a polyoxometalate [(A-α-SiW9 O34)2Co8(OH)6(H2O)2(CO3)3](16-) (Co8 POM). As a cobalt(II)-based cubane water oxidation catalyst, Co8POM embeds double Co(II)4O3 cores. The self-assembled catalyst is similar to the oxygen evolving complex (OEC) of photosystem II (PS II). Using [Ru(bpy)3](2+) as a photosensitizer and persulfate as a sacrificial electron acceptor, Co8POM exhibits excellent water oxidation activity with a turnover number (TON) of 1436, currently the highest among bioinspired catalysts with a cubical core, and a high initial turnover frequency (TOF). Investigation by several spectroscopy, spectrometry, and other techniques confirm that Co8POM is a stable and efficient catalyst for visible light-driven water oxidation. The results offer a useful insight into the design of water oxidation catalysts.

  7. Inhibitory effect of water on the oxygen reduction catalyzed by cobalt(II) tetraphenylporphyrin.

    PubMed

    Trojánek, Antonín; Langmaier, Jan; Kvapilová, Hana; Záliš, Stanislav; Samec, Zdeněk

    2014-03-20

    Stopped-flow kinetic measurements, UV-vis spectroscopy, rotating disk voltammetry, and quantum chemical calculations are used to clarify the role of water in the homogeneous two-electron reduction of O2 to H2O2 in 1,2-dichloroethane (DCE) using ferrocene (Fc) as an electron donor, tetrakis(pentafluorophenyl)boric acid (HTB) as a proton donor, and [5,10,15,20-tetraphenyl-21H,23H-porphine]cobalt(II) (Co(II)TTP) as a catalyst. Kinetic analysis suggests that the reaction is controlled by the intramolecular proton coupled electron transfer to the O2 molecule coordinated to the metal center producing the O2H(•) radical. This rate-determining step is common to both the O2 reduction by Fc catalyzed by Co(II)TPP and the O2 reduction by Co(II)TPP itself. Experimental data point to the competitive coordination of water to the metal center leading to a strong inhibition of the catalytic reaction. In agreement with this finding, quantum chemical calculations indicate that water is bound to the metal center much more strongly than triplet O2. A similar effect is demonstrated also for the O2 reduction catalyzed by the porphyrin free base (H2TPP), though its rate is lower by 2 orders of magnitude.

  8. Kinetics of Formation of Cobalt(II)- and Nickel(II) Carbonic Anhydrase.

    ERIC Educational Resources Information Center

    McQuate, Robert S.; Reardon, John E.

    1978-01-01

    Discusses the kinetic behavior associated with the interaction of metal ions with apocarbonic anhydrase, focusing on the formation of two metallocarbonic anhydrase--the biochemically active Co(II) and the inactive Ni(II)derivatives. (GA)

  9. Kinetics of Formation of Cobalt(II)- and Nickel(II) Carbonic Anhydrase.

    ERIC Educational Resources Information Center

    McQuate, Robert S.; Reardon, John E.

    1978-01-01

    Discusses the kinetic behavior associated with the interaction of metal ions with apocarbonic anhydrase, focusing on the formation of two metallocarbonic anhydrase--the biochemically active Co(II) and the inactive Ni(II)derivatives. (GA)

  10. Engineering surface atomic structure of single-crystal cobalt (II) oxide nanorods for superior electrocatalysis

    PubMed Central

    Ling, Tao; Yan, Dong-Yang; Jiao, Yan; Wang, Hui; Zheng, Yao; Zheng, Xueli; Mao, Jing; Du, Xi-Wen; Hu, Zhenpeng; Jaroniec, Mietek; Qiao, Shi-Zhang

    2016-01-01

    Engineering the surface structure at the atomic level can be used to precisely and effectively manipulate the reactivity and durability of catalysts. Here we report tuning of the atomic structure of one-dimensional single-crystal cobalt (II) oxide (CoO) nanorods by creating oxygen vacancies on pyramidal nanofacets. These CoO nanorods exhibit superior catalytic activity and durability towards oxygen reduction/evolution reactions. The combined experimental studies, microscopic and spectroscopic characterization, and density functional theory calculations reveal that the origins of the electrochemical activity of single-crystal CoO nanorods are in the oxygen vacancies that can be readily created on the oxygen-terminated {111} nanofacets, which favourably affect the electronic structure of CoO, assuring a rapid charge transfer and optimal adsorption energies for intermediates of oxygen reduction/evolution reactions. These results show that the surface atomic structure engineering is important for the fabrication of efficient and durable electrocatalysts. PMID:27650485

  11. Engineering surface atomic structure of single-crystal cobalt (II) oxide nanorods for superior electrocatalysis.

    PubMed

    Ling, Tao; Yan, Dong-Yang; Jiao, Yan; Wang, Hui; Zheng, Yao; Zheng, Xueli; Mao, Jing; Du, Xi-Wen; Hu, Zhenpeng; Jaroniec, Mietek; Qiao, Shi-Zhang

    2016-09-21

    Engineering the surface structure at the atomic level can be used to precisely and effectively manipulate the reactivity and durability of catalysts. Here we report tuning of the atomic structure of one-dimensional single-crystal cobalt (II) oxide (CoO) nanorods by creating oxygen vacancies on pyramidal nanofacets. These CoO nanorods exhibit superior catalytic activity and durability towards oxygen reduction/evolution reactions. The combined experimental studies, microscopic and spectroscopic characterization, and density functional theory calculations reveal that the origins of the electrochemical activity of single-crystal CoO nanorods are in the oxygen vacancies that can be readily created on the oxygen-terminated {111} nanofacets, which favourably affect the electronic structure of CoO, assuring a rapid charge transfer and optimal adsorption energies for intermediates of oxygen reduction/evolution reactions. These results show that the surface atomic structure engineering is important for the fabrication of efficient and durable electrocatalysts.

  12. Syntheses, structures and characterization of novel cobalt(II) mono- and bi-triazole complexes

    NASA Astrophysics Data System (ADS)

    Huang, Yong-Quan; Ding, Bin; Gao, Hong-Ling; Cheng, Peng; Liao, Dai-Zheng; Yan, Shi-Ping; Jiang, Zhong-Hui

    2005-05-01

    Using the bi- and mono-triazole ligand, two novel cobalt(II) complexes [Co(L 1) 2(NCS) 2(H 2O) 2]·2H 2O ( 1) and [Co 3(L 2) 6(NCS) 4(H 2O) 2](NCS) 2·H 2O ( 2) (L 1=4-[3-(1,2,4-triazolyl)-1,2,4-triazole] and L 2=4-aminotriazole) have been synthesized. The crystal structures of 1 and 2 have been determined by X-ray single-crystal diffraction. 1 has the mononuclear fundamental structure unit while 2 form the linear trinuclear structure unit. 1 and 2 were furthermore assembled into two-dimensional (2D) network and three-dimensional (3D) supramolecular complex via the intermolecular hydrogen-bonds, respectively. The complexes 1 and 2 also have been characterized by elemental analysis, FT-IR, UV/vis spectra.

  13. Coordination conversion of cobalt(II) in binary aqueous-organic solvents

    SciTech Connect

    Khvostova, N.O.; Karapetyan, G.O.; Yanush, O.V.

    1985-11-01

    It has been shown that the thermochromic conversions of cobalt(II) in binary solvents are influenced by a number of factors: the nature of the solvent, the strength of the complexes of octahedral symmetry formed, the outer-sphere influence of the solvent on the complexes, the form of the anion, the solvation of the participants in the reaction, and the interaction of the components of the solvent with one another. A correlation between the strength and the spectral position of the absorption bands of the complexes of the activator has been established, and a spectroscopic criterion for selecting the solvents has been proposed. The expediency of using binary solvents to create effective thermochromic media with variable phototransmission has been substantiated.

  14. Single-ion magnet behaviour in mononuclear and two-dimensional dicyanamide-containing cobalt(ii) complexes.

    PubMed

    Switlicka-Olszewska, Anna; Palion-Gazda, Joanna; Klemens, Tomasz; Machura, Barbara; Vallejo, Julia; Cano, Joan; Lloret, Francesc; Julve, Miguel

    2016-06-21

    Three cobalt(ii) complexes of formulae [Co(dca)2(bim)4] (), [Co(dca)2(bim)2]n () and [Co(dca)2(bmim)2]n () [dca = dicyanamide, bim = 1-benzylimidazole and bmim = 1-benzyl-2-methylimidazole] were prepared and structurally analyzed by single-crystal X-ray crystallography. Compound is a mononuclear species where the cobalt(ii) ion is six-coordinate with four bim molecules in the equatorial positions [Co-Nbim = 2.1546(15) and 2.1489(15) Å] and two trans-positioned dca ligands [Co-Ndca = 2.1575(18) Å] in the axial sites of a somewhat distorted octahedral surrounding. The structures of and consist of two-dimensional grids of cobalt(ii) ions where each metal atom is linked to the other four metal centres by single dca bridges exhibiting the μ1,5-dca coordination mode [Co-Ndca = 2.190(3)-2.220(3) () and 2.127(3)-2.153(3) Å ()]. Two trans-coordinated bim ()/bmim () molecules achieve the six-coordination around each cobalt(ii) ion [Co-Nbim = 2.128(3)-2.134(4) Å () and Co-Nbmim = 2.156(3)-2.163(39) Å ()]. The values of the cobalt-cobalt separation through the single dca bridges are 8.927(2) and 8.968(2) Å in and 8.7110(5) and 8.7158(5) Å in . Magnetic susceptibility measurements for in the temperature range of 2.0-300 K reveal that these compounds behave as magnetically isolated high-spin cobalt(ii) ions with a significant orbital contribution to the magnetic moment. Alternating current (ac) magnetic susceptibility measurements for show a frequency dependence of out-of-phase susceptibility under static applied fields in the range of 500-2500 G, a feature which is characteristic of the single-ion magnet behaviour (SIM) of the Co(ii) ion in them. The values of the energy barrier for the magnetic relaxation (Ea) are 5.45-7.74 (), 4.53-9.24 () and 11.48-15.44 cm(-1) (). They compare well with those previously reported for the analogous dca-bridged 2D compound [Co(dca)2(atz)2]n () (Ea = 5.1 cm(-1) under an applied static field of 1000 G), which was the subject of a

  15. Adsorptive separation of rhodium(III) using Fe(III)-templated oxine type of chemically modified chitosan

    SciTech Connect

    Alam, M.S.; Inoue, Katsutoshi; Yoshizuka, Kazuharu; Ishibashi, Hideaki

    1998-03-01

    The oxine type of chemically modified chitosan was prepared by the template crosslinking method using Fe(III) as a template ion. Batchwise adsorption of rhodium(III) on this chemically modified chitosan was examined from chloride media in the absence and presence of a large amount of tin(II). It was observed that the Fe(III)-templated oxine type of chemically modified chitosan shows better performance for rhodium adsorption than that of the original chitosan. When Sn(II) is absent from the solution, Rh(III) is hardly adsorbed on the modified chitosan and the order of selectivity of the adsorption of Rh(III), Pt(IV), and Cu(II) was found to be Pt(IV) > Cu(II) {approx} Rh(III). On the other hand, adsorption of rhodium is significantly increased in the presence of Sn(II) and the selectivity order of the adsorption was drastically changed to Rh(III) > Pt(IV) {much_gt} Cu(II), which ensures selective separation of Rh(III) from their mixture. Adsorption of Rh(III) increases with an increase in the concentration of Sn(II) in the aqueous solution, and maximum adsorption is achieved at a molar ratio, [Sn]/[Rh], of >6. The adsorption of Rh(III) decreases at a high concentration of hydrochloric acid. The maximum adsorption capacity was evaluated to be 0.92 mol/kg-dry adsorbent. Stripping tests of rhodium from the loaded chemically modified chitosan were carried out using different kinds of stripping agents containing some oxidizing agent. The maximum stripping of rhodium under these experimental conditions was found to be 72.5% by a single contact with 0.5 M HCl + 8 M HNO{sub 3}.

  16. Cytotoxic copper(II), cobalt(II), zinc(II), and nickel(II) coordination compounds of clotrimazole.

    PubMed

    Betanzos-Lara, Soledad; Gómez-Ruiz, Celedonio; Barrón-Sosa, Lidia R; Gracia-Mora, Isabel; Flores-Álamo, Marcos; Barba-Behrens, Noráh

    2012-09-01

    Sixteen novel mononuclear Cu(II), Co(II), Zn(II), and Ni(II) complexes of the biologically active ligand clotrimazole (clotri) of the forms [M(clotri)(2)Cl(2)]·nH(2)O (1-4), [M(clotri)(2)Br(2)]·nH(2)O (5-7), [M(clotri)(3)Br(2)] (8), [M(clotri)(3)NO(3)]NO(3)·nH(2)O (9, 11), [M(clotri)(3)(NO(3))(2)]·nH(2)O (10), and [M(clotri)(3)(OH(2))(2)NO(3)]NO(3)·nH(2)O (12) were synthesized and fully characterized. Dinuclear [Cu(2)(clotri)(4)μ(2)-Cl(4)]·2H(2)O (1a) and [Cu(2)(clotri)(4)μ(2)-Br(2)]·2H(2)O (5b) as well as tetranuclear [Cu(4)(clotri)(4)μ(4)-Br(6)μ(4)-O] (5a) complexes were also isolated. Complexes 1-7, 9, and 11 present a tetrahedral geometry; complex 8 exhibits a pentacoordinated structure; complexes 1a, 10 and 12 an octahedral geometry. X-ray crystal structures of [Cu(clotri)(2)Cl(2)](1), [Cu(clotri)(2)(EtOH)Cl(2)](1·EtOH), [Zn(clotri)(2)Cl(2)] (3), [Zn(clotri)(2)Br(2)] (7), and [Cu(4)(clotri)(4)μ(4)-Br(6)μ(4)-O] (5a) were obtained. Complexes 1-12 were tested for cytotoxic activity against the human carcinoma cell lines HeLa (cervix-uterine), PC3 (prostate), and HCT-15 (colon) displaying IC(50) values <30 μM. Confocal microscopy and nuclear dying (DAPI) for complex 1 showed condensation of cromatin and nuclear membrane fragmentation. Immunocytochemical detection/expression of biomarkers suggests that complexes 1 and 9 induce cell death via apoptosis. TUNEL assay detected DNA fragmentation in HeLa cells, resulting from apoptotic signaling cascades induced by Cu(II) complexes 1 and 9. (1)H NMR studies of the Zn(II) complexes showed that they can bind to nucleotides.

  17. Crystal and molecular structures of trichloro-cobalt(II) complexes of epiquinine, epiquinidine, and epidihydrocinchonine.

    PubMed

    Tesarowicz, Iwona; Oleksyn, Barbara J; Nitek, Wojciech

    2007-02-01

    Cinchona alkaloids are very well known antimalarials but the mechanism of their biological action still remains to be elucidated. The structural studies of active erythro and inactive threo alkaloid complexes are an important step to this aim. In this paper results of crystal structure analysis of three cobalt complexes of threo alkaloids are presented: (epiquininium)trichlorocobalt(II) (EpiQnCoCl3), (epiquinidinium)trichlorocobalt(II) (EpiQdCoCl3) and (epidihydrocinchoninium)trichlorocobalt(II) (EpiCnCoCl3). The complexes are zwitterions in which trichlorocobalt substituents are coordinated to quinoline nitrogen atoms and quinuclidine nitrogen atoms are protonated. EpiQnCoCl3 adopts uncommon conformation with quinoline moiety oriented in the opposite direction in comparison to the analogous uncomplexed alkaloid. The packing in the crystal structures is determined mainly by the hydrogen bonds, in which the chlorine atoms of substituents and solvent molecules contribute. Atoms participating in hydrogen bonds in EpiQnCoCl3 and EpiQdCoCl3 form large rings, while in EpiCnCoCl3 only chains are present. Solvent molecules are very important for the packing mode. In contrast to most erythro alkaloids, the hydroxyl oxygen atom in the title complexes forms weak or not well defined hydrogen bonds. The contribution of very weak intramolecular interactions N1--H1...O12 cannot be excluded. Such "trace" interactions can be considered a relic of the unprotonated status of an epi alkaloid.

  18. Octanuclear zinc(II) and cobalt(II) clusters produced by cooperative tetrameric assembling of oxime chelate ligands.

    PubMed

    Akine, Shigehisa; Dong, Wenkui; Nabeshima, Tatsuya

    2006-06-12

    We have synthesized an octanuclear zinc(II) cluster [L4Zn8(H2O)3] by the complexation of 3-hydroxysalamo (H4L) with zinc(II) acetate. The complex crystallizes in the triclinic system, space group P, with unit cell parameters a = 18.233(10) A, b = 20.518(11) A, c = 21.366(11) A, alpha = 98.7557(2) degrees, beta = 99.191(11) degrees, gamma = 108.309(10) degrees, and Z = 4. The crystallographic analysis revealed the S4 symmetrical assembling of four ligands and that the tetrameric complex has three water molecules in an unsymmetrical fashion. Spectroscopic analysis of the complex strongly suggests that the octanuclear cluster also exists in solution and maintains a conformation similar to that in the crystal structure, although exchange of the coordinating water molecules presumably takes place. In addition, the formation process of the octanuclear complex is highly cooperative. A high coordinating ability of the [(salamo)Zn] unit as well as the catecholato2- moieties probably stabilizes the octanuclear assembly and makes the complexation process cooperative. The corresponding octanuclear cobalt(II) cluster [L4Co8(EtOH)3] was prepared in a similar manner. Complex [L4Co8(H2O)2X] (X = H2O or EtOH) was obtained by the recrystallization from chloroform/hexane. The complex crystallizes in the triclinic system, space group P, with unit cell parameters a = 15.2359(10) A, b = 16.9625(12) A, c = 18.9325(13) A, alpha = 101.9710(10) degrees, beta = 105.5410(10) degrees, gamma = 97.1290(10) degrees, and Z = 2. Temperature dependence of magnetic susceptibility showed a continuous decrease in the chi(M)T value with decreasing temperature, suggesting antiferromagnetic interaction among cobalt(II) ions. The magnetic susceptibility above 40 K obeys the Curie-Weiss law with a Weiss constant theta of -39 K and a Curie constant C of 19.7 cm(3) K mol(-1).

  19. Cobalt(II) sheet-like systems based on diacetic ligands: from subtle structural variances to different magnetic behaviors.

    PubMed

    Fabelo, Oscar; Pasán, Jorge; Cañadillas-Delgado, Laura; Delgado, Fernando S; Lloret, Francesc; Julve, Miguel; Ruiz-Pérez, Catalina

    2009-07-06

    The preparation, X-ray crystallography, and magnetic investigation of the compounds [Co(H(2)O)(2)(phda)](n) (1), [Co(phda)](n) (2), and [Co(chda)](n) (3) [H(2)phda = 1,4-phenylenediacetic acid and H(2)chda = 1,1-cyclohexanediacetic acid] are described herein. The cobalt atoms in this series are six- (1) and four-coordinated (2 and 3) in distorted octahedral (CoO(6)) and tetrahedral (CoO(4)) environments. The structures of 1-3 consists of rectangular-grids which are built up by sheets of cobalt atoms linked through anti-syn carboxylate bridges, giving rise to either a three-dimensional structure across the phenyl ring (1 and 2) or to regularly stacked layers with the cyclohexyl groups acting as organic separators (3). The magnetic properties of 1-3 were investigated as a function of the temperature and the magnetic field. Ferromagnetic coupling between the six-coordinate cobalt(II) ions across the anti-syn carboxylate bridge occurs in 1 (J = +1.2 cm(-1)) whereas antiferromagnetic coupling among the tetrahedral cobalt(II) centers within the sheets is observed in 2 and 3 [J = -1.63 (2) and -1.70 cm(-1) (3)] together with a spin-canted structure in 3 giving rise a long-range magnetic ordering (T(c) = 7.5 K).

  20. Synthesis and oxidation catalysis of [tris(oxazolinyl)borato]cobalt(II) scorpionates

    SciTech Connect

    Reinig, Regina R.; Mukherjee, Debabrata; Weinstein, Zachary B.; Xie, Weiwei; Albright, Toshia; Baird, Benjamin; Gray, Tristan S.; Ellern, Arkady; Miller, Gordon J.; Winter, Arthur H.; Bud'ko, Sergey L.; Sadow, Aaron D.

    2016-04-28

    The reaction of CoCl2·THF and thallium tris(4,4-dimethyl-2-oxazolinyl)phenylborate (TlToM) in tetrahydrofuran (THF) provides ToMCoCl (1) in 95 % yield; however, appropriate solvents and starting materials are required to favor 1 over two other readily formed side-products, (ToM)2Co (2) and {HToM}CoCl2 (3). ESR, NMR, FTIR, and UV/Vis spectroscopies were used to distinguish these cobalt(II) products and probe their electronic and structural properties. Even after the structures indicated by these methods were confirmed by X-ray crystallography, the spectroscopic identification of trace contaminants in the material was challenging. The recognition of possible contaminants in the synthesis of ToMCoCl in combination with the paramagnetic nature of these complexes provided impetus for the utilization of X-ray powder diffraction to measure the purity of the ToMCoCl bulk sample. Furthermore, the X-ray powder diffraction results provide support for the bulk-phase purity of ToMCoCl in preparations that avoid 2 and 3. Thus, 1 is a precursor for new [tris(oxazolinyl)borato]cobalt chemistry, as exemplified by its reactions with KOtBu and NaOAc to give ToMCoOtBu (4) and ToMCoOAc (5), respectively. Compound 5 is a catalyst for the oxidation of cyclohexane with meta-chloroperoxybenzoic acid (mCPBA), and the rate constants and selectivity for cyclohexanol versus cyclohexanone and ϵ-caprolactone were assessed.

  1. Synthesis and oxidation catalysis of [tris(oxazolinyl)borato]cobalt(II) scorpionates

    DOE PAGES

    Reinig, Regina R.; Mukherjee, Debabrata; Weinstein, Zachary B.; ...

    2016-04-28

    The reaction of CoCl2·THF and thallium tris(4,4-dimethyl-2-oxazolinyl)phenylborate (TlToM) in tetrahydrofuran (THF) provides ToMCoCl (1) in 95 % yield; however, appropriate solvents and starting materials are required to favor 1 over two other readily formed side-products, (ToM)2Co (2) and {HToM}CoCl2 (3). ESR, NMR, FTIR, and UV/Vis spectroscopies were used to distinguish these cobalt(II) products and probe their electronic and structural properties. Even after the structures indicated by these methods were confirmed by X-ray crystallography, the spectroscopic identification of trace contaminants in the material was challenging. The recognition of possible contaminants in the synthesis of ToMCoCl in combination with the paramagnetic naturemore » of these complexes provided impetus for the utilization of X-ray powder diffraction to measure the purity of the ToMCoCl bulk sample. Furthermore, the X-ray powder diffraction results provide support for the bulk-phase purity of ToMCoCl in preparations that avoid 2 and 3. Thus, 1 is a precursor for new [tris(oxazolinyl)borato]cobalt chemistry, as exemplified by its reactions with KOtBu and NaOAc to give ToMCoOtBu (4) and ToMCoOAc (5), respectively. Compound 5 is a catalyst for the oxidation of cyclohexane with meta-chloroperoxybenzoic acid (mCPBA), and the rate constants and selectivity for cyclohexanol versus cyclohexanone and ϵ-caprolactone were assessed.« less

  2. Cobalt(II) β-ketoaminato complexes as novel inhibitors of neuroinflammation.

    PubMed

    Madeira, Jocelyn M; Beloukhina, Natalia; Boudreau, Kalun; Boettcher, Tyson A; Gurley, Lydia; Walker, Douglas G; McNeil, W Stephen; Klegeris, Andis

    2012-02-15

    Neuroinflammation contributes to the pathogenesis of neurological disorders including stroke, head trauma, multiple sclerosis, amyotrophic lateral sclerosis as well as age-associated neurodegenerative disorders including Alzheimer's and Parkinson's diseases. Therefore, anti-inflammatory drugs could be used to slow the progression of these diseases. We studied the anti-neuroinflammatory activity of four novel square planar cobalt(II) compounds bearing tetradentate β-ketoaminato ligands with variation in the number of CF(3) ligand substituents, as well as their corresponding unmetallated organic ligands. Cobalt (Co) complexes were consistently more active than their corresponding ligands. One of the complexes, L(3)Co at concentrations (1-10 μM) that were not toxic to cells, significantly reduced cytotoxic secretions by human monocytic THP-1 cells, astrocytoma U-373 MG cells, and primary human microglia. This anti-neurotoxic action of L(3)Co was reduced by SP600125 and PD98059, selective inhibitors of c-Jun NH2-terminal kinase (JNK) and extracellular signal regulated kinase (ERK) kinase (MEK)1/2 respectively. L(3)Co had no effect on secretion of monocyte chemotactic protein-1 (MCP-1) by THP-1 cells, but it inhibited the NADPH oxidase-dependent respiratory burst activity of differentiated human HL-60 cells. L(3)Co upregulated heme oxygenase-1 (HOX-1) expression by THP-1 cells, which may be one of the molecular mechanisms responsible for its anti-inflammatory properties. Two of the Co compounds tested showed activity only at high concentrations (50 μM), but L(2)Co was highly toxic to all cell types used. Select Co complexes, such as L(3)Co, may exhibit pharmacological properties beneficial in human diseases involving neuroinflammatory processes. Further studies of the in vivo efficacy, safety and pharmacokinetics of L(3)Co are warranted.

  3. 31-day study of cobalt(II) chloride ingestion in humans: pharmacokinetics and clinical effects.

    PubMed

    Finley, Brent L; Unice, Kenneth M; Kerger, Brent D; Otani, Joanne M; Paustenbach, Dennis J; Galbraith, David A; Tvermoes, Brooke E

    2013-01-01

    The United Kingdom Expert Group on Vitamins and Minerals concluded that ingesting cobalt (Co)-containing supplements up to 1400 μg Co/d is unlikely to produce adverse health effects. However, the associated blood Co concentrations and safety of Co-containing dietary supplements have not been fully characterized. Thus, blood Co kinetics and a toxicological assessment of hematological and biochemical parameters were evaluated following Co dietary supplementation in 5 male and 5 female volunteers who ingested approximately 1000 μg Co/d (10-19 μg Co/kg-d) as cobalt(II) chloride for a period of 31 d. Supplement intake was not associated with significant overt adverse events, alterations in clinical chemistries including blood counts and indicators of thyroid, cardiac, liver, or kidney functions, or metal sensitization. A non-clinically significant (<5%) increase in hemoglobin, hematocrit, and red blood cell (RBC) counts were observed in males but not females 1 wk after dose termination. Mean Co concentrations in whole blood/serum after 31 d of dosing were approximately two-fold higher in females (33/53 μg/L) than in males (16/21 μg/L). In general, steady-state concentrations of Co were achieved in whole blood and/or red blood cells (RBC) within 14-24 d. Temporal patterns of whole blood and serum Co concentrations indicated metal sequestration in RBC accompanied by slower whole blood clearance compared to serum. Data also indicated that peak whole blood Co concentrations up to 91.4 μg/L were not associated with clinically significant changes in clinical chemistries. In addition, Co blood concentrations and systemic uptake via ingestion were generally higher in females.

  4. Recent Advances of Cobalt(II/III) Redox Couples for Dye-Sensitized Solar Cell Applications.

    PubMed

    Giribabu, Lingamallu; Bolligarla, Ramababu; Panigrahi, Mallika

    2015-08-01

    In recent years dye-sensitized solar cells (DSSCs) have emerged as one of the alternatives for the global energy crisis. DSSCs have achieved a certified efficiency of >11% by using the I(-) /I3 (-) redox couple. In order to commercialize the technology almost all components of the device have to be improved. Among the various components of DSSCs, the redox couple that regenerates the oxidized sensitizer plays a crucial role in achieving high efficiency and durability of the cell. However, the I(-) /I3 (-) redox couple has certain limitations such as the absorption of triiodide up to 430 nm and the volatile nature of iodine, which also corrodes the silver-based current collectors. These limitations are obstructing the commercialization of this technology. For this reason, one has to identify alternative redox couples. In this regard, the Co(II/III) redox couple is found to be the best alternative to the existing I(-) /I3 (-) redox couple. Recently, DSSC test cell efficiency has risen up to 13% by using the cobalt redox couple. This review emphasizes the recent development of Co(II/III) redox couples for DSSC applications.

  5. Cobalt(II) chloride adducts with acetonitrile, propan-2-ol and tetrahydrofuran: considerations on nuclearity, reactivity and synthetic applications.

    PubMed

    Stinghen, Danilo; Rüdiger, André Luis; Giese, Siddhartha O K; Nunes, Giovana G; Soares, Jaísa F; Hughes, David L

    2017-02-01

    High-spin cobalt(II) complexes are considered useful building blocks for the synthesis of single-molecule magnets (SMM) because of their intrinsic magnetic anisotropy. In this work, three new cobalt(II) chloride adducts with labile ligands have been synthesized from anhydrous CoCl2, to be subsequently employed as starting materials for heterobimetallic compounds. The products were characterized by elemental, spectroscopic (EPR and FT-IR) and single-crystal X-ray diffraction analyses. trans-Tetrakis(acetonitrile-κN)bis(tetrahydrofuran-κO)cobalt(II) bis[(acetonitrile-κN)trichloridocobaltate(II)], [Co(C2H3N)4(C4H8O)2][CoCl3(C2H3N)]2, (1), comprises mononuclear ions and contains both acetonitrile and tetrahydrofuran (thf) ligands, The coordination polymer catena-poly[[tetrakis(propan-2-ol-κO)cobalt(II)]-μ-chlorido-[dichloridocobalt(II)]-μ-chlorido], [Co2Cl4(C3H8O)4], (2'), was prepared by direct reaction between anhydrous CoCl2 and propan-2-ol in an attempt to rationalize the formation of the CoCl2-alcohol adduct (2), probably CoCl2(HO(i)Pr)m. The binuclear complex di-μ-chlorido-1:2κ(4)Cl:Cl-dichlorido-2κ(2)Cl-tetrakis(tetrahydrofuran-1κO)dicobalt(II), [Co2Cl4(C4H8O)4], (3), was obtained from (2) after recrystallization from tetrahydrofuran. All three products present cobalt(II) centres in both octahedral and tetrahedral environments, the former usually less distorted than the latter, regardless of the nature of the neutral ligand. Product (2') is stabilized by an intramolecular hydrogen-bond network that appears to favour a trans arrangement of the chloride ligands in the octahedral moiety; this differs from the cis disposition found in (3). The expected easy displacement of the bound solvent molecules from the metal coordination sphere makes the three compounds good candidates for suitable starting materials in a number of synthetic applications.

  6. Investigation of non-corrin cobalt(II)-containing sites in protein structures of the Protein Data Bank.

    PubMed

    Abriata, Luciano Andres

    2013-04-01

    Protein X-ray structures with non-corrin cobalt(II)-containing sites, either natural or substituting another native ion, were downloaded from the Protein Data Bank and explored to (i) describe which amino acids are involved in their first ligand shells and (ii) analyze cobalt(II)-donor bond lengths in comparison with previously reported target distances, CSD data and EXAFS data. The set of amino acids involved in Co(II) binding is similar to that observed for catalytic Zn(II) sites, i.e. with a large fraction of carboxylate O atoms from aspartate and glutamate and aromatic N atoms from histidine. The computed Co(II)-donor bond lengths were found to depend strongly on structure resolution, an artifact previously detected for other metal-donor distances. Small corrections are suggested for the target bond lengths to the aromatic N atoms of histidines and the O atoms of water and hydroxide. The available target distance for cysteine (Scys) is confirmed; those for backbone O and other donors remain uncertain and should be handled with caution in refinement and modeling protocols. Finally, a relationship between both Co(II)-O bond lengths in bidentate carboxylates is quantified.

  7. Biosorption of cobalt(II) with sunflower biomass from aqueous solutions in a fixed bed column and neural networks modelling.

    PubMed

    Oguz, Ensar; Ersoy, Muhammed

    2014-01-01

    The effects of inlet cobalt(II) concentration (20-60 ppm), feed flow rate (8-19 ml/min) and bed height (5-15 cm), initial solution pH (3-5) and particle size (0.25cobalt(II) concentration, 5 cm bed height and 8 ml/min flow rate, pH 6.5 and 0.25cobalt(II) in fixed bed columns.

  8. Cobalt(II/III) redox electrolyte in ZnO nanowire-based dye-sensitized solar cells.

    PubMed

    Fan, Jiandong; Hao, Yan; Cabot, Andreu; Johansson, Erik M J; Boschloo, Gerrit; Hagfeldt, Anders

    2013-03-01

    In this work, we explore the use of cobalt complex redox shuttles in dye sensitized solar cells (DSCs) based on ZnO nanowires (NWs). Arrays of vertically aligned ZnO NWs produced by a low-cost hydrothermal method are used to fabricate DSCs with [Co(bpy)3](2+/3+) as electrolyte. A direct comparison of the performance of [Co(bpy)3](2+/3+)-based ZnO DSC with I(-)/I3(-)-based ones demonstrates the higher suitability of the cobalt complex, both in terms of a larger open circuit voltage (VOC) and a higher photocurrent. The [Co(bpy)3](2+/3+) electrolyte results in VOC enhancements above 200 mV. This VOC increase is associated to the better match between the cobalt complex redox potential and the oxidation potential of the dye. The incident photon-to-current efficiency (IPCE) enhancement is attributed to a less competitive visible light absorption of the cobalt redox couple. Thus the present study opens new opportunities to improve energy conversion efficiency in ZnO-based DSCs.

  9. Cobalt(II) and Nickel(II) Transfer through Charged Polysulfonated Cation Exchange Membranes.

    PubMed

    Ersoz; Kara

    2000-12-15

    The transport of Co(II) and Ni(II) ions through charged polysulfonated ion exchange membranes under Donnan dialysis conditions has been studied as a function of pH gradient at 25 degrees C. In the Donnan dialysis process, the membrane is bounded by two electrolyte solutions, the one side (donor phase) initially containing metal salts and the other H(2)SO(4) with no external potential field applied. The transport of metal ions through membranes was correlated with the flux data as well as with estimated diffusion coefficients and was found to depend on the interaction between the fixed groups in the membrane and the metal ions. It was observed that the pH gradient influences the transport of metals and the flux of ions increases with H ion concentration in the receiver phase. Copyright 2000 Academic Press.

  10. Quinolones and non-steroidal anti-inflammatory drugs interacting with copper(II), nickel(II), cobalt(II) and zinc(II): structural features, biological evaluation and perspectives.

    PubMed

    Psomas, George; Kessissoglou, Dimitris P

    2013-05-14

    The structural features of copper(II), nickel(II), cobalt(II) and zinc(II) complexes with the antimicrobial drugs quinolones and non-steroidal anti-inflammatory drugs (NSAIDs) as ligands are discussed. The binding properties of these complexes to biomolecules (calf-thymus DNA, bovine or human serum albumin) are presented and evaluated. The biological activity (antimicrobial, antioxidant and antiproliferative) of selected complexes is investigated. Further perspectives concerning the synthesis and the biological activity of novel complexes with quinolones or NSAIDs attractive to synthetic chemists, biochemists and/or biologists are presented.

  11. trans-Dichlorido­tetra­kis­[(di­methyl­phosphor­yl)methanaminium-κO]cobalt(II) tetra­chloridocobaltate(II)

    PubMed Central

    Reiss, Guido J.

    2013-01-01

    The asymmetric unit of the title structure, [CoCl2(C3H11NOP)4][CoCl4]2, consists of one half of the trans-dichlorido­tetra­kis­[(di­methyl­phosphor­yl)methanaminium]cobalt(II) tetra­cation lying on an inversion center and one tetra­chloridocobaltate(II) dianion on a general position. Four O-coordinated cationic (di­methyl­phosphor­yl)methanaminium (dpmaH+) ligands occupy the equatorial coordination sites, whereas the chloride ligands occupy axial positions of the roughly o­cta­hedral coordination polyhedron of the cobalt metal center. Intra­molecular hydrogen bonds between the aminium groups and the O atom of the phosphoryl groups and additional hydrogen bonds between the aminium groups and the chloride ligands are present. Furthermore, four of the six H atoms not involved in intra­molecular bonding of each cobalt(II) tetra­cation form weak hydrogen bonds to four adjacent tetra­chloridocobaltate(II) counter-anions. By these inter­molecular hydrogen bonds, one-dimensional polymeric strands are formed along the b-axis direction. The hydrogen bonding is analyzed using the graph-set method and the structural similarity with dpmaHCl is discussed. PMID:23723763

  12. Vibrational spectroscopic and DFT calculation studies of cobalt(II) complexes with 3-hydroxypicolinic acid

    NASA Astrophysics Data System (ADS)

    Furić, Krešimir; Kodrin, Ivan; Kukovec, Boris-Marko; Mihalić, Zlatko; Popović, Zora

    2013-01-01

    Two cobalt(II) complexes with 3-hydroxypicolinic acid (3-hydroxypyridine-2-carboxylic acid, 3-OHpicH), trans-[Co(3-OHpic)2(py)2] (2) and cis-[Co(3-OHpic)2(4-pic)2] (3) (py = pyridine; 4-pic = 4-picoline or 4-methylpyridine), previously synthesized and characterized by X-ray diffraction, are here studied by Raman and mid-infrared spectroscopy with the help from the corresponding DFT vibrational calculations using B3LYP/6-311G(d,p) computational model. Intramolecular O-H⋯O hydrogen bond appears in both complexes 2 and 3, while weak C-H⋯O hydrogen bonds assemble molecules of 2 or 3 into 3D architecture. A complete presentation of all Raman, infrared and theoretical results is given for complex 3. The measured spectra are shown, relative intensities and bandwidths are discussed and the assignment of vibrational bands is given on the basis of the DFT calculations. The calculated spectra agree very well with the presented experimental findings, thanks to the suitable grouping of modes. The same vibrational calculations also reveal insignificant influence of H → CH3 substitution for the spectroscopic characterization of the complex. A careful study of differences between calculated and observed wavenumbers suggests that modified single-factor scaling is actually better than the classic multi-factor scaling approach.

  13. EPR study of Cu(2+) ion doped orotato(nicotinamid)cobalt(II) single crystal.

    PubMed

    Yıldırım, I; Karabulut, B; Büyükgüngör, O

    2016-01-05

    We have studied the Cu(2+) ion doped orotato(nicotinamid)cobalt(II) complex by using EPR spectroscopy and X-ray diffraction. The single crystal is triclinic with the space group P1‾. The unit cell dimensions of the crystal are a=7.2785(4)Å, b=10.2349(5)Å, c=12.7372(6)Å, α=69.297(4)°, β=74.791(4)° and γ=76.995(4)°, with Z=2. We analyzed the EPR spectra of both single crystal and powder of the complex at room temperature. EPR analysis indicates the presence of only one Cu(2+) site. We obtained the spin Hamiltonian parameters from the single crystal data for the complex. The spin Hamiltonian parameters are gx=2.032, gy=2.116, gz=2.319, Ax=28G, Ay=66G, Az=126G. These data indicate that the symmetry of paramagnetic center is rhombic. We constructed the ground state wave function of the Cu(2+) ion.

  14. Photoinduced hydrogen evolution with new tetradentate cobalt(ii) complexes based on the TPMA ligand.

    PubMed

    Natali, Mirco; Badetti, Elena; Deponti, Elisa; Gamberoni, Marta; Scaramuzzo, Francesca A; Sartorel, Andrea; Zonta, Cristiano

    2016-10-07

    Hydrogen production from water splitting is nowadays recognized as a target, fundamental reaction for the production of clean fuels. Indeed, tremendous efforts have been devoted towards the research of suitable catalysts capable of performing this reaction. With respect to heterogeneous systems, molecular catalysts such as metal complexes are amenable to chemical functionalization in order to fine tune the catalytic properties. In this paper a new class of tris(2-pyridylmethyl)-amine (TPMA) cobalt(ii) complexes (CoL0-4) has been synthesized and employed as hydrogen evolving catalysts under photochemical conditions taking advantage of Ru(bpy)3(2+) (where bpy is 2,2'-bipyridine) as a light-harvesting sensitizer and ascorbic acid as a sacrificial electron donor. Tuning of the photocatalytic activity has been attempted through the introduction of different substituents at the catalyst periphery rather than through a direct chemical modification of the chelating TPMA ligand. The results show that CoL0-4 behave as competent hydrogen evolving catalysts (HECs), although the effects played by the different substituents on the catalysis are relatively modest. Possible reasons supporting the observed behavior as well as possible improvements of the aforementioned tuning approach are discussed.

  15. Determination of Amineptine and Amprolium Hydrochlorides through Ion Associates with Cobalt (II) Thiocyanate.

    PubMed

    Fekria M, Abou Attia

    2017-08-15

    Two new methods for the determination of amineptine (AMN) and amprolium (AMP) have been developed. The methods consist of extractin the ion - pairs between the drug and the inorganic complex [Co (SCN)₄](-2). The optimal experimental conditions of both methods including pH, concentration of Co (II) and tlxocyanate ions, and the organic solvents were studied. The optimum pH was found to be 3.9, nitrobenzene proved to be the most suitable solvent, giving quantitative extraction for the two drugs. The two drugs can be determined in the organic phase spectrophotometrically at 625 nm showing Sandell sensitivities of 0.19 and 0.12 µg cm(-2) with relative standard deviation of 0.46 and 0.87 % for amineptine and amprolium, respectively.The indirect method was also applied to measure cobalt in the organic phase by atomic absorption spectrometry at 240.7 nm, and the relative standard deviation of the method is approximately 0.35 and 0.29 % for amineptine and amprolium, respectively. The proposed methods were found to be suitable for the accurate, simple and rapid analysis of amineptine and amprolium hydrochlorides in the bulk drugs and in pharmaceutical forms.

  16. Rapid detection of Cr(VI) ions based on cobalt(II)-doped carbon dots.

    PubMed

    Zhang, Hong-Yu; Wang, Yu; Xiao, Shan; Wang, Han; Wang, Ji-Hui; Feng, Liang

    2017-01-15

    A new type of cobalt(II)-doped carbon dots (CCDs) have been fabricated and used successfully for sensing Cr(VI) ions on the basis of photoluminescence quenching. The structural characterization of as-obtained CCDs was thoroughly performed by transmission electron microscopy (TEM), Fourier transform infrared (FT-IR) and X-ray photoelectron (XPS) spectroscopy. The optical properties were also determined by absorption and fluorescence spectra. By recording 3D fluorescence spectrum, a unique intra-particle Förster resonance energy transfer (FRET) system was investigated. In addition, fluorescence quenching of CCDs was observed in the presence of Cr(VI) ions due to inner filter effect. A good linear relationship between the concentration of Cr(VI) ions and fluorescent intensity was obtained in the range from 5μM to 125μM (R(2)=0.99), and the limit of detection was calculated as 1.17μM (0.12ppm for Cr(VI)). Importantly, this method was capable of rapidly detecting Cr(VI) ions in tap water and fish samples, which may be helpful in risk reduction of intake Cr(VI) contamination from water and seafood. Copyright © 2016 Elsevier B.V. All rights reserved.

  17. Aspartic acid interaction with cobalt(II) in dilute aqueous solution: A 57Co emission Mössbauer spectroscopic study

    NASA Astrophysics Data System (ADS)

    Kamnev, Alexander A.; Tugarova, Anna V.; Kovács, Krisztina; Homonnay, Zoltan; Kuzmann, Erno; Vértes, Attila

    2012-03-01

    Emission (57Co) Mössbauer spectra of the aspartic acid—57CoCl2 system were measured at T = 80 K in frozen aqueous solution and in the form of a dried residue of this solution. The Mössbauer spectra, besides a weak contribution from after-effects, showed two Fe2 + /Co2 + components which were ascribed to octahedrally and tetrahedrally coordinated 57CoII microenvironments in the Asp-cobalt(II) complex. This dual coordination mode may be due to the involvement of the second terminal carboxylic group of aspartic acid in the coordination sphere of Co.

  18. Dynamic interactions of dissolution, surface adsorption, and precipitation in an aging cobalt(II)-clay-water system

    NASA Astrophysics Data System (ADS)

    Thompson, Hillary A.; Parks, George A.; Brown, Gordon E.

    1999-06-01

    We have studied the dynamic interactions of mineral dissolution, cation surface adsorption, and precipitation in aqueous slurries initially containing kaolinite and millimolar quantities of cobalt(II) in 0.1 molar NaNO 3 solution. Batch slurries spent an initial 24 hours at pH 4.2, then NaOH was added to increase pH to 7.8, where pH was maintained for several months. Dissolved Co, Al, and Si concentrations were monitored by ICP-MS; solid-phase products were characterized using EXAFS and TEM. At low pH, kaolinite dissolved, releasing Al and Si to solution. Aluminum hydroxide and aluminosilicate phases precipitated rapidly as pH increased. Cobalt uptake from solution began as pH increased and continued throughout the remainder of the experiment. Rapid surface adsorption and precipitation accounted for early Co uptake; much slower precipitation caused continued Co uptake. Cobalt adsorbed on kaolinite in the form of hydroxy-bridged polymers or multimers and precipitated as a hydrotalcite-like solid that contained aluminum ions derived from kaolinite and aluminum hydroxide dissolution. The cobalt hydrotalcite precipitate had the approximate stoichiometry [Co 6Al 2(OH) 16(A n-) 2/n], with nitrate or silicate anions occupying A sites. Precipitate particles were several nanometers in diameter and some probably precipitated homogeneously. Some of the Co originally adsorbed was later incorporated into precipitate. Slow kaolinite dissolution near neutral pH limited the rate of Co uptake by precipitation, thereby accounting for the slow second stage of Co uptake. Continued changes in solution composition indicate that even this relatively simple system did not reach equilibrium under fixed solution conditions after several months. For this set of conditions, cobalt hydrotalcite appears to be the stable Co-containing phase, and its precipitation can reduce dissolved metal ion concentrations below levels achievable by simple adsorption on kaolinite.

  19. Dynamic interactions of dissolution, surface adsorption, and precipitation in an aging cobalt(II)-clay-water system

    SciTech Connect

    Thompson, H.A.; Parks, G.A.; Brown, G.E. Jr. |

    1999-06-01

    The authors have studied the dynamic interactions of mineral dissolution, cation surface adsorption, and precipitation in aqueous slurries initially containing kaolinite and millimolar quantities of cobalt(II) in 0.1 molar NaNO{sub 3} solution. Batch slurries spent an initial 24 hours at pH 4.2, then NaOH was added to increase pH to 7.8, where pH was maintained for several months. Dissolved Co, Al, and Si concentrations were monitored by ICP-MS; solid-phase products were characterized using EXAFS and TEM. At low pH, kaolinite dissolved, releasing Al and Si to solution. Aluminum hydroxide and aluminosilicate phases precipitated rapidly as pH increased. Cobalt uptake from solution began as pH increased and continued throughout the remainder of the experiment. Rapid surface adsorption and precipitation accounted for early Co uptake; much slower precipitation caused continued Co uptake. Cobalt adsorbed on kaolinite in the form of hydroxy-bridged polymers or multimers and precipitated as a hydrotalcite-like solid that contained aluminum ions derived from kaolinite and aluminum hydroxide dissolution. The cobalt hydrotalcite precipitate had the approximate stoichiometry [Co{sub 6}Al{sub 2}(OH){sub 16}(N{sup n{minus}}){sub 2/n}], with nitrate or silicate anions occupying A sites. Precipitate particles were several nanometers in diameter and some probably precipitated homogeneously. Some of the Co originally adsorbed was later incorporated into precipitate. Slow kaolinite dissolution near neutral pH limited the rate of Co uptake by precipitation, thereby accounting for the slow second stage of Co uptake. Continued changes in solution composition indicate that even this relatively simple system did not reach equilibrium under fixed solution conditions after several months. For this set of conditions, cobalt hydrotalcite appears to be the stable Co-containing phase, and its precipitation can reduce dissolved metal ion concentrations below levels achievable by simple

  20. [Study on the interaction of copper-zinc superoxide dismutase with cobalt (II)-histidine by spectral analysis. II. Effects of pH, interaction time].

    PubMed

    Zheng, X; Hu, J; Cheng, G; Xu, Y; Zhao, Y; Liu, M

    1999-12-01

    The direct interaction of Cu2Zn2SOD with organic metal compound (Cobalt (II)-Histidine) was studied by ICP, VIS and the measurement of enzyme activity, and also investigated the effect of pH values and different interaction times for this interaction. The results showed that with the increased in pH values and the more longer interaction times, the intensity of interaction were increased and the corresponding catalytic activity of enzyme were affected.

  1. Cobalt(II) and cobalt(III) complexes of thioether-containing hexadentate pyrazine amide ligands: C-S bond cleavage and cyclometallation reaction.

    PubMed

    Singh, Akhilesh Kumar; Mukherjee, Rabindranath

    2008-01-14

    Anaerobic reaction of Co(O2CMe)2.4H2O with the thioether-containing acyclic pyrazine amide hexadentate ligand 1,4-bis[o-(pyrazine-2-carboxamidophenyl)]-1,4-dithiobutane (H2L1) (-CH2CH2- spacer between the two pyrazine amide tridentate coordination units) furnishes [CoII(L1)].MeOH (1a) having CoN2(pyrazine)N'2(amide)S2(thioether) coordination. It exhibits an eight-line EPR spectrum, attesting to a low-spin (S = 1/2) state of CoII. A similar reaction in air, however, furnishes [CoIII(L3a)(L3b)].2MeOH (2a) (S = 0), resulting from a C-S bond cleavage reaction triggered by an acetate ion as a base, having CoN2(pyrazine)N'2(amide)S(thioether)S'(thiolate) coordination. On the other hand, the reaction of Co(O2CMe)2.4H2O with 1,4-bis[o-(pyrazine-2-carboxamidophenyl)]-1,5-dithiopentane (H2) (-CH2CH2CH2- spacer between the two pyrazine amide tridentate coordination units) in air affords a cobalt(II) complex [CoII(L2)].MeOH (1b.MeOH) (S = 1/2); its structurally characterized variety has the composition 1b.C6H6. Interestingly, 1b.MeOH undergoes facile metal-centred oxidation by aerial O2-H2O2-[Fe(eta5-C5H5)2][PF6], which led to the isolation of the corresponding cobalt(iii) complex [CoIII(L2)][ClO4] (2b). When treated with methanolic KOH, 2b affords a low-spin (S = 0) organocobalt(III) complex [Co(III)((L2')] (3). Structures of all complexes, except 1a, have been authenticated by X-ray crystallography. A five-membered chelate-ring forming ligand L1(2-) effects C-S bond cleavage and a six-membered chelate-ring forming ligand L2(2-) gives rise to Co-C bond formation, in cobalt(III)-coordinated thioether functions due to alpha C-H bond activation by the base. A rationale has been provided for the observed difference in the reactivity properties. The spectroscopic properties of the complexes have also been investigated. Cyclic voltammetry experiments in MeCN-CH2Cl2 reveal facile metal-centred reversible-to-quasireversible CoIV-CoIII (or a ligand-centred redox process; 2a), CoIII-CoII

  2. Supported cobalt oxide on graphene oxide: highly efficient catalysts for the removal of Orange II from water.

    PubMed

    Shi, Penghui; Su, Ruijing; Zhu, Shaobo; Zhu, Mincong; Li, Dengxin; Xu, Shihong

    2012-08-30

    The current paper investigated the removal of the azo dye Orange II from water using advanced oxidation processes based on sulfate radicals. The cobalt oxide catalyst immobilized on graphene oxide (GO) can activate peroxymonosulfate (PMS) for the degradation of Orange II in water. The Co(3)O(4)/GO catalyst system was characterized via X-ray diffraction, Fourier transform infrared spectroscopy, Raman spectroscopy, scanning electron microscopy, and X-ray spectroscopy. Results showed that Co(3)O(4) was distributed on GO. The Co(3)O(4)/GO catalyst system exhibited high activity in Orange II oxidation when the Co(3)O(4)/GO catalyst has an optimum Co(3)O(4) loading. In addition, 100% decomposition could be achieved within 6 min with 0.2mM Orange II, 0.1 g L(-1) catalyst, and 2mM PMS. Meanwhile, inductively coupled plasma analysis revealed that the leach of cobalt ions was low. The catalyst also exhibited stable performance after several rounds of regeneration. Several operational parameters, such as catalyst amount, oxidant amount, pH, temperature, and oxidation rate, affected the degradation of Orange II. Copyright © 2012 Elsevier B.V. All rights reserved.

  3. Synthesis and characterization of cobalt(II), nickel(II), copper(II) and zinc(II) complexes with Schiff base derived from 4-amino-3-mercapto-6-methyl-5-oxo-1,2,4-triazine.

    PubMed

    Singh, Kiran; Barwa, Manjeet Singh; Tyagi, Parikshit

    2007-03-01

    A few (1:1) and (1:2) metal complexes of cobalt(II), nickel(II), copper(II) and zinc(II) have been isolated with ligand derived from the condensation of 4-amino-3-mercapto-6-methyl-5-oxo-1,2,4-triazine with 2-acetylpyridine (L(1)) and characterized by elemental analysis, conductivity measurements, infrared, electronic, (1)H NMR spectral data, magnetic and thermogravimetric analyses. Due to insolubility in water and most of the common organic solvents and infusibility at higher temperatures, all the complexes are thought to be polymeric in nature. A square-planar geometry was suggested for copper(II) and octahedral proposed for cobalt(II), nickel(II) and zinc(II). Some of the chemically synthesized compounds have been screened in vitro against the three Gram-positive (Staphylococcus aureus, Staphylococcus epidermidis and Bacillus subtilis) and two Gram-negative (Salmonella typhi and Escherichia coli) organisms. It is observed that the coordination of metal ion has pronounced effect on the microbial activities of the ligand. The metal complexes have higher antimicrobial effect than the free ligands.

  4. Biosorption of copper(II), lead(II), iron(III) and cobalt(II) on Bacillus sphaericus-loaded Diaion SP-850 resin.

    PubMed

    Tuzen, Mustafa; Uluozlu, Ozgur Dogan; Usta, Canan; Soylak, Mustafa

    2007-01-09

    The biosorption of copper(II), lead(II), iron(III) and cobalt(II) on Bacillus sphaericus-loaded Diaion SP-850 resin for preconcentration-separation of them have been investigated. The sorbed analytes on biosorbent were eluted by using 1 mol L(-1) HCl and analytes were determined by flame atomic absorption spectrometry. The influences of analytical parameters including amounts of pH, B. sphaericus, sample volume etc. on the quantitative recoveries of analytes were investigated. The effects of alkaline, earth alkaline ions and some metal ions on the retentions of the analytes on the biosorbent were also examined. Separation and preconcentration of Cu, Pb, Fe and Co ions from real samples was achieved quantitatively. The detection limits by 3 sigma for analyte ions were in the range of 0.20-0.75 microg L(-1) for aqueous samples and in the range of 2.5-9.4 ng g(-1) for solid samples. The validation of the procedure was performed by the analysis of the certified standard reference materials (NRCC-SLRS 4 Riverine Water, SRM 2711 Montana soil and GBW 07605 Tea). The presented method was applied to the determination of analyte ions in green tea, black tea, cultivated mushroom, boiled wheat, rice and soil samples with successfully results.

  5. /sup 111/In-oxine platelet survivals in thrombocytopenic infants

    SciTech Connect

    Castle, V.; Coates, G.; Kelton, J.G.; Andrew, M.

    1987-09-01

    Thrombocytopenia is a common occurrence (20%) in sick neonates, but the causes have not been well studied. In this report we demonstrate that thrombocytopenia in the neonate is characterized by increased platelet destruction as shown by shortened homologous /sup 111/In-oxine-labeled platelet life spans. Thirty-one prospectively studied thrombocytopenic neonates were investigated by measuring the /sup 111/In-labeled platelet life span, platelet-associated IgG (PAIgG), and coagulation screening tests. In every infant, the thrombocytopenia was shown to have a destructive component since the mean platelet life span was significantly shortened to 65 +/- 6 (mean +/- SEM) hours with a range of one to 128 hours compared with adult values (212 +/- 8; range, 140 to 260; gamma function analysis). The platelet survival was directly related to the lowest platelet count and inversely related to both the highest mean platelet volume and duration of the thrombocytopenia. In 22 infants the percent recovery of the radiolabeled platelets was less than 50%, which suggested that increased sequestration also contributed to the thrombocytopenia. Infants with laboratory evidence of disseminated intravascular coagulation (n = 8) or immune platelet destruction evidenced by elevated levels of PAIgG (n = 13) had even shorter platelet survivals and a more severe thrombocytopenia compared with the ten infants in whom an underlying cause for the thrombocytopenia was not apparent. Full-body scintigraphic images obtained in 11 infants showed an increased uptake in the spleen and liver, with a spleen-to-liver ratio of 3:1. This study indicates that thrombocytopenia in sick neonates is primarily destructive, with a subgroup having evidence of increased platelet sequestration.

  6. Development of an reliable analytical method for synergistic extractive spectrophotometric determination of cobalt(II) from alloys and nano composite samples by using chromogenic chelating ligand

    NASA Astrophysics Data System (ADS)

    Kamble, Ganesh S.; Ghare, Anita A.; Kolekar, Sanjay S.; Han, Sung H.; Anuse, Mansing A.

    2011-12-01

    A synergistic simple and selective spectrophotometric method was developed for the determination of cobalt(II) with 1-(2',4'-dinitro aminophenyl)-4,4,6-trimethyl-1,4-dihydropyrimidine-2-thiol [2',4'-dinitro APTPT] as a chromogenic reagent. The proposed method has been described on the basis of synergistic effective extraction of cobalt(II) in presence of pyridine at pH range 9.5-10.2, showed orange-red coloured ternary complex having molar ratio 1:2:2 (M:L:Py). The equilibrium time is 10 min for extraction of cobalt(III) from organic phase. The absorbance of coloured organic layer in chloroform is measured spectrophotometrically at 490 nm against reagent blank. The Beer's law was obeyed in the concentration range 2.5-15 μg mL -1 of cobalt(II) and optimum concentration range was 5-12.5 μg mL -1 of cobalt(II) and it was evaluated from Ringbom's plot. The molar absorptivity and Sandell's sensitivity of cobalt(II)-2',4'-dinitro APTPT-pyridine complex in chloroform are 1.109 × 10 3 L mol -1 cm -1 and 0.053 μg cm -2, respectively while molar absorptivity and Sandell's sensitivity of cobalt(II)-2',4'-dinitro APTPT complex in chloroform are 6.22 × 10 2 L mol -1 cm -1 and 0.096 μg cm -2, respectively. The composition of cobalt(II)-2',4'-dinitro APTPT-pyridine complex (1:2:2) was established by slope ratio method, mole ratio method and Job's method of continuous variation. The ternary complex was stable for more than 48 h. The interfering effects of various cations and anions were also studied, and use of suitable masking agents enhances the selectivity of the method. The method is successfully applied for the determination of cobalt(II) in binary, synthetic mixtures and real samples. A repetition of the method was checked by finding relative standard deviation (R.S.D.) for n = 5 which was 0.15%. The reliability of the method is confirmed by comparison of experimental results with atomic absorption spectrophotometer.

  7. Development of an reliable analytical method for synergistic extractive spectrophotometric determination of cobalt(II) from alloys and nano composite samples by using chromogenic chelating ligand.

    PubMed

    Kamble, Ganesh S; Ghare, Anita A; Kolekar, Sanjay S; Han, Sung H; Anuse, Mansing A

    2011-12-15

    A synergistic simple and selective spectrophotometric method was developed for the determination of cobalt(II) with 1-(2',4'-dinitro aminophenyl)-4,4,6-trimethyl-1,4-dihydropyrimidine-2-thiol [2',4'-dinitro APTPT] as a chromogenic reagent. The proposed method has been described on the basis of synergistic effective extraction of cobalt(II) in presence of pyridine at pH range 9.5-10.2, showed orange-red coloured ternary complex having molar ratio 1:2:2 (M:L:Py). The equilibrium time is 10 min for extraction of cobalt(III) from organic phase. The absorbance of coloured organic layer in chloroform is measured spectrophotometrically at 490 nm against reagent blank. The Beer's law was obeyed in the concentration range 2.5-15 μg mL(-1) of cobalt(II) and optimum concentration range was 5-12.5 μg mL(-1) of cobalt(II) and it was evaluated from Ringbom's plot. The molar absorptivity and Sandell's sensitivity of cobalt(II)-2',4'-dinitro APTPT-pyridine complex in chloroform are 1.109×10(3) L mol(-1) cm(-1) and 0.053 μg cm(-2), respectively while molar absorptivity and Sandell's sensitivity of cobalt(II)-2',4'-dinitro APTPT complex in chloroform are 6.22×10(2) L mol(-1) cm(-1) and 0.096 μg cm(-2), respectively. The composition of cobalt(II)-2',4'-dinitro APTPT-pyridine complex (1:2:2) was established by slope ratio method, mole ratio method and Job's method of continuous variation. The ternary complex was stable for more than 48 h. The interfering effects of various cations and anions were also studied, and use of suitable masking agents enhances the selectivity of the method. The method is successfully applied for the determination of cobalt(II) in binary, synthetic mixtures and real samples. A repetition of the method was checked by finding relative standard deviation (R.S.D.) for n=5 which was 0.15%. The reliability of the method is confirmed by comparison of experimental results with atomic absorption spectrophotometer.

  8. Chiral cobalt(ii) complex catalyzed Friedel-Crafts aromatization for the synthesis of axially chiral biaryldiols.

    PubMed

    Xu, Chaoran; Zheng, Haifeng; Hu, Bowen; Liu, Xiaohua; Lin, Lili; Feng, Xiaoming

    2017-08-29

    An efficient atroposelective synthesis of axially chiral biaryldiols via asymmetric Friedel-Crafts aromatization between p-quinones and 2-naphthols was developed. A chiral cobalt(ii) complex of N,N'-dioxide enabled the process to generate axially chiral biaryldiols in up to 98% yield and 95% ee. A large range of substituents at different positions of p-quinones and 2-naphthols was tolerable. The configuration of the product and the chiral N,N'-dioxide-Co(ClO4)2 catalyst was identified by X-ray crystal diffraction analysis and a possible catalytic model was suggested.

  9. Scanning tunneling microscopy study of the structure and orbital-mediated tunneling spectra of cobalt(II) phthalocyanine and cobalt(II) tetraphenylporphyrin on au(111): mixed composition films.

    PubMed

    Barlow, Dan E; Scudiero, L; Hipps, K W

    2004-05-25

    Binary thin films of cobalt(II) phthalocyanine (CoPc) and cobalt(II) tetraphenylporphyrin (CoTPP) were prepared at submonolayer coverage on Au(111)/mica substrates byvapor deposition. All sample preparation and analysis were done under an ultrahigh vacuum. Scanning tunneling microscopy (STM) constant-current images of CoPc/CoTPP mixtures showed two close-packed surface structures, with different compositional percentages and some disorder. CoPc was also observed exclusively in one-dimensional chains and as single, isolated molecules below 220 K. Occupied and unoccupied orbital energy levels were identified by STM and tunnel-diode-based orbital-mediated tunneling spectroscopy. Occupied energy levels were also confirmed by ultraviolet photoelectron spectroscopy. The transient oxidation of the Co d(z2) orbital is identified in STM dI/dV(V) curves just negative of the 0 V sample bias for both molecules. Nearly identical constant-current contours are observed over the central Co2+ ions of CoTPP and CoPc, indicating that the attenuation of the d(z)2 orbital-mediated tunneling current induced by the structure of TPP relative to Pc is at most a factor of about 10. The orbital-mediated tunneling spectra of CoTPP and CoPc are distinctly different and allow these structurally similar species to be differentially identified.

  10. Cobalt (II) removal from aqueous solutions by natural hemp fibers: Batch and fixed-bed column studies

    NASA Astrophysics Data System (ADS)

    Tofan, Lavinia; Teodosiu, Carmen; Paduraru, Carmen; Wenkert, Rodica

    2013-11-01

    Natural hemp fibers were explored as sorbent for the removal of Co(II) ions from aqueous solutions in batch and dynamic conditions. The batch Co(II) sorption capacity increased up to pH 5, reached the maximum (7.5-7.8 mg/g) over the initial pH of 4.5-5. As the initial concentration of metal ion increased (in the range of 25-200 mg/L), the cobalt uptake was enhanced, but the Co(II) removal efficiency decreased. The batch sorption of Co(II) on the tested hemp follows a pseudo-second order model, which relies on the assumption that the chemisorptions may be the rate-controlling step. The Langmuir model better described the Co(II) sorption process on the natural hemp fibers in comparison with the Freundlich model. This finding complies with the results of fixed-bed studies which emphasize that the optimal solution for describing the behavior of the investigated hemp bed column is provided by the Thomas model. The sorption capacity of the hemp fibers column (15.44 mg/g) performed better than that of the Co(II)-hemp batch system (13.58 mg/g). The possibility to use hemp fibers as an alternative in the Co(II) wastewater treatment should be studied under pilot scale applications, so as to complete the studies concerning the removal efficiencies with technical and economic factors that influence process scale-up.

  11. Mercury-based cobalt magnetic fluids and cobalt nanoparticles

    NASA Astrophysics Data System (ADS)

    Massart, R.; Rasolonjatovo, B.; Neveu, S.; Cabuil, V.

    2007-01-01

    This paper describes the synthesis of a magnetic and conducting liquid consisting of cobalt nanoparticles dispersed in mercury. The magnetic nanoparticles are obtained in one step by the electroreduction of a cobalt(II) solution on mercury. These particles are then extracted using an organic solution of surfactant in order to obtain a ferrofluid based on cobalt nanoparticles.

  12. Penta­cobalt(II) divanadium(III) tetrakis(diphosphate), Co5V2(P2O7)4

    PubMed Central

    Bronova, Anna; Glaum, Robert; Litterscheid, Christian

    2013-01-01

    Co5V2(P2O7)4 was crystallized by chemical vapour transport using HCl as transport agent. Its crystal structure is isotypic to that of FeII 5FeIII 2(P2O7)4 and can be regarded as a member of the thortveitite structure family with corrugated layers of metal–oxygen polyhedra extending parallel to (010). Significant occupational disorder between cobalt(II) and vanadium(III) is observed. Four of the five cation sites are occupied by both cobalt and vanadium. The fifth cation site (Co1) is occupied by cobalt only. Sites Co1, M3 and M4 are located on twofold axes. Sites Co1, M2, M3 and M4 show o­cta­hedral coordination by oxygen; M5 has a square-pyramidal environment. PMID:23723750

  13. Anodic Oxidation and Amperometric Sensing of Hydrazine at a Glassy Carbon Electrode Modified with Cobalt (II) Phthalocyanine–cobalt (II) Tetraphenylporphyrin (CoPc-(CoTPP)4) Supramolecular Complex

    PubMed Central

    Ozoemena, Kenneth I.

    2006-01-01

    This paper describes the electrocatalytic behaviour of a glassy carbon electrode (GCE) modified with cobalt(II)phthalocyanine (CoPc) complex peripherally tetrasubstituted with cobalt(II)tetraphenylporphyrin (CoTPP) complexes via ether linkages (i.e., CoPc-(CoTPP)4). The features of the immobilised pentamer were interrogated with cyclic voltammetry and electrochemical impedance spectroscopy (EIS) using [Fe(CN)6]3-/4- as redox probe revealed enhanced electron transfer properties with kapp ≈ 18 × 10-6 cms-1 compared to that of the bare GCE (4.7 × 10-6 cms-1). The viability of this supramolecular complex as a redox mediator for the anodic oxidation and sensitive amperometric determination of hydrazine in alkaline conditions is described. The electrocatalytic oxidation of hydrazine by GCE-CoPc-(CoTPP)4 was characterised with satisfactory catalytic current response with low non-Faradaic current (ca. 30 times lower than the bare GCE) and at much lower oxidation potential (ca. 300 mV lower than the bare GCE). A mechanism for the studied electrocatalytic reaction was proposed based on the spectrophotometric evidence that revealed the major involvement of the Co(III)/Co(II) redox couple of the central CoPc species rather than the CoTPP component of the pentamer. Rate constant for the anodic oxidation of hydrazine was estimated from chronoamperometry as ∼ 3×103 M-1s-1. The proposed amperometric sensor displayed excellent charateristics towards the determination of hydrazine in 0.2 M NaOH; such as low overpotentials (+100 mV vs Ag|AgCl), very fast amperometric response time (1 s), linear concentration range of up to 230 μM, with micromolar detection limit, high sensitivity and stability.

  14. 2,6-Bis(2,6-diethylphenyliminomethyl)pyridine coordination compounds with cobalt(II), nickel(II), copper(II), and zinc(II): synthesis, spectroscopic characterization, X-ray study and in vitro cytotoxicity.

    PubMed

    Martinez-Bulit, Pablo; Garza-Ortíz, Ariadna; Mijangos, Edgar; Barrón-Sosa, Lidia; Sánchez-Bartéz, Francisco; Gracia-Mora, Isabel; Flores-Parra, Angelina; Contreras, Rosalinda; Reedijk, Jan; Barba-Behrens, Norah

    2015-01-01

    Coordination compounds with cobalt(II), nickel(II), copper(II) and zinc(II) and the ligand 2,6-bis(2,6-diethylphenyliminomethyl)pyridine (L) were synthesized and fully characterized by IR and UV-Vis-NIR spectroscopy, elemental analysis, magnetic susceptibility and X-ray diffraction for two representative cases. These novel compounds were designed to study their activity as anti-proliferative drugs against different human cancer cell lines. The tridentate ligand forms heptacoordinated compounds from nitrate metallic salts, where the nitrate acts in a chelating form to complete the seven coordination positions. In vitro cell growth inhibition was measured for Co(II), Cu(II) and Zn(II) complexes, as well as for the free ligand. Upon coordination, the IC50 value of the transition-metal compounds is improved compared to the free ligand. The copper(II) and zinc(II) compounds are the most promising candidates for further in vitro and in vivo studies. The activity against colon and prostate cell lines merits further research, in views of the limited therapeutic options for such cancer types. Copyright © 2014 Elsevier Inc. All rights reserved.

  15. Binuclear cobalt(II), nickel(II), copper(II) and palladium(II) complexes of a new Schiff-base as ligand: synthesis, structural characterization, and antibacterial activity.

    PubMed

    Geeta, B; Shravankumar, K; Reddy, P Muralidhar; Ravikrishna, E; Sarangapani, M; Reddy, K Krishna; Ravinder, V

    2010-11-01

    A binucleating new Schiff-base ligand with a phenylene spacer, afforded by the condensation of glycyl-glycine and o-phthalaldehyde has been served as an octadentate N₄O₄ ligand in designing some binuclear complexes of cobalt(II), nickel(II), copper(II), and palladium(II). The binding manner of the ligand to the metal and the composition and geometry of the metal complexes were examined by elemental analysis, conductivity measurements, magnetic moments, IR, ¹H, ¹³C NMR, ESR and electronic spectroscopies, and TGA measurements. There are two different coordination/chelation environments present around two metal centers of each binuclear complex. The composition of the complexes in the coordination sphere was found to be [M₂(L)(H(2)O)₄] (where M=Co(II) and Ni(II)) and [M₂(L)] (where M=Cu(II) and Pd(II)). In the case of Cu(II) complexes, ESR spectra provided further information to confirm the binuclear structure and the presence of magnetic interactions. All the above metal complexes have shown moderate to good antibacterial activity against Gram-positive and Gram-negative bacteria.

  16. A controllable gate effect in cobalt(II) organic frameworks by reversible structure transformations.

    PubMed

    Chen, Qiang; Chang, Ze; Song, Wei-Chao; Song, Han; Song, Hai-Bin; Hu, Tong-Liang; Bu, Xian-He

    2013-10-25

    With H2 O or NH3 stimuli, the blue cobalt-based metal-organic framework (MOF) BP can reversibly transform to red RP. The removal/recovery of terephthalate ligands accompanied by the transformation leads to a gate effect, which allows the encapsulation and release of small solvent molecules under certain conditions. This is the first example of topology transformation from a self-penetrating to interpenetrating net in 3D MOFs.

  17. Carbonaceous material obtained from exhausted coffee by an aqueous solution combustion process and used for cobalt (II) and cadmium (II) sorption.

    PubMed

    Serrano-Gómez, J; López-González, H; Olguín, M T; Bulbulian, S

    2015-06-01

    New carbonaceous materials were obtained using a fast aqueous solution combustion process from mixtures of exhausted coffee, ammonium nitrate (oxidizer) and urea (fuel) heated at 600, 700, 800 or 900 °C. The resulting powders were effective adsorbents for removing Co(II) and Cd(II) from aqueous solutions. Exhausted coffee was also calcined at different temperatures and compared. The products were characterized, and the obtained carbons had BET specific surface areas of 114.27-390.85 m(2)/g and pore diameters of 4.19 to 2.44 nm when the temperature was increased from 600 to 800 °C. Cobalt and cadmium adsorption by the carbonaceous materials was correlated with the maximum adsorption capacities and specific surface areas of the materials. The method reported here is advantageous because it only required 5 min of reaction to improve the textural properties of carbon obtained from exhausted coffee, which play an important role in the material's cobalt and cadmium adsorption capacities.

