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Sample records for monocapped trisdioxime mnii

  1. Novel Biscapped and Monocapped Tris(dioxime) Mn(II) Complexes

    Science.gov (United States)

    Hsieh, Wen-Yuan; Liu, Shuang

    2008-01-01

    This report describes the synthesis and characterization of a series of novel biscapped and monocapped tris(dioxime) Mn(II) complexes: [Mn(dioxime)3(BR)2] and [Mn(dioxime)3BR]+ (dioxime = cyclohexanedione dioxime (CDOH2) and 1,2-dimethylglyoxyl dioxime (DMGH2); R = Me, n-Bu, and Ph). All tris(dioxime) Mn(II) complexes have been characterized by elemental analysis, IR, UV/vis, cyclic voltammetry, ESI-MS, and in cases of [Mn(CDOH)3BPh]OH·CHCl3 and [Mn(CDO)(CDOH)2(BBu(OC2H5))2] by X-ray crystallography. It was found that the biscapped Mn(II) complexes [Mn(dioxime)3(BR)2] are not stable in the presence of water, and readily hydrolyze to form the monocapped cationic complexes [M(dioxime)3BR]+. This instability is most likely caused by mismatch between the size of Mn(II) and the coordination cavity of the biscapped tris(dioxime) ligands. In contrast, the monocapped cationic complexes [M(dioxime)3BR]+ are very stable in aqueous solution even in the presence of PDTA (1,2-diaminopropane-N,N,N’,N’-tetraacetic acid) due to their kinetic inertness imposed by the monocapped tris(dioxime) chelators that are able to completely “wrap” Mn(II) into their N6 coordination cavity. [Mn(CDO)3BPh]OH has a distorted trigonal prismatic coordination geometry with the Mn(II) being bonded by six imine-N donors. The hydroxyl groups from three dioxime chelating arms form very strong intramolecular hydrogen bonds with the hydroxide counter ion so that the structure of [Mn(CDOH)3BPh]OH can be considered as the clathrochelate with the hydroxide counter ion as a “cap”. PMID:16780325

  2. Novel biscapped and monocapped tris(dioxime) Mn(II) complexes: x-ray crystal structure of the first cationic tris(dioxime) Mn(II) complex [Mn(CDOH)3BPh]OH (CDOH2= 1,2-cyclohexanedione dioxime).

    Science.gov (United States)

    Hsieh, Wen-Yuan; Liu, Shuang

    2006-06-26

    This report describes the synthesis and characterization of a series of novel biscapped and monocapped tris(dioxime) Mn(II) complexes [Mn(dioxime)3(BR)2] and [Mn(dioxime)3BR]+ (dioxime = cyclohexanedione dioxime (CDOH2) and 1,2-dimethylglyoxyl dioxime (DMGH(2)); R = Me, n-Bu, and Ph). All tris(dioxime) Mn(II) complexes have been characterized by elemental analysis, IR, UV/vis, cyclic voltammetry, ESI-MS, and, in the cases of [Mn(CDOH)3BPh]OH.CHCl3 and [Mn(CDO)(CDOH)2(BBu(OC2H5))2], X-ray crystallography. It was found that biscapped Mn(II) complexes [Mn(dioxime)3(BR)2] are not stable in the presence of water and readily hydrolyze to form monocapped cationic complexes [M(dioxime)3BR]+. This instability is most likely caused by mismatch between the size of Mn(II) and the coordination cavity of the biscapped tris(dioxime) ligands. In contrast, monocapped cationic complexes [M(dioxime)3BR]+ are very stable in aqueous solution even in the presence of PDTA (1,2-diaminopropane-N,N,N',N'-tetraacetic acid) because of the kinetic inertness imposed by the monocapped tris(dioxime) chelators that are able to completely "wrap" Mn(II) into their N6 coordination cavity. [Mn(CDO)3BPh]OH has a distorted trigonal prismatic coordination geometry, with the Mn(II) being bonded by six imine-N donors. The hydroxyl groups from three dioxime chelating arms form very strong intramolecular hydrogen bonds with the hydroxide counterion so that the structure of [Mn(CDOH)3BPh]OH can be considered as being the clathrochelate with the hydroxide counterion as a "cap".

  3. Kinetics of Mn(II) oxidation by spores of the marine Bacillus sp. SG-1

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    Toyoda, Kazuhiro; Tebo, Bradley M.

    2016-09-01

    The kinetics of Mn(II) oxidation by spores of the marine Bacillus sp. SG-1 was measured under controlled conditions of the initial Mn(II) concentration, spore concentration, chemical speciation, pH, O2, and temperature. Mn(II) oxidation experiments were performed with spore concentrations ranging from 0.7 to 11 × 109 spores/L, a pH range from 5.8 to 8.1, temperatures between 4 and 58 °C, a range of dissolved oxygen from 2 to 270 μM, and initial Mn(II) concentrations from 1 to 200 μM. The Mn(II) oxidation rates were directly proportional to the spore concentrations over these ranges of concentration. The Mn(II) oxidation rate increased with increasing initial Mn(II) concentration to a critical concentration, as described by the Michaelis-Menten model (Km = ca. 3 μM). Whereas with starting Mn(II) concentrations above the critical concentration, the rate was almost constant in low ionic solution (I = 0.05, 0.08). At high ionic solution (I = 0.53, 0.68), the rate was inversely correlated with Mn(II) concentration. Increase in the Mn(II) oxidation rate with the dissolved oxygen concentration followed the Michaelis-Menten model (Km = 12-19 μM DO) in both a HEPES-buffered commercial drinking (soft) water and in artificial and natural seawater. Overall, our results suggest that the mass transport limitations of Mn(II) ions due to secondary Mn oxide products accumulating on the spores cause a significant decrease of the oxidation rate at higher initial Mn(II) concentration on a spore basis, as well as in more concentrated ionic solutions. The optimum pH for Mn(II) oxidation was approximately 7.0 in low ionic solutions (I = 0.08). The high rates at the alkaline side (pH > 7.5) may suggest a contribution by heterogeneous reactions on manganese bio-oxides. The effect of temperature on the Mn(II) oxidation rate was studied in three solutions (500 mM NaCl, ASW, NSW solutions). Thermal denaturation occurred at 58 °C and spore germination was evident at 40 °C in all three

  4. Rapid reaction of nanomolar Mn(II) with superoxide radical in seawater and simulated freshwater

    Science.gov (United States)

    Hansard, S.P.; Easter, H.D.; Voelker, B.M.