  18. Aromatic carboxylate effect on dimensionality of three bis(benzimidazole)-based cobalt(II) coordination polymers: Syntheses, structures and properties

    SciTech Connect

    Zhang, Ju-Wen; Gong, Chun-Hua; Hou, Li-Li; Tian, Ai-Xiang; Wang, Xiu-Li

    2013-09-15

    Three new metal-organic coordination polymers [Co(4-bbc){sub 2}(bbbm)] (1), [Co(3,5-pdc)(bbbm)]·2H{sub 2}O (2) and [Co(1,4-ndc)(bbbm)] (3) (4-Hbbc=4-bromobenzoic acid, 3,5-H{sub 2}pdc=3,5-pyridinedicarboxylic acid, 1,4-H{sub 2}ndc=1,4-naphthalenedicarboxylic acid and bbbm=1,1-(1,4-butanediyl)bis-1H-benzimidazole) were hydrothermally synthesized and structurally characterized. Polymer 1 is a 1D chain formed by the bbbm ligands and Co{sup II} ions. Polymer 2 exhibits a 2D network with a (3·4·5)(3{sup 2}·4·5·6{sup 2}·7{sup 4}) topology. Polymer 3 possesses a 3D three-fold interpenetrating framework. The versatile structures of title polymers indicate that the aromatic carboxylates have an important influence on the dimensionality of 1–3. Moreover, the thermal stability, electrochemical and luminescent properties of 1–3 were investigated. - graphical abstract: Three bis(benzimidazole)-based cobalt(II) coordination polymers tuned by aromatic carboxylates were hydrothermally synthesized and structurally characterized. The aromatic carboxylates play a key role in the dimensionality of three polymers. The electrochemical and luminescent properties of three polymers were investigated. Display Omitted - Highlights: • Three bis(benzimidazole)-based cobalt(II) coordination polymers tuned by aromatic carboxylates were obtained. • The aromatic carboxylates have an important influence on the dimensionality of three polymers. • The electrochemical and luminescent properties of three polymers were investigated.

  19. Three cobalt(II)-linked {P8W48} network assemblies: syntheses, structures, and magnetic and photocatalysis properties.

    PubMed

    Jiao, Yan-Qing; Qin, Chao; Wang, Xin-Long; Wang, Chun-Gang; Sun, Chun-Yi; Wang, Hai-Ning; Shao, Kui-Zhan; Su, Zhong-Min

    2014-02-01

    Three cobalt(II)-containing tungstophosphate compounds, Na8Li8Co5[Co5.5(H2O)19P8W48.5O184]⋅60 H2O (1), K2Na4Li11Co5[Co7(H2O)28P8W48O184]Cl⋅ 59 H2O (2), and K2Na4LiCo11[Co8(H2O)32P8W48O184](CH3COO)4Cl⋅47 H2O (3), have been synthesized and characterized by IR spectroscopy, thermogravimetric analysis, elemental analyses, and magnetic measurements. The pH value impacts the formation of distinct cobalt-linked frameworks. The cyclic cavity of the polyanion accommodates 5.5, 7, and 8 cobalt ions in 1, 2, and 3, respectively. In compounds 1 and 2, each {Co5.5P8W48} and {Co7P8W48} fragment links to four others through multiple {Co-O-W} coordination bonds to generate a two-dimensional network. Compound 3 can be considered as a 3D network based on the {Co-O-W} coordination bonds and the {Co3(CH3COO)2(H2O)10} linkers between the {P8W48} fragments. Interestingly, acetate ligands have been employed to form the {Co3(CH3COO)2(H2O)10} unit, thereby inducing the construction of a 12-connected framework. To the best of our knowledge, compound 3 contains the largest-ever number of cobalt ions in a {P8W48}-based polyoxometalate when counterions are taken into account and the {P8W48} unit shows the highest number of connections thanks to the carboxyl bridges. The UV/Vis diffuse reflectance spectra of these powder samples indicate that the corresponding well-defined optical absorption associated with Eg can be assessed at 2.58, 2.48, and 2.73 eV and reveal the presence of an optical band gap. The photocatalytic H2 evolution activities of these {P8W48}-based compounds are evaluated.

  20. Bis[bis­(penta­methyl­cyclo­penta­dien­yl)cobalt(III)] tetra­chlorido­cobaltate(II) di­chloro­methane disolvate

    PubMed Central

    Merola, Joseph S.; Ngo, Mai; Karpin, George W.

    2013-01-01

    The title compound, [Co(C10H15)2]2[CoCl4]·2CH2Cl2, was isolated as a dichloromethane solvate and was formed in the reaction between lithium penta­methyl­cyclo­penta­dienide and anyhydrous cobalt(II) chloride in tetra­hydro­furan. There are two deca­methyl­cobaltocenium cations, one tetrachloridocobaltate(II) anion and two di­chloro­methane solvent mol­ecules in the formula unit. There is a slight disorder of the di­chloro­methane solvent which was treated with a two-site model [occupancy rates = 0.765 (4) and 0.235 (4)]. The di­chloro­methane mol­ecules display significant C—H⋯Cl inter­actions with the tetrachloridocobaltate(II) dianion. The cobalt atom of the deca­methyl­cobaltocenium cation sits on a twofold rotation axis, with only one penta­methyl­cyclo­penta­diene ligand being unique and the second generated by symmetry. The cobalt atom of the [CoCl4]−2 ion sits on a special site with -4 symmetry, with one unique chloride ligand and the others generated by the fourfold inversion axis. PMID:24426998

  1. Pharmacological Role of Anions (Sulphate, Nitrate, Oxalate and Acetate) on the Antibacterial Activity of Cobalt(II), Copper(II) and Nickel(II) Complexes With Nicotinoylhydrazine-Derived ONO, NNO and SNO Ligands

    PubMed Central

    Rauf, Abdur

    1996-01-01

    Mixed ligands biologically active complexes of cobalt(II), copper(II) and nickel(II) with nicotinoylhydrazine-derived ONO, NNO and SNO donor schiff-base ligands having the same metal ion but different anions such as sulphate, nitrate, oxalate and acetate have been synthesised and characterised on the basis of their physical, analytical and spectral data. In order to evaluate the role of anions on their bioability, these ligands and their synthesised metal complexes with various anions have been screened against bacterial species such as Escherichia coli, Pseudomonas aeruginosa and Staphylococcus aureus and the title studies have proved a definative role of anions in increasing the biological activity PMID:18472896

  2. Energy transfer between terbium (III) and cobalt (II) in thermolysin: a new class of metal--metal distance probes.

    PubMed Central

    Horrocks, W D; Holmquist, B; Vallee, B L

    1975-01-01

    The visible fluorescence of terbium(III) when bound to a calcium binding site of thermolysin is greatly enhanced with an excitation maximum at 280 nm but substitution of cobalt(II) for zinc at the active site decreases the intensity by 89.5%. Treatment with N-bromosuccinimide quenches enzyme tryptophan and Tb(III) fluorescence to a similar extent and suggests the operation of tryptophan vector Tb(III) vector Co(II) energy relay system in the enzyme. Dipoledipole radiationless energy transfer between the Tb(III) donor and the Co(II) acceptor can account for this quenching. The inherent characteristics of the metal pair limits the value of the orientation factor, K2, of the Förster equation, thereby reducing uncertainties in distance measurements by energy transfer compared with other systems. A quantum yield of 0.51 yields a value of R0, the distance for 50% energy transfer, of 19.6 A, and a distance, R, between Tb(III) and Co(II) of 13.7 A, a value identical to that measured for the distance between the active site zinc atom and calcium atom number 1 by x-ray analysis in native thermolysin crystals. The limits of confidence of this measurement are discussed. Energy transfer between two different metal atom sites of a protein provides a new class of probes to measure intramolecular distances of biological macromolecules in solution. PMID:1061067

  3. Synthesis and characterization of iron(III), manganese(II), cobalt(II), nickel(II), copper(II) and zinc(II) complexes of salicylidene-N-anilinoacetohydrazone (H2L1) and 2-hydroxy-1-naphthylidene-N-anilinoacetohydrazone (H2L2).

    PubMed

    AbouEl-Enein, S A; El-Saied, F A; Kasher, T I; El-Wardany, A H

    2007-07-01

    Salicylidene-N-anilinoacetohydrazone (H(2)L(1)) and 2-hydroxy-1-naphthylidene-N-anilinoacetohydrazone (H(2)L(2)) and their iron(III), manganese(II), cobalt(II), nickel(II), copper(II) and zinc(II) complexes have been synthesized and characterized by IR, electronic spectra, molar conductivities, magnetic susceptibilities and ESR. Mononuclear complexes are formed with molar ratios of 1:1, 1:2 and 1:3 (M:L). The IR studies reveal various modes of chelation. The electronic absorption spectra and magnetic susceptibility measurements show that the iron(III), nickel(II) and cobalt(II) complexes of H(2)L(1) have octahedral geometry. While the cobalt(II) complexes of H(2)L(2) were separated as tetrahedral structure. The copper(II) complexes have square planar stereochemistry. The ESR parameters of the copper(II) complexes at room temperature were calculated. The g values for copper(II) complexes proved that the Cu-O and Cu-N bonds are of high covalency.

  4. Skeletal muscle satellite cell migration to injured tissue measured with 111In-oxine and high-resolution SPECT imaging

    PubMed Central

    Elster, Jennifer L.; Rathbone, Christopher R.; Liu, Zhonglin; Liu, Xiasong; Barrett, Harrison H.; Rhoads, Robert P.; Allen, Ronald E.

    2014-01-01

    The delivery of adult skeletal muscle stem cells, called satellite cells, to several injured muscles via the circulation would be useful, however, an improved understanding of cell fate and biodistribution following their delivery is important for this goal to be achieved. The objective of this study was to evaluate the ability of systemically delivered satellite cells to home to injured skeletal muscle using single-photon emission computed tomography (SPECT) imaging of 111In-labeled satellite cells. Satellite cells labeled with 111In-oxine and green fluorescent protein (GFP) were injected intravenously after bupivicaine-induced injury to the tibialis anterior muscle. Animals were imaged with a high-resolution SPECT system called FastSPECT II for up to 7 days after transplantation. In vivo FastSPECT II imaging demonstrated a three to five-fold greater number of transplanted satellite cells in bupivicaine-injured muscle as compared to un-injured muscle after transplantation; a finding that was verified through autoradiograph analysis and quantification of GFP expression. Satellite cells also accumulated in other organs including the lung, liver, and spleen, as determined by biodistribution measurements. These data support the ability of satellite cells to home to injured muscle and support the use of SPECT and autoradiograph imaging techniques to track systemically transplanted 111In labeled satellite cells in vivo, and suggest their homing may be improved by reducing their entrapment in filter organs. PMID:24190365

  5. A four-coordinate cobalt(II) single-ion magnet with coercivity and a very high energy barrier

    PubMed Central

    Rechkemmer, Yvonne; Breitgoff, Frauke D.; van der Meer, Margarethe; Atanasov, Mihail; Hakl, Michael; Orlita, Milan; Neugebauer, Petr; Sarkar, Biprajit; van Slageren, Joris

    2016-01-01

    Single-molecule magnets display magnetic bistability of molecular origin, which may one day be exploited in magnetic data storage devices. Recently it was realised that increasing the magnetic moment of polynuclear molecules does not automatically lead to a substantial increase in magnetic bistability. Attention has thus increasingly focussed on ions with large magnetic anisotropies, especially lanthanides. In spite of large effective energy barriers towards relaxation of the magnetic moment, this has so far not led to a big increase in magnetic bistability. Here we present a comprehensive study of a mononuclear, tetrahedrally coordinated cobalt(II) single-molecule magnet, which has a very high effective energy barrier and displays pronounced magnetic bistability. The combined experimental-theoretical approach enables an in-depth understanding of the origin of these favourable properties, which are shown to arise from a strong ligand field in combination with axial distortion. Our findings allow formulation of clear design principles for improved materials. PMID:26883902

  6. Porphyrin-sensitized solar cells with cobalt (II/III)-based redox electrolyte exceed 12 percent efficiency.

    PubMed

    Yella, Aswani; Lee, Hsuan-Wei; Tsao, Hoi Nok; Yi, Chenyi; Chandiran, Aravind Kumar; Nazeeruddin, Md Khaja; Diau, Eric Wei-Guang; Yeh, Chen-Yu; Zakeeruddin, Shaik M; Grätzel, Michael

    2011-11-04

    The iodide/triiodide redox shuttle has limited the efficiencies accessible in dye-sensitized solar cells. Here, we report mesoscopic solar cells that incorporate a Co((II/III))tris(bipyridyl)-based redox electrolyte in conjunction with a custom synthesized donor-π-bridge-acceptor zinc porphyrin dye as sensitizer (designated YD2-o-C8). The specific molecular design of YD2-o-C8 greatly retards the rate of interfacial back electron transfer from the conduction band of the nanocrystalline titanium dioxide film to the oxidized cobalt mediator, which enables attainment of strikingly high photovoltages approaching 1 volt. Because the YD2-o-C8 porphyrin harvests sunlight across the visible spectrum, large photocurrents are generated. Cosensitization of YD2-o-C8 with another organic dye further enhances the performance of the device, leading to a measured power conversion efficiency of 12.3% under simulated air mass 1.5 global sunlight.

  7. A cobalt(ii)heteroarylalkenolate precursor for homogeneous Co3O4 coatings by atomic layer deposition.

    PubMed

    Büyükyazi, Mehtap; Fischer, Thomas; Yu, Penmgei; Coll, Mariona; Mathur, Sanjay

    2017-10-14

    We present a new and efficient cobalt precursor, Co(II)(DMOCHCOCF3)2, to prepare Co3O4 thin films and conformal coatings. In the synthesis of this Co complex, heteroaryl moieties and CF3-groups were combined leading to the precursor with high thermal stability and volatility. The suitability of this precursor for ALD deposition was tested on flat silicon substrates and TiO2/C nanofibers upon process optimization. Deposition at 200 °C results in homogeneous and smooth Co3O4 thin films with a growth rate of 0.02 nm per cycle. Conformal coatings have been successfully obtained on TiO2/C nanofibers, making them an attractive platform for surface chemistry studies on high aspect ratio structures for future photocatalysts, sensors, supercapacitors and batteries.

  8. Studies on the sorption of praseodymium (III), holmium (III) and cobalt (II) from nitrate medium using TVEX-PHOR resin.

    PubMed

    El-Dessouky, S I; El-Sofany, E A; Daoud, J A

    2007-05-08

    The use of TVEX-PHOR resin for the sorption of praseodymium (III), holmium (III) and cobalt (II) from nitrate medium was carried out using batch and column techniques. Various parameters affecting the uptake of these metal ions such as v/m ratio, pH and the metal ion concentration were separately studied. Effect of temperature on the equilibrium distribution values has been studied to evaluate the changes in standard thermodynamic quantities. Experimental results of the investigated metal ions were found to fit to Freundlich isotherm model over the entire studied concentration range. Selectivity sequence of the resin for these metals is Ho>Pr>Co. The recovery of the investigated metals from the loaded resin is preformed with 0.1M sulphuric acid.

  9. Molecular, crystal, and electronic structure of the cobalt(II) complex with 10-(2-benzothiazolylazo)-9-phenanthrol

    SciTech Connect

    Linko, R. V.; Sokol, V. I.; Polyanskaya, N. A.; Ryabov, M. A.; Strashnov, P. V.; Davydov, V. V.; Sergienko, V. S.

    2013-05-15

    The reaction of 10-(2-benzothiazolylazo)-9-phenanthrol (HL) with cobalt(II) acetate gives the coordination compound [CoL{sub 2}] {center_dot} CHCl{sub 3} (I). The molecular and crystal structure of I is determined by X-ray diffraction. The coordination polyhedron of the Co atom in complex I is an octahedron. The anion L acts as a tridentate chelating ligand and is coordinated to the Co atom through the phenanthrenequinone O1 atom and the benzothiazole N1 atom of the moieties L and the N3 atom of the azo group to form two five-membered metallocycles. The molecular and electronic structures of the compounds HL, L, and CoL{sub 2} are studied at the density functional theory level. The results of the quantum-chemical calculations are in good agreement with the values determined by X-ray diffraction.

  10. Molecular, crystal, and electronic structure of the cobalt(II) complex with 10-(2-benzothiazolylazo)-9-phenanthrol

    NASA Astrophysics Data System (ADS)

    Linko, R. V.; Sokol, V. I.; Polyanskaya, N. A.; Ryabov, M. A.; Strashnov, P. V.; Davydov, V. V.; Sergienko, V. S.

    2013-05-01

    The reaction of 10-(2-benzothiazolylazo)-9-phenanthrol (H L) with cobalt(II) acetate gives the coordination compound [Co L 2] · CHCl3 ( I). The molecular and crystal structure of I is determined by X-ray diffraction. The coordination polyhedron of the Co atom in complex I is an octahedron. The anion L acts as a tridentate chelating ligand and is coordinated to the Co atom through the phenanthrenequinone O1 atom and the benzothiazole N1 atom of the moieties L and the N3 atom of the azo group to form two five-membered metallocycles. The molecular and electronic structures of the compounds H L, L, and Co L 2 are studied at the density functional theory level. The results of the quantum-chemical calculations are in good agreement with the values determined by X-ray diffraction.

  11. Assembling an alkyl rotor to access abrupt and reversible crystalline deformation of a cobalt(II) complex.

    PubMed

    Su, Sheng-Qun; Kamachi, Takashi; Yao, Zi-Shuo; Huang, You-Gui; Shiota, Yoshihito; Yoshizawa, Kazunari; Azuma, Nobuaki; Miyazaki, Yuji; Nakano, Motohiro; Maruta, Goro; Takeda, Sadamu; Kang, Soonchul; Kanegawa, Shinji; Sato, Osamu

    2015-11-04

    Harnessing molecular motion to reversibly control macroscopic properties, such as shape and size, is a fascinating and challenging subject in materials science. Here we design a crystalline cobalt(II) complex with an n-butyl group on its ligands, which exhibits a reversible crystal deformation at a structural phase transition temperature. In the low-temperature phase, the molecular motion of the n-butyl group freezes. On heating, the n-butyl group rotates ca. 100° around the C-C bond resulting in 6-7% expansion of the crystal size along the molecular packing direction. Importantly, crystal deformation is repeatedly observed without breaking the single-crystal state even though the shape change is considerable. Detailed structural analysis allows us to elucidate the underlying mechanism of this deformation. This work may mark a step towards converting the alkyl rotation to the macroscopic deformation in crystalline solids.

  12. Optical, thermal, mechanical and dielectric properties of hexakis(urea)cobalt(II) sulfate monohydrate: A semiorganic crystal

    NASA Astrophysics Data System (ADS)

    Muthu, K.; Rajasekar, M.; Meenakshisundaram, SP.

    2013-04-01

    Single crystals of hexakis(urea)cobalt(II) sulfate monohydrate have been grown by slow evaporation solution growth technique at room temperature. The single crystal X-ray diffraction study reveals that the crystal belongs to orthorhombic system with noncentrosymmetric space group Pca21 and the cell parameters are, a=15.0549(6) Å, b=7.2105(3) Å, c=20.0284(9) Å, V=2174.15 (16) Å3 and Z=4. The functional groups of the metal-urea complex were confirmed by Fourier transform infrared spectroscopy. The powder X-ray diffraction study reveals the crystallinity of the as-grown material. The band-gap energy of the specimen is estimated by Kubelka-Munk algorithm. The dielectric results indicate an increase in dielectric and conductivity parameters with an increase of temperature at all frequencies. The crystal is further characterized by mechanical and thermal analysis.

  13. catena-Poly[[cobalt(II)-μ-aqua-μ-propano-ato-κO:O'-μ-propano-ato-κO:O] monohydrate].

    PubMed

    Fischer, A I; Gurzhiy, V V; Belyaev, A N

    2010-10-31

    The title compound, {[Co(C(2)H(5)COO)(2)(H(2)O)]·H(2)O}(n), was synthesized by the reaction of cobalt(II) carbonate hydrate with aqueous propionic acid. The structure consists of polymeric infinite linear chains with composition [Co(C(2)H(5)COO)(4/2)(H(2)O)(2/2)](∞) running along [010]. The chains are formed by Co(2+) ions linked with bridging propionate groups and water mol-ecules, with a Co⋯Co distance along the chains of 3.2587 (9) Å. The Co(2+) ion is six-coordinated in a strongly distorted octa-hedral geometry. The chains are connected to each other by a network of O-H⋯O hydrogen bonds involving solvent water mol-ecules.

  14. Photophysical and photochemical studies of chlorophyll a and cobalt(II)tetraphenylporphyrin in poly(L-glutamate)-decylammonium ion complex.

    PubMed

    Ngweniform, Pascaline; Kusumoto, Yoshihumi; Ikeda, Miyuki; Somekawa, Shouichi; Ahmmad, Bashir; Kurawaki, Junichi; Hayakawa, Katumitu

    2007-06-26

    Spectroscopic studies were carried out on chlorophyll a and cobalt(II)tetraphenylporphyrin solubilized in a poly(L-glutamate) (Poly(Glu))-decylammonium chloride (DeAC) complex system, in the presence of methylviologen (MV2+). The cooperative binding occurred between the anionic Poly(Glu) and the cationic DeAC, leading to the formation of micelle-like hydrophobic clusters of DeAC and also the change in conformation of the Poly(Glu) from the random coil to the alpha-helix. All of the absorption spectra, the fluorescence quantum yields and the fluorescence lifetimes indicated the existence of equilibrium between the aggregated biofunctional molecules in the bulk phase and the monomeric species in the complex phase of the Poly(Glu)-DeAC solution. The fluorescence quenching of the biofunctional molecules by methylviologen indicates that the conformation-dependent electron transfer occurs in the complex phase.

  15. Assembling an alkyl rotor to access abrupt and reversible crystalline deformation of a cobalt(II) complex

    NASA Astrophysics Data System (ADS)

    Su, Sheng-Qun; Kamachi, Takashi; Yao, Zi-Shuo; Huang, You-Gui; Shiota, Yoshihito; Yoshizawa, Kazunari; Azuma, Nobuaki; Miyazaki, Yuji; Nakano, Motohiro; Maruta, Goro; Takeda, Sadamu; Kang, Soonchul; Kanegawa, Shinji; Sato, Osamu

    2015-11-01

    Harnessing molecular motion to reversibly control macroscopic properties, such as shape and size, is a fascinating and challenging subject in materials science. Here we design a crystalline cobalt(II) complex with an n-butyl group on its ligands, which exhibits a reversible crystal deformation at a structural phase transition temperature. In the low-temperature phase, the molecular motion of the n-butyl group freezes. On heating, the n-butyl group rotates ca. 100° around the C-C bond resulting in 6-7% expansion of the crystal size along the molecular packing direction. Importantly, crystal deformation is repeatedly observed without breaking the single-crystal state even though the shape change is considerable. Detailed structural analysis allows us to elucidate the underlying mechanism of this deformation. This work may mark a step towards converting the alkyl rotation to the macroscopic deformation in crystalline solids.

  16. Magnetic circular dichroism and cobalt(II) binding equilibrium studies of Escherichia coli methionyl aminopeptidase.

    PubMed

    Larrabee, James A; Leung, Chin Hin; Moore, Rhonda L; Thamrong-nawasawat, Thun; Wessler, Benjamin S H

    2004-10-06

    Equilibrium dialysis of methionyl aminopeptidase from Escherichia coli (EcMetAP) monitored by atomic absorption spectrometry and magnetic circular dichroism (MCD) shows that the enzyme binds up to 1.1 +/- 0.1 equiv of Co(2+) in the metal concentration range likely to be found in vivo. The dissociation constant, K(d), is estimated to be between 2.5 and 4.0 microM. Analysis of the temperature and magnetization behavior of the two major peaks in the MCD spectrum at 495 and 567 nm suggests that these transitions arise from Co(2+) with different ground states. Ligand field calculations using AOMX are used to assign the 495 nm peak to Co(2+) in the 6-coordinate binding site and the 567 nm peak to Co(2+) in the 5-coordinate site. This is further supported by the fact that the binding affinity of the Co(2+) associated with the 567 nm peak is enhanced when the pH is increased from 7.5 to 9.0, consistent with having an imidazole ligand from a histidine amino acid residue. On the basis of the MCD intensities, it is estimated that, when the 5-coordinate site is fully occupied, 0.1 equiv of cobalt is in the 6-coordinate site. Even when the cobalt concentration is very low, there is a small fraction of binuclear sites in EcMetAP formed through cooperative binding between the 5- and 6-coordinate Co(2+) ions. The magnetization behavior of the 6-coordinate Co(2+) MCD peak is consistent with an isolated pseudo-Kramer doublet ground state, suggesting that the cobalt ions in the binuclear sites are not magnetically coupled.

  17. Syntheses, structures and magnetic properties of two new one-dimensional cobalt (II) phosphites with organic amines acting as ligands

    SciTech Connect

    Li Gaijuan; Xing Yan Song Shuyan

    2008-04-15

    Two new one-dimensional (1D) inorganic-organic hybrid cobalt (II) phosphites Co(HPO{sub 3}) (py) (1) and [Co(OH)(py){sub 3}][Co(py){sub 2}][HPO{sub 2}(OH)]{sub 3} (2) have been prepared under solvothermal conditions in the presence of pyridine (py). Compound 1 crystallizes in the monoclinic system, space group p2(1)/c, a=5.3577(7) A, b=7.7503(10) A, c=17.816(2) A, {beta}=94.327(2){sup o}, V=737.67(16) A{sup 3}, Z=4. Compound 2 is orthorhombic, Cmcm, a=16.3252(18) A, b=15.7005(16) A, c=13.0440(13) A, {beta}=90.00{sup o}V=3343.4(6) A{sup 3} and Z=4. Compound 1 possesses a 1D ladder-like framework constructed from CoO{sub 3}N tetrahedral, HPO{sub 3} pseudo-pyramids and pyridine ligands. While compound 2 is an unusual inorganic-organic hybrid 1D chain, which consists of corner-shared six-membered rings made of CoO{sub 3}N{sub 3}/CoO{sub 4}N{sub 2} octahedra and HPO{sub 3} pseudo-pyramids through sharing vertices. - Graphical abstract: Two new 1D inorganic-organic hybrid cobalt (II) phosphites have been prepared under solvothermal conditions in the presence of pyridine. Co(HPO{sub 3}) (py) possesses a 1D ladder-like framework constructed from CoO{sub 3}N tetrahedral, HPO{sub 3} pseudo-pyramids and pyridine ligands (left); 1D-chain structure of [Co(OH)(py){sub 3}][Co(py){sub 2}][HPO{sub 2}(OH)]{sub 3} consists of corner-shared six-membered rings (right)

  18. What Controls the Sign and Magnitude of Magnetic Anisotropy in Tetrahedral Cobalt(II) Single-Ion Magnets?

    PubMed

    Vaidya, Shefali; Tewary, Subrata; Singh, Saurabh Kumar; Langley, Stuart K; Murray, Keith S; Lan, Yanhua; Wernsdorfer, Wolfgang; Rajaraman, Gopalan; Shanmugam, Maheswaran

    2016-10-03

    A family of mononuclear tetrahedral cobalt(II) thiourea complexes, [Co(L1)4](NO3)2 (1) and [Co(Lx)4](ClO4)2 where x = 2 (2), 3 (3), 4 (4) (where L1 = thiourea, L2 = 1,3-dibutylthiourea, L3 = 1,3-phenylethylthiourea, and L4 = 1,1,3,3-tetramethylthiourea), has been synthesized using a rationally designed synthetic approach, with the aim of stabilizing an Ising-type magnetic anisotropy (-D). On the basis of direct-current, alternating-current, and hysteresis magnetic measurements and theoretical calculations, we have identified the factors that govern the sign and magnitude of D and ultimately the ability to design a single-ion magnet for a tetrahedral cobalt(II) ion. To better understand the magnetization relaxation dynamics, particularly for complexes 1 and 2, dilution experiments were performed using their diamagnetic analogues, which are characterized by single-crystal X-ray diffraction with the general molecular formulas of [Zn(L1)4](NO3)2 (5) and [Zn(L2)4](ClO4)2 (6). Interestingly, intermolecular interactions are shown to play a role in quenching the quantum tunneling of magnetization in zero field, as evidenced in the hysteresis loop of 1. Complex 2 exhibits the largest Ueff value of 62 cm(-1) and reveals open hysteresis loops below 4 K. Furthermore, the influence of the hyperfine interaction on the magnetization relaxation dynamics is witnessed in the hysteresis loops, allowing us to determine the electron/nuclear spin S(Co) = (3)/2/I(Co) = (7)/2 hyperfine coupling constant of 550 MHz, a method ideally suited to determine the hyperfine coupling constant of highly anisotropic metal ions stabilized with large D value, which are otherwise hard to determine by conventional methods such as electron paramagnetic resonance.

  19. Human lymphocyte traffic assessed by indium-111 oxine labelling: clinical observations.

    PubMed Central

    Wagstaff, J; Gibson, C; Thatcher, N; Ford, W L; Sharma, H; Crowther, D

    1981-01-01

    Clinical studies using indium-111 oxine labelling of human peripheral blood lymphocytes are presented. Data from animal models of lymphocyte migration are compared with results found in healthy subjects and patients with malignant neoplasms. The physiological significance of bone marrow and liver localization on gamma camera imaging is discussed and the importance of considering the surface marker characteristics of the lymphocytes under study, when interpreting results, is emphasized. The possibility that the redistribution of lymphocytes within the body is a cause of the peripheral blood lymphopenia in patients with Hodgkin's disease and other malignancies is suggested, and the usefulness of indium-111 oxine labelling in clarifying this problem is proposed. Images Fig. 4 Fig. 5 Fig. 6 PMID:7285388

  20. Characterization of the Unusual Product from the Reaction between Cobalt(II) Chloride, Ethane-1,2-diamine, and Hydrochloric Acid: An Undergraduate Project Involving an Unknown Metal Complex.

    ERIC Educational Resources Information Center

    Curtis, Neil F.; And Others

    1986-01-01

    Discusses the need for student research-type chemistry projects based upon "unknown" metal complexes. Describes an experiment involving the product from the reaction between cobalt(II) chloride, ethane-1,2-diamine (en) and concentrated hydrochloric acid. Outlines the preparation of the cobalt complex, along with procedure, results and…

  1. Characterization of the Unusual Product from the Reaction between Cobalt(II) Chloride, Ethane-1,2-diamine, and Hydrochloric Acid: An Undergraduate Project Involving an Unknown Metal Complex.

    ERIC Educational Resources Information Center

    Curtis, Neil F.; And Others

    1986-01-01

    Discusses the need for student research-type chemistry projects based upon "unknown" metal complexes. Describes an experiment involving the product from the reaction between cobalt(II) chloride, ethane-1,2-diamine (en) and concentrated hydrochloric acid. Outlines the preparation of the cobalt complex, along with procedure, results and…

  2. The Porphyromonas gingivalis HmuY haemophore binds gallium(iii), zinc(ii), cobalt(iii), manganese(iii), nickel(ii), and copper(ii) protoporphyrin IX but in a manner different to iron(iii) protoporphyrin IX.

    PubMed

    Wójtowicz, Halina; Bielecki, Marcin; Wojaczyński, Jacek; Olczak, Mariusz; Smalley, John W; Olczak, Teresa

    2013-04-01

    Porphyromonas gingivalis, a major etiological agent of chronic periodontitis, acquires haem from host haemoproteins through a haem transporter HmuR and a haemophore HmuY. The aim of this study was to analyse the binding specificity of HmuY towards non-iron metalloporphyrins which may be employed as antimicrobials to treat periodontitis. HmuY binds gallium(iii), zinc(ii), cobalt(iii), manganese(iii), nickel(ii), and copper(ii) protoporphyrin IX but in a manner different to iron(iii) protoporphyrin IX which uses His(134) and His(166) as axial ligands. The metal ions in Ga(iii)PPIX and Zn(ii)PPIX can accept only His(166) as an axial ligand, whereas nickel(ii) and copper(ii) interact exclusively with His(134). Two forms of pentacoordinate manganese(iii) are present in the Mn(iii)PPIX-HmuY complex since the metal accepts either His(134) or His(166) as a single axial ligand. The cobalt ion is hexacoordinate in the Co(iii)PPIX-HmuY complex and binds His(134) and His(166) as axial ligands; however, some differences in their environments exist. Despite different coordination modes of the central metal ion, gallium(iii), zinc(ii), cobalt(iii), and manganese(iii) protoporphyrin IX bound to the HmuY haemophore cannot be displaced by excess haem. All of the metalloporphyrins examined bind to a P. gingivalis wild-type strain with higher ability compared to a mutant strain lacking a functional hmuY gene, thus corroborating binding of non-iron metalloporphyrins to purified HmuY protein. Our results further clarify the basis of metalloporphyrin acquisition by P. gingivalis and add to understanding of the interactions with porphyrin derivatives which exhibit antimicrobial activity against P. gingivalis.

  3. Differential diagnosis of CT-hypodense cranial lesions with indium-111-oxine-labeled leukocytes

    SciTech Connect

    Bellotti, C.; Aragno, M.G.; Medina, M.; Viglietti, A.L.; Oliveri, G.; Ettorre, F.; Barrale, S.; Camuzzini, G.

    1986-05-01

    Scintigraphy using indium-111-oxine-labeled white blood cells was used as a complementary diagnostic study in the differential diagnosis of 20 intracerebral cystic lesions for which computerized tomography scanning did not exclude abscess. To lower the rate of false-positive findings with scintiscanning, three criteria of positivity were tested in the 20 lesions. The most stringent criterion yielded 100% sensitivity, 94% specificity, and 96% diagnostic accuracy. The clinical and surgical implications of these results are discussed.

  4. Rapid and simple methods for labeling white blood cells and platelets with indium-111-oxine

    SciTech Connect

    Steffel, F.G.; Rao, S.A.

    1987-06-01

    Simple procedures in a kit form for labeling white blood cells (WBCs) and platelets with commercially available indium-111 (/sup 111/In)-oxine have been developed for the convenience of small community hospitals. The time required for the labeling procedure is less than 2 hr. The resulting scintigrams from the clinical studies in both WBCs and platelets showed that the /sup 111/In-labeled cells have a high degree of viability.

  5. Ternary complexes of copper(II) and cobalt(II) involving nitrite/pyrazole and tetradentate N4-coordinate ligand: Synthesis, characterization, structures and antimicrobial activity

    NASA Astrophysics Data System (ADS)

    Solanki, Ankita; Sadhu, Mehul H.; Kumar, Sujit Baran

    2015-12-01

    Five new mononuclear mixed ligand complexes of the type [Cu(NCCH3)(dbdmp)](ClO4)2, [M(ONO)(dbdmp)]ClO4, [M(pz) (dbdmp)](ClO4)2 where M = Cu(II) and Co(II), pz = 3,5-dimethylpyrazole and dbdmp = N,N-diethyl-N‧,N‧-bis((3,5-dimethyl-1H-pyrazol-1-yl)methyl)ethane-1,2-diamine have been synthesized and characterized by physico-chemical and spectroscopy studies. The crystal structures of three copper(II) complexes [Cu(NCCH3)(dbdmp)](ClO4)2, [Cu(ONO)(dbdmp)]ClO4 and [Cu(pz)(dbdmp)](ClO4)2 have been determined by single crystal X-ray diffraction studies. Structural analyses reveal the geometry of [Cu(pz)(dbdmp)](ClO4)2 is distorted square pyramidal and other two copper(II) complexes have distorted trigonal bipyramidal geometry. Molecular composition of cobalt(II) complexes have been determined by mass spectral data. The EPR spectra of copper(II) complexes in frozen acetonitrile solution exhibit axial spectra, characteristic of dx2-y2 ground state. Electrochemical studies of copper(II) complexes using glassy carbon as working electrode in acetonitrile solution show Cu(II)/Cu(I) couple with quasi reversible electron transfer versus Ag/Ag+ reference electrode. Antimicrobial activity of all the synthesized complexes were investigated against two Gram positive and two Gram negative bacterial strains.

  6. Ferromagnetic coupling and magnetic anisotropy in oxalato-bridged trinuclear chromium(III)-cobalt(II) complexes with aromatic diimine ligands.

    PubMed

    Vallejo, Julia; Castro, Isabel; Cañadillas-Delgado, Laura; Ruiz-Pérez, Catalina; Ferrando-Soria, Jesús; Ruiz-García, Rafael; Cano, Joan; Lloret, Francesc; Julve, Miguel

    2010-03-07

    Two novel heterotrinuclear chromium(III)-cobalt(II) complexes of formula {[Cr(III)(bpy)(ox)(2)](2)Co(II)(Me(2)bpy)}.2H(2)O (1) and {[Cr(III)(phen)(ox)(2)](2)Co(II)(Me(2)bpy)}.1.5H(2)O (2) [ox = oxalato, bpy = 2,2'-bipyridine, Me(2)bpy = 6,6'-dimethyl-2,2'-bipyridine, and phen = 1,10-phenanthroline] have been synthesized using the "complex-as-ligand/complex-as-metal" strategy. The X-ray crystal structure of 2 consists of neutral oxalato-bridged Cr(III)(2)Co(II) bent entities formed by the coordination of two anionic [Cr(III)(phen)(ox)(2)](-) complexes through one of their oxalato groups toward a cationic cis-[Co(II)(Me(2)bpy)](2+) complex. The three tris(chelated), six-coordinated metal atoms possess alternating propeller chiralities leading thus to a racemic mixture of heterochiral (Lambda,Delta,Lambda)- and (Delta,Lambda,Delta)-Cr(III)Co(II)Cr(III) triads, whereby the two peripheral chromium(III) ions adopt a trigonal distorted trapezoidal bipyramidal geometry and the central high-spin cobalt(II) ion exhibits a compressed rectangular bipyramidal one. The intermolecular pi-pi stacking interactions between the enantiomeric pairs of heterochiral Cr(III)(2)Co(II) entities through the aromatic diimine terminal ligands lead to a unique two-dimensional supramolecular network. Variable temperature (2.0-300 K) magnetic susceptibility and variable-field (0-5.0 T) magnetization measurements for 1 and 2 reveal the presence of weak but non-negligible intermolecular antiferromagnetic interactions [zj = -0.012 (2a) and -0.08 cm(-1) (2b)] between the Cr(III)(2)Co(II) molecules possessing a moderately anisotropic S = 9/2 ground state. This results from the moderately weak intramolecular ferromagnetic coupling [J = +2.43 (1) and +2.34 cm(-1) (2)] between the two peripheral Cr(III) (S(Cr) = 3/2) and the central high-spin Co(II) (S(Co) = 3/2) ions across the oxalato bridge as well as the appreciable single-ion axial magnetic anisotropy of the central high-spin Co(II) (S(Co) = 3

  7. Crystal structure and EPR studies of mixed ligand complex of cobalt(II) with saccharin and ethylisonicotine

    NASA Astrophysics Data System (ADS)

    Uçar, İbrahim; Karabulut, Bünyamin; Bulut, Ahmet; Büyükgüngör, Orhan

    2008-12-01

    The tetraaquabis(ethylisonicotinate)cobalt(II) disaccharinate, [Co(ein) 2(H 2O) 4]·(sac) 2, (CENS), (ein: ethylisonicotinate and sac: saccharinate) complex has been synthesized and its crystal structure has been determined by X-ray diffraction analysis. The title complex crystallizes in monoclinic system with space group P2 1/ c and Z = 2. The Co(II) cations present a slightly distorted CoN 2O 4 octahedral environment, with equatorially coordinated water molecules and axially pyridine N-bound ethylisonicotinate ligands. The magnetic environments of Cu 2+-doped Co(II) complex have been identified by electron paramagnetic resonance (EPR) technique. Cu 2+-doped CENS single crystals have been studied at room temperature in three mutually perpendicular planes. The calculated results of the Cu 2+-doped CENS indicate that Cu 2+ ion substitute with the Co 2+ ion in the host lattice. The angular variations of the EPR spectra have shown that two different Cu 2+ complexes are located in different chemical environments, and each environment contains two magnetically inequvalent Cu 2+sites in distinct orientations occupying substitutional positions in the lattice and show very high angular dependence. The cyclic voltammogram of the title complex investigated in dimethylformamide (DMF) solution exhibits only metal centerd electroactivity in the potential range -1.0-1.25 V versus Ag/AgCl reference electrode.

  8. A method for following human lymphocyte traffic using indium-111 oxine labelling.

    PubMed Central

    Wagstaff, J; Gibson, C; Thatcher, N; Ford, W L; Sharma, H; Benson, W; Crowther, D

    1981-01-01

    A method is described whereby large numbers of human lymphocytes are separated from peripheral blood and labelled in vitro with indium-111 oxine. Following autologous reinjection, the distribution within the body is followed by means of serial blood samples, surface-probe counting and gamma camera imaging. The distribution of radioactivity following reinjection of heat-damaged labelled lymphocytes and free indium-111 oxine is different from that of 'normal' lymphocytes. The results suggest that the separation and labelling procedure does not cause significant physical damage to the lymphocytes The importance of restricting the specific lymphocyte activity to 20-40 microCi per 10(8) cells in order to minimize radiation damage to the lymphocytes is emphasized. Good resolution of lymphoid structures is obtained using gamma camera imaging and the changes recorded in organ distribution correlate well with data from animal models of lymphocyte migration. Thus, indium-111 oxine labelling of human lymphocytes provides a non-invasive method whereby the migratory properties of human lymphocytes can be followed. Images Fig. 2 Fig. 3 Fig. 4 PMID:7285387

  9. Cobalt(II), nickel(II) and copper(II) complexes of a hexadentate pyridine amide ligand. Effect of donor atom (ether vs. thioether) on coordination geometry, spin-state of cobalt and M(III)-M(II) redox potential.

    PubMed

    Pandey, Sharmila; Das, Partha Pratim; Singh, Akhilesh Kumar; Mukherjee, Rabindranath

    2011-10-28

    Using an acyclic hexadentate pyridine amide ligand, containing a -OCH(2)CH(2)O- spacer between two pyridine-2-carboxamide units (1,4-bis[o-(pyrydine-2-carboxamidophenyl)]-1,4-dioxabutane (H(2)L(9)), in its deprotonated form), four new complexes, [Co(II)(L(9))] (1) and its one-electron oxidized counterpart [Co(III)(L(9))][NO(3)]·2H(2)O (2), [Ni(II)(L(9))] (3) and [Cu(II)(L(9))] (4), have been synthesized. Structural analyses revealed that the Co(II) centre in 1 and the Ni(II) centre in 3 are six-coordinate, utilizing all the available donor sites and the Cu(II) centre in 4 is effectively five-coordinated (one of the ether O atoms does not participate in coordination). The structural parameters associated with the change in the metal coordination environment have been compared with corresponding complexes of thioether-containing hexadentate ligands. The μ(eff) values at 298 K of 1-4 correspond to S = 3/2, S = 0, S = 1 and S = 1/2, respectively. Absorption spectra for all the complexes have been investigated. EPR spectral properties of the copper(II) complex 4 have been investigated, simulated and analyzed. Cyclic voltammetric experiments in CH(2)Cl(2) reveal quasireversible Co(III)-Co(II), Ni(III)-Ni(II) and Cu(II)-Cu(I) redox processes. In going from ether O to thioether S coordination, the effect of the metal coordination environment on the redox potential values of Co(III)-Co(II) (here the effect of spin-state as well), Ni(III)-Ni(II) and Cu(II)-Cu(I) processes have been systematically analyzed.

  10. Diaquatetrakis(tert-butyl isocyanide)cobalt(II) bis(perchlorate): an example of cobalt(II) coordinated by only four alkyl isocyanide ligands.

    PubMed

    Becker, Clifford A L; Forbes, Roy P; Black, Robert S

    2009-08-01

    The title compound, [Co(C5H9N)4(H2O)2](ClO4)2, crystallizes in the monoclinic space group C2/m. The cation has space-group-imposed 2/m symmetry, while the perchlorate ion is disordered about a mirror plane. The two slightly non-equivalent Co-C bonds [1.900 (3) and 1.911 (3) A] form a rectangular plane, with a C-Co-C bond angle of 86.83 (11) degrees, and the linear O-Co-O C2 axis is perpendicular to this plane. The C[triple-bond]N bond lengths are 1.141 (4) A and the Co-C[triple-bond]N and C[triple-bond]N-C angles average 175.5 (4) degrees. The perchlorate counter-ions are hydrogen bonded to the water molecules. The title compound is the first example of four alkyl isocyanide ligands coordinating Co(II) upon initial reaction of Co(ClO4)(2).6H2O/EtOH with alkyl isocyanide. In all other known examples, five alkyl isocyanide molecules are coordinated, as in [(RNC)5Co-Co(CNR)5](ClO4)4 (R = Me, Et, CHMe2, CH2Ph, C4H9-n or C6H11) or [Co(CNC8H17-t)5](ClO4)2. This complex, therefore, is unique and somewhat unexpected.

  11. Cobalt(II)-selective membrane electrode based on a recently synthesized benzo-substituted macrocyclic diamide.

    PubMed

    Shamsipur, M; Poursaberi, T; Rouhani, S; Niknam, K; Sharghi, H; Ganjali, M R

    2001-09-01

    A PVC-membrane electrode based on a recently synthesized 18-membered macrocyclic diamide is presented. The electrode reveals a Nernstian potentiometric response for Co2+ over a wide concentration range (2.0 x 10(-6)-1.0 x 10(-2) M). The electrode has a response time of about 10 s and can be used for at least 2 months without any divergence. The proposed sensor revealed very good selectivities for Co2+ over a wide variety of other metal ions, and could be used over a wide pH range (3.0-8.0). The detection limit of the sensor is 6.0 x 10(-7) M. It was successfully applied to the direct determination and potentiometric titration of cobalt ion.

  12. Synthesis, Structures and Antimicrobial Activities of Two Cobalt(II) Complexes [Co(L1)2(OH2)2] and [Co(L2)2].

    PubMed

    Han, Yong-Jun; Wang, Li; Li, Qing-Bin; Xue, Ling-Wei

    2017-01-01

    A new cobalt(II) complex, [Co(L1)2(OH2)2] (1), was prepared by the reaction of 3-bromo-5-chlorosalicylaldehyde (HL1) with cobalt nitrate in methanol. Reaction of 1 with cyclopropylamine in methanol afforded the Schiff base cobalt(II) complex, [Co(L2)2] (2), where L2 is the deprotonated form of 2-bromo-4-chloro-6-(cyclopropyliminomethyl)phenol (HL2). The complexes have been characterized by elemental analyses, IR spectroscopy, and single-crystal X-ray diffraction. The L1 ligand coordinates to the Co atom through the phenolate O and carbonyl O atoms, while the L2 ligand coordinates to the Co atom through the phenolate O and imino N atoms. The Co atom in complex 1 adopts octahedral coordination and that in complex 2 adopts tetrahedral coordination. The effect of the free ligands and the cobalt complexes on the antimicrobial activities against Staphylococcus aureus, Escherichia coli, and Candida albicans was studied.

  13. pH-dependent properties of cobalt(II) carboxypeptidase A-inhibitor complexes.

    PubMed

    Auld, D S; Bertini, I; Donaire, A; Messori, L; Moratal, J M

    1992-04-21

    1H NMR spectroscopy of the isotropically shifted signals in cobalt carboxypeptidase, CoCPD, permits a direct and selective detection of protons belonging to the residues liganded to the metal. The chemical shift of these protons in the free enzyme and enzyme-inhibitor complexes with changing pH monitors the state of ionization of the ligands directly and of other residues in the active center indirectly. The 1H NMR spectrum of CoCPD at pH 6 shows three well-resolved isotropically shifted signals in the downfield region at 62 (a), 52 (c), and 45 (d) ppm which have been assigned to the NH proton of His-69 and to the C-4 H's of His-69 and His-196, respectively. Titration of signal a with pH is characterized by a pKa of 8.8 which is identical to that seen in prior electronic absorption and kinetic studies. The fact that the signal reflecting the NH of His-69 is still observed at pH 10 and no major shifts occur for the signals reflecting the C-4 H's indicates the alkaline pKa in carboxypeptidase A catalysis, pKEH, cannot be ascribed to ionization of the histidyl NH of either His-69 or His-196. Binding of L-Phe shifts this pKa to 7.7 while not greatly perturbing the downfield 1H NMR signals that reflect the ligation shell of the cobalt coordination sphere. These results indicate the pKa of 8.8 in CoCPD and the pKa of 7.7 in the CoCPD.L-Phe adduct reflect ionization of the same group.(ABSTRACT TRUNCATED AT 250 WORDS)

  14. 89Zr-Oxine Complex PET Cell Imaging in Monitoring Cell-based Therapies

    PubMed Central

    Wu, Haitao; Asiedu, Kingsley O.; Szajek, Lawrence P.; Griffiths, Gary L.; Choyke, Peter L.

    2015-01-01

    Purpose To develop a clinically translatable method of cell labeling with zirconium 89 (89Zr) and oxine to track cells with positron emission tomography (PET) in mouse models of cell-based therapy. Materials and Methods This study was approved by the institutional animal care committee. 89Zr-oxine complex was synthesized in an aqueous solution. Cell labeling conditions were optimized by using EL4 mouse lymphoma cells, and labeling efficiency was examined by using dendritic cells (DCs) (n = 4), naïve (n = 3) and activated (n = 3) cytotoxic T cells (CTLs), and natural killer (NK) (n = 4), bone marrow (n = 4), and EL4 (n = 4) cells. The effect of 89Zr labeling on cell survival, proliferation, and function were evaluated by using DCs (n = 3) and CTLs (n = 3). Labeled DCs (444–555 kBq/[5 × 106] cells, n = 5) and CTLs (185 kBq/[5 × 106] cells, n = 3) transferred to mice were tracked with microPET/CT. In a melanoma immunotherapy model, tumor targeting and cytotoxic function of labeled CTLs were evaluated with imaging (248.5 kBq/[7.7 × 106] cells, n = 4) and by measuring the tumor size (n = 6). Two-way analysis of variance was used to compare labeling conditions, the Wilcoxon test was used to assess cell survival and proliferation, and Holm-Sidak multiple tests were used to assess tumor growth and perform biodistribution analyses. Results 89Zr-oxine complex was synthesized at a mean yield of 97.3% ± 2.8 (standard deviation). It readily labeled cells at room temperature or 4°C in phosphate-buffered saline (labeling efficiency range, 13.0%–43.9%) and was stably retained (83.5% ± 1.8 retention on day 5 in DCs). Labeling did not affect the viability of DCs and CTLs when compared with nonlabeled control mice (P > .05), nor did it affect functionality. 89Zr-oxine complex enabled extended cell tracking for 7 days. Labeled tumor-specific CTLs accumulated in the tumor (4.6% on day 7) and induced tumor regression (P < .05 on day 7). Conclusion We have developed a 89Zr-oxine

  15. Antibacterial cobalt (II), copper (II), nickel (II) and zinc (II) complexes of mercaptothiadiazole--derived furanyl, thienyl, pyrrolyl, salicylyl and pyridinyl Schiff bases.

    PubMed

    Chohan, Zahid H; Pervez, Humayun; Rauf, Abdul; Khan, Khalid M; Supuran, Claudiu T

    2006-04-01

    A series of Co (II), Cu (II), Ni (II) and Zn (II) complexes of mercaptothiadiazole-derived furanyl, thienyl, pyrrorlyl, salicylyl and pyridinyl Schiff bases were synthesized, characterized and screened for their in vitro antibacterial activity against four Gram-negative, Escherichia coli, Pseudomonas aeruginosa, Salmonella typhi and Shigella fexneri, and two Gram-positive; Bacillus subtilis and Staphylococcus aureous bacterial strains. The results of these studies show the metal complexes to be more antibacterial as compared to the prepared un-complexed Schiff bases.

  16. Coordination chemistry of a bis(benzimidazole) disulfide: eleven membered chelate ring in cobalt(II), zinc(II) and cadmium(II) halide compounds; oxidative disulfide cleavage when coordinated to nickel(II).

    PubMed

    Esparza-Ruiz, Adriana; González-Gómez, Guadalupe; Mijangos, Edgar; Peña-Hueso, Adrián; López-Sandoval, Horacio; Flores-Parra, Angelina; Contreras, Rosalinda; Barba-Behrens, Norah

    2010-07-21

    Herein we report the synthesis, structural and spectroscopic characterization of coordination compounds with bis[2-(1H-benzimidazol-2-yl)phenyl]disulfide [bis-(2phSbz)] (1) and cobalt(II), zinc(II) and cadmium(II) halides (2-7). Their X-ray diffraction analyses showed that the metal ions present similar distorted tetrahedral structures, with the disulfide ligand coordinated through the imidazolic nitrogen atoms, forming a twisted eleven membered chelate ring. Structures of nickel(II) compounds 8 and 9, showed that the disulfide bond in the ligand was cleaved forming six membered chelates. In 8, the two ligands are sulfides, however in 9 one of them was oxidized to a sulfone. In both compounds the nickel(II) has a distorted square planar geometry and the sulfur atoms are in cis positions. The oxidation reaction of bis-(2phSbz) was performed in KMnO4/NaOH, giving the 2-(1H,3H-benzimidazolium-2-yl)-benzene sulfonate (10). The solid state structure of compounds 2-5 and 7-10 was determined by X-ray diffraction analyses.

  17. Single-crystal EPR investigation of Mn(II)-doped biomineral cobalt ammonium phosphate hexahydrate: a case of multiple substitutions

    NASA Astrophysics Data System (ADS)

    Deepa, S.; Natarajan, B.; Mithira, S.; Velavan, K.; Rao, P. S.

    2005-08-01

    Single-crystal electron paramagnetic resonance (EPR) study of Mn(II)-doped cobalt ammonium phosphate hexahydrate has been carried out at room temperature. The impurity shows more than 30 line pattern EPR spectra along the three crystallographic axes, suggesting the existence of more than one type of impurity ion in the host lattice. The spin Hamiltonian parameters, estimated from the three mutually orthogonal crystal rotations, are: site 1: g(xx) =1.989, g(yy) =1.994, g(zz) =1.999, A(xx) =-8.97, A(yy) =-9.52, A(zz) =-9.71 mT, D-xx =-8.09 mT, D-yy =-6.05 mT, D-zz =14.14 mT, site 2: g(xx) =1.988, g(yy) =2.009, g(zz) =2.019, A(xx) =-9.11 mT, A(yy) =-9.58 mT, A(zz) =-9.93 mT, D-xx =-6.61 mT, D-yy =-6.11 mT, D-zz =12.72 mT. The angular variation studies further reveal that the Mn(II) impurities enter the lattice substitutionally. The other Mn(II) sites which are at interstitial locations are difficult to follow due to their low intensity. The variation of zero-field splitting parameter with temperature indicates no phase transition. The observation of well-resolved Mn(II) spectrum at room temperature has been interpreted in terms of 'host spin-lattice relaxation narrowing mechanism.

  18. New Cobalt-Mediated Radical Polymerization (CMRP) of Methyl Methacrylate Initiated by Two Single-Component Dinuclear β-Diketone Cobalt (II) Catalysts

    PubMed Central

    Bao, Feng; Feng, Lingling; Gao, Jie; Tan, Zhifang; Xing, Bin; Ma, Rui; Yan, Chunjie

    2010-01-01

    Two dinuclear cobalt complexes based on bis-diketonate ligands (ligand 1: 3,3′-(1,3-phenylene)bis(1-phenylpropane-1,3-dione); ligand 2: 3,3′-(1,4-phenylene)bis(1-phenylpropane-1,3-dione)) were successfully synthesized. The two neutral catalysts all showed satisfactory activities in the cobalt-mediated radical polymerization (CMRP) of methyl methacrylate (MMA) with the common initiator of azodiisobutyronitrile (AIBN). The resulting polymerizations have all of the characteristics of a living polymerization and displayed linear semilogarithmic kinetic plots, a linear correlation between the number-average molecular weight and the monomer conversion, and low polydispersities. Mono- or dicomponent low polydispersity polymers could be obtained by using the two dinuclear catalysts under proper reaction conditions. All these improvements facilitate the implementation of the acrylate CMRP and open the door to the scale-up of the syntheses and applications of the multicomponent low polydispersity polymers. PMID:21049027

  19. Synthesis, characterization, and catalytic properties of cationic hydrogels containing copper(II) and cobalt(II) ions.

    PubMed

    Lombardo Lupano, Lucía Victoria; Lázaro Martínez, Juan Manuel; Piehl, Lidia Leonor; Rubín de Celis, Emilio; Torres Sánchez, Rosa María; Campo Dall' Orto, Viviana

    2014-03-18

    Here, we report the synthesis and characterization of a hydrogel based on ethylene glycol diglycidyl ether (EGDE) and 1,8-diamino-3,6-dioxaoctane (DA). Chemically stable Co(II) and Cu(II) coordination complexes were prepared with this nonsoluble polyelectrolyte, poly(EGDE-DA), and studied by ss-NMR, FT-IR, thermogravimetry, and microscopy. Mesopores were found in all the samples, the thermal stability of the polymer matrix was highly affected by the presence of metal ions, and the (13)C CP-MAS spectrum for the Cu(II)-complex evidenced a significant increase in the reticulation degree by Cu(II) ions. The catalytic activity of these materials on H2O2 activation was studied by electron spin resonance (ESR). The Co(II)-poly(EGDE-DA)/H2O2 heterogeneous system produced O2, an anion superoxide (O2(•)¯), and a hydroxyl radical (OH(•)), which diffused into the solution at the time that a decrease in pH was detected. In the same way, the Cu(II)-poly(EGDE-DA)/H2O2 heterogeneous system produced O2 and OH(•). H2O2 activation by the poly(EGDE-DA) complexes with Co(II) and Cu(II) were applied on the decolorization of solutions of the azo-dye methyl orange (MO). In the presence of 63 mM H2O2, 87% of MO was removed in 10 min with Cu(II)-poly(EGDE-DA) and in 110 min with Co(II)-poly(EGDE-DA). In addition, the pharmaceutical product epinephrine was partially oxidized to adrenochrome by the O2(•)¯ released from the Co(II)-poly(EGDE-DA)/H2O2 heterogeneous system.

  20. Cobalt(II), nickel(II), copper(II), zinc(II) and hafnium(IV) complexes of N'-(furan-3-ylmethylene)-2-(4-methoxyphenylamino)acetohydrazide.

    PubMed

    Emam, Sanaa M; El-Saied, Fathy A; Abou El-Enein, Saeyda A; El-Shater, Heba A

    2009-03-01

    Cobalt(II), nickel(II), copper(II), zinc(II) and hafnium(IV) complexes of furan-2-carbaldehyde 4-methoxy-N-anilinoacetohydrazone were synthesized and characterized by elemental and thermal (TG and DTA) analyses, IR, UV-vis and (1)H NMR spectra as well as magnetic moment and molar conductivity. Mononuclear complexes are obtained with 1:1 molar ratio except complexes 3 and 9 which are obtained with 1:2 molar ratios. The IR spectra of ligand and metal complexes reveal various modes of chelation. The ligand behaves as a neutral bidentate one and coordination occurs via the carbonyl oxygen atom and azomethine nitrogen atom. The ligand behaves also as a monobasic tridentate one and coordination occurs through the enolic oxygen atom, azomethine nitrogen atom and the oxygen atom of furan ring. Moreover, the ligand behaves as a neutral tridentate and coordination occurs via the carbonyl oxygen, azomethine nitrogen and furan oxygen atoms as well as a monobasic bidentate and coordination occurs via the enolic oxygen atom and azomethine nitrogen atom. The electronic spectra and magnetic moment measurements reveal that all complexes possess octahedral geometry except the copper complex 10 possesses a square planar geometry. The thermal studies showed the type of water molecules involved in metal complexes as well as the thermal decomposition of some metal complexes.

  1. Role of direct reactivity with metals in chemoprotection by N-acetylcysteine against chromium(VI), cadmium(II) and cobalt(II)

    PubMed Central

    Luczak, Michal W.; Zhitkovich, Anatoly

    2013-01-01

    The antioxidant N-acetylcysteine (NAC) is widely used for the assessment of the role of reactive oxygen species (ROS) in various biological processes and adverse drug reactions. NAC has been found to effectively inhibit toxicity of carcinogenic metals, which was attributed to its potent ROS-suppressive properties. However, the absence of redox activity among some metals and findings from genetic models suggested a more diverse, smaller role of oxidative stress in metal toxicity. Here, we examined mechanisms of chemoprotection by NAC against Cd(II), Co(II) and Cr(VI) in human cells. We found that NAC displayed a broad-spectrum chemoprotective activity against all three metals, including suppression of cytotoxicity, apoptosis, p53 activation and HSP72 and HIF-1α upregulation. Cytoprotection by NAC was independent of cellular glutathione. NAC strongly inhibited uptake of all three metals in histologically different types of human cells, explaining its high chemoprotective potential. A loss of Cr(VI) accumulation by cells was caused by NAC-mediated extracellular reduction of chromate to membrane-impermeable Cr(III). Suppression of Co(II) uptake resulted from a rapid formation of Co(II)-NAC conjugates that were unable to enter cells. Our results demonstrate that NAC acts through more than one mechanism in preventing metal toxicity and its chemoprotective activity can be completely ROS-independent. A good clinical safety and effectiveness in Co(II) sequestration suggest that NAC could be useful for prevention of tissue accumulation and toxic effects of Co ions released by cobalt-chromium hip prostheses. PMID:23792775

  2. Role of direct reactivity with metals in chemoprotection by N-acetylcysteine against chromium(VI), cadmium(II), and cobalt(II).

    PubMed

    Luczak, Michal W; Zhitkovich, Anatoly

    2013-12-01

    The antioxidant N-acetylcysteine (NAC) is widely used for the assessment of the role of reactive oxygen species (ROS) in various biological processes and adverse drug reactions. NAC has been found to effectively inhibit the toxicity of carcinogenic metals, which was attributed to its potent ROS-suppressive properties. However, the absence of redox activity among some metals and findings from genetic models suggested a more diverse, smaller role of oxidative stress in metal toxicity. Here, we examined mechanisms of chemoprotection by NAC against Cd(II), Co(II), and Cr(VI) in human cells. We found that NAC displayed a broad-spectrum chemoprotective activity against all three metals, including suppression of cytotoxicity, apoptosis, p53 activation, and HSP72 and HIF-1α upregulation. Cytoprotection by NAC was independent of cellular glutathione. NAC strongly inhibited the uptake of all three metals in histologically different types of human cells, explaining its high chemoprotective potential. A loss of Cr(VI) accumulation by cells was caused by NAC-mediated extracellular reduction of chromate to membrane-impermeative Cr(III). Suppression of Co(II) uptake resulted from a rapid formation of Co(II)-NAC conjugates that were unable to enter cells. Our results demonstrate that NAC acts through more than one mechanism in preventing metal toxicity and its chemoprotective activity can be completely ROS-independent. Good clinical safety and effectiveness in Co(II) sequestration suggest that NAC could be useful in the prevention of tissue accumulation and toxic effects of Co ions released by cobalt-chromium hip prostheses. Copyright © 2013 Elsevier Inc. All rights reserved.

  3. Dichloridobis[2-methyl-sulfanyl-4-(pyridin-2-yl)pyrimidine-κN,N]cobalt(II).

    PubMed

    Yang, Wen-Na

    2011-09-01

    The asymmetric unit of the title compound, [CoCl(2)(C(10)H(9)N(3)S)(2)], contains one half-mol-ecule with the Co(II) atom situtated on a twofold rotational axis. The Co(II) atom, in an octa-hedral enviroment, is coordinated by four N atoms from two 2-methyl-sulfanyl-4-(pyridin-2-yl)pyrimidine ligands and two Cl atoms.

  4. Coordination modes of a schiff base pentadentate derivative of 4-aminoantipyrine with cobalt(II), nickel(II) and copper(II) metal ions: synthesis, spectroscopic and antimicrobial studies.

    PubMed

    Chandra, Sulekh; Jain, Deepali; Sharma, Amit Kumar; Sharma, Pratibha

    2009-01-01

    Transition metal complexes of Co(II), Ni(II) and Cu(II) metal ions with general stoichiometry [M(L)X]X and [M(L)SO(4)], where M = Co(II), Ni(II) and Cu(II), L = 3,3'-thiodipropionic acid bis(4-amino-5-ethylimino-2,3-dimethyl-1-phenyl-3-pyrazoline) and X = NO(3)(-), Cl(-) and OAc(-), have been synthesized and structurally characterized by elemental analyses, molar conductance measurements, magnetic susceptibility measurements and spectral techniques like IR, UV and EPR. The nickel(II) complexes were found to have octahedral geometry, whereas cobalt(II) and copper(II) complexes were of tetragonal geometry. The covalency factor (beta) and orbital reduction factor (k) suggest the covalent nature of the complexes. The ligand and its complexes have been screened for their antifungal and antibacterial activities against three fungi, i.e. Alternaria brassicae, Aspergillus niger and Fusarium oxysporum and two bacteria, i.e. Xanthomonas compestris and Pseudomonas aeruginosa.

  5. Solvent effects of N-nitroso, N-(2-chloroethyl), N',N'-dibenzylsulfamid and its copper(II) and cobalt(II) complexes: fluorescence studies.

    PubMed

    Bensouilah, Nadjia; Fisli, Hassina; Dhaoui, Nabila; Benali-Cherif, Nourredine; Abdaoui, Mohamed

    2013-01-01

    The structure of N-nitroso, N-(2-chloroethyl), N',N'-dibenzylsulfamid (CENS) was established by X-ray crystallography. The atomic coordinates, factors of isotropic thermal agitation, bond lengths and valence angles were determined. The solvent effects on the electronic absorption and fluorescence spectra of CENS were investigated at room temperature. The effects of solvent polarity and of hydrogen bonding were interpreted by means of linear solvation energy relationships (LSERs). Multiple linear regression analysis indicated that the hydrogen donation properties of the solvent play an important role in determining the position of the absorption maximum, while the classical polarity of the medium is the only dominating parameter in determining the emission maximum and the Stokes' shift. Complexation of the investigated compound by two different transition metal ions was studied. Fluorescence measurements show that fluorescence quenching by cobalt(II) is more important than that by copper(II). This phenomenon can be attributed to good stereo-structural matching between the electronic configuration of the Co(2+) ion and the active site distribution of CENS in aqueous solution.

  6. Metalloantibiotics: synthesis, characterization and in-vitro antibacterial studies on cobalt (II), copper (II), nickel (II) and zinc (II) complexes with cloxacillin.

    PubMed

    Chohan, Zahid H; Supuran, Claudiu T

    2006-08-01

    The synthesis and characterization of cloxacillin (clox) complexes with divalent metal ions [Co (II), Cu (II), Ni (II) and Zn (II)] is described. The nature of bonding of the chelated cloxacillin and the structures of the metal complexes have been elucidated on the basis of their physical and spectroscopic data. In all the complexes, the cloxacillin acts as a uninegatively charged bidentate ligand with coordination involving the carboxylate-O and endocyclic-N of the beta-lactam ring. The new compounds have been screened for in-vitro antibacterial activity against Escherichia coli (a), Klebsiella pneumonae (b), Proteus mirabilis (c), Pseudomonas aeruginosa (d), Salmonella typhi (e), Shigella dysentriae (f), Bacillus cereus (g), Corynebacterium diphtheriae (h), Staphylococcus aureus (j) and Streptococcus pyogenes (k) bacterial strains. The brine shrimp bioassay was also carried out to study their in-vitro cytotoxic properties. All compounds, respectively, showed a promising activity (90%) against five bacterial species at 10 microg/ml concentration and a significant activity (52%) against the same test bacteria at 25 microg/ml concentration.

  7. Corroborative models of the cobalt(II) inhibited Fe/Mn superoxide dismutases.

    PubMed

    Scarpellini, Marciela; Wu, Amy J; Kampf, Jeff W; Pecoraro, Vincent L

    2005-07-11

    Attempting to model superoxide dismutase (SOD) enzymes, we designed two new N3O-donor ligands to provide the same set of donor atoms observed in the active site of these enzymes: K(i)Pr2TCMA (potassium 1,4-diisopropyl-1,4,7-triazacyclononane-N-acetate) and KBPZG (potassium N,N-bis(3,5-dimethylpyrazolylmethyl) glycinate). Five new Co(II) complexes (1-5) were obtained and characterized by X-ray crystallography, mass spectrometry, electrochemistry, magnetochemistry, UV-vis, and electron paramagnetic resonance (EPR) spectroscopies. The crystal structures of 1 and 3-5 revealed five-coordinate complexes, whereas complex 2 is six-coordinate. The EPR data of complexes 3 and 4 agree with those of the Co(II)-substituted SOD, which strongly support the proposition that the active site of the enzyme structurally resembles these models. The redox behavior of complexes 1-5 clearly demonstrates the stabilization of the Co(II) state in the ligand field provided by these ligands. The irreversibility displayed by all of the complexes is probably related to an electron-transfer process followed by a rearrangement of the geometry around the metal center for complexes 1 and 3-5 that probably changes from a trigonal bipyramidal (high spin, d7) to octahedral (low spin, d6) as Co(II) is oxidized to Co(III), which is also expected to be accompanied by a spin-state conversion. As the redox potentials to convert the Co(II) to Co(III) are high, it can be inferred that the redox potential of the Co(II)-substituted SOD may be outside the range required to convert the superoxide radical (O2*-) to hydrogen peroxide, and this is sufficient to explain the inactivity of the enzyme. Finally, the complexes reported here are the first corroborative structural models of the Co(II)-substituted SOD.

  8. [(89)Zr]oxinate4 for long-term in vivo cell tracking by positron emission tomography.

    PubMed

    Charoenphun, Putthiporn; Meszaros, Levente K; Chuamsaamarkkee, Krisanat; Sharif-Paghaleh, Ehsan; Ballinger, James R; Ferris, Trevor J; Went, Michael J; Mullen, Gregory E D; Blower, Philip J

    2015-02-01

    (111)In (typically as [(111)In]oxinate3) is a gold standard radiolabel for cell tracking in humans by scintigraphy. A long half-life positron-emitting radiolabel to serve the same purpose using positron emission tomography (PET) has long been sought. We aimed to develop an (89)Zr PET tracer for cell labelling and compare it with [(111)In]oxinate3 single photon emission computed tomography (SPECT). [(89)Zr]Oxinate4 was synthesised and its uptake and efflux were measured in vitro in three cell lines and in human leukocytes. The in vivo biodistribution of eGFP-5T33 murine myeloma cells labelled using [(89)Zr]oxinate4 or [(111)In]oxinate3 was monitored for up to 14 days. (89)Zr retention by living radiolabelled eGFP-positive cells in vivo was monitored by FACS sorting of liver, spleen and bone marrow cells followed by gamma counting. Zr labelling was effective in all cell types with yields comparable with (111)In labelling. Retention of (89)Zr in cells in vitro after 24 h was significantly better (range 71 to >90%) than (111)In (43-52%). eGFP-5T33 cells in vivo showed the same early biodistribution whether labelled with (111)In or (89)Zr (initial pulmonary accumulation followed by migration to liver, spleen and bone marrow), but later translocation of radioactivity to kidneys was much greater for (111)In. In liver, spleen and bone marrow at least 92% of (89)Zr remained associated with eGFP-positive cells after 7 days in vivo. [(89)Zr]Oxinate4 offers a potential solution to the emerging need for a long half-life PET tracer for cell tracking in vivo and deserves further evaluation of its effects on survival and behaviour of different cell types.

  9. Efficient removal of dyes in water using chitosan microsphere supported cobalt (II) tetrasulfophthalocyanine with H2O2.

    PubMed

    Shen, Chensi; Song, Shufang; Zang, Lili; Kang, Xiaodong; Wen, Yuezhong; Liu, Weiping; Fu, Liusong

    2010-05-15

    A new efficient catalyst, CoTSPc@chitosan, was developed by immobilizing water soluble cobalt (II) tetrasulfophthalocyanine onto adsorbent chitosan microspheres covalently for the heterogeneous catalytic oxidation of C. I. Acid Red 73 with H(2)O(2). The result indicated that the COD removal and discoloration of C. I. Acid Red 73 made 55 and 95% respectively in the presence of CoTSPc@chitosan with H(2)O(2) in 4h. In addition, CoTSPc@chitosan-H(2)O(2) system could proceed efficiently in a relatively wide pH range and remain high catalytic activity after 6 reuse cycles. Furthermore, the adsorption study of CoTSPc@chitosan confirmed that chitosan was an outstanding support which contributed a lot to the removal reaction. In conclusion, the combination of adsorption process and catalytic oxidation made the CoTSPc@chitosan-H(2)O(2) system achieve a simple, efficiently and environmentally friendly water treatment. Copyright (c) 2009 Elsevier B.V. All rights reserved.