    2011-01-01

    Superoxide radical (O2-) has been proposed to be an important participant in oxidation-reduction reactions of metal ions in natural waters. Here, we studied the reaction of nanomolar Mn(II) with O 2- in seawater and simulated freshwater, using chemiluminescence detection of O2- to quantify the effect of Mn(II) on the decay kinetics of O2-. With 3-24 nM added [Mn(II)] and superoxide could maintain a significant fraction of dissolved Mn in the +III oxidation state. ?? 2011 American Chemical Society.

  5. Mechanism of the catalytic ozonization of lignin in the presence of Mn(II) ions

    Science.gov (United States)

    Mitrofanova, A. N.; Khudoshin, A. G.; Lunin, V. V.

    2013-07-01

    The reaction between ozone and lignin in aqueous solutions catalyzed by Mn(II) ions is studied. The rate of destruction for aromatic structures of lignin is found to increase in the presence of Mn(II) ions. However, the greatest catalytic effect is observed upon the transformation of aliphatic acids that are difficult to oxidize with ozone. The introduction of catalyst raises the total consumption of ozone from 3 to 7 mol per each structural unit of lignin. A scheme is proposed for the transformation of phenol fragments of lignin using ozone with the participation of Mn(II) ions: at the initial stage, we observe the ozone oxidation of lignin and Mn(II) to Mn(III) ions stabilized with products of lignin oxidation and accompanied by the formation of chelate complexes, and the Mn(III) chelate complexes act as low-molecular mediators, attacking phenol structures and initiating radical processes.

  6. Bioelectrochemical Mn(II) leaching from manganese ore by Lactococcus lactis SK071115.

    Science.gov (United States)

    Jeon, Bo Young; Park, Doo Hyun

    2011-02-01

    L. lactis sk071115 has been shown to grow more actively and generate lower levels of lactate in glucose-defined medium with nitrate than in medium with Mn(IV). By adding Mn(IV) to a L. lactis culture, lactate production was relatively reduced in combination with Mn(II) production, but cell mass production levels did not increase. Both cell-free extract and intact L. lactis cells reacted electrochemically with Mn(IV) but did not react with Mn(II) upon cyclic voltammetry using neutral red (NR) as an electron mediator. A modified graphite felt cathode with NR (NR-cathode) was employed to induce electrochemical reducing equivalence for bacterial metabolism. Cell-free L. lactis extract catalyzed the reduction of Mn(IV) to Mn(II) under both control and electrochemical reduction conditions; however, the levels of Mn(II) generated under electrochemical reduction conditions were approximately 4 times those generated under control conditions. The levels of Mn(II) generated by the catalysis of L. lactis immobilized in the NR-cathode (L-NR-cathode) under electrochemical reduction conditions were more than 4 times that generated under control conditions. Mn(II) production levels were increased by approximately 2.5 and 4.5 times by the addition of citrate to the reactant under control and electrochemical reduction conditions, respectively. The cumulative Mn(II) produced from manganese ore by catalysis of the L-NR-cathode for 30 days reached levels of approximately 3,800 and 16,000 mg/l under control and electrochemical reduction conditions, respectively. In conclusion, the electrochemical reduction reaction generated by the NR-cathode activated the biochemical reduction of Mn(IV) to Mn(II) by L. lactis.

  7. Mn(II) binding to human serum albumin: a ¹H-NMR relaxometric study.

    Science.gov (United States)

    Fanali, Gabriella; Cao, Yu; Ascenzi, Paolo; Fasano, Mauro

    2012-12-01

    Human serum albumin (HSA) displays several metal binding sites, participating to essential and toxic metal ions disposal and transport. The major Zn(II) binding site, called Site A, is located at the I/II domain interface, with residues His67, Asn99, His247, and Asp249 contributing with five donor atoms to the metal ion coordination. Additionally, one water molecule takes part of the octahedral coordination geometry. The occurrence of the metal-coordinated water molecule allows the investigation of the metal complex geometry by water (1)H-NMR relaxation, provided that the diamagnetic Zn(II) is replaced by the paramagnetic Mn(II). Here, the (1)H-NMR relaxometric study of Mn(II) binding to HSA is reported. Mn(II) binding to HSA is modulated by Zn(II), pH, and myristate through competitive inhibition and allosteric mechanisms. The body of results indicates that the primary binding site of Zn(II) corresponds to the secondary binding site of Mn(II), i.e. the multimetal binding site A. Excess Zn(II) completely displaces Mn(II) from its primary site suggesting that the primary Mn(II) site corresponds to the secondary Zn(II) site. This uncharacterized site is functionally-linked to FA1; moreover, metal ion binding is modulated by myristate and pH. Noteworthy, water (1)H-NMR relaxometry allowed a detailed analysis of thermodynamic properties of HSA-metal ion complexes.

  8. Structural response of phyllomanganates to wet aging and aqueous Mn(II)

    Science.gov (United States)

    Hinkle, Margaret A. G.; Flynn, Elaine D.; Catalano, Jeffrey G.

    2016-11-01

    Naturally occurring Mn(IV/III) oxides are often formed through microbial Mn(II) oxidation, resulting in reactive phyllomanganates with varying Mn(IV), Mn(III), and vacancy contents. Residual aqueous Mn(II) may adsorb in the interlayer of phyllomanganates above vacancies in their octahedral sheets. The potential for interlayer Mn(II)-layer Mn(IV) comproportionation reactions and subsequent formation of structural Mn(III) suggests that aqueous Mn(II) may cause phyllomanganate structural changes that alters mineral reactivity or trace metal scavenging. Here we examine the effects of aging phyllomanganates with varying initial vacancy and Mn(III) content in the presence and absence of dissolved Mn(II) at pH 4 and 7. Three phyllomanganates were studied: two exhibiting turbostratic layer stacking (δ-MnO2 with high vacancy content and hexagonal birnessite with both vacancies and Mn(III) substitutions) and one with rotationally ordered layer stacking (triclinic birnessite containing predominantly Mn(III) substitutions). Structural analyses suggest that during aging at pH 4, Mn(II) adsorbs above vacancies and promotes the formation of phyllomanganates with rotationally ordered sheets and mixed symmetries arranged into supercells, while structural Mn(III) undergoes disproportionation. These structural changes at pH 4 correlate with reduced Mn(II) uptake onto triclinic and hexagonal birnessite after 25 days relative to 48 h of reaction, indicating that phyllomanganate reactivity decreases upon aging with Mn(II), or that recrystallization processes involving Mn(II) uptake occur over 25 days. At pH 7, Mn(II) adsorbs and causes limited structural effects, primarily increasing sheet stacking in δ-MnO2. These results show that aging-induced structural changes in phyllomanganates are affected by aqueous Mn(II), pH, and initial solid-phase Mn(III) content. Such restructuring likely alters manganese oxide reactions with other constituents in environmental and geologic systems

  9. Extracellular haem peroxidases mediate Mn(II) oxidation in a marine Roseobacter bacterium via superoxide production.

    Science.gov (United States)

    Andeer, Peter F; Learman, Deric R; McIlvin, Matt; Dunn, James A; Hansel, Colleen M

    2015-10-01

    Manganese (Mn) oxides are among the strongest sorbents and oxidants in environmental systems. A number of biotic and abiotic pathways induce the oxidation of Mn(II) to Mn oxides. Here, we use a combination of proteomic analyses and activity assays, to identify the enzyme(s) responsible for extracellular superoxide-mediated Mn oxide formation by a bacterium within the ubiquitous Roseobacter clade. We show that animal haem peroxidases (AHPs) located on the outer membrane and within the secretome are responsible for Mn(II) oxidation. These novel peroxidases have previously been implicated in direct Mn(II) oxidation by phylogenetically diverse bacteria. Yet, we show that in this Roseobacter species, AHPs mediate Mn(II) oxidation not through a direct reaction but by producing superoxide and likely also by degrading hydrogen peroxide. These findings point to a eukaryotic-like oscillatory oxidative-peroxidative enzymatic cycle by these AHPs that leads to Mn oxide formation by this organism. AHP expression appears unaffected by Mn(II), yet the large energetic investment required to produce and secrete these enzymes points to an as yet unknown physiological function. These findings are further evidence that bacterial peroxidases and secreted enzymes, in general, are unappreciated controls on the cycling of metals and reactive oxygen species (ROS), and by extension carbon, in natural systems. © 2015 Society for Applied Microbiology and John Wiley & Sons Ltd.

  10. Mechanisms of Mn(II) catalytic oxidation on ferrihydrite surfaces and the formation of manganese (oxyhydr)oxides

    Science.gov (United States)

    Lan, Shuai; Wang, Xiaoming; Xiang, Quanjun; Yin, Hui; Tan, Wenfeng; Qiu, Guohong; Liu, Fan; Zhang, Jing; Feng, Xionghan

    2017-08-01

    Oxidation of Mn(II) is an important process that controls the mobility and bioavailability of Mn, as well as the formation of Mn (oxyhydr)oxides in natural systems. It was found that the surfaces of minerals, such as iron (oxyhydr)oxides, can accelerate Mn(II) oxidation to a certain degree, but the underlying mechanism has not been clearly understood. This study explores the reaction pathways and mechanisms of Mn(II) oxidation on ferrihydrite surfaces at neutral pH, commonly found in natural environments, by comparisons with montmorillonite, amorphous Al(OH)3, goethite, and magnetite using macroscopic experiments and spectroscopic analyses. Results show that when Mn(II) concentrations are below 4 mM, macroscopic Mn(II) adsorption on the three iron (oxyhydr)oxide surfaces conforms well to the Langmuir equation, with ferrihydrite showing the highest adsorption capacity. With Mn(II) concentrations ranging within 6-24 mM, the adsorbed Mn(II) is mainly oxidized into manganite (γ-MnOOH) and/or feitknechtite (β-MnOOH) by dissolved O2, and Mn(II) removal on a unit mass basis in the presence of magnetite is the highest compared with ferrihydrite and goethite. Ferrihydrite, a semiconductor material, shows stronger catalytic ability for Mn(II) oxidation on the same surface area than insulator minerals (i.e., montmorillonite and amorphous Al(OH)3). Additionally, the products of Mn(II) oxidation in the presence of semiconductor iron (oxyhydr)oxides (i.e., ferrihydrite, goethite, or magnetite) at the same Fe/Mn molar ratio include both manganite and a small amount of Mn(IV) minerals, and the Mn average oxidation states (Mn AOSs) of these products follow the order: magnetite > goethite > ferrihydrite. Magnetite and goethite, with relatively smaller SSAs and lower band gap energies, exhibit greater catalysis for Mn(II) oxidation than ferrihydrite at the same Fe/Mn ratio, which goes against the conventional interfacial effect and is related to the electrochemical properties. Thus

  11. Mn(II) Oxidation by the Multicopper Oxidase Complex Mnx: A Binuclear Activation Mechanism.

    Science.gov (United States)

    Soldatova, Alexandra V; Tao, Lizhi; Romano, Christine A; Stich, Troy A; Casey, William H; Britt, R David; Tebo, Bradley M; Spiro, Thomas G