  10. Lutein Attenuates Both Apoptosis and Autophagy upon Cobalt (II) Chloride-Induced Hypoxia in Rat Műller Cells.

    PubMed

    Fung, Frederic K C; Law, Betty Y K; Lo, Amy C Y

    2016-01-01

    Retinal ischemia/reperfusion injury is a common feature of various retinal diseases such as glaucoma and diabetic retinopathy. Lutein, a potent anti-oxidant, is used to improve visual function in patients with age-related macular degeneration (AMD). Lutein attenuates apoptosis, oxidative stress and inflammation in animal models of acute retinal ischemia/hypoxia. Here, we further show that lutein improved Műller cell viability and enhanced cell survival upon hypoxia-induced cell death through regulation of intrinsic apoptotic pathway. Moreover, autophagy was activated upon treatment of cobalt (II) chloride, indicating that hypoxic injury not only triggered apoptosis but also autophagy in our in vitro model. Most importantly, we report for the first time that lutein treatment suppressed autophagosome formation after hypoxic insult and lutein administration could inhibit autophagic event after activation of autophagy by a pharmacological approach (rapamycin). Taken together, lutein may have a beneficial role in enhancing glial cell survival after hypoxic injury through regulating both apoptosis and autophagy.

  11. Investigate the ultrasound energy assisted adsorption mechanism of nickel(II) ions onto modified magnetic cobalt ferrite nanoparticles: Multivariate optimization.

    PubMed

    Mehrabi, Fatemeh; Alipanahpour Dil, Ebrahim

    2017-07-01

    In present study, magnetic cobalt ferrite nanoparticles modified with (E)-N-(2-nitrobenzylidene)-2-(2-(2-nitrophenyl)imidazolidine-1-yl) ethaneamine (CoFe2O4-NPs-NBNPIEA) was synthesized and applied as novel adsorbent for ultrasound energy assisted adsorption of nickel(II) ions (Ni(2+)) from aqueous solution. The prepared adsorbent characterized by Fourier transforms infrared spectroscopy (FT-IR), transmission electron microscope (TEM), vibrating sample magnetometer (VSM) and X-ray diffraction (XRD). The dependency of adsorption percentage to variables such as pH, initial Ni(2+) ions concentration, adsorbent mass and ultrasound time were studied with response surface methodology (RSM) by considering the desirable functions. The quadratic model between the dependent and independent variables was built. The proposed method showed good agreement between the experimental data and predictive value, and it has been successfully employed to adsorption of Ni(2+) ions from aqueous solution. Subsequently, the experimental equilibrium data at different concentration of Ni(2+) ions and 10mg amount of adsorbent mass was fitted to conventional isotherm models like Langmuir, Freundlich, Tempkin, Dubinin-Radushkevich and it was revealed that the Langmuir is best model for explanation of behavior of experimental data. In addition, conventional kinetic models such as pseudo-first and second-order, Elovich and intraparticle diffusion were applied and it was seen that pseudo-second-order equation is suitable to fit the experimental data. Copyright © 2016 Elsevier B.V. All rights reserved.

  12. Lutein Attenuates Both Apoptosis and Autophagy upon Cobalt (II) Chloride-Induced Hypoxia in Rat Műller Cells

    PubMed Central

    Fung, Frederic K. C.; Law, Betty Y. K.; Lo, Amy C. Y.

    2016-01-01

    Retinal ischemia/reperfusion injury is a common feature of various retinal diseases such as glaucoma and diabetic retinopathy. Lutein, a potent anti-oxidant, is used to improve visual function in patients with age-related macular degeneration (AMD). Lutein attenuates apoptosis, oxidative stress and inflammation in animal models of acute retinal ischemia/hypoxia. Here, we further show that lutein improved Műller cell viability and enhanced cell survival upon hypoxia-induced cell death through regulation of intrinsic apoptotic pathway. Moreover, autophagy was activated upon treatment of cobalt (II) chloride, indicating that hypoxic injury not only triggered apoptosis but also autophagy in our in vitro model. Most importantly, we report for the first time that lutein treatment suppressed autophagosome formation after hypoxic insult and lutein administration could inhibit autophagic event after activation of autophagy by a pharmacological approach (rapamycin). Taken together, lutein may have a beneficial role in enhancing glial cell survival after hypoxic injury through regulating both apoptosis and autophagy. PMID:27936094

  13. Metal binding properties of single amino acid deletion mutants of zinc finger peptides: studies using cobalt(II) as a spectroscopic probe.

    PubMed

    Shi, Y; Beger, R D; Berg, J M

    1993-03-01

    Peptides corresponding to Cys2His2 zinc finger domains from which one amino acid has been deleted have been synthesized and their metal-binding properties characterized. In contrast to earlier reports (Párraga, G., S. Horvath, L. Hood, E. T. Young, and R. E. Klevit. 1990. Proc. Natl. Acad. Sci. USA. 87:137-141.), such peptides do bind metal ions such as cobalt(II). A peptide with the sequence ProTyrLysCysProGluCysLysSerPheSerGlnLysSerAspLeuValLysHisGlnArgThrHis ThrGly (which corresponds to a previously characterized consensus zinc finger sequence from which a Gly residue immediately following the second Cys residue has been deleted) was found to form a 1:1 peptide to cobalt(II) complex with an absorption spectrum quite similar to those previously observed for zinc finger peptide-cobalt(II) complexes. The dissociation constant for this complex is 6 x 10(-6)M, a factor of 100 times higher than that for the parent peptide. A peptide with the sequence LysProTyrProCysGlyLeuCysArgCysPheThrArgArgAspLeuLeulleArgHisAlaGln - LyslleHisSerGlyAsnLeu corresponding to a similar mutation of the peptide ADR1 was also characterized. Spectroscopic studies with cobalt(II) revealed that this peptide forms both 1:1 and 2:1 peptide to cobalt(II) complexes. The absorption spectra of the two forms and the dissociation constants were determined via deconvolution methods. In contrast, the parent peptide ADR1a was found to form only a 1:1 complex under comparable conditions and this 1:1 complex was found to be more stable than that for the mutant. These results reveal that deletion mutations do adversely affect the stability of zinc finger peptide-metal complexes but that the effects are not as drastic as had been previously described.

  14. Tc-99m hexamethylpropylene-amine oxine (HM-PAO) uptake in a bone metastasis

    SciTech Connect

    Hoshi, H.; Jinnouchi, S.; Sameshima, M.; Uwada, O.; Watanabe, K.

    1988-08-01

    Uptake of Tc-99m Hexamethylpropylene-amine Oxine (HM-PAO) was seen in bone metastases from carcinoma of the lung. The uptake was prominent when compared to Tc-99m MDP, I-123 IMP, and Ga-67 citrate. Brain imaging with Tc-99m HM-PAO and N-isopropyl-p-(I-123) iodoamphetamine (IMP) is now frequently performed. Uptake of these agents has been reported in brain tumors and melanomas. In this report, uptake of Tc-99m HM-PAO in a metastatic lesion in bone is discussed.

  15. Synthesis, characterization and investigation of electrochemical and spectroelectrochemical properties of peripherally tetra 4-phenylthiazole-2-thiol substituted metal-free, zinc(II), copper(II) and cobalt(II) phthalocyanines

    NASA Astrophysics Data System (ADS)

    Demirbaş, Ümit; Akçay, Hakkı Türker; Koca, Atıf; Kantekin, Halit

    2017-08-01

    In this study novel peripherally tetra 4-phenylthiazole-2-thiol substituted metal-free phthalocyanine (4) and its zinc(II) (5), copper(II) (6) and cobalt(II) (7) derivatives were synthesized and characterized by a combination of various spectroscopic techniques such as FT-IR, 1H-NMR, UV-vis and MALDI-TOF mass. Electrochemical characterizations of metallo-phthalocyanine complexes were conducted by voltammetric and in situ spectroelectrochemical measurements. CoIIPc went [CoIIPc-2]/[CoIPc-2]1-, [CoIPc-2]1-/[CoIPc-3]2-, [CoIPc-3]2-/[CoIPc-4]3- and [CoIIPc-2]/[CoIIPc-2]1+ reduction and oxidation processes respectively. Differently ZnIIPc only showed four ligand-based reductions and two ligand based oxidation processes.

  16. [Study on the interaction of copper-zinc superoxide dismutase with cobalt (II)-histidine by spectral analysis--II. Effect of amount of external added Co(His)n, phosphate].

    PubMed

    Zheng, X; Hu, J; Cheng, G; Xu, Y; Zhao, Y; Liu, M

    1999-12-01

    The effect of changing the amount of external added Co(His)n and phosphate on the interaction of Cu2Zn2SOD with organic metal compound (Cobalt (II)-Histidine) have been studied by means of ICP, VIS and measurement of enzyme activity. It has found that in aqueous solution, there exists a direct interaction of the metal ions of the active center in the metalloenzyme (Cu2Zn2SOD) with external added Co(His)n. As a result, part of the metal ions in metalloenzyme were replaced and the corresponding metalloenzyme derivatives (Co (II)-substituted derivatives of SOD) were produced and the catalytic activity of enzyme were affected. It has also studied the intensity of interactions in different molar ratios (Cobalt (II)-Histidine) and of the presence of phosphate and got some results under the effect of corresponding factors.

  17. Ring-opening of unsymmetrical 1,2-dioxines using cobalt(II) salen complexes.

    PubMed

    Greatrex, Ben W; Taylor, Dennis K

    2005-01-21

    The regioselectivity of the metal-catalyzed ring opening of unsymmetrical 1,2-dioxines to cis-gamma-hydroxyenones was investigated using two different Co(II) salen complexes. Regioselectivity was determined by direct examination of the enone ratios and by derivitization with a stabilized phosphorus ylide. The steric influence of the substituents on the 1,2-dioxine was the primary influence on regioselectivity. Temperature played little role; however, solvent and selection of Co(II) complex could be used to mildly influence the outcome of the rearrangement for selected substrates. The origins of the selectivity for the reaction are discussed.

  18. Synthesis and characterisation of cobalt(II) phosphonate cage complexes utilizing carboxylates and pyridonates as co-ligands.

    PubMed

    Langley, Stuart K; Helliwell, Madeleine; Teat, Simon J; Winpenny, Richard E P

    2012-11-07

    The synthesis and structures of fifteen new cobalt complexes containing phosphonate ligands are reported. The compounds also utilize carboxylates and 6-chloro-2-pyridonate (chp) as co-ligands. The majority of the compounds are decametallic: [Co(10)(chp)(12)(O(3)PPh)(2)(O(2)CPh)(4)(H(2)O)(4)], [Co(10)(chp)(12)(O(3)PPh)(2)(O(2)C(t)Bu)(4)(H(2)O)(4)], [Co(10)(chp)(12)(O(3)PPh)(2)(O(2)CPh(t)Bu)(4)(H(2)O)(4)], [Co(10)(chp)(6)(O(3)PCH(2)Ph)(2)(O(2)CPh)(8)(F)(2) (H(2)O)(2)(EtOAc)(2)], [Co(10)(chp)(8)(O(3)PCH(2)Ph)(2)(O(2)CPh)(8)(F)(2)(MeCN)(2)](HNEt(3))(2), [Co(10)(chp)(6)(O(3)PCH(2)Ph)(2)(O(2)C(t)Bu)(8)(F)(2)(H(2)O)(2)(MeCOMe)(2)], [Co(10)(chp)(6)(O(3)PMe)(2) (O(2)C(t)Bu)(8)(F)(2)(MeCN)(4)], [Co(10)(chp)(6)(O(3)PEt)(2)(O(2)CPh)(8)(F)(2)(MeCN)(4)], [Co(10)(chp)(6)(O(3)POct)(2)(O(2)CPh)(8)(F)(2)(MeCN)(4)], [Co(10)(chp)(8)(Hchp)(2)(O(3)PCH(2)Nap) (O(2)CPh)(7)(OH)(3)(H(2)O)], [Co(10)(chp)(12)(O(3)PPh)(2)(O(2)CPh-2-Ph)(4)(H(2)O)(4)] and [Co(10)(chp)(12)(O(3)PMe)(2)(O(2)CPh-2-Ph)(4)(H(2)O)(4)]. Two nine-metal cages and one hexametallic cage are also reported: [Co(9)(chp)(9)(O(3)P(t)Bu)(O(2)C(t)Bu)(6)(OH)], [Co(9)(chp)(7)(O(3)PCH(2)Ph)(2)(O(3)PCH(2)Ph)(O(2)CCPh(3))(5)(OH)(H(2)O)(2)(MeCN)] and [Co(6)(chp)(6)(Hchp)(2)(O(3)P(t)Bu)(O(2)CPh-2-Ph)(3)(F)(H(2)O)](HNEt(3))(Cl). Magnetic studies show predominantly anti-ferromagnetic exchange interactions between the cobalt(ii) sites, with diamagnetic ground states for most of the compounds studied.

  19. Kagóme Cobalt(II)-Organic Layers as Robust Scaffolds for Highly Efficient Photocatalytic Oxygen Evolution.

    PubMed

    Xu, Jiaheng; Wang, Zhi; Yu, Wenguang; Sun, Di; Zhang, Qing; Tung, Chen-Ho; Wang, Wenguang

    2016-05-23

    Two Kagóme cobalt(II)-organic layers of [Co3 (μ3 -OH)2 (bdc)2 ]n (1) and [Co3 (μ3 -OH)2 (chdc)2 ]n (2) (bdc=o-benzenedicarboxylate and chdc=1,2-cyclohexanedicarboxylate) that bear bridging OH(-) ligands were explored as water oxidation catalysts (WOCs) for photocatalytic O2 production. The activities of 1 and 2 towards H2 O oxidation were assessed by monitoring the in situ O2 concentration versus time in the reaction medium by utilizing a Clark-type oxygen electrode under photochemical conditions. The oxygen evolution rate (RO2 ) was 24.3 μmol s(-1)  g(-1) for 1 and 48.8 μmol s(-1)  g(-1) for 2 at pH 8.0. Photocatalytic reaction studies show that 1 and 2 exhibit enhanced activities toward the oxidation of water compared to commercial nanosized Co3 O4 . In scaled-up photoreactions, the pH value of the reaction medium decreased from 8.0 to around 7.0 after 20 min and the O2 production ceased. Based on the amounts of the sacrificial oxidant (K2 S2 O8 ) used, the yield of O2 produced is 49.6 % for 2 and 29.8 % for 1. However, the catalyst can be recycled without a significant loss of catalytic activity. Spectroscopic studies suggest that the structure and composition of recycled 1 and 2 are maintained. In isotope-labeling H2 (18) O (97 % enriched) experiments, the distribution of (16) O(16) O/(16) O(18) O/(18) O(18) O detected was 0:7.55:92.45, which is comparable to the theoretical values of 0.09:5.82:94.09. This work not only provides new catalysts that resemble ligand-protected cobalt oxide materials but also establishes the significance of the existence of OH(-) (or H2 O) binding sites at the metal center in WOCs.

  20. Reversible Oxygenation of α-Amino Acid–Cobalt(II) Complexes

    PubMed Central

    Zhang, Xincun; Yue, Fan; Li, Hui; Huang, Yan; Zhang, Yi; Wen, Hongmei; Wang, Jide

    2016-01-01

    We systematically investigated the reversibility, time lapse, and oxygenation-deoxygenation properties of 15 natural α-amino acid–Co(II) complexes through UV-vis spectrophotometer, polarographic oxygen electrode, and DFT calculations, respectively, to explore the relationship between the coordinating structure and reversible oxygenation of α-amino acid–Co(II) complexes. Results revealed that the α-amino acid structure plays a key role in the reversible oxygenation properties of these complexes. The specific configuration of the α-amino acid group affects the eg1 electron of Co(II) transfer to the π⁎ orbit of O2; this phenomenon also favors the reversible formation and dissociation of Co–O2 bond when O2 coordinates with Co(II) complexes. Therefore, the co-coordination of amino and carboxyl groups is a determinant of Co complexes to absorb O2 reversibly. The group adjacent to the α-amino acid unit evidently influences the dioxygen affinity and antioxidation ability of the complexes. The presence of amino (or imino) and hydroxy groups adjacent to the α-amino acid group increases the oxygenation-deoxygenation rate and the number of reversible cycles. Our findings demonstrate a new mechanism to develop reversible oxygenation complexes and to reveal the oxygenation of oxygen carriers. PMID:27022316

  1. Formation of a cobalt(III)-phenoxyl radical complex by acetic acid promoted aerobic oxidation of a Co(II)salen complex.

    PubMed

    Vinck, Evi; Murphy, Damien M; Fallis, Ian A; Strevens, Robert R; Van Doorslaer, Sabine

    2010-03-01

    The activation of N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexane-diamino Co(II), [Co(II)(1)], by the addition of acetic acid under aerobic conditions has been investigated by a range of spectroscopic techniques including continuous-wave EPR, HYSCORE, pulsed ENDOR, and resonance Raman. These measurements have revealed for the first time the formation of a coordinated cobalt(III)-bound phenoxyl radical labeled [Co(III)(1(*))(OAc)(n)](OAc)(m) (n = m = 1 or n = 2, m = 0). This cobalt(III)-bound phenoxyl radical is characterized by the following spin Hamiltonian parameters: g(x) = 2.0060, g(y) = 2.0031, g(z) = 1.9943, A(x) = 17 MHz, A(y) = 55 MHz, and A(z) = 14 MHz. Although the radical contains coordinated acetate(s), the experiments unambiguously proved that the phenoxyl radical is situated on ligand (1) as opposed to a phenoxyl radical ligated to cobalt in the axial position. Density functional theory computations on different models corroborate the stability of such a phenoxyl radical species and suggest the ligation of one or two acetate molecules to the complex. A mechanism is proposed, which accounts for the formation of this unusual and extremely robust phenoxyl radical, never previously observed for [Co(1)].

  2. Mechanistic aspects of the quenching of triplet methylene blue by complexes of cobalt(II)

    SciTech Connect

    Ohno, T.; Lichtin, N.N.

    1980-11-13

    A Q-switched ruby laser emitting 1.0-J flashes at 693.4 nm was used in a flash-photolytic, kinetic-spectrometric investigation of the mechanism of quenching of 10 ..mu..M triplet methylene blue by Co/sup II/(edta)/sup 2 -/, Co/sup II/(TIM)(H/sub 2/O)/sub 2//sup 2 +/, Co/sup II/(phen)/sub 3//sup 2 +/, and Co/sup II/(tpy)/sub 2//sup 2 +/ (edta = ethylenediamine-N,N-N',N'-tetraacetic acid; TIM = 1,4,8,11-tetraaza-2,3-dimethylcyclotetradeca-1,3,8,10-tetraene; phen = 1,10-phenanthroline; and tpy = 2,2',2''-terpyridine) in water and aqueous EtOH at pH approx. 2 and approx. 6, where the species quenched and the product of its reductive quenching are, respectively, /sup 3/MBH/sup 2 +/ and MBH/sup +/. Specific rates of quenching, k/sub q/, of net electron transfer during quenching, k/sub et/, and the kinetics of decay of the products of quenching were determined. Specific rates, k/sub ret/, of reverse electron transfer from MBH/sup +/. to complexes of Co(III), Co/sup III/L/sub x//sup m+1/, were evaluated by generating MBH/sup +/. by quenching /sup 3/MBH/sup 2 +/ with diphenylamine in the presence of Co/sup III/L/sub x//sup m+1/. Values of F/sub 1/ = k/sub et//k/sub q/, of F/sub 2/ = k/sub ret//k/sub D/, where k/sub D/ is the diffusion-controlled specific rate of encounter, and of F/sub 1/ + F/sub 2/ are compared with analogous data for quenching of /sup 3/MBH/sup 2 +/ by complexes of Fe(II) and with the detailed reversible electron-transfer model which was developed for the latter processes. It is concluded that reversible electron transfer is not the only significant mechanism of quenching of /sup 3/MBH/sup 2 +/ by the four complexes of Co(II) employed in this research. At least one other mechanism, e.g., energy transfer or physical quenching, is followed to a significant degree.

  3. Diaqua­bis­(hydrogen tartrato)cobalt(II) dihydrate

    PubMed Central

    Du, Chao-Jun; Zhang, Qun-An; Wang, Li-Sheng; Du, Chao-Ling

    2012-01-01

    The title complex, [Co(C4H5O6)2(H2O)2]·2H2O, contains a CoII ion, two single deprotonated tartrate anions, two coordinated water mol­ecules and two lattice water mol­ecules. The coordination geometry of the CoII ion is a distorted octa­hedron with two O atoms from two coordinated water mol­ecules occupying cis positions in the equatorial plane and four O atoms from two hydrogen tartrate ions occupying the remaining positions. In the crystal, inter­molecular O—H⋯O hydrogen bonds link the mol­ecules into a three-dimensional network. PMID:22346896

  4. Chemical modification of silica gel with synthesized new Schiff base derivatives and sorption studies of cobalt (II) and nickel (II)

    NASA Astrophysics Data System (ADS)

    Kursunlu, Ahmed Nuri; Guler, Ersin; Dumrul, Hakan; Kocyigit, Ozcan; Gubbuk, Ilkay Hilal

    2009-08-01

    In this study, three Schiff base ligands and their complexes were synthesized and characterized by infrared spectroscopy (IR), thermogravimetric analyses (TGA), nuclear magnetic resonance (NMR), elemental analysis and magnetic susceptibility apparatuses. Silica gel was respectively modified with Schiff base derivatives, (E)-2-[(2-chloroethylimino)methyl]phenol, (E)-4-[(2-chloroethylimino)methyl]phenol and N, N'-[1,4-phenilendi(E)methylidene]bis(2-chloroethanamine), after silanization of silica gel by (3-aminopropyl)trimethoxysilane (APTS) by using a suitable method. Characterization of the surface modification was also performed with IR, TGA and elemental analysis. The immobilized surfaces were used for Co(II) and Ni(II) sorption from aqueous solutions and values of sorption were detected by atomic absorption spectrometer (AAS).

  5. Physicochemical and biological properties of oxovanadium(IV), cobalt(II) and nickel(II) complexes with oxydiacetate anions.

    PubMed

    Wyrzykowski, Dariusz; Kloska, Anna; Pranczk, Joanna; Szczepańska, Aneta; Tesmar, Aleksandra; Jacewicz, Dagmara; Pilarski, Bogusław; Chmurzyński, Lech

    2015-03-01

    The potentiometric and conductometric titration methods have been used to characterize the stability of series of VO(IV)-, Co(II)- and Ni(II)-oxydiacetato complexes in DMSO-water solutions containing 0-50 % (v/v) DMSO. The influence of DMSO as a co-solvent on the stability of the complexes as well as the oxydiacetic acid was evaluated. Furthermore, the reactivity of the complexes towards superoxide free radicals was assessed by employing the nitro blue tetrazolium (NBT) assay. The biological properties of the complexes were investigated in relation to their cytoprotective activity against the oxidative damage generated exogenously by using hydrogen peroxide in the Human Dermal Fibroblasts adult (HDFa) cell line as well as to their antimicrobial activity against the bacteria (Bacillus subtilis, Escherichia coli, Enterococcus faecalis, Pseudomonas aeruginosa, Staphylococcus aureus, Staphylococcus epidermidis). The relationship between physicochemical and biological properties of the complexes was discussed.

  6. Radical polymerization of vinyl acetate with bis(tetramethylheptadionato)cobalt(II): coexistence of three different mechanisms.

    PubMed

    Santhosh, Kumar; Gnanou, Yves; Champouret, Yohan; Daran, Jean-Claude; Poli, Rinaldo

    2009-01-01

    The complex [Co(II)(tmhd)(2)] (4; tmhd = 2,2,6,6-tetramethylhepta-3,5-dionato) has been investigated as a mediator for controlled radical polymerization of vinyl acetate (VAc) and compared with the analogue [Co(II)(acac)(2)] (1; acac = acetylacetonato). A relatively well controlled process occurs, after an induction time, with 2,2'-azobis(4-methoxyl-2,4-dimethylvaleronitrile) (V-70) as radical initiator at 30 degrees C. However, whereas the polymerization essentially stops after about six initiator half-lives in the presence of 1, it continues with a first-order rate law in the presence of 4. The successful simulation of the kinetic data shows that 4 operates simultaneously by associative (degenerative transfer, DT) and dissociative (organometallic radical polymerization, OMRP) mechanisms. The occurrence of OMRP was confirmed by an independent polymerization experiment starting from an isolated and purified [Co(tmhd)(2)](PVAc) macroinitiator. The polymer molecular weight evolves linearly with conversion in accordance with the expected values for one chain per Co atom when DT is the predominant mechanism and also during the pure OMRP process; however, observation of stagnating molecular weights at long reaction times with concomitant breakdown of the first-order rate law for monomer consumption indicates a competitive chain-transfer process catalyzed by an increasing amount of Co(II). In the presence of external donors L (water, pyridine, triethylamine) the DT pathway is blocked and the OMRP pathway is accelerated, and polymerization with complex 4 is then about five times slower than with complex 1. The reversal of relative effective OMRP rate constants k(eff) (4>1 in the absence of external donors, 4<1 in their presence) is rationalized through competitive steric effects on Co(III)-C and Co(II)-L bond strengths. These propositions are supported by (1)H NMR studies and by DFT calculations.

  7. Completing the bis[hydroxybis(pyridin-2-yl)methanesulfonato-κ3N,O,N']M(II) series (M = Mn to Zn) with the copper(II) and cobalt(II) structures.

    PubMed

    Haghjoo, Farhad; Pritchard, Robin

    2013-01-01

    The Cu(II) complex bis[hydroxybis(pyridin-2-yl)methanesulfonato-κ(3)N,O,N']copper(II) hexahydrate, [Cu(C(11)H(9)N(2)O(4)S)(2)]·6H(2)O, (I), crystallizes in the space group P1, compared with P2(1)/c for the anhydrous Co(II) analogue bis[hydroxybis(pyridin-2-yl)methanesulfonato-κ(3)N,O,N']cobalt(II), [Co(C(11)H(9)N(2)O(4)S)(2)], (II). However, both molecules sit on a crystallographic inversion centre and are thus very similar in appearance. Jahn-Teller elongation of the Cu-O bonds [2.347 (3) Å in (I) and 2.064 (2) Å in (II)] influences the S-O bond lengths, which are all around 1.455 (3) Å in (I) and 1.436 (2)-1.473 (2) Å in (II).

  8. Cobalt(II) complexes with bis(N-imidazolyl/benzimidazolyl) pyridazine: Structures, photoluminescent and photocatalytic properties

    NASA Astrophysics Data System (ADS)

    Li, Jin-Ping; Fan, Jian-Zhong; Wang, Duo-Zhi

    2016-07-01

    Six new CoII complexes [Co(L1)4(OH)2] (1), {[Co(L1)(H2O)4]·2ClO4}∞ (2), {[Co(L1)(H2O)4]·SiF6}∞ (3), {[Co(L1)3]·2ClO4}∞ (4), [Co(L2)Cl2]∞ (5) and {[Co(L2)2]·SiF6}∞ (6) [L1=3,6-bis(N-imidazolyl) pyridazine, L2=3,6-bis (N-benzimidazolyl) pyridazine] have been synthesized and characterized by elemental analysis, IR spectra and single crystal X-ray diffraction. Complex 1 has a mononuclear structure, while complexes 2 and 3 have 1-D chain structures. Considering the CoII centers were linked by the L1 ligands, the 3-D framework of complex 4 can be rationalized to be a {4^12.6^3} 6-c topological net with the stoichiometry uninodal net. 5 reveals a coordination 1-D zigzag chain structure consisting of a neutral chain [Co(L2)Cl2]n with the CoII centers. Complex 6 has a rhombohedral grid with a (4, 4) topology. The TGA property, fluorescent property and photocatalytic activity of complexes 1-6 have been investigated and discussed.

  9. Cobalt(II) complexes with bis(N-imidazolyl/benzimidazolyl) pyridazine: Structures, photoluminescent and photocatalytic properties

    SciTech Connect

    Li, Jin-Ping; Fan, Jian-Zhong; Wang, Duo-Zhi

    2016-07-15

    Six new Co{sup II} complexes [Co(L{sup 1}){sub 4}(OH){sub 2}] (1), {[Co(L"1)(H_2O)_4]·2ClO_4}{sub ∞} (2), {[Co(L"1)(H_2O)_4]·SiF_6}{sub ∞} (3), {[Co(L"1)_3]·2ClO_4}{sub ∞} (4), [Co(L{sup 2})Cl{sub 2}]{sub ∞} (5) and {[Co(L"2)_2]·SiF_6}{sub ∞} (6) [L{sup 1}=3,6-bis(N-imidazolyl) pyridazine, L{sup 2}=3,6-bis (N-benzimidazolyl) pyridazine] have been synthesized and characterized by elemental analysis, IR spectra and single crystal X-ray diffraction. Complex 1 has a mononuclear structure, while complexes 2 and 3 have 1-D chain structures. Considering the Co{sup II} centers were linked by the L{sup 1} ligands, the 3-D framework of complex 4 can be rationalized to be a {4^12.6^3} 6-c topological net with the stoichiometry uninodal net. 5 reveals a coordination 1-D zigzag chain structure consisting of a neutral chain [Co(L{sup 2})Cl{sub 2}]{sub n} with the Co{sup II} centers. Complex 6 has a rhombohedral grid with a (4, 4) topology. The TGA property, fluorescent property and photocatalytic activity of complexes 1–6 have been investigated and discussed. - Graphical abstract: Six Co{sup II} complexes of bis(N-imidazolyl/benzimidazolyl)pyridazine were synthesized and structurally characterized. The fluorescence properties and photocatalytic activity for dye degradation under UV light of all complexes have been investigated and discussed. Display Omitted - Highlights: • Six new Co{sup II} complexes with bis(N-imidazolyl/benzimidazolyl) pyridazine. • Structural analysis of all complexes. • Fluorescent property of all complexes. • Photocatalytic activity for dye degradation under UV light of all complexes.

  10. In vivo traffic of indium-111-oxine labeled human lymphocytes collected by automated apheresis

    SciTech Connect

    Read, E.J.; Keenan, A.M.; Carter, C.S.; Yolles, P.S.; Davey, R.J. )

    1990-06-01

    The in vivo traffic patterns of autologous lymphocytes were studied in five normal human volunteers using lymphocytes obtained by automated apheresis, separated on Ficoll-Hypaque gradients, and labeled ex vivo with {sup 111}In-oxine. Final lymphocyte infusions contained 1.8-3.1 X 10(9) cells and 270-390 microCi (9.99-14.43 MBq) {sup 111}In, or 11-17 microCi (0.41-0.63 MBq) per 10(8) lymphocytes. Gamma imaging showed transient lung uptake and significant retention of radioactivity in the liver and spleen. Progressive uptake of activity in normal, nonpalpable axillary and inguinal lymph nodes was seen from 24 to 96 hr. Accumulation of radioactivity also was demonstrated at the forearm skin test site, as well as in its associated epitrochlear and axillary lymph nodes, in a subject who had been tested for delayed hypersensitivity with tetanus toxoid. Indium-111-oxine labeled human lymphocytes may provide a useful tool for future studies of normal and abnormal lymphocyte traffic.

  11. A cobalt (II) complex with 6-methylpicolinate: Synthesis, characterization, second- and third-order nonlinear optical properties, and DFT calculations

    NASA Astrophysics Data System (ADS)

    Altürk, Sümeyye; Avcı, Davut; Tamer, Ömer; Atalay, Yusuf; Şahin, Onur

    2016-11-01

    A cobalt(II) complex of 6-methylpicolinic acid, [Co(6-Mepic)2(H2O)2]·2H2O, was prepared and fully determined by single crystal X-ray crystal structure analysis as well as FT-IR, FT-Raman. UV-vis spectra were recorded within different solvents, to illustrate electronic transitions and molecular charge transfer within complex 1. The coordination sphere of complex 1 is a distorted octahedron according to single crystal X-ray results. Moreover, DFT (density functional theory) calculations with HSEH1PBE/6-311 G(d,p) level were carried out to back up the experimental results, and form base for future work in advanced level. Hyperconjugative interactions, intramolecular charge transfer (ICT), molecular stability and bond strength were researched by the using natural bond orbital (NBO) analysis. X-ray and NBO analysis results demonsrate that O-H···O hydrogen bonds between the water molecules and carboxylate oxygen atoms form a 2D supramolecular network, and also adjacent 2D networks connected by C-H···π and π···π interactions to form a 3D supramolecular network. Additionally, the second- and third-order nonlinear optical parameters of complex 1 were computed at DFT/HSEH1PBE/6-311 G(d,p) level. The refractive index (n) was calculated by using the Lorentz-Lorenz equation in order to investigate polarization behavior of complex 1 in different solvent polarities. The first-order static hyperpolarizability (β) value is found to be lower than pNA value because of the inversion symmetry around Co (II). But the second-order static hyperpolarizability (γ) value is 2.45 times greater than pNA value (15×10-30 esu). According to these results, Co(II) complex can be considered as a candidate to NLO material. Lastly molecular electrostatic potential (MEP), frontier molecular orbital energies and related molecular parameters for complex 1 were evaluated.

  12. Open-Framework Manganese(II) and Cobalt(II) Borophosphates with Helical Chains: Structures, Magnetic, and Luminescent Properties.

    PubMed

    Li, Min; Smetana, Volodymyr; Wilk-Kozubek, Magdalena; Mudryk, Yaroslav; Alammar, Tarek; Pecharsky, Vitalij K; Mudring, Anja-Verena

    2017-09-01

    Two borophosphates, (NH4)1-2xM1+x(H2O)2(BP2O8)·yH2O with M = Mn (I) and Co (II), synthesized hydrothermally crystallize in enantiomorphous space groups P6522 and P6122 with a = 9.6559(3) and 9.501(3) Å, c = 15.7939(6) and 15.582(4) Å, and V = 1275.3(1) and 1218.2(8) Å(3) for I and II, respectively. Both compounds feature helical chains composed of vertex-sharing tetrahedral PO4 and BO4 groups that are connected through O atoms to transition-metal cations, Mn(2+) and Co(2+), respectively. For the two crystallographically distinct transition-metal cation sites present in the structure, this results in octahedral coordination with different degrees of distortion from the ideal symmetry. The crystal-field parameters, calculated from the corresponding absorption spectra, indicate that Mn(2+) and Co(2+) ions are located in a weak octahedral-like crystal field and suggest that the Co-ligand interactions are more covalent than the Mn-ligand ones. Luminescence measurements at room temperature reveal an orange emission that red-shifts upon lowering of the temperature to 77 K for I, while II is not luminescent. The luminescence lifetimes of I are 33.4 μs at room temperature and 1.87 ms at 77 K. Both compounds are Curie-Weiss paramagnets with negative Weiss constants and effective magnetic moments expected for noninteracting Mn(2+) and Co(2+) cations but no clear long-range magnetic order above 2 K.

  13. Bis[μ-4-(4-carb-oxy-phen-oxy)phthalato]bis-[triaqua-cobalt(II)].

    PubMed

    Wang, Liang

    2013-02-01

    The dinuclear title complex, [Co(2)(C(15)H(8)O(7))(2)(H(2)O)(6)], lies across an inversion center. The unique Co(II) ion is coordinated in a slightly distorted octa-hedral coordination geometry by two O atoms from a chelating 4-(carb-oxy-phen-oxy)phthalate ligand, three water O atoms and a further O atom from a bridging carboxyl-ate group of a symmetry-related 4-(carb-oxy-phen-oxy)phthalate ligand. In the crystal, O-H⋯O hydrogen bonds link the mol-ecules into a three-dimensional network.

  14. Dibromidobis(3,5-dimethyl-1H-pyrazole-κN 2)cobalt(II)

    PubMed Central

    Tomyn, Stefania; Pavlenko, Vadim A.; Gumienna-Kontecka, Elżbieta; Penkova, Larysa; Kotova, Natalia V.

    2011-01-01

    In the mononuclear title complex, [CoBr2(C5H8N2)2], the CoII atom is coordinated by two N atoms from two monodentate 3,5-dimethyl­pyrazole ligands and two Br atoms in a highly distorted tetra­hedral geometry. In the crystal, the complex mol­ecules are linked by inter­molecular N—H⋯Br hydrogen bonds into chains along [101]. An intra­molecular N—H⋯Br hydrogen bond is also present. PMID:22219744

  15. Bis(2-amino­benzonitrile)tetra­aqua­cobalt(II) dichloride

    PubMed Central

    Ru, Zong-Ling; Wang, Guo-Xi

    2009-01-01

    In the crystal structure of the title compound, [Co(C7H6N2)2(H2O)4]Cl2, the CoII cation lies on an inversion center and is coordinated by two 2-amino­benzonitrile ligands and four water mol­ecules in a distorted octa­hedral geometry. The Cl− counter-anion links with the complex cations via O—H⋯Cl and N—H⋯Cl hydrogen bonding. Inter­molecular O—H⋯N hydrogen bonding links the complex cations, forming supra­molecular chains running along the b axis. PMID:21578693

  16. Di- and tetra-nuclear copper(II), nickel(II), and cobalt(II) complexes of four bis-tetradentate triazole-based ligands: synthesis, structure, and magnetic properties.

    PubMed

    Olguín, Juan; Kalisz, Marguerite; Clérac, Rodolphe; Brooker, Sally

    2012-05-07

    Four bis-tetradentate N(4)-substituted-3,5-{bis[bis-N-(2-pyridinemethyl)]aminomethyl}-4H-1,2,4-triazole ligands, L(Tz1)-L(Tz4), differing only in the triazole N(4) substituent R (where R is amino, pyrrolyl, phenyl, or 4-tertbutylphenyl, respectively) have been synthesized, characterized, and reacted with M(II)(BF(4))(2)·6H(2)O (M(II) = Cu, Ni or Co) and Co(SCN)(2). Experiments using all 16 possible combinations of metal salt and L(TzR) were carried out: 14 pure complexes were obtained, 11 of which are dinuclear, while the other three are tetranuclear. The dinuclear complexes include two copper(II) complexes, [Cu(II)(2)(L(Tz2))(H(2)O)(4)](BF(4))(4) (2), [Cu(II)(2)(L(Tz4))(BF(4))(2)](BF(4))(2) (4); two nickel(II) complexes, [Ni(II)(2)(L(Tz1))(H(2)O)(3)(CH(3)CN)](BF(4))(4)·0.5(CH(3)CN) (5) and [Ni(II)(2)(L(Tz4))(H(2)O)(4)](BF(4))(4)·H(2)O (8); and seven cobalt(II) complexes, [Co(II)(2)(L(Tz1))(μ-BF(4))](BF(4))(3)·H(2)O (9), [Co(II)(2)(L(Tz2))(μ-BF(4))](BF(4))(3)·2H(2)O (10), [Co(II)(2)(L(Tz3))(H(2)O)(2)](BF(4))(4) (11), [Co(II)(2)(L(Tz4))(μ-BF(4))](BF(4))(3)·3H(2)O (12), [Co(II)(2)(L(Tz1))(SCN)(4)]·3H(2)O (13), [Co(II)(2)(L(Tz2))(SCN)(4)]·2H(2)O (14), and [Co(II)(2)(L(Tz3))(SCN)(4)]·H(2)O (15). The tetranuclear complexes are [Cu(II)(4)(L(Tz1))(2)(H(2)O)(2)(BF(4))(2)](BF(4))(6) (1), [Cu(II)(4)(L(Tz3))(2)(H(2)O)(2)(μ-F)(2)](BF(4))(6)·0.5H(2)O (3), and [Ni(II)(4)(L(Tz3))(2)(H(2)O)(4)(μ-F(2))](BF(4))(6)·6.5H(2)O (7). Single crystal X-ray structure determinations revealed different solvent content from that found by microanalysis of the bulk sample after drying under a vacuum and confirmed that 5', 8', 9', 11', 12', and 15' are dinuclear while 1' and 7' are tetranuclear. As expected, magnetic measurements showed that weak antiferromagnetic intracomplex interactions are present in 1, 2, 4, 7, and 8, stabilizing a singlet spin ground state. All seven of the dinuclear cobalt(II) complexes, 9-15, have similar magnetic behavior and remain in the [HS-HS] state

  17. Bioaccessibility testing of cobalt compounds.

    PubMed

    Stopford, Woodhall; Turner, John; Cappellini, Danielle; Brock, Tom

    2003-08-01

    Testing of metal compounds for solubility in artificial fluids has been used for many years to assist determining human health risk from exposure to specific compounds of concern. In lieu of obtaining bioavailability data from samples of urine, blood, or other tissues, these studies measured solubility of compounds in various artificial fluids as a surrogate for bioavailability. In this context, the measurement of metal "bioaccessibility" can be used as an in vitro substitute for measuring metal bioavailability. Bioaccessibility can be defined as a value representing the availability of metal for absorption when dissolved in in vitro surrogates of body fluids or juices. The aim of this study was to measure and compare the bioaccessibility of selected cobalt compounds in artificial human tissue fluids and human serum. A second aim was to initiate studies to experimentally validate an in vitro methodology that would provide a conservative estimate of cobalt bioavailability in the assessment of dose from human exposure to various species of cobalt compounds. This study evaluated the bioaccessibility of cobalt(II) from 11 selected cobalt compounds and an alloy in 2 physical forms in 5 surrogate human tissue fluids and human serum. Four (4) separate extraction times were used up to 72 hours. The effect of variables such as pH, dissolution time, and mass-ion effect on cobalt bioaccessibility were assessed as well. We found that the species of cobalt compound as well as the physico-chemical properties of the surrogate fluids, especially pH, had a major impact on cobalt solubility. Cobalt salts such as cobalt(II) sulfate heptahydrate were highly soluble, whereas cobalt alloys used in medical implants and cobalt aluminate spinels used as pigments, showed minimal dissolution over the period of the assay.

  18. Crystal structure of bis-(di-methyl-ammonium) hexa-aqua-cobalt(II) bis-(sulfate) dihydrate.

    PubMed

    Held, Peter

    2015-04-01

    The title salt, (C2H8N)2[Co(H2O)6)](SO4)2·2H2O, is isotypic with (C2H8N)2[Ni(H2O)6)](SO4)2·2H2O. The Co-O bond lengths in the [Co(H2O)6](2+) complex cation show very similar distances as in the related Tutton salt (NH4)2[Co(H2O)6)](SO4)2 [average 2.093 (17) Å], but are significantly longer than in the isotypic Ni(II) compound (Δd ≃ 0.04 Å). The cobalt cation reaches an overall bond-valence sum of 1.97 valence units. The S-O distances are nearly equal, ranging from 1.454 (4) to 1.470 (3) Å [mean 1.465 (12) Å]; however, the O-S-O angles vary clearly from 108.1 (2) to 110.2 (2)° [average bond angle 109.5 (9)°]. The non-coordinating water mol-ecules and di-methyl-ammonium cations connect the sulfate tetrahedra and the [Co(H2O)6](2+) octa-hedron via O-H⋯O and N-H⋯O hydrogen bonds of weak up to medium strength into a three-dimensional framework whereby the complex metal cations and sulfate anions are arranged in sheets parallel to (001).

  19. New dinuclear cobalt(II) and zinc(II) complexes of a carboxylate-rich dinucleating ligand: synthesis, structure, spectroscopic characterization, and their interactions with sugars.

    PubMed

    Bera, Manindranath; Curtiss, Ashley B S; Musie, Ghezai T; Powell, Douglas R

    2012-11-19

    Sugar-metal ion interactions in aqueous medium are involved in many biochemical processes such as the transport and storage of metals, the function and regulation of sugar-metabolizing metalloenzymes, the mechanism of action of metal-containing pharmaceuticals, and toxic metal metabolism. To understand such interactions we synthesized and fully characterized two new dinuclear cobalt(II) and zinc(II) complexes as carbohydrate binding models for xylose/glucose isomerases (XGI). Synthesis of the dicobalt complex, Na3[Co2(ccdp)(μ-HCO2)]BF4·9H2O·2CH3OH (1), was performed in methanol with stoichiometric amounts of Co(BF4)2·6H2O and the dinucleating ligand, H5ccdp (H5ccdp = N,N'-bis[2-carboxybenzomethyl]-N,N'-bis[carboxymethyl]-1,3-diaminopropan-2-ol), in the presence of NaOH at ambient temperature in an argon glovebox. Similarly, the dizinc complex, [NMe4]2[Zn2(ccdp)(μ-OAc)]·CH3OH (2), was synthesized from Zn(OAc)2·2H2O and H5ccdp in the presence of NMe4OH at ambient temperature in methanol. Binding of the complexes with carbohydrates was investigated under different reaction conditions. In aqueous alkaline media, complexes 1 and 2 showed chelating ability towards the biologically important sugars, d-glucose and d-xylose, and a polyalcohol enzyme inhibitor (xylitol). In solution, each complex forms a 1:1 complex-substrate bound product with specific binding constant values. Synthesis, characterization details, and substrate binding using spectroscopic techniques and single-crystal X-ray diffraction are reported.

  20. Di-μ-acetato-μ-aqua-bis-[acetatobis(1H-benzimidazole)cobalt(II)].

    PubMed

    Zimmermann, Iwan; Keene, Tony D; Neels, Antonia; Decurtins, Silvio

    2008-05-30

    In the title compound, [Co(2)(C(2)H(3)O(2))(4)(C(7)H(6)N(2))(4)(H(2)O)], the half-mol-ecule in the asymmetric unit is completed by a crystallographic twofold rotation axis to give the full mol-ecule. The Co(II) ions are approximately octahedrally coordinated with a cis-N(2)O(4) coordination sphere. The compound features intra-molecular O-H⋯O hydrogen bonds between the non-bridging acetate groups and the bridging water mol-ecule, and inter-molecular N-H⋯O hydrogen bonds between the acetates and amine H atoms of the benzimidazoles which determine the mol-ecular packing in the crystal structure.

  1. Di-μ-acetato-μ-aqua-bis­[acetatobis(1H-benzimidazole)cobalt(II)

    PubMed Central

    Zimmermann, Iwan; Keene, Tony D.; Neels, Antonia; Decurtins, Silvio

    2008-01-01

    In the title compound, [Co2(C2H3O2)4(C7H6N2)4(H2O)], the half-mol­ecule in the asymmetric unit is completed by a crystallographic twofold rotation axis to give the full mol­ecule. The CoII ions are approximately octahedrally coordinated with a cis-N2O4 coordination sphere. The compound features intra­molecular O—H⋯O hydrogen bonds between the non-bridging acetate groups and the bridging water mol­ecule, and inter­molecular N—H⋯O hydrogen bonds between the acetates and amine H atoms of the benzimidazoles which determine the mol­ecular packing in the crystal structure. PMID:21202524

  2. Rates of water exchange for two cobalt(II) heteropoly-oxotungstate compounds in aqueous solution

    SciTech Connect

    Ohlin, C. Andre; Harley, Stephen J.; McAlpin, J. Gregory; Hocking, Rosalie K.; Mercado, Brandon Q.; Johnson, Rene L.; Villa, Eric M.; Fidler, Mary Kate; Olmstead, Marilyn M.; Spiccia, Leone; Britt, R. David; Casey, William H.

    2011-03-17

    Polyoxometalate ions are used as ligands in water-oxidation processes related to solar energy production. An important step in these reactions is the association and dissociation of water from the catalytic sites, the rates of which are unknown. Here we report the exchange rates of water ligated to CoII atoms in two polyoxotungstate sandwich molecules using the 17O-NMR-based Swift–Connick method. The compounds were the [Co4(H2O)2(B-α-W9O34)2]-10 and the larger αββα-[Co4(H2O)2(P2W15O56)2]-16 ions, each with two water molecules bound trans to one another in a CoII sandwich between the tungstate ligands. The clusters, in both solid and solution state, were characterized by a range of methods, including NMR, EPR, FT-IR, UV-Vis, and EXAFS spectroscopy, ESI-MS, single-crystal X-ray crystallography, and potentiometry. For [Co4(H2O)2(B-α-PW9O34)2]-10 at pH 5.4, we estimate: k 298=1.5(5)±0.3×106 s-1, ΔH=39.8±0.4 kJ mol-1, ΔS=+7.1±1.2 J mol-1 K-1 and ΔV=5.6 ±1.6 cm3 mol-1. For the Wells–Dawson sandwich cluster (αββα-[Co4(H2O)2(P2W15O56)2]-16) at pH 5.54, we find: k298=1.6(2)±0.3×106 s-1, ΔH=27.6±0.4 kJ mol-1 ΔS=-33±1.3 J mol-1 K-1 and ΔV=2.2±1.4 cm3mol-1 at pH 5.2. The molecules are clearly stable and monospecific in slightly acidic solutions, but dissociate in strongly acidic solutions. This dissociation is detectable by EPR

  3. Effect of ligand denticity on the nitric oxide reactivity of cobalt(ii) complexes.

    PubMed

    Deka, Hemanta; Ghosh, Somnath; Saha, Soumen; Gogoi, Kuldeep; Mondal, Biplab

    2016-07-05

    The activation of nitric oxide (NO) by transition metal complexes has attracted a wide range of research activity. To study the role of ligand denticity on the NO reactivity of Co(ii) complexes, three complexes (, and ) were prepared with ligands , and [ = N(1),N(2)-bis(2,4,6-trimethylbenzyl)ethane-1,2-diamine; = N(1)-(2,4,6-trimethylbenzyl)-N(2)-(2-((2,4,6-trimethylbenzyl)amino)ethyl)ethane-1,2-diamine] and = N(1)-(2,4,6-trimethylbenzyl)-N(2),N(2)-bis(2-((2,4,6-trimethylbenzyl)amino)ethyl)ethane-1,2-diamine], respectively. The complexes differ from each other in terms of denticity and flexibility of the ligand frameworks. In degassed methanol solution, they were exposed to NO gas and their reactivity was studied using various spectroscopic techniques. In the case of complex with a bidentate ligand, reductive nitrosylation of the metal ion with concomitant dinitrosation of the ligand framework was observed. Complex with a tridentate ligand did not undergo reductive nitrosylation; rather, the formation of [Co(III)(NO(-))] was observed. The nitrosyl complexes were isolated and structurally characterized. On the other hand, complex with a tetradentate tripodal ligand did not react with NO. This can be attributed to the geometry of the complex as well as due to the accessibility of the corresponding redox potential.

  4. Tetra-aqua-bis(nicotinamide-κN)cobalt(II) bis-(2-fluoro-benzoate).

    PubMed

    Ozbek, F Elif; Tercan, Barış; Sahin, Ertan; Necefoğlu, Hacali; Hökelek, Tuncer

    2009-02-28

    The title complex, [Co(C(6)H(6)N(2)O)(2)(H(2)O)(4)](C(7)H(4)FO(2))(2), contains one Co(II) atom (site symmetry ), two monodentate nicotin-amide (NA) ligands, four coordinated water mol-ecules and two 2-fluoro-benzoate (FB) anions. The four O atoms in the equatorial plane around the Co atom form a slightly distorted square-planar arrangement, while the slightly distorted octa-hedral coordination is completed by the two N atoms of the NA ligands in the axial positions. The dihedral angle between the carboxyl group and the adjacent benzene ring is 29.8 (3)°, while the pyridine and benzene rings are oriented at a dihedral angle of 7.97 (12)°. In the crystal structure, mol-ecules are linked by O-H⋯O, N-H⋯O and N-H⋯F hydrogen bonds, forming an infinite three-dimensional network. π-π Contacts between the pyridine and benzene rings [centroid-centroid distance = 3.673 (3) Å] may further stabilize the crystal structure.

  5. Synthesis, structure, properties and immobilization on a gold surface of the monoribbed-functionalized tris-dioximate cobalt(II) clathrochelates and an electrocatalytic hydrogen production from H+ ions.

    PubMed

    Voloshin, Y Z; Belov, A S; Vologzhanina, A V; Aleksandrov, G G; Dolganov, A V; Novikov, V V; Varzatskii, O A; Bubnov, Y N

    2012-05-28

    The cycloaddition of the mono- and dichloroglyoximes to the cobalt(II) bis-α-benzyldioximate afforded the cobalt(II) mono- and dichloroclathrochelates in moderate yields (40-60%). These complexes undergo nucleophilic substitution of their reactive chlorine atoms with aliphatic amines, alcohols and thiolate anions. In the case of ethylenediamine and 1,2-ethanedithiol, only the macrobicyclic products with α,α'-N(2)- and α,α'-S(2)-alicyclic six-numbered ribbed fragments were obtained. The cobalt(II) cage complexes with terminal mercapto groups were synthesized using aliphatic dithiols. The crystal and molecular structures of the six cobalt(II) clathrochelates were obtained by X-ray diffraction. Their CoN(6)-coordination polyhedra possess a geometry intermediate between a trigonal prism and a trigonal antiprism, and the encapsulated cobalt(II) ions are shifted from their centres due to the structural Jahn-Teller effect with the Co-N distances varying significantly (by 0.10-0.26 Å). The electrochemistry of the complexes obtained was studied by cyclic voltammetry (CV). The anodic waves correspond to the quasi-reversible Co(2+/3+) oxidations, whereas the cathodic ranges contain the quasi-reversibile waves assigned to the Co(2+/+) reductions; all the cobalt(i)-containing clathrochelate anions formed are stable in the CV time scale. The electrocatalytic properties of the cobalt complexes obtained were studied in the production of hydrogen from H(+) ions: the addition of HClO(4) resulted in the formation of the same catalytic cathodic reduction Co(2+/+) waves. The controlled-potential electrolysis with gas chromatography analysis confirmed the production of H(2) in high Faraday yields. The efficiency of this electrocatalytic process was enhanced by an immobilization of the complexes with terminal mercapto groups on a surface of the working gold electrode.

  6. Site-specific substituted cobalt(II) horse liver alcohol dehydrogenases. Preparation and characterization in solution, crystalline and immobilized state.

    PubMed

    Maret, W; Andersson, I; Dietrich, H; Schneider-Bernlöhr, H; Einarsson, R; Zeppezauer, M

    1979-08-01

    The specific substitution, using highly selective techniques, of catalytic and/or noncatalytic zinc ions by cobaltous ions in horse liver alcohol dehydrogenase (EC 1.1.1.1) has been studied with dissolved, crystalline and agarose-immobilised enzyme, in order to examine the effect of protein structure on the specificity of the metal exchange. The different binding sites can be clearly distinguished by the absorption spectra of their cobalt derivatives. In solution an anaerobic column chromatographic method made it possible to exchange half of the zinc in the enzyme by cobalt ions in a much shorter time than previous procedures. By raising the temperature in the exchange step, even the slowly exchanging zinc ions were substituted by cobalt, yielding products similar to cobalt alcohol dehydrogenases described earlier. Treatment of crystal suspensions of the enzyme with chelating agents (preferentially dipicolinic acid) gave an inactive protein with two zinc ions remaining bound. The enzyme could be reactivated by treatment of the crystalline protein with 5 mM zinc or cobaltous ions or by dialysis of dissolved inactive protein against 20 microM zinc or 1 mM cobaltous ions. Higher metal concentrations led to denaturation but the inactive protein could be crystallized from solution and then reactivated completely at higher metal concentrations. The preparation and absorption spectrum show that cobalt is bound specifically at the catalytic sites. Since metal substitution at these sites critically depends on the maintenance of the correct tertiary and quaternary structure, these must be preserved in the crystal lattice and partially altered in solution when the catalytic zinc ions are removed (or when excess of metal ions is applied), thus demonstrating the structure-stabilizing role of the catalytic metal ions. The enzyme immobilised on agarose, with unchanged content of active sites [Schneider-Bernlöhr et al. (1978) Eur. J. Biochem. 41, 475--484], was treated like the

  7. gamma-Tocotrienol modulates the paracrine secretion of VEGF induced by cobalt(II) chloride via ERK signaling pathway in gastric adenocarcinoma SGC-7901 cell line.

    PubMed

    Bi, Sheng; Liu, Jia-Ren; Li, Yang; Wang, Qi; Liu, Hui-Kun; Yan, Ya-Geng; Chen, Bing-Qing; Sun, Wen-Guang

    2010-01-01

    Hypoxia is a common characteristic feature of solid tumors, and carcinoma cells are known to secrete many growth factors. These growth factors, such as vascular endothelial growth factor (VEGF), play a major role in the regulation of tumor angiogenesis and metastasis. In this study, the effect of gamma-tocotrienol, a natural product commonly found in palm oil and rice bran, on the accumulation of HIF-1alpha protein and the paracrine secretion of VEGF in human gastric adenocarcinoma SGC-7901 cell line induced by cobalt(II) chloride (as a hypoxia mimic) was investigated. These results showed that cobalt(II) chloride induced the high expression of VEGF in SGC-7901 cells at dose of 150 micromol/L for 24h. Both basal level and cobalt(II) chloride-induced HIF-1alpha protein accumulation and VEGF paracrine secretion were inhibited in SGC-7901 cells treated with gamma-tocotrienol at 60 micromol/L treatment for 24 h. U0126, a MEK1/2 inhibitor, decreased the expression of HIF-1alpha protein and the paracrine secretion of VEGF under normoxic and hypoxic conditions. In this study, gamma-tocotrienol also significantly inhibited the hypoxia-stimulated expression of phosphorylated extracellular signal-regulated kinase 1/2 (p-ERK1/2). The mechanism seems to involve in inhibiting hypoxia-mediated activation of p-ERK1/2, it leads to a marked decrease in hypoxia-induced HIF-1alpha protein accumulation and VEGF secretion. These data suggest that HIF-1alpha/VEGF could be a promising target for gamma-tocotrienol in an effective method of chemoprevention and chemotherapy in human gastric cancer.

  8. Cobalt(II) Porphyrin-Catalyzed Intramolecular Cyclopropanation of N-Alkyl Indoles/Pyrroles with Alkylcarbene: Efficient Synthesis of Polycyclic N-Heterocycles.

    PubMed

    Reddy, Annapureddy Rajasekar; Hao, Fei; Wu, Kai; Zhou, Cong-Ying; Che, Chi-Ming

    2016-01-26

    A protocol on chemoselective cobalt(II) porphyrin-catalyzed intramolecular cyclopropanation of N-alkyl indoles/pyrroles with alkylcarbenes has been developed. The reaction enables the rapid construction of a range of nitrogen-containing polycyclic compounds in moderate to high yields from readily accessible materials. These N-containing polycyclic compounds can be converted into a variety of N-heterocycles with potential synthetic and biological interest. Compared to their N-tosylhydrazone counterparts, the use of bulky N-2,4,6-triisopropylbenzenesulfonyl hydrazones as carbene precursors allows cyclopropanation to occur under milder reaction conditions.

  9. 1,2,4,5-benzenetetracarboxylate- and 2,2'-bipyrimidine-containing cobalt(II) coordination polymers: preparation, crystal structure, and magnetic properties.

    PubMed

    Fabelo, Oscar; Pasán, Jorge; Lloret, Francesc; Julve, Miguel; Ruiz-Pérez, Catalina

    2008-05-05

    Three new mixed-ligand cobalt(II) complexes of formula [Co2(H2O)6(bta)(bpym)]n.4nH2O (1), [Co2(H2O)2(bta)(bpym)]n (2), and [Co2(H2O)4(bta)(bpym)]n.2nH2O ( 3) (bpym = 2,2'-bipyrimidine and H 4bta = 1,2,4,5-benzenetretracaboxylic acid) have been synthesized and characterized by single crystal X-ray diffraction. 1 is a chain compound of mer-triaquacobalt(II) units which are linked through regular alternating bis-bidentate bpym and bis-monodentate bta groups. 2 and 3 are three-dimensional compounds where aquacobalt(II) ( 2) and cis-diaquacobalt(II) ( 3) entities are linked by bis-bidentate bpym ( 2 and 3) and tetrakis- ( 2 and 3) and octakis-monodentate ( 2) bta ligands. The cobalt atoms in 1- 3 exhibit somewhat distorted octahedral surroundings. Two bpym-nitrogen atoms ( 1- 3) and either two bta-oxygens ( 2) or one bta-oxygen and a water molecule ( 1 and 3) build the equatorial plane, whereas the axial positions are filled either by two water molecules ( 1) or by a bta-oxygen atom and a water molecule ( 2 and 3). The values of the cobalt-cobalt separation across the bridging bpym vary in the range 5.684(2)-5.7752(7) A, whereas those through the bta bridge cover the ranges 5.288(2)-5.7503(5) A (across the anti-syn carboxylate) and 7.715(3)-11.387(1) A (across the phenyl ring). The magnetic properties of 1- 3 have been investigated in the temperature range 1.9-290 K. They are all typical of an overall antiferromagnetic coupling with the maxima of the magnetic susceptibility at 14.5 ( 1) and 11.5 K ( 2 and 3). Although exchange pathways through bis-bidentate bpym and carboxylate-bta in different coordination modes are involved in 1- 3, their magnetic behavior is practically governed by that across the bpym bridge, the magnitude of the exchange coupling being J = -5.59(2) ( 1), -4.41(2) ( 2), and -4.49(2) ( 3) with the Hamiltonian H = - JS 1 S 2.

  10. The determination of cobalt(II) at DME using catalytic hydrogen current technique in various water samples, agricultural materials and pharmaceuticals.

    PubMed

    Kanchi, S; Saraswathi, K; Venkatasubba Naidu, N

    2011-12-01

    Two novel and facile ligands ammonium piperidine dithiocarbamate (Amm Pip-DTC) and ammonium morpholine dithiocarbamate (Amm Mor-DTC) were synthesized for the development of rapid and cost effective catalytic hydrogen current technique to analyze cobalt(II) in the presence of NH(4)Cl-NH(4)OH at pH 7.8 and 8.4 with Amm Pip-DTC and Amm Mor-DTC. These ligands produce catalytic hydrogen currents with Co(II) at peak potentials -1.24 V and -1.44 V vs. SCE respectively. Quantitative experimental conditions are developed by studying effect of pH, supporting electrolyte (NH(4)Cl), ligand and metal ion concentrations and effect of adverse ions on peak height to improve the sensitivity, selectivity and detection limits of the catalytic hydrogen current technique and compared it in terms of Student's t test and variance ratio f test with differential pulse polarographic (DPP) method. The developed technique was applied for the analysis of cobalt(II) in various water samples, agricultural materials and pharmaceuticals and the results obtained are in good agreement with the DPP data.

  11. Diastereoselective Radical‐Type Cyclopropanation of Electron‐Deficient Alkenes Mediated by the Highly Active Cobalt(II) Tetramethyltetraaza[14]annulene Catalyst

    PubMed Central

    Chirila, Andrei; Gopal Das, Braja; Paul, Nanda D.

    2017-01-01

    Abstract A new protocol for the catalytic synthesis of cyclopropanes using electron‐deficient alkenes is presented, which is catalysed by a series of affordable, easy to synthesise and highly active substituted cobalt(II) tetraaza[14]annulenes. These catalysts are compatible with the use of sodium tosylhydrazone salts as precursors to diazo compounds in one‐pot catalytic transformations to afford the desired cyclopropanes in almost quantitative yields. The reaction takes advantage of the metalloradical character of the Co complexes to activate the diazo compounds. The reaction is practical and fast, and proceeds from readily available starting materials. It does not require the slow addition of diazo reagents or tosylhydrazone salts or heating and tolerates many solvents, which include protic ones such as MeOH. The CoII complexes derived from the tetramethyltetraaza[14]annulene ligand are easier to prepare than cobalt(II) porphyrins and present a similar catalytic carbene radical reactivity but are more active. The reaction proceeds at 20 °C in a matter of minutes and even at −78 °C in a few hours. The catalytic system is robust and can operate with either the alkene or the diazo reagent as the limiting reagent, which inhibits the dimerisation of diazo compounds totally. The protocol has been applied to synthesise a variety of substituted cyclopropanes. High yields and selectivities were achieved for various substrates with an intrinsic preference for trans cyclopropanes. PMID:28529668

  12. Cobalt(II) complexes with azole-pyridine type ligands for non-aqueous redox-flow batteries: Tunable electrochemistry via structural modification

    NASA Astrophysics Data System (ADS)

    Armstrong, Craig G.; Toghill, Kathryn E.

    2017-05-01

    A single species redox flow battery employing a new class of cobalt(II) complexes with 'tunable' tridentate azole-pyridine type ligands is reported. Four structures were synthesised and their electrochemical, physical and battery characteristics were investigated as a function of successive substitution of the ligand terminal pyridyl donors. The Co(II/I) and Co(III/II) couples are stable and quasi-reversible on gold and glassy carbon electrodes, however redox potentials are tunable allowing the cobalt potential difference to be preferentially increased from 1.07 to 1.91 V via pyridine substitution with weaker σ-donating/π-accepting 3,5-dimethylpyrazole groups. The charge-discharge properties of the system were evaluated using an H-type glass cell and graphite rod electrodes. The complexes delivered high Coulombic efficiencies of 89.7-99.8% and very good voltaic efficiencies of 70.3-81.0%. Consequently, energy efficiencies are high at 63.1-80.8%, marking an improvement on other similar non-aqueous systems. Modification of the ligands also improved solubility from 0.18 M to 0.50 M via pyridyl substitution with 3,5-dimethylpyrazole, though the low solubility of the complexes limits the overall energy capacity to between 2.58 and 12.80 W h L-1. Preliminary flow cell studies in a prototype flow cell are also demonstrated.

  13. Bis[4-chloro-2-(quinolin-8-yl-imino-meth-yl)phenolato-κ(3) N,N',O]cobalt(III) trichlorido-methano-lcobaltate(II).

    PubMed

    Luo, Xu-Jian; Zhang, Chuan-Hui; Zhou, Jie; Liu, Yan-Cheng

    2013-05-01

    The reaction of 4-chloro-2-(quinolin-8-yl-imino-meth-yl)phenol (HClQP) with cobalt(II) dichloride hexa-hydrate in methanol/chloro-form under solvothermal conditions yielded the title compound, [Co(C16H10ClN2O)2][CoCl3(CH3OH)]. The Co(III) atom is six-coordinated in a slightly distorted octa-hedral geometry by four N atoms and two O atoms of two tridentate HClQP ligands, which are nearly perpendicular to each other, making a dihedral angle of 86.95°. The Co(II) atom is four-coordinated by three Cl atoms and one O atom from a methanol ligand in a distorted tetra-hedral geometry. The crystal packing is consolidated by inter-molecular O-H⋯Cl, C-H⋯Cl and C-H⋯O hydrogen bonds, forming a three-dimensional supra-molecular structure, in which [Co(II)Cl3(CH3OH)] anions are connected via O-H⋯Cl and C-H⋯Cl hydrogen bonds into centrosymmetric dimers. Neighboring cobalt(III) complexes form dimers through C-H⋯O hydrogen bonds, as well as π-π stacking [centroid-centroid distances = 3.30 (2) Å] between the planar quinoline systems of one HClQP ligand and the phenolate ring of another.

  14. Binding Selectivity of Methanobactin from Methylosinus trichosporium OB3b for Copper(I), Silver(I), Zinc(II), Nickel(II), Cobalt(II), Manganese(II), Lead(II), and Iron(II)

    NASA Astrophysics Data System (ADS)

    McCabe, Jacob W.; Vangala, Rajpal; Angel, Laurence A.

    2017-08-01

    Methanobactin (Mb) from Methylosinus trichosporium OB3b is a member of a class of metal binding peptides identified in methanotrophic bacteria. Mb will selectively bind and reduce Cu(II) to Cu(I), and is thought to mediate the acquisition of the copper cofactor for the enzyme methane monooxygenase. These copper chelating properties of Mb make it potentially useful as a chelating agent for treatment of diseases where copper plays a role including Wilson's disease, cancers, and neurodegenerative diseases. Utilizing traveling wave ion mobility-mass spectrometry (TWIMS), the competition for the Mb copper binding site from Ag(I), Pb(II), Co(II), Fe(II), Mn(II), Ni(II), and Zn(II) has been determined by a series of metal ion titrations, pH titrations, and metal ion displacement titrations. The TWIMS analyses allowed for the explicit identification and quantification of all the individual Mb species present during the titrations and measured their collision cross-sections and collision-induced dissociation patterns. The results showed Ag(I) and Ni(II) could irreversibly bind to Mb and not be effectively displaced by Cu(I), whereas Ag(I) could also partially displace Cu(I) from the Mb complex. At pH ≈ 6.5, the Mb binding selectivity follows the order Ag(I)≈Cu(I)>Ni(II)≈Zn(II)>Co(II)>>Mn(II)≈Pb(II)>Fe(II), and at pH 7.5 to 10.4 the order is Ag(I)>Cu(I)>Ni(II)>Co(II)>Zn(II)>Mn(II)≈Pb(II)>Fe(II). Breakdown curves of the disulfide reduced Cu(I) and Ag(I) complexes showed a correlation existed between their relative stability and their compact folded structure indicated by their CCS. Fluorescence spectroscopy, which allowed the determination of the binding constant, compared well with the TWIMS analyses, with the exception of the Ni(II) complex. [Figure not available: see fulltext.

  15. Computational, electrochemical, and spectroscopic studies of two mononuclear cobaloximes: the influence of an axial pyridine and solvent on the redox behaviour and evidence for pyridine coordination to cobalt(i) and cobalt(ii) metal centres.

    PubMed

    Lawrence, Mark A W; Celestine, Michael J; Artis, Edward T; Joseph, Lorne S; Esquivel, Deisy L; Ledbetter, Abram J; Cropek, Donald M; Jarrett, William L; Bayse, Craig A; Brewer, Matthew I; Holder, Alvin A

    2016-06-21

    [Co(dmgBF2)2(H2O)2] (where dmgBF2 = difluoroboryldimethylglyoximato) was used to synthesize [Co(dmgBF2)2(H2O)(py)]·0.5(CH3)2CO (where py = pyridine) in acetone. The formulation of complex was confirmed by elemental analysis, high resolution MS, and various spectroscopic techniques. The complex [Co(dmgBF2)2(solv)(py)] (where solv = solvent) was readily formed in situ upon the addition of pyridine to complex . A spectrophotometric titration involving complex and pyridine proved the formation of such a species, with formation constants, log K = 5.5, 5.1, 5.0, 4.4, and 3.1 in 2-butanone, dichloromethane, acetone, 1,2-difluorobenzene/acetone (4 : 1, v/v), and acetonitrile, respectively, at 20 °C. In strongly coordinating solvents, such as acetonitrile, the lower magnitude of K along with cyclic voltammetry, NMR, and UV-visible spectroscopic measurements indicated extensive dissociation of the axial pyridine. In strongly coordinating solvents, [Co(dmgBF2)2(solv)(py)] can only be distinguished from [Co(dmgBF2)2(solv)2] upon addition of an excess of pyridine, however, in weakly coordinating solvents the distinctions were apparent without the need for excess pyridine. The coordination of pyridine to the cobalt(ii) centre diminished the peak current at the Epc value of the Co(I/0) redox couple, which was indicative of the relative position of the reaction equilibrium. Herein we report the first experimental and theoretical (59)Co NMR spectroscopic data for the formation of Co(i) species of reduced cobaloximes in the presence and absence of py (and its derivatives) in CD3CN. From spectroelectrochemical studies, it was found that pyridine coordination to a cobalt(i) metal centre is more favourable than coordination to a cobalt(ii) metal centre as evident by the larger formation constant, log K = 4.6 versus 3.1, respectively, in acetonitrile at 20 °C. The electrosynthesis of hydrogen by complexes and in various solvents demonstrated the dramatic effects of the axial

  16. Effects of mechanism-based reversible inhibitors on the metal environment of cobalt(II)carboxypeptidase A: an electronic spectral study.

    PubMed

    Martin, M T; Holmquist, B; Riordan, J F

    1989-05-01

    Electronic absorption, circular dichroic (CD), and magnetic circular dichroic (MCD) spectra have been determined for complexes of cobalt(II)-substituted carboxypeptidase A and five reversible inhibitors. Three of the inhibitors, N-(1-carboxy-5-butyloxycarbonylaminopentyl)-L-phenylalanine, (I); (R,S)-2-benzyl-4-oxobutanoic acid, (III); and 2-benzyl-4-oxo-5,5,5-trifluoropentanoic acid, (IV) are mechanism-based inhibitors. Another, N-(1-carboxy-5-carbobenzoxyaminopentyl)-glycyl-L-phenylalanine, (II), is a tight binding, slowly hydrolyzed substrate. The fifth, phosphoramidon, (V), is a mechanism-based inhibitor of thermolysin, and may also bind to carboxypeptidase in a mechanism-based mode. The absorption and CD spectra of the enzyme-inhibitor complexes all differ from the spectrum of the free enzyme and from each other. The MCD spectra indicate that the tetrahedral coordination geometry of cobalt, which is distorted in the free enzyme, is also distorted in the inhibitor complexes, although to various degrees. The complexes of I and III are spectrally similar despite being structurally dissimilar, and that of IV, whose structure resembles III, is spectrally distinct, indicating that I and III, but not IV, may perturb the metal in nearly the same way. The absorption spectrum of IV is identical to that, at high pH, of Co(II)carboxypeptidase in which Glu-270 has been modified by a carbodiimide reagent, possibly pointing to a common perturbation of this residue. The absorption and CD spectra of II are similar to those of the catalytic intermediate that precedes the rate-limiting step in peptide hydrolysis [D. S. Auld, A. Galdes, K. F. Geoghegan, B. Holmquist, R. Martinelli, and B. L. Vallee, Proc. Natl. Acad. Sci. USA 81, 4675-4681 (1984)]. Since II is a substrate, the steady-state bound species that it generates may therefore be a true productive intermediate rather than a nonproductive mimic of an intermediate. The spectra of the complexes with II and V differ

  17. Interaction of cobalt ions with carboxypeptidase A.

    PubMed

    Moratal, J M; Castells, J; Donaire, A; Salgado, J; Jiménez, H R; Domingo, R

    1994-01-01

    The interaction of cobalt(II) with native and cobalt(II)-substituted carboxypeptidase has been investigated, at pH 7.5, by electronic absorption and 1H NMR spectroscopies. The reaction of the cobalt(II) uptake by the metalloenzyme [MCPA] (M = Zn or Co) occurs very slowly and a bimetallic complex, [MCPA(Co)], is formed. On the basis of the 1H NOE experiments, the isotropically shifted proton resonances were assigned as belonging to a coordinated histidine residue. 1H NMR titrations of [ZnCPA(Co)] with zinc(II) show that the zinc ion does not compete with cobalt for binding to the noncatalytic site. The temperature dependence of the isotropic shifts, molar absorbance, and longitudinal relaxation time values are indicative of a five-coordinated geometry for the cobalt ion. The identification of the noncatalytic cobalt binding site is also discussed.