    2017-08-23

    The bacterial protein complex Mnx contains a multicopper oxidase (MCO) MnxG that, unusually, catalyzes the two-electron oxidation of Mn(II) to MnO2 biomineral, via a Mn(III) intermediate. Although Mn(III)/Mn(II) and Mn(IV)/Mn(III) reduction potentials are expected to be high, we find a low reduction potential, 0.38 V (vs Normal Hydrogen Electrode, pH 7.8), for the MnxG type 1 Cu(2+), the electron acceptor. Indeed the type 1 Cu(2+) is not reduced by Mn(II) in the absence of molecular oxygen, indicating that substrate oxidation requires an activation step. We have investigated the enzyme mechanism via electronic absorption spectroscopy, using chemometric analysis to separate enzyme-catalyzed MnO2 formation from MnO2 nanoparticle aging. The nanoparticle aging time course is characteristic of nucleation and particle growth; rates for these processes followed expected dependencies on Mn(II) concentration and temperature, but exhibited different pH optima. The enzymatic time course is sigmoidal, signaling an activation step, prior to turnover. The Mn(II) concentration and pH dependence of a preceding lag phase indicates weak Mn(II) binding. The activation step is enabled by a pKa > 8.6 deprotonation, which is assigned to Mn(II)-bound H2O; it induces a conformation change (consistent with a high activation energy, 106 kJ/mol) that increases Mn(II) affinity. Mnx activation is proposed to decrease the Mn(III/II) reduction potential below that of type 1 Cu(II/I) by formation of a hydroxide-bridged binuclear complex, Mn(II)(μ-OH)Mn(II), at the substrate site. Turnover is found to depend cooperatively on two Mn(II) and is enabled by a pKa 7.6 double deprotonation. It is proposed that turnover produces a Mn(III)(μ-OH)2Mn(III) intermediate that proceeds to the enzyme product, likely Mn(IV)(μ-O)2Mn(IV) or an oligomer, which subsequently nucleates MnO2 nanoparticles. We conclude that Mnx exploits manganese polynuclear chemistry in order to facilitate an otherwise difficult

  12. Mn(II) oxidation by an ascomycete fungus is linked to superoxide production during asexual reproduction

    Energy Technology Data Exchange (ETDEWEB)

    Hansel, C. M.; Zeiner, C. A.; Santelli, C. M.; Webb, S. M.

    2012-07-16

    Manganese (Mn) oxides are among the most reactive minerals within the environment, where they control the bioavailability of carbon, nutrients, and numerous metals. Although the ability of microorganisms to oxidize Mn(II) to Mn(III/IV) oxides is scattered throughout the bacterial and fungal domains of life, the mechanism and physiological basis for Mn(II) oxidation remains an enigma. Here, we use a combination of compound-specific chemical assays, microspectroscopy, and electron microscopy to show that a common Ascomycete filamentous fungus, Stilbella aciculosa, oxidizes Mn(II) to Mn oxides by producing extracellular superoxide during cell differentiation. The reactive Mn oxide phase birnessite and the reactive oxygen species superoxide and hydrogen peroxide are colocalized at the base of asexual reproductive structures. Mn oxide formation is not observed in the presence of superoxide scavengers (e.g., Cu) and inhibitors of NADPH oxidases (e.g., diphenylene iodonium chloride), enzymes responsible for superoxide production and cell differentiation in fungi. Considering the recent identification of Mn(II) oxidation by NADH oxidase-based superoxide production by a common marine bacterium (Roseobacter sp.), these results introduce a surprising homology between some prokaryotic and eukaryotic organisms in the mechanisms responsible for Mn(II) oxidation, where oxidation appears to be a side reaction of extracellular superoxide production. Finally, given the versatility of superoxide as a redox reactant and the widespread ability of fungi to produce superoxide, this microbial extracellular superoxide production may play a central role in the cycling and bioavailability of metals (e.g., Hg, Fe, Mn) and carbon in natural systems.

  13. Mn(II) oxidation by an ascomycete fungus is linked to superoxide production during asexual reproduction.

    Science.gov (United States)

    Hansel, Colleen M; Zeiner, Carolyn A; Santelli, Cara M; Webb, Samuel M

    2012-07-31

    Manganese (Mn) oxides are among the most reactive minerals within the environment, where they control the bioavailability of carbon, nutrients, and numerous metals. Although the ability of microorganisms to oxidize Mn(II) to Mn(III/IV) oxides is scattered throughout the bacterial and fungal domains of life, the mechanism and physiological basis for Mn(II) oxidation remains an enigma. Here, we use a combination of compound-specific chemical assays, microspectroscopy, and electron microscopy to show that a common Ascomycete filamentous fungus, Stilbella aciculosa, oxidizes Mn(II) to Mn oxides by producing extracellular superoxide during cell differentiation. The reactive Mn oxide phase birnessite and the reactive oxygen species superoxide and hydrogen peroxide are colocalized at the base of asexual reproductive structures. Mn oxide formation is not observed in the presence of superoxide scavengers (e.g., Cu) and inhibitors of NADPH oxidases (e.g., diphenylene iodonium chloride), enzymes responsible for superoxide production and cell differentiation in fungi. Considering the recent identification of Mn(II) oxidation by NADH oxidase-based superoxide production by a common marine bacterium (Roseobacter sp.), these results introduce a surprising homology between some prokaryotic and eukaryotic organisms in the mechanisms responsible for Mn(II) oxidation, where oxidation appears to be a side reaction of extracellular superoxide production. Given the versatility of superoxide as a redox reactant and the widespread ability of fungi to produce superoxide, this microbial extracellular superoxide production may play a central role in the cycling and bioavailability of metals (e.g., Hg, Fe, Mn) and carbon in natural systems.

  14. Switching of the magnetocaloric effect of Mn(II) glycolate by water molecules.

    Science.gov (United States)

    Chen, Yan-Cong; Guo, Fu-Sheng; Liu, Jun-Liang; Leng, Ji-Dong; Vrábel, Peter; Orendáč, Martin; Prokleška, Jan; Sechovský, Vladimír; Tong, Ming-Liang

    2014-03-10

    The transformation of Mn(II) glycolates (glc) between the three-dimensional coordination polymer [Mn(glc)2]n (1) and discrete mononuclear phase [Mn(glc)2 (H2O)2] (2) can be reversibly switched by water molecules, which dramatically change the magnetocaloric effect (MCE) of Mn(II) glycolates from the maximum of 6.9 J kg(-1)  K(-1) in 1 to 60.3 J kg(-1)  K(-1) in 2. This case example reveals that the effect of magnetic coupling on MCE plays a dominant role over that of other factors such as magnetic density for 3d-type magnetic refrigerants.