  18. Kinetics and fate of /sup 111/In oxine-labeled platelets in patients with aortic aneurysms

    SciTech Connect

    Heyns, A.D.; Loetter, M.G.; Badenhorst, P.N.; Pieters, H.; Nel, C.J.; Minnaar, P.C.

    1982-09-01

    The survival and sites of sequestration of /sup 111/In oxine-labeled autologous platelets were studied quantitatively in six patients with aortic aneurysms. The in vivo distribution was quantitated daily with a scintillation camera and a computer-assisted imaging system. Data of platelet survival curves were fitted to a gamma function model. Mean platelet survival was shortened and the disappearance curves were exponential in all but two patients who had normal platelet survival. Platelet radioactivity in the aneurysm was 5.1 +/- 3% of whole-body radioactivity at the end of platelet survival. Platelet were sequestered in the spleen, liver, and bone marrow. Accumulation of platelets, presumably due to microembolization, was prominent in the lower limbs. This indicates that although platelets were deposited in the aneurysm, many are damaged and are eventually sequestered in the reticuloendothelial system.

  19. Characteristics of polyaniline cobalt supported catalysts for epoxidation reactions.

    PubMed

    Kowalski, Grzegorz; Pielichowski, Jan; Grzesik, Mirosław

    2014-01-01

    A study of polyaniline (PANI) doping with various cobalt compounds, that is, cobalt(II) chloride, cobalt(II) acetate, and cobalt(II) salen, is presented. The catalysts were prepared by depositing cobalt compounds onto the polymer surface. PANI powders containing cobalt ions were obtained by one- or two-step method suspending PANI in the following acetonitrile/acetic acid solution or acetonitrile and then acetic acid solution. Moreover different ratios of Co(II) : PANI were studied. Catalysts obtained with both methods and at all ratios were investigated using various techniques including AAS and XPS spectroscopy. The optimum conditions for preparation of PANI/Co catalysts were established. Catalytic activity of polyaniline cobalt(II) supported catalysts was tested in dec-1-ene epoxidation with molecular oxygen at room temperature. The relationship between the amount of cobalt species, measured with both AAS and XPS techniques, and the activity of PANI-Co catalysts has been established.

  20. Characteristics of Polyaniline Cobalt Supported Catalysts for Epoxidation Reactions

    PubMed Central

    Kowalski, Grzegorz; Pielichowski, Jan; Grzesik, Mirosław

    2014-01-01

    A study of polyaniline (PANI) doping with various cobalt compounds, that is, cobalt(II) chloride, cobalt(II) acetate, and cobalt(II) salen, is presented. The catalysts were prepared by depositing cobalt compounds onto the polymer surface. PANI powders containing cobalt ions were obtained by one- or two-step method suspending PANI in the following acetonitrile/acetic acid solution or acetonitrile and then acetic acid solution. Moreover different ratios of Co(II) : PANI were studied. Catalysts obtained with both methods and at all ratios were investigated using various techniques including AAS and XPS spectroscopy. The optimum conditions for preparation of PANI/Co catalysts were established. Catalytic activity of polyaniline cobalt(II) supported catalysts was tested in dec-1-ene epoxidation with molecular oxygen at room temperature. The relationship between the amount of cobalt species, measured with both AAS and XPS techniques, and the activity of PANI-Co catalysts has been established. PMID:24701183

  1. Indium-111-oxine labeled platelet kinetics in patients with diabetes mellitus

    SciTech Connect

    Forstrom, L.A.; Luikens, B.; Johnson, T.

    1984-01-01

    The possible role of abnormal platelet function in the pathogenesis of vascular disease in patients with diabetes mellitus remains controversial. In vitro studies have shown variable alterations in platelet function in such patients. Studies of in vivo platelet kinetics in diabetic patients have been inconclusive, although decreased platelet survival has been observed in some cases. Earlier studies were carried out using chromium-51 or selenium-75 for platelet labeling. The authors have performed Indium-111-oxine labeled platelet kinetic and biodistribution studies in 4 patients with diabetes mellitus (ages 49-61 years), and in 4 control subjects (ages 46-60 years). All subjects were male. All diabetic patients were poorly controlled at the time of study, with blood glucose > 140 mg% and hemoglobin A-1c > 10%. Autologous platelets were labeled with Indium-111-oxine in ACD:plasma by previously reported methods, and reinjected in a dose of approximately 50 ..mu..Ci (range 42-67..mu..Ci). Average recovery of the injected platelets was 67% (range 41-85%). Computer analyzed images at 24 hours showed no significant difference in liver uptake between diabetic and control subjects. Mildly increased splenic uptake in diabetic patients was of borderline significance (p=.07). Platelet survival was slightly decreased in diabetic subjects by 3 of 4 models utilized (linear, exponential, multiple hit and weighted mean), although the difference achieved significance only for the weighted man model (p=.05). These data support observations by earlier methods which suggest that platelet survival may be decreased in patients with diabetes mellitus.

  2. In vivo crossmatching with Tc-99m-RBC's and In-111-oxine-RBC's

    SciTech Connect

    Marcus, C.S.; Myhre, B.A.; Angulo, M.C.; Salk, R.D.; Essex, C.E.

    1984-01-01

    In vitro crossmatching techniques are often inadequate for patients who have received multiple prior transfusions. These patients usually have multiple antibodies to minor blood groups, not all of which are necessarily important to vivo. It becomes increasingly difficult to obtain appropriate units for transfusion, and often units are used with hopes that a minor group antibody will not be significantly active in vivo. If a transfusion reaction occurs, the unit is stopped. The authors have developed and successfully tested a method whereby 1.5 to 3c of potential donor RBC's are labeled with 25-50 ..mu..Ci of Tc-99m using the BNL kits. After injection, samples are drawn at 10, 20, 60, and 120 minutes and the RBC survival is measured. If it is desirable to test 2 units simultaneously, the authors use 400 ..mu..Ci Tc-99m to label an RBC aliquot of one unit and 25 ..mu..Ci In-111-oxine to label the other; both labeled aliquots are injected together. The method is simple and reliable. In addition to assessing compatibility, the authors may also estimate the % viability of transfused, compatible RBC's by starting with 400 ..mu..Ci of Tc-99m and multiplying % survival at 24 hours by 1.2. For 24 hr. survival measurements of IN-111-oxine-RBC's, 25 ..mu..Ci is adequate and no multiplication factor is necessary. The authors have performed 13 in vivo crossmatches, 4 of which were double, in 6 patients. One documented mild transfusion reaction occurred. There were no false positive or false negative results.

  3. Crystal structure of a Co(II) coordination polymer: catena-poly[[μ-aqua-bis-(μ-2-methyl-propano-ato)-κ(2)O:O';κ(2)O:O-cobalt(II)] monohydrate].

    PubMed

    Fischer, Andrei I; Gurzhiy, Vladislav V; Aleksandrova, Julia V; Pakina, Maria I

    2017-03-01

    In the title cobalt(II) coordination polymer with isobutyrate ligands, {[Co{CH(CH3)2CO2}2(H2O)]·H2O} n , the Co(2+) ion is hexa-coordinated in a slightly distorted octa-hedral coordination environment defined by two O atoms from two bridging water mol-ecules and four O atoms from four bridging carboxyl-ate ligands. The carboxyl-ates adopt two different coordination modes, μ-(κ(2)O:O') and μ-(κ(2)O:O), forming a one-dimensional polymeric chain extending along [010]. The intra-chain cobalt⋯cobalt separation is 3.2029 (2) Å. The polymeric chains are linked by hydrogen bonds involving the water mol-ecules of solvation, giving a two-dimensional network structure lying parallel to (100).

  4. Crystal structure of a CoII coordination polymer: catena-poly[[μ-aqua-bis­(μ-2-methyl­propano­ato)-κ2 O:O′;κ2 O:O-cobalt(II)] monohydrate

    PubMed Central

    Gurzhiy, Vladislav V.; Aleksandrova, Julia V.; Pakina, Maria I.

    2017-01-01

    In the title cobalt(II) coordination polymer with isobutyrate ligands, {[Co{CH(CH3)2CO2}2(H2O)]·H2O}n, the Co2+ ion is hexa­coordinated in a slightly distorted octa­hedral coordination environment defined by two O atoms from two bridging water mol­ecules and four O atoms from four bridging carboxyl­ate ligands. The carboxyl­ates adopt two different coordination modes, μ-(κ2 O:O′) and μ-(κ2 O:O), forming a one-dimensional polymeric chain extending along [010]. The intra-chain cobalt⋯cobalt separation is 3.2029 (2) Å. The polymeric chains are linked by hydrogen bonds involving the water mol­ecules of solvation, giving a two-dimensional network structure lying parallel to (100). PMID:28316799

  5. Binding, Electrochemical Activation and Cleavage of DNA by Cobalt(II)tetrakis-N-Methylpyridyl Porphyrin and its β-Pyrrole Brominated Derivative

    PubMed Central

    Yellappa, Shivaraj; Seetharamappa, Jaldappagari; Rogers, Lisa M.; Chitta, Raghu; Singhal, Ram P.; D’Souza, Francis

    2008-01-01

    The binding of nucleic acids by water soluble cobalt(II) tetrakis-N-methylpyridyl porphyrin, (TMPyP)Co and its highly electron deficient derivative, cobalt(II) tetrakis-N-methyl pyridyl-β-octabromoporphyrin, (Br8TMPyP)Co was investigated by UV-visible absorption, circular dichroism (CD), electrochemical and gel electrophoresis methods. The changes of the absorption spectra during the titration of these complexes with polynucleotides revealed a shift in the absorption maxima and a hypochromicity of the porphyrin Soret bands. The intrinsic binding constants were found to be in the range of 105 – 106 M−1. These values were higher for more electron deficient (Br8TMPyP)Co. Induced CD bands were noticed in the Soret region of the complexes due to the interaction of these complexes with different polynucleotides and an analysis of the CD spectra supported mainly external mode of binding. Electrochemical studies revealed the cleavage of polynucleotide by (TMPyP)Co and (Br8TMPyP)Co in the presence of oxygen preferentially at the A-T base pair region. Gel electrophoresis experiments further supported the cleavage of nucleic acids. The results indicate that the β-pyrrole brominated porphyrin, (Br8TMPyP)Co binds strongly and cleaves nucleic acids efficiently as compared to (TMPyP)Co. This electrolytic procedure offers a unique tool in biotechnology for cleaving double-stranded DNA with specificity at the A-T regions. PMID:17105219

  6. Design, synthesis, spectral characterization, DNA interaction and biological activity studies of copper(II), cobalt(II) and nickel(II) complexes of 6-amino benzothiazole derivatives

    NASA Astrophysics Data System (ADS)

    Daravath, Sreenu; Kumar, Marri Pradeep; Rambabu, Aveli; Vamsikrishna, Narendrula; Ganji, Nirmala; Shivaraj

    2017-09-01

    Two novel Schiff bases, L1 = (2-benzo[d]thiazol-6-ylimino)methyl)-4,6-dichlorophenol), L2 = (1-benzo[d]thiazol-6-ylimino)methyl)-6-bromo-4-chlorophenol) and their bivalent transition metal complexes [M(L1)2] and [M(L2)2], where M = Cu(II), Co(II) and Ni(II) were synthesized and characterized by elemental analysis, NMR, IR, UV-visible, mass, magnetic moments, ESR, TGA, SEM, EDX and powder XRD. Based on the experimental data a square planar geometry around the metal ion is assigned to all the complexes (1a-2c). The interaction of synthesized metal complexes with calf thymus DNA was explored using UV-visible absorption spectra, fluorescence and viscosity measurements. The experimental evidence indicated that all the metal complexes strongly bound to CT-DNA through an intercalation mode. DNA cleavage experiments of metal(II) complexes with supercoiled pBR322 DNA have also been explored by gel electrophoresis in the presence of H2O2 as well as UV light, and it is found that the Cu(II) complexes cleaved DNA more effectively compared to Co(II), Ni(II) complexes. In addition, the ligands and their metal complexes were screened for antimicrobial activity and it is found that all the metal complexes were more potent than free ligands.

  7. Molybdophosphonate clusters as building blocks in the oxomolybdate-organodiphosphonate/cobalt(II)-organoimine system: structural influences of secondary metal coordination preferences and diphosphonate tether lengths.

    PubMed

    Armatas, N Gabriel; Allis, Damian G; Prosvirin, Andrew; Carnutu, Gabriel; O'Connor, Charles J; Dunbar, Kim; Zubieta, Jon

    2008-02-04

    Hydrothermal conditions have been used in the preparation of a series of organic-inorganic hybrid materials of the cobalt-molybdophosphonate family. The reactions of MoO(3), cobalt(II) acetate or cobalt(II) acetylacetonate, tetra-2-pyridylpyrazine (tpyprz), and organodiphosphonic acids H(2)O(3)P(CH(2))nPO(3)H(2) (n = 1-5 and 9) of varying tether lengths yielded compounds of the general type {Co(2)(tpyprz)(H(2)O)(m)}4+/MoxOy{O(3)P(CH(2))(n)PO(3)}z. The recurring theme of the structural chemistry is the incorporation of {Mo(5)O(15)(O(3)PR)(2)}(4-) clusters as molecular building blocks observed in the structures of nine phases (compounds 2-9 and 11). The structural consequences of variations in reaction conditions are most apparent in the series with propylene diphosphonate, where four unique structures 4-7 are observed, including two distinct three-dimensional architectures for compounds 5 and 6 whose formulations differ only in the number of water molecules of crystallization. With pentyldiphosphonate, a second phase 10 is obtained which exhibits a unique cluster building block, the hexamolybdate [Mo(6)O(18){O(3)P(CH(2))(5)PO(3)}](4-). In the case of methylenediphosphonic acid, a third structural motif, the trinuclear {(Mo(3)O(8))(O(3)PCH(2)PO(3))}2- subunit, is observed in compound 1. The structural chemistry of compounds 1-11 of this study is quite distinct from that of the {Ni(2)(tpyprz)(H(2)O)(m)}(4+)/Mo(x)O(y){O(3)P(CH(2))(n)PO(3)}z family, as well as that of the copper-based family. The structural diversity of this general class of materials reflects the coordination preferences of the M(II) sites, the extent of aqua ligation to the M(II) sites, the participation of both phosphate oxygen atoms and molybdate oxo-groups in linking to the M(II) sites, and the variability in the number of attachment sites at the molybdophosphonate clusters. Since the charge densities at the peripheral oxygen atoms of the clusters are quite uniform, the attachment of {M(2)(tpyprz

  8. Tetra­aqua­bis­[2-(2-nitro­phen­yl)acetato-κO]cobalt(II)

    PubMed Central

    Danish, Muhammad; Tahir, Muhammad Nawaz; Iftikhar, Sana; Raza, Muhammad Asam; Ashfaq, Muhammad

    2015-01-01

    The mol­ecule of the title compound, [Co(C8H6NO4)2(H2O)4], is centrosymmetric. It is a cobalt(II) complex, bearing two (2-nitro­phen­yl)acetate and four aqua ligands. The coordination around the CoII atom is distorted octa­hedral, defined by four O atoms of water mol­ecules in the equatorial plane and by two carboxyl­ate O atoms at axial positions. The dihedral angles between the benzene ring and the acetate and nitro groups are 61.90 (10) and 19.21 (11)°, respectively. The water mol­ecules form O—H⋯O hydrogen bonds with the nitro and carboxyl­ate groups, leading to a layered structural arrangement parallel to (001). PMID:25844208

  9. Structural, MALDI-TOF-MS, magnetic and spectroscopic studies of new dinuclear copper(II), cobalt(II) and zinc(II) complexes containing a biomimicking μ-OH bridge.

    PubMed

    Núñez, Cristina; Bastida, Rufina; Macías, Alejandro; Valencia, Laura; Neuman, Nicolás I; Rizzi, Alberto C; Brondino, Carlos D; González, Pablo J; Capelo, José Luis; Lodeiro, Carlos

    2010-12-28

    The Py(2)N(4)S(2) octadentate coordinating ligand afforded dinuclear cobalt, copper and zinc complexes and the corresponding mixed metal compounds. The overall geometry and bonding modes have been deduced on the basis of elemental analysis data, MALDI-TOF-MS, IR, UV-vis and EPR spectroscopies, single-crystal X-Ray diffraction, conductivity and magnetic susceptibility measurements. In the copper and zinc complexes, a μ-hydroxo bridge links the two metal ions. In both cases, the coordination geometry is distorted octahedral. Magnetic and EPR data reveal weakly antiferromagnetic high spin Co(II) ions, compatible with a dinuclear structure. The magnetic characterization of the dinuclear Cu(II) compound indicates a ferromagnetically coupled dimer with weak antiferromagnetic intermolecular interactions. The intra-dimer ferromagnetic behaviour was unexpected for a Cu(II) dimer with such μ-hydroxo bridging topology. We discuss the influence on the magnetic properties of non-covalent interactions between the bridging moiety and the lattice free water molecules.

  10. Synthesis, structural and magnetic characterisation of iron(II/III), cobalt(II) and copper(II) cluster complexes of the polytopic ligand: N-(2-pyridyl)-3-carboxypropanamide.

    PubMed

    Russell, Mark E; Hawes, Chris S; Ferguson, Alan; Polson, Matthew I J; Chilton, Nicholas F; Moubaraki, Boujemaa; Murray, Keith S; Kruger, Paul E

    2013-10-07

    Herein we describe the synthesis, structural and magnetic characterisation of three transition metal cluster complexes that feature the polytopic ligand N-(2-pyridyl)-3-carboxypropanamide (H2L): [Fe3(III)Fe2(II)(HL)6(O)(H2O)3][ClO4]5·3MeCN·4H2O, 1, [Co8(HL)8(O)(OH)4(MeOH)3(H2O)]-[ClO4]3·5MeOH·2H2O, 2, and [Cu6(L(ox))4(MeOH)(H2O)3]·MeOH, 3. Complex 1 is a mixed valence penta-nuclear iron cluster containing the archetypal {Fe3(III)O} triangular basic carboxylate cluster at its core, with two Fe(II) ions above and below the core coordinated to three bidentate pyridyl-amide groups. The structure of the octanuclear Co(II) complex, 2, is based upon a central Co4 square with the remaining four Co(II) centres at the 'wing-tips' of the complex. The cluster core is replete with bridging oxide, hydroxide and carboxylate groups. Cluster 3 contains an oxidised derivative of the ligand, L(ox), generated in situ through hydroxylation of an α-carbon atom. This hexanuclear cluster has a 'barrel-like' core and contains Cu(II) ions in both square planar and square-based pyramidal geometries. Bridging between Cu(II) centres is furnished by alkoxide and carboxylate groups. Magnetic studies on 1-3 reveals dominant antiferro-magnetic interactions for 1 and 2, leading to small non-zero spin ground states, while 3 shows ferro-magnetic exchange between the Cu(II) centres to give an S = 3 spin ground state.

  11. Technical considerations in the study of /sup 111/In-oxine labelled platelet survival patterns in dogs

    SciTech Connect

    Sharefkin, J.; Rich, N.M.

    1982-04-01

    A detailed technique for labelling canine platelets with /sup 111/In-oxine for the study of platelet survival patterns in four to six dogs at a time was developed. Useful modifications of earlier methods included splitting of the platelet rich plasma into multiple aliquots to improve pelleting efficiency at low gravity forces, use of saved platelet poor plasma to flush out injection syringes, and prompt use of commercial /sup 111/In-oxine sources 3 to 5 minutes after mixing with Ringer's Citrate Dextrose. Avoidable pitfalls of the method included excessive lengths of incubation time in plasma free medium and loss of labelling efficacy by exposure of the chelate to iron or other metal contaminants in glassware. The method was used to study changes in platelet survival time in dogs with large synthetic arterial prostheses, and gave results in good agreement with earlier studies using /sup 51/Cr labelled platelets.

  12. Enrichment of iron(III), cobalt(II), nickel(II), and copper(II) by solid-phase extraction with 1,8-dihydroxyanthraquinone anchored to silica gel before their determination by flame atomic absorption spectrometry.

    PubMed

    Goswami, Anupama; Singh, Ajai K

    2002-10-01

    A chelating matrix prepared by immobilizing 1,8-dihydroxyanthraquinone on silica gel modified with 3-aminopropyltriethoxysilane has been characterized by use of cross-polarization magic angle spinning (CPMAS) NMR, diffuse reflectance infrared Fourier transformation (DRIFT) spectroscopy, and thermogravimetric analysis and used to preconcentrate Fe(III), Co(II), Ni(II), and Cu(II) before their determination by flame atomic absorption spectrometry. The optimum pH ranges for quantitative sorption are 6.5-8.0, 6.0-7.0, 6.0-8.0, and 7.0-8.5 for Cu, Fe, Co, and Ni, respectively. All the metal ions can be desorbed with 2 mol L(-1) HCl or HNO3. The sorption capacity ( micromol g(-1) matrix) and preconcentration factor were 226.6, 250; 365.6, 300; 101.8, 150; and 109.0, 250 for Cu, Fe, Co, and Ni, respectively. The lowest concentration for quantitative recovery was 4.0, 3.3, 6.6, and 4.0 ng mL(-1), respectively for the four metal ions. The limits up to which electrolytes NaNO3, NaCl, NaBr, Na2SO4, and Na3PO4 and cations Ca(II) and Mg(II) can coexist with the four metal ions during their sorption without adverse effect are reported. The simultaneous enrichment and determination of all the four metals is possible if the total load of metal ions is less than the sorption capacity. Flame AAS was used to determine the metal ions in underground, tap, and river water samples (RSDcobalt content of pharmaceutical samples (multivitamin tablet) preconcentrated by use of this silica gel matrix and determined by FAAS was found to be 2.00 microg g(-1), with RSDtilde;1.7% (reported concentration level, 1.99 microg g(-1)).

  13. New cobalt(II) and nickel(II) complexes of benzyl carbazate Schiff bases: Syntheses, crystal structures, in vitro DNA and HSA binding studies.

    PubMed

    Nithya, Palanivelu; Helena, Sannasi; Simpson, Jim; Ilanchelian, Malaichamy; Muthusankar, Aathi; Govindarajan, Subbiah

    2016-12-01

    In the present study, new Schiff base complexes with the composition [M(NCS)2(L1)2]·nH2O, where M=Co (n=0) (1) and Ni (n=2) (2); [M(NCS)2(L2)2], M=Co (3) and Ni (4) as well as [M(NCS)2(L3)2], M=Co (5) and Ni (6); (L1=benzyl 2-(propan-2-ylidene)hydrazinecarboxylate, L2=benzyl 2-(butan-2-ylidene)hydrazinecarboxylate and L3=benzyl 2-(pentan-3-ylidene)hydrazinecarboxylate) have been synthesized by a template method. The complexes were characterised by analytical methods, spectroscopic studies, thermal and X-ray diffraction techniques. The structures of all the complexes explore that the metal(II) cation has a trans-planar coordination environment, the monomeric units containing a six-coordinated metal center in octahedral geometry with N-bound isothiocyanate anions coordinated as terminal ligands. Furthermore, the binding of the two Schiff base ligands to the metal centers involves the azomethine nitrogen and the carbonyl oxygen in mutually trans configuration. The binding interactions of all the complexes with Calf thymus-deoxyribonucleic acid (CT-DNA) and human serum albumin (HSA) have been investigated using absorption and emission spectral techniques. The CT-DNA binding properties of these complexes reveal that they bind to CT-DNA through a partial intercalation mode and the binding constant values were calculated using the absorption and emission spectral data. The binding constant values (~10×10(6)moldm(-3)) indicate strong binding of metal complexes with CT-DNA. HSA binding interaction studies showed that the cobalt and nickel complexes can quench the intrinsic fluorescence of HSA through static quenching process. Also, molecular docking studies were supported out to apprehend the binding interactions of these complexes with DNA and HSA which offer new understandings into the experimental model observations. Copyright © 2016 Elsevier B.V. All rights reserved.

  14. Magnetic excitations in an exchange-coupled tetramer cluster of cobalt (II): a study by inelastic neutron scattering

    NASA Astrophysics Data System (ADS)

    Gómez-García, C. J.; Coronado, E.; Borrás-Almenar, J. J.; Aebersold, M.; Güdel, H. U.; Mutka, H.

    1992-06-01

    The polyoxometalate K 10[Co 4(H 2O) 2(PW 9O 34) 2].20H 2O contains a ferromagnetically exchange-coupled tetramer of Co 11 encapsulated in between two diamagnetic molecules (PW 9O 34-9. At 2.5K several inelastic peaks are observed in the energy range 1.5-7 meV, which are assigned to magnetic excitations in the cluster. A tentative interpretation of these data from an anisotropic exchange model yields a cobalt-cobalt interaction of 3meV (24cm -1) and an amount of anisotropy Jxy/ Jz≌0.6. These values are consistent with the magnetic susceptibility measurements.

  15. Unique ligand-radical character of an activated cobalt salen catalyst that is generated by aerobic oxidation of a cobalt(II) salen complex.

    PubMed

    Kurahashi, Takuya; Fujii, Hiroshi

    2013-04-01

    The Co(salen)(X) complex, where salen is chiral N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediamine and X is an external axial ligand, has been widely utilized as a versatile catalyst. The Co(salen)(X) complex is a stable solid that has been conventionally described as a Co(III)(salen)(X) complex. Recent theoretical calculations raised a new proposal that the Co(salen)(H2O)(SbF6) complex contains appreciable contribution from a Co(II)(salen(•+)) electronic structure (Kochem, A.; Kanso, H.; Baptiste, B.; Arora, H.; Philouze, C.; Jarjayes, O.; Vezin, H.; Luneau, D.; Orio, M.; Thomas, F. Inorg. Chem. 2012, 51, 10557-10571), while other theoretical calculations for Co(salen)(Cl) indicated a triplet Co(III)(salen) electronic structure (Kemper, S.; Hrobárik, P.; Kaupp, M.; Schlörer, N. E. J. Am. Chem. Soc. 2009, 131, 4172-4173). However, there have been no experimental data to evaluate these theoretical proposals. We herein report key experimental data on the electronic structure of the Co(salen)(X) complex (X = CF3SO3(-), SbF6(-), and p-MeC6H4SO3(-)). The X-ray crystallography shows that Co(salen)(OTf) has a square-planar N2O2 equatorial coordination sphere with OTf as an elongated external axial ligand. Magnetic susceptibility data indicate that Co(salen)(OTf) complexes belong to the S = 1 spin system. (1)H NMR measurements provide convincing evidence for the Co(II)(salen(•+))(X) character, which is estimated to be about 40% in addition to 60% Co(III)(salen)(X) character. The CH2Cl2 solution of Co(salen)(X) shows an intense near-IR absorption, which is assigned as overlapped transitions from a ligand-to-metal charge transfer in Co(III)(salen)(X) and a ligand-to-ligand charge transfer in Co(II)(salen(•+))(X). The present experimental study establishes that the electronic structure of Co(salen)(X) contains both Co(II)(salen(•+))(X) and Co(III)(salen)(X) character.

  16. In vivo tracing of indium-111 oxine-labeled human peripheral blood mononuclear cells in patients with lymphatic malignancies

    SciTech Connect

    Mueller, C.Z.; Zielinski, C.C.; Linkesch, W.; Ludwig, H.; Sinzinger, H.

    1989-06-01

    The in vivo migration of (/sup 111/In)oxine-labeled peripheral mononuclear cells (PMNC) was studied in 20 patients with various lymphatic malignancies and palpable enlarged lymph nodes. The maximal labeling dose of 10 microCi (0.37 MBq) (/sup 111/In)oxine/10(8) PMNC was found not to adversely influence either cell viability or lymphocyte proliferation in vitro. For in vivo studies, 1.5 X 10(9) PMNC were gained by lymphapheresis and reinjected intravenously after radioactive labeling, 150 microCi (5.55 MBq). The labeling of enlarged palpable lymph nodes was achieved in three out of three patients with Hodgkin's disease and in five out of five with high-malignant lymphoma, whereas three out of seven patients with low malignant lymphoma and no patient with chronic lymphatic leukemia had positive lymph node imaging. We thus conclude that PMNC retain their ability to migrate after (/sup 111/In)oxine labeling and that these cells traffic to involved lymph nodes of some, but not all hematologic malignancies.

  17. Nanocellulose/nanobentonite composite anchored with multi-carboxyl functional groups as an adsorbent for the effective removal of Cobalt(II) from nuclear industry wastewater samples.

    PubMed

    Anirudhan, T S; Deepa, J R; Christa, J

    2016-04-01

    A novel adsorbent, poly(itaconic acid/methacrylic acid)-grafted-nanocellulose/nanobentonite composite [P(IA/MAA)-g-NC/NB] with multi carboxyl functional groups for the effective removal of Cobalt(II) [Co(II)] from aqueous solutions. The adsorbent was characterized using FTIR, XRD, SEM-EDS, AFM and potentiometric titrations before and after adsorption of Co(II) ions. FTIR spectra revealed that Co(II) adsorption on to the polymer may be due to the involvement of COOH groups. The surface morphological changes were observed by the SEM images. The pH was optimized as 6.0. An adsorbent dose of 2.0g/L found to be sufficient for the complete removal of Co(II) from 100mg/L at room temperature. Pseudo-first-order and pseudo-second-order models were tested to describe kinetic data and adsorption of Co(II) follows pseudo-second-order model. The equilibrium attained at 120min. Isotherm studies were conducted and data were analyzed using Langmuir, Freundlich and Sips isotherm models and best fit was Sips model. Thermodynamic study confirmed endothermic and physical nature of adsorption of the Co(II) onto the adsorbent. Desorption experiments were done with 0.1MHCl proved that without significant loss in performance adsorbent could be reused for six cycles. The practical efficacy and effectiveness of the adsorbent were tested using nuclear industrial wastewater. A double stage batch adsorption system was designed from the adsorption isotherm data of Co(II) by constructing operating lines.

  18. Solid-phase extraction of cobalt(II) from lithium chloride solutions using a poly(vinyl chloride)-based polymer inclusion membrane with Aliquat 336 as the carrier.

    PubMed

    Kagaya, Shigehiro; Cattrall, Robert W; Kolev, Spas D

    2011-01-01

    The extraction of cobalt(II) from solutions containing various concentrations of lithium chloride, hydrochloric acid, and mixtures of lithium chloride plus hydrochloric acid is reported using a poly(vinyl chloride) (PVC)-based polymer inclusion membrane (PIM) containing 40% (w/w) Aliquat 336 as a carrier. The extraction from lithium chloride solutions and mixtures with hydrochloric acid is shown to be more effective than extraction from hydrochloric acid solutions alone. The solution concentrations giving the highest amounts of extraction are 7 mol L(-1) for lithium chloride and 8 mol L(-1) lithium chloride plus 1 mol L(-1) hydrochloric acid for mixed solutions. Cobalt(II) is easily stripped from the membrane using deionized water. The cobalt(II) species extracted into the membrane are CoCl(4)(2-) for lithium chloride solutions and HCoCl(4)(-) for mixed solutions; these form ion-pairs with Aliquat 336. It is also shown that both lithium chloride and hydrochloric acid are extracted by the PIM and suppress the extraction of cobalt(II) by forming ion-pairs in the membrane (i.e. R(3)MeN(+)·HCl(2)(-) for hydrochloric acid and R(3)MeN(+)·LiCl(2)(-) for lithium chloride).

  19. Cobalt poisoning

    MedlinePlus

    ... the wear and tear of some cobalt/chromium metal-on-metal hip implants. This type of implant is an ... hip socket that is created by fitting a metal ball into a metal cup. Sometimes, metal particles ( ...

  20. Low-temperature CVD of iron, cobalt, and nickel nitride thin films from bis[di(tert-butyl)amido]metal(II) precursors and ammonia

    SciTech Connect

    Cloud, Andrew N.; Abelson, John R.; Davis, Luke M.; Girolami, Gregory S.

    2014-03-15

    Thin films of late transition metal nitrides (where the metal is iron, cobalt, or nickel) are grown by low-pressure metalorganic chemical vapor deposition from bis[di(tert-butyl)amido]metal(II) precursors and ammonia. These metal nitrides are known to have useful mechanical and magnetic properties, but there are few thin film growth techniques to produce them based on a single precursor family. The authors report the deposition of metal nitride thin films below 300 °C from three recently synthesized M[N(t-Bu){sub 2}]{sub 2} precursors, where M = Fe, Co, and Ni, with growth onset as low as room temperature. Metal-rich phases are obtained with constant nitrogen content from growth onset to 200 °C over a range of feedstock partial pressures. Carbon contamination in the films is minimal for iron and cobalt nitride, but similar to the nitrogen concentration for nickel nitride. X-ray photoelectron spectroscopy indicates that the incorporated nitrogen is present as metal nitride, even for films grown at the reaction onset temperature. Deposition rates of up to 18 nm/min are observed. The film morphologies, growth rates, and compositions are consistent with a gas-phase transamination reaction that produces precursor species with high sticking coefficients and low surface mobilities.

  1. Effect of three bis-pyridyl-bis-amide ligands with various spacers on the structural diversity of new multifunctional cobalt(II) coordination polymers

    SciTech Connect

    Lin, Hong-Yan; Lu, Huizhe; Le, Mao; Luan, Jian; Wang, Xiu-Li; Liu, Guocheng; Zhang, Juwen

    2015-03-15

    Three new cobalt(II) coordination polymers [Co{sub 2}(1,4-NDC){sub 2}(3-bpye)(H{sub 2}O)] (1), [Co(1,4-NDC)(3-bpfp)(H{sub 2}O)] (2) and [Co(1,4-NDC)(3-bpcb)] (3) [3-bpye=N,N′-bis(3-pyridinecarboxamide)-1,2-ethane, 3-bpfp=bis(3-pyridylformyl)piperazine, 3-bpcb=N,N′-bis(3-pyridinecarboxamide)-1,4-benzene, and 1,4-H{sub 2}NDC=1,4-naphthalenedicarboxylic acid] have been hydrothermally synthesized. The structures of complexes 1–3 have been determined by X-ray single crystal diffraction analyses and further characterized by infrared spectroscopy (IR), powder X-ray diffraction (PXRD) and thermogravimetric analyses (TGA). Complex 1 is a 3D coordination structure with 8-connected (4{sup 20}.6{sup 8}) topology constructed from 3D [Co{sub 2}(1,4-NDC){sub 2}(H{sub 2}O)]{sub n} framework and bidentate 3-bpye ligands. Complex 2 shows 1D “cage+cage”-like chain formed by 1D [Co{sub 2}(1,4-NDC){sub 2}]{sub n} ribbon chains and [Co{sub 2}(3-bpfp){sub 2}] loops, which are further linked by hydrogen bonding interactions to form a 3D supramolecular network. Complex 3 displays a 3D coordination network with a 6-connected (4{sup 12}.6{sup 3}) topology based on 2D [Co{sub 2}(1,4-NDC){sub 2}]{sub n} layers and bidentate 3-bpcb bridging ligands. The influences of different bis-pyridyl-bis-amide ligands with various spacers on the structures of title complexes are studied. Moreover, the fluorescent properties, electrochemical behaviors and magnetic properties of complexes 1–3 have been investigated. - Graphical abstract: Three multifunctional cobalt(II) complexes constructed from three bis-pyridyl-bis-amide and 1,4-naphthalenedicarboxylic acid have been hydrothermally synthesized and characterized. The fluorescent, electrochemical and magnetic properties of 1–3 have been investigated. - Highlights: • Three multifunctional cobalt(II) complexes based on various bis-pyridyl-bis-amide ligands. • Complex 1 is a 3D coordination structure with 8-connected (4{sup 20}.6{sup 8

  2. Part I. Synthesis and applications of molecular sieves. Part II. The effect of temperature and support in reduction of cobalt oxide: An in situ XRD study

    NASA Astrophysics Data System (ADS)

    Garces Trujillo, Luis Javier

    Part I. Alkylation of aniline (PhNH2) with methanol (MeOH) over co-crystallized zeolite RHO-Zeolite X (FAU) and over zeolite Linde Type L (Sr,K-LTL) as catalysts has been studied. Co-crystallized zeolite RHO-Zeolite X (FAU) favors the formation of N,N-dimethylaniline (NNDMA), with high selectivity >90%, having an advantage over pure zeolite X(FAU) of staying active even after 10 h of reaction. Activity of co-crystallized RHO-Zeolite X (FAU) is higher than that for Sr,K-LTL in terms of production of NNDMA. Octahedral molecular sieves (OMS-2) have been reported as catalysts for oxidation reactions. Effects of using polyvinyl alcohol (PVA) and polyvinyl pyrrolidone (PVP) in the synthesis of OMS-2 have been studied. Structure of OMS-2 was kept when PVA or PVP were used as indicated by XRD and FTIR data. PVA and PVP were useful to improve the film hardness of OMS-2 applied on glass surfaces as measured by the pencil hardness test, and Knoop microhardness test. By using PVA or PVP as non-chelating agents, an increase in surface area from 59 (m2/g) to 114 (m2/g), a decrease in particle size, from 29.8 nm to 12.1 nm, and a hardness value of 4H using the pencil hardness test, and 17.73 HK by Knoops micro hardness tests for OMS-2 prepared with PVA were observed. ZK-5 (KFI) molecular sieve was synthesized in the K2O: SrO: Al2O3: SiO2: 160 H2O: THF system using conventional hydrothermal heating. Products were characterized by XRD, TGA, FESEM, EDX and TPD-MS. Molar ratios of THF/Al2O3 from 0.4 to 1.0 gives best results in terms of crystallinity and purity for the prepared ZK-5. Part II. Reduction of cobalt oxide (Co 3O4) at different temperatures and in combination with different modifiers and supported on gamma-Al2O3 was monitored by in situ X-ray diffraction. Complete reduction of cobalt oxide to the (hcp) phase is observed at 250°C. Different reduction sequence can give different results in terms of crystalline phase obtained for cobalt even if the same maximum reduction

  3. Catalytic hydrogen evolution in cathodic stripping voltammetry on a mercury electrode in the presence of cobalt(II) ion and phenylthiourea or thiourea.

    PubMed

    Spătaru, N; Bănica, F G

    2001-11-01

    The system Co(II)-phenylthiourea (PTU)-borax buffer was investigated by cathodic stripping voltammetry (CSV) at a hanging mercury drop electrode. The results of the voltammetric measurements showed that the presence of both PTU and Co(II) gives rise to a new irreversible peak at about -1.5 V. Based upon our previous results obtained in the study of other sulfur compounds and the sulfide ion itself, the peak was ascribed to the catalytic hydrogen evolution superimposed on the reduction of the coordinated Co(II) ion. The catalyst itself is a Co(II) complex with the sulfide ion produced by the decomposition of the analyte during the deposition step. The influence of PTU and cobalt concentration, accumulation conditions and stripping parameters was investigated and complementary data on thiourea are included. The results showed that the measurement of the catalytic hydrogen evolution peak current can be used as a basis for a simple, accurate and rapid method for the determination of PTU within the concentration range 10-100 nM. The catalytic method is relatively free of interferences and could be a suitable alternative for cases in which the stripping peak due to mercury ion reduction in the accumulated mercury compound is disturbed by some interference.

  4. XAFS Studies of Cobalt(II) Binding by Solid Peat and Soil-derived Humic Acids and Plant-derived Humic Acid-like Substances

    SciTech Connect

    Ghabbour,E.; Scheinost, A.; Davies, G.

    2007-01-01

    This work has examined cobalt(II) binding by a variety of solid humic acids (HAs) isolated from peat, plant and soil sources at temperatures down to 60 K. The results confirm that X-ray absorption near-edge spectroscopy (XANES) measurements cannot distinguish between aquo and carboxylato ligands in the inner coordination sphere of Co(II). However, between 1 and 2 inner-sphere carboxylato ligands can be detected in all the peat, plant and soil-derived HA samples by extended X-ray absorption fine structure (EXAFS) measurements, indicating inner-sphere coordination of HA-bound Co(II). The precision of C(carboxylate) detection is limited by the extent and quality of the data and the contribution from inner-sphere O to the Fourier transformed peaks used to detect carbon. Putative chelate ring formation is consistent with a relatively negative entropy change in step A, the stronger Co(II) binding step by HA functional groups, and could relate to 'non-exchangeable' metal binding by HSs.

  5. XAFS studies of cobalt(II) binding by solid peat and soil-derived humic acids and plant-derived humic acid-like substances.

    PubMed

    Ghabbour, Elham A; Scheinost, Andreas C; Davies, Geoffrey

    2007-02-01

    This work has examined cobalt(II) binding by a variety of solid humic acids (HAs) isolated from peat, plant and soil sources at temperatures down to 60K. The results confirm that X-ray absorption near-edge spectroscopy (XANES) measurements cannot distinguish between aquo and carboxylato ligands in the inner coordination sphere of Co(II). However, between 1 and 2 inner-sphere carboxylato ligands can be detected in all the peat, plant and soil-derived HA samples by extended X-ray absorption fine structure (EXAFS) measurements, indicating inner-sphere coordination of HA-bound Co(II). The precision of C(carboxylate) detection is limited by the extent and quality of the data and the contribution from inner-sphere O to the Fourier transformed peaks used to detect carbon. Putative chelate ring formation is consistent with a relatively negative entropy change in step A, the stronger Co(II) binding step by HA functional groups, and could relate to 'non-exchangeable' metal binding by HSs.

  6. Structural and spectroscopic characterization of iron(II), cobalt(II), and nickel(II) ortho-dihalophenolate complexes: insights into metal-halogen secondary bonding.

    PubMed

    Machonkin, Timothy E; Boshart, Monica D; Schofield, Jeremy A; Rodriguez, Meghan M; Grubel, Katarzyna; Rokhsana, Dalia; Brennessel, William W; Holland, Patrick L

    2014-09-15

    Metal complexes incorporating the tris(3,5-diphenylpyrazolyl)borate ligand (Tp(Ph2)) and ortho-dihalophenolates were synthesized and characterized in order to explore metal-halogen secondary bonding in biorelevant model complexes. The complexes Tp(Ph2)ML were synthesized and structurally characterized, where M was Fe(II), Co(II), or Ni(II) and L was either 2,6-dichloro- or 2,6-dibromophenolate. All six complexes exhibited metal-halogen secondary bonds in the solid state, with distances ranging from 2.56 Å for the Tp(Ph2)Ni(2,6-dichlorophenolate) complex to 2.88 Å for the Tp(Ph2)Fe(2,6-dibromophenolate) complex. Variable temperature NMR spectra of the Tp(Ph2)Co(2,6-dichlorophenolate) and Tp(Ph2)Ni(2,6-dichlorophenolate) complexes showed that rotation of the phenolate, which requires loss of the secondary bond, has an activation barrier of ~30 and ~37 kJ/mol, respectively. Density functional theory calculations support the presence of a barrier for disruption of the metal-halogen interaction during rotation of the phenolate. On the other hand, calculations using the spectroscopically calibrated angular overlap method suggest essentially no contribution of the halogen to the ligand-field splitting. Overall, these results provide the first quantitative measure of the strength of a metal-halogen secondary bond and demonstrate that it is a weak noncovalent interaction comparable in strength to a hydrogen bond. These results provide insight into the origin of the specificity of the enzyme 2,6-dichlorohydroquinone 1,2-dioxygenase (PcpA), which is specific for ortho-dihalohydroquinone substrates and phenol inhibitors.

  7. Growth mechanism of Cobalt(II) Phthalocyanine(CoPc) thin films on SiO{sub 2} and muscovite substrates

    SciTech Connect

    Gedda, Murali; Subbarao, Nimmakayala V. V.; Goswami, Dipak K.

    2014-01-28

    Thin films of Cobalt(II) Phthalocyanine (CoPc) were grown by thermal evaporation technique on two different substrates namely SiO{sub 2} and atomically cleaned muscovite mica(001) at various substrate temperatures. Deposition rate has been maintained to 0.3Å/sec during the growth of the films. The growth process is studied by means of atomic force microscopy (AFM). Films on SiO{sub 2} exhibit only three-dimensional islands and uniformity of these islands improved with substrate temperatures, whereas films on mica (001) consist of long oriented percolated structures. The results revealed that the growth mechanism of CoPc strongly depends on substrate temperatures as well as nature of substrate used. Optical properties were characterized by UV-Visible spectroscopy and structural properties were studied using X-ray diffraction.

  8. Studies on the Interaction Mechanism of 1,10-Phenanthroline Cobalt(II) Complex with DNA and Preparation of Electrochemical DNA Biosensor

    PubMed Central

    Niu, Shuyan; Li, Feng; Zhang, Shusheng; Wang, Long; Li, Xuemei; Wang, Shiying

    2006-01-01

    Fluorescence spectroscopy and ultraviolet (UV) spectroscopy techniques coupled with cyclic voltammetry (CV) were used to study the interaction between salmon sperm DNA and 1,10-Phenanthroline cobalt(II) complex, [Co(phen)2(Cl)(H2O)]Cl·H2O, where phen = 1,10-phenanthroline. The interaction between [Co(phen)2(Cl)(H2O)]+ and double-strand DNA (dsDNA) was identified to be intercalative mode. An electrochemical DNA biosensor was developed by covalent immobilization of probe single-strand DNA (ssDNA) related to human immunodeficiency virus (HIV) on the activated glassy carbon electrode (GCE). With [Co(phen)2(Cl)(H2O)]+ being the novel electrochemical hybridization indicator, the selectivity of ssDNA-modified electrode was investigated and selective detection of complementary ssDNA was achieved using differential pulse voltammetry (DPV).

  9. Poly[di-μ(2)-aqua-μ(5)-(pyridine-2,6-dicarboxyl-ato)-μ(3)-(pyridine-2,6-dicarboxyl-ato)-cobalt(II)disodium].

    PubMed

    Boyko, Alexander N; Golenya, Irina A; Izotova, Yulia A; Haukka, Matti; Prisyazhnaya, Elena V

    2011-12-01

    In the title compound, [CoNa(2)(C(7)H(3)NO(4))(2)(H(2)O)(2)](n), the Co(II) atom is coordinated by two pyridine N atoms and four carboxyl-ate O atoms from two doubly deprotonated pyridine-2,6-dicarboxyl-ate ligands in a distorted octa-hedral geometry. One Na(+) cation is coordinated by three carboxyl-ate O atoms and two water mol-ecules and the other is coordinated by five carboxyl-ate O atoms and two water mol-ecules in an irregular geometry. The bis-(pyridine-2,6-dicarboxyl-ato)cobalt complex units are connected by Na(+) cations and bridging water mol-ecules into a three-dimensional coordination network. O-H⋯O hydrogen bonds are formed between the water mol-ecules and the carboxyl-ate O atoms.

  10. The investigation of the solvent effect on coordination of nicotinato ligand with cobalt(II) complex containing tris(2-benzimidazolylmethyl)amine: A computational study

    NASA Astrophysics Data System (ADS)

    Sayin, Koray; Karakaş, Duran

    2014-11-01

    The electronic structure of [Co(ntb)(nic)]+ complex ion are optimized by using density functional theory (DFT) method with mix basis set. Where (ntb) represents tris(2-benzimidazolylmethyl)amine ligand and (nic) is the anion of nicotinic acids. Six different fields, vacuum, chloroform, butanonitrile, methanol, water and formamide solvents are used in these calculations. The calculated structural parameters indicate that (nic) ligand coordinates to cobalt(II) containing (ntb) ligand with one oxygen atom in butanonitrile, methanol, water and formamide solvents but coordinates with two oxygen atoms in vacuum. These results are supported with IR, UV and 1H NMR spectra. According to the calculated results, the geometry of [Co(ntb)(nic)]+ complex ion is distorted octahedral in vacuum while the geometry is distorted square pyramidal in the all other solvents. Distorted octahedral [Co(ntb)(nic)]+ complex ion have not been synthesized as experimentally and it is predicted with computational chemistry methods.

  11. Slow Magnetic Relaxations in Cobalt(II) Tetranitrate Complexes. Studies of Magnetic Anisotropy by Inelastic Neutron Scattering and High-Frequency and High-Field EPR Spectroscopy

    DOE PAGES

    Chen, Lei; Cui, Hui-Hui; Stavretis, Shelby E.; ...

    2016-12-07

    We synthesized and studied three mononuclear cobalt(II) tetranitrate complexes (A)2[Co(NO3)4] with different countercations, Ph4P+ (1), MePh3P+ (2), and Ph4As+ (3), using X-ray single-crystal diffraction, magnetic measurements, inelastic neutron scattering (INS), high-frequency and high-field EPR (HF-EPR) spectroscopy, and theoretical calculations. Furthermore, the X-ray diffraction studies reveal that the structure of the tetranitrate cobalt anion varies with the countercation. 1 and 2 exhibit highly irregular seven-coordinate geometries, while the central Co(II) ion of 3 is in a distorted-dodecahedral configuration. The sole magnetic transition observed in the INS spectroscopy of 1–3 corresponds to the zero-field splitting (2(D2 + 3E2)1/2) from 22.5(2) cm–1 inmore » 1 to 26.6(3) cm–1 in 2 and 11.1(5) cm–1 in 3. The positive sign of the D value, and hence the easy-plane magnetic anisotropy, was demonstrated for 1 by INS studies under magnetic fields and HF-EPR spectroscopy. The combined analyses of INS and HF-EPR data yield the D values as +10.90(3), +12.74(3), and +4.50(3) cm–1 for 1–3, respectively. Frequency- and temperature-dependent alternating-current magnetic susceptibility measurements reveal the slow magnetization relaxation in 1 and 2 at an applied dc field of 600 Oe, which is a characteristic of field-induced single-molecule magnets (SMMs). Finally, the electronic structures and the origin of magnetic anisotropy of 1–3 were revealed by calculations at the CASPT2/NEVPT2 level.« less

  12. Binding, electrochemical activation, and cleavage of DNA by cobalt(II) tetrakis-N-methylpyridyl porphyrin and its beta-pyrrole brominated derivative.

    PubMed

    Yellappa, Shivaraj; Seetharamappa, Jaldappagari; Rogers, Lisa M; Chitta, Raghu; Singhal, Ram P; D'Souza, Francis

    2006-01-01

    The binding of nucleic acids by water-soluble cobalt(II) tetrakis-N-methylpyridyl porphyrin, (TMPyP)Co, and its highly electron-deficient derivative cobalt(II) tetrakis-N-methyl pyridyl-beta-octabromoporphyrin, (Br(8)TMPyP)Co, was investigated by UV-visible absorption, circular dichroism (CD), and electrochemical and gel electrophoresis methods. The changes of the absorption spectra during the titration of these complexes with polynucleotides revealed a shift in the absorption maxima and a hypochromicity of the porphyrin Soret bands. The intrinsic binding constants were found to be in the range of 10(5)-10(6) M(-1). These values were higher for the more electron-deficient (Br(8)TMPyP)Co. Induced CD bands were noticed in the Soret region of the complexes due to the interaction of these complexes with different polynucleotides, and an analysis of the CD spectra supported a mainly external mode of binding. Electrochemical studies revealed the cleavage of polynucleotides by (TMPyP)Co and (Br(8)TMPyP)Co in the presence of oxygen preferentially at the A-T base pair region. Gel electrophoresis experiments further supported the cleavage of nucleic acids. The results indicate that the beta-pyrrole brominated porphyrin, (Br(8)TMPyP)Co, binds strongly and cleaves nucleic acids efficiently as compared with (TMPyP)Co. This electrolytic procedure offers a unique tool in biotechnology for cleaving double-stranded DNA with specificity at the A-T regions.

  13. Series of Hydrated Heterometallic Uranyl-Cobalt(II) Coordination Polymers with Aromatic Polycarboxylate Ligands: Formation of U═O-Co Bonding upon Dehydration Process.

    PubMed

    Falaise, Clément; Delille, Jason; Volkringer, Christophe; Vezin, Hervé; Rabu, Pierre; Loiseau, Thierry

    2016-10-06

    Five new heterometallic UO2(2+)-Co(2+) coordination polymers have been obtained by hydrothermal reactions of uranyl nitrate and metallic cobalt with aromatic polycarboxylic acids. Single-crystal X-ray diffraction reveals the formation of four 3D frameworks with the mellitate (noted mel) ligand and one 2D network with the isophthalate (noted iso) ligand. The compounds [(UO2(H2O))2Co(H2O)4(mel)]·4H2O (1), [UO2Co(H2O)4(H2mel)]·2H2O (2), and [(UO2(H2O))2Co(H2O)4(mel)] (4) consist of 3D frameworks built up from the connection of mellitate ligands and mononuclear metallic centers. These three compounds exhibit two types of geometry for the uranyl cation: pentagonal bipyramidal environment for 1 and 4, and hexagonal bipyramidal environment for 2. Using the mellitate ligand, the uranyl dinuclear unit is isolated in the compound [(UO2)2(OH)2(Co(H2O)4)2(mel)]·2H2O (3). Due to their 2D framework and the presence of uncoordinated cobalt(II) cations, the compound [(UO2)(iso)3][Co(H2O)6]·3(H2O) (5) is drastically different than the previous one. The thermal behavior of compounds 1, 2, and 3 has been studied by thermogravimetric analysis, X-ray thermodiffraction, and in situ infrared. By heating, the dehydration of compounds 1 and 2 promotes two structural transitions (1 → 1' and 2 → 2'). The crystal structures of [(UO2(H2O))2Co(H2O)2(mel)] (1') and [(UO2)Co(H2mel)] (2') were determined by single-crystal X-ray diffraction; each of them presents a heterometallic interaction between uranyl bond and the Co(II) center. Due to the rarely reported coordination environment for the cobalt center in compound 2' (square pyramidal configuration), the magnetic properties and EPR characterizations of the compounds 2 and 2' were also investigated.

  14. Synthesis, crystal structure, antibacterial activity and theoretical studies on a novel mononuclear cobalt(II) complex based on 2,4,6-tris(2-pyridyl)-1,3,5-triazine ligand

    NASA Astrophysics Data System (ADS)

    Maghami, Mahboobeh; Farzaneh, Faezeh; Simpson, Jim; Ghiasi, Mina; Azarkish, Mohammad

    2015-08-01

    A cobalt complex was prepared from CoCl2·6H2O and 2,4,6-tris(2-pyridyl)-1,3,5-triazine (tptz) in methanol and designated as [Co(tptz)(CH3OH)Cl2]·CH3OH·0.5H2O (1). It was characterized by several techniques including TGA analysis and FT-IR, UV-Vis and 1H NMR spectral studies. The crystal structure of 1 was determined by single-crystal X-ray diffraction. The Co(II) metal center in 1 is six coordinated with a distorted octahedral geometry. The tptz ligand is tridentate and coordinates to the cobalt through coplanar nitrogen atoms from the triazine and two pyridyl rings. Two chloride anions and a methanol molecule complete the inner coordination sphere of the metal ion. The optimized geometrical parameters obtained by DFT calculation are in good agreement with single XRD data. The in vitro antibacterial activity of various tptz complexes of Co(II), Ni(II), Cu(II), Mn(II) and Rh(III) were evaluated against Gram-positive (Bacillus subtilis, Staphylococcus aureus and Gram-negative (Escherichia coli and Pseudomonas aeruginosa) bacteria. Whereas all complexes exhibited good activity in comparison to standard antibacterial drugs, the inhibitory effects of complexes were found to be more than that of the parent ligand. Overall, the obtained results strongly suggest that the cobalt(II) complex is a suitable candidate for counteracting antibiotic resistant microorganisms.

  15. Endothelial cell labeling with indium-111-oxine as a marker of cell attachment to bioprosthetic surfaces

    SciTech Connect

    Sharefkin, J.B.; Lather, C.; Smith, M.; Rich, N.M.

    1983-03-01

    Canine vascular endothelium labeled with indium-111-oxine was used as a marker of cell attachment to vascular prosthetic surfaces with complex textures. Primarily cultured and freshly harvested endothelial cells both took up the label rapidly. An average of 72% of a 32 micro Ci labeling dose was taken up by 1.5 X 10(6) cells in 10 min in serum-free medium. Over 95% of freshly labeled cells were viable by trypan blue tests and only 5% of the label was released after 1 h incubations at 37 degrees C. Labeled and unlabeled cells had similar rates of attachment to plastic dishes. Scanning electron microscopic studies showed that labeled cells retained their ability to spread on tissue culture dishes even at low (1%) serum levels. Labeled endothelial cells seeded onto Dacron or expanded polytetrafluoroethylene vascular prostheses by methods used in current surgical models could be identified by autoradiography of microscopic sections of the prostheses, and the efficiency of cell attachment to the prosthesis could be measured by gamma counting. Indium-111 labeling affords a simple and rapid way to measure initial cell attachment to, and distribution on, vascular prosthetic materials. The method could also allow measurement of early cell loss from a flow surface in vivo by using external gamma imaging.

  16. In vitro effects on Indium-111-Oxine labeled leukocytes functions of N-etilmycin

    SciTech Connect

    Iacovo, R.D.; Perna, M.; Esposito, G.; Polese, C.; Frizzi, L.

    1985-05-01

    In order to study in vitro chemotaxis, phagocytosis and bactericydal efficiencies of granulocytes (PMN) and monocytes (Mo) of cancer patients with solid tumours, the authors have undertaken the evaluation of a method of measuring PMN and Mo chemotaxis with modified Boyden chambers, using In-111-oxine. The tests were performed in order to evaluate the interference of N-etilmycin with leukocyte functions, a currently fashionable antibiotic used in the treatment of gram-negative infections. The results both compare well with the visual method and are objective. Cancer patients, disease-free for a minimum of one year, were compared and evidenced normal chemotaxis and normal controls. No difference between the two groups was found (20.46% of those tested). The addition of N-etilmy-cin (6..mu..g/ml) to PMN and Mo further decreased the chemotaxis from 20.46% to 16.07% (t=2.81, P=0.0102). The addition of 30..mu..g/ml further decreased the chemotaxis from the mean control values to 5.925% (t=4.55,P 1%). The use of N-etilmycin in disease-free cancer patients should be avoided in the possible event of tumour enhancement.

  17. Cobalt(II) complexation with small biomolecules as studied by 57Co emission Mössbauer spectroscopy

    NASA Astrophysics Data System (ADS)

    Kamnev, Alexander A.; Perfiliev, Yurii D.; Kulikov, Leonid A.; Tugarova, Anna V.; Kovács, Krisztina; Homonnay, Zoltán; Kuzmann, Ernő

    2017-02-01

    In the emission (57Co) variant of Mössbauer spectroscopy (EMS), the 57Co radionuclide (with a half-life of 9 months) is used that undergoes a nuclear decay 57Co → 57Fe via electron capture followed by the emission of a γ-quantum, the energy of which is modified by the chemical state and the close coordination environment of the parent 57Co atom. While EMS has been used largely in materials science and nuclear chemistry, its high sensitivity can also be of great advantage in revealing fine structural features and for speciation analysis of biological complexes, whenever the 57Co2 + cation can be used directly as the coordinating metal or as a substitute for native cobalt or other metal ions. As such EMS applications are yet rare, in order to reliably interpret emission spectra of sophisticated 57Co2 +-doped biosystems, model EMS studies of simple cobalt biocomplexes are necessary. In this work, EMS spectroscopic data are analysed and discussed for 57Co2 + complexes with a range of small biomolecules of different structures, including 4-n-hexylresorcinol, homoserine lactone and a few amino acids (spectra measured in rapidly frozen dilute aqueous solutions or in the dried state at T = 80 K). The EMS data obtained are discussed with regard to the available literature data related to the coordination modes of the biocomplexes under study.

  18. 3,4-Dimethyl diphenyldithiophosphate of mononuclear cobalt(II) with N-donor ligands: Synthesis, structural characterization, DFT and antibacterial studies

    NASA Astrophysics Data System (ADS)

    Kumar, Sandeep; Kour, Gurpreet; Schreckenbach, Georg; Andotra, Savit; Hundal, Geeta; Sharma, Vishal; Jaglan, Sundeep; Pandey, Sushil K.

    2017-08-01

    3,4-Dimethyl diphenyldithiophosphate of cobalt(II) with N-donor ligands [{(ArO)2PS2}2CoL2] [Ar = 3,4-(CH3)2C6H3 (1-3); L = C5H5N (1), 3,4-(CH3)2C5H3N (2) and 4-(C2H5)C5H4N (3)] have been synthesized and characterized by elemental analyses, infrared spectroscopy (IR), powder X-ray diffraction (PXRD) and single crystal X-ray analysis. Complex 1 crystallizes in the monoclinic space group P21/n whereas complexes 2 and 3 crystallize in the triclinic space group Pbar1. The crystal structures of complexes 1-3 reveal mononuclear units with the Co(II) center chelated in bidentate fashion by four S atoms of the two diphenyldithiophosphate ligands. The N atoms from two donor ligands are axially coordinated, leading to distorted octahedral geometry around Co(II). The complexes have been optimized using density functional theory (DFT), structural parameters have been calculated, and the energy gaps of the frontier orbitals (HOMO-LUMO) have been predicted. Mayer bond orders have also been calculated. Structural parameters from the crystallographic and DFT studies are in good agreement with each other. To explore the biological potential, complexes were evaluated for their antibacterial activity against three bacterial strains. The bacterial growth inhibition capacity of the ligand and complexes followed the order of 3 > 2 > 1 > L1.

  19. Effects of the host matrix on the 57Fe-species produced through EC-decay in 57Co-labelled tris(phenanthroline) cobalt (II) perchlorate.

    PubMed

    Endo, K; Amano, M; Sano, H

    1979-04-01

    Emission Mössbauer spectroscopic studies of 57Co-labelled [Co(phen)3]clO4)2 in host matrices [M(II)(phen)3](ClO4)2(M=Co, Fe, and Ni) indicate that the relative intensities of the anomalous species produced through the EC-decay depend on the kind of the host matrix. The largest intensity was observed with the cobalt (II) matrix, and the smallest with the iron (II) matrix. Emission spectra of 57Co-labelled [Co(2-CH3-phen)3](ClO4)2 2H2O in the matrix of [Fe(2-CH3-phen)3](ClO4)2 were also studied. The high-spin state (5T2) was predominantly observed at 4.2 K in the emission spectrum, while the low-spin state (1A1) was mainly observed in the absorption spectrum at 78 K. The results are discussed in terms of the stability of the lattice.

  20. Synthesis, physico-chemical studies of manganese(II), cobalt(II), nickel(II), copper(II) and zinc(II) complexes with some p-substituted acetophenone benzoylhydrazones and their antimicrobial activity.

    PubMed

    Singh, Vinod P; Singh, Shweta; Katiyar, Anshu

    2009-04-01

    Complexes of the type [M(pabh)(H2O)Cl], [M(pcbh)(H2O)Cl] and [M(Hpabh)(H2O)2 (SO4)] where, M = Mn(II), Co(II), Ni(II), Cu(II) and Zn(II); Hpabh = p-amino acetophenone benzoyl hydrazone and Hpcbh = p-chloro acetophenone benzoyl hydrazone have been synthesized and characterized with the help of elemental analyses, electrical conductance, magnetic susceptibility measurements, electronic, ESR and IR spectra, thermal (TGA & DTA) and X-ray diffraction studies. Co(II), Ni(II) and Cu(II) chloride complexes are square planar, whereas their sulfate complexes have spin-free octahedral geometry. ESR spectra of Cu(II) complexes with Hpabh are axial and suggest d(x(2)-y(2) as the ground state. The ligand is bidentate bonding through > C = N--and deprotonated enolate group in all the chloro complexes, whereas, >C = N and >C = O groups in all the sulfato complexes. Thermal studies (TGA & DTA) on [Cu(Hpabh)(H2O)2(SO4)] indicate a multistep decomposition pattern, which are both exothermic and endothermic in nature. X-ray powder diffraction parameters for [Co(pabh)(H2O)Cl] and [Ni(Hpabh)(H2O)2(SO4)] correspond to tetragonal and orthorhombic crystal lattices, respectively. The ligands as well as their complexes show a significant antifungal and antibacterial activity. The metal complexes are more active than the ligand.

  1. [Suppression of activity of Candida albicans proteinases by cobalt chloride].

    PubMed

    Kutyreva, M P; Mukhametzianova, A R; Ulakhovich, N A

    2012-01-01

    Influence of cobalt (II) chloride on the system of Candida albicans proteinase (SAP C. alb.) (both in solution and immobilized on a surface of nitrocellulose membranes) has been investigated. In solution cobalt chloride inactivated inducible but not constitute enzyme. In the heterogenous sytem proteolitical effect of the cobalt ion on inductible proteinase was also observed.

  2. Anisotropic Fermi couplings due to large unquenched orbital angular momentum: Q-band (1)H, (14)N, and (11)B ENDOR of bis(trispyrazolylborate) cobalt(II).

    PubMed

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

    2009-08-05

    We report Q-band ENDOR of (1)H, (14)N, and (11)B at the g( parallel) extreme of the EPR spectrum of bis(trispyrazolylborate) cobalt(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( parallel) = 8.48, g( perpendicular) = 1.02). The large g-anisotropy is shown to result in large dipolar couplings near g( parallel) and uniquely anisotropic (14)N Fermi couplings, which arise from spin transferred to the nitrogen 2s orbital (2.2%) via antibonding interactions with singly occupied metal d(x(2)-y(2)) and d(z(2)) orbitals. Large, well-resolved (1)H and (11)B dipolar couplings were also observed. Taken in concert with our previous X-band ENDOR measurements at g( perpendicular) ( Myers, W. K.; 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 approximately 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 (11)B quadrupolar coupling showed approximately 30% electronic inequivalence between the B-H and B-C sp(3) bonds. This is the first comprehensive ENDOR study of any hs Co(II) species and lays the foundation for future development.

  3. Cobalt superalloy

    SciTech Connect

    Crook, P.

    1983-11-15

    Disclosed is a cobalt-base superalloy containing about 32% cobalt, 8% nickel, 26.5% chromium, 2.5% tungsten, 5% niobium, about 1% each manganese and silicon, about 0.4% carbon, and the balance about 23% iron plus incidental impurities and modifiers normally found in alloys of this class. The alloy is readily processed in the form of wrought products, castings, metal powder and all forms of welding and hardfacing materials. The outstanding characteristics of the new alloy include the resistance to cavitation erosion and galling, low cost and minimal use of strategic metals.

  4. Trigonal Prismatic Tris-pyridineoximate Transition Metal Complexes: A Cobalt(II) Compound with High Magnetic Anisotropy.

    PubMed

    Pavlov, Alexander A; Savkina, Svetlana A; Belov, Alexander S; Nelyubina, Yulia V; Efimov, Nikolay N; Voloshin, Yan Z; Novikov, Valentin V

    2017-06-19

    High magnetic anisotropy is a key property of paramagnetic shift tags, which are mostly studied by NMR spectroscopy, and of single molecule magnets, for which magnetometry is usually used. We successfully employed both these methods in analyzing magnetic properties of a series of transition metal complexes, the so-called clathrochelates. A cobalt complex was found to be both a promising paramagnetic shift tag and a single molecule magnet because of it having large axial magnetic susceptibility tensor anisotropy at room temperature (22.5 × 10(-32) m(3) mol(-1)) and a high effective barrier to magnetization reversal (up to 70.5 cm(-1)). The origin of this large magnetic anisotropy is a negative value of zero-field splitting energy that reaches -86 cm(-1) according to magnetometry and NMR measurements.

  5. Sonochemical synthesis of a new cobalt(II) complex: Crystal structure, thermal behavior, Hirshfeld surface analysis and its usage as precursor for preparation of CoO/Co3O4 nanoparticles.

    PubMed

    Montazerozohori, Morteza; Masoudiasl, Ardavan; Farokhiyani, Sara; Joohari, Shiva; McArdle, Patrick

    2017-09-01

    A bidentate Schiff base ligand and its nano-structured cobalt(II) complex were synthesized under ultrasound irradiation and then their structures were identified by physical and spectral techniques SEM and XRD techniques were used to confirm the nanostructure character of the complex. Single crystal X-ray diffraction analysis showed that the complex crystallizes in the triclinic system with space group of P1¯ and two crystallographically independent molecules participate in its asymmetric unit. In the structure of complex, cobalt center is four-coordinated by two iminic nitrogens of bidentate Schiff base ligand and two bromide anions in a distorted tetrahedral geometry. Crystal packing analysis well indicates that C-H⋯Br, C-H⋯π and π⋯π are the most intermolecular interactions. Moreover Hirshfeld surface analysis and 2D Fingerprint plots were applied for more investigation of intermolecular interactions. In addition, sonochemically prepared cobalt(II) bromide complex was subjected to calcination process under air atmosphere for preparation of cobalt oxide nanoparticles. The XRD pattern confirmed the simultaneous formation of CoO and Co3O4 nanoparticles. Copyright © 2017 Elsevier B.V. All rights reserved.

  6. Pyrazolate-based cobalt(II)-containing metal-organic frameworks in heterogeneous catalytic oxidation reactions: elucidating the role of entatic states for biomimetic oxidation processes.

    PubMed

    Tonigold, Markus; Lu, Ying; Mavrandonakis, Andreas; Puls, Angela; Staudt, Reiner; Möllmer, Jens; Sauer, Joachim; Volkmer, Dirk

    2011-07-25

    Crystal structures of two metal-organic frameworks (MFU-1 and MFU-2) are presented, both of which contain redox-active Co(II) centres coordinated by linear 1,4-bis[(3,5-dimethyl)pyrazol-4-yl] ligands. In contrast to many MOFs reported previously, these compounds show excellent stability against hydrolytic decomposition. Catalytic turnover is achieved in oxidation reactions by employing tert-butyl hydroperoxide and the solid catalysts are easily recovered from the reaction mixture. Whereas heterogeneous catalysis is unambiguously demonstrated for MFU-1, MFU-2 shows catalytic activity due to slow metal leaching, emphasising the need for a deeper understanding of structure-reactivity relationships in the future design of redox-active metal-organic frameworks. Mechanistic details for oxidation reactions employing tert-butyl hydroperoxide are studied by UV/Vis and IR spectroscopy and XRPD measurements. The catalytic process accompanying changes of redox states and structural changes were investigated by means of cobalt K-edge X-ray absorption spectroscopy. To probe the putative binding modes of molecular oxygen, the isosteric heats of adsorption of O(2) were determined and compared with models from DFT calculations. The stabilities of the frameworks in an oxygen atmosphere as a reactive gas were examined by temperature-programmed oxidation (TPO). Solution impregnation of MFU-1 with a co-catalyst (N-hydroxyphthalimide) led to NHPI@MFU-1, which oxidised a range of organic substrates under ambient conditions by employing molecular oxygen from air. The catalytic reaction involved a biomimetic reaction cascade based on free radicals. The concept of an entatic state of the cobalt centres is proposed and its relevance for sustained catalytic activity is briefly discussed. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Concentration of In-111-oxine-labeled autologous leukocytes in noninfected and nonrejecting renal allografts: concise communication

    SciTech Connect

    Collier, B.D.; Isitman, A.T.; Kaufman, H.M.; Rao, S.A.; Knobel, J.; Hellman, R.S.; Zielonka, J.S.; Pelc, L.

    1984-02-01

    Autologous leukocytes labeled with In-111 oxine (ILL) concentrated in the renal allografts of eight patients for whom transplant rejection, infection, or acute tubular necrosis (ATN) could be excluded. All patients had good-to-adequate renal function at the time of ILL scintigraphy, and none developed rejection or renal transplant failure during a 1-mo follow-up period. It is concluded that normally functioning renal allografts without evidence of rejection, infection, or ATN often will concentrate ILL. When a baseline study is not available for comparison, this phenomenon limits the value of ILL scintigraphy as a diagnostic test for transplant rejection or infection.

  8. Cobalt (II) complex with novel unsymmetrical tetradentate Schiff base (ON) ligand: in vitro cytotoxicity studies of complex, interaction with DNA/protein, molecular docking studies, and antibacterial activity.

    PubMed

    Shokohi-Pour, Zahra; Chiniforoshan, Hossein; Sabzalian, Mohammad R; Esmaeili, Seyed-Alireza; Momtazi-Borojeni, Amir Abbas

    2017-03-08

    [C20H17N3O2] and cobalt (II) complex [Co(L(2))(MeOH)2].ClO4, (L(2) = 4-((E)-1-((2-(((E)-pyridin-2-ylmethylene) amino) phenyl) imino) ethyl) benzene-1, 3-diol) novel Schiff base has been synthesiszed and chracterized by Fourier transform infrared, UV-vis, (1)H-NMR spectroscopy, and elemental analysis techniques. The interaction of Co(II) complex with DNA and BSA was investigated by electronic absorption spectroscopy, fluorescence spectroscopy, circular dichroism, and thermal denaturation studies. Our experiments indicate that this complex could strongly bind to CT-DNA via minor groove mechanism. In addition, fluorescence spectrometry of BSA with the complex showed that the fluorescence quenching mechanism of BSA was of static type. The complex exhibited significant in vitro cytotoxicity against three human cancer cell lines (JURKAT, SKOV3, and U87). The molecular docking experiment effectively proved the binding of complex to DNA and BSA. Finally, antibacterial assay over gram-positive and gram-negative pathogenic bacterial strains was studied.

  9. Through-space and through-bond mixed charge transfer mechanisms on the hydrazine oxidation by cobalt(II) phthalocyanine in the gas phase.

    PubMed

    Paredes-García, V; Cardenas-Jirón, G I; Venegas-Yazigi, D; Zagal, J H; Paez, M; Costamagna, J

    2005-02-17

    Two quantum chemistry theoretical models in the gas phase at the density functional theory B3LYP/LACVP(d) level of calculation are proposed to rationalize the hydrazine oxidation by cobalt(II) phthalocyanine (Co(II)Pc). This oxidation reaction involves the net transfer of four electrons. These theoretical models that are described in terms of energy profiles include a through-space mechanism for the transfer of the first electron of the hydrazine and a through-bond mechanism proposed for the transfer of the three electrons remaining. The main difference between both models arises from a one-electron and one-proton alternate transfer for model 1 and a two-electron and two-proton alternate transfer for model 2. The main problem for experimental studies is to determine if the first transfer corresponds to an electron or a chemical transfer. Under this point of view, we proposed two models which deal with this problem. We conclude that model 1 is more reasonable than model 2 because the whole oxidation process is always exergonic.

  10. The feed forward neural network model for liquid-liquid extraction and separation of cobalt (II) from sodium acetate media using cyanex 272

    NASA Astrophysics Data System (ADS)

    Sudibyo, Aji, B. B.; Priyanto, S.

    2017-03-01

    Cobalt is one of the precious ferromagnetic metals, which widely used in the preparation of magnetic, wear-resistant and high-strength alloys. This metal was not found naturally in single metal form but is found as impurities in nickel or copper ore. The extraction process is one of the methods to separate cobalt from its impurities. However, this process needs an expensive organic solution. In practice, changing the composition of chemicals composition in extraction process always affect at a high cost. Therefore, the development of the artificial neural network (ANN) model to model the cobalt extraction process can serve as an important tool for predicting and investigating the optimum production for the cobalt extraction without the need to run the actual experiment. Hence, the development of the ANN model of cobalt extraction model is essential to simulate the process, which can lead to high yields of cobalt production. In this work a selected optimum multiple-input-single-output (MISO) model of feed forward neural network (FFNN) was used to predict the percentage of cobalt extraction. MISO FFNN with 20, 30 and 50 hidden nodes were used to simulate cobalt extraction process. The simulation results achieved was compared with data available in the literature. The results show that MISO FFNN with 50 hidden nodes has the best performance. The optimum result of MISO FFNN then exported to Simulink model in Matlab environment, hence make it easy to use in predicting and investigating for the optimum production of the cobalt extraction.

  11. Slow Magnetic Relaxations in Cobalt(II) Tetranitrate Complexes. Studies of Magnetic Anisotropy by Inelastic Neutron Scattering and High-Frequency and High-Field EPR Spectroscopy

    SciTech Connect

    Chen, Lei; Cui, Hui-Hui; Stavretis, Shelby E.; Hunter, Seth C.; Zhang, Yi-Quan; Chen, Xue-Tai; Sun, Yi-Chen; Wang, Zhenxing; Song, You; Podlesnyak, Andrey A.; Ouyang, Zhong-Wen; Xue, Zi-Ling

    2016-12-07

    We synthesized and studied three mononuclear cobalt(II) tetranitrate complexes (A)2[Co(NO3)4] with different countercations, Ph4P+ (1), MePh3P+ (2), and Ph4As+ (3), using X-ray single-crystal diffraction, magnetic measurements, inelastic neutron scattering (INS), high-frequency and high-field EPR (HF-EPR) spectroscopy, and theoretical calculations. Furthermore, the X-ray diffraction studies reveal that the structure of the tetranitrate cobalt anion varies with the countercation. 1 and 2 exhibit highly irregular seven-coordinate geometries, while the central Co(II) ion of 3 is in a distorted-dodecahedral configuration. The sole magnetic transition observed in the INS spectroscopy of 1–3 corresponds to the zero-field splitting (2(D2 + 3E2)1/2) from 22.5(2) cm–1 in 1 to 26.6(3) cm–1 in 2 and 11.1(5) cm–1 in 3. The positive sign of the D value, and hence the easy-plane magnetic anisotropy, was demonstrated for 1 by INS studies under magnetic fields and HF-EPR spectroscopy. The combined analyses of INS and HF-EPR data yield the D values as +10.90(3), +12.74(3), and +4.50(3) cm–1 for 1–3, respectively. Frequency- and temperature-dependent alternating-current magnetic susceptibility measurements reveal the slow magnetization relaxation in 1 and 2 at an applied dc field of 600 Oe, which is a characteristic of field-induced single-molecule magnets (SMMs). Finally, the electronic structures and the origin of magnetic anisotropy of 1–3 were revealed by calculations at the CASPT2/NEVPT2 level.

  12. Spectrally-resolved third-harmonic generation and the fundamental role of O-HCl hydrogen bonding in Oh, Td-cobalt(ii) tetraphenylmethane-based coordination polymers.

    PubMed

    Zaręba, J K; Janczak, J; Samoć, M; Nyk, M

    2017-07-25

    The reaction of a phosphonate-diester tetraphenylmethane-based tecton, tetrakis[4-(diethoxyphosphoryl)phenyl]methane, (L) with cobalt(ii) chloride afforded a centrosymmetric coordination polymer (CP), [L·2Co(H2O)4(2+)·2CoCl4(2-)]n, 2-Cl, possessing simultaneously octahedral (Oh) and tetrahedral (Td) metal centers. This material served as a model compound for the demonstration of factors influencing the spectral dependence of one of the nonlinear optical (NLO) phenomena, the third-harmonic generation (THG). The spectrally-resolved THG (SR-THG) measurements in the range from 1125 to 1750 nm revealed that a maximum of THG response is obtained when the fundamental beam is around 1300 nm. The SR-THG study was combined with an analysis of the self-absorption effects of pumping and of third-harmonic radiation; based on these results, we put forward a hypothesis that the THG action spectrum is influenced more by the ability of the material to self-absorb the third harmonic rather than by the extent of self-absorption of the pumping radiation. Apart from investigations of NLO properties, we have explored coordination and particularly the supramolecular interactions that build up the 2-Cl CP. Despite the tetrahedral, spatial shape of the ligand L, CP 2-Cl has a two-dimensional net. The structure was found to be strongly supported by O-HCl hydrogen bonds, since each CoCl4(2-) complex anion is an acceptor of eight of such interactions within a distorted square grid layer of cobalt(ii) ions. While coordination and hydrogen-bonded nets are both featuring the sql topology when treated separately, the consideration of both of them as topological paths yields a trinodal 4,4,6-connected net, described by the point symbol (4(2)·8(4))(4(5)·6)2(4(6)·6(6)·8(3))2. SR-THG and structural studies of 2-Cl have been also supported by far- and mid-infrared spectroscopy, UV-Vis-NIR solid state absorption analysis, thermogravimetry and preliminary magnetic characterization.

  13. Nickel acts as an adjuvant during cobalt sensitization.

    PubMed

    Bonefeld, Charlotte Menné; Nielsen, Morten Milek; Vennegaard, Marie T; Johansen, Jeanne Duus; Geisler, Carsten; Thyssen, Jacob P

    2015-03-01

    Metal allergy is the most frequent form of contact allergy with nickel and cobalt being the main culprits. Typically, exposure comes from metal-alloys where nickel and cobalt co-exist. Importantly, very little is known about how co-exposure to nickel and cobalt affects the immune system. We investigated these effects by using a recently developed mouse model. Mice were epicutaneously sensitized with i) nickel alone, ii) nickel in the presence of cobalt, iii) cobalt alone, or iv) cobalt in the presence of nickel, and then followed by challenge with either nickel or cobalt alone. We found that sensitization with nickel alone induced more local inflammation than cobalt alone as measured by increased ear-swelling. Furthermore, the presence of nickel during sensitization to cobalt led to a stronger challenge response to cobalt as seen by increased ear-swelling and increased B and T cell responses in the draining lymph nodes compared to mice sensitized with cobalt alone. In contrast, the presence of cobalt during nickel sensitization only induced an increased CD8(+) T cell proliferation during challenge to nickel. Thus, the presence of nickel during cobalt sensitization potentiated the challenge response against cobalt more than the presence of cobalt during sensitization to nickel affected the challenge response against nickel. Taken together, our study demonstrates that sensitization with a mixture of nickel and cobalt leads to an increased immune response to both nickel and cobalt, especially to cobalt, and furthermore that the adjuvant effect appears to correlate with the inflammatory properties of the allergen. © 2015 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

  14. Cobalt(II) chloride complexes with 1,1'-dimethyl-4,4'-bipyrazole featuring first- and second-sphere coordination of the ligand.

    PubMed

    Domasevitch, Konstantin V

    2014-03-01

    In catena-poly[[dichloridocobalt(II)]-μ-(1,1'-dimethyl-4,4'-bipyrazole-κ(2)N(2):N(2'))], [CoCl2(C8H10N4)]n, (1), two independent bipyrazole ligands (Me2bpz) are situated across centres of inversion and in tetraaquabis(1,1'-dimethyl-4,4'-bipyrazole-κN(2))cobalt(II) dichloride-1,1'-dimethyl-4,4'-bipyrazole-water (1/2/2), [Co(C8H10N4)2(H2O)4]Cl2·2C8H10N4·2H2O, (2), the Co(2+) cation lies on an inversion centre and two noncoordinated Me2bpz molecules are also situated across centres of inversion. The compounds are the first complexes involving N,N'-disubstituted 4,4'-bipyrazole tectons. They reveal a relatively poor coordination ability of the ligand, resulting in a Co-pyrazole coordination ratio of only 1:2. Compound (1) adopts a zigzag chain structure with bitopic Me2bpz links between tetrahedral Co(II) ions. Interchain interactions occur by means of very weak C-H...Cl hydrogen bonding. Complex (2) comprises discrete octahedral trans-[Co(Me2bpz)2(H2O)4](2+) cations formed by monodentate Me2bpz ligands. Two equivalents of additional noncoordinated Me2bpz tectons are important as `second-sphere ligands' connecting the cations by means of relatively strong O-H...N hydrogen bonding with generation of doubly interpenetrated pcu (α-Po) frameworks. Noncoordinated chloride anions and solvent water molecules afford hydrogen-bonded [(Cl(-))2(H2O)2] rhombs, which establish topological links between the above frameworks, producing a rare eight-coordinated uninodal net of {4(24).5.6(3)} (ilc) topology.

  15. Correlations of synthetic, spectroscopic, structural, and speciation studies in the biologically relevant cobalt(II)-citrate system: the tale of the first aqueous dinuclear cobalt(II)-citrate complex.

    PubMed

    Kotsakis, N; Raptopoulou, C P; Tangoulis, V; Terzis, A; Giapintzakis, J; Jakusch, T; Kiss, T; Salifoglou, A

    2003-01-13

    Synthetic efforts targeting soluble species of Co(II) with the low molecular mass physiological ligand citric acid led to the isolation of the first dinuclear complex [Co(2)(C(6)H(5)O(7))(2)(H(2)O)(4)](2-), at pH approximately 5, in the form of its K+ (1) and Na+ (2) salts. Both 1 and 2 were characterized analytically, spectroscopically (FT-IR, UV/visible, EPR), and magnetically. Complex 1 crystallizes in the monoclinic space group P2(1)/n, with a = 10.348(5) A, b = 11.578(6) A, c = 12.138(6) A, beta = 112.62(2) degrees, V = 1342(1) A(3), and Z = 2. Complex 2 crystallizes in the monoclinic space group P2(1)/c, with a = 9.234(4) A, b = 11.913(4) A, c = 11.728(6) A, beta = 99.93(2) degrees, V = 1271(1) A(3), and Z = 2. X-ray crystallography on 1 and 2 reveals the presence of two Co(II) ions, in a dinuclear assembly, octahedrally coordinated by two citrate ligands in a tridentate fashion. The octahedral environment around each Co(II) is complemented by another singly bonded citrate belonging to the adjacent Co(II) unit and two water molecules. Magnetic susceptibility and EPR studies on 1, in the solid state, corroborate the X-ray results, indicating a weak interaction between the two Co(II) ions. Moreover, EPR and UV/visible studies in solution suggest that 1 does not retain its dimeric structure, yielding a mononuclear octahedral Co(II)-citrate species. Detailed speciation studies suggest the presence of a number of species including the mononuclear complex [Co(C(6)H(5)O(7))](-), optimally present around pH approximately 5. In consonance with EPR and UV/visible spectroscopy, [Co(C(6)H(5)O(7))](-) is likely the scaffolding unit on the basis of which the dimer [Co(2)(C(6)H(5)O(7))(2)(H(2)O)(4)](2-) is isolated from aqueous solutions. Collectively, this comprehensive study offers significant structural insight into the Co(II)-citrate speciation and the elucidation of the role of Co(II) in biological fluids.

  16. Anti-oxidant, in vitro, in vivo anti-inflammatory activity and antiproliferative activity of mefenamic acid and its metal complexes with manganese(II), cobalt(II), nickel(II), copper(II) and zinc(II).

    PubMed

    Kovala-Demertzi, Dimitra; Hadjipavlou-Litina, Dimitra; Staninska, Malgorzata; Primikiri, Alexandra; Kotoglou, Chronis; Demertzis, Mavroudis A

    2009-06-01

    Some new complexes of mefenamic acid with potentially interesting biological activity are described. The complexes of mefenamic acid [Mn(mef)(2)(H(2)O)(2)], 1, [Co(mef)(2)(H(2)O)(2)], 2, [Ni(mef)(2)(H(2)O)(2)], 3, [Cu(mef)(2)(H(2)O)](2), 4 and [Zn(mef)(2)], 5, were prepared by the reaction of mefenamic acid, a potent anti-inflammatory drug with metal salts. Optical and infrared spectral data of these new complexes are reported. Monomeric six-coordinated species were isolated in the solid state for Mn(II), Ni(II) and Co(II), dimeric five-coordinated for Cu(II) and monomeric four-coordinated for Zn(II). In DMF or CHCl(3) solution the coordination number is retained and the coordinated molecules of water are replaced by solvent molecules. The anti-oxidant properties of the complexes were evaluated using the 1,1-diphenyl-2-picrylhydrazyl, DPPH, free radical scavenging assay. The scavenging activities of the complexes were measured and compared with those of the free drug and vitamin C. We have explored their ability to inhibit soybean lipoxygenase, beta-glucuronidase and trypsin- induced proteolysis. The complex [Mn(mef)(2)(H(2)O)(2)] exhibits the highest antioxidant activity and the highest inhibitory effect against the soybean lipogygenase (LOX), properties that are not demonstrated by mefenamic acid. Their inhibitory effects on rat paw edema induced by Carrageenan was studied and compared with those of mefenamic acid. The complex [Zn(mef)(2)] exhibited a strong inhibitory effect at 0.1 mmol/Kg B.W. (81.5 +/- 1.3% inhibition), superior to the inhibition induced by mefenamic acid at the same dose (61.5 +/- 2.3% inhibition). Mefenamic acid and its metal complexes have been evaluated for antiproliferative activity in vitro against the cells of three human cancer cell lines: MCF-7 (human 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 copper(II) complex displays against T24, MCF-7

  17. Crystal structures, spectroscopic features, and catalytic properties of cobalt(II), copper(II), nickel(II), and mercury(II) derivatives of the zinc endopeptidase astacin. A correlation of structure and proteolytic activity.

    PubMed

    Gomis-Rüth, F X; Grams, F; Yiallouros, I; Nar, H; Küsthardt, U; Zwilling, R; Bode, W; Stöcker, W

    1994-06-24

    The catalytic zinc ion of astacin, a prototypical metalloproteinase from crayfish, has been substituted by Co(II), Cu(II), Hg(II), and Ni(II) in order to probe the role of the metal for both catalysis and structure. Compared to Zn(II)-astacin, Co(II)- and Cu(II)-astacin display enzymatic activities of about 140 and 37%, respectively, while Ni(II)- and Hg(II)-astacin are almost inactive. The electron paramagnetic resonance spectrum of Cu(II)-astacin is typical of 5-fold coordinated copper(II), and its intense absorption maxima at 445 and 325 nm are probably due to ligand-metal charge-transfer transitions involving Tyr-149. This residue had been identified previously by x-ray crystallography of the zinc enzyme as a zinc ligand, in addition to three imidazoles and a glutamic acid-bound water molecule. We present now the refined high-resolution x-ray crystal structures of Cu(II)-, Co(II)-, and Ni(II)-astacin, which exhibit a virtually identical protein framework to the previously analyzed structures of Zn(II)-, apo-, and Hg(II)-astacin. In Co(II)- and Cu(II)-astacin, the metal is penta-coordinated similarly to the native zinc enzyme. In the Ni(II) derivative, however, an additional solvent molecule expands the metal coordination sphere to a distorted octahedral ligand geometry, while in Hg(II)-astacin, no ordered solvent molecule at all is observed in the inner coordination sphere of the metal. This indicates a close correlation between catalytic properties and ground-state metal coordination of astacin.

  18. Synthesis and antibacterial activity of cephradine metal complexes : part II complexes with cobalt, copper, zinc and cadmium.

    PubMed

    Sultana, Najma; Arayne, M Saeed; Afzal, M

    2005-01-01

    Cephradine, the first generation cephalosporin, is active against a wide range of Gram-positive and Gram-negative bacteria including penicillinase-producing Staphylococci. Since the presence of complexing ligand may affect the bioavailability of a metal in the blood or tissues, therefore, in order to study the probable interaction of cephradine with essential and trace elements present in human body, cephradine has been reacted with cobalt, copper, zinc and cadmium metal halides in L:M ratio of 2:1 in methanol and the products recrystallized from suitable solvents to pure crystals of consistent melting points. Infrared and ultraviolet studies of these complexes were carried out and compared with ligand. Magnetic susceptibility studies of these complexes were also carried out showing their paramagnetic behavior. From the infra red studies and elemental analysis of the complexes, it has been shown that the drug molecule serves as a bidentate ligand coordinating through both its carboxylate at C-3 and beta-lactam nitrogen and the metal having a square planar or octahedral geometry. To evaluate the changes in microbiological activity of cephradine after complexation, antibacterial studies were carried out by observing the changes in MIC (minimum inhibitory concentration) of the complexes and compared with the parent drug by measuring the zone of inhibition of complexes and compared with the parent cephalosporin against both Gram-positive and Gram-negative organisms. For MIC observation, serial dilution method was employed and zone series were determined by disk diffusion method. Our investigations reveal that formation of complexes results in decrease in antibacterial activity of cephradine and MIC values are increased.

  19. Toxicity and bioactivity of cobalt nanoparticles on the monocytes.

    PubMed

    Liu, Ya-ke; Ye, Jun; Han, Qing-lin; Tao, Ran; Liu, Fan; Wang, Wei

    2015-05-01

    To explore the toxicity and biological activity of cobalt nanoparticles on the osteoclasts. Analyze the relationship between cobalt nanoparticles and osteolysis. Monocyte-macrophages (RAW 264.7) was cultured in vitro, osteoclast-like cells were induced by lipopolysaccharides (LPS). After RAW 264.7 was induced for 24 h, Methyl Thiazolium Tetrazolium (MTT) biological toxicity test of osteoclast-like cell was preceded using Cobalt nanoparticles (set 4 concentrations: 10, 20, 50, 100 μM) and cobalt chloride (set 4 concentrations: 10, 20, 50, 100 μM) at 2, 4, 8, 24 and 48 h respectively. The relative expression of mRNA of CA II and Cat K after RAW 264.7 induction was determined by Q-PCR. mRNA relative expression of CA II, Cat K were reduced at multiple concentrations both cobalt nanoparticles and cobalt chloride, and was time and concentration dependent, cobalt nanoparticles are more significant than cobalt chloride group. But when the cobalt nanoparticles concentration is in 10-50 μM, the mRNA relative expression of CA II, Cat K increased. Cobalt nanoparticles have biological toxicity. At multiple concentrations, the differentiation and proliferation of osteoclasts was inhibited, but when the concentration of cobalt nanoparticles is in 10-50 μM, it has been strengthened. © 2015 Chinese Orthopaedic Association and Wiley Publishing Asia Pty Ltd.

  20. Synthesis, structure and magnetic properties of Na 9Co 2O 7, a new mixed-valent sodium cobaltate(II,III)

    NASA Astrophysics Data System (ADS)

    Sofin, M.; Peters, E.-M.; Jansen, M.

    2004-04-01

    Na 9Co 2O 7 was prepared via the azide/nitrate route. Stoichiometric mixtures of the precursors (Co 3O 4, NaN 3 and NaNO 3) were heated in a special regime up to 450 °C and annealed at this temperature for 100 h in specially designed silver containers. Single crystals have been grown by annealing a Na 2O/Na 9Co 2O 7 mixture (molar ratio 1:2) at 500 °C for 2000 h in silver crucibles, which were sealed in glass ampoules under dried Ar. According to the X-ray analysis of the crystal structure ( Pca2 1, Z=4, a=9.5477(6) Å, b=9.9040(6) Å, c=10.1919(7) Å, 4103 independent reflections, R1=5.23% (all data)) there are isolated Co IIIO 4 tetrahedra and Co IIO 3 triangles. Na 9Co 2O 7 is isostructural to Na 9Fe 2O 7, and shows Curie-Weiss behaviour down to ˜25 K. The best fit (for Co II ( S=3/2) and Co III ( S=2)) yields an average value of the magnetic moment (per cobalt) μ=3.23 μB ( g=2.07) and Θ=-6 K. At 20 K one observes an onset of ferromagnetic order.

  1. Spectrophotometric determination of some anti-tussive and anti-spasmodic drugs through ion-pair complex formation with thiocyanate and cobalt(II) or molybdenum(V)

    NASA Astrophysics Data System (ADS)

    El-Shiekh, Ragaa; Zahran, Faten; El-Fetouh Gouda, Ayman Abou

    2007-04-01

    Two rapid, simple and sensitive extractive specrophotometric methods has been developed for the determination of anti-tussive drugs, e.g., dextromethorphan hydrobromide (DEX) and pipazethate hydrochloride (PiCl) and anti-spasmodic drugs, e.g., drotaverine hydrochloride (DvCl) and trimebutine maleate (TM) in bulk and in their pharmaceutical formulations. The proposed methods depend upon the reaction of cobalt(II)-thiocyanate (method A) and molybdenum(V)-thiocyanate ions (method B) with the cited drugs to form stable ion-pair complexes which extractable with an n-butnol-dichloromethane solvent mixture (3.5:6.5) and methylene chloride for methods A and B, respectively. The blue and orange red color complexes are determined either colorimetrically at λmax 625 nm (using method A) and 467 or 470 nm for (DEX and PiCl) or (DvCl and TM), respectively (using method B). The concentration range is 20-400 and 2.5-50 μg mL -1 for methods A and B, respectively. The proposed method was successfully applied for the determination of the studied drugs in pure and in pharmaceutical formulations applying the standard additions technique and the results obtained in good agreement well with those obtained by the official method.

  2. Spectrophotometric determination of some anti-tussive and anti-spasmodic drugs through ion-pair complex formation with thiocyanate and cobalt(II) or molybdenum(V).

    PubMed

    El-Shiekh, Ragaa; Zahran, Faten; El-Fetouh Gouda, Ayman Abou

    2007-04-01

    Two rapid, simple and sensitive extractive specrophotometric methods has been developed for the determination of anti-tussive drugs, e.g., dextromethorphan hydrobromide (DEX) and pipazethate hydrochloride (PiCl) and anti-spasmodic drugs, e.g., drotaverine hydrochloride (DvCl) and trimebutine maleate (TM) in bulk and in their pharmaceutical formulations. The proposed methods depend upon the reaction of cobalt(II)-thiocyanate (method A) and molybdenum(V)-thiocyanate ions (method B) with the cited drugs to form stable ion-pair complexes which extractable with an n-butnol-dichloromethane solvent mixture (3.5:6.5) and methylene chloride for methods A and B, respectively. The blue and orange red color complexes are determined either colorimetrically at lambdamax 625 nm (using method A) and 467 or 470 nm for (DEX and PiCl) or (DvCl and TM), respectively (using method B). The concentration range is 20-400 and 2.5-50 microg mL-1 for methods A and B, respectively. The proposed method was successfully applied for the determination of the studied drugs in pure and in pharmaceutical formulations applying the standard additions technique and the results obtained in good agreement well with those obtained by the official method.

  3. Comparative cytotoxicity and genotoxicity of cobalt (II, III) oxide, iron (III) oxide, silicon dioxide, and aluminum oxide nanoparticles on human lymphocytes in vitro.

    PubMed

    Rajiv, S; Jerobin, J; Saranya, V; Nainawat, M; Sharma, A; Makwana, P; Gayathri, C; Bharath, L; Singh, M; Kumar, M; Mukherjee, A; Chandrasekaran, N

    2016-02-01

    Despite the extensive use of nanoparticles (NPs) in various fields, adequate knowledge of human health risk and potential toxicity is still lacking. The human lymphocytes play a major role in the immune system, and it can alter the antioxidant level when exposed to NPs. Identification of the hazardous NPs was done using in vitro toxicity tests and this study mainly focuses on the comparative in vitro cytotoxicity and genotoxicity of four different NPs including cobalt (II, III) oxide (Co3O4), iron (III) oxide (Fe2O3), silicon dioxide (SiO2), and aluminum oxide (Al2O3) on human lymphocytes. The Co3O4 NPs showed decrease in cellular viability and increase in cell membrane damage followed by Fe2O3, SiO2, and Al2O3 NPs in a dose-dependent manner after 24 h of exposure to human lymphocytes. The oxidative stress was evidenced in human lymphocytes by the induction of reactive oxygen species, lipid peroxidation, and depletion of catalase, reduced glutathione, and superoxide dismutase. The Al2O3 NPs showed the least DNA damage when compared with all the other NPs. Chromosomal aberration was observed at 100 µg/ml when exposed to Co3O4 NPs and Fe2O3 NPs. The alteration in the level of antioxidant caused DNA damage and chromosomal aberration in human lymphocytes. © The Author(s) 2015.

  4. High-performance liquid chromatography of N-terminal tyrosine-containing oligopeptides by pre-column fluorescence derivatization with hydroxylamine, cobalt (II) and borate reagents.

    PubMed

    Nakano, M; Kai, M; Ohno, M; Ohkura, Y

    1987-12-18

    A pre-column fluorescence derivatization method is described for the high-performance liquid chromatographic determination of N-terminal tyrosine-containing oligopeptides involving methionine-enkephalin and leucine-enkephalin. The peptides are converted into fluorescent derivatives by heating in a weakly alkaline medium (pH 8.5) containing hydroxylamine, cobalt(II) ion and borate. The derivatives are separated on a reversed-phase column (TSKgel ODS-120T) by gradient elution of acetonitrile in a mobile phase containing borate buffer (pH 8.5) and tetra-n-butylammonium chloride, and then determined by fluorimetry. The derivatization provides a single fluorescent product for each N-terminal tyrosine-containing oligopeptide, but does not allow the production of fluorescent derivatives for peptides having no tyrosyl residue at the N-terminal. The method is selective and sensitive; the lower limits of detection for the N-terminal tyrosine-containing oligopeptides tested were 140-310 fmol per 100 microliters injected.

  5. Two isostructural cobalt(II) coordination polymers with both polyrotaxane and polycatenane features assembled with a V-shaped rigid ligand

    NASA Astrophysics Data System (ADS)

    Li, Yue; Yao, Xiao-Qiang; Xiao, Guo-Bin; Ma, Heng-Chang; Yang, Yun-Xia; Liu, Jia-Cheng

    2015-06-01

    Two novel cobalt(II) coordination polymers (CPs), [Co(BPFP)2(sca)]n (1), [Co(BPFP)2(sda)]n (2), [BPFP = 2,8-di(pyridin-4-yl)dibenzo[b,d]furan, H2sca = succinic acid, H2sda = thiophene-2,5-dicarboxylic acid], have been synthesized hydrothermally based on a V-shaped rigid ligand BPFP. Their structures were fully characterized by elemental analysis, FT-IR spectroscopy and X-ray single-crystal diffraction methods. Compound 1 is a 2-fold parallel interpenetrating network consist of two identical sets of 2D layer motifs and shows both polyrotaxane and polycatenane characters. Compound 2 has the same structural feature as compound 1, except that the sca2- anions are replaced by the sda2- anions. The Powder X-ray diffraction (PXRD) analyses and thermogravimetric analyses were carried out to confirm the phase purity and the thermal stabilities of the compounds 1 and 2. In addition, the solid-state UV-vis absorption spectra were also investigated.

  6. Chemometrics-assisted simultaneous determination of cobalt(II) and chromium(III) with flow-injection chemiluminescence method

    NASA Astrophysics Data System (ADS)

    Li, Baoxin; Wang, Dongmei; Lv, Jiagen; Zhang, Zhujun

    2006-09-01

    In this paper, a flow-injection chemiluminescence (CL) system is proposed for simultaneous determination of Co(II) and Cr(III) with partial least squares calibration. This method is based on the fact that both Co(II) and Cr(III) catalyze the luminol-H 2O 2 CL reaction, and that their catalytic activities are significantly different on the same reaction condition. The CL intensity of Co(II) and Cr(III) was measured and recorded at different pH of reaction medium, and the obtained data were processed by the chemometric approach of partial least squares. The experimental calibration set was composed with nine sample solutions using orthogonal calibration design for two component mixtures. The calibration curve was linear over the concentration range of 2 × 10 -7 to 8 × 10 -10 and 2 × 10 -6 to 4 × 10 -9 g/ml for Co(II) and Cr(III), respectively. The proposed method offers the potential advantages of high sensitivity, simplicity and rapidity for Co(II) and Cr(III) determination, and was successfully applied to the simultaneous determination of both analytes in real water sample.

  7. Spectroscopic, Structural, and Kinetic Investigation of the Ultrafast Spin Crossover in an Unusual Cobalt(II) Semiquinonate Radical Complex.

    PubMed

    Rupp, Fabian; Chevalier, Katharina; Graf, Michèle; Schmitz, Markus; Kelm, Harald; Grün, Anneken; Zimmer, Manuel; Gerhards, Markus; van Wüllen, Christoph; Krüger, Hans-Jörg; Diller, Rolf

    2017-02-10

    A comprehensive spectroscopic and structural investigation of [Co(II) (l-N4  tBu2 )(dbsq)][B(p-C6 H4 Cl)4 ] (1, l-N4  tBu2 =N,N'-di-tert-butyl-2,11-diaza[3.3](2,6)pyridinophane, dbsq(1-) =3,5-di-tert-butylsemiquinonate), the first known octahedral complex with a low-spin (ls) Co(II) semiquinonate ground state, is reported. Above 200 K, solids as well as solutions of 1 exhibit thermally induced spin-crossover (SCO) from the ls to the high-spin (hs) Co(II) semiquinonate state instead of the frequently observed valence tautomerism from ls Co(III) catecholate to hs Co(II) semiquinonate. DFT calculations demonstrate that the (closed shell) Co(III) catecholate suffers from a triplet instability leading to the ls Co(II) semiquinonate ground state. The thorough temperature-dependent spectroscopic study of the SCO enables a photophysical investigation. Thus, by selective photoexcitation of the ls fraction of 1 in solution at room temperature, ultrafast conversion to the hs state is observed using femtosecond electronic and IR-vibrational (infrared) transient absorption spectroscopy. The kinetics of the photocycle is described by a stretched exponential with τ=3.3-3.6 ps and β=0.52-0.54, representing an upper limit for the hs-ls relaxation time. This is, to our knowledge, the fastest interconversion ever determined for a SCO complex, and is attributed to the special situation that in 1 a Co(II) complex is coordinated to a π-radical ligand allowing very efficient coupling between the ls and hs spin states. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Crystal structure of tetra-aqua-bis(3,5-di-amino-4H-1,2,4-triazol-1-ium)cobalt(II) bis-[bis-(pyridine-2,6-di-carboxyl-ato)cobaltate(II)] dihydrate.

    PubMed

    Johnson, Atim; Mbonu, Justina; Hussain, Zahid; Loh, Wan-Sin; Fun, Hoong-Kun

    2015-06-01

    The asymmetric unit of the title compound, [Co(C2H6N5)2(H2O)4][Co(C7H3NO4)2]2·2H2O, features 1.5 Co(II) ions (one anionic complex and one half cationic complex) and one water mol-ecule. In the cationic complex, the Co(II) atom is located on an inversion centre and is coordinated by two triazolium cations and four water mol-ecules, adopting an octa-hedral geometry where the N atoms of the two triazolium cations occupy the axial positions and the O atoms of the four water mol-ecules the equatorial positions. The two triazole ligands are parallel offset (with a distance of 1.38 Å between their planes). In the anionic complex, the Co(II) ion is six-coordinated by two N and four O atoms of the two pyridine-2,6-di-carboxyl-ate anions, exhibiting a slightly distorted octa-hedral coordination geometry in which the mean plane of the two pyridine-2,6-di-carboxyl-ate anions are almost perpendicular to each other, making a dihedral angle of 85.87 (2)°. In the crystal, mol-ecules are linked into a three-dimensional network via C-H⋯O, C-H⋯N, O-H⋯O and N-H⋯O hydrogen bonds.

  9. Reversible guest exchange and ferrimagnetism (T(C) = 60.5 K) in a porous cobalt(II)-hydroxide layer structure pillared with trans-1,4-cyclohexanedicarboxylate.

    PubMed

    Kurmoo, Mohamedally; Kumagai, Hitoshi; Hughes, Suzanne M; Kepert, Cameron J

    2003-10-20

    The synthesis, characterization, and reversible guest-exchange chemistry of a new porous magnetic material that orders ferrimagnetically at 60.5 K are described. The material, Co(5)(OH)(8)(chdc).4H(2)O (chdc = trans-1,4-cyclohexanedicarboxylate), contains tetrahedral-octahedral-tetrahedral Co(II)-hydroxide layers of composition Co((oct))(3)Co((tet))(2)(OH)(8) that are linked together by bis(unidentate) chdc pillars. Noncoordinated water molecules occupy 1-D channels situated between the chdc pillars. The material remains monocrystalline during dehydration from Co(5)(OH)(8)(chdc).4H(2)O (CDCC.4H(2)O) to Co(5)(OH)(8)(chdc) (CDCC) via an intermediate Co(5)(OH)(8)(chdc).2H(2)O (CDCC.2H(2)O) upon heating or evacuation. In-situ single crystal and powder X-ray diffraction analyses indicate that the interlayer spacing decreases in two steps, each corresponding to the loss of two water molecules per formula unit as determined by thermogravimetry. The single crystal structure of the fully dehydrated material, CDCC, has no void volume due to a tilting of the pillars and 9% decrease of the interlayer spacing with water removal. Exposure of CDCC to air causes rapid rehydration of this material to CDCC.4H(2)O, as determined by single crystal X-ray diffraction, powder X-ray diffraction, thermogravimetry, and vibrational spectroscopy. Both the hydrated and dehydrated forms order magnetically below 60.5 K. The susceptibility data are consistent with ferrimagnetic behavior, and the value of the saturation magnetization at 2 K (ca. 2 micro(B)) is explained by a model of two sublattices, one comprising three octahedral cobalt atoms and another comprising two tetrahedral cobalt atoms. There is an enhanced 2-D correlation within the layer at temperatures just above the Curie temperature, as seen by nonlinearity in the ac susceptibility data and remanence in the isothermal magnetization. The crossover from 2-D to 3-D ordering occurs at T(C). The large anisotropy in the magnetization data

  10. Cobalt Alums. A Demonstration Experiment

    NASA Astrophysics Data System (ADS)

    Schäffer, Claus E.; Steenberg, Paul

    2002-08-01

    The demonstration experiment describes the isolation of [Co(H2O)6]3+ both as the pure blue crystalline cesium cobalt alum, CsCo(SO4)2·12H2O, and as a light greenish-blue solid solution of ammonium cobalt alum in (NH4)Al(SO4)2·12H2O. The hexaaquacobalt(III) ion is prepared chemically by oxidation with hydrogen peroxide, taking advantage of the stabilization of CoIII relative to CoII by complexation with the carbonate ligand. A brief description of alum structure and a characterization of alum subclasses are included.

  11. Synthesis, characterization, antimicrobial activity and carbonic anhydrase enzyme inhibitor effects of salicilaldehyde-N-methyl p-toluenesulfonylhydrazone and its Palladium(II), Cobalt(II) complexes

    NASA Astrophysics Data System (ADS)

    Alyar, Saliha; Adem, Şevki

    2014-10-01

    We report the synthesis of the ligand, salicilaldehyde-N-methyl p-toluenesulfonylhydrazone (salptsmh) derived from p-toluenesulfonicacid-1-methylhydrazide (ptsmh) and its Pd(II) and Co(II) metal complexes were synthesized for the first time. The structure of the ligand and their complexes were investigated using elemental analysis, magnetic susceptibility, molar conductance and spectral (IR, NMR and LC-MS) measurements. Salptsmh has also been characterized by single crystal X-ray diffraction. 1H and 13C shielding tensors for crystal structure were calculated with GIAO/DFT/B3LYP/6-311++G(d,p) methods in CDCl3. The complexes were found to have general composition [ML2]. The results of elemental analysis showed 1:2 (metal/ligand) stoichiometry for all the complex. Magnetic and spectral data indicate a square planar geometry for Pd(II) complex and a distorted tetrahedral geometry for Co(II) complexes. The ligand and its metal chelates have been screened for their antimicrobial activities using the disk diffusion method against the selected Gram positive bacteria: Bacillus subtilis, Bacillus cereus, Staphylococcus aureus, Enterococcus faecalis, Gram negative bacteria: Eschericha coli, Pseudomonas aeruginosa, Klebsiella pneumonia. The inhibition activities of these compounds on carbonic anhydrase II (CA II) and carbonic anhydrase I (CA I) have been investigated by comparing IC50 and Ki values and it has been found that Pd(II) complex have more enzyme inhibition efficiency than salptsmh and Co(II) complex.

  12. A cobalt(II) bis(salicylate)-based ionic liquid that shows thermoresponsive and selective water coordination

    SciTech Connect

    Kohno, Y; Cowan, MG; Masuda, M; Bhowmick, I; Shores, MP; Gin, DL; Noble, RD

    2014-01-01

    A metal-containing ionic liquid (MCIL) has been prepared in which the [CoII(salicylate)(2)](2-) anion is able to selectively coordinate two water molecules with a visible colour change, even in the presence of alcohols. Upon moderate heating or placement in vacuo, the hydrated MCIL undergoes reversible thermochromism by releasing the bound water molecules.

  13. Crystal structure and magnetic properties of two isomeric three-dimensional pyromellitate-containing cobalt(II) complexes.

    PubMed

    Fabelo, Oscar; Pasán, Jorge; Cañadillas-Delgado, Laura; Delgado, Fernando S; Lloret, Francesc; Julve, Miguel; Ruiz-Pérez, Catalina

    2008-09-15

    The hydrothermal preparation, crystal structure determination, and magnetic study of two isomers made up of 1,2,4,5-benzenetetracarboxylate and high-spin Co(II) ions of formula [Co2(bta)(H2O)4]n x 2n H2O (1 and 2; H4bta = 1,2,4,5-benzenetetracarboxylic acid) are reported. 1 and 2 are three-dimensional compounds whose structures can be described as (4,4) rectangular layers of trans-diaquacobalt(II) units with the bta(4-) anion acting as tetrakis-monodentate ligand through the four carboxylate groups, which are further connected through other trans-[Co(H2O)2](2+) (1) and planar [Co(H2O)4](2+) (2) entities, with the bridging units being a carboxylate group in either the anti-syn (1) or syn-syn (2) conformations and a water molecule (2). The study of the magnetic properties of 1 and 2 in the temperature range 1.9-300 K shows the occurrence of weak antiferromagnetic interactions between the high-spin Co(II) ions, with the strong decrease of chi(M)T upon cooling being mainly due to the depopulation of the higher energy Kramers doublets of the six-coordinated Co(II) ions. The computed values of the exchange coupling between the Co(II) ions across anti-syn carboxylate (1) and syn-syn carboxylate/water (2) bridges are J = -0.060 (1) and -1.90 (2) cm(-1) (with the Hamiltonian being defined as H = -Jsigma(i,j)S(i) x S(j)). These values follow the different conformations of the carboxylate bridge in 1 (anti-syn) and 2 (syn-syn) with the occurrence of a double bridge in 2 (water/carboxylate).

  14. Investigation of intermediates and transition states in the catalytic mechanisms of active site substituted cobalt(II), nickel(II), zinc(II), and cadmium(II) horse liver alcohol dehydrogenase

    SciTech Connect

    Dunn, M.F.; Dietrich, H.; MacGibbon, A.K.H.; Koerber, S.C.; Zeppezauer, M.

    1982-01-12

    Active site substituted Co(II)-, Ni(II)-, and Cd(II)-horse liver alcohol dehydrogenase derivatives are compared to the native Zn(II)-enzyme with respect to the kinetic properties associated with the formation and decay of the intermediate observed in the reaction of the binary E-(NADH) complex with the intense substrate chromophore trans-4-(N,N-dimethylamino) cinnamaldehyde (DACA), lambda/sub max/ 398 nm (H/sub 2/O). All the metal ion subsituted enzymes were found to form intermediates with red-shifted spectra upon reaction with DACA and NADH. The magnitudes of (1) the red shifts, (2) the specific rate constants (k/sub off/) for dissociation of DACA from the intermediate, and (3) the hydride transfer rate constants (k /sub H/) were found to correlate with the expected order of the Lewis acid acidities (assuming tetrahedral coordination); i.e., Co(II) > Ni(II) greater than or equal to Zn(II) >> Cd(II). The k/sub H/ value for the Co(II)-E was found to be 1.4-fold greater than the value of 7.2 s/sup -1/ for Zn(II)-E, while the Cd(II)-E was40-fold lower. It is concluded that the close similarities in kinetic properties exhibited by Co(II)-, Ni(II)-, and Zn(II)-enzymes arise from the close similarities in coordination geometries and Lewis acid strengths which lead to highly similar transition states for the processes of intemediate formation and decay. (JMT)

  15. Microwave Mapping Demonstration Using the Thermochromic Cobalt Chloride Equilibrium

    ERIC Educational Resources Information Center

    Nguyen, Vu D.; Birdwhistell, Kurt R.

    2014-01-01

    An update to the thermochromic cobalt(II) chloride equilibrium demonstration is described. Filter paper that has been saturated with aqueous cobalt(II) chloride is heated for seconds in a microwave oven, producing a color change. The resulting pink and blue map is used to colorfully demonstrate Le Châtelier's principle and to illuminate the…

  16. Microwave Mapping Demonstration Using the Thermochromic Cobalt Chloride Equilibrium

    ERIC Educational Resources Information Center

    Nguyen, Vu D.; Birdwhistell, Kurt R.

    2014-01-01

    An update to the thermochromic cobalt(II) chloride equilibrium demonstration is described. Filter paper that has been saturated with aqueous cobalt(II) chloride is heated for seconds in a microwave oven, producing a color change. The resulting pink and blue map is used to colorfully demonstrate Le Châtelier's principle and to illuminate the…

  17. The renewable bismuth bulk annular band working electrode: fabrication and application in the adsorptive stripping voltammetric determination of nickel(II) and cobalt(II).

    PubMed

    Baś, Bogusław; Węgiel, Krystian; Jedlińska, Katarzyna

    2015-06-30

    The paper presents the first report on fabrication and application of a user friendly and mercury free electrochemical sensor, with the renewable bismuth bulk annular band working electrode (RBiABE), in stripping voltammetry (SV). The sensor body is partly filled with the internal electrolyte solution, in which the RBiABE is cleaned and activated before each measurement. Time of the RBiABE contact with the sample solution is precisely controlled. The usefulness of this sensor was tested by Ni(II) and Co(II) traces determination by means of differential pulse adsorptive stripping voltammetry (DP AdSV), after complexation with dimethylglyoxime (DMG) in ammonia buffer (pH 8.2). The experimental variables (composition of the supporting electrolyte, pre-concentration potential and time, potential of the RBiABE activation, and DP parameters), as well as possible interferences, were investigated. The linear calibration graphs for Ni(II) and Co(II), determined individually and together, in the range from 1×10(-8) to 70×10(-8)molL(-1) and from 1×10(-9) to 70×10(-9)molL(-1) respectively, were obtained. The calculated limit of detection (LOD), for 30s of the accumulation time, was 3×10(-9)molL(-1) for Ni(II) in case of a single element's analysis, whereas the LOD was 5×10(-9)molL(-1) for Ni(II) and 3×10(-10)molL(-1) for Co(II), when both metal ions were measured together. The repeatability of the Ni(II) and Co(II) adsorptive stripping voltammetric signals obtained at the RBiABE were equal to 5.4% and 2.5%, respectively (n=5). Finally, the proposed method was validated by determining Ni(II) and Co(II) in the certified reference waters (SPS-SW1 and SPS-SW2) with satisfactory results.

  18. Anisotropic Change in the Magnetic Susceptibility of a Dynamic Single Crystal of a Cobalt(II) Complex.

    PubMed

    Yao, Zi-Shuo; Wu, Shu-Qi; Kitagawa, Yasutaka; Su, Sheng-Qun; Huang, You-Gui; Li, Guo-Ling; Ni, Zhong-Hai; Nojiri, Hiroyuki; Shiota, Yoshihito; Yoshizawa, Kazunari; Kang, Soonchul; Kanegawa, Shinji; Sato, Osamu

    2017-01-16

    Atypically anisotropic and large changes in magnetic susceptibility, along with a change in crystalline shape, were observed in a Co(II) complex at near room temperature. This was achieved by combining oxalate molecules, acting as rotor, and a Co(II) ion with unquenched orbital angular momentum. A thermally controlled 90° rotation of the oxalate counter anion triggered a symmetry-breaking ferroelastic phase transition, accompanied by contraction-expansion behavior (ca. 4.5 %) along the long axis of a rod-like single crystal. The molecular rotation induced a minute variation in the coordination geometry around the Co(II) ion, resulting in an abrupt decrease and a remarkable increase in magnetic susceptibility along the direction perpendicular and parallel to the long axis of the crystal, respectively. Theoretical calculations suggested that such an unusual anisotropic change in magnetic susceptibility was due to a substantial reorientation of magnetic anisotropy induced by slight disruption in the ideal D3 coordination environment of the complex cation.

  19. Adsorption of iron(III), cobalt(II), and nickel(II) on activated carbon derived from Xanthoceras Sorbifolia Bunge hull: mechanisms, kinetics and influencing parameters.

    PubMed

    Zhang, Xiaotao; Hao, Yinan; Wang, Ximing; Chen, Zhangjing

    2017-04-01

    Xanthoceras Sorbifolia Bunge hull activated carbon (XSA) was prepared and characterized by Brunauer-Emmett-Teller analysis, scanning electron microscopy and energy dispersive X-ray (EDX) spectroscopy. The ability of XSA as an adsorbent was investigated for the removal of the iron group ions Fe(III), Co(II), and Ni(II) from aqueous solution. Optimum adsorption parameters were determined based on the initial concentrations of the iron group ions, pH, adsorption temperature, and adsorption time in adsorption studies. The maximum monolayer adsorption capacities were 241.13 mg/g for Fe(III), 126.05 mg/g for Co(II), and 187.96 mg/g for Ni(II), respectively. Adsorption kinetics and isotherms showed that the adsorption process best fitted the nonlinear pseudo-second-order and Langmuir models, and the affinity of the ions for XSA decreased as follows: Fe(III) > Ni(II) > Co(II). Regeneration studies indicated that XSA could be used after several consecutive adsorption/desorption cycles using HNO3. Fourier transform infrared and EDX spectra revealed the chemical adsorption value of XSA as an adsorbent for removing iron group ions from aqueous solutions.

  20. New complexes of cobalt(II) ions with pyridinecarboxylic acid N-oxides and 4,4‧-byp

    NASA Astrophysics Data System (ADS)

    Hnatejko, Zbigniew; Dutkiewicz, Grzegorz; Kubicki, Maciej; Lis, Stefan

    2013-02-01

    This paper reports a study concerning the isolation and characterization of mixed ligand complexes of the Co(II) ions with pyridinecarboxylic acids N-oxides (picolinic (PNO), nicotinic (NNO) and isonicotinic (INO)), [Co(PNO)2(4,4'-byp)]·6H2O 1, [Co(NNO)(4,4'-byp)NO3]·8H2O 2 and [Co(INO)(4,4'-byp)NO3]·7H2O 3; (4,4'-byp = 4,4'-bipyridine). The complexes 2 and 3 were prepared by the hydrothermal synthesis. The structures of the complexes were elucidated on the basis of elemental analysis, thermal decomposition, IR and mass spectroscopy. IR spectra show that N-oxides act as bidentate ligands, in which both the N-oxide and the carboxylate groups are involved in coordination. In 2 and 3 the Co(II) ion exists in the same coordination environment. For 1, the X-ray crystal structure has been determined and it turned out that it contains the coordination polymers, created by the chains of Co ions joined by 4,4'-byp ligands. The Co(II) ion occupies the center of symmetry in the space group C2/c. This ion is coordinated by two nitrogen atoms (from two 4,4'-byp ligands) and four oxygen atoms from two PNO anions. The extensive network of hydrogen bonds involving six different water molecules connects the one-dimensional polymers into three-dimensional crystal structure.

  1. Dichloridobis(3,5-dimethyl-1H-pyrazol-4-amine-κN 2)cobalt(II)

    PubMed Central

    Cai, Xing-Wei; Zhao, Yu-Yuan; Han, Guang-Fan

    2008-01-01

    In the title compound, [CoCl2(C5H9N3)2], the CoII atom adopts a slightly distorted tetra­hedral coordination geometry provided by two chloride anions and two N atoms from the organic ligands. The dihedral angle between the pyrazole rings is 85.91 (10)°. In the crystal structure, mol­ecules are linked into a three-dimensional network by inter­molecular N—H⋯N and N—H⋯Cl hydrogen-bonding inter­actions. PMID:21203006

  2. Electron-transfer reactions of cobalt(III) complexes. 1. The kinetic investigation of the reduction of various surfactant cobalt(III) complexes by iron(II) in surface active ionic liquids.

    PubMed

    Nagaraj, Karuppiah; Senthil Murugan, Krishnan; Thangamuniyandi, Pilavadi; Sakthinathan, Subramanian

    2015-05-15

    The kinetics of outer sphere electron transfer reaction of surfactant cobalt(III) complex ions, cis-[Co(en)2(C12H25NH2)2](3+) (1), cis-[Co(dp)2(C12H25NH2)2](3+) (2), cis-[Co(trien)(C12H25NH2)2](3+) (3), cis-[Co(bpy)2(C12H25NH2)2](3+) (4) and cis-[Co(phen)2(C12H25NH2)2](3+) (5) (en: ethylenediamine, dp: diaminopropane, trien : triethylenetetramine, bpy: 2,2'-bipyridyl, phen: 1,10-phenanthroline and C12H25NH2 : dodecylamine) have been interrogated by Fe(2+) ion in ionic liquid (1-butyl-3-methylimidazoliumbromide) medium at different temperatures (298, 303, 308, 313, 318 and 323K) by the spectrophotometry method under pseudo first order conditions using an excess of the reductant. Experimentally the reactions were found to be of second order and the electron transfer as outer sphere. The second order rate constant for the electron transfer reaction in ionic liquids was found to increase with increase in the concentration of all these surfactant cobalt(III) complexes. Among these complexes (from en to phen ligand), complex containing the phenanthroline ligand rate is higher compared to other complexes. By assuming the outer sphere mechanism, the results have been explained based on the presence of aggregated structures containing cobalt(III) complexes at the surface of ionic liquids formed by the surfactant cobalt(III) complexes in the reaction medium. The activation parameters (enthalpy of activation ΔH(‡) and entropy of activation ΔS(‡)) of the reaction have been calculated which substantiate the kinetics of the reaction.

  3. Diaqua-bis-(2-iodo-benzoato-κO)bis-(nicotinamide-κN(1))cobalt(II).

    PubMed

    Aydın, Omür; Caylak Delibaş, Nagihan; Necefoğlu, Hacali; Hökelek, Tuncer

    2012-04-01

    In the title complex, [Co(C(7)H(4)IO(2))(2)(C(6)H(6)N(2)O)(2)(H(2)O)(2)], the Co(II) cation is located on an inversion center and is coordinated by two monodentate 2-iodo-benzoate (IB) anions, two nicotin-amide (NA) ligands and two water mol-ecules. The four O atoms in the equatorial plane around the Co(II) cation form a slightly distorted square-planar arrangement, while the slightly distorted octa-hedral coordination is completed by the two N atoms of the NA ligands in the axial positions. The dihedral angle between the carboxyl-ate group and the adjacent benzene ring is 22.3 (3)°, while the pyridine ring and the benzene ring are oriented at a dihedral angle of 84.59 (13)°. Intra-molecular O-H⋯O hydrogen bonding occurs between the carboxyl-ate group and coordinated water mol-ecule. In the crystal, N-H⋯O, O-H⋯O and weak C-H⋯O hydrogen bonds link the mol-ecules into a three-dimensional supra-molecular network.

  4. Diaqua-bis-(2-chloro-benzoato-κO)bis-(nicotinamide-κN (1))cobalt(II).

    PubMed

    Dincel, Oznur; Tercan, Barış; Oztürkkan, Füreya Elif; Necefoğlu, Hacali; Hökelek, Tuncer

    2013-03-01

    In the title complex, [Co(C7H4ClO2)2(C6H6N2O)2(H2O)2], the Co(II) cation is located on an inversion center and is coord-inated by two 2-chloro-benzoate anions, two nicotin-amide (NA) ligands and two water mol-ecules. The four O atoms in the equatorial plane around the Co(II) cation form a slightly distorted square-planar arrangement, while the slightly distorted octa-hedral coordination is completed by the two pyridine N atoms of the NA ligands in the axial positions. The dihedral angle between the carboxyl-ate group and the adjacent benzene ring is 29.7 (4)°, while the pyridine and benzene rings are oriented at a dihedral angle of 83.17 (15)°. Intra-molecular O-H⋯O hydrogen bonding occurs between the carboxyl-ate group and coordinating water mol-ecule. In the crystal, inter-molecular N-H⋯O, O-H⋯O and weak C-H⋯O hydrogen bonds link the mol-ecules into a three-dimensional network.

  5. Thiocyanate-free ruthenium(II) sensitizers for dye-sensitized solar cells based on the cobalt redox couple.

    PubMed

    Wu, Kuan-Lin; Clifford, John N; Wang, Sheng-Wei; Aswani, Yella; Palomares, Emilio; Lobello, Maria Grazia; Mosconi, Edoardo; De Angelis, Filippo; Ku, Wan-Ping; Chi, Yun; Nazeeruddin, Mohammad K; Grätzel, Michael

    2014-10-01

    Two thiocyanate-free ruthenium(II) sensitizers, TFRS-41 and TFRS-42, with distinctive dialkoxyphenyl thienyl substituents were successfully prepared and tested for potential applications in making dye-sensitized solar cells (DSCs). Subsequent device fabrication was conducted by using a [Co(bpy)3 ](2+/3+) -based (bpy=2,2'-bipyridine) electrolyte, for which the best performance data, namely, JSC =13.11 mA cm(-2) , VOC =862 mV, fill factor=0.771, and η=8.71%, were recorded for the sensitizer TFRS-42 with a 2,6-dialkoxyphenyl substituent under AM 1.5G irradiation. The markedly higher Voc value was confirmed by the longer electron lifetime revealed in transient photovoltage (TPV) measurements versus the TFRS-1 sensitizer. In addition, DFT calculation and detailed first-principles computational analysis were conducted to provide a rationale for the observed trends in their photovoltaic performances and electron lifetimes, with reference to different performances exhibited by three thiocyanate-free sensitizers, TFRS-1, TFRS-41 and TFRS-42, versus Z907 reference. Through the proper control of peripheral substituents, the thiocyanate-free ruthenium(II)-based DSC sensitizers can positively influence the performances of DSCs, with better light-harvesting capability and suppressed charge recombination, for DSC cells fabricated by using a [Co(bpy)3 ](2+/3+) -based electrolyte. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Crystal structure of aqua-tris-(isonicotinamide-κN)bis-(thio-cyanato-κN)cobalt(II) 2.5-hydrate.

    PubMed

    Neumann, Tristan; Jess, Inke; Näther, Christian

    2016-09-01

    The asymmetric unit of the title compound, [Co(NCS)2(C6H6N2O)3(H2O)]·2.5H2O, comprises one Co(II) cation, three isonicotinamide ligands, two thio-cyanate anions, one aqua ligand and two water solvent mol-ecules in general positions, as well as one water solvent mol-ecule that is located on a twofold rotation axis. The Co(II) cations are octa-hedrally coordinated by two terminally N-bonded thio-cyanate anions, one water mol-ecule and three isonicotinamide ligands, each coordinating via the pyridine N atom. The discrete complexes are linked by inter-molecular O-H⋯O, N-H⋯O and N-H⋯S hydrogen bonding into a three-dimensional network that contains cavities in which the solvent water mol-ecules are located. The latter are linked by further O-H⋯O hydrogen bonds to the network. There are additional short contacts present in the crystal, indicative of weak C-H⋯S, C-H⋯O and C-H⋯N inter-actions.

  7. In situ tetrazole templated chair-like decanuclear azido-cobalt(II) SMM containing both tetra- and octa-hedral Co(II) ions.

    PubMed

    Zhang, Yuan-Zhu; Gao, Song; Sato, Osamu

    2015-01-14

    An azido-bridged chair-like decanuclear cluster: [Co(II)10(bzp)8(Metz)2(N3)18]·4MeOH·3H2O (1, bzp = 2-benzoylpyridine and HMetz = 5-methyl-1H-tetrazole) was prepared with in situ tetrazolate anions as templates in a sealed system. 1 containing both octahedral and tetrahedral Co(II) ions exhibited slow relaxation of magnetization with an effective barrier of 26 K under an applied dc field of 1 kOe.

  8. Spectrophotometric analysis of 5-coordinate cobalt(II) species for ligand substitution of hexakis(acetonitrile)cobalt(II) with bulky 1,1,3,3-tetramethylurea in noncoordinating nitromethane.

    PubMed

    Inada, Y; Hotta, N; Kuwabara, H; Funahashi, S

    2001-01-01

    The ligand substitution reaction of [Co(an)6]2+ (an = acetonitrile) with 1,1,3,3-tetramethylurea (TMU) in the noncoordinating solvent, nitromethane, was spectrophotometrically investigated by titration. The observed spectral changes were analyzed using a model with the four steps of ligand substitution. The component complexes involved in the substitution were found to be 6-coordinate [Co(an)6]2+ and [Co(an)5(tmu)]2+, 5-coordinate [Co(an)3(tmu)2]2+ and [Co(an)2(tmu)3]2+, and 4-coordinate [Co(tmu)4]2+. The logarithmic values of the stepwise equilibrium constant are 2.17 +/- 0.26, 1.06 +/- 0.15, 1.19 +/- 0.06, and -0.4 +/- 0.4 at 25 degrees C. The decrease in the coordination number of the Co(II) ion from 6 to 5 during the formation of [Co(an)3(tmu)2]2+ and from 5 to 4 during the formation of [Co(tmu)4]2+ is ascribed to the steric repulsion between the coordinating bulky TMU molecules.

  9. Uptake of indium-111-labeled platelets and indium-111 oxine by murine kidneys after total-body irradiation

    SciTech Connect

    Ebbe, S.; Taylor, S.; Maurer, H.; Kullgren, B.

    1996-08-01

    Radiation nephropathy is a well-known late manifestation of renal irradiation in human beings and experimental animals. Its pathogenesis is unclear, but vascular injury may play a role. Endothelial cells have been demonstrated to manifest a variety of abnormalities within hours of exposure to radiation. In the present experiments mice were exposed to lethal doses of whole-body radiation, and the distribution of {sup 111}In-labeled platelets was evaluated during the first week after irradiation. The purpose was to determine if early abnormalities of endothelial cells would be manifested by altered sequestration of platelets in kidneys and other organs. It was found that the indium accumulated in the kidneys of irradiated mice to a greater extent than in nonirradiated mice, but the pattern of accumulation differed from that seen after injection of radiolabeled platelets. Renal hyperemia was not demonstrable with {sup 51}Cr-labeled red cells, renal vascular permeability was not detected with {sup 125}I-labeled albumin, and the pattern of renal uptake of plasma proteins labeled albumin, and the pattern of renal uptake of plasma proteins labeled with {sup 59}Fe {sup 111}In did not coincide with that seen from {sup 111}In administered as labeled platelets or oxine. Renal uptake of {sup 111}In-oxine was not associated with alterations in urinary or fecal excretion or an increase in total-body retention of the radioisotope. The findings are consistent with the notion that renal vascular injury at the time of irradiation results in accumulation of platelets or platelet constituents during the first week after total-body irradiation of mice. 29 refs., 5 figs., 3 tabs.

  10. Sperm-macrophage interaction in the mouse: a quantitative assay in vitro using 111indium oxine-labeled sperm

    SciTech Connect

    Olive, D.L.; Weinberg, J.B.; Haney, A.F.

    1987-12-01

    The role of reproductive tract macrophages in contraception and reproductive failure has become widely recognized. However, in vitro analysis of sperm phagocytosis by macrophages has relied upon a semi-quantitative method of sperm counting that is of limited accuracy and reproducibility. We have developed an assay using murine sperm labeled with /sup 111/indium oxine, and results indicate the labeling to be rapid and efficient. Incorporation of /sup 111/indium into sperm increased the dose and sperm concentration and reached 90% maximal uptake after 15 min incubation, with maximal uptake occurring at 30 min. No decrease in sperm motility was noted with levels of oxine in excess of those required for significant labeling. Maximal labeling efficiency occurred in phosphate-buffered saline (PBS), with Dulbecco's modified Eagle's medium (DMEM) + 10% adult bovine serum (ABS) producing significantly less uptake. Label dissociation was detectable in PBS at room temperature, but at 37 degrees C in DMEM + 10% ABS, loss of label occurred at a rate of 23.5%/h. Addition of labeled sperm to murine macrophage monolayers under optimal conditions resulted in uptake of /sup 111/indium by macrophages, while free label was unincorporated. Results indicated assay specificity for macrophage-limited uptake, with insignificant label uptake by nonphagocytic murine fibroblasts and better sensitivity than sperm counting. Macrophages from Bacillus Calmette-Guerin (BCG)-infected mice resulted in a decrease in sperm uptake. Female macrophages showed greater capacity for sperm uptake than those of the male mouse. These initial studies demonstrated the utility of this model system in enhancing the understanding of sperm-macrophage interaction in the female reproductive tract.

  11. Synthesis, characterization and antitumoral activity of new cobalt(II)complexes: Effect of the ligand isomerism on the biological activity of the complexes.

    PubMed

    Morcelli, Samila R; Bull, Érika S; Terra, Wagner S; Moreira, Rafaela O; Borges, Franz V; Kanashiro, Milton M; Bortoluzzi, Adailton J; Maciel, Leide L F; de A Almeida, João Carlos; Júnior, Adolfo Horn; Fernandes, Christiane

    2016-08-01

    The synthesis, physico-chemical characterization and cytotoxicity against five human tumoral cell lines (THP-1, U937, Molt-4, Colo205 and H460) of three new cobalt(II) coordination compounds are reported (i.e. Co(HL1)Cl (1), Co(HL2)Cl (2) and [Co(HL3)Cl]0.0.5 (CH3)2CHOH (3)). H2L2 (2-{[[2-hydroxy-3-(1-naphthyloxy)propyl](pyridin-2-ylmethyl)amino]methyl}phenol) and H2L3 (2-{[[2-hydroxy-3-(2-naphthyloxy)propyl](pyridin-2-ylmethyl)amino]methyl}phenol) present α and β-naphthyl groups respectively, which is absent in H2L1 (N-(2-hydroxybenzyl)-N-(2-pyridylmethyl)[(3-chloro)(2-hydroxy)]propylamine. These compounds were characterized by a range of physico-chemical methods. X-ray diffraction studies were performed for complex (3), indicating the formation of a mononuclear complex. Complexes (2) and (3), which contain α and β-naphthyl groups respectively, have presented lower IC50 values than those exhibited by complex (1). Complex (3) presents IC50 values lower than cisplatin against Colo205 (90 and 196μmolL(-1), respectively) and H460 (147 and 197μmolL(-1), respectively). These human neoplastic cells under investigation were also more susceptible toward complex (3) than peripheral blood mononuclear cells. Transmission electron microscopy investigations are in agreement with the loss of mitochondrial membrane potential (ΔΨm) observed by JC-1 mitochondrial potential sensor and indicate that the activity of complex (3) against leukemic cell line (U937) is mediated by an apoptotic mechanism associated with mitochondrial dysfunction (intrinsic pathway).

  12. Effect of Low Dose Lead (Pb) Administration on Tail Immersion Test and Formalin-induced Pain in Wistar Rats: Possible Modulatory Role of Cobalt (II) Chloride.

    PubMed

    Umar, A H; Suleiman, I; Muhammed, H

    2017-03-06

    Lead (Pb) is cheap and there is a long tradition of its use, but its toxic effects have also been recognized. There is increased public health concern regarding the hazards of low dose Pb exposure to adults and children. Studies have shown the risks for hypertension, decrements in renal function, subtle decline in cognitive function, and adverse reproductive outcome at low blood Pb level. In this study, the possible modulatory role of cobalt (II) chloride (CoCl2) on low level Pb exposure on tail immersion test and formalin induced pain was investigated. Twenty adult Wistar rats of both sexes (weight 150g to 200g) were used. The animals were divided into four groups (n = 5) and administered Pb (5mg/kg), Pb (5mg/kg) + CoCl2 (50mg/kg) and CoCl2 (50mg/kg) orally for twenty-eight days. The last group served as control and were given distilled water only. In the tail immersion test, there was no significant change in reaction time for all three groups when compared to the control. In the formalin-induced pain, pain score after five and forty-five minutes also do not show significant change for all the three groups when compared to control. This work suggested that exposure to 5mg/kg Pb for twenty-eight days do not significantly impair reaction time in tail immersion test and pain score in formalin induced pain in Wistar rats. Also, administration of 50mg/kg CoCl2 do not improve performance of the animals in the experiments.

  13. Effect of dispersion on surface interactions of cobalt(II) octaethylporphyrin monolayer on Au(111) and HOPG(0001) substrates: a comparative first principles study.

    PubMed

    Chilukuri, Bhaskar; Mazur, Ursula; Hipps, K W

    2014-07-21

    A density functional theory study of a cobalt(II) octaethylporphyrin (CoOEP) monolayer on Au(111) and HOPG(0001) surfaces was performed under periodic boundary conditions. Calculations with and without dispersion corrections are performed and the effect of van der Waals forces on the interface properties is analyzed. Calculations have determined that the CoOEP molecule tends to bind at the 3-fold and the 6-fold center sites on Au(111) and HOPG(0001), respectively. Geometric optimizations at the center binding sites have indicated that the porphyrin molecules (in the monolayer) lie flat on both substrates. Calculations also reveal that the CoOEP monolayer binds slightly more strongly to Au(111) than to HOPG(0001). Charge density difference plots disclose that charge is redistributed mostly around the porphyrin plane and the first layer of the substrates. Dispersion interactions cause a larger substrate to molecule charge pushback on Au(111) than on HOPG. CoOEP adsorption tends to lower the work functions of either substrate, qualitatively agreeing with the experimental photoelectron spectroscopic data. Comparison of the density of states (DOS) of the isolated CoOEP molecule with that on gold and HOPG substrates showed significant band shifts around the Fermi energy due to intermolecular orbital hybridization. Simulated STM images were plotted with the Tersoff-Hamann approach using the local density of states, which also agree with the experimental results. This study elucidates the role of dispersion for better describing porphyrin-substrate interactions. A DFT based overview of geometric, adsorption and electronic properties of a porphyrin monolayer on conductive surfaces is presented.

  14. Bio-relevant cobalt(II) complexes with compartmental polyquinoline ligand: synthesis, crystal structures and biological activities.

    PubMed

    Li, Jun-Ling; Jiang, Lin; Wang, Bi-Wei; Tian, Jin-Lei; Gu, Wen; Liu, Xin; Yan, Shi-Ping

    2015-04-01

    Three new Co(II) complexes, [Co4(L)2(μ3-CrO4)2](ClO4)2·2CH3CN (1), [Co2(L)(μ2-na)(H2O)](ClO4)2 (2) and [Co2(L)(μ2-ba)](ClO4)2·0.5CH3CN (3) (Hna=nicotinic acid, Hba=benzoic acid, HL=N,N,N',N'-tetrakis (2-quinolylmethyl)-1,3-diaminopropan-2-ol), have been synthesized and characterized by various physicochemical techniques. The Co(II) centers are connected by endogenous alkoxy bridge from L(-) and various extrinsic auxiliary linkers, some of which display coordination number asymmetry (5, 6-coordinated for 1 and 2; 5, 5-coordinated for 3). It is worth mentioning that complex 1 contains two rare reported μ3-η(1), η(1), η(1)-CrO4(2-) moieties. Susceptibility data of three complexes indicated intramolecular antiferromagnetic coupling of high-spin Co(II) atoms with exchange integral values (J) -14.94 cm(-1), -11.26 cm(-1) and -13.66 cm(-1) for 1, 2 and 3, respectively. Interaction of compounds with calf thymus DNA (CT-DNA) have been investigated by absorption spectral titration, ethidium bromide (EB) displacement assay and viscosity measurement, which revealed that compounds bound to CT-DNA with a moderate intercalative mode, accompanied the affinities order: 1>2≈3. Three complexes exhibit oxidative cleavage of pBR322 plasmid DNA including a reliance on H2O2 as the activator. Compound 1 demonstrates an increased DNA cleavage activity as compared with 2 and 3, which could degrade super coiled DNA (SC DNA) into nicked coiled DNA (NC DNA) in lower concentration (5 μM). Moreover, all compounds could quench the intrinsic fluorescence of bovine serum albumin (BSA) in a static quenching process. Complex 1 also shows higher anticancer activity than cisplatin with lower IC50 value of incubation for both 24 h and 48 h.

  15. Light-activated protein inhibition through photoinduced electron transfer of a ruthenium(II)–cobalt(III) bimetallic complex

    DOE PAGES

    Holbrook, Robert J.; Weinberg, David J.; Peterson, Mark D.; ...

    2015-02-11

    In this paper, we describe a mechanism of light activation that initiates protein inhibitory action of a biologically inert Co(III) Schiff base (Co(III)-sb) complex. Photoinduced electron transfer (PET) occurs from a Ru(II) bipyridal complex to a covalently attached Co(III) complex and is gated by conformational changes that occur in tens of nanoseconds. Reduction of the Co(III)-sb by PET initiates displacement of the inert axial imidazole ligands, promoting coordination to active site histidines of α-thrombin. Upon exposure to 455 nm light, the rate of ligand exchange with 4-methylimidazole, a histidine mimic, increases by approximately 5-fold, as observed by NMR spectroscopy. Similarly,more » the rate of α-thrombin inhibition increases over 5-fold upon irradiation. Finally, these results convey a strategy for light activation of inorganic therapeutic agents through PET utilizing redox-active metal centers.« less

  16. Bis[2,4-dibromo-6-(n-propyl-imino-methyl)phenolato-κN,O]cobalt(II).

    PubMed

    Li, Chunyan; Li, Rui; Zhang, Shufang

    2010-08-18

    In the title complex, [Co(C(10)H(10)Br(2)NO)(2)], the Co(II) atom lies on a twofold rotation axis, the N(2)O(2) units having distorted tetra-hedral coordination environments comprising two bidentate chelate 2,4-dibromo-6-(n-propyl-imino-meth-yl)phenolate Schiff base ligands [Co-N = 1.989 (3) Å, Co-O = 1.924 (2) Å and O/N-Co-O/N = 94.53 (10)-125.40 (15)°]. In the crystal structure, the mol-ecules are linked via weak inter-molecular C-H⋯O hydrogen bonds [3.334 (5) Å] and there are also short inversion-related intermolecular Br⋯Br contacts [3.4263 (6) Å].

  17. Light-Activated Protein Inhibition through Photoinduced Electron Transfer of a Ruthenium(II)–Cobalt(III) Bimetallic Complex

    PubMed Central

    Holbrook, Robert J.; Weinberg, David J.; Peterson, Mark D.; Weiss, Emily A.; Meade, Thomas J.