  15. Hydroxy double salts intercalated with Mn(II) complexes as potential contrast agents

    Science.gov (United States)

    Jin, Miao; Li, Wanjing; Spillane, Dominic E. M.; Geraldes, Carlos F. G. C.; Williams, Gareth R.; Bligh, S. W. Annie

    2016-03-01

    A series of Mn(II) aminophosphonate complexes were successfully synthesized and intercalated into the hydroxy double salt [Zn5(OH)8]Cl2·yH2O. Complex incorporation led to an increase in the interlayer spacing from 7.8 to 10-12 Å. Infrared spectroscopy showed the presence of the characteristic vibration peaks of the Mn(II) complexes in the intercalates' spectra, indicating successful incorporation. The complex-loaded composites had somewhat lower proton relaxivities than the pure complexes. Nevertheless, these intercalates may have use as MRI contrast agents for patients with poor kidney function, where traditional Gd(III)-based contrast agents cause severe renal failure.

  16. Removal of Mn(II) from the acid mine wastewaters using coal fired bottom ash

    Science.gov (United States)

    Mahidin, M.; Sulaiman, T. N.; Muslim, A.; Gani, A.

    2017-06-01

    Acid mine wastewater (AMW), the wastewater from mining activities which has low pH about 3-5 and contains hazardous heavy metals such as Cu, Fe, Mn, Zn, Pb, etc. Those heavy metals pollution is of prime concern from the environmental view point. Among the heavy metals, Mn occupies the third position in the AMW from one the iron ore mining company in Aceh, Indonesia. In this study, the possibility use of bottom ash from coal fired boiler of steam power plants for the removal of Mn(II) in AMW has been investigated. Experimental has been conducted as follows. Activation of bottom ash was done both by physical and chemical treatments through heating at 270 °C and washing with NaOH activator 0.5 and 1 M. Adsorption test contains two parts observation; preliminary and primary experiments. Preliminary study is addressed to select the best condition of three independent variables i.e.: pH of AMW (3 & 7), bottom ash particle size (40, 60 & 100 mesh) and initial Mn(II) concentrations (100 & 600 mg/l). AMW used was synthetics wastewater. It was found that the best value for NaOH is 1 M, pH is 7, particle size is 100 meshes and initial Mn(II) concentration is 600 mg/l from the adsorption efficiency point of view. The maximum adsorption capacity (q e) is 63.7 mg/g with the efficiency of 85%.

  17. Cu(II) and Zn(II) ions alter the dynamics and distribution of Mn(II) in cultured chick glial cells

    Energy Technology Data Exchange (ETDEWEB)

    Wedler, F.C.; Ley, B.W. (Dept. of Molecular Cell Biology, Pennsylvania State University, University Park (USA))

    1990-12-01

    Previous studies revealed that Mn(II) is accumulated in cultured glial cells to concentrations far above those present in whole brain or in culture medium. The data indicated that Mn(II) moves across the plasma membrane into the cytoplasm by facilitated diffusion or counter-ion transport with Ca(II), then into mitochondria by active transport. The fact that 1-10 microM Mn(II) ions activate brain glutamine synthetase makes important the regulation of Mn(II) transport in the CNS. Since Cu(II) and Zn(II) caused significant changes in the accumulation of Mn(II) by glia, the mechanisms by which these ions alter the uptake and efflux of Mn(II) ions has been investigated systematically under chemically defined conditions. The kinetics of (54MN)-Mn(II) uptake and efflux were determined and compared under four different sets of conditions: no adducts, Cu(II) or Zn(II) added externally, and with cells preloaded with Cu(II) or Zn(II) in the presence and absence of external added metal ions. Zn(II) ions inhibit the initial velocity of Mn(II) uptake, increase total Mn(II) accumulated, but do not alter the rate or extent Mn(II) efflux. Cu(II) ions increase both the initial velocity and the net Mn(II) accumulated by glia, with little effect on rate or extent of Mn(II) efflux. These results predict that increases in Cu(II) or Zn(II) levels may also increase the steady-state levels of Mn(II) in the cytoplasmic fraction of glial cells, which may in turn alter the activity of Mn(II)-sensitive enzymes in this cell compartment.

  18. Acclimation of a marine microbial consortium for efficient Mn(II) oxidation and manganese containing particle production

    Energy Technology Data Exchange (ETDEWEB)

    Zhou, Hao, E-mail: zhouhao@dlut.edu.cn [Key Laboratory of Industrial Ecology and Environmental Engineering (Ministry of Education), School of Food and Environment, Dalian University of Technology, Panjin 124221 (China); Pan, Haixia [Key Laboratory of Industrial Ecology and Environmental Engineering (Ministry of Education), School of Food and Environment, Dalian University of Technology, Panjin 124221 (China); Xu, Jianqiang [School of Life Science and Medicine, Dalian University of Technology, Panjin 124221 (China); Xu, Weiping; Liu, Lifen [Key Laboratory of Industrial Ecology and Environmental Engineering (Ministry of Education), School of Food and Environment, Dalian University of Technology, Panjin 124221 (China)

    2016-03-05

    Highlights: • An efficient Mn(II) oxidation marine sediments microbial community was obtained. • High-throughput sequencing indicated new Mn(II) oxidation associated genus. • Na{sub 3}MnPO{sub 4}CO{sub 3} and MnCO{sub 3} were synthesized by the consortium. • Consortium exhibited Mn(II) oxidation performance over a range of harsh conditions. - Abstract: Sediment contamination with metals is a widespread concern in the marine environment. Manganese oxidizing bacteria (MOB) are extensively distributed in various environments, but a marine microbial community containing MOB is rarely reported. In this study, a consortium of marine metal-contaminated sediments was acclimated using Mn(II). The shift in community structure was determined through high-throughput sequencing. In addition, the consortium resisted several harsh conditions, such as toxic metals (1 mM Cu(II) and Fe(III)), and exhibited high Mn(II) oxidation capacities even the Mn(II) concentration was up to 5 mM. Meanwhile, biogenic Mn containing particles were characterized by scanning electron microscope (SEM), X-ray powder diffraction (XRD), and N{sub 2} adsorption/desorption. Dye removal performance of the Mn containing particles was assayed using methylene blue, and 20.8 mg g{sup −1} adsorption capacity was obtained. Overall, this study revealed several new genera associated with Mn(II) oxidation and rare biogenic Na{sub 3}MnPO{sub 4}CO{sub 3.} Results suggested the complexity of natural microbe-mediated Mn transformation.

  19. Generic tags for Mn(ii) and Gd(iii) spin labels for distance measurements in proteins.

    Science.gov (United States)

    Yang, Yin; Gong, Yan-Jun; Litvinov, Aleksei; Liu, Hong-Kai; Yang, Feng; Su, Xun-Cheng; Goldfarb, Daniella

    2017-09-28

    High-affinity chelating tags for Gd(iii) and Mn(ii) ions that provide valuable high-resolution distance restraints for biomolecules were used as spin labels for double electron-electron resonance (DEER) measurements. The availability of a generic tag that can bind both metal ions and provide a narrow and predictable distance distribution for both ions is attractive owing to their different EPR-related characteristics. Herein we introduced two paramagnetic tags, 4PSPyMTA and 4PSPyNPDA, which are conjugated to cysteine residues through a stable thioether bond, forming a short and, depending on the metal ion coordination mode, a rigid tether with the protein. These tags exhibit high affinity for both Mn(ii) and Gd(iii) ions. The DEER performance of the 4PSPyMTA and 4PSPyNPDA tags, in complex with Gd(iii) or Mn(ii), was evaluated for three double cysteine mutants of ubiquitin, and the Gd(iii)-Gd(iii) and Mn(ii)-Mn(ii) distance distributions they generated were compared. All three Gd(iii) complexes of the ubiquitin-PyMTA and ubiquitin-PyNPDA conjugates produced similar and expected distance distributions. In contrast, significant variations in the maxima and widths of the distance distributions were observed for the Mn(ii) analogs. Furthermore, whereas PyNPDA-Gd(iii) and PyNPDA-Mn(ii) delivered similar distance distributions, appreciable differences were observed for two mutants with PyMTA, with the Mn(ii) analog exhibiting a broader distance distribution and shorter distances. ELDOR (electron-electron double resonance)-detected NMR measurements revealed some distribution in the Mn(ii) coordination environment for the protein conjugates of both tags but not for the free tags. The broader distance distributions generated by 4PSPyMTA-Mn(ii), as compared with Gd(iii), were attributed to the distributed location of the Mn(ii) ion within the PyMTA chelate owing to its smaller size and lower coordination number that leave the pyridine nitrogen uncoordinated. Accordingly, in

  20. Direct measurement of the Mn(II) hydration state in metal complexes and metalloproteins through 17O NMR line widths.

    Science.gov (United States)

    Gale, Eric M; Zhu, Jiang; Caravan, Peter

    2013-12-11

    Here we describe a simple method to estimate the inner-sphere hydration state of the Mn(II) ion in coordination complexes and metalloproteins. The line width of bulk H2(17)O is measured in the presence and absence of Mn(II) as a function of temperature, and transverse (17)O relaxivities are calculated. It is demonstrated that the maximum (17)O relaxivity is directly proportional to the number of inner-sphere water ligands (q). Using a combination of literature data and experimental data for 12 Mn(II) complexes, we show that this method provides accurate estimates of q with an uncertainty of ±0.2 water molecules. The method can be implemented on commercial NMR spectrometers working at fields of 7 T and higher. The hydration number can be obtained for micromolar Mn(II) concentrations. We show that the technique can be extended to metalloproteins or complex:protein interactions. For example, Mn(II) binds to the multimetal binding site A on human serum albumin with two inner-sphere water ligands that undergo rapid exchange (1.06 × 10(8) s(-1) at 37 °C). The possibility of extending this technique to other metal ions such as Gd(III) is discussed.

  1. Mn(II) complexes of different nuclearity: synthesis, characterization and catecholase-like activity.

    Science.gov (United States)

    Chakraborty, Prateeti; Majumder, Ishani; Banu, Kazi Sabnam; Ghosh, Bipinbihari; Kara, Hulya; Zangrando, Ennio; Das, Debasis

    2016-01-14

    Two "end-off" compartmental ligands, 2-formyl-4-chloro-6-N-ethylmorpholine-iminomethyl-phenol (HL1) and 2-formyl-4-methyl-6-N-ethylpyrrolidine-iminomethyl-phenol (HL2) have been designed and three complexes of Mn(ii), one mono-, one di- and a polynuclear, namely Mn(L1)(SCN)2(H2O)] (), [Mn2(L1)(OAc)2](BPh4)] (), and [Mn2(L2)(OAc)2(dca)]n () have been synthesized and structurally characterized. Variable temperature magnetic studies of and have been performed and data analyses reveal that Mn centers are antiferromagnetic coupled with J = -9.15 cm(-1) and J = -46.89, respectively. Catecholase activity of all the complexes has been investigated using 3,5-di-tert-butyl catechol (3,5-DTBC). All are highly active and the activity order on the basis of the kcat value is > > . In order to unveil whether the metal centered redox participation or the radical pathway is responsible for the catecholase-like activity of the complexes, detailed EPR and cyclic voltammetric (CV) studies have been performed. In addition to the six-line EPR spectrum characteristic to Mn(ii), an additional peak at g ∼ 2 is observed when the EPR study is done with the mixture of 3,5-DTBC and the catalyst, suggesting the formation of an organic radical, most likely ligand centered. The CV experiment with the mixture of 3,5-DTBC and the catalyst reveals ligand centered reduction rather than reduction of Mn(ii) to Mn(i). It is thus inferred that complexes show catecholase-like activity due to radical generation.

  2. Structural alteration of hexagonal birnessite by aqueous Mn(II): Impacts on Ni(II) sorption

    Energy Technology Data Exchange (ETDEWEB)

    Lefkowitz, Joshua P.; Elzinga, Evert J.

    2017-09-01

    We studied the impacts of aqueous Mn(II) (1 mM) on the sorption of Ni(II) (200 μM) by hexagonal birnessite (0.1 g L- 1) at pH 6.5 and 7.5 with batch experiments and XRD, ATR-FTIR and Ni K-edge EXAFS analyses. In the absence of Mn(II)aq, sorbed Ni(II) was coordinated predominantly as triple corner-sharing complexes at layer vacancies at both pH values. Introduction of Mn(II)aq into Ni(II)-birnessite suspensions at pH 6.5 caused Ni(II) desorption and led to the formation of edge-sharing Ni(II) complexes. This was attributed to competitive displacement of Ni(II) from layer vacancies by either Mn(II) or by Mn(III) formed through interfacial Mn(II)-Mn(IV) comproportionation, and/or incorporation of Ni(II) into the birnessite lattice promoted by Mn(II)-catalyzed recrystallization of the sorbent. Similar to Mn(II)aq, the presence of HEPES or MES caused the formation of edge-sharing Ni(II) sorption complexes in Ni(II)-birnessite suspensions, which was attributed to partial reduction of the sorbent by the buffers. At pH 7.5, interaction with aqueous Mn(II) caused reductive transformation of birnessite into secondary feitknechtite that incorporated Ni(II), enhancing removal of Ni(II) from solution. These results demonstrate that reductive alteration of phyllomanganates may significantly affect the speciation and solubility of Ni(II) in anoxic and suboxic environments.