    2015-01-01

    We describe a mechanism of light activation that initiates protein inhibitory action of a biologically inert Co(III) Schiff base (Co(III)-sb) complex. Photoinduced electron transfer (PET) occurs from a Ru(II) bipyridal complex to a covalently attached Co(III) complex and is gated by conformational changes that occur in tens of nanoseconds. Reduction of the Co(III)-sb by PET initiates displacement of the inert axial imidazole ligands, promoting coordination to active site histidines of α-thrombin. Upon exposure to 455 nm light, the rate of ligand exchange with 4-methylimidazole, a histidine mimic, increases by approximately 5-fold, as observed by NMR spectroscopy. Similarly, the rate of α-thrombin inhibition increases over 5-fold upon irradiation. These results convey a strategy for light activation of inorganic therapeutic agents through PET utilizing redox-active metal centers. PMID:25671465

  18. Bis[bis-(1-ethyl-benzimidazol-2-ylmeth-yl) ether]cobalt(II) dipicrate dimethyl-formamide disolvate.

    PubMed

    Wu, Huilu; Yun, Ruirui; Sun, Tao; Li, Ke; Meng, Xuan

    2009-09-12

    In the title complex, [Co(C(20)H(22)N(4)O)(2)](C(6)H(2)N(3)O(7))(2)·2C(3)H(7)NO, the Co(II) ion is coordinated by two sets of two N atoms and an O atom from two independent tridendate ligands in a distorted octa-hedral coordination environment. There are significant differences between chemically equivalent coordination bond lengths. The crystal structure is stabilized by weak inter-molecular C-H⋯O hydrogen bonds and weak π-π stacking inter-actions [centroid-centroid distance 3.495 (1) Å]. In one of the anions one nitro group is rotationally disordered about the C-N bond with refined occupancies of 0.524 (8) and 0.476 (8).

  19. Light-activated protein inhibition through photoinduced electron transfer of a ruthenium(II)–cobalt(III) bimetallic complex

    SciTech Connect

    Holbrook, Robert J.; Weinberg, David J.; Peterson, Mark D.; Weiss, Emily A.; Meade, Thomas J.

    2015-02-11

    In this paper, we describe a mechanism of light activation that initiates protein inhibitory action of a biologically inert Co(III) Schiff base (Co(III)-sb) complex. Photoinduced electron transfer (PET) occurs from a Ru(II) bipyridal complex to a covalently attached Co(III) complex and is gated by conformational changes that occur in tens of nanoseconds. Reduction of the Co(III)-sb by PET initiates displacement of the inert axial imidazole ligands, promoting coordination to active site histidines of α-thrombin. Upon exposure to 455 nm light, the rate of ligand exchange with 4-methylimidazole, a histidine mimic, increases by approximately 5-fold, as observed by NMR spectroscopy. Similarly, the rate of α-thrombin inhibition increases over 5-fold upon irradiation. Finally, these results convey a strategy for light activation of inorganic therapeutic agents through PET utilizing redox-active metal centers.

  20. Synthesis and Reactivity of Four- and Five-Coordinate Low-Spin Cobalt(II) PCP Pincer Complexes and Some Nickel(II) Analogues.

    PubMed

    Murugesan, Sathiyamoorthy; Stöger, Berthold; Carvalho, Maria Deus; Ferreira, Liliana P; Pittenauer, Ernst; Allmaier, Günter; Veiros, Luis F; Kirchner, Karl

    2014-11-10

    Anhydrous CoCl2 or [NiCl2(DME)] reacts with the ligand PCP(Me)-iPr (1) in the presence of nBuLi to afford the 15e and 16e square planar complexes [Co(PCP(Me)-iPr)Cl] (2) and [Ni(PCP(Me)-iPr)Cl] (3), respectively. Complex 2 is a paramagnetic d(7) low-spin complex, which is a useful precursor for a series of Co(I), Co(II), and Co(III) PCP complexes. Complex 2 reacts readily with CO and pyridine to afford the five-coordinate square-pyramidal 17e complexes [Co(PCP(Me)-iPr)(CO)Cl] (4) and [Co(PCP(Me)-iPr)(py)Cl] (5), respectively, while in the presence of Ag(+) and CO the cationic complex [Co(PCP(Me)-iPr)(CO)2](+) (6) is afforded. The effective magnetic moments μeff of all Co(II) complexes were derived from the temperature dependence of the inverse molar magnetic susceptibility by SQUID measurements and are in the range 1.9 to 2.4 μB. This is consistent with a d(7) low-spin configuration with some degree of spin-orbit coupling. Oxidation of 2 with CuCl2 affords the paramagnetic Co(III) PCP complex [Co(PCP(Me)-iPr)Cl2] (7), while the synthesis of the diamagnetic Co(I) complex [Co(PCP(Me)-iPr)(CO)2] (8) was achieved by stirring 2 in toluene with KC8 in the presence of CO. Finally, the cationic 16e Ni(II) PCP complex [Ni(PCP(Me)-iPr)(CO)](+) (10) was obtained by reacting complex 3 with 1 equiv of AgSbF6 in the presence of CO. The reactivity of CO addition to Co(I), Co(II), and Ni(II) PCP square planar complexes of the type [M(PCP(Me)-iPr)(CO)] (n) (n = +1, 0) was investigated by DFT calculations, showing that formation of the Co species, 6 and 8, is thermodynamically favorable, while Ni(II) maintains the 16e configuration since CO addition is unfavorable in this case. X-ray structures of most complexes are provided and discussed. A structural feature of interest is that the apical CO ligand in 4 deviates significantly from linearity, with a Co-C-O angle of 170.0(1)°. The DFT-calculated value is 172°, clearly showing that this is not a packing but an electronic effect.

  1. Electrochemical-driven water splitting catalyzed by a water-soluble cobalt(II) complex supported by N,N‧-bis(2‧-pyridinecarboxamide)-1,2-benzene with high turnover frequency

    NASA Astrophysics Data System (ADS)

    Wang, Zhuo-Qiang; Tang, Ling-Zhi; Zhang, Yun-Xiao; Zhan, Shu-Zhong; Ye, Jian-Shan

    2015-08-01

    The oxidation and reduction of water is a key challenge in the production of chemical fuels from electricity. Reported here is a soluble cobalt (II) complex, [Co(bpbH2)Cl2] 1 (bpbH2: N,N‧-bis(2‧-pyridinecarboxamide)-1,2-benzene), a highly active homogeneous electrocatalyst for both electrolytic water oxidation and reduction in purely aqueous solution. Electrochemical studies indicate that the catalyst is a water-soluble molecular species, that is among the most rapid homogeneous catalysts for water oxidation, with a turnover frequency of ∼81.54 s-1 (at pH 8.6, the lowest pH among those of any reported electrocatalysts) at an overpotential of 560 mV. 1 also can catalyze hydrogen evolution from water with a TOF of 376 mol of hydrogen per mole of catalyst per hour at an overpotential of 687.6 mV (pH 7.0). This is attributed to the planar ligand (bpbH2), that coordinates strongly through four nitrogen atoms to the cobalt center, leaving two Cl- ions in axial position and making the Cl- ion ionize in organic solvents or water, and can stabilize both the high and low oxidation states of cobalt well.

  2. In-vitro antibacterial, antifungal and cytotoxic activity of cobalt (II), copper (II), nickel (II) and zinc (II) complexes with furanylmethyl- and thienylmethyl-dithiolenes: [1, 3-dithiole- 2-one and 1,3-dithiole-2-thione].

    PubMed

    Chohan, Zahid H; Shaikh, Ali U; Supuran, Claudiu T

    2006-12-01

    Some antibacterial and antifungal furanylmethyl-and thienylmethyl dithiolenes and, their Co(II), Cu(II), Ni (II) and Zn (II) complexes have been synthesized, characterized and screened for their in vitro antibacterial activity against four Gram-negative; Escherichia coli, Pseudomonas aeruginosa, Salmonella typhi and Shigella flexeneri, and two Gram-positive; Bacillus subtilis and Staphylococcus aureus bacterial strains, and for in-vitro antifungal activity against Trichophyton longifusus, Candida albicans, Aspergillus flavus, Microsporum canis, Fusarium solani and Candida glaberata. All compounds showed significant antibacterial and antifungal activity. The metal complexes, however, were shown to possess better activity as compared to the simple ligands. The brine shrimp bioassay was also carried out to study their in-vitro cytotoxic properties.

  3. Biogenic glutamic acid-based resin: Its synthesis and application in the removal of cobalt(II).

    PubMed

    Jamiu, Zakariyah A; Saleh, Tawfik A; Ali, Shaikh A

    2017-04-05

    Inexpensive biogenic glutamic acid has been utilized to synthesize a cross-linked dianionic polyelectrolyte (CDAP) containing metal chelating ligands. Cycloterpolymerization, using azoisobutyronitrile as an initiator, of N,N-diallylglutamic acid hydrochloride, sulfur dioxide and a cross-linker afforded a pH-responsive cross-linked polyzwitterionic acid (CPZA) which upon basification with NaOH was converted into CDAP. The new resin, characterized by a multitude of spectroscopic techniques as well as Scanning Electron Microscopy (SEM) and Brunauer-Emmett-Teller (BET) analyses, was evaluated for the removal of Co(II) as a model case under different conditions. The adsorption capacity of 137mgg(-1) does indeed make the resin as one of the most effective sorbents in recent times. The resin leverages its cheap natural source and ease of regeneration in combination with its high and fast uptake capacities to offer a great promise for wastewater treatment. The resin has demonstrated remarkable efficiency in removing toxic metal ions including arsenic from a wastewater sample.

  4. Diacridinium trans-diaqua­bis(pyrazine-2,3-dicarboxyl­ato)cobaltate(II) hexa­hydrate

    PubMed Central

    Aghabozorg, Hossein; Attar Gharamaleki, Jafar; Parvizi, Mahdieh; Derikvand, Zohreh

    2010-01-01

    The title compound, (C13H10N)2[Co(C6H2N2O4)2(H2O)2]·6H2O, consists of mononuclear trans-[Co(pz-2,3-dc)2(H2O)2]2− complex anions, (acrH)+ cations and uncoordinated water mol­ecules (acr is acridine and pz-2,3-dcH2 is pyrazine-2,3-dicarboxylic acid). The CoII atom, which lies on a crystallographic center of symmetry, has a slightly distorted octa­hedral coordination environment, with two N and two O atoms from the (pz-2,3-dc)2− ligands in the equatorial plane and with two water mol­ecules in axial positions. In the crystal, the components are held together by two distinct N—H⋯O and C—H⋯O hydrogen bonds with R 2 2(8) graph-sets. The coordinated and uncoordinated water mol­ecules are also involved in O—H⋯O hydrogen bonds, which lead to the formation of layers with R 3 3(12) graph-set motifs. Extensive π–π stacking inter­actions between parallel aromatic rings of the acridinium ions, with distances ranging from 3.533 (1) to 3.613 (1) Å, occur in the structure. PMID:21579976

  5. The binding of 1,10-phenanthroline to specifically active-site cobalt(II)-substituted horse-liver alcohol dehydrogenase. A probe for the open-enzyme conformation.

    PubMed

    Sartorius, C; Dunn, M F; Zeppezauer, M

    1988-11-15

    We have studied the binding of 1,10-phenanthroline to specifically active-site cobalt(II)-substituted horse-liver alcohol dehydrogenase [Co(II)-LADH]. The dissociation constant is a factor of 6500 smaller than in the native enzyme. Spectral evidence is given which shows that 1,10-phenanthroline does not remove the catalytic Co(II) ion and that binding of 1,10-phenanthroline renders the catalytic metal ion pentacoordinate. The maximum limiting rate constant for the association of 1,10-phenanthroline to Co(II)-LADH is about 60 s-1. This is about a third of the value (169 s-1) determined for native horse-liver alcohol dehydrogenase, Zn(II)LADH [Frolich et al. (1978) Arch. Biochem. Biophys. 189, 471-480]. For cadmium(II)-substituted horse-liver alcohol dehydrogenase, [Cd(II)LADH] the maximum limiting rate constant for association of 1,10-phenanthroline increased to 590 s-1. These findings demonstrate that the rate-limiting step is strongly dependent on the chemical nature of the catalytic metal ion and its immediate environment. 1,10-Phenanthroline is shown to bind to the Co(II)-LADH.NAD+ complex in the open conformation. The maximum limiting rate constant remains unchanged in the presence of NAD+. The data have been used to derive a kinetic scheme for the formation of ternary complexes including NAD+ that involves a slow intermediary step.

  6. Homoleptic trimethylsilylacetylide complexes of chromium(III), iron(II), and cobalt(III): syntheses, structures, and ligand field parameters.

    PubMed

    Berben, Louise A; Long, Jeffrey R

    2005-11-14

    A straightforward method for synthesizing soluble homoleptic trimethylsilylacetylide complexes of first-row transition metal ions is presented. Reaction of anhydrous CrCl2 with an excess of LiCCSiMe3 in THF at -25 degrees C affords orange Li3[Cr(CCSiMe3)6].6THF (1), while analogous reactions employing M(CF3SO3)2 (M = Fe or Co) generate pale yellow Li4[Fe(CCSiMe3)6].4LiCCSiMe3.4Et2O (2) and colorless Li3[Co(CCSiMe3)6].6THF (3). Slightly modified reaction conditions lead to Li8[Cr2O4(CCSiMe3)6].6LiCCSiMe3.4glyme (4), featuring a bis-mu-oxo-bridged binuclear complex, and Li3[Co(CCSiMe3)5(CCH)].LiCF3SO3.8THF (5). The crystal structures of 1-3 show the trimethylsilylacetylide complexes to display an octahedral coordination geometry, with M-C distances of 2.077(3), 1.917(7)-1.935(7), and 1.908(3) angstroms for M = Cr(III), Fe(II), and Co(III), respectively, and nearly linear M-C[triple bond]C angles. The UV-visible absorption spectrum of [Cr(CCSiMe3)6]3- in hexanes exhibits one spin-allowed d-d transition (4T2g <-- 4A1g) and three lower-energy spin-forbidden d-d transitions. The spectra of [Fe(CCSiMe3)6]4- and [Co(CCSiMe3)6]3- in acetonitrile display high-intensity charge-transfer bands, which obscure all d-d transitions except for the lowest-energy spin-allowed band (1T1g <-- 1A1g) of the latter complex. Time-dependent density functional theory (TD-DFT) calculations were employed as an aide in assigning the observed transitions. Taken together, the results are most consistent with the ligand field parameters delta(o) = 20,200 cm(-1) and B = 530 cm(-1) for [Cr(CCSiMe3)6]3-, delta(o) = 32 450 cm(-1) and B = 460 cm(-1) for [Fe(CCSiMe3)6]4- and delta(o) = 32 500 cm(-1) and B = 516 cm(-1) for [Co(CCSiMe3)6]3-. Ground-state DFT calculations support the conclusion that trimethylsilylacetylide acts as a pi-donor ligand.

  7. Immobilization of cobalt(II) Schiff base complexes on polystyrene resin and a study of their catalytic activity for the aerobic oxidation of alcohols.

    PubMed

    Jain, Suman; Reiser, Oliver

    2008-01-01

    The copper-catalyzed [3+2] azide-alkyne cycloaddition and the Staudinger ligation are readily applicable and highly efficient for the immobilization of cobalt Schiff base complexes onto polystyrene resins. Stepwise synthesis of polymer-bound Schiff bases followed by their subsequent complexation with metal ions were successfully carried out. Direct covalent attachment of preformed homogeneous cobalt Schiff base complexes to the resins was also possible. The catalytic efficiency of the so-prepared polystyrene-bound cobalt Schiff bases was studied for the oxidation of alcohols to carbonyl compounds using molecular oxygen as oxidant. The immobilized complexes were highly efficient and even more reactive than the corresponding homogenous analogues, thus affording better yields of oxidized products within shorter reaction times. The supported catalysts could easily be recovered from the reaction mixture by simple filtration and reused for subsequent experiments with consistent catalytic activity.

  8. 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 Pna21 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.

  9. Cobalt free maraging steel

    SciTech Connect

    Floreen, S.

    1984-04-17

    The subject invention is directed to ferrous-base alloys, particularly to a cobalt-free maraging steel of novel chemistry characterized by a desired combination of strength and toughness, notwithstanding that cobalt is non-essential.

  10. Cadmium(II) and cobalt(II) complexes generated from benzimidazole-5-carboxylate: Self-assembly by hydrogen bonding and {pi}-{pi} interactions

    SciTech Connect

    Liu Zheng; Chen Yun; Liu Ping . E-mail: pliu@ms.fjirsm.ac.cn; Wang Jian; Huang Meihua

    2005-07-15

    Self-assembly of L{sup -} (HL=benzimidazole-5-carboxylic acid) with Cd(II) and Co(II), respectively, by layer-separating diffusion method at ambient temperature gives rise to two new supramolecular architectures [(CdL{sub 2}.H{sub 2}O).2CH{sub 3}OH]{sub n} (1) and {l_brace}[CoL{sub 2}(H{sub 2}O){sub 2}].2H{sub 2}O{r_brace}{sub n} (2), both of which are stabilized by the hydrogen bonding interactions and the intermolecular {pi}-{pi} interactions. 1 crystallizes in the triclinic system, space group P-1, with cell parameters M=516.78, a=9.084(2)A, b=10.063(10)A, c=11.533(8)A, {alpha}=90.21(11){sup o}, {beta}=99.48(6){sup o}, {gamma}=98.34(9){sup o}, V=1028.4(12)A{sup 3}, Z=2, R{sub 1}[I>2{sigma}(I)]=0.0257, wR{sub 2}[I>2{sigma}(I)]=0.0719. 2 crystallizes in the monoclinic system, space group C2/c, with cell parameters M=453.27, a=16.119(2)A, b=8.8952(13)A, c=14.195(2)A, {beta}=118.507(2){sup o}, V=1788.5(4)A{sup 3}, Z=4, R{sub 1}[I>2{sigma}(I)]=0.0802, wR{sub 2}[I>2{sigma}(I)]=0.1515. Complex 1 displays a remarkable three-dimensional (3-D) structure with unusual channels generated from the interlayer voids. Complex 2 exhibits the 3-D structure consisting of 1-D zigzag chains. The thermal and fluorescence properties associated with their crystal structures have been measured, and complex 1 displays intense blue emission in the solid state.

  11. A new strategy to obtain tetranuclear cobalt(ii) metal-organic frameworks based on the [Co4(μ3-OH)2] cluster: synthesis, structures and properties.

    PubMed

    Li, Ke; Lv, Xiu-Xiu; Shi, Lu-Lu; Liu, Lu; Li, Bao-Long; Wu, Bing

    2016-09-27

    Three metal-organic frameworks (MOFs) {[Co4(OH)2(adc)6(H2O)5][Co2(OH)(btrb)]2·8H2O}n (1), {[Co4(OH)2(btrb)(nip)3(H2O)3]·4H2O}n (2·4H2O) and {[Co4(OH)2(btrb)(btc)2(H2O)2]·9H2O}n (3·9H2O) (btrb = 1,4-bis(1,2,4-triazol-4-ylmethyl)benzene, H2adc = 1,3-adamantanedicarboxylic acid, H2nip = 5-nitroisophthalic acid and H3btc = 1,3,5-benzenetricarboxylic acid) were synthesized by a hydrothermal method. 1 shows an unusual (3,4)-connected 2D network with a point symbol of (4·6(2))2(4(2)·6(2)·8(2)) based on [Co4(μ3-OH)2] and [Co2(μ3-OH)] units. 2 is a 6-connected pcu topology based on the [Co4(μ3-OH)2] unit. 3 is a rare (3,8)-connected 3D framework with a rare point symbol of (4·5·6)2(4(2)·5(6)·6(16)·7(2)·8(2)) based on the [Co4(μ3-OH)2] unit. The magnetic measurements reveal that 1-3 exhibit antiferromagnetic interactions between the adjacent cobalt(ii) centers. 1-3 are good photocatalysts for the degradation of methylene blue (MB). The 1,2-position nitrogen atoms of the 4-substituted 1,2,4-triazole ligand act as strong σ-donators to form a quite stable coordination quadrangle with two metal ions. The btrb ligand containing two 4-substituted 1,2,4-triazole rings is favorable to form tetranuclear metal units. By the regulation of the multicarboxylate ligands, the connection number of [Co4(μ3-OH)2] clusters increases from 4 in 1 to 6 in 2 and then 8 in 3. This work presents a novel but effective method to design and regulate the connection number (4, 6 and 8 connected in this work) of MOFs with 4-substituted 1,2,4-triazole and rigid multicarboxylate ligands.

  12. Splitting water with cobalt.

    PubMed

    Artero, Vincent; Chavarot-Kerlidou, Murielle; Fontecave, Marc

    2011-08-01

    The future of energy supply depends on innovative breakthroughs regarding the design of cheap, sustainable, and efficient systems for the conversion and storage of renewable energy sources, such as solar energy. The production of hydrogen, a fuel with remarkable properties, through sunlight-driven water splitting appears to be a promising and appealing solution. While the active sites of enzymes involved in the overall water-splitting process in natural systems, namely hydrogenases and photosystem II, use iron, nickel, and manganese ions, cobalt has emerged in the past five years as the most versatile non-noble metal for the development of synthetic H(2)- and O(2)-evolving catalysts. Such catalysts can be further coupled with photosensitizers to generate photocatalytic systems for light-induced hydrogen evolution from water.

  13. Copper catalysis for enhancement of cobalt leaching and acid utilization efficiency in microbial fuel cells.

    PubMed

    Liu, Yaxuan; Shen, Jingya; Huang, Liping; Wu, Dan

    2013-11-15

    Enhancement of both cobalt leaching from LiCoO2 and acid utilization efficiency (AUE) in microbial fuel cells (MFCs) was successfully achieved by the addition of Cu(II). A dosage of 10mg/L Cu(II) improved both cobalt leaching up to 308% and AUE of 171% compared to the controls with no presence of Cu(II). The apparent activation energy of cobalt leaching catalyzed by Cu(II) in MFCs was only 11.8 kJ/mol. These results demonstrate cobalt leaching in MFCs using Cu(II) as a catalyst may be an effective strategy for cobalt recovery and recycle of spent Li-ion batteries, and the evidence of influence factors including solid/liquid ratio, temperature, and pH and solution conductivity can contribute to improving understanding of and optimizing cobalt leaching catalyzed by Cu(II) in MFCs.

  14. Thrombus detection with a radiolabeled antiplatelet monoclonal antibody: Comparison with In-111-oxine technique in coronary and peripheral thrombi in dogs

    SciTech Connect

    Srivastava, S.C.; Esekowitz, M.D.; Meinken, G.E.; Lange, R.C.; Smith, E.; Carbo, P.; Scudder, L.E.; Coller, B.

    1985-05-01

    Platelets (P) labeled with low concentrations of an I-123 or In-111 labeled anti-P monoclonal antibody (7E3) were shown earlier to successfully image in-vivo thrombi. This study was carried out to compare this technique with In-111-oxine-P for localizing coronary and venous thrombi (CT and DVT) in dogs. Thrombi were induced using either transcatheter placement of a dacron pug, mechanical trauma, or electrocoagulation. 7E3 was labeled with I-131 in 70 +- 10% yield (labeling conditions: 100 ..mu..g 7E3; 5 ..mu..g chloramine T; I/sup -//7E3 less than or equal to1; 2 min reaction; 200 ..mu..l pH 7 phosphate buffer; Sp. act. 10-30 ..mu..Ci/..mu..g). Binding of I-131-7E3 to dog P was 75 +- 10% after 1 hr incubation with whole blood. The dogs were injected with 0.5 mCi In-111-oxine-P and 1 mCi I-131-7E3-P in quick succession and data (blood clearance and imaging) were collected for 4 hr. In one experiment, DVT were clearly imaged within 10 min and CT in 30-60 min with I-131-7E3-P. In contrast, In-oxine-P required at least 30 min for imaging DVT and CT were only faintly visualized at 3-4 hr. The DVT to blood and CT to blood ratios at 2.4 hr were 16 and 12.3 for I-131-7E3-P and 9.4 and 6.5 for In-111-oxine-P respectively. In these preliminary studies, I-131-7E3-P thus appears to be superior to In-oxine-P for imaging venous and coronary thrombi. Additionally, 7E3 can be labeled with Tc-99m and I-123 for reduced dose and better imaging properties.

  15. Comparison of different surface modification techniques for electrodes by means of electrochemistry and micro synchrotron radiation X-ray fluorescence. dimerization of cobalt(II) tetrasulfonated phthalocyanine and its influence on the electrodeposition on gold surfaces.

    PubMed

    Peeters, Karl; De Wael, Karolien; Vincze, Laszlo; Adriaens, Annemie

    2005-09-01

    This paper compares different electrochemical surface modification techniques with special attention to the immobilization of cobalt(II) tetrasulfonated phthalocyanine tetrasodium salt (Co(II)TSPc) on gold electrodes. Electrochemical and synchrotron radiation X-ray fluorescence (SR-XRF) microbeam analysis were performed in order to compare the amount of adsorbed CoTSPc onto the gold electrode and to determine the level of uniformity of the deposited layer. The nondestructive, quantitative characterization of CoTSPc deposition on gold electrodes by means of scanning SR-XRF on the microscopic scale has never been described before. The described methodology can be in general used for thin-film characterization. Depending on the degree of dimerization of the CoTSPc molecules, different electrochemical behavior is observed.

  16. Update on the genotoxicity and carcinogenicity of cobalt compounds

    PubMed Central

    Lison, D; De Boeck, M; Verougstraete, V; Kirsch-Volders, M

    2001-01-01

    OBJECTIVE—To integrate recent understandings of the mechanisms of genotoxicity and carcinogenicity of the different cobalt compounds.
METHOD—A narrative review of the studies published since the last IARC assessment in 1991 (genotoxicity, experimental carcinogenesis, and epidemiology).
RESULTS—Two different mechanisms of genotoxicity, DNA breakage induced by cobalt metal and especially hard metal particles, and inhibition of DNA repair by cobalt (II) ions contribute to the carcinogenic potential of cobalt compounds. There is evidence that soluble cobalt (II) cations exert a genotoxic and carcinogenic activity in vitro and in vivo in experimental systems but evidence in humans is lacking. Experimental data indicate some evidence of a genotoxic potential for cobalt metal in vitro in human lymphocytes but there is no evidence available of a carcinogenic potential. There is evidence that hard metal particles exert a genotoxic and carcinogenic activity in vitro and in human studies, respectively. There is insufficient information for cobalt oxides and other compounds.
CONCLUSION—Although many areas of uncertainty remain, an assessment of the carcinogenicity of cobalt and its compounds requires a clear distinction between the different compounds of the element and needs to take into account the different mechanisms involved.


Keywords: cobalt; DNA breakage; inhibition of DNA repair PMID:11555681

  17. A quantitative method to measure human platelet chemotaxis using /sup 111/In-oxine-labeled gel-filtered platelets

    SciTech Connect

    Lowenhaupt, R.W.; Silberstein, E.B.; Sperling, M.I.; Mayfield, G.

    1982-12-01

    Human blood platelets have been shown to migrate directionally and specifically toward collagen in plasma in vitro. We have developed a new system to monitor this behavior using a linear 7-compartment chamber with /sup 111/In-oxine-labeled gel-filtered platelets. The compartments are separated by various Nuclepore and Millipore filter membranes. Radiolabeled platelets suspended in plasma are placed in the central compartment and the other compartments are filled with platelet-free plasma. When collagen is added to an end compartment, platelets migrate toward that end. The degree of this directed movement or chemotaxis can be measured by counting the radioactivity of the contents of each compartment and then comparing the counts from radiolabeled platelets that have moved to the end that holds the chemotactic inducer with those that have randomly migrated to the opposite end, containing only plasma. This assay system allows quantitative comparisons between the chemotaxis-inducing abilities of different substances and permits the study of soluble materials. Experiments to determine the optimal conditions for the procedure are reported, and the advantages of this new method for the investigation of platelet chemotaxis and the identification of chemotaxins are discussed.

  18. A quantitative method to measure human platelet chemotaxis using indium-111-oxine-labeled gel-filtered platelets

    SciTech Connect

    Lowenhaupt, R.W.; Silberstein, E.B.; Sperling, M.I.; Mayfield, G.

    1982-12-01

    Human blood platelets have been shown to migrate directionally and specifically toward collagen in plasma in vitro. We have developed a new system to monitor this behavior using a linear 7-compartment chamber with /sup 111/In-oxine-labeled gel-filtered platelets. The compartments are separated by various Nuclepore and Millipore filter membranes. Radiolabeled platelets suspended in plasma are placed in the central compartment and the other compartments are filled with platelet-free plasma. When collagen is added to an end compartment, platelets migrate toward that end. The degree of this directed movement or chemotaxis can be measured by counting the radioactivity of the contents of each compartment and then comparing the counts from radiolabeled platelets that have moved to the end that holds the chemotactic inducer with those that have randomly migrated to the opposite end, containing only plasma. This assay system allows quantitative comparisons between the chemotaxis-inducing abilities of different substances and permits the study of soluble materials. Experiments to determine the optimal conditons for the procedure are reported, and the advantages of this new method for the investigation of platelet chemotaxis and the identification of chemotaxins are discussed.

  19. Complete cobalt recovery from lithium cobalt oxide in self-driven microbial fuel cell - Microbial electrolysis cell systems

    NASA Astrophysics Data System (ADS)

    Huang, Liping; Yao, Binglin; Wu, Dan; Quan, Xie

    2014-08-01

    Complete cobalt recovery from lithium cobalt oxide requires to firstly leach cobalt from particles LiCoO2 and then recover cobalt from aqueous Co(II). A self-driven microbial fuel cell (MFC)-microbial electrolysis cell (MEC) system can completely carry out these two processes, in which Co(II) is firstly released from particles LiCoO2 on the cathodes of MFCs and then reduced on the cathodes of MECs which are powered by the cobalt leaching MFCs. A cobalt leaching rate of 46 ± 2 mg L-1 h-1 with yield of 1.5 ± 0.1 g Co g-1 COD (MFCs) and a Co(II) reduction rate of 7 ± 0 mg L-1 h-1 with yield of 0.8 ± 0.0 g Co g-1 COD (MECs), as well as a overall system cobalt yield of 0.15 ± 0.01 g Co g-1 Co can be achieved in this self-driven MFC-MEC system. Coulombic efficiencies reach 41 ± 1% (anodic MFCs), 75 ± 0% (anodic MECs), 100 ± 2% (cathodic MFCs), and 29 ± 1% (cathodic MECs) whereas overall system efficiency averages 34 ± 1%. These results provide a new process of linking MFCs to MECs for complete recovery of cobalt and recycle of spent lithium ion batteries with no external energy consumption.

  20. Spectral and thermal studies of 4-(1H-pyrazolo {3,4-d} pyrimidin-4-ylazo) benzene-1,3-diol complexes of cobalt(II), nickel(II) and copper(II)

    NASA Astrophysics Data System (ADS)

    Gaber, M.; El-Baradie, K. Y.; El-Sayed, Y. S. Y.

    2008-02-01

    4-(1H-Pyrazolo {3,4-d} pyrimidin-4-ylazo) benzene-1,3-diol was synthesized and characterized by various spectral and analytical techniques. Semiempirical quantum calculations using the AM1 method have been performed in order to evaluate the geometry and electronic structure of the title azodye in the ground state. The complex formation between Co(II), Ni(II) and Cu(II) ions and the title azodye was studied conductometrically and spectrophotometrically. The spectrophotometric determination of the title metal ions and titration using EDTA are reported. Co(II), Ni(II) and Cu(II) complexes of the title azodye have been synthesized and characterized by elemental analysis, conductivity, magnetic susceptibility, IR, UV-Vis and thermal analysis (TGA and DTA).The spectral and magnetic data suggested the octahedral geometry for Co(II) and Ni(II) complexes while Cu(II) complexes have square planar geometry. The thermal studies confirmed the chemical formulations of the title complexes. The thermal degradation takes place in two or three steps depending on the type of the metal and the geometry of the complexes. The kinetics of the decomposition was examined by using Coats-Redfern relation. The activation energies and other activation parameters (Δ H, Δ S and Δ G) were computed and related to the bonding and stereochemistry of the complexes.

  1. Thin film assembly of nanosized cobalt(II) bis(5-phenyl-azo-8-hydroxyquinolate) using static step-by-step soft surface reaction technique: Structural characterization and optical properties

    NASA Astrophysics Data System (ADS)

    Seleim, S. M.; Hamdalla, Taymour A.; Mahmoud, Mohamed E.

    2017-09-01

    Nanosized (NS) cobalt (II) bis(5-phenyl-azo-8-hydroxyquinolate) (NS Co(II)-(5PA-8HQ)2) thin films have been synthesized using static step-by-step soft surface reaction (SS-b-SSR) technique. Structural and optical characterizations of these thin films have been carried out using thermal gravimetric analysis (TGA), Fourier transform infrared (FT-IR), scanning electron microscopy (SEM), high resolution transmission electron microscopy (HR-TEM) and X-ray diffraction (XRD). The HR-TEM results revealed that the assembled Co(II)-complex exhibited a uniformly NS structure particles in the form of nanorods with width and length up to 16.90 nm and 506.38 nm, respectively. The linear and nonlinear optical properties have been investigated. The identified energy gap of the designed thin film materials was found 4.01 eV. The refractive index of deposited Co(II)-complex thin film was identified by thickness-dependence and found as 1.9 at wavelength 1100 nm. In addition, the refractive index was varied by about 0.15 due to an increase in the thickness by 19 nm.

  2. Scintigraphic assessment of bowel involvement and disease activity in Crohn's disease using technetium 99m-hexamethyl propylene amine oxine as leukocyte label

    SciTech Connect

    Schoelmerich, J.S.; Schmidt, E.; Schuemichen, C.B.; Billmann, P.; Schmidt, H.; Gerok, W.

    1988-11-01

    Using a novel labeling technique with technetium 99m-hexamethyl propylene amine oxine, we studied 29 patients with known or suspected Crohn's disease. Technetium 99m-hexamethyl propylene amine oxine leukocyte scanning (99mTc scan) was prospectively compared with the results of independently performed radiologic, endoscopic, and histologic examinations, and with findings at surgery, to assess the clinical usefulness of this technique to localize inflammatory lesions. In addition, uptake of technetium 99m-hexamethyl propylene amine oxine in the bowel was graded by comparing it with the uptake in liver and bone marrow and correlating this with established parameters of disease activity. The viability of homologous labeled leukocytes was greater than 95%. Less than 5% of lymphocytes were found in the final preparation. It was found that 45% +/- 12% of the label was bound to granulocytes, and 98% of the unbound label was washed off before reinjection. The results of 99mTc scan revealed a good correlation with those of barium enema (r = 0.880, p less than 0.001), of endoscopy/surgery (r = 0.983, p less than 0.001), and of all combined reference methods (r = 0.981, p less than 0.001). Activity as determined by 99mTc scan was weakly correlated with the results of Crohn's disease activity index (r = 0.559, p less than 0.01), van Hees index (r = 0.606, p less than 0.01), and erythrocyte sedimentation rate (r = 0.456, p less than 0.05) in 24 patients with proven Crohn's disease. The correlation was improved when the 99mTc scan was compared with a combination of these activity parameters and C-reactive protein (r = 0.781, p less than 0.001). Extraintestinal manifestations (joints) and complications (cholecystitis) were also identified correctly by the 99mTc scan.

  3. Solvent extraction of cobalt from laterite-ammoniacal leach liquors

    SciTech Connect

    Nilsen, D.N.; Siemens, R.E.; Rhoads, S.C.

    1980-01-01

    The Bureau of Mines is developing a method to recover Ni, Co, and Cu from laterites containing less than 1.2% Ni and 0.25% Co. The method consists of the following basic unit operations: (1) reduction roasting, (2) leaching, (3) solvent extraction, and (4) electrowinning. The method reflects three Bureau of Mines objectives: (1) recovery of critical minerals that are domestically in short supply from low-grade domestic laterites, (2) lower processing energy requirements, and (3) solution recycling. This report deals with the extraction of cobalt and the preparation of a suitable cobalt electrolyte by solvent extraction from liquor produced by this method. Nickel and copper are coextracted with LIX64N from an ammoniacal ammonium sulfate leach liquor containing about 1.00 g/1 Ni, 0.30 g/1 Co, 0.03 g/1 Cu, and 0.02 g/1 Zn. Cobalt (III) in the nickel-copper barren raffinate is reduced to cobalt (II) with cobalt metal. Reduction of cobalt (III) to cobalt (II) greatly aids subsequent extraction. Commercially available XI-51 extracts about 94% of the cobalt from the treated raffinate in one stage in a laboratory mixer-settler continuous circuit. Ammonia loaded on the solvent is removed in two washing steps. About 94% of the cobalt then is stripped from the XI-51 in one stage with spent cobalt electrolyte containing about 77 g/1 Co and 18 g/1 sulfuric acid (H/sub 2/SO/sub 4/). Electrolytes containing less H/sub 2/SO/sub 4/ also may be used. Preliminary data indicate that coextracted zinc may be removed from pregnant cobalt electrolyte containing 3 g/1 or less H/sub 2/SO/sub 4/ with di-(2 ethylhexyl) phosphoric acid (D2EHPA).

  4. Deprotonation or protonation: The coordination properties, crystal structures and spectra of cobalt (II) complex with 1-(2-pyridylazo)-2-acenaphthequinol ligand

    NASA Astrophysics Data System (ADS)

    Zhou, Jian-Liang; Sun, Hong-Wen; Yin, Dong-Hong; Li, Yan-Ling; Tuo, Su-Xing; Xu, Ya-Hui; Yan, Jun

    2017-04-01

    The reaction of 1-(2-pyridylazo)-2-acenaphthequinol (PAAL) with cobalt acetate in CHCl3 gave the complex of Co(PAAL-H)2 (1), and (PAAL + H)2[CoCl4]·2H2O (2) was isolated in the same system with ultraviolet light irradiation. Structures of both compounds were determined by X-Ray diffraction. The PAAL ligand was deprotonated in 1, but it further protonated on N position at pyridine group in 2 and form cations. The spectra of these two compounds were also studied, as well as the fluorescence properties. Also, the redox property of 1 was preliminary investigated by cyclic voltammogram.

  5. Cobalt(II)-mediated synthesis of 2,6-bis[5,7-di-tert-butyl-1,3-benzoxazol-2-yl]-pyridine: Structural analysis and coordination behavior

    NASA Astrophysics Data System (ADS)

    Garza-Ortíz, Ariadna; Martínez, Pablo A.; Duarte-Hernández, Angelica M.; Mijangos, Edgar; Flores-Álamo, Marcos; Pérez-Casas, Carol; Camacho-Camacho, Carlos; Contreras, Rosalinda; Flores-Parra, Angelina; Reedijk, Jan; Barba-Behrens, Norah

    2013-01-01

    The oxidative cyclization of 2,6-bis[2,4-di-tert-butyl-6-(methylidenylamino)phenol]-pyridine (L1) in acetonitrile, through the cobalt(II) coordination compound of L1, has resulted in a convenient route for the preparation of 2,6-bis[5,7-di-tert-butyl-1,3-benzoxazol-2-yl]-pyridine (L3). The X-ray diffraction analysis of L3 shows a planar molecule, with the oxygen atoms from the benzoxazole rings oriented to the pyridine nitrogen atom (conformer L3a). Ab initio calculations indicate that from the three possible planar conformers of L3, the more stable is L3a. The solid state conformation of the free ligand L3 and the relative energy of the three calculated conformers indicated stabilizing N → O interactions. Calculations of the protonated derivative of L3, compound 7, indicated that the most stable conformer has the benzoxazole nitrogen atoms pointing to the protonated pyridine NH (7c). The X-ray crystal analysis of ligand L3 coordinated to cobalt(II) nitrate, compound 4 is presented and conformer L3c is found in this compound. Two acid:base complexes [Zn(NO3)2(H2O)2][L3c]2, compound 5, and [NEt2H2Cl][L3c], compound 6, have also been investigated. Complex 5 crystallized and its X-ray diffraction analysis is reported, whereas compound 6 was studied in solution by NMR, mass spectrometry and ab initio calculations. Both complexes show that conformer L3c can form stable hydrogen bonding associations, with molecules having the motif YH2 (Y = N or O), that are of interest for building up supramolecular associations.

  6. Resonance Raman spectra of iron(III)-, copper(II)-, cobalt(III)-, and manganese(III)-transferrins and of bis(2,4,6-trichlorophenolato)diimidazolecopper(II) monohydrate, a possible model for copper(II) binding to transferrins.

    PubMed

    Tomimatsu, Y; Kint, S; Scherer, J R

    1976-11-02

    Fe(III), Cu(II), Co(III), and Mn(III) complexes of ovo- and human serum transferrins show resonance enhanced Raman bands near 1600, 1500, 1270, and 1170 cm-1 upon excitation with laser frequencies which fall within the visible absorption bands of those metalloproteins. Comparison of the visible absorption and resonance Raman spectra of the Cu(II)-transferrin complexes with those for the Cu(II) model compound, bis(2,4,6-trichlorophenolato)diimidazolecopper(II) monohydrate, indicates that the resonance Raman bands are due to enhancement of phenolic vibrational modes. For the model (Cu(II) compound, a normal coordinate analysis was used to aid our assignment of the observed resonance bands at 1562, 1463, 1311, and 1122 cm-1 to A1 vibrational modes of the 2,4,6-trichlorophenolato moiety. These assignments are consistent with those made for Cu(II)-transferrins. The latter assignments were based upon calculated A1 frequencies for p-methylphenol (Cummings, D.L., and Wood, J.L. (1974), J. Mol. Struct. 20, 1). The wavelength shifts in the resonance bands for the model compound from those for Cu(II)-transferrins are due to the influence of the chloro substituents on the planar vibrations of phenol. These results clearly identify tyrosine as a ligand in copper binding to transferrins.

  7. Binuclear copper(II), cobalt(II) and nickel(II) complexes of N1-ethyl-N2-(pyridin-2-yl) hydrazine-1,2-bis(carbothioamide): structural, spectral, pH-metric and biological studies.

    PubMed

    El-Gammal, O A; Abu El-Reash, G M; El-Gamil, M M

    2012-10-01

    Binuclear Cu(II), Co(II) and Ni(II) complexes derived from N(1)-ethyl-N(2)-(pyridin-2-yl) hydrazine-1,2-bis(carbothioamide) (H(2)PET) have been prepared and characterized by elemental analysis, spectral (IR, UV-vis, EI mass, ESR and (1)HNMR) and magnetic measurements. The isolated complexes assigned the general formula, [M(HPET)(H(2)O)(n)Cl](2)·xH(2)O where M=Cu(II), Co(II) and Ni(II), n=2, 1, 0 and x=0, 0.5 and 0, respectively. IR data revealed that the ligand behaves as monobasic tridentate through (CN)(py), (C-S) and new azomethine, (NC)(∗) groups in the Co(II) complex but in Cu(II) complex, the ligand coordinate via both (CS) groups, one of them in thiol form as well as the new azomethine group. In Ni(II) complex, H(2)PET acts as NSNS monobasic tetradente via (CN)(py), (C-S), (CS) and the new azomethine, (NC)(∗) groups. An octahedral geometry is proposed for all complexes. pH- metric titration was carried out in 50% dioxane-water mixture at 298, 308 and 318 °K, respectively and the dissociation constant of the ligand as well as the stability constants of its complexes were evaluated. Also the kinetic and thermodynamic parameters for the different thermal decomposition steps of the complexes were determined by Coats-Redfern and Horowitz-Metzger methods. Moreover, the anti-oxidant, anti-hemolytic, and cytotoxic activities of the compounds have been tested.

  8. Co(II) derivatives of Cu,Zn-superoxide dismutase with the cobalt bound in the place of copper. A new spectroscopic tool for the study of the active site.

    PubMed

    Desideri, A; Cocco, D; Calabrese, L; Rotilio, G

    1984-03-29

    Co(II) derivatives of Cu,Zn-superoxide dismutase having cobalt substituted for the copper (Co,Zn-superoxide dismutase and Co,Co-superoxide dismutase) were studied by optical and EPR spectroscopy. EPR and electronic absorption spectra of Co,Zn-superoxide dismutase are sensitive to solvent perturbation, and in particular to the presence of phosphate. This behaviour suggests that cobalt in Co,Zn-superoxide dismutase is open to solvent access, at variance with the Co(II) of the Cu,Co-superoxide dismutase, which is substituted for the Zn. Phosphate binding as monitored by optical titration is dependent on pH with an apparent pKa = 8.2. The absorption spectrum of Co,Zn-superoxide dismutase in water has three weak bands in the visible region (epsilon = 75 M-1 X cm-1 at 456 nm; epsilon = 90 M-1 X cm-1 at 520 nm; epsilon = 70 M-1 X cm-1 at 600 nm) and three bands in the near infrared region, at 790 nm (epsilon = 18 M-1 X cm-1), 916 nm (epsilon = 27 M-1 X cm-1) and 1045 nm (epsilon = 25 M-1 X cm-1). This spectrum is indicative of five-coordinate geometry. In the presence of phosphate, three bands are still present in the visible region but they have higher intensity (epsilon = 225 M-1 X cm-1 at 544 nm; epsilon = 315 M-1 X cm-1 at 575 nm; epsilon = 330 M-1 X cm-1 at 603 nm), whilst the lowest wavelength band in the near infrared region is at much lower energy, 1060 nm (epsilon = 44 M-1 X cm-1). The latter property suggests a tetrahedral coordination around the Co(II) centre. Addition of 1 equivalent of CN- gives rise to a stable Co(II) low-spin intermediate, which is characterized by an EPR spectrum with a highly rhombic line shape. Formation of this CN- complex was found to require more cyanide equivalents in the case of the phosphate adduct, suggesting that binding of phosphate may inhibit binding of other anions. Titration of the Co,Co-derivative with CN- provided evidence for magnetic interaction between the two metal centres. These results substantiate the contention

  9. Synthesis and characterization of dinuclear macrocyclic cobalt(II), copper(II) and zinc(II) complexes derived from 2,2,2('),2(')-S,S[bis(bis-N,N-2-thiobenzimidazolyloxalato-1,2-ethane)]: DNA binding and cleavage studies.

    PubMed

    Arjmand, Farukh; Aziz, Mubashira

    2009-02-01

    New homodinuclear macrocyclic complexes of cobalt(II), copper(II) and zinc(II) were isolated from the newly synthesized ligand 2,2,2',2'-S,S[bis(bis-N,N-2-thiobenzimidazolyloxalato-1,2-ethane)]. The structures of the complexes were elucidated by elemental analysis, molar conductance measurements, IR, 1H NMR, 13C NMR, electronic and ESI-MS spectroscopic techniques. In complex 1, Co(II) ions possess a tetrahedral coordination environment composed of O2S2 donor atoms while its Cu(II) and Zn(II) counterparts 2 and 3, respectively, reveal a six coordinate octahedral structure, defined by the O2S2 donors from the macrocyclic ring and two chloride ions. Molar conductance and spectroscopic data also support the proposed geometry of the complexes. DNA binding properties of complexes 1-3 were investigated using electronic absorption spectroscopy, fluorescence spectroscopy, viscosity measurements and cyclic voltammetry. The absorption spectra of complexes 2 and 3 with calf thymus DNA showed hypochromism, while complex 1 showed hyperchromism attributed to a partial intercalation and electrostatic binding modes, respectively. The intrinsic binding constant K(b) of complexes 1-3 were determined as 16.6 x 10(4) M(-1), 4.25 x 10(4) M(-1) and 3.0 x 10(4) M(-1), respectively. The decrease in the relative specific viscosity of calf thymus DNA with increasing concentration of the complexes authenticates the partial intercalation binding mode. Gel electrophoresis of complex 2 with plasmid DNA demonstrated that complex exhibits excellent "artificial" nuclease activity.

  10. International strategic minerals inventory summary report; cobalt

    USGS Publications Warehouse

    Crockett, R.N.; Chapman, G.R.; Forrest, M.D.

    1987-01-01

    Major world resources of cobalt are described in this summary report of information in the International Strategic Minerals Inventory {ISMI}. ISMI is a cooperative data-collection effort of earth-science and mineral-resource agencies in Australia, Canada, the Federal Republic of Germany, the Republic of South Africa, and the United States of America. This report, designed to be of benefit to policy analysts, contains two parts. Part I presents an overview of the resources and potential supply of cobalt on the basis of inventory information. Part II contains tables of some of the geologic information and mineral-resource and production data that were collected by ISMI participants.

  11. A redox-silent analogue of tocotrienol inhibits cobalt(II) chloride-induced VEGF expression via Yes signaling in mesothelioma cells.

    PubMed

    Sato, Ayami; Virgona, Nantiga; Ando, Akira; Ota, Masako; Yano, Tomohiro

    2014-01-01

    Vascular endothelial growth factor (VEGF) plays a crucial role in tumor angiogenesis and represents an attractive anticancer target. We have previously demonstrated that a redox-silent analogue of α-tocotrienol, 6-O-carboxypropyl-α-tocotrienol (T3E) exhibits potent anti-carcinogenic property in human malignant mesothelioma (MM) cells. However, inhibition of tumor growth by targeting VEGF pathway remains undetermined. In this study, we explored the inhibitory effect of T3E on the paracrine secretion of VEGF in MM cells under mimicked hypoxia by cobalt chloride (CoCl2). In this study we examine whether T3E can suppress the secretion of VEGF in MM cells exposed to mimic hypoxia by cobalt chloride (CoCl2). We found that CoCl2-induced hypoxia treatment leads to increased up-regulated hypoxia-inducible factor-2α (HIF-2α) and subsequently induced the secretion of VEGF in MM cells. This up-regulation activation mainly depended on the activation of Yes, a member of the Src family of kinases. Treatment of hypoxic MM cells with T3E effectively inhibited the secretion of VEGF, On the other hand, T3E inhibited CoCl2-induced gene expression of VEGF due to the inactivation of Yes/HIF-2α signaling. These data suggest that Yes/HIF2-α/VEGF could be a promising therapeutic target of T3E in MM cells.

  12. Crystallographic studies of metal ion-DNA interactions: different binding modes of cobalt(II), copper(II) and barium(II) to N7 of guanines in Z-DNA and a drug-DNA complex.

    PubMed Central

    Gao, Y G; Sriram, M; Wang, A H

    1993-01-01

    Metal ion coordination to nucleic acids is not only required for charge neutralization, it is also essential for the biological function of nucleic acids. The structural impact of different metal ion coordinations of DNA helices is an open question. We carried out X-ray diffraction analyses of the interactions of the two transition metal ions Co(II) and Cu(II) and an alkaline earth metal ion Ba(II), with DNA of different conformations. In crystals, Co(II) ion binds exclusively at the N7 position of guanine bases by direct coordination. The coordination geometry around Co(II) is octahedral, although some sites have an incomplete hydration shell. The averaged Co-N7 bond distance is 2.3 A. The averaged Co-N7-C8 angle is 121 degrees, significantly smaller than the value of 128 degrees if the Co-N7 vector were to bisect the C5-N7-C8 bond angle. Model building of Co(II) binding to guanine N7 in B-DNA indicates that the coordinated waters in the axial positions would have a van der Waals clash with the neighboring base on the 5' side. In contrast, the major groove of A-DNA does not have enough room to accommodate the entire hydration shell. This suggests that Co(II) binding to either B-DNA or A-DNA may induce significant conformational changes. The Z-DNA structure of Cu(II)-soaked CGCGTG crystal revealed that the Cu(II) ion is bis-coordinated to N7 position of G10 and #G12 (# denotes a symmetry-related position) bases with a trigonal bipyramid geometry, suggesting a possible N7-Cu-N7 crosslinking mechanism. A similar bis-coordination to two guanines has also been seen in the interaction of Cu(II) in m5CGUAm5CG Z-DNA crystal and of Ba(II) with two other Z-DNA crystals. PMID:8371984

  13. Marine cobalt resources

    USGS Publications Warehouse

    Manheim, F. T.

    1986-01-01

    Ferromanganese oxides in the open oceans are more enriched in cobalt than any other widely distributed sediments or rocks. Concentrations of cobalt exceed 1 percent in ferromanganese crusts on seamounts, ocean ridges, and other raised areas of the ocean. The cobalt-rich crusts may be the slowest growing of any earth material, accumulating one molecular layer every 1 to 3 months. Attention has been drawn to crusts as potential resources because they contain cobalt, manganese, and platinum, three of the four priority strategic metals for the United States. Moreover, unlike abyssal nodules, whose recovery is complicated by their dominant location in international waters, some of the most cobalt-rich crusts occur within the exclusive economic zone of the United States and other nations. Environmental impact statements for crust exploitation are under current development by the Department of the Interior.

  14. A green preconcentration method for determination of cobalt and lead in fresh surface and waste water samples prior to flame atomic absorption spectrometry.

    PubMed

    Naeemullah; Kazi, Tasneem Gul; Shah, Faheem; Afridi, Hassan Imran; Khan, Sumaira; Arian, Sadaf Sadia; Brahman, Kapil Dev

    2012-01-01

    Cloud point extraction (CPE) has been used for the preconcentration and simultaneous determination of cobalt (Co) and lead (Pb) in fresh and wastewater samples. The extraction of analytes from aqueous samples was performed in the presence of 8-hydroxyquinoline (oxine) as a chelating agent and Triton X-114 as a nonionic surfactant. Experiments were conducted to assess the effect of different chemical variables such as pH, amounts of reagents (oxine and Triton X-114), temperature, incubation time, and sample volume. After phase separation, based on the cloud point, the surfactant-rich phase was diluted with acidic ethanol prior to its analysis by the flame atomic absorption spectrometry (FAAS). The enhancement factors 70 and 50 with detection limits of 0.26 μg L(-1) and 0.44 μg L(-1) were obtained for Co and Pb, respectively. In order to validate the developed method, a certified reference material (SRM 1643e) was analyzed and the determined values obtained were in a good agreement with the certified values. The proposed method was applied successfully to the determination of Co and Pb in a fresh surface and waste water sample.

  15. A Green Preconcentration Method for Determination of Cobalt and Lead in Fresh Surface and Waste Water Samples Prior to Flame Atomic Absorption Spectrometry

    PubMed Central

    Naeemullah; Kazi, Tasneem Gul; Shah, Faheem; Afridi, Hassan Imran; Khan, Sumaira; Arian, Sadaf Sadia; Brahman, Kapil Dev

    2012-01-01

    Cloud point extraction (CPE) has been used for the preconcentration and simultaneous determination of cobalt (Co) and lead (Pb) in fresh and wastewater samples. The extraction of analytes from aqueous samples was performed in the presence of 8-hydroxyquinoline (oxine) as a chelating agent and Triton X-114 as a nonionic surfactant. Experiments were conducted to assess the effect of different chemical variables such as pH, amounts of reagents (oxine and Triton X-114), temperature, incubation time, and sample volume. After phase separation, based on the cloud point, the surfactant-rich phase was diluted with acidic ethanol prior to its analysis by the flame atomic absorption spectrometry (FAAS). The enhancement factors 70 and 50 with detection limits of 0.26 μg L−1 and 0.44 μg L−1 were obtained for Co and Pb, respectively. In order to validate the developed method, a certified reference material (SRM 1643e) was analyzed and the determined values obtained were in a good agreement with the certified values. The proposed method was applied successfully to the determination of Co and Pb in a fresh surface and waste water sample. PMID:23227429

  16. Synthesis and electrochemistry of β-pyrrole nitro-substituted cobalt(II) porphyrins. The effect of the NO₂ group on redox potentials, the electron transfer mechanism and catalytic reduction of molecular oxygen in acidic media.

    PubMed

    Sun, Bin; Ou, Zhongping; Yang, Shuibo; Meng, Deying; Lu, Guifen; Fang, Yuanyuan; Kadish, Karl M

    2014-07-28

    Four cobalt(II) porphyrins, two of which contain a β-pyrrole nitro substituent, were synthesized and characterized by electrochemistry and spectroelectrochemistry. The investigated compounds are represented as (TRPP)Co and (NO2TRPP)Co, where TRPP is the dianion of a substituted tetraphenylporphyrin and R is a CH3 or OCH3 substituent on the four phenyl rings of the macrocycle. Two reductions and three oxidations are observed for each compound in CH2Cl2 containing 0.10 M tetra-n-butylammonium perchlorate. The first reduction of the compounds without a nitro substituent is metal-centered and leads to formation of a Co(I) porphyrin which then reacts with the CH2Cl2 solvent to generate a carbon σ-bonded Co(III)-R complex. A further reduction then occurs at more negative potentials to generate an unstable Co(II) σ-bonded compound. In contrast to these reactions, the first reduction of the nitro-substituted porphyrins is macrocycle-centered under the same solution conditions and gives a Co(II) porphyrin π-anion radical product. This reversible electron transfer is then followed at more negative potentials by a second reversible one-electron addition to give a Co(II) dianion. Three reversible one-electron oxidations are also seen for each compound. The first is metal-centered and the next two involve the conjugated π-system of the macrocycle. Each neutral Co(II) porphyrin was also examined as to its catalytic activity for electroreduction of molecular oxygen when coated on an edge-plane pyrolytic graphite electrode in 1.0 M HClO4. The β-pyrrole nitro-substituted derivatives were shown to be better catalysts than the non-nitro substituted compounds under the utilized experimental conditions.

  17. Cobalt(II), Nickel(II) and Copper(II) complexes of a tetradentate Schiff base as photosensitizers: Quantum yield of 1O2 generation and its promising role in anti-tumor activity.

    PubMed

    Pradeepa, S M; Bhojya Naik, H S; Vinay Kumar, B; Indira Priyadarsini, K; Barik, Atanu; Ravikumar Naik, T R

    2013-01-15

    In the present investigation, a Schiff base N'1,N'3-bis[(E)-(5-bromo-2-hydroxyphenyl)methylidene]benzene-1,3-dicarbohydrazide and its metal complexes have been synthesized and characterized. The DNA-binding studies were performed using absorption spectroscopy, emission spectra, viscosity measurements and thermal denatuaration studies. The experimental evidence indicated that, the Co(II), Ni(II) and Cu(II) complexes interact with calf thymus DNA through intercalation with an intrinsic binding constant Kb of 2.6×10(4) M(-1), 5.7×10(4) M(-1) and 4.5×10(4) M(-1), respectively and they exhibited potent photodamage abilities on pUC19 DNA, through singlet oxygen generation with quantum yields of 0.32, 0.27 and 0.30 respectively. The cytotoxic activity of the complexes resulted that they act as a potent photosensitizers for photochemical reactions.

  18. Cobalt(II), Nickel(II) and Copper(II) complexes of a tetradentate Schiff base as photosensitizers: Quantum yield of 1O2 generation and its promising role in anti-tumor activity

    NASA Astrophysics Data System (ADS)

    Pradeepa, S. M.; Bhojya Naik, H. S.; Vinay Kumar, B.; Indira Priyadarsini, K.; Barik, Atanu; Ravikumar Naik, T. R.

    2013-01-01

    In the present investigation, a Schiff base N'1,N'3-bis[(E)-(5-bromo-2-hydroxyphenyl)methylidene]benzene-1,3-dicarbohydrazide and its metal complexes have been synthesized and characterized. The DNA-binding studies were performed using absorption spectroscopy, emission spectra, viscosity measurements and thermal denatuaration studies. The experimental evidence indicated that, the Co(II), Ni(II) and Cu(II) complexes interact with calf thymus DNA through intercalation with an intrinsic binding constant Kb of 2.6 × 104 M-1, 5.7 × 104 M-1 and 4.5 × 104 M-1, respectively and they exhibited potent photodamage abilities on pUC19 DNA, through singlet oxygen generation with quantum yields of 0.32, 0.27 and 0.30 respectively. The cytotoxic activity of the complexes resulted that they act as a potent photosensitizers for photochemical reactions.

  19. Effects of pH and inhibitors on the absorption spectrum of cobalt(II)-substituted carbonic anhydrase III from bovine skeletal muscle.

    PubMed

    Engberg, P; Lindskog, S

    1984-05-21

    Bovine apocarbonic anhydrase III has been prepared by incubation with 2-carboxy-1,10-phenanthroline at pH 5.5. The Co(II)-substituted enzyme has been prepared and its absorption spectrum has been studied. The spectrum is nearly pH-independent above pH 6. It is very similar to the high pH spectral forms of Co(II)-carbonic anhydrases I and II. The spectra of complexes with the sulfonamide inhibitor, acetazolamide, and with CN- and NCO - are virtually identical to the spectra of the corresponding complexes with Co(II)-isoenzymes I and II. The spectrum of the N-3 complex indicates that this anion is bound somewhat differently in Co(II) isoenzyme III than in the other Co(II)-substituted isoenzymes.

  20. Magnetism in cobalt clusters

    NASA Astrophysics Data System (ADS)

    Emmert, Jeffrey Wayne

    The results of Stern-Gerlach type magnetic deflection experiments on clusters of cobalt consisting of 15 to 200 atoms are reported. These cobalt clusters exhibit superparamagnetic behavior over a wide range of temperatures and applied magnetic fields. The average magnetic moment per atom was determined for each cluster size. These range from 2.28 muB to 3.40 mu B, significantly exceeding the 1.72 muB per atom moment of bulk cobalt. This enhanced magnetism predictably decreases with increasing cluster size, but the evolution to the bulk is not smooth and exhibits detailed structure.

  1. Crystal structure of bis-(azido-κN)bis[2,5-bis(pyridin-2-yl)-1,3,4-thia-diazole-κ(2) N (2),N (3)]cobalt(II).

    PubMed

    Laachir, Abdelhakim; Bentiss, Fouad; Guesmi, Salaheddine; Saadi, Mohamed; El Ammari, Lahcen

    2015-05-01

    In the mononuclear title complex, [Co(N3)2(C12H8N4S)2], the cobalt(II) atom is located on an inversion centre and displays an axially weakly compressed octa-hedral coordination geometry. The equatorial positions are occupied by the N atoms of two 2,5-bis-(pyridin-2-yl)-1,3,4-thia-diazole ligands, whereas the axial positions are occupied by N atoms of the azide anions. The thia-diazole and pyridine rings linked to the metal are almost coplanar, with a maximum deviation from the mean plane of 0.0273 (16) Å. The cohesion of the crystal is ensured by weak C-H⋯N hydrogen bonds and by π-π inter-actions between pyridine rings [inter-centroid distance = 3.6356 (11) Å], forming a layered arrangement parallel to (001). The structure of the title compound is isotypic with that of the analogous nickel(II) complex [Laachir et al. (2013 ▶). Acta Cryst. E69, m351-m352].

  2. Crystal structure of bis­(azido-κN)bis[2,5-bis(pyridin-2-yl)-1,3,4-thia­diazole-κ2 N 2,N 3]cobalt(II)

    PubMed Central

    Laachir, Abdelhakim; Bentiss, Fouad; Guesmi, Salaheddine; Saadi, Mohamed; El Ammari, Lahcen

    2015-01-01

    In the mononuclear title complex, [Co(N3)2(C12H8N4S)2], the cobalt(II) atom is located on an inversion centre and displays an axially weakly compressed octa­hedral coordination geometry. The equatorial positions are occupied by the N atoms of two 2,5-bis­(pyridin-2-yl)-1,3,4-thia­diazole ligands, whereas the axial positions are occupied by N atoms of the azide anions. The thia­diazole and pyridine rings linked to the metal are almost coplanar, with a maximum deviation from the mean plane of 0.0273 (16) Å. The cohesion of the crystal is ensured by weak C—H⋯N hydrogen bonds and by π–π inter­actions between pyridine rings [inter­centroid distance = 3.6356 (11) Å], forming a layered arrangement parallel to (001). The structure of the title compound is isotypic with that of the analogous nickel(II) complex [Laachir et al. (2013 ▸). Acta Cryst. E69, m351–m352]. PMID:25995853

  3. Phenyl-hydrazinium (6-carb-oxy-pyridine-2-carboxyl-ato)(pyridine-2,6-dicarboxyl-ato)cobaltate(II)-pyridine-2,6-dicarb-oxy-lic acid-water (1/1/3).

    PubMed

    Yuste, Consuelo; Ramos Silva, Manuela; Ghadermazi, Mohammad; Feizi, Fariba; Motieiyan, Elham

    2010-11-24

    The asymmetric unit of the title compound, (C(6)H(9)N(2))[Co(C(7)H(3)NO(4))(C(7)H(4)NO(4))]·C(7)H(5)NO(4)·3H(2)O, contains one (6-carb-oxy-pyridine-2-carboxyl-ato)(pyridine-2,6-dicarboxyl-ato)cobaltate(II) anion, one phenyl-hydrazinium cation, one pyridine-2,6-dicarb-oxy-lic acid mol-ecule and three uncoordin-ated water mol-ecules, part of which are disordered. The Co(II) ion is coordinated by a pyridine-2,6-dicarboxyl-ate ion and a 6-carb-oxy-pyridine-2-carboxyl-ate ligand almost perpendicular to each other [the angle between the least-squares planes is 87.38 (4)°] and is surrounded by two O atoms and two N atoms in the equatorial plane and two O atoms in axial positions, resulting in a distorted octa-hedral coordination geometry. There is an extensive three-dimensional network of O-H⋯O and N-H⋯O hydrogen bonds, which link the components.

  4. Study of a series of cobalt(II) sulfonamide complexes: Synthesis, spectroscopic characterization, and microbiological evaluation against M. tuberculosis. Crystal structure of [Co(sulfamethoxazole)2(H2O)2]·H2O

    NASA Astrophysics Data System (ADS)

    Mondelli, Melina; Pavan, Fernando; de Souza, Paula C.; Leite, Clarice Q.; Ellena, Javier; Nascimento, Otaciro R.; Facchin, Gianella; Torre, María H.

    2013-03-01

    Nowadays, the research for new and better antimicrobial compounds is an important field due to the increase of immunocompromised patients, the use of invasive medical procedures and extensive surgeries, among others, that can affect the incidence of infections. Another big problem associated is the occurrence of drug-resistant microbial strains that impels a ceaseless search for new antimicrobial agents. In this context, a series of heterocyclic-sulfonamide complexes with Co(II) was synthesized and characterized with the aim of obtaining new antimicrobial compounds. The structural characterization was performed using different spectroscopic methods (UV-Vis, IR, and EPR). In spite of the fact that the general stoichiometry for all the complexes was Co(sulfonamide)2·nH2O, the coordination atoms were different depending on the coordinated sulfonamide. The crystal structure of [Co(sulfamethoxazole)2(H2O)2]·H2O was obtained by X-ray diffraction showing that Co(II) is in a slightly tetragonal distorted octahedron where sulfamethoxazole molecules act as a head-to-tail bridges between two cobalt atoms, forming polymeric chains. Besides, the activity against Mycobacterium tuberculosis, one of the responsible for tuberculosis, and the cytotoxicity on J774A.1 macrophage cells were evaluated.

  5. Efficacy and safety of a biodegradable polymer Cobalt-Chromium sirolimus-eluting stent (EXCEL2) in treating de novo coronary artery disease: A pooled analysis of the CREDIT II and CREDIT III trials.

    PubMed

    Wang, Geng; Wang, Heyang; Xu, Bo; Yang, Yuejin; Yang, Zhiming; Li, Hui; Zhang, Zheng; Wang, Haichang; Yang, Lixia; Han, Yaling

    2017-03-01

    The safety and efficacy of the second-generation biodegradable polymer Cobalt-Chromium sirolimus-eluting stent (EXCEL2) in daily clinical practice remains unknown. Additionally, to meet the China Food and Drug Administration requirements, we conducted an objective performance criterion study from the CREDIT II and CREDIT III trials. CREDIT II was a randomized trial comparing the EXCEL2 versus EXCEL stent in patients with up to 2 de novo coronary lesions. CREDIT III was a prospective, single-arm study evaluating the efficacy and safety of EXCEL2 in broad types of de novo coronary artery lesions. This pooled analysis included patients in the CREDIT III and EXCEL2 arm of the CREDIT II trial. The primary outcome was 12-month target lesion failure (TLF), a composite of cardiac death, target vessel myocardial infarction (TV-MI), and clinical indicated target lesion revascularization (CI-TLR). The patient-oriented composite endpoint (PoCE) of all-cause death, all MI, or any revascularization was also analyzed. A total of 833 patients were included, consisting of 625 in the CREDIT III trial and 208 in the EXCEL2 arm of the CREDIT II trial. Twelve-month TLF occurred in 6.1% patients, cardiac death in 0.4%, TV-MI in 5%, and CI-TLR in 1.1%. Additionally, 64 (7.7%) PoCE and 3 probable late stent thromboses (0.4%) were recorded. EXCEL2 stent met the objective performance criterion on efficacy and safety with a low level of 12-month TLF as well as stent thrombosis when treating patients with de novo coronary lesions. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

  6. Isostructural dinuclear phenoxo-/acetato-bridged manganese(II), cobalt(II), and zinc(II) complexes with labile sites: kinetics of transesterification of 2-hydroxypropyl-p-nitrophenylphosphate.

    PubMed

    Arora, Himanshu; Barman, Suman K; Lloret, Francesc; Mukherjee, Rabindranath

    2012-05-21

    Using the dinucleating phenol-based ligand 2,6-bis[3-(pyridin-2-yl)pyrazol-1-ylmethyl]-4-methylphenol] (HL(2)), in its deprotonated form, the six new dinuclear complexes [M(II)(2)(L(2))(μ-O(2)CMe)(2)(MeCN)(2)][PF(6)] (M = Mn (2a), Co (3a), Zn (4a)) and [M(II)(2)(L(2))(μ-O(2)CMe)(2)(MeCN)(2)][BPh(4)] (M = Mn (2b), Co (3b), Zn (4b)) have been synthesized. Crystallographic analyses on 2b·2MeCN, 3b·2MeCN, and 4b·2MeCN reveal that these complexes have closely similar μ-phenoxo bis(μ-carboxylato) structures. The physicochemical properties (absorption and ESI-MS spectral data, 2a,b, 3a,b, and 4a,b; (1)H NMR, 4a,b) of the cations of 2a-4a are identical with those of 2b-4b. Each metal ion is terminally coordinated by a pyrazole nitrogen and a pyridyl nitrogen from a 3-(pyridin-2-yl)pyrazole unit and a solvent molecule (MeCN). Thus, each metal center assumes distorted-octahedral M(II)N(3)O(3) coordination. Temperature-dependent magnetic studies on Mn(II) and Co(II) dimers reveal the presence of intramolecular antiferromagnetic (J = -8.5 cm(-1)) for 2b and ferromagnetic exchange coupling (J = +2.51 cm(-1)) for 3b, on the basis of the Hamiltonian H = -JS(1)·S(2). The exchange mechanism is discussed on the basis of magneto-structural parameters (M···M distance). Spectroscopic properties of the complexes have also been investigated. The pH titration and kinetics of phosphatase (transesterification) activity on 2-hydroxypropyl-p-nirophenylphosphate (HPNP) were studied in MeOH/H(2)O (33%, v/v) with 2a-4a, due to solubility reasons. This comparative kinetic study revealed the effect of the metal ion on the rate of hydrolysis of HPNP, which has been compared with what we recently reported for [Ni(II)(2)(L(2))(μ-O(2)CMe)(2)(MeOH)(H(2)O)][ClO(4)] (1a). The efficacy in the order of conversion of substrate to product (p-nitrophenolate ion) follows the order 4a > 3a > 2a > 1a, under identical experimental conditions. Notably, this trend follows the decrease of pK(a) values of

  7. Samarium/Cobalt Magnets

    NASA Technical Reports Server (NTRS)

    Das, D.; Kumar, K.; Frost, R.; Chang, C.

    1985-01-01

    Intrinsic magnetic coercivities of samarium cobalt magnets made to approach theoretical limit of 350 kA/m by carefully eliminating oxygen from finished magnet by hot isostatic pressing (HIP). HIP process viable alternative to currently used sintering process.

  8. Samarium/Cobalt Magnets

    NASA Technical Reports Server (NTRS)

    Das, D.; Kumar, K.; Frost, R.; Chang, C.

    1985-01-01

    Intrinsic magnetic coercivities of samarium cobalt magnets made to approach theoretical limit of 350 kA/m by carefully eliminating oxygen from finished magnet by hot isostatic pressing (HIP). HIP process viable alternative to currently used sintering process.

  9. Isolation and (111)In-Oxine Labeling of Murine NK Cells for Assessment of Cell Trafficking in Orthotopic Lung Tumor Model.