  3. Mn(II) Oxidation in Fenton and Fenton Type Systems: Identification of Reaction Efficiency and Reaction Products.

    Science.gov (United States)

    van Genuchten, Case M; Peña, Jasquelin

    2017-03-07

    Efficient and low-cost methods of removing aqueous Mn(II) are required to improve the quality of impacted groundwater supplies. In this work, we show that Fe(0) electrocoagulation (EC) permits the oxidative removal of Mn(II) from solution by reaction with the reactive oxidant species produced through Fe(II) oxidation. Manganese(II) removal was enhanced when the accumulation of aqueous Fe(II) was minimized, which was achieved at low Fe(II) production rates, high pH, the presence of H2O2 instead of O2 as the initial Fe(II) oxidant, or a combination of all three. In addition, in the EC-H2O2 system, Mn(II) removal efficiency increased as pH decreased from 6.5 to 4.5 and as pH increased from 6.5 to 8.5, which implicates different reactive oxidants in acidic and alkaline solutions. Chemical analyses and X-ray absorption spectroscopy revealed that Mn(II) removal during Fe(0) EC leads to the formation of Mn(III) (0.02 to >0.26 Mn·Fe(-1) molar ratios) and its incorporation into the resulting Fe(III) coprecipitates (lepidocrocite and hydrous ferric oxide for EC-O2 and EC-H2O2, respectively), regardless of pH and Fe(II) production rate. The Mn(II) oxidation pathways elucidated in this study set the framework to develop kinetic models on the impact of Mn(II) during EC treatment and in other Fenton type systems.

  4. Mn(II) complexes with bipyridine, phenanthroline and benzoic acid: Biological and catalase-like activity

    Indian Academy of Sciences (India)

    Ibrahim Kani; Özlem Atlier; Kiymet Güven

    2016-04-01

    Five mononuclear Mn(II) complexes, [Mn(phen)2(ClO4)2] (1), [Mn(phen)3](ClO4)2(H2CO3)2(2), [Mn(bipy)2(ClO4)2] (3), [Mn(bipy)3](ClO4)2) (4), and Mn(phen)2(ba)(H2O)](ClO4)(CH3OH) (5), where bipy = 2,2’-bipyridine, phen = 1,10-phenanthroline, and ba = benzoic acid were prepared and characterized by Xray, IR and UV-Vis spectroscopies, and their catalase-like and biological activities were studied. The presence of two different types and the number of chelating NN-donor neutral ligands allowed for analysis of their effects on the catalase and biological activities. It was observed that the presence and number of phen ligands improved the activity more than the bipy ligand. Complexes 1 and 2, which contain more basic phen ligands, disproportionate H2O2 faster than complexes 3 and 4, which contain less basic bipy ligands. The in vitro antimicrobial activities of all the complexes were also tested against seven bacterial strains by microdilution tests. All the bacterial isolates demonstrated sensitivity to the complexes and the antifungal (anticandidal) activities of the Mn(II) complexes were remarkably higher than the reference drug ketoconazole.

  5. Transformation of tetracyclines mediated by Mn(II) and Cu(II) ions in the presence of oxygen.

    Science.gov (United States)

    Chen, Wan-Ru; Huang, Ching-Hua

    2009-01-15

    Complexation of tetracyclines (TCs) with dissolved Mn(II) and Cu(II) ions were found to significantly enhance the transformation of these antibiotics in the presence of oxygen at pH 8-9.5 and pH 4-6, respectively. In the TC-Mn(II)-O2 system, oxidation of the TC-complexed Mn(II) to Mn(III) by oxygen occurs, followed by oxidation of TC by Mn(III) to regenerate Mn(II). In the TC-Cu(II)-O2 system, Cu(II) oxidizes TC within the complex and the yielded Cu(I) is reoxidized by the present oxygen. Opposite reactivity trends were observed with the two metals: OTC (oxytetracycline) > TTC (tetracycline) > iso-CTC (iso-chlorotetracycline) for the Mn(II)-mediated reaction, whereas CTC > TTC > OTC > epimers for the Cu(II)-mediated reaction. The reactivity results and examination of TC-metal ion complexation and transformation products suggest that the BCD-ring and A-ring of TC are crucial to interact with Mn(II) and Cu(II), respectively. This study highlights that the fate of TCs in aquatic environments may differ significantly by their strong interactions with different metal species present in the systems.

  6. Rational serendipity: "undirected" synthesis of a large {MnCu} complex from pre-formed Mn(II) building blocks.

    Science.gov (United States)

    Frost, Jamie M; Kettles, Fraser J; Wilson, Claire; Murrie, Mark

    2016-11-15

    Use of an aminopolyalcohol-based Mn(II) complex in solvothermal Cu(II) chemistry leads to a rare example of a high nuclearity heterometallic {MnCu} system, in which four Cu(II)(H1Edte) units trap an inner {MnCu(II)} oxide core.