    PubMed

    Malviya, Gaurav; Nayak, Tapan; Gerdes, Christian; Dierckx, Rudi A J O; Signore, Alberto; de Vries, Erik F J

    2016-04-04

    A noninvasive in vivo imaging method for NK cell trafficking is essential to gain further understanding of the pathogenesis of NK cell mediated immune response to the novel cancer treatment strategies, and to discover the homing sites and physiological distribution of NK cells. Although human NK cells can be labeled for in vivo imaging, little is known about the murine NK cell labeling and its application in animal models. This study describes the isolation and ex vivo radiolabeling of murine NK cells for the evaluation of cell trafficking in an orthotopic model of human lung cancer in mice. Scid-Tg(FCGR3A)Blt transgenic SCID mice were used to isolate NK cells from mouse splenocytes using the CD49b (DX5) MicroBeads positive selection method. The purity and viability of the isolated NK cells were confirmed by FACS analysis. Different labeling buffers and incubation times were evaluated to optimize (111)In-oxine labeling conditions. Functionality of the radiolabeled NK cell was assessed by (51)Cr-release assay. We evaluated physiological distribution of (111)In-oxine labeled murine NK cells in normal SCID mice and biodistribution in irradiated and nonirradiated SCID mice with orthotopic A549 human lung tumor lesions. Imaging findings were confirmed by histology. Results showed that incubation with 0.011 MBq of (111)In-oxine per million murine NK cells in PBS (pH 7.4) for 20 min is the best condition that provides optimum labeling efficiency without affecting cell viability and functionality. Physiological distribution in normal SCID mice demonstrated NK cells homing mainly in the spleen, while (111)In released from NK cells was excreted via kidneys into urine. Biodistribution studies demonstrated a higher lung uptake in orthotopic lung tumor-bearing mice than control mice. In irradiated mice, lung tumor uptake of radiolabeled murine NK cells decreased between 24 h and 72 h postinjection (p.i.), which was accompanied by tumor regression, while in nonirradiated mice

  10. Synthesis and Characterization of a New Cobalt(II) Complex with 2-(2-Pyridyl)Imino-N-(2-Thiazolin-2-yl)Thiazolidine (PyTT)

    PubMed Central

    García-Barros, F. J.; Higes-Rolando, F. J.; Luna-Giles, F.; Pacheco-Rodríguez, M. M.; Viñuelas-Zahínos, E.

    2004-01-01

    The compound aquanitrate-кObis[2-(2-pyridy)-imin-кN-N-(2-thiazin-кN-2-y)thiazidine]cbat() nitrate has been isolated and characterized by single crystal X-ray diffraction, IR spectroscopy, UV-Vis-NIR diffuse reflectance and magnetic susceptibility measurements. The environment around the cobalt atom may be described as a distorted octahedral geometry with the ligand-metal-ligand bite angles varying between 84.07(8)° and 98.66(8)°.The metallic atom is coordinated to two thiazoline nitrogens [av. Co-N =2.067 Å], two imino nitrogens [av. Co-N =2.122 Å], one oxygen atom of the nitrate group monodentate [Co-O(1)= 2.249(2) Å] and the oxygen atom of the water molecule [Co-O(IW)= 2.105(2) Å]. Electronic UV-Vis-NIR spectral data and the calculated magnetic moment are indicative of octahedral Co(ll) complexes. In the same way as other PyTT complexes, the organic moiety preserves the imino-thiazolidine form detected in the structure of PyTT. PMID:18365082

  11. New mixed ligand cobalt(II/III) complexes based on the drug sodium valproate and bioactive nitrogen-donor ligands. Synthesis, structure and biological properties

    NASA Astrophysics Data System (ADS)

    Abu Ali, Hijazi; Abu Shamma, Amani; Kamel, Shayma

    2017-08-01

    New cobalt valproate complexes with different nitrogen based ligands were synthesized and characterized using various techniques such as IR, UV-Vis, single crystal X-ray diffraction as well as other physical properties. The general formula of the prepared complexes is [Con(valp)m(L)z], (n = 1, 2 …; m = 1, 2, …; Z = 1, 2 …). The complexes [Co2(valp)4] (1), [Co(valp)2(2-ampy)2] (2) and [Co2(valp)4(quin)2] (3) showed different carboxylate coordination modes. The crystal structures of the complexes 2 and 3 were determined using single crystal X-ray diffraction. Kinetic studies of hydrolysis reactions of BNPP [bis-(p-nitrophenyl)phosphate] with complexes 2 and 3 were performed. The hydrolysis rate of BNPP was studied at different temperatures, pH and concentrations by UV-Vis spectrophotometric method. The results showed that the hydrolysis rate of BNPP was 7.70 × 102 L mol-1 s-1 for (3) and 2.60 × 10-1 L mol-1 s-1 for (2).

  12. Simple and sensitive detection method for Cobalt(II) in water using CePO4:Tb3+ nanocrystals as fluorescent probes.

    PubMed

    Chen, Hongqi; Yuan, Fei; Xu, Juan; Zhang, Yiyang; Wu, Yong; Wang, Lun

    2013-04-15

    A simple and sensitive method for detecting cobalt by synchronous fluorescence spectrometry technique with a novel fluorescence probe CePO4:Tb(3+) has been developed. CePO4:Tb(3+) nanocrystals were synthesized in aqueous solutions and characterized by transmission electron microscopy, electron diffraction pattern spectroscopy and spectrofluorometry. When Δλ=210 nm, the selected synchronous fluorescence is produced at 284 nm. CePO4:Tb(3+) nanocrystals were negatively charged under weakly basic conditions (pH=8.2), which can interact with Co(2+) via electrostatic interaction. Moreover, there is the spectrum overlap between the emission wavelength of CePO4:Tb(3+) NCs and the absorbance of Co(2+). So the energy transfer would occur, leading to the quenching phenomenon. The quenching equation of the system was agreed with the Stern-Volmer equation. The linear range and detection limit of Co(2+) were 5-1.8 μM and 3.5 nM, respectively. The method is successfully applied to the quantification of Co(2+) in water samples.

  13. Enhanced third-order nonlinear optical properties determined in thin films using the Z-scan technique: bis(μ-4,4'-oxydibenzoato)bis[(4'-phenyl-2,2':6',2''-terpyridine)cobalt(II)].

    PubMed

    Liu, Runqiang; Zhao, Ning; Liu, Ping; An, Caixia; Lian, Zhaoxun

    2016-05-01

    π-Conjugated organic materials exhibit high and tunable nonlinear optical (NLO) properties, and fast response times. 4'-Phenyl-2,2':6',2''-terpyridine (PTP) is an important N-heterocyclic ligand involving π-conjugated systems, however, studies concerning the third-order NLO properties of terpyridine transition metal complexes are limited. The title binuclear terpyridine Co(II) complex, bis(μ-4,4'-oxydibenzoato)-κ(3)O,O':O'';κ(3)O'':O,O'-bis[(4'-phenyl-2,2':6',2''-terpyridine-κ(3)N,N',N'')cobalt(II)], [Co2(C14H8O5)2(C21H15N3)2], (1), has been synthesized under hydrothermal conditions. In the crystal structure, each Co(II) cation is surrounded by three N atoms of a PTP ligand and three O atoms, two from a bidentate and one from a symmetry-related monodentate 4,4'-oxydibenzoate (ODA(2-)) ligand, completing a distorted octahedral coordination geometry. Neighbouring [Co(PTP)](2+) units are bridged by ODA(2-) ligands to form a ring-like structure. The third-order nonlinear optical (NLO) properties of (1) and PTP were determined in thin films using the Z-scan technique. The title compound shows a strong third-order NLO saturable absorption (SA), while PTP exhibits a third-order NLO reverse saturable absorption (RSA). The absorptive coefficient β of (1) is -37.3 × 10(-7) m W(-1), which is larger than that (8.96 × 10(-7) m W(-1)) of PTP. The third-order NLO susceptibility χ((3)) values are calculated as 6.01 × 10(-8) e.s.u. for (1) and 1.44 × 10(-8) e.s.u. for PTP.

  14. The azide-bridged mixed-valent cobalt(II,III) compound [(CH(3))(3)NH](2)[CoCo(2)(N(3))(10)].

    PubMed

    Liu, Yan-Ju; Li, Yu-Xian; Xu, Min; Wang, Xia

    2010-12-04

    The crystal structure of the title compound, poly[bis-(tri-methyl-ammonium) hexa-μ(1,1)-azido-tetra-azido-tricobalt-ate(II,III)], [(CH(3))(3)NH](2)[Co(II)Co(III) (2)(N(3))(10)], consists of anionic chains [Co(II)Co(III) (2)(N(3))(10)](2-) extending parallel to the c axis and [(CH(3))(3)NH](+) counter-cations situated between the chains. In the anionic chain, one tetra-hedrally coordinated Co(II) atom (site symmetry 2) and two octa-hedrally coordinated Co(III) atoms are arranged alternately and are linked by μ(1,1)-azide bridges. The anionic chains and cations are connected via N-H⋯N hydrogen bonding into a three-dimensional structure.

  15. Complexation-Based Detection of Nickel(II) at a Graphene-Chelate Probe in the Presence of Cobalt and Zinc by Adsorptive Stripping Voltammetry.

    PubMed

    Pokpas, Keagan; Jahed, Nazeem; Baker, Priscilla G; Iwuoha, Emmanuel I

    2017-07-25

    The adsorptive stripping voltammetric detection of nickel and cobalt in water samples at metal film electrodes has been extensively studied. In this work, a novel, environmentally friendly, metal-free electrochemical probe was constructed for the ultra-trace determination of Ni(2+) in water samples by Adsorptive Cathodic Stripping Voltammetry (AdCSV). The electrochemical platform is based on the adsorptive accumulation of Ni(2+) ions directly onto a glassy carbon electrode (GCE) modified with dimethylglyoxime (DMG) as chelating agent and a Nafion-graphene (NGr) nanocomposite to enhance electrode sensitivity. The nafion-graphene dimethylglyoxime modified glassy carbon electrode (NGr-DMG-GCE) shows superior detection capabilities as a result of the improved surface-area-to-volume ratio and enhanced electron transfer kinetics following the incorporation of single layer graphene, while limiting the toxic effects of the sensor by removal of the more common mercury, bismuth and lead films. Furthermore, for the first time the NGr-DMG-GCE, in the presence of common interfering metal ions of Co(2+) and Zn(2+) demonstrates good selectivity and preferential binding towards the detection of Ni(2+) in water samples. Structural and morphological characterisation of the synthesised single layer graphene sheets was conducted by Raman spectrometry, HRTEM and HRSEM analysis. The instrumental parameters associated with the electrochemical response, including accumulation potential and accumulation time were investigated and optimised in addition to the influence of DMG and graphene concentrations. The NGr-DMG-GCE demonstrated well resolved, reproducible peaks, with RSD (%) below 5% and a detection limit of 1.5 µg L(-1) for Ni(2+) reduction at an accumulation time of 120 s., the prepared electrochemical sensor exhibited good detection and quantitation towards Ni(2+) detection in tap water samples, well below 0.1 mg L(-1) set by the WHO and EPA standards. This comparable to the South

  16. Polymeric cobalt(ii) thiolato complexes - syntheses, structures and properties of [Co(SMes)2] and [Co(SPh)2NH3].

    PubMed

    Eichhöfer, Andreas; Buth, Gernot

    2016-11-01

    Reactions of [Co(N(SiMe3)2)2thf] with 2.1 equiv. of MesSH (Mes = C6H2-2,4,6-(CH3)3) yield dark brown crystals of the one dimensional chain compound [Co(SMes)2]. In contrast reactions of [Co(N(SiMe3)2)2thf] with 2.1 equiv. of PhSH result in the formation of a dark brown almost X-ray amorphous powder of 'Co(SPh)2'. Addition of aliquots of CH3OH to the latter reaction resulted in the almost quantitative formation of crystalline ammonia thiolato complexes either [Co(SPh)2(NH3)2] or [Co(SPh)2NH3]. Single crystal XRD reveals that [Co(SPh)2NH3] forms one-dimensional chains in the crystal via μ2-SPh bridges whereas [Co(SPh)2(NH3)2] consists at a first glance of isolated distorted tetrahedral units. Magnetic measurements suggest strong antiferromagnetic coupling for the two chain compounds [Co(SMes)2] (J = -38.6 cm(-1)) and [Co(SPh)2NH3] (J = -27.1 cm(-1)). Interestingly, also the temperature dependence of the susceptibility of tetrahedral [Co(SPh)2(NH3)2] shows an antiferromagnetic transition at around 6 K. UV-Vis-NIR spectra display d-d bands in the NIR region between 500 and 2250 nm. Thermal gravimetric analysis of [Co(SPh)2(NH3)2] and [Co(SPh)2NH3] reveals two well separated cleavage processes for NH3 and SPh2 upon heating accompanied by the stepwise formation of 'Co(SPh)2' and cobalt sulfide.

  17. Crystal structure of di­aqua­bis­(4-tert-butyl­benzoato-κO)bis­(nicotinamide-κN 1)cobalt(II) dihydrate

    PubMed Central

    Aşkın, Gülçin Şefiye; Necefoğlu, Hacali; Özkaya, Safiye; Çatak Çelik, Raziye; Hökelek, Tuncer

    2016-01-01

    The asymmetric unit of the mononuclear cobalt complex, [Co(C11H13O2)2(C6H6N2O)2(H2O)2]·2H2O, contains one half of the complex mol­ecule, one coordinating and one non-coordinating water mol­ecule, one 4-tert-butyl­benzoate (TBB) ligand and one nicotinamide (NA) ligand; the Co atom lies on an inversion centre. All ligands coordinating to the Co atom are monodentate. The four nearest O atoms around the Co atom form a slightly distorted square-planar arrangement, with the distorted octa­hedral coordination completed by the two pyridine N atoms of the NA ligands at distances of 2.1638 (11) Å. The coordinating water mol­ecules are hydrogen bonded to the carboxyl O atoms [O ⋯ O = 2.6230 (17) Å], enclosing an S(6) hydrogen-bonding motif, while inter­molecular O—H⋯O hydrogen bonds link two of the non-coordinating water mol­ecules to the coordinating water mol­ecules and NA anions. The dihedral angle between the planar carboxyl­ate group and the adjacent benzene ring is 29.09 (10)°, while the benzene and pyridine rings are oriented at a dihedral angle of 88.53 (4)°. In the crystal, O—H⋯O and N—H⋯O hydrogen bonds link the mol­ecules, enclosing R 2 2(8), R 2 2(10) and R 4 4(12) ring motifs, forming layers parallel to (001). The C and H atoms of the tert-butyl group of the TBB ligand are disordered over two sets of sites with an occupancy ratio of 0.631 (5):0.369 (5). PMID:27555924

  18. Complexation-Based Detection of Nickel(II) at a Graphene-Chelate Probe in the Presence of Cobalt and Zinc by Adsorptive Stripping Voltammetry

    PubMed Central

    Pokpas, Keagan; Jahed, Nazeem; Baker, Priscilla G.

    2017-01-01

    The adsorptive stripping voltammetric detection of nickel and cobalt in water samples at metal film electrodes has been extensively studied. In this work, a novel, environmentally friendly, metal-free electrochemical probe was constructed for the ultra-trace determination of Ni2+ in water samples by Adsorptive Cathodic Stripping Voltammetry (AdCSV). The electrochemical platform is based on the adsorptive accumulation of Ni2+ ions directly onto a glassy carbon electrode (GCE) modified with dimethylglyoxime (DMG) as chelating agent and a Nafion-graphene (NGr) nanocomposite to enhance electrode sensitivity. The nafion-graphene dimethylglyoxime modified glassy carbon electrode (NGr-DMG-GCE) shows superior detection capabilities as a result of the improved surface-area-to-volume ratio and enhanced electron transfer kinetics following the incorporation of single layer graphene, while limiting the toxic effects of the sensor by removal of the more common mercury, bismuth and lead films. Furthermore, for the first time the NGr-DMG-GCE, in the presence of common interfering metal ions of Co2+ and Zn2+ demonstrates good selectivity and preferential binding towards the detection of Ni2+ in water samples. Structural and morphological characterisation of the synthesised single layer graphene sheets was conducted by Raman spectrometry, HRTEM and HRSEM analysis. The instrumental parameters associated with the electrochemical response, including accumulation potential and accumulation time were investigated and optimised in addition to the influence of DMG and graphene concentrations. The NGr-DMG-GCE demonstrated well resolved, reproducible peaks, with RSD (%) below 5% and a detection limit of 1.5 µg L−1 for Ni2+ reduction at an accumulation time of 120 s. The prepared electrochemical sensor exhibited good detection and quantitation towards Ni2+ detection in tap water samples, well below 0.1 mg L−1 set by the WHO and EPA standards. This is comparable to the South African

  19. V-shaped ligand 1,3-bis(1-ethylbenzimidazol-2-yl)-2-thiapropane and manganese(II), cobalt(II) and copper(II) complexes: Synthesis, crystal structure, DNA-binding properties and antioxidant activities.

    PubMed

    Wu, Huilu; Yang, Zaihui; Wang, Fei; Peng, Hongping; Zhang, Han; Wang, Cuiping; Wang, Kaitong

    2015-07-01

    A V-shaped ligand 1,3-bis(1-ethylbenzimidazol-2-yl)-2-thiapropane (bebt) and its transition metal complexes, [Mn(bebt)(pic)2]·CH3OH (pic=picrate) 1, [Co(bebt)2](pic)22 and [Cu(bebt)2](pic)2·2DMF 3, have been synthesized and characterized. The coordinate forms of complexes 1 and 2 are basically alike, which can be described as six-coordinated distorted octahedron. The geometric structure around Cu(II) atom can be described as distorted tetrahedral in complex 3. The DNA-binding properties of the ligand bebt and complexes have been investigated by electronic absorption, fluorescence, and viscosity measurements. The results suggest that bebt and complexes bind to DNA via an intercalative binding mode and the order of the binding affinity is 1<2<3

  20. Catalysis: Cobalt gets in shape

    NASA Astrophysics Data System (ADS)

    Claeys, Michael

    2016-10-01

    Solid cobalt-based catalysts are used commercially to convert carbon monoxide and hydrogen into synthetic fuels. It emerges that much more valuable chemicals can be produced by using a different form of cobalt catalyst. See Letter p.84

  1. Enhanced photovoltaic performance of nanowire dye-sensitized solar cells based on coaxial TiO2@TiO heterostructures with a cobalt(II/III) redox electrolyte.

    PubMed

    Fan, Jiandong; Fàbrega, Cristian; Zamani, Reza R; Hao, Yan; Parra, Andres; Andreu, Teresa; Arbiol, Jordi; Boschloo, Gerrit; Hagfeldt, Anders; Morante, Joan Ramon; Cabot, Andreu

    2013-10-23

    The growth of a TiO shell at the surface of TiO2 nanowires (NWs) allowed us to improve the power conversion efficiency of NW-based dye-sensitized solar cells (DSCs) by a factor 2.5. TiO2@TiO core-shell NWs were obtained by a two-step process: First, rutile-phase TiO2 NWs were hydrothermally grown. Second, a hongquiite-phase TiO shell was electrochemically deposited at the surface of the TiO2 NWs. Bare TiO2 and heterojunction TiO2@TiO NW-based DSCs were obtained using a cobalt(II/III) redox electrolyte and LEG4 as the dye. With this electrolyte/dye combination, DSCs with outstanding Voc values above 900 mV were systematically obtained. While TiO2@TiO NW-based DSCs had slightly lower Voc values than bare TiO2 NW-based DSCs, they provided 3-fold higher photocurrents, overall reaching 2.5-fold higher power conversion efficiencies. The higher photocurrents were associated with the larger surface roughness and an enhanced charge-carrier separation/transfer at the NW/dye interface.

  2. Gallium(III), cobalt(III) and copper(II) protoporphyrin IX exhibit antimicrobial activity against Porphyromonas gingivalis by reducing planktonic and biofilm growth and invasion of host epithelial cells.

    PubMed

    Olczak, Teresa; Maszczak-Seneczko, Dorota; Smalley, John W; Olczak, Mariusz

    2012-08-01

    Porphyromonas gingivalis acquires heme for growth, and initiation and progression of periodontal diseases. One of its heme acquisition systems consists of the HmuR and HmuY proteins. This study analyzed the antimicrobial activity of non-iron metalloporphyrins against P. gingivalis during planktonic growth, biofilm formation, epithelial cell adhesion and invasion, and employed hmuY, hmuR and hmuY-hmuR mutants to assess the involvement of HmuY and HmuR proteins in the acquisition of metalloporphyrins. Iron(III) mesoporphyrin IX (mesoheme) and iron(III) deuteroporphyrin IX (deuteroheme) supported planktonic growth of P. gingivalis cells, biofilm accumulation, as well as survival, adhesion and invasion of HeLa cells in a way analogous to protoheme. In contrast, cobalt(III), gallium(III) and copper(II) protoporphyrin IX exhibited antimicrobial activity against P. gingivalis, and thus represent potentially useful antibacterial compounds with which to target P. gingivalis. P. gingivalis hmuY, hmuR and hmuY-hmuR mutants showed decreased growth and infection of epithelial cells in the presence of all metalloporphyrins examined. In conclusion, the HmuY protein may not be directly involved in transport of free metalloporphyrins into the bacterial cell, but it may also play a protective role against metalloporphyrin toxicity by binding an excess of these compounds.

  3. Mixed-ligand cobalt(II) complexes of bioinorganic and medicinal relevance, involving dehydroacetic acid and β-diketones: Their synthesis, hyphenated experimental-DFT, thermal and bactericidal facets

    NASA Astrophysics Data System (ADS)

    Maurya, R. C.; Malik, B. A.; Mir, J. M.; Vishwakarma, P. K.; Rajak, D. K.; Jain, N.

    2015-11-01

    The present report pertains to synthesis and combined experimental-DFT studies of a series of four novel mixed-ligand complexes of cobalt(II) of the general composition [Co(dha)(L)(H2O)2], where dhaH = dehydroacetic acid, LH = β-ketoenolates viz., o-acetoacetotoluidide (o-aatdH), o-acetoacetanisidide (o-aansH), acetylacetone (acacH) or 1-benzoylacetone (1-bac). The resulting complexes were formulated based on elemental analysis, molar conductance, magnetic measurements, mass spectrometric, IR, electronic, electron spin resonance and cyclic voltammetric studies. The TGA based thermal behavior of one representative complex was evaluated. Molecular geometry optimizations and vibrational frequency calculations have been performed with Gaussian 09 software package by using density functional theory (DFT) methods with B3LYP/LANL2MB combination for dhaH and one of its complexes, [Co(dha)(1-bac)(H2O)2]. Theoretical data has been found in an excellent agreement with the experimental results. Based on experimental and theoretical data, suitable trans-octahedral structure has been proposed for the present class of complexes. Moreover, the complexes also showed a satisfactory antibacterial activity.

  4. Determination of trace cobalt(II) by adsorptive stripping voltammetry on disposable microfabricated electrochemical cells with integrated planar metal-film electrodes.

    PubMed

    Kokkinos, Christos; Economou, Anastasios; Koupparis, Michael

    2009-01-15

    This work reports the determination of trace Co(II) by adsorptive stripping voltammetry on disposable three-electrode cells with on-chip metal-film electrodes. The heart of the sensors was a bismuth-film electrode (BiFE) with Ag and Pt planar strips serving as the reference and counter electrodes, respectively. Metals were deposited on a silicon chip by sputtering while the areas of the electrodes were patterned via a metal mask. Co(II) was determined by square wave adsorptive stripping voltammetry (SWAdSV) after complexation with dimethylglyoxime (DMG). The experimental variables (the DMG concentration, the preconcentration potential, the accumulation time and the SW parameters), as well as potential interferences, were investigated. Using the selected conditions, the 3 sigma limit of detection was 0.09 microg l(-1) of Co(II) (for 90s of preconcentration) and the relative standard deviation for Co(II) was 3.8% at the 2 microg l(-1) level (n=8). The method was applied to the determination of Co(II) in a certified river water sample. These mercury-free electrochemical devices present increased scope for field analysis and mu-TAS applications.

  5. Novel Cobalt(II) complexes containing N,N-di(2-picolyl)amine based ligands; Synthesis, characterization and application towards methyl methacrylate polymerisation

    NASA Astrophysics Data System (ADS)

    Ahn, Seoung Hyun; Choi, Sang-Il; Jung, Maeng Joon; Nayab, Saira; Lee, Hyosun

    2016-06-01

    The reaction of [CoCl2·6H2O] with N‧-substituted N,N-di(2-picolyl)amine ligands such as 1-cyclohexyl-N,N-bis(pyridin-2-ylmethyl)methanamine (LA), 2-methoxy-N,N-bis(pyridin-2-ylmethyl)ethan-1-amine (LB), and 3-methoxy-N,N-bis(pyridin-2-ylmethyl)propan-1-amine (LC), yielded [LnCoCl2] (Ln = LA, LB and LC), respectively. The Co(II) centre in [LnCoCl2] (Ln = LA, and LC) adopted distorted bipyramidal geometries through coordination of nitrogen atoms of di(2-picolyl)amine moiety to the Co(II) centre along with two chloro ligands. The 6-coordinated [LBCoCl2] showed a distorted octahedral geometry, achieved through coordination of the two pyridyl units, two chloro units, and bidentate coordination of nitrogen and oxygen in the N‧-methoxyethylamine to the Co(II) centre. [LCCoCl2] (6.70 × 104 gPMMA/molCo h) exhibited higher catalytic activity for the polymerisation of methyl methacrylate (MMA) in the presence of modified methylaluminoxane (MMAO) compared to rest of Co(II) complexes. The catalytic activity was considered as a function of steric properties of ligand architecture and increased steric bulk around the metal centre resulted in the decrease catalytic activity. All Co(II) initiators yielded syndiotactic poly(methylmethacrylate) (PMMA).

  6. Oxygenation of Cobalt Porphyrinates: Coordination or Oxidation?

    PubMed Central

    Li, Jianfeng; Noll, Bruce C.; Oliver, Allen G.; Ferraudi, Guillermo; Lappin, A. Graham; Scheidt, W. Robert

    2010-01-01

    The X-ray characterization of the five-coordinate picket-fence porphyrin complex, [Co(TpivPP)(2-MeHim)], is reported. The complex has the displacement of cobalt from the porphyrin plane = 0.15 Å, and Co–NIm = 2.145 (3) and (Co–Np)av = 1.979(3) Å. This five-coordinate complex, in the presence of dioxygen and excess 2-methylimidazole, undergoes an unanticipated, photoinitiated atropisomerization of the porphyrin ligand, oxidation of cobalt(II) and the formation of the neutral cobalt(III) complex [Co(α,α,β,β-TpivPP)(2-MeHim)(2-MeIm−]. Two distinct examples of this complex have been structurally characterized, both have structural parameters consistent with cobalt(III). The two new Co(III) porphyrin complexes have axial Co–NIm distances ranging from 1.952 to 1.972 Å, but which allow for the distinction between imidazole and imidazolate. An interesting intermolecular hydrogen bonding network is observed that leads to infinite helical chains. UV-vis spectroscopic study suggests that [Co(TpivPP)(2-MeHIm)(O2)] is an intermediate state for the oxidation reaction and the atropisomerization process is photocatalyzed. A reaction route is proposed based on the spectroscopic studies. PMID:20104874

  7. [Co(x)Cu(1-x)(DDOP)(OH2)(NO3)](NO3): hydrogen bond-driven distortion of cobalt(II) by solid solution 'network mismatch'.

    PubMed

    Fielden, John; Long, De-Liang; Speldrich, Manfred; Kögerler, Paul; Cronin, Leroy

    2012-04-28

    Late-first row transition metal nitrate complexes of the tetradentate N-donor ligand cis-3,5-bis[(2-pyridinyleneamino]-trans-hydroxycyclohexane (DDOP) adopt a mono-cationic [M(DDOP)(H(2)O)(NO(3))](+) structure (M = Co, 1; Cu, 2; Zn, 3) in which the DDOP ligand occupies the equatorial plane. The complexes are essentially isostructural and isomorphous, allowing the Co(II) and Cu(II) complexes to co-crystallize in mixed-metal solid solutions with the formula [Co(x)Cu(1-x)(DDOP)(NO(3))(H(2)O)](NO(3)), where x = 0.4 (4), 0.1 (5), and 0.7 (6). For 4, structural and magnetochemical analysis indicate that the geometry of the octahedral Co(II) complex distorts to match that of the dominant Jahn-Teller distorted Cu(II) center. Magnetic susceptibility data of octahedral Co(II) are sensitive to ligand geometry distortions and have been analyzed accordingly, comparing 4 to the reference systems 1 and 2. Bond valence calculations have been used to estimate the relative stabilities of the six hydrogen bonded networks, suggesting that the stretching of the Co(II) coordination sphere 4 in is assisted by adoption of the most stable hydrogen bonded network; but that in 6 this is overcome by a higher loading of Co. This family of complexes therefore represent predictable metal-based tectons which can help probe the influence of secondary non-covalent interactions over metal coordination geometries and properties.

  8. Crystal structure of di­aqua­bis­(N,N-di­ethyl­nicotinamide-κN 1)bis­(2,4,6-tri­methyl­benzoato-κO 1)cobalt(II)

    PubMed Central

    Aşkın, Gülçin Şefiye; Necefoğlu, Hacali; Özkaya, Safiye; Çatak Çelik, Raziye; Hökelek, Tuncer

    2016-01-01

    The centrosymmetric mol­ecule in the monomeric title cobalt complex, [Co(C10H11O2)2(C10H14N2O)2(H2O)2], contains two water mol­ecules, two 2,4,6-tri­methyl­benzoate (TMB) ligands and two di­ethyl­nicotinamide (DENA) ligands. All ligands coordinate to the CoII atom in a monodentate fashion. The four O atoms around the CoII atom form a slightly distorted square-planar arrangement, with the distorted octa­hedral coordination sphere completed by two pyridine N atoms of the DENA ligands. The dihedral angle between the planar carboxyl­ate group and the adjacent benzene ring is 84.2 (4)°, while the benzene and pyridine rings are oriented at a dihedral angle of 38.87 (10)°. The water mol­ecules exhibit both intra­molecular (to the non-coordinating carboxyl­ate O atom) and inter­molecular (to the amide carbonyl O atom) O—H⋯O hydrogen bonds. The latter lead to the formation of layers parallel to (100), enclosing R 4 4(32) ring motifs. These layers are further linked via weak C—H⋯O hydrogen bonds, resulting in a three-dimensional network. One of the two ethyl groups of the DENA ligand is disordered over two sets of sites with an occupancy ratio of 0.490 (13):0.510 (13). PMID:27375874

  9. Spectroscopic studies of zinc(II)- and cobalt(II)-associated Escherichia coli formamidopyrimidine-DNA glycosylase: extended X-ray absorption fine structure evidence for a metal-binding domain.

    PubMed

    Buchko, G W; Hess, N J; Bandaru, V; Wallace, S S; Kennedy, M A

    2000-10-10

    Formamidopyrimidine-DNA glycosylase (Fpg) is a 30.2 kDa protein that plays an important role in the base excision repair of oxidatively damaged DNA in Escherichia coli. Sequence analysis and genetic evidence suggest that zinc is associated with a C4-type motif, C(244)-X(2)-C(247)-X(16)-C(264)-X(2)-C(267), located at the C-terminus of the protein. The zinc-associated motif has been shown to be essential for damaged DNA recognition. Extended X-ray absorption fine structure (EXAFS) spectra collected on the zinc-associated protein (ZnFpg) in the lyophilized state and in 10% frozen aqueous glycerol solution show directly that the metal is coordinated to the sulfur atom of four cysteine residues. The average Zn-S bond length is 2.33 +/- 0.01 and 2.34 +/- 0.01 A, respectively, in the lyophilized state and in 10% frozen aqueous glycerol solution. Fpg was also expressed in minimal medium supplemented with cobalt nitrate to yield a blue-colored protein that was primarily cobalt-associated (CoFpg). The profiles of the circular dichroism spectra for CoFpg and ZnFpg are identical, suggesting that the substitution of Co(2+) for Zn(2+) does not alter the structure of Fpg. A similar conclusion is reached upon the analysis of two-dimensional (15)N/(1)H HSQC spectra of uniformly (15)N-labeled samples of ZnFpg and CoFpg; the spectra are similar and display features characteristic of a structured protein. Biochemical assays with a 54 nt DNA oligomer containing 7, 8-dihydro-8-oxoguanine at a specific location show that CoFpg and ZnFpg are equally active at cleaving the DNA at the site of the oxidized guanine. EXAFS spectra of CoFpg indicate that the cobalt is coordinated to the sulfur atom of four cysteine residues with an average Co-S bond length of 2.28 +/- 0.01 and 2.29 +/- 0.01 A, respectively, in the lyophilized state and in 10% frozen aqueous glycerol solution. The structural similarity between CoFpg and ZnFpg suggests that it is biologically relevant to use the paramagnetic

  10. Preparation of a Cobalt(II) Cage: An Undergraduate Laboratory Experiment That Produces a ParaSHIFT Agent for Magnetic Resonance Spectroscopy

    ERIC Educational Resources Information Center

    Burns, Patrick J.; Tsitovich, Pavel B.; Morrow, Janet R.

    2016-01-01

    Laboratory experiments that demonstrate the effect of paramagnetic complexes on chemical shifts and relaxation times of protons are a useful way to introduce magnetic resonance spectroscopy (MRS) probes or magnetic resonance imaging (MRI) contrast agents. In this undergraduate inorganic chemistry experiment, a paramagnetic Co(II) cage complex is…

  11. DNA-interaction and in vitro antimicrobial studies of some mixed-ligand complexes of cobalt(II) with fluoroquinolone antibacterial agent ciprofloxacin and some neutral bidentate ligands.

    PubMed

    Patel, M N; Chhasatia, M R; Gandhi, D S

    2009-05-15

    Six new mixed-ligand complexes of Co(II) with ciprofloxacin (Cip) and neutral bidentate ligands have been synthesized and characterized. Binding and cleavage of DNA with the complex were investigated using spectroscopic method, viscosity measurements and gel electrophoresis techniques. Antibacterial activity has been assayed against two Gram((-ve)) and three Gram((+ve)) microorganisms using the doubling dilution technique.

  12. Preparation of a Cobalt(II) Cage: An Undergraduate Laboratory Experiment That Produces a ParaSHIFT Agent for Magnetic Resonance Spectroscopy

    ERIC Educational Resources Information Center

    Burns, Patrick J.; Tsitovich, Pavel B.; Morrow, Janet R.

    2016-01-01

    Laboratory experiments that demonstrate the effect of paramagnetic complexes on chemical shifts and relaxation times of protons are a useful way to introduce magnetic resonance spectroscopy (MRS) probes or magnetic resonance imaging (MRI) contrast agents. In this undergraduate inorganic chemistry experiment, a paramagnetic Co(II) cage complex is…

  13. Some new chromogens for iron, cobalt, and copper Substituted hydrazidines and 1,2,4-triazines containing the ferroin group.

    PubMed

    Schilt, A A

    1966-07-01

    The spectral characteristics and solution conditions requisite for formation of the iron(II), cobalt(II), and copper(I) complexes of some newly synthesised compounds containing the ferroin functional grouping have been determined. These properties are useful for evaluation of the possible analytical effectiveness of the compounds as spectrophotometric reagents for the determination of iron, cobalt, and copper.

  14. Porous cobalt spheres for high temperature gradient magnetically assisted fluidized beds

    NASA Technical Reports Server (NTRS)

    Atwater, James E.; Akse, James R.; Jovanovic, Goran N.; Wheeler, Richard R Jr; Sornchamni, Thana

    2003-01-01

    Porous metallic cobalt spheres have been prepared as high temperature capable media for employment in gradient magnetically assisted fluidization and filtration technologies. Cobalt impregnated alginate beads are first formed by extrusion of an aqueous suspension of Co3O4 into a Co(II) chloride solution. The organic polymer is thermally decomposed yielding cobalt oxide spheres, followed by reduction to the metallic state, and densification. Cobalt beads have been produced with porosities ranging between 10 and 50%, depending upon sintering conditions. The product media have been characterized by scanning electron microscopy (SEM), nitrogen adsorption porosimetry, and vibrating sample magnetometry. c2003 Elsevier Science Ltd. All rights reserved.

  15. Porous cobalt spheres for high temperature gradient magnetically assisted fluidized beds

    SciTech Connect

    Atwater, James E.; Akse, James R.; Jovanovic, Goran N.; Wheeler, Richard R.; Sornchamni, Thana

    2003-02-20

    Porous metallic cobalt spheres have been prepared as high temperature capable media for employment in gradient magnetically assisted fluidization and filtration technologies. Cobalt impregnated alginate beads are first formed by extrusion of an aqueous suspension of Co{sub 3}O{sub 4} into a Co(II) chloride solution. The organic polymer is thermally decomposed yielding cobalt oxide spheres, followed by reduction to the metallic state, and densification. Cobalt beads have been produced with porosities ranging between 10 and 50%, depending upon sintering conditions. The product media have been characterized by scanning electron microscopy (SEM), nitrogen adsorption porosimetry, and vibrating sample magnetometry.

  16. Porous cobalt spheres for high temperature gradient magnetically assisted fluidized beds

    NASA Technical Reports Server (NTRS)

    Atwater, James E.; Akse, James R.; Jovanovic, Goran N.; Wheeler, Richard R Jr; Sornchamni, Thana

    2003-01-01

    Porous metallic cobalt spheres have been prepared as high temperature capable media for employment in gradient magnetically assisted fluidization and filtration technologies. Cobalt impregnated alginate beads are first formed by extrusion of an aqueous suspension of Co3O4 into a Co(II) chloride solution. The organic polymer is thermally decomposed yielding cobalt oxide spheres, followed by reduction to the metallic state, and densification. Cobalt beads have been produced with porosities ranging between 10 and 50%, depending upon sintering conditions. The product media have been characterized by scanning electron microscopy (SEM), nitrogen adsorption porosimetry, and vibrating sample magnetometry. c2003 Elsevier Science Ltd. All rights reserved.

  17. Porous cobalt spheres for high temperature gradient magnetically assisted fluidized beds.

    PubMed

    Atwater, James E; Akse, James R; Jovanovic, Goran N; Wheeler, Richard R; Sornchamni, Thana

    2003-02-20

    Porous metallic cobalt spheres have been prepared as high temperature capable media for employment in gradient magnetically assisted fluidization and filtration technologies. Cobalt impregnated alginate beads are first formed by extrusion of an aqueous suspension of Co3O4 into a Co(II) chloride solution. The organic polymer is thermally decomposed yielding cobalt oxide spheres, followed by reduction to the metallic state, and densification. Cobalt beads have been produced with porosities ranging between 10 and 50%, depending upon sintering conditions. The product media have been characterized by scanning electron microscopy (SEM), nitrogen adsorption porosimetry, and vibrating sample magnetometry.

  18. Effect of the metal environment on the ferromagnetic interaction in the Co-NC-W pairs of octacyanotungstate(V)-Cobalt(II) three-dimensional networks.

    PubMed

    Clima, Sergiu; Hendrickx, Marc F A; Chibotaru, Liviu F; Soncini, Alessandro; Mironov, Vladimir; Ceulemans, Arnout

    2007-04-02

    State of the art CASSCF and CASPT2 calculations have been performed to elucidate the nature of ferromagnetism of CoII-NC-WV pairs in the three-dimensional compound [[WV(CN)2]2[(micro-CN)4CoII(H2O)2]3.4H2O]n, which has been recently synthesized and investigated by a number of experimental techniques (Herrera, J. M.; Bleuzen, A.; Dromzée, Y.; Julve, M.; Lloret, F.; Verdaguer, M. Inorg. Chem. 2003, 42, 7052-7059). In this network, the Co ions are in the high-spin (S = 3/2) state, while the single unpaired electron on the W centers occupies the lowest orbital of the dz2 type of the 5d shell. In agreement with the suggestion made by Herrera et al., we find that the ferromagnetism is due to a certain occupation scheme of the orbitals from the parent octahedral t2g shell on CoII sites, in which the orbital accommodating the unpaired electron is orthogonal to the dz2 orbitals of the surrounding W ions. We investigate the stabilization of such an orbital configuration on the Co sites and find that it cannot be achieved in the ground state of isolated mononuclear fragments [CoII(NC)4(OH2)2]2- for any conformations of the coordinated water molecules and Co-N-C bond angles. On the other hand, it is stabilized by the interaction of the complex with neighboring W ions, which are simulated here by effective potentials. The calculated exchange coupling constants for the CoII-NC-WV binuclear fragments are in reasonable agreement with the measured Curie-Weiss constant for this compound. As additional evidence for the inferred electronic configuration on the Co sites, the ligand-field transitions, the temperature-dependent magnetic susceptibility, and the field-dependent low-temperature magnetization, simulated ab initio for the mononuclear Co fragments, are in agreement with the available data for another compound [WIV[(micro-CN)4-CoII(H2O)2]2.4H2O]n containing diamagnetic W and high-spin Co ions in an isostructural environment.

  19. Crystal structure of poly[{μ-N,N′-bis[(pyridin-4-yl)meth­yl]oxalamide}-μ-oxalato-cobalt(II)

    PubMed Central

    Zou, Hengye; Qi, Yanjuan

    2014-01-01

    In the polymeric title compound, [Co(C2O4)(C14H14N4O2)]n, the CoII atom is six-coordinated by two N atoms from symmetry-related bis­[(pyridin-4-yl)meth­yl]oxalamide (BPMO) ligands and four O atoms from two centrosymmetric oxalate anions in a distorted octa­hedral coordination geometry. The CoII atoms are linked by the oxalate anions into a chain running parallel to [100]. The chains are linked by the BPMO ligands into a three-dimensional architecture. In addition, N—H⋯O hydrogen bonds stabilize the crystal packing. PMID:25309173

  20. Two-dimensional frameworks formed by pentagonal bipyramidal cobalt(ii) ions and hexacyanometallates: antiferromagnetic ordering, metamagnetism and slow magnetic relaxation.

    PubMed

    Shao, Dong; Zhou, Yan; Pi, Qian; Shen, Fu-Xing; Yang, Si-Run; Zhang, Shao-Liang; Wang, Xin-Yi

    2017-07-18

    We herein report the syntheses, structures, and magnetic properties of two isostructural two-dimensional (2D) coordination polymers based on a pentagonal bipyramidal Co(II) unit [Co(TODA)](2+) and two hexacyanometallates, namely [M(III)(CN)6]2[Co(II)(TODA)]3·9H2O (M = Cr (1), Co (2), TODA = 1,4,10-trioxa-7,13-diazacyclopentadecane). Structure analyses show that both complexes have 2D honeycomb structures where the [Co(TODA)](2+) units are bridged by the [M(III)(CN)6](3-) groups through three cyano groups in the facial positions. Magnetic investigation reveals ferromagnetic coupling between the Cr(III) and Co(II) centres through cyanides in 1. Due to the antiferromagnetic interaction between the layers, compound 1 exhibits an antiferromagnetic ordering below 11.4 K, and shows a metamagnetic phase transition under an external dc field. Due to the disorder of the TODA ligands, compound 1 shows a spin glass behavior, which leads to slow magnetic relaxation in 1. A butterfly-shaped hysteresis loop at 1.8 K can be observed with a coercive field of 720 Oe, which is quite large for cyano-bridged Cr-Co molecular magnets. For compound 2 containing the diamagnetic [Co(III)(CN)6](3-) unit, field-induced slow magnetic relaxation was also verified, which makes compound 2 a rare example of an SIM assembled in a 2D network. An easy-plane magnetic anisotropy with a positive D value (29.9 cm(-1) by PHI and 26.5 cm(-1) by Anisofit2.0) was deduced for hepta-coordinated Co(II) centers. These results show the efficiency of the strategy of combining cyanometallates and pentagonal bipyramidal precursors for novel molecular magnetic materials.

  1. Cobalt toxicity: chemical and radiological combined effects on HaCaT keratinocyte cell line.

    PubMed

    Gault, N; Sandre, C; Poncy, J-L; Moulin, C; Lefaix, J-L; Bresson, C

    2010-02-01

    Cobalt (Co) is an essential trace element well known as a constituent of vitamin B(12), but different compounds of Co are also described as highly toxic and/or radiotoxic for individuals or the environment. In nuclear power plants, (58)Co and (60)Co are radioactive isotopes of cobalt present as activation products of stable Co and Ni used in alloys. Skin exposure is a current occupational risk in the hard metal and nuclear industries. As biochemical and molecular cobalt-induced toxicological mechanisms are not fully identified, we investigated cobalt toxicity in a model human keratinocyte cell line, HaCaT. In this study, we propose a model to determine the in vitro chemical impact on cell viability of a soluble form of cobalt (CoCl(2)) with or without gamma-ray doses to mimic contamination by (60)Co, to elucidate the mechanisms of cobalt intracellular chemical and radiological toxicity. Intracellular cobalt concentration was determined after HaCaT cell contamination and chemical toxicity was evaluated in terms of cellular viability and clonogenic survival. We investigated damage to DNA in HaCaT cells by combined treatment with chemical cobalt and a moderate gamma-ray dose. Additive effects of cobalt and irradiation were demonstrated. The underlying mechanism of cobalt toxicity is not clearly established, but our results seem to indicate that the toxicity of Co(II) and of irradiation arises from production of reactive oxygen species.

  2. Co(II)-mediated effects of plain and plasma immersion ion implanted cobalt-chromium alloys on the osteogenic differentiation of human mesenchymal stem cells.

    PubMed

    Schröck, Kathleen; Lutz, Johanna; Mändl, Stephan; Hacker, Michael C; Kamprad, Manja; Schulz-Siegmund, Michaela

    2015-03-01

    Medical CoCr is one of the main alloys used for metal-on-metal prosthesis in patients with total hip arthroplasty. CoCr surfaces modified by nitrogen plasma immersion ion implantation (PIII) are characterized by improved wear resistance but also showed increased Co(II) ion release under in vitro conditions. For the first time, CoCr modified by nitrogen PIII was evaluated with regard to its effect on the osteogenic differentiation of MSC. The activity of alkaline phosphatase, the expression of the osteogenic genes Runt-related transcription factor 2, osteopontin as well as integrin-binding bone sialoprotein and the production of osteocalcin and hydroxyapatite were determined. The results of our study demonstrate that Co(II) ions released from the alloy affected the osteogenic differentiation of MSC. Distinct differences in differentiation markers were found between pristine and modified alloys for osteocalcin but not for integrin-binding sialoprotein and hydroxyapatite. Interestingly, osteopontin was upregulated in naive and differentiated MSC by Co(II) ions and modified CoCr, likely through the induction of a cellular hypoxic response. The findings of this study contribute to a better understanding of possible risk factors with regard to a clinical applicability of surface modified CoCr implant materials.

  3. Probing the Effects of Ligand Field and Coordination Geometry on Magnetic Anisotropy of Pentacoordinate Cobalt(II) Single-Ion Magnets.

    PubMed

    Mondal, Amit Kumar; Goswami, Tamal; Misra, Anirban; Konar, Sanjit

    2017-06-19

    In this work, the effects of ligand field strength as well as the metal coordination geometry on magnetic anisotropy of pentacoordinated Co(II) complexes have been investigated using a combined experimental and theoretical approach. For that, a strategic design and synthesis of three pentacoordinate Co(II) complexes [Co(bbp)Cl2]·(MeOH) (1), [Co(bbp)Br2]·(MeOH) (2), and [Co(bbp)(NCS)2] (3) has been achieved by using the tridentate coordination environment of the ligand in conjunction with the accommodating terminal ligands (i.e., chloride, bromide, and thiocyanate). Detailed magnetic studies disclose the occurrence of slow magnetic relaxation behavior of Co(II) centers with an easy-plane magnetic anisotropy. A quantitative estimation of ZFS parameters has been successfully performed by density functional theory (DFT) calculations. Both the sign and magnitude of ZFS parameters are prophesied well by this DFT method. The theoretical results also reveal that the α → β (SOMO-SOMO) excitation contributes almost entirely to the total ZFS values for all complexes. It is worth noting that the excitation pertaining to the most positive contribution to the ZFS parameter is the dxy → dx(2)-y(2) excitation for complexes 1 and 2, whereas for complex 3 it is the dz(2) → dx(2)-y(2) excitation.

  4. New topology in azide-bridged cobalt(II) complexes: the weak ferromagnet [Co(2)(N(3))(4)(Hexamethylenetetramine)(H(2)O)](n).

    PubMed

    Mautner, Franz A; Ohrström, Lars; Sodin, Beate; Vicente, Ramon

    2009-07-06

    A new polynuclear azido-bridged Co(II) compound with formula [Co(2)(N(3))(4)(HMTA)(H(2)O)](n) (1) (HMTA = hexamethylenetetramine) has been structurally and magnetically characterized. The compound 1 crystallizes in the monoclinic system C2/m space group, and consist of a complex three-dimensional system in which end-to-end and end-on azido bridging ligands between the Co(II) atoms coexist. The HMTA ligand is also linking three different Co(II) atoms. The network analysis shows for 1 a three- and six-connected network topology not previously reported. The magnetic properties of 1 are also reported, and it was found that the magnetic interactions define another new three- and four-connected net assigned as a (6.8(2))(6(4).10(2))-tfo net. In the high temperature region the chi(M) versus T plot can be fitted by using the Curie-Weiss law, and the best fit theta value is -26.6 K. For 1 magnetic ordering and spontaneous magnetization is achieved below T(c) = 15.6 K.

  5. Cobalt catalysis involving π components in organic synthesis.

    PubMed

    Gandeepan, Parthasarathy; Cheng, Chien-Hong

    2015-04-21

    Over the last three decades, transition-metal-catalyzed organic transformations have been shown to be extremely important in organic synthesis. However, most of the successful reactions are associated with noble metals, which are generally toxic, expensive, and less abundant. Therefore, we have focused on catalysis using the abundant first-row transition metals, specifically cobalt. In this Account, we demonstrate the potential of cobalt catalysis in organic synthesis as revealed by our research. We have developed many useful catalytic systems using cobalt complexes. Overall, they can be classified into several broad types of reactions, specifically [2 + 2 + 2] and [2 + 2] cycloadditions; enyne reductive coupling; reductive [3 + 2] cycloaddition of alkynes/allenes with enones; reductive coupling of alkyl iodides with alkenes; addition of organoboronic acids to alkynes, alkenes, or aldehydes; carbocyclization of o-iodoaryl ketones/aldehydes with alkynes/electron-deficient alkenes; coupling of thiols with aryl and alkyl halides; enyne coupling; and C-H bond activation. Reactions relying on π components, specifically cycloaddition, reductive coupling, and enyne coupling, mostly afford products with excellent stereo- and regioselectivity and superior atom economy. We believe that these cobalt-catalyzed π-component coupling reactions proceed through five-membered cobaltacyclic intermediates formed by the oxidative cyclometalation of two coordinated π bonds of the substrates to the low-valent cobalt species. The high regio- and stereoselectivity of these reactions are achieved as a result of the electronic and steric effects of the π components. Mostly, electron-withdrawing groups and bulkier groups attached to the π bonds prefer to be placed near the cobalt center of the cobaltacycle. Most of these transformations proceed through low-valent cobalt complexes, which are conveniently generated in situ from air-stable Co(II) salts by Zn- or Mn-mediated reduction

  6. Halogenation of cobalt dicarbollide

    DOEpatents

    Hurlburt, P.K.; Abney, K.D.; Kinkead, S.A.

    1997-05-20

    A method for selectively adding chlorine, bromine, or iodine to cobalt dicarbollide anions by means of electrophilic substitution reactions. Halogens are added only to the B10 and B10{prime} positions of the anion. The process involves use of hypohalous acid or N-halosuccinimide or gaseous chlorine in the presence of iron. 1 fig.

  7. Halogenation of cobalt dicarbollide

    DOEpatents

    Hurlburt, Paul K.; Abney, Kent D.; Kinkead, Scott A.

    1997-01-01

    A method for selectively adding chlorine, bromine, or iodine to cobalt dicarbollide anions by means of electrophilic substitution reactions. Halogens are added only to the B10 and B10' positions of the anion. The process involves use of hypohalous acid or N-halosuccinimide or gaseous chlorine in the presence of iron.

  8. Coordination Complexes of Cobalt.

    ERIC Educational Resources Information Center

    Williams, Gregory M.; And Others

    1989-01-01

    Described is an experiment involving the synthesis and spectral studies of cobalt complexes that not only give general chemistry students an introduction to inorganic synthesis but allows them to conduct a systematic study on the effect of different ligands on absorption spectra. Background information, procedures, and experimental results are…

  9. Coordination Complexes of Cobalt.

    ERIC Educational Resources Information Center

    Williams, Gregory M.; And Others

    1989-01-01

    Described is an experiment involving the synthesis and spectral studies of cobalt complexes that not only give general chemistry students an introduction to inorganic synthesis but allows them to conduct a systematic study on the effect of different ligands on absorption spectra. Background information, procedures, and experimental results are…

  10. Two Polymorphic Forms of a Six-Coordinate Mononuclear Cobalt(II) Complex with Easy-Plane Anisotropy: Structural Features, Theoretical Calculations, and Field-Induced Slow Relaxation of the Magnetization.

    PubMed

    Roy, Subhadip; Oyarzabal, Itziar; Vallejo, Julia; Cano, Joan; Colacio, Enrique; Bauza, Antonio; Frontera, Antonio; Kirillov, Alexander M; Drew, Michael G B; Das, Subrata

    2016-09-06

    A mononuclear cobalt(II) complex [Co(3,5-dnb)2(py)2(H2O)2] {3,5-Hdnb = 3,5-dinitrobenzoic acid; py = pyridine} was isolated in two polymorphs, in space groups C2/c (1) and P21/c (2). Single-crystal X-ray diffraction analyses reveal that 1 and 2 are not isostructural in spite of having equal formulas and ligand connectivity. In both structures, the Co(II) centers adopt octahedral {CoN2O4} geometries filled by pairs of mutually trans terminal 3,5-dnb, py, and water ligands. However, the structures of 1 and 2 disclose distinct packing patterns driven by strong intermolecular O-H···O hydrogen bonds, leading to their 0D→2D (1) or 0D→1D (2) extension. The resulting two-dimensional layers and one-dimensional chains were topologically classified as the sql and 2C1 underlying nets, respectively. By means of DFT theoretical calculations, the energy variations between the polymorphs were estimated, and the binding energies associated with the noncovalent interactions observed in the crystal structures were also evaluated. The study of the direct-current magnetic properties, as well as ab initio calculations, reveal that both 1 and 2 present a strong easy-plane magnetic anisotropy (D > 0), which is larger for the latter polymorph (D is found to exhibit values between +58 and 117 cm(-1) depending on the method). Alternating current dynamic susceptibility measurements show that these polymorphs exhibit field-induced slow relaxation of the magnetization with Ueff values of 19.5 and 21.1 cm(-1) for 1 and 2, respectively. The analysis of the whole magnetic data allows the conclusion that the magnetization relaxation in these polymorphs mainly takes place through a virtual excited state (Raman process). It is worth noting that despite the notable difference between the supramolecular networks of 1 and 2, they exhibit almost identical magnetization dynamics. This fact suggests that the relaxation process is intramolecular in nature and that the virtual state involved in the

  11. Tetra-aqua-bis-{3-carb-oxy-5-[(4-carb-oxy-phen-yl)diazen-yl]benzoato-κO}cobalt(II) dihydrate.

    PubMed

    Bai, Liang; Zhao, Jun

    2011-12-01

    In the title complex, [Co(C(15)H(9)N(2)O(6))(2)(H(2)O)(4)]·2H(2)O, the Co(II) ion is located on an inversion center and is coordinated by two monodentate 3-carb-oxy-5-[(4-carb-oxy-phen-yl)diazen-yl]benzo-ate ligands and four water mol-ecules in a distorted octa-hedral geometry. In the crystal, inter-molecular O-H⋯O hydrogen bonds link the mol-ecules into a three-dimensional supra-molecular network.

  12. Diaqua­bis­(4-meth­oxy­benzoato-κO 1)bis­(nicotinamide-κN 1)cobalt(II) dihydrate

    PubMed Central

    Hökelek, Tuncer; Dal, Hakan; Tercan, Barış; Tenlik, Erdinç; Necefoğlu, Hacali

    2010-01-01

    In the mononuclear title compound, [Co(C8H7O3)2(C6H6N2O)2(H2O)2]·2H2O, the CoII ion is located on a crystallographic inversion center. The asymmetric unit is completed by one 4-meth­oxy­benzoate anion, one nicotinamide (NA) ligand and one coordinated and one uncoordinated water mol­ecule. All ligands act in a monodentate mode. The four O atoms in the equatorial plane around the CoII ion form a slightly distorted square-planar arrangement, while the slightly distorted octa­hedral coordination is completed by the two pyridine N atoms of the NA ligands in the axial positions. The dihedral angle between the carboxyl­ate group and the attached benzene ring is 6.47 (7)°, while the pyridine and benzene rings are oriented at a dihedral angle of 72.80 (4)°. An O—H⋯O hydrogen bond links the uncoordinated water mol­ecule to one of the carboxyl­ate groups. In the crystal structure, inter­molecular O—H⋯O, N—H⋯O and C—H⋯O hydrogen bonds link the mol­ecules into a three-dimensional network. PMID:21588149

  13. Synthesis and biophysical studies of bis-macrocyclic cobalt/copper(II) complexes having a pyridine spacer with CT DNA and 5'-GMP.

    PubMed

    Arjmand, Farukh; Aziz, Mubashira

    2009-12-01

    New bis-macrocyclic complexes of Co(III), 1, Ni(II), 2, and Cu(II), 3, containing pyridyl bridges between 13-membered macrocyclic subunits, have been synthesized via an in situ one-pot template condensation reaction (IOPTCR). The proposed structures of these new dinuclear complexes are consistent with the data obtained from elemental analysis, molar conductance, IR, EPR, UV/VIS, (1)H- and 13C-NMR, and ESI-MS. The complexes 2 and 3 possess square-planar geometry with four secondary N-atoms coordinated to the metal ion, while complex 1 reveals octahedral geometry in solution due to coordinated H(2)O molecules. DNA-Binding properties of the complexes 1 and 3 were investigated by absorption and emission titrations, cyclic voltammetry, and viscosity measurements. Complexes 1 and 3 are strong DNA binders with binding constants, K(b), of 1.64 x 10(5) and 2.05 x 10(5) M(-1), respectively. Hyperchromism, decrease in emission intensity of DNA-bound ethidium bromide (EB), and changes observed in the viscosity and cyclic voltammograms in the presence of added metal complexes reveals that the complexes bind to DNA predominantly by electrostatic attraction, substantiated by absorption titration with 5'-GMP.

  14. Crystal structure of aqua­tris­(isonicotinamide-κN)bis­(thio­cyanato-κN)cobalt(II) 2.5-hydrate

    PubMed Central

    Neumann, Tristan; Jess, Inke; Näther, Christian

    2016-01-01

    The asymmetric unit of the title compound, [Co(NCS)2(C6H6N2O)3(H2O)]·2.5H2O, comprises one CoII cation, three isonicotinamide ligands, two thio­cyanate anions, one aqua ligand and two water solvent mol­ecules in general positions, as well as one water solvent mol­ecule that is located on a twofold rotation axis. The CoII cations are octa­hedrally coordinated by two terminally N-bonded thio­cyanate anions, one water mol­ecule and three isonicotinamide ligands, each coordinating via the pyridine N atom. The discrete complexes are linked by inter­molecular O—H⋯O, N—H⋯O and N—H⋯S hydrogen bonding into a three-dimensional network that contains cavities in which the solvent water mol­ecules are located. The latter are linked by further O—H⋯O hydrogen bonds to the network. There are additional short contacts present in the crystal, indicative of weak C—H⋯S, C—H⋯O and C—H⋯N inter­actions. PMID:27920913

  15. Crystal structure of tetra­kis­(isonicotinamide-κN)bis­(thio­cyanato-κN)cobalt(II)–isonicotinamide–ethanol (1/2/1)

    PubMed Central

    Neumann, Tristan; Jess, Inke; Näther, Christian

    2016-01-01

    The asymmetric unit of the title compound, [Co(NCS)2(C6H6N2O)4]·2C6H6N2O·C2H5OH, comprises one CoII cation, two thio­cyanate anions, four coordinating and two solvent isonicotinamide molecules and one ethanol solvent mol­ecule. The CoII cations are octa­hedrally coordinated by four N-coordinating isonicotinamide ligands and two terminally N-bonded thio­cyanate anions. These discrete complexes are linked by inter­molecular N—H⋯O and N—H⋯S hydrogen-bonding inter­actions into a three-dimensional network. The two isonicotinamide and the ethanol solvent mol­ecules are embedded in channels of this network and are linked through further N—H⋯O and N—H⋯N hydrogen bonds to the network. The ethanol solvent mol­ecule is disordered over two sets of sites (occupancy ratio 0.6:0.4). PMID:27536386

  16. Crystal structure of catena-poly[[di-aqua-bis-(4-formyl-benzoato-κO (1))cobalt(II)]-μ-pyrazine-κ(2) N:N'].

    PubMed

    Aşkın, Gülçin Şefiye; Çelik, Fatih; Dilek, Nefise; Necefoğlu, Hacali; Hökelek, Tuncer

    2015-04-01

    In the title polymeric compound, [Co(C8H5O3)2(C4H4N2)(H2O)2] n , the Co(II) atom is located on a twofold rotation axis and has a slightly distorted octa-hedral coordination sphere. In the equatorial plane, it is coordinated by two carboxyl-ate O atoms of two symmetry-related monodentate formyl-benzoate anions and by two N atoms of two bridging pyrazine ligands. The latter are bis-ected by the twofold rotation axis. The axial positions are occupied by two O atoms of the coordinating water mol-ecules. In the formyl-benzoate anion, the carboxyl-ate group is twisted away from the attached benzene ring by 7.50 (8)°, while the benzene and pyrazine rings are oriented at a dihedral angle of 64.90 (4)°. The pyrazine ligands bridge the Co(II) cations, forming linear chains running along the b-axis direction. Strong intra-molecular O-H⋯O hydrogen bonds link the water mol-ecules to the carboxyl-ate O atoms. In the crystal, weak O-Hwater⋯Owater hydrogen bonds link adjacent chains into layers parallel to the bc plane. The layers are linked via C-Hpyrazine⋯Oform-yl hydrogen bonds, forming a three-dimensional network. There are also weak C-H⋯π inter-actions present.

  17. Effect of substituent on structures and catalytic properties of cobalt(II) isophthalate coordination polymers with a semi-rigid bis(benzimidazole)

    NASA Astrophysics Data System (ADS)

    Zhang, Xu; Meng, Xiang-Li; Huang, Cui-Miao; Cui, Guang-Hua

    2015-11-01

    Three Co(II) coordination polymers based on flexible bis(2-dimethylbenzimidazole) and the derivatives of the familiar isophthalate co-ligands, namely [Co(L)(ip)]n (1), [Co2(L)2(nip)2]n (2) and [Co2(L)2(tbip)2·2H2O]n (3) (L = 1,2-bis(2-methylbenzimidazol-1-ylmethyl)benzene, H2ip = isophthalic acid, H2nip = 5-nitroisophthalic acid, H2tbip = 5-tert-butylisophthalic acid) have been synthesized by hydrothermal methods and characterized by elemental analyses, IR spectra, thermogravimetric analyses and single-crystal X-ray diffraction. Both complexes 1 and 2 exhibit a 2-fold interpenetrating 3D network with 66-dia topology, whereas complex 3 is bridged by the L and tbip2- ligands to form a rarely tri-nodal (3,3,5) layer with 3,3,5L18 topology. The results indicate that Co(II) mixed coordination polymers structurally modulated by the substituent effect of isophthalate-involved co-ligands. In addition, the fluorescence and catalytic activity of the complexes for the degradation of methyl orange by the sodium persulfate in a Fenton-like process have been investigated.

  18. A new direction in dye-sensitized solar cells redox mediator development: in situ fine-tuning of the cobalt(II)/(III) redox potential through Lewis base interactions.

    PubMed

    Kashif, Muhammad K; Axelson, Jordan C; Duffy, Noel W; Forsyth, Craig M; Chang, Christopher J; Long, Jeffrey R; Spiccia, Leone; Bach, Udo

    2012-10-10

    Dye-sensitized solar cells (DSCs) are an attractive renewable energy technology currently under intense investigation. In recent years, one area of major interest has been the exploration of alternatives to the classical iodide/triiodide redox shuttle, with particular attention focused on cobalt complexes with the general formula [Co(L)(n)](2+/3+). We introduce a new approach to designing redox mediators that involves the application of [Co(PY5Me(2))(MeCN)](2+/3+) complexes, where PY5Me(2) is the pentadentate ligand, 2,6-bis(1,1-bis(2-pyridyl)ethyl)pyridine. It is shown, by X-ray crystallography, that the axial acetonitrile (MeCN) ligand can be replaced by more strongly coordinating Lewis bases (B) to give complexes with the general formula [Co(PY5Me(2))(B)](2+/3+), where B = 4-tert-butylpyridine (tBP) or N-methylbenzimidazole (NMBI). These commonly applied DSC electrolyte components are used for the first time to fine-tune the potential of the redox couple to the requirements of the dye through coordinative interactions with the Co(II/III) centers. Application of electrolytes based on the [Co(PY5Me(2))(NMBI)](2+/3+) complex in combination with a commercially available organic sensitizer has enabled us to attain DSC efficiencies of 8.4% and 9.2% at a simulated light intensity of 100% sun (1000 W m(-2) AM1.5 G) and at 10% sun, respectively, higher than analogous devices applying the [Co(bpy)(3)](2+/3+) redox couple, and an open circuit voltage (V(oc)) of almost 1.0 V at 100% sun for devices constructed with the tBP complex.

  19. Active-site cobalt(II)-substituted horse liver alcohol dehydrogenase: characterization of intermediates in the oxidation and reduction processes as a function of pH.

    PubMed

    Sartorius, C; Gerber, M; Zeppezauer, M; Dunn, M F

    1987-02-10

    Substitution of Co(II) for the catalytic site Zn(II) of horse liver alcohol dehydrogenase (LADH) yields an active enzyme derivative, CoIIE, with characteristic Co(II) charge-transfer and d-d electronic transitions that are sensitive to the events which take place during catalysis [Koerber, S. C., MacGibbon, A. K. H., Dietrich, H., Zeppezauer, M., & Dunn, M. F. (1983) Biochemistry 22, 3424-3431]. In this study, UV-visible spectroscopy and rapid-scanning stopped-flow (RSSF) kinetic methods are used to detect and identify intermediates in the LADH catalytic mechanism. In the presence of the inhibitor isobutyramide, the pre-steady-state phase of alcohol (RCH2OH) oxidation at pH above 7 is characterized by the formation and decay of an intermediate with lambda max = 570, 640, and 672 nm for both aromatic and aliphatic alcohols (benzyl alcohol, p-nitrobenzyl alcohol, anisyl alcohol, ethanol, and methanol). By comparison with the spectrum of the stable ternary complex formed with oxidized nicotinamide adenine dinucleotide (NAD+) and 2,2',2''-trifluoroethoxide ion (TFE-), CoIIE(NAD+, TFE-), the intermediate which forms is proposed to be the alkoxide ion (RCH2O-) complex, CoIIE(NAD+, RCH2O-). The timing of reduced nicotinamide adenine dinucleotide (NADH) formation indicates that intermediate decay is limited by the interconversion of ternary complexes, i.e., CoIIE(NAD+, RCH2O-) in equilibrium CoIIE(NADH, RCHO). From competition experiments, we infer that, at pH values below 5, NAD+ and alcohol form a CoIIE(NAD+, RCH2OH) ternary complex. RSSF studies carried out as a function of pH indicate that the apparent pKa values for the ionization of alcohol within the ternary complex, i.e., CoIIE(NAD+, RCH2OH) in equilibrium CoIIE(NAD+, RCH2O-) + H+, fall in the range 5-7.5. Using pyrazole as the dead-end inhibitor, we find that the single-turnover time courses for the reduction of benzaldehyde, p-nitrobenzaldehyde, anisaldehyde, and acetaldehyde at pH above 7 all show evidence for

  20. OMCVD of cobalt and cobalt silicide

    NASA Astrophysics Data System (ADS)

    Dormans, G. J. M.; Meekes, G. J. B. M.; Staring, E. G. J.

    1991-11-01

    Cobalt and cobalt silicide layers were deposited by OMCVD using the Co precursors Co(C 5H 5) 2, Co 2(CO) 8, Co(C 5H 5)(CO) 2 and CoCF 3(CO) 4, and the Si precursors SiH 4 and Si 2H 6. Strongly textured (111)-β Co layers were grown from Co(C 5H 5) 2, Co(C 5H 5)(CO) 2 and CoCF 3(CO) 4 at temperatures above 300°C in H 2 at atmospheric pressure. Growth from Co(C 5H 5) 2 is inhibited on Si substrates. For temperatures ≥600°C the Co layers deposited from Co(C 5H 5)(CO) 2 react with the Si(100) substrate to form CoSi 2(00 l) aligned with the substrate orientation. Co 2(CO) 8 gives amorphous Co between 200 and 300°C. The upper temperature is set by the occurrence of homogeneous gas-phase reactions at atmospheric reactor pressure. Cobalt silicide layers can be grown from CO 2(CO) 8 and (di)silane at temperatures between 200 and 400°C. The Co/Si ratio in the layers decreases with increasing temperature and is independent of the gas-phase Co/Si ratio. Stoichiometric CoSi 2 is obtained at ~ 300°C. Both Co(C 5H 5) 2 and Co(C 5H 5)(CO) 2 react with (di)silane, leading to the incorporation of carbon in the layer. The Co/Si ration and the carbon content in the layers are practically independent of the deposition conditions. With CoCF 3(CO) 4 no contamination-free silicide could be grown. The carbon incorporation with Co(C 5H 5) 2 and Co(C 5H 5)(CO) 2 can be avoided by a pulsed growth method in which the Co precursor and the Si precursor are introduced alternately into the reactor. With Co(C 5H 5) 2 the growth is then inhibited on Si substrates.

  1. Synthesis, characterization, biological activity, molecular modeling and docking studies of complexes 4-(4-hydroxy)-3-(2-pyrazine-2-carbonyl)hydrazonomethylphenyl-diazen-yl-benzenesulfonamide with manganese(II), cobalt(II), nickel(II), zinc(II) and cadmium(II)

    NASA Astrophysics Data System (ADS)

    Alaghaz, Abdel-Nasser M. A.; Zayed, Mohamed E.; Alharbi, Suliman A.; Ammar, Reda A. A.; Elhenawy, Ahmed

    2015-03-01

    A new series of complexes of 4-(4-hydroxy)-3-(2-pyrazine-2-carbonyl)hydrazonomethylphenyl-diazen-yl-benzenesulfonamide (HL) with Mn(II), Co(II), Ni(II), Zn(II) and Cd(II) have been prepared and characterized by different physical techniques. The IR spectra of the prepared complexes were suggested that the ligand behaves as a tri-dentate ligand through the carbonyl oxygen, azomethine nitrogen and phenolic oxygen atoms (ONO). Electronic spectra and magnetic susceptibility measurements reveal octahedral geometry for all complexes. The elemental analyses and mass spectral data have justified the ML2 composition of complexes. The EPR spectra of Mn(II), Co(II) and Ni(II) complexes support the mononuclear structure. The crystal field splitting, Racah repulsion and nephelauxetic parameters and determined from the electronic spectra of the complexes. Thermal properties and decomposition kinetics of all complexes are investigated. The geometry of the metal complexes has been optimized with the help of molecular modeling. The biological activity of these compounds against various fungi has been investigated.

  2. Bis(3-amino­pyrazine-2-carboxyl­ato-κ2 N 1,O)diaqua­cobalt(II)

    PubMed Central

    Bouchene, Rafika; Bouacida, Sofiane; Berrah, Fadila; Belhouas, Ratiba; Merazig, Hocine

    2013-01-01

    In the title compound, [Co(C5H4N3O2)2(H2O)2], the CoII atom is situated on a twofold rotation axis and is N,O-chelated by two 3-amino­pyrazine-2-carboxyl­ate anions and additionally bonded to the O atoms of two water mol­ecules, leading to a slightly distorted octa­hedral coordination environment. The crystal packing is dominated by inter­molecular O—H⋯O, O—H⋯N and N—H⋯O hydrogen bonding involving the water mol­ecules and amino groups as donors and carboxyl­ate O atoms, as well as the non-coordinating heterocyclic N atoms as acceptors, resulting in a three-dimensional network. An intra­molecular N—H⋯O hydrogen bond is also observed. PMID:23424419

  3. Solvent-rich layered cobalt(II) 1,4-benzenedicarboxylate based on binuclear {Co2(μ-OH2)(RCOO)2} secondary building unit

    NASA Astrophysics Data System (ADS)

    Croitor, Lilia; Chisca, Diana; Coropceanu, Eduard B.; Volodina, Galina F.; Petuhov, Oleg; Fonari, Marina S.

    2017-06-01

    The reaction of a ditopic ligand, 1,4-benzenedicarboxylic acid (H2bdc) with Co(CH3COO)2·4H2O in solution resulted in a solvent-rich layered coordination polymer with the composition {[Co2(μ2-OH2)(bdc)2(dmf)2(H2O)2]·(dmf)·3(H2O)}n (1) whose crystal structure was determined by single crystal X-ray diffraction. The compound is built on the binuclear {Co2(μ2-OH2)(COO)2} metal clusters, where each Co(II) atom is coordinated by six oxygen atoms in a distorted octahedral arrangement. The crystal lattice of 1 hosts the dmf and water solvent molecules via the OH⋯O hydrogen bonding with coordination network. The easy destruction of the crystals due to the partial solvent loss occurs rapidly in ambient conditions and is confirmed by the TGA data.

  4. Diaqua­bis­(1-methyl-1H-imidazole-κN 3)bis­[2-(naphthalen-1-yl)acetato-κO]cobalt(II)

    PubMed Central

    Zhao, Hong; Yin, Fu-Jun; Xu, Xing-You; Han, Li-Jun

    2012-01-01

    In the title compound, [Co(C12H9O2)2(C4H6N2)2(H2O)2], the CoII ion is located on an inversion centre and displays a distorted octa­hedral coordination geometry. Two O atoms from two water mol­ecules and two carboxyl­ate O atoms from two 2-(naphthalen-1-yl)acetate ligands are in the equatorial plane and two N atoms from two 1-methyl-1H-imidazole ligands are in the axial positions. The structure is stabilized by intra­molecular O—H⋯O hydrogen bonds. Inter­molecular O—H⋯O hydrogen bonds link the complex mol­ecules into chains along [100]. PMID:22590060

  5. Light driven water oxidation by a single site cobalt salophen catalyst.

    PubMed

    Pizzolato, Erica; Natali, Mirco; Posocco, Bianca; Montellano López, Alejandro; Bazzan, Irene; Di Valentin, Marilena; Galloni, Pierluca; Conte, Valeria; Bonchio, Marcella; Scandola, Franco; Sartorel, Andrea

    2013-11-04

    A salophen cobalt(II) complex enables water oxidation at neutral pH in photoactivated sacrificial cycles under visible light, thus confirming the high appeal of earth abundant single site catalysis for artificial photosynthesis.

  6. Discovery of a cobalt complex with high MEK1 binding affinity.

    PubMed

    Li, Hongyue; Zhou, Tongliang; Liu, Hui; Xu, Fengrong; Niu, Yan; Wang, Chao; Liang, Lei; Xu, Ping

    2017-05-15

    A series of Schiff base ligands (L(1)-L(5)) and their cobalt(II) complexes (1-5) were designed and synthesized for MEK1 binding experiment. The biological evaluation results showed that Bis(N,N'-disalicylidene)-3,4-phenylenediamine-cobalt(II) 1 and Bis(N,N'-disalicylidene)-1,2-cyclohexanediamine-cobalt(II) 2 are much more effective than the parent Schiff bases (L(1) and L(2)). Importantly, 2 exhibited MEK1 binding affinity with IC5071nM, which is so far the best result for metal complexes and more potent than U0126 (7.02μM) and AZD6244 (2.20μM). Docking study was used to elucidate the binding modes of complex 2 with MEK1. Thus cobalt(II) complex 2 may be further developed as a novel MEK1 inhibitor. Copyright © 2017 Elsevier Ltd. All rights reserved.

  7. Tetra­aqua­bis(nicotinamide-κN 1)cobalt(II) bis­(2-fluoro­benzoate)

    PubMed Central

    Özbek, F. Elif; Tercan, Barış; Şahin, Ertan; Necefoğlu, Hacali; Hökelek, Tuncer

    2009-01-01

    The title complex, [Co(C6H6N2O)2(H2O)4](C7H4FO2)2, contains one Co(II) atom (site symmetry ), two monodentate nicotin­amide (NA) ligands, four coordinated water mol­ecules and two 2-fluoro­benzoate (FB) anions. The four O atoms in the equatorial plane around the Co atom form a slightly distorted square-planar arrangement, while the slightly distorted octa­hedral coordination is completed by the two N atoms of the NA ligands in the axial positions. The dihedral angle between the carboxyl group and the adjacent benzene ring is 29.8 (3)°, while the pyridine and benzene rings are oriented at a dihedral angle of 7.97 (12)°. In the crystal structure, mol­ecules are linked by O—H⋯O, N—H⋯O and N—H⋯F hydrogen bonds, forming an infinite three-dimensional network. π–π Contacts between the pyridine and benzene rings [centroid–centroid distance = 3.673 (3) Å] may further stabilize the crystal structure. PMID:21582108

  8. Synthesis, physicochemical analysis of two new hemilabile ether-phosphine ligands and their first stable bis-ether-phosphine/cobalt(II) tetrahedral complexes

    NASA Astrophysics Data System (ADS)

    Warad, Ismail; Barakat, Assem

    2017-04-01

    New tridentate ether-phosphine {P, 2O} and ether-phosphine oxide {OP, 2O} ligands with P and O donor-atoms have been synthesized starting from ClCH2CH(OCH3)2. The oxidation process of Ph2PCH2CH(OCH3)2 to its oxide derivative Ph2P(dbnd O)CH2CH(OCH3)2 was monitored by 31P NMR for the first time. The desired ligands and their Co(II) complexes structures were deduced from IR, EA, MS, NMR, UV-Vis., TG/DTG and XRD physical measurements. The tridentate chelating coordination behavior of the ether-phosphine wasn't detected leading only to the mono-dentate coordination mode through the phosphorous atoms to set up a X2Co[η1-Ph2PCH2CH(OCH3)2]2 as final isomer formula (X = Cl or Br). The Cl2Co[η1-Ph2PCH2CH(OCH3)2]2 isomer belongs to complex 1 was supported by single crystal measurement. Polar/non-polar intermolecular short contacts were detected by XRD and Hirshfeld surface theoretical analysis.

  9. Cobalt sorption in silica-pillared clays.

    PubMed

    Sampieri, A; Fetter, G; Bosch, P; Bulbulian, S

    2006-01-03

    Silicon pillared samples were prepared following conventional and microwave irradiation methods. The samples were characterized and tested in cobalt sorption. Ethylenediammine was added before cobalt addition to improve the amount of cobalt retained. The amount of cobalt introduced in the original clay in the presence of ethylenediammine was the highest. In calcined pillared clays the cobalt retention with ethylenediammine was lower (ca. 40%). In all cases the presence of ethylenediammine increased twice the amount of cobalt sorption measured for aqueous solutions.

  10. Synthesis and characterization of a series of transition metal complexes with a new symmetrical polyoxaaza macroacyclic Schiff base ligand: X-ray crystal structure of cobalt(II) and nickel(II) complexes and their antibacterial properties

    NASA Astrophysics Data System (ADS)

    Keypour, Hassan; Shayesteh, Maryam; Rezaeivala, Majid; Chalabian, Firoozeh; Valencia, Laura

    2013-01-01

    A new symmetrical [N4O2] hexadentate Schiff base ligand, (E)-N-(pyridin-2-ylmethylene)-2-(3-(2-((E)-pyridin-2-lmethyleneamino)phenoxy)naphthalen-2-yloxy)benzenamine, abbreviated to L, and its complexes of Ni(II), Cu(II), Zn(II), Co(II), Cd(II) and Mn(II) have been synthesized in the presence of metal ions. The complexes were structurally characterized by elemental analyses, IR, UV-Vis, NMR and molar conductivity. The crystal structures of two complexes, [NiL(ONO2)2]·2H2O and [CoLCl2]CH3OH·0.5H2O, have been determined by a single crystal X-ray diffraction study. In these complexes, the ligand is coordinated in a neutral form via pyridine and azomethine nitrogen atoms. The metal ions complete their six coordination with two coordinated nitrate or chloride ions, forming a distorted octahedral geometry. The synthesized compounds have antibacterial activity against the three Gram-positive bacteria: Enterococcus faecalis, Bacillus cereus and Staphylococcus epid and also against the three Gram-negative bacteria: Citrobacter freundii, Enterobacter aerogenes and Salmonella typhi. The activity data show that the complexes are more potent antibacterials than the parent Schiff base.

  11. Synthesis and characterization of a series of transition metal complexes with a new symmetrical polyoxaaza macroacyclic Schiff base ligand: X-ray crystal structure of cobalt(II) and nickel(II) complexes and their antibacterial properties.

    PubMed

    Keypour, Hassan; Shayesteh, Maryam; Rezaeivala, Majid; Chalabian, Firoozeh; Valencia, Laura

    2013-01-15

    A new symmetrical [N4O2] hexadentate Schiff base ligand, (E)-N-(pyridin-2-ylmethylene)-2-(3-(2-((E)-pyridin-2-lmethyleneamino)phenoxy)naphthalen-2-yloxy)benzenamine, abbreviated to L, and its complexes of Ni(II), Cu(II), Zn(II), Co(II), Cd(II) and Mn(II) have been synthesized in the presence of metal ions. The complexes were structurally characterized by elemental analyses, IR, UV-Vis, NMR and molar conductivity. The crystal structures of two complexes, [NiL(ONO2)2]·2H2O and [CoLCl2]CH3OH·0.5H2O, have been determined by a single crystal X-ray diffraction study. In these complexes, the ligand is coordinated in a neutral form via pyridine and azomethine nitrogen atoms. The metal ions complete their six coordination with two coordinated nitrate or chloride ions, forming a distorted octahedral geometry. The synthesized compounds have antibacterial activity against the three Gram-positive bacteria: Enterococcus faecalis, Bacillus cereus and Staphylococcus epid and also against the three Gram-negative bacteria: Citrobacter freundii, Enterobacter aerogenes and Salmonella typhi. The activity data show that the complexes are more potent antibacterials than the parent Schiff base.

  12. Synthesis and Characterization of Cobalt(III), Nickel(II) and Copper(II) Mononuclear Complexes with the Ligand 1,3-bis[(2-aminoethyl)amino]-2-propanol and Their Catalase-Like Activity.

    PubMed

    Pires, Bianca M; Silva, Daniel M; Visentin, Lorenzo C; Rodrigues, Bernardo L; Carvalho, Nakédia M F; Faria, Roberto B

    2015-01-01

    In this work, we present the synthesis and characterization of two new mononuclear complexes with the ligand 1,3-bis[(2-aminoethyl)amino]-2-propanol (HL), [Co(L)(H2O)](ClO4)2 (1), [Ni(HL)](ClO4)2 (2), as well as the known complex [Cu(HL)](ClO4)2 (3) for comparison. Their abilities to catalyze the dismutation of H2O2 and the oxidation of cyclohexane were investigated. The complexes were characterized by X-ray diffraction, elemental analysis, electronic and infrared spectroscopy, cyclic voltammetry, electrospray ionization mass spectrometry (ESI-MS) and conductivity measurements. The X-ray structures showed that the nickel (2) and copper (3) complexes are tetracoordinated, with the metal ion bound to the nitrogen atoms of the ligand. On the other hand, the cobalt complex (1) is hexacoordinated, possessing additional bonds to the alkoxo group of the ligand and to a water molecule. Neither of the complexes was able to catalyze the oxidation of cyclohexane, but all of them exhibited catalase-like activity, following Michaelis-Menten kinetics, which suggest resemblance with the catalase natural enzymes. The catalytic activity followed the order: [Ni(HL)](ClO4)2 (2) > [Cu(HL)](ClO4)2 (3) > [Co(L)(H2O)](ClO4)2 (1). As far as we know, this is the first description of a nickel complex presenting a significant catalase-like activity.

  13. Synthesis and Characterization of Cobalt(III), Nickel(II) and Copper(II) Mononuclear Complexes with the Ligand 1,3-bis[(2-aminoethyl)amino]-2-propanol and Their Catalase-Like Activity

    PubMed Central

    Silva, Daniel M.; Visentin, Lorenzo C.; Rodrigues, Bernardo L.

    2015-01-01

    In this work, we present the synthesis and characterization of two new mononuclear complexes with the ligand 1,3-bis[(2-aminoethyl)amino]-2-propanol (HL), [Co(L)(H2O)](ClO4)2 (1), [Ni(HL)](ClO4)2 (2), as well as the known complex [Cu(HL)](ClO4)2 (3) for comparison. Their abilities to catalyze the dismutation of H2O2 and the oxidation of cyclohexane were investigated. The complexes were characterized by X-ray diffraction, elemental analysis, electronic and infrared spectroscopy, cyclic voltammetry, electrospray ionization mass spectrometry (ESI-MS) and conductivity measurements. The X-ray structures showed that the nickel (2) and copper (3) complexes are tetracoordinated, with the metal ion bound to the nitrogen atoms of the ligand. On the other hand, the cobalt complex (1) is hexacoordinated, possessing additional bonds to the alkoxo group of the ligand and to a water molecule. Neither of the complexes was able to catalyze the oxidation of cyclohexane, but all of them exhibited catalase-like activity, following Michaelis-Menten kinetics, which suggest resemblance with the catalase natural enzymes. The catalytic activity followed the order: [Ni(HL)](ClO4)2 (2) > [Cu(HL)](ClO4)2 (3) > [Co(L)(H2O)](ClO4)2 (1). As far as we know, this is the first description of a nickel complex presenting a significant catalase-like activity. PMID:26379038

  14. Cobalt ion-containing epoxies

    NASA Technical Reports Server (NTRS)

    Stoakley, D. M.; St.clair, A. K.

    1983-01-01

    Varying concentrations of an organometallic cobalt complex were added to an epoxy system currently used by the aerospace industry as a composite matrix resin. Methods for combining cobalt (III) acetylacetonate with a tetraglycidyl 4,4 prime - diaminodiphenylmethane-based epoxy were investigated. The effects of increasing cobalt ion concentration on the epoxy cure were demonstrated by epoxy gel times and differential scanning calorimetry cure exotherms. Analysis on cured cobalt-containing epoxy castings included determination of glass transition temperatures by thermomechanical analysis, thermooxidative stabilities by thermogravimetric analysis, and densities in a density gradient column. Flexural strength and stiffness were also measured on the neat resin castings.

  15. Application of aqueous two-phase systems for the development of a new method of cobalt(II), iron(III) and nickel(II) extraction: a green chemistry approach.

    PubMed

    Patrício, Pamela da Rocha; Mesquita, Maiby Cabral; da Silva, Luis Henrique Mendes; da Silva, Maria C Hespanhol

    2011-10-15

    We have investigated the extraction behavior of the metallic ions Co(II), Fe(III) and Ni(II) as a function of the amount of potassium thiocyanate used as an extracting agent, using the following aqueous two-phase systems (ATPS): PEO + (NH(4))(2)SO(4) + H(2)O, PEO + Li(2)SO(4) + H(2)O, L35 + (NH(4))(2)SO(4) + H(2)O and L35 + (Li)(2)SO(4)+H(2)O. Metal extraction from the salt-rich phase to the polymer-rich phase is affected by the following parameters: amount of added extractant, pH, and the nature of the electrolyte and polymer that forms the ATPS. Maximal extraction percentages were obtained for Co(II) (99.8%), Fe(III) (12.7%) and Ni(II) (3.17%) when the ATPS was composed of PEO1500 + (NH(4))(2)SO(4) + H(2)O containing 1.4 mmol of KSCN at pH 4.0, providing separation factors as high as S(Co, Fe) = 3440 and S(Co, Ni) = 15,300. However, when the same ATPS was used at pH 2.0, the maximal extraction percentages for iron and nickel were 99.5% and 4.34%, respectively, with S(Fe, Ni) equal to 4380. The proposed technique was shown to be efficient in the extraction of Co(II) and Fe(III), with large viability for the selective separation of Co(II) and Fe(III) ions in the presence of Ni(II).

  16. Dioxygen bound cobalt corroles.

    PubMed

    Mittra, Kaustuv; Mondal, Biswajit; Mahammed, Atif; Gross, Zeev; Dey, Abhishek

    2017-01-10

    Two cobalt-dioxygen adducts, [CoH8]-O2 and [CoCl8]-O2, chelated by electron-rich and electron-poor corroles, respectively, were isolated in solution. Characterization by resonance Raman (rR) and EPR spectroscopy, together with DFT analyses, point towards (corrole) cobalt(iii)-O2˙(-) structures in both cases. The most significant insight was obtained from the Co-O and O-O stretching frequencies, which revealed that the Co-O bond in [CoH8]-O2 is somewhat stronger than in [CoCl8]-O2 and its O-O is weaker, but also that the differences are truly minute (8-10 cm(-1) for the O-O stretch). These conclusions are vital regarding the various applications that rely on efficient reduction of molecular oxygen. In particular, these kinds of cobalt complexes are perfectly suited for serving as electrocatalysts that may be tuned to operate at minimal overpotential without losing almost anything in terms of activity.

  17. Cobalt tyrosinase: replacement of the binuclear copper of Neurospora tyrosinase by cobalt.

    PubMed

    Rüegg, C; Lerch, K

    1981-03-03

    The antiferromagnetically spin-coupled copper(II) pair in Neurospora tyrosinase was substituted by cobalt, yielding a stoichiometry of 2 mol of Co/mol of protein. The low magnitude of the high-spin Co(II) EPR signal indicates spin coupling of the two Co(II) ions similar to that observed in the native enzyme. The absorption spectrum with four transitions in the visible region of intermediate intensity (epsilon 607(670), epsilon 564(630), epsilon 526(465)), a shoulder at 635 nm, and the near-infrared bands at 1180 (epsilon 30) and 960 nm (epsilon 15) indicate tetrahedral coordination around the Co(II) center. The cobalt(II) tyrosinase is enzymatically inactive, and there is no evidence that it binds molecular oxygen. Upon addition of cyanide or the competitive tyrosinase inhibitors L-mimosine, benzoic acid, or benzhydroxamic acid te absorption spectrum changes in a characteristic manner. This optical perturbation shows that binding of these inhibitors (and presumably of the substrates) occurs at or near the metal site. One Co(II) ion can be removed preferentially by incubation with KCN at high pH, indicating the two ions not to be in an identical environment.

  18. Towards accurate estimates of the spin-state energetics of spin-crossover complexes within density functional theory: a comparative case study of cobalt(II) complexes.

    PubMed

    Vargas, Alfredo; Krivokapic, Itana; Hauser, Andreas; Lawson Daku, Latévi Max

    2013-03-21

    We report a detailed DFT study of the energetic and structural properties of the spin-crossover Co(ii) complex [Co(tpy)(2)](2+) (tpy = 2,2':6',2''-terpyridine) in the low-spin (LS) and the high-spin (HS) states, using several generalized gradient approximation and hybrid functionals. In either spin-state, the results obtained with the functionals are consistent with one another and in good agreement with available experimental data. Although the different functionals correctly predict the LS state as the electronic ground state of [Co(tpy)(2)](2+), they give estimates of the HS-LS zero-point energy difference which strongly depend on the functional used. This dependency on the functional was also reported for the DFT estimates of the zero-point energy difference in the HS complex [Co(bpy)(3)](2+) (bpy = 2,2'-bipyridine) [A. Vargas, A. Hauser and L. M. Lawson Daku, J. Chem. Theory Comput., 2009, 5, 97]. The comparison of the and estimates showed that all functionals correctly predict an increase of the zero-point energy difference upon the bpy → tpy ligand substitution, which furthermore weakly depends on the functionals, amounting to . From these results and basic thermodynamic considerations, we establish that, despite their limitations, current DFT methods can be applied to the accurate determination of the spin-state energetics of complexes of a transition metal ion, or of these complexes in different environments, provided that the spin-state energetics is accurately known in one case. Thus, making use of the availability of a highly accurate ab initio estimate of the HS-LS energy difference in the complex [Co(NCH)(6)](2+) [L. M. Lawson Daku, F. Aquilante, T. W. Robinson and A. Hauser, J. Chem. Theory Comput., 2012, 8, 4216], we obtain for [Co(tpy)(2)](2+) and [Co(bpy)(3)](2+) best estimates of and , in good agreement with the known magnetic behaviour of the two complexes.

  19. Synthesis, spectroscopic and DNA binding ability of Co(II), Ni(II), Cu(II) and Zn(II) complexes of Schiff base ligand (E)-1-(((1H-benzo[d]imidazol-2-yl)methylimino)methyl)naphthalen-2-ol. X-ray crystal structure determination of cobalt (II) complex.

    PubMed

    Yarkandi, Naeema H; El-Ghamry, Hoda A; Gaber, Mohamed

    2017-06-01

    A novel Schiff base ligand, (E)-1-(((1H-benzo[d]imidazol-2-yl)methylimino)methyl)naphthalen-2-ol (HL), has been designed and synthesized in addition to its metal chelates [Co(L)2]·l2H2O, [Ni(L)Cl·(H2O)2].5H2O, [Cu(L)Cl] and [Zn(L)(CH3COO)]. The structures of the isolated compounds have been confirmed and identified by means of different spectral and physicochemical techniques including CHN analysis, (1)H &(13)C NMR, mass spectral analysis, molar conductivity measurement, UV-Vis, infrared, magnetic moment in addition to TGA technique. The infrared spectral results ascertained that the ligand acts as monobasic tridentate binding to the metal centers via deprotonated hydroxyl oxygen, azomethine and imidazole nitrogen atoms. The UV-Vis, magnetic susceptibility and molar conductivity data implied octahedral geometry for Co(II) & Ni(II) complexes, tetrahedral for Zn(II) complex and square planar for Cu(II) complex. X-ray structural analysis of Co(II) complex 1 has been reported and discussed. Moreover, the type of interaction between the ligand & its complexes towards salmon sperm DNA (SS-DNA) has been examined by the measurement of absorption spectra and viscosity which confirmed that the ligand and its complexes interact with DNA via intercalation interaction as concluded from the values of binding constants (Kb). Copyright © 2017 Elsevier B.V. All rights reserved.

  20. Synthesis, structures and properties of the new lithium cobalt(II) phosphate Li{sub 4}Co(PO{sub 4}){sub 2}

    SciTech Connect

    Glaum, R.; Gerber, K.; Schulz-Dobrick, M.

    2012-04-15

    {alpha}-Li{sub 4}Co(PO{sub 4}){sub 2} has been synthesized and crystallized by solid-state reactions. The new phosphate crystallizes in the monoclinic system (P2{sub 1}/a, Z=4, a=8.117(3) Angstrom-Sign , b=10.303(8) Angstrom-Sign , c=8.118(8) Angstrom-Sign , {beta}=104.36(8) Angstrom-Sign ) and is isotypic to {alpha}-Li{sub 4}Zn(PO{sub 4}){sub 2}. The structure of {alpha}-Li{sub 4}Co(PO{sub 4}){sub 2} has been determined from single-crystal X-ray diffraction data {l_brace}R{sub 1}=0.040, wR{sub 2}=0.135, 2278 unique reflections with F{sub o}>4{sigma}(F{sub o}){r_brace}. The crystal structure, which might be regarded as a superstructure of the wurtzite structure type, is build of layers of regular CoO{sub 4}, PO{sub 4} and Li1O{sub 4} tetrahedra. Lithium atoms Li2, Li3 and Li4 are located between these layers. Thermal investigations by in-situ XRPD, DTA/TG and quenching experiments suggest decomposition followed by formation and phase transformation of Li{sub 4}Co(PO{sub 4}){sub 2}: {alpha}-Li{sub 4}Co(PO{sub 4}){sub 2} Long-Rightwards-Double-Arrow {sup 442 Degree-Sign C}{beta}-Li{sub 3}PO{sub 4}+LiCoPO{sub 4} Rightwards-Harpoon-Over-Leftwards-Harpoon {sup 773 Degree-Sign C}{beta}-Li{sub 4}Co(PO{sub 4}){sub 2} Long-Rightwards-Double-Arrow {sup quenchingto25 Degree-Sign C}{alpha}-Li{sub 4} Co(PO{sub 4}){sub 2} According to HT-XRPD at {theta}=850 Degree-Sign C{beta}-Li{sub 4}Co(PO{sub 4}){sub 2} (Pnma, Z=2, 10.3341(8) A, b=6.5829(5) A, c=5.0428(3) Angstrom-Sign ) is isostructural to {gamma}-Li{sub 3}PO{sub 4}. The powder reflectance spectrum of {alpha}-Li{sub 4}Co(PO{sub 4}){sub 2} shows the typical absorption bands for the tetrahedral chromophore [Co{sup II}O{sub 4}]. - Graphical abstract: The complex formation and decomposition behavior of Li{sub 4}Co(PO{sub 4}){sub 2} with temperature has been elucidated. The crystal structure of its {alpha}-phase was determined from single crystal data, HT-XRPD allowed derivation of a structure model for the {beta}-phase. Both

  1. A 1982-1992 surveillance programme on Danish pottery painters. Biological levels and health effects following exposure to soluble or insoluble cobalt compounds in cobalt blue dyes.

    PubMed

    Christensen, J M; Poulsen, O M

    1994-06-30

    effect of cobalt exposure at low levels revealed no inhibitory effects on thyroid function, but the ratio between T4 and T3 increased, indicating that low cobalt exposure may have an impact on the metabolism of thyroid hormones. Parallel studies were conducted on the metabolism and excretion of cobalt. The gastrointestinal uptake of soluble CoCl was considerably higher than the uptake of insoluble cobalt(II) oxide. In addition, it was demonstrated that ingestion of controlled amounts of the soluble cobalt compound resulted in significantly higher concentrations of cobalt in urine and blood (Co-B) from females compared with males (P < 0.01). Future studies will involve epidemiology and genotoxicity to evaluate the previous and present cancer risk, and detailed process-related exposure assessment studies to select the methods most reliable for surveillance of low-dose cobalt exposure.

  2. Cobalt-phosphate oxygen-evolving compound.

    PubMed

    Kanan, Matthew W; Surendranath, Yogesh; Nocera, Daniel G

    2009-01-01

    The utilization of solar energy on a large scale requires efficient storage. Solar-to-fuels has the capacity to meet large scale storage needs as demonstrated by natural photosynthesis. This process uses sunlight to rearrange the bonds of water to furnish O2 and an H2-equivalent. We present a tutorial review of our efforts to develop an amorphous cobalt-phosphate catalyst that oxidizes water to O2. The use of earth-abundant materials, operation in water at neutral pH, and the formation of the catalyst in situ captures functional elements of the oxygen evolving complex of Photosystem II.

  3. Protective Agent-Free Synthesis of Colloidal Cobalt Nanoparticles

    SciTech Connect

    Balela, M. D. L.; Lockman, Z.; Azizan, A.; Matsubara, E.; Amorsolo, A. V. Jr.

    2010-03-11

    Spherical colloidal cobalt (Co) nanoparticles of about 2-7 nm were synthesized by hydrazine reduction in ethylene glycol at 80 deg. C. The mean diameter of the Co nanoparticles was varied to some extent by changing the pH, temperature, Co(II) chloride hexahydrate concentration, and amount of hydrazine. The Co particle size was reduced by decreasing Co(II) chloride concentration and increasing amount of hydrazine.

  4. Synthesis and structural characterization of silver(I), aluminium(III) and cobalt(II) complexes with 4-isopropyltropolone (hinokitiol) showing noteworthy biological activities. Action of silver(I)-oxygen bonding complexes on the antimicrobial activities.

    PubMed

    Nomiya, Kenji; Yoshizawa, Akira; Tsukagoshi, Ken; Kasuga, Noriko Chikaraishi; Hirakawa, Shoko; Watanabe, Jun

    2004-01-01

    Through two unequivalent oxygen donor atoms of the hinokitiol (Hhino; C10H12O2; 4-isopropyltropolone) ligand that showed noteworthy biological activities, the dimeric, silver(I)-oxygen bonding complex [Ag(hino)]2 1, the monomeric aluminium(III) complex [Al(hino)3].0.5H2O 4 and the cobalt(II) complex "[Co(hino)2]2.H2O" 6 were synthesized and characterized with elemental analysis, thermogravimetric and differential thermal analysis (TG/DTA), FTIR and solution (1H and 13C) NMR spectroscopy. The crystal structure of 1 was determined by Rietveld analysis based on X-ray powder diffraction (XPD) data and those of [Al(hino)3].MeOH 4a and [Co(hino)2(EtOH)]2 6a, being obtained as yellow block crystals and red platelet crystals, respectively, by crystallization of 4 and 6, were determined by single-crystal X-ray analysis. The antimicrobial activities of 1, 4 and 6, evaluated with minimum inhibitory concentration (MIC; microg ml(-1)), were compared with those of other metal complexes (M=Na, Li, Cs, Ca, V, Zn) with the hino- ligand. The antimicrobial activities observed in the alkali-metal salts strongly suggested that they were attributed to the effect of the anionic hino- species. The antimicrobial activities of 1 were significantly enhanced, whereas those of other metal complexes were suppressed, compared with those of the neutral Hhino and anionic hino- molecules. The antimicrobial activities observed in 1 were comparable with those of other recently found silver(I)-oxygen bonding complexes, the ligands of which had no activity. Thus, it is proposed that the antimicrobial activities of the silver(I)-oxygen bonding complexes are due to a direct interaction or complexation of the silver(I) ion with biological ligands such as protein, enzyme and membrane, and the coordinating ligands of the silver(I) complexes play the role of a carrier of the silver(I) ion to the biological system.

  5. Cobalt source calibration

    SciTech Connect

    Rizvi, H.M.

    1999-12-03

    The data obtained from these tests determine the dose rate of the two cobalt sources in SRTC. Building 774-A houses one of these sources while the other resides in room C-067 of Building 773-A. The data from this experiment shows the following: (1) The dose rate of the No.2 cobalt source in Building 774-A measured 1.073 x 10{sup 5} rad/h (June 17, 1999). The dose rate of the Shepherd Model 109 Gamma cobalt source in Building 773-A measured 9.27 x 10{sup 5} rad/h (June 25, 1999). These rates come from placing the graduated cylinder containing the dosimeter solution in the center of the irradiation chamber. (2) Two calibration tests in the 774-A source placed the graduated cylinder with the dosimeter solution approximately 1.5 inches off center in the axial direction. This movement of the sample reduced the measured dose rate 0.92% from 1.083 x 10{sup 5} rad/h to 1.073 x 10{sup 5} rad/h. and (3) A similar test in the cobalt source in 773-A placed the graduated cylinder approximately 2.0 inches off center in the axial direction. This change in position reduced the measured dose rate by 10.34% from 1.036 x 10{sup 6} to 9.27 x 10{sup 5}. This testing used chemical dosimetry to measure the dose rate of a radioactive source. In this method, one determines the dose by the chemical change that takes place in the dosimeter. For this calibration experiment, the author used a Fricke (ferrous ammonium sulfate) dosimeter. This solution works well for dose rates to 10{sup 7} rad/h. During irradiation of the Fricke dosimeter solution the Fe{sup 2+} ions ionize to Fe{sup 3+}. When this occurs, the solution acquires a slightly darker tint (not visible to the human eye). To determine the magnitude of the change in Fe ions, one places the solution in an UV-VIS Spectrophotometer. The UV-VIS Spectrophotometer measures the absorbency of the solution. Dividing the absorbency by the total time (in minutes) of exposure yields the dose rate.

  6. Enhancement of trichothecene production in Fusarium graminearum by cobalt chloride.

    PubMed

    Tsuyuki, Rie; Yoshinari, Tomoya; Sakamoto, Naoko; Nagasawa, Hiromichi; Sakuda, Shohei

    2011-03-09

    The effects of cobalt chloride on the production of trichothecene and ergosterol in Fusarium graminearum were examined. Incorporation experiments with (13)C-labeled acetate and leucine confirmed that both 3-acetyldeoxynivalenol and ergosterol were biosynthesized via a mevalonate pathway by the fungus, although hydroxymethyl-glutaryl CoA (HMG-CoA) from intact leucine was able to be partially used for ergosterol production. Addition of cobalt chloride at concentrations of 3-30 μM into liquid culture strongly enhanced 3-acetyldeoxynivalenol production by the fungus, whereas the amount of ergosterol and the mycelial weight of the fungus did not change. The mRNA levels of genes encoding trichothecene biosynthetic proteins (TRI4 and TRI6), ergosterol biosynthetic enzymes (ERG3 and ERG25), and enzymes involved in the mevalonate pathway (HMG-CoA synthase (HMGS) and HMG-CoA reductase (HMGR)) were all strongly up-regulated in the presence of cobalt chloride. Precocene II, a specific trichothecene production inhibitor, suppressed the effects of cobalt chloride on Tri4, Tri6, HMGS, and HMGR, but did not affect erg3 and erg25. These results indicate that cobalt chloride is useful for investigating regulatory mechanisms of trichothecene and ergosterol production in F. graminearum.

  7. Crystal structure of an unknown solvate of {2,2'-[ethane-1,2-diylbis(nitrilo-methanylyl-idene)]diphenolato-κ(4) O,N,N',O'}(N-ferrocenylisonicotinamide-κN (1))cobalt(II): a Co(II)-salen complex that forms hydrogen-bonded dimers.

    PubMed

    Brautigam, Bryan; Herholdt, Chelsea; Farnsworth, William; Brudi, Ellen; McDonald, Eric; Wu, Guang; Contakes, Stephen

    2015-09-01

    The title compound, [CoFe(C5H5)(C16H14N2O2)(C11H9N2O)], was prepared as an air-stable red-brown solid by mixing equimolar amounts of {2,2'-[ethane-1,2-diylbis(nitrilo-methanylyl-idene)]diphenolato}cobalt(II) and N-ferrocenylisonicotinamide in dry di-chloro-methane under nitro-gen and was characterized by ESI-MS, IR, and single-crystal X-ray diffraction. The structure at 100 K has triclinic (P-1) symmetry and indicates that the complex crystallizes as a mixture of λ and δ conformers. It exhibits the expected square pyramidal geometry about Co, and forms hydrogen-bonded dimers through amide N-H groups and phenolate O atoms on an adjacent mol-ecule. The involvement of only half of the salen ring structure in hydrogen-bonding inter-actions results in slight folding of the salen ring away from the pyridine coordination site in the δ conformer with an inter-salicyl-idene fold angle of 9.9 (7)°. In contrast, the λ conformer is nearly planar. The dimers pack into an open structure containing channels filled with highly disordered solvent mol-ecules. These solvent molecules' contributions to the intensity data were removed with the SQUEEZE procedure [Spek (2015). Acta Cryst. C71, 9-18] available in PLATON.

  8. Resonance Raman Spectra of Cobalt-Substituted Hemoglobin: Cooperativity and Displacement of the Cobalt Atom upon Oxygenation

    PubMed Central

    Woodruff, William H.; Spiro, Thomas G.; Yonetani, Takashi

    1974-01-01

    The resonance Raman spectra of oxy and deoxy cobalt-substituted hemoglobin (CoHb) are reported. Comparison of these spectra to those of hemoglobin, methemoglobin, cytochrome c, and model cobalt porphyrin complexes suggests that the displacement of the cobalt atom upon oxygenation of CoHb is no greater than the out-of-plane distance in five-coordinate Co(II) porphyrins, 0.15 Å. Combining this distance with the expected contraction of the cobalt-histidine bond, Ibers has estimated a maximum displacement of 0.37 Å for the proximal histidine with respect to the heme plane upon oxygenation, about one-third the corresponding distance estimated for iron hemoglobin. The free energy of cooperativity for cobalt hemoglobin is also estimated to be one-third that of iron hemoglobin. These results are therefore consistent with Hopfield's distributed energy model, which predicts proportionality between proximal histidine displacement and the free energy of cooperativity. By implication they support Perutz's trigger mechanism for cooperativity. PMID:4524615

  9. Use of indium-111 oxine to study pulmonary and hepatic leukocyte sequestration in endotoxin shock and effects of the beta-2 receptor agonist terbutaline

    SciTech Connect

    Sigurdsson, G.H.; Christenson, J.T.; al-Mousawi, M.; Owunwanne, A. )

    1989-01-01

    The dynamic behavior of indium-111 oxine-labeled leukocytes was simultaneously recorded in multiple organs during endotoxin shock in sheep. Also, the effects of the beta-2 receptor agonist terbutaline were studied. An experimental protocol was designed to mimic a clinical condition in an intensive care setting as far as possible. The animals were ventilated with 50% oxygen to avoid hypoxemia and were given large amounts of intravenous fluids to reduce adverse effects of hypovolemia. A moderate dose of E. coli endotoxin (10 micrograms/kg bwt) was given by intravenous infusion to 14 adult sheep, seven of them receiving continuous intravenous infusion of terbutaline (20 micrograms/kg/hr) during 4 hr, starting 30 min after endotoxin, when signs of lung injury had developed. The other seven acted as controls. A marked pulmonary and hepatic leukocyte sequestration together with a sharp drop in leukocyte counts in peripheral blood occurred within minutes after start of the endotoxin infusion in both groups. However, no changes were observed in the kidneys or the gut. After 60 min and until the end of the experiment, there was a significantly lower activity in the lungs and in the liver of the animals treated with terbutaline than in the controls (P less than .01). Furthermore, less marked hemodynamic and respiratory alterations occurred in the terbutaline group compared with the controls. This study confirms the results of other investigators showing that significant leukocyte sequestration occurs in the lungs during endotoxemia, but it also demonstrates that leukocytes sequestrate in the liver, although slightly less than in the lungs.

  10. Adapting Ruthenium Sensitizers to Cobalt Electrolyte Systems.

    PubMed

    Amit Kumar, Sangeeta; Urbani, Maxence; Medel, María; Ince, Mine; González-Rodríguez, David; Chandiran, Aravind Kumar; Bhaskarwar, Ashok N; Torres, Tomás; Nazeeruddin, Md K; Grätzel, Michael

    2014-02-06

    In this work, we report the use of bulky substitutions in a new heteroleptic ruthenium(II) bipyridine complex, Ru(NCS)2LL', coded TT-230 to obtain high open-circuit potential in a dye-sensitized solar cell (where L is a bipyridine ligand appended with two cyclopenta(2,1-b;3,4-bA)dithiophene moieties, and L' = 4,4,'-dicarboxylic acid 2,2'-bipyridine). The electrolytes based on cobalt complexes have shown significant advantages in terms of attainable open-circuit potential compared to the standard iodide/tri-iodide redox mediators. These merits of the cobalt complexes were previously realized with a porphyrin sensitizer, achieving a VOC greater than 1 V in DSC. However, with conventional Ru(II)-polypyridyl complexes such as the C101 dye, similar increase in the VOC could not be attained due to the enhanced recombination. In this work, we have shown that the use of bulky substituents can prevent the back reaction of photogenerated electron and subsequently increase the open-circuit potential of the device. The recombination processes were investigated by transient photovoltage decay measurements.

  11. Effects of cobalt chloride on nitric oxide and cytokines/chemokines production in microglia.

    PubMed

    Mou, Yan Hua; Yang, Jing Yu; Cui, Nan; Wang, Ji Ming; Hou, Yue; Song, Shuang; Wu, Chun Fu

    2012-05-01

    The involvement of microglial activation in metal neurotoxicity is becoming increasingly recognized. Some metal ions, such as zinc (II) and manganese (II), have been recently reported as microglial activators to induce the release of inflammatory mediators including cytokines, chemokines and nitric oxide (NO) which are involved in the pathogenesis of neurological diseases. Cobalt is essential for human life. However, excessive cobalt is cytotoxic and neurotoxic. In the present study, we determined cobalt-induced production of NO and cytokines/chemokines in N9 cells, a murine microglial cell line. High levels of cobalt significantly up-regulated iNOS mRNA and protein expression, which resulted in the release of NO. Cobalt induced the production of tumor necrosis factor α (TNF-α) and interleukin-6 (IL-6) in a concentration- and time-dependent manner in both N9 cells and primary mouse microglia and increased lipopolysaccharides (LPS)-induced cytokine production. Further study showed that cobalt induced cytokine production by a mechanism involving both nuclear factor kappa B (NF-κB) and p38 mitogen-activated protein kinase (MAPK) signaling pathways. The involvement of reactive oxygen species (ROS) in microglial activation was also confirmed. These findings suggested that cobalt neurotoxicity should be attributed not only directly to neuronal damage but also indirectly to microglial activation which might potentiate neuronal injury via elevation of proinflammatory mediator levels.

  12. Synthesis of certain pyridinyl and diazinyl hydrazones containing one or more ferroin groups, and their chromogenic reactions with iron, copper, cobalt and nickel.

    PubMed

    Schilt, A A; Mohamed, N; Case, F H

    1979-02-01

    Fifteen new hydrazones with one or more ferroin groups were prepared, and their chelation and chromogenic properties with iron(II), copper(I), cobalt(II) and nickel(II) were investigated. Improved sensitivity in the spectrophotometric determination of cobalt, copper, and nickel is provided by several of the new compounds. Several others are capable of forming unusually stable and interesting binuclear iron(II) complexes.

  13. Cobalt: for strength and color

    USGS Publications Warehouse

    Boland, Maeve A.; Kropschot, S.J.

    2011-01-01

    Cobalt is a shiny, gray, brittle metal that is best known for creating an intense blue color in glass and paints. It is frequently used in the manufacture of rechargeable batteries and to create alloys that maintain their strength at high temperatures. It is also one of the essential trace elements (or "micronutrients") that humans and many other living creatures require for good health. Cobalt is an important component in many aerospace, defense, and medical applications and is a key element in many clean energy technologies. The name cobalt comes from the German word kobold, meaning goblin. It was given this name by medieval miners who believed that troublesome goblins replaced the valuable metals in their ore with a substance that emitted poisonous fumes when smelted. The Swedish chemist Georg Brandt isolated metallic cobalt-the first new metal to be discovered since ancient times-in about 1735 and identified some of its valuable properties.

  14. Cobalt(I), -(II), and -(III) complexes of a tetraaza 14-membered macrocycle, 5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene (L). Crystal and molecular structures of (CoL(CO))ClO sub 4 , trans-CoLCl sub 2 , and cis-(CoL(CO sub 3 ))ClO sub 4

    SciTech Connect

    Szalda, D.J.; Fujita, E.; Creutz, C. )

    1989-04-19

    The carbon monoxide adduct of the cobalt(I) title macrocycle has been prepared via reaction of CoL{sup +} with CO{sub 2} and with CO and isolated as a perchlorate salt: IR (Nujol){nu}{sub CO} 1916 cm{sup {minus}1}; UV-vis (CH{sub 3}CH, {lambda}{sub max} ({epsilon})) 310 nm (3900 M{sup {minus}1} cm{sup {minus}1}), 430 sh (770), 510 sh (360), 1040 (240). In CH{sub 3}CN solvent its stability constant is {approx} 3 {times} 10{sup 8} M{sup {minus}1} at 25{degree}C. Structures of the square-pyramidal carbonyl complex and two other complexes of the title macrocycle have been determined from single-crystal x-ray diffraction data collected with use of Mo K{alpha} radiation. Crystallographic data: (CoL(CO))(ClO{sub 4}) (1), C2, a = 15.362 (3) {angstrom}, b = 7.580 (5) {angstrom}, c = 9.611 (3) {angstrom}, {beta} = 108.91 (2){degree}, V = 1059 (1) {angstrom}{sup 3}, Z = 2 (R = 0.057, R{sub w} = 0.069); N-meso,trans-CoLCl{sub 2} (2), Pbca, a = 11.570 (3) {angstrom}, b = 12.695 (3) {angstrom}, c = 13.309 (2) {angstrom}, V = 1954 (1) {angstrom}{sup 3}, Z = 4 (R = 0.075, R{sub w} = 0.070); cis-(CoL(CO{sub 3}))ClO{sub 4} (3), C2, a = 15.072 (5) {angstrom}, b = 7.603 (4) {angstrom}, c = 9.703 (3) {angstrom}, {beta} = 109.74 (3){degree}, V = 1047 (1) {angstrom}{sup 3}, Z = 2 (R = 0.033, R{sub w} = 0.048). The three structures contain square-pyramidal, five-coordinate cobalt(I) (1), strongly axially distorted six-coordinate cobalt(II) (2), and six-coordinate cobalt(III) with L occupying cis-coordination positions (3). They thus provide a striking illustration of the adaptability of L to a variety of coordination numbers and oxidation states. 30 refs., 3 figs., 8 tabs.

  15. Molecular cobalt pentapyridine catalysts for generating hydrogen from water.

    PubMed

    Sun, Yujie; Bigi, Julian P; Piro, Nicholas A; Tang, Ming Lee; Long, Jeffrey R; Chang, Christopher J

    2011-06-22

    A set of robust molecular cobalt catalysts for the generation of hydrogen from water is reported. The cobalt complex supported by the parent pentadentate polypyridyl ligand PY5Me(2) features high stability and activity and 100% Faradaic efficiency for the electrocatalytic production of hydrogen from neutral water, with a turnover number reaching 5.5 × 10(4) mol of H(2) per mole of catalyst with no loss in activity over 60 h. Control experiments establish that simple Co(II) salts, the free PY5Me(2) ligand, and an isostructural PY5Me(2) complex containing redox-inactive Zn(II) are all ineffective for this reaction. Further experiments demonstrate that the overpotential for H(2) evolution can be tuned by systematic substitutions on the ancillary PY5Me(2) scaffold, presaging opportunities to further optimize this first-generation platform by molecular design.

  16. In vitro human leukocyte labeling with (64)Cu: an intraindividual comparison with (111)In-oxine and (18)F-FDG.

    PubMed

    Bhargava, Kuldeep K; Gupta, Raj K; Nichols, Kenneth J; Palestro, Christopher J

    2009-07-01

    We investigated labeling human leukocytes [white blood cells (WBCs)] in vitro with copper-64 (Cu) comparing labeling efficiency, viability and stability of Cu-WBCs with (111)In-oxine (In) WBCs and (18)F-FDG (FDG) WBCs. Leukocytes from 10 volunteers were labeled with Cu, In and FDG. Forty milliliters of venous blood was collected and leukocyte separation was performed according to standard methods. In-WBCs and FDG-WBCs were labeled according to published methods. For Cu-WBCs, tropolone initially was used as a single chelating agent. Because of poor intracellular Cu retention (54+/-4% at 3 h and 24+/-5% at 24 h), the fluorinated, membrane-permeable divalent cation chelator quin-MF was added. WBCs were incubated in 5 ml saline containing 100 microl of 1mM quin-MF/AM in 2% dimethyl sulfoxide and 74-185 MBq Cu-tropolone for 45 min at 37 degrees C. Labeling efficiencies; in vitro cellular viabilities at 1, 3 and 24 h; and in vitro stabilities at 1, 2, 3, 4 and 24 h (except FDG-WBCs) were determined. Mean Cu-WBCs (87+/-4%) and In-WBCs (86+/-4%) labeling efficiencies were comparable and were significantly higher than FDG-WBCs (60+/-19%, P<.001). Cell viabilities, similar at 1 h, were significantly higher for (64)Cu-WBCs at 3 and 24 h. Intracellular retention of activity was always significantly higher for In-WBCs than for Cu-WBCs and FDG-WBCs. At 24 h, intracellular retention was 88+/-4% for In-WBCs and 79+/-6% for Cu-WBCs. Cu-WBC labeling efficiency and viability were comparable or superior to In-WBCs and significantly higher than FDG-WBCs. Although significantly more activity eluted from Cu-WBCs than from In-WBCs, Cu-WBC probably is adequate for imaging. These data suggest that further investigation of in vitro copper-64-labeled leukocytes for PET imaging of infection is warranted.

  17. Concerning the deactivation of cobalt(III)-based porphyrin and salen catalysts in epoxide/CO2 copolymerization.

    PubMed

    Xia, Wei; Salmeia, Khalifah A; Vagin, Sergei I; Rieger, Bernhard

    2015-03-09

    Functioning as active catalysts for propylene oxide (PO) and carbon dioxide copolymerization, cobalt(III)-based salen and porphyrin complexes have drawn great attention owing to their readily modifiable nature and promising catalytic behavior, such as high selectivity for the copolymer formation and good regioselectivity with respect to the polymer microstructure. Both cobalt(III)-salen and porphyrin catalysts have been found to undergo reduction reactions to their corresponding catalytically inactive cobalt(II) species in the presence of propylene oxide, as evidenced by UV/Vis and NMR spectroscopies and X-ray crystallography (for cobalt(II)-salen). Further investigations on a TPPCoCl (TPP = tetraphenylporphyrin) and NaOMe system reveal that such a catalyst reduction is attributed to the presence of alkoxide anions. Kinetic studies of the redox reaction of TPPCoCl with NaOMe suggests a pseudo-first order in cobalt(III)-porphyrin. The addition of a co-catalyst, namely bis(triphenylphosphine)iminium chloride (PPNCl), into the reaction system of cobalt(III)-salen/porphyrin and PO shows no direct stabilizing effect. However, the results of PO/CO2 copolymerization by cobalt(III)-salen/porphyrin with PPNCl suggest a suppressed catalyst reduction. This phenomenon is explained by a rapid transformation of the alkoxide into the carbonate chain end in the course of the polymer formation, greatly shortening the lifetime of the autoreducible PO-ring-opening intermediates, cobalt(III)-salen/porphyrin alkoxides.

  18. Electronic spectroscopy of cobalt angiotensin converting enzyme and its inhibitor complexes.

    PubMed

    Bicknell, R; Holmquist, B; Lee, F S; Martin, M T; Riordan, J F

    1987-11-17

    Zinc, the catalytically essential metal of angiotensin converting enzyme (ACE), has been replaced by cobalt(II) to give an active, chromophoric enzyme that is spectroscopically responsive to inhibitor binding. Visible absorption spectroscopy and magnetic circular dichroic spectropolarimetry have been used to characterize the catalytic metal binding site in both the cobalt enzyme and in several enzyme-inhibitor complexes. The visible absorption spectrum of cobalt ACE exhibits a single broad maximum (525 nm) of relatively low absorptivity (epsilon = 75 M-1 cm-1). In contrast, the spectra of enzyme-inhibitor complexes display more clearly defined maxima at longer wavelengths (525-637 nm) and of markedly higher absorptivities (130-560 M-1 cm-1). The large spectral response indicates that changes in the cobalt ion coordination sphere occur on inhibitor binding. Magnetic circular dichroic spectropolarimetry has shown that the metal coordination geometry in the inhibitor complexes is tetrahedral and of higher symmetry than in cobalt ACE alone. The presence of sulfur----cobalt charge-transfer bands in both the visible absorption and magnetic circular dichroic spectra of the cobalt ACE-Captopril complex confirm direct ligation of the thiol group of the inhibitor to the active-site metal.

  19. Wrought cobalt-base superalloys

    SciTech Connect

    Klarstrom, D.L. )

    1993-08-01

    Wrought cobalt-base superalloys are used extensively in gas turbine engines because of their excellent high-temperature creep and fatigue strength and resistance to hot corrosion attach. In addition, the unique character of the oxide scales that form on some of the alloys provides outstanding resistance to high-temperature sliding wear. This article provides a review of the evolutionary development of wrought cobalt-base alloys in terms of alloy design and physical metallurgy. The topics include solid-solution strengthening, carbide precipitation characteristics, and attempts to introduce age hardening. The use of PHACOMP to enhance thermal stability characteristics and the incorporation of rare-earth elements to improve oxidation resistance is also reviewed and discussed. The further development of cobalt-base superalloys has been severely hampered by past political events, which have accentuated the strategic vulnerability of cobalt as a base or as an alloying element. Consequently, alternative alloys have been developed that use little or no cobalt. One such alternative, Haynes 230 alloy, is discussed briefly.

  20. Cobalt-60 production at Savannah River

    SciTech Connect

    Allen, H.F.

    1995-02-01

    Over the past 8 or 9 years, the Savannah River Plant (SRP) has produced close to 4 million curies of cobalt-60 by irradiating cobalt-59 in the production reactors. This paper reviews past and current irradiations, cobalt-60 production methods, and costs.

  1. Transport of cobalt-60 industrial radiation sources

    NASA Astrophysics Data System (ADS)

    Kunstadt, Peter; Gibson, Wayne

    This paper will deal with safety aspects of the handling of Cobalt-60, the most widely used industrial radio-isotope. Cobalt-60 is a man-made radioisotope of Cobalt-59, a naturally occurring non radioactive element, that is made to order for radiation therapy and a wide range of industrial processing applications including sterilization of medical disposables, food irradiation, etc.

  2. Nano-Web Cobalt Modified Silica Nanoparticles Catalysts for Water Oxidation and MB Oxidative Degradation.

    PubMed

    Wang, Li; Chen, Qiuyun; Li, Chenghao; Fang, Fang

    2016-05-01

    Dioxygen generating materials, using water as oxygen source, can be used as catalysts in hypoxic environments. Cobalt(II) modified silica (SiO2@NPCo) nanoparticles were synthesized through coordination of cobalt(II) ions with nitrogen atoms from 2-acetylpyridine modified silica (SiO2@NP). The SiO2@NPCo nanoparticles further reacted with 1,3,5-benzenetricarboxylic acids, forming porous nano-web nanoparticles (SiO2@NPCoCOOH). The synthesized SiO2@NPCoCOOH nanoparticles were demonstrated as better white LED light driven photochemical catalysts for oxidation of water than individual nanoparticles (SiO2@NPCo). Moreover, the SiO2@NPCoCOOH/water system could decrease the content of methylene blue (MB) in solution and therefore, the nanoweb cobalt(II) modified silica nanoparticles can be environmentally friendly catalysts for oxidative degradation of MB, using water as the oxygen source.

  3. Structure and optical properties of glasses in binary liquid crystalline systems based on cobalt octanoate

    NASA Astrophysics Data System (ADS)

    Mirnaya, T. A.; Tokmenko, I. I.; Yaremchuk, G. G.; Tolochko, A. S.

    2015-04-01

    The effect of composition and aggregative state (melt, mesophase, glass) on the coordination state of Co (II) ions in an octanoate ligand field has been studied for binary liquid crystalline systems based on cobalt (II) octanoate by the analysis of electronic absorption spectra. It has been shown that several coordination forms of Co (II) ions: octahedral, tetrahedral and dodecahedral ones can coexist in cobalt octanoate based systems. It has been found by positron annihilation lifetime spectroscopy and small-angle X-ray scattering that glasses of cobalt octanoate based systems have a bilayer and nanoporous structure. The thickness of cation-anion bilayers in mesophases and glasses of binary systems depends on the polarizing power of cations: it is the smaller, the higher the polarizing power of cations.

  4. Determination of trace cobalt concentrations in human serum by adsorptive stripping voltammetry.

    PubMed

    Kajic, Petra; Milosev, Ingrid; Pihlar, Boris; Pisot, Venceslav

    2003-01-01

    The goal of our study was to develop an accurate and reliable method for determining trace cobalt concentrations in human serum. The method was used to determine cobalt in the sera of healthy persons and patients with orthopaedic implants containing cobalt - a possible source of systemic release of cobalt into the human body. This goal is of vital interest since cobalt and its compounds are classified by IARC as potentially carcinogenic to humans. We used an electrochemical method, adsorptive stripping voltammetry (AdSV), which made possible the low detection limit and high sensitivity needed for measurements in human serum. The serum was acid digested by a combination of H2SO4, HNO3 and H2O2 in a 10 mL Kjeldhal flask. The digested sample was then dissolved in 0.1 mol/L ammonia buffer, pH 9.0 +/- 0.2. The determination is based on the adsorptive collection of the complex of cobalt (II) with dimethylglyoxime on a hanging mercury drop electrode (HMDE). The optimum values of adsorption potential and time were determined to be -0.8 V and 60 s. The optimisation of the sample digestion protocol and measurement procedures ensured the reliable assessment of low cobalt concentrations, down to 0.03 microg/L. The mean concentration of serum cobalt in four healthy persons was 0.11 +/- 0.06 microg/L, and in four patients with total hip replacements 0.34 +/- 0.07 microg/L. This method will be used routinely for measuring serum cobalt levels in patients with total hip replacements.

  5. Orientational disorder in the one-dimensional coordination polymer catena-poly[[bis­(acetyl­acetonato-κ2 O,O′)cobalt(II)]-μ-1,4-di­aza­bicyclo­[2.2.2]octane-κ2 N 1:N 4

    PubMed Central

    Dumitru, Florina; Englert, Ulli; Braun, Beatrice

    2016-01-01

    The title compound, [Co(C5H7O2)2(C6H12N2)]n, was obtained as a one-dimensional coordination polymer from bis­(acetyl­acetonato)di­aqua­cobalt(II), [Co(acac)2(OH2)2], and 1,4-di­aza­bicyclo­[2.2.2]octane (DABCO), a di­amine with good bridging ability and rod-like spacer function. In the chain complex that extends along the c axis, the CoII atom is six-coordinated, the O-donor atoms of the chelating acac ligands occupying the equatorial positions and the bridging DABCO ligands being in trans-axial positions. In the crystal structure, the DABCO ligand is conformationally disordered in a 50:50 manner as a result of its location across a crystallographic mirror plane. The metal–metal distance is very close to that in a related compound exhibiting weak anti­ferromagnetic exchange between the CoII ions, and the title compound can thus be useful for obtaining more information about the contribution of different bridges to the magnetic coupling between paramagnetic ions. PMID:27375886

  6. Controlling the misuse of cobalt in horses.

    PubMed

    Ho, Emmie N M; Chan, George H M; Wan, Terence S M; Curl, Peter; Riggs, Christopher M; Hurley, Michael J; Sykes, David

    2015-01-01

    Cobalt is a well-established inducer of hypoxia-like responses, which can cause gene modulation at the hypoxia inducible factor pathway to induce erythropoietin transcription. Cobalt salts are orally active, inexpensive, and easily accessible. It is an attractive blood doping agent for enhancing aerobic performance. Indeed, recent intelligence and investigations have confirmed cobalt was being abused in equine sports. In this paper, population surveys of total cobalt in raceday samples were conducted using inductively coupled plasma mass spectrometry (ICP-MS). Urinary threshold of 75 ng/mL and plasma threshold of 2 ng/mL could be proposed for the control of cobalt misuse in raceday or in-competition samples. Results from administration trials with cobalt-containing supplements showed that common supplements could elevate urinary and plasma cobalt levels above the proposed thresholds within 24 h of administration. It would therefore be necessary to ban the use of cobalt-containing supplements on raceday as well as on the day before racing in order to implement and enforce the proposed thresholds. Since the abuse with huge quantities of cobalt salts can be done during training while the use of legitimate cobalt-containing supplements are also allowed, different urinary and plasma cobalt thresholds would be required to control cobalt abuse in non-raceday or out-of-competition samples. This could be achieved by setting the thresholds above the maximum urinary and plasma cobalt concentrations observed or anticipated from the normal use of legitimate cobalt-containing supplements. Urinary threshold of 2000 ng/mL and plasma threshold of 10 ng/mL were thus proposed for the control of cobalt abuse in non-raceday or out-of-competition samples. Copyright © 2014 John Wiley & Sons, Ltd.

  7. Following the Formation of Active Co(III) Sites in Cobalt Substituted Aluminophosphates Catalysts by In-Situ Combined UV-VIS/XAFS/XRD Technique

    SciTech Connect

    Sankar, Gopinathan; Fiddy, Steven; Harvey, Ian; Hayama, Shusaku; Bushnell-Wye, Graham; Beale, Andrew M.

    2007-02-02

    Cobalt substituted aluminophosphates, CoAlPO-34 (Chabazite structure) and DAF-8 (Phillipsite structure) were investigated by in situ combined XRD/EXAFS/UV-VIS technique. In-situ combined XRD, Co K-edge EXAFS and UV-Vis measurements carried out during the calcination process reveal that CoAlPO-34 containing 10 wt percent cobalt is stable and the cobalt ions are converted from Co(II) in the as synthesised form to Co(III); DAF-8 containing about 25 percent cobalt is not stable and does not show change in oxidation state.

  8. Characterization of feline serum-cobalt binding.

    PubMed

    Schnelle, Amy N; Barger, Anne M; MacNeill, Amy L; Mitchell, Mark M; Solter, Philip

    2015-06-01

    Oxidative stress inhibits albumin's ability to complex with cobalt. Feline serum-cobalt binding has not been described. The objective was to develop a cobalt binding test for use with feline serum, and correlate the results with other biochemical and cellular constituents in blood, and with clinical diseases of cats. A colorimetric test of cobalt binding, based on the oxidation-reduction reaction of Co(+2) and dithiothreitol, was developed using feline serum. The test was used to measure cobalt binding in stored serum from 176 cats presented to the University of Illinois Veterinary Teaching Hospital for a variety of disease conditions. Time-matched hematology and biochemical data, and clinical information, were obtained from the medical record of each cat and correlated with the serum-cobalt binding results. Serial dilution of feline serum with phosphate-buffered saline resulted in a highly linear decrease in serum-cobalt binding (r(2)  = .9984). Serum-cobalt binding of the clinical samples also correlated with albumin concentrations in a stepwise linear regression model (r(2)  = .425), and both cobalt binding and albumin were significantly decreased in cases of inflammation. Albumin and cobalt binding also shared significant correlations with several erythron variables, and serum concentration of total calcium and bilirubin. The correlation of cobalt binding measured by a colorimetric test with albumin concentration in the clinical samples and with serum dilution is consistent with feline albumin-cobalt complex formation. Hypoalbuminemia is the likely cause of reduced serum-cobalt binding in inflammation and the correlations observed between cobalt binding and other variables. © 2015 American Society for Veterinary Clinical Pathology.

  9. COBALT Flight Demonstrations Fuse Technologies

    NASA Image and Video Library

    2017-06-07

    This 5-minute, 50-second video shows how the CoOperative Blending of Autonomous Landing Technologies (COBALT) system pairs new landing sensor technologies that promise to yield the highest precision navigation solution ever tested for NASA space landing applications. The technologies included a navigation doppler lidar (NDL), which provides ultra-precise velocity and line-of-sight range measurements, and the Lander Vision System (LVS), which provides terrain-relative navigation. Through flight campaigns conducted in March and April 2017 aboard Masten Space Systems' Xodiac, a rocket-powered vertical takeoff, vertical landing (VTVL) platform, the COBALT system was flight tested to collect sensor performance data for NDL and LVS and to check the integration and communication between COBALT and the rocket. The flight tests provided excellent performance data for both sensors, as well as valuable information on the integrated performance with the rocket that will be used for subsequent COBALT modifications prior to follow-on flight tests. Based at NASA’s Armstrong Flight Research Center in Edwards, CA, the Flight Opportunities program funds technology development flight tests on commercial suborbital space providers of which Masten is a vendor. The program has previously tested the LVS on the Masten rocket and validated the technology for the Mars 2020 rover.

  10. Radiation regression patterns after cobalt plaque insertion for retinoblastoma

    SciTech Connect

    Buys, R.J.; Abramson, D.H.; Ellsworth, R.M.; Haik, B.

    1983-08-01

    An analysis of 31 eyes of 30 patients who had been treated with cobalt plaques for retinoblastoma disclosed that a type I radiation regression pattern developed in 15 patients; type II, in one patient, and type III, in five patients. Nine patients had a regression pattern characterized by complete destruction of the tumor, the surrounding choroid, and all of the vessels in the area into which the plaque was inserted. This resulting white scar, corresponding to the sclerae only, was classified as a type IV radiation regression pattern. There was no evidence of tumor recurrence in patients with type IV regression patterns, with an average follow-up of 6.5 years, after receiving cobalt plaque therapy. Twenty-nine of these 30 patients had been unsuccessfully treated with at least one other modality (ie, light coagulation, cryotherapy, external beam radiation, or chemotherapy).

  11. Electrodeposition of cobalt-chromium alloy from trivalent chromium solutions

    SciTech Connect

    Dasarathy, H.; Riley, C.; Coble, H.D. . Dept. of Chemistry and Materials Science)

    1994-07-01

    Cobalt-chromium alloy was deposited from plating solutions containing cobalt(II) chloride and chromium(III) chloride at 3.5 pH. The deposits were obtained using both single and mixed complex solutions. Deposit morphology showed significant dependence on the complexing agent(s) used. Partitioning of the two components in the deposit as determined by energy dispersive spectroscopy depended on plating parameters such as concentration ratio of the two salts in the solution, complexing agent, type of current (both dc and pulsed current were studied), and current density. X-ray photoelectron spectroscopy spectra collected from as-deposited alloy revealed the presence of both oxides and metals. X-ray diffraction spectra for the alloy deposit indicated solid solution formation.

  12. Preparation and characterization of copper-doped cobalt oxide electrodes.

    PubMed

    Rosa-Toro, A La; Berenguer, R; Quijada, C; Montilla, F; Morallón, E; Vazquez, J L

    2006-11-30

    Cobalt oxide (Co3O4) and copper-doped cobalt oxide (CuxCo(3-x)O4) films have been prepared onto titanium support by the thermal decomposition method. The electrodes have been characterized by different techniques such as cyclic voltammetry, scanning electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy (XPS). The effect on the electrochemical and crystallographic properties and surface morphology of the amount of copper in the oxide layer has been analyzed. The XPS spectra correspond to a characteristic monophasic Cu-Co spinel oxides when x is below 1. However, when the copper content exceeds that for the stoichiometric CuCo2O4 spinel, a new CuO phase segregates at the surface. The analysis of the surface cation distribution indicates that Cu(II) has preference for octahedral sites.

  13. Modification of Wide-Band-Gap Oxide Semiconductors with Cobalt Hydroxide Nanoclusters for Visible-Light Water Oxidation.

    PubMed

    Maeda, Kazuhiko; Ishimaki, Koki; Tokunaga, Yuki; Lu, Daling; Eguchi, Miharu

    2016-07-11

    Cobalt-based compounds, such as cobalt(II) hydroxide, are known to be good catalysts for water oxidation. Herein, we report that such cobalt species can also activate wide-band-gap semiconductors towards visible-light water oxidation. Rutile TiO2 powder, a well-known wide-band-gap semiconductor, was capable of harvesting visible light with wavelengths of up to 850 nm, and thus catalyzed water oxidation to produce molecular oxygen, when decorated with cobalt(II) hydroxide nanoclusters. To the best of our knowledge, this system constitutes the first example that a particulate photocatalytic material that is capable of water oxidation upon excitation by visible light can also operate at such long wavelengths, even when it is based on earth-abundant elements only.

  14. Cobalt release from inexpensive jewellery: has the use of cobalt replaced nickel following regulatory intervention?

    PubMed

    Thyssen, Jacob Pontoppidan; Jellesen, Morten S; Menné, Torkil; Lidén, Carola; Julander, Anneli; Møller, Per; Johansen, Jeanne Duus

    2010-08-01

    Before the introduction of the EU Nickel Directive, concern was raised that manufacturers of jewellery might turn from the use of nickel to cobalt following the regulatory intervention on nickel exposure. The aim was to study 354 consumer items using the cobalt spot test. Cobalt release was assessed to obtain a risk estimate of cobalt allergy and dermatitis in consumers who would wear the jewellery. The cobalt spot test was used to assess cobalt release from all items. Microstructural characterization was made using scanning electron microscope (SEM) and energy-dispersive spectroscopy (EDS). Cobalt release was found in 4 (1.1%) of 354 items. All these had a dark appearance. SEM/EDS was performed on the four dark appearing items which showed tin-cobalt plating on these. This study showed that only a minority of inexpensive jewellery purchased in Denmark released cobalt when analysed with the cobalt spot test. As fashion trends fluctuate and we found cobalt release from dark appearing jewellery, cobalt release from consumer items should be monitored in the future. Industries may not be fully aware of the potential cobalt allergy problem.

  15. Cosine (Cobalt Silicide Growth Through Nitrogen-Induced Epitaxy) Process For Epitaxial Cobalt Silicide Formation For High Performance Sha

    DOEpatents

    Lim, Chong Wee; Shin, Chan Soo; Gall, Daniel; Petrov, Ivan Georgiev; Greene, Joseph E.

    2004-09-28

    A method for forming an epitaxial cobalt silicide layer on a MOS device includes sputter depositing cobalt in an ambient to form a first layer of cobalt suicide on a gate and source/drain regions of the MOS device. Subsequently, cobalt is sputter deposited again in an ambient of argon to increase the thickness of the cobalt silicide layer to a second thickness.

  16. trans-Bis[4-amino-3,5-bis­(2-pyrid­yl)-4H-1,2,4-triazole-κN 3]diaqua­cobalt(II) bis­(3-carb­oxy-5-nitro­benzoate)

    PubMed Central

    Wang, Xi; Shao, Chun-Fu; Li, Cheng-Peng

    2011-01-01

    The title complex, [Co(C12H10N6)2(H2O)2](C8H4NO6)2, is composed of a mononuclear cobalt(II) cation and two 3-carb­oxy-5-nitro­benzoate anions for charge balance. In the cation, the CoII atom is six-coordinated in a distorted octa­hedral geometry. It bonds to two O atoms of two water mol­ecules, and two pairs of N atoms from two 4-amino-3,5-bis­(2-pyrid­yl)-4H-1,2,4-triazole mol­ecules, which behave as bidentate chelating ligands. There are intra­molecular N—H⋯N hydrogen bonds in the cation. In the crystal, there are a number of inter­molecular N—H⋯O and O—H⋯O hydrogen bonds, as well as inter­molecular π–π stacking inter­actions [centroid–centroid distances = 3.657 (2) and 3.847 (2) Å], that link the mol­ecules into two-dimensional networks lying parallel to the ab plane. The presence of C—H⋯O inter­actions leads to the formation of a three-dimensional network. PMID:22058688

  17. Electrosynthesis of highly transparent cobalt oxide water oxidation catalyst films from cobalt aminopolycarboxylate complexes.

    PubMed

    Bonke, Shannon A; Wiechen, Mathias; Hocking, Rosalie K; Fang, Xi-Ya; Lupton, David W; MacFarlane, Douglas R; Spiccia, Leone

    2015-04-24

    Efficient catalysis of water oxidation represents one of the major challenges en route to efficient sunlight-driven water splitting. Cobalt oxides (CoOx ) have been widely investigated as water oxidation catalysts, although the incorporation of these materials into photoelectrochemical devices has been hindered by a lack of transparency. Herein, the electrosynthesis of transparent CoOx catalyst films is described by utilizing cobalt(II) aminopolycarboxylate complexes as precursors to the oxide. These complexes allow control over the deposition rate and morphology to enable the production of thin, catalytic CoOx films on a conductive substrate, which can be exploited in integrated photoelectrochemical devices. Notably, under a bias of 1.0 V (vs. Ag/AgCl), the film deposited from [Co(NTA)(OH2 )2 ](-) (NTA=nitrilotriacetate) decreased the transmission by only 10 % at λ=500 nm, but still generated >80 % of the water oxidation current produced by a [Co(OH2 )6 ](2+) -derived oxide film whose transmission was only 40 % at λ=500 nm.

  18. A triclinic polymorph of catena-poly[[bis-(N,N-dimethyl-formamide-κO)cobalt(II)]-di-μ-1,5-dicyanamido-κ(4)N(1):N(5)].

    PubMed

    Meng, S C

    2012-11-01

    The title compound, [Co(C(2)N(3))(2)(C(3)H(7)NO)(2)](n), is a triclinic polymorph of the previously reported monoclinic structure [Tong et al. (2003 ▶). Acta Cryst. E59, m405-m407]. The Co(II) ion lies on an inversion centre and adopts an almost regular octa-hedral N(4)O(2) coordination geometry. Adjacent Co(II) atoms are connected by two bridging dicyanamide ligands, resulting in the formation of neutral chains parallel to the b axis. The title complex is isotypic with the Mn(II) analogue but not with the Ni(II) analogue.

  19. Cobalt and antimony: genotoxicity and carcinogenicity.

    PubMed

    De Boeck, Marlies; Kirsch-Volders, Micheline; Lison, Dominique

    2003-12-10

    The purpose of this review is to summarise the data concerning genotoxicity and carcinogenicity of Co and Sb. Both metals have multiple industrial and/or therapeutical applications, depending on the considered species. Cobalt is used for the production of alloys and hard metal (cemented carbide), diamond polishing, drying agents, pigments and catalysts. Occupational exposure to cobalt may result in adverse health effects in different organs or tissues. Antimony trioxide is primarily used as a flame retardant in rubber, plastics, pigments, adhesives, textiles, and paper. Antimony potassium tartrate has been used worldwide as an anti-shistosomal drug. Pentavalent antimony compounds have been used for the treatment of leishmaniasis. Co(II) ions are genotoxic in vitro and in vivo, and carcinogenic in rodents. Co metal is genotoxic in vitro. Hard metal dust, of which occupational exposure is linked to an increased lung cancer risk, is proven to be genotoxic in vitro and in vivo. Possibly, production of active oxygen species and/or DNA repair inhibition are mechanisms involved. Given the recently provided proof for in vitro and in vivo genotoxic potential of hard metal dust, the mechanistic evidence of elevated production of active oxygen species and the epidemiological data on increased cancer risk, it may be advisable to consider the possibility of a new evaluation by IARC. Both trivalent and pentavalent antimony compounds are generally negative in non-mammalian genotoxicity tests, while mammalian test systems usually give positive results for Sb(III) and negative results for Sb(V) compounds. Assessment of the in vivo potential of Sb2O3 to induce chromosome aberrations (CA) gave conflicting results. Animal carcinogenicity data were concluded sufficient for Sb2O3 by IARC. Human carcinogenicity data is difficult to evaluate given the frequent co-exposure to arsenic. Possible mechanisms of action, including potential to produce active oxygen species and to interfere with

  20. Polytypic transformations during the thermal decomposition of cobalt hydroxide and cobalt hydroxynitrate

    SciTech Connect

    Ramesh, Thimmasandra Narayan

    2010-06-15

    The isothermal decomposition of cobalt hydroxide and cobalt hydroxynitrate at different intervals of temperature leads to the formation of Co{sub 3}O{sub 4}. The phase evolution during the decomposition process was monitored using powder X-ray diffraction. The transformation of cobalt hydroxide to cobalt oxide occurs via three phase mixture while cobalt hydroxynitrate to cobalt oxide occurs through a two phase mixture. The nature of the sample and its preparation method controls the decomposition mechanism. The comparison of topotactical relationship between the precursors to the decomposed product has been reported in relation to polytypism. - Graphical abstract: Isothermal thermal decomposition studies of cobalt hydroxide and cobalt hydroxynitrate at different intervals of temperature show the metastable phase formed prior to Co{sub 3}O{sub 4} phase.