  7. An intramolecular antiferromagnetically coupled pentanuclear Mn(II) cluster containing acetate and tetracarboxylate linkers: Synthesis, structure and magnetism

    Science.gov (United States)

    Wu, Jian; Liu, Wei-Cong; Wu, Xi-Ren; Liu, Jian-Qiang; Sakiyama, Hiroshi; Yadav, Reena; Kumar, Abhinav

    2016-06-01

    A new Mn(II) complex {[Mn5(CH3COO)2(L)2(DMF)8](DMF)}n (1), (H4L = 3,5-bis(3‧,5‧-dicarboxylphenyl)-1H-1,2,3-triazole), has been synthesized and structurally characterized. The complex 1 have pentanuclear Mn(II) core, where the two sides of metal centers (Mn2 and Mn3) have trigonal bipyramidal arrangement and the middle metal center (Mn1) have octahedral environment utilizing two O atoms from adjacent bridging bidentate carboxylate groups and four O atoms from four coordinated DMF molecules. The planar arrangement of pentanuclear Mn(II) atoms are linked by L linkage to generate two dimensional sheet. The magnetic property of the compound indicates χMT value for the five Mn(II) unit to be 21.3 cm3 K mol-1 at 300 K, which is close to the spin-only value (21.9 cm3 K mol-1) for the pentamer having S = 5/2. Also, the Hirshfeld surface analyses have been performed which indicated the absence of weak Mn···Mn interaction thereby corroborating the results of observed magnetic properties.

  8. New Methods of Simulation of Mn(II) EPR Spectra: Single Crystals, Polycrystalline and Amorphous (Biological) Materials

    Science.gov (United States)

    Misra, Sushil K.

    Biological systems exhibit properties of amorphous materials. The Mn(II) ion in amorphous materials is characterized by distributions of spin-Hamiltonian parameters around mean values. It has a certain advantage over other ions, being one of the most abundant elements on the earth. The extent to which living organisms utilize manganese varies from one organism to the other. There is a fairly high concentration of the Mn(II) ion in green plants, which use it in the O2 evolution reaction of photosynthesis (Sauer, 1980). Structure-reactivity relationships in Mn(II)-O2 complexes are given in a review article by Coleman and Taylor (1980). Manganese is a trace requirement in animal nutrition; highly elevated levels of manganese in the diet can be toxic, probably because of an interference with iron homeostasis (Underwood, 1971). On the other hand, animals raised with a dietary deficiency of manganese exhibit severe abnormalities in connective tissue; these problems have been attributed to the obligatory role of Mn(II) in mucopolysaccharide metabolism (Leach, 1971). Mn(II) has been detected unequivocally in living organisms.

  9. Cathodic stripping voltammetry of trace Mn(II) at carbon film electrodes.

    Science.gov (United States)

    Filipe, Olga M S; Brett, Christopher M A

    2003-12-04

    A sensitive voltammetric method is presented for the determination of tract levels of Mn (II) using carbon film electrodes fabricated from carbon resistors of 2 Omega. Determination of manganese was made by square wave cathodic stripping voltammetry (CSV), with deposition of manganese as manganese dioxide. Chronoamperometric experiments were made to study MnO(2) nucleation and growth. As a result, it was found to be necessary to perform electrode conditioning at a more positive potential to initiate MnO(2) nucleation. Under optimised conditions the detection limit obtained was 4 nM and the relative standard deviation for eight measurements of 0.22 nM was 5.3%. Interferences from various metal ions on the response CSV of Mn(II) were investigated, namely Cd(II), Ni(II), Cu(II), Cr(VI), Pb(II), Zn(II) and Fe(II). Application to environmental samples was demonstrated.

  10. Mn(II) Oxidation by the Multicopper Oxidase Complex Mnx: A Coordinated Two-Stage Mn(II)/(III) and Mn(III)/(IV) Mechanism.

    Science.gov (United States)

    Soldatova, Alexandra V; Romano, Christine A; Tao, Lizhi; Stich, Troy A; Casey, William H; Britt, R David; Tebo, Bradley M; Spiro, Thomas G

    2017-08-23

    The bacterial manganese oxidase MnxG of the Mnx protein complex is unique among multicopper oxidases (MCOs) in carrying out a two-electron metal oxidation, converting Mn(II) to MnO2 nanoparticles. The reaction occurs in two stages: Mn(II) → Mn(III) and Mn(III) → MnO2. In a companion study , we show that the electron transfer from Mn(II) to the low-potential type 1 Cu of MnxG requires an activation step, likely forming a hydroxide bridge at a dinuclear Mn(II) site. Here we study the second oxidation step, using pyrophosphate (PP) as a Mn(III) trap. PP chelates Mn(III) produced by the enzyme and subsequently allows it to become a substrate for the second stage of the reaction. EPR spectroscopy confirms the presence of Mn(III) bound to the enzyme. The Mn(III) oxidation step does not involve direct electron transfer to the enzyme from Mn(III), which is shown by kinetic measurements to be excluded from the Mn(II) binding site. Instead, Mn(III) is proposed to disproportionate at an adjacent polynuclear site, thereby allowing indirect oxidation to Mn(IV) and recycling of Mn(II). PP plays a multifaceted role, slowing the reaction by complexing both Mn(II) and Mn(III) in solution, and also inhibiting catalysis, likely through binding at or near the active site. An overall mechanism for Mnx-catalyzed MnO2 production from Mn(II) is presented.

  11. Surface Mn(II) oxidation actuated by a multicopper oxidase in a soil bacterium leads to the formation of manganese oxide minerals

    Science.gov (United States)

    Zhang, Zhen; Zhang, Zhongming; Chen, Hong; Liu, Jin; Liu, Chang; Ni, Hong; Zhao, Changsong; Ali, Muhammad; Liu, Fan; Li, Lin

    2015-01-01

    In this manuscript, we report that a bacterial multicopper oxidase (MCO266) catalyzes Mn(II) oxidation on the cell surface, resulting in the surface deposition of Mn(III) and Mn(IV) oxides and the gradual formation of bulky oxide aggregates. These aggregates serve as nucleation centers for the formation of Mn oxide micronodules and Mn-rich sediments. A soil-borne Escherichia coli with high Mn(II)-oxidizing activity formed Mn(III)/Mn(IV) oxide deposit layers and aggregates under laboratory culture conditions. We engineered MCO266 onto the cell surfaces of both an activity-negative recipient and wild-type strains. The results confirmed that MCO266 governs Mn(II) oxidation and initiates the formation of deposits and aggregates. By contrast, a cell-free substrate, heat-killed strains, and intracellularly expressed or purified MCO266 failed to catalyze Mn(II) oxidation. However, purified MCO266 exhibited Mn(II)-oxidizing activity when combined with cell outer membrane component (COMC) fractions in vitro. We demonstrated that Mn(II) oxidation and aggregate formation occurred through an oxygen-dependent biotic transformation process that requires a certain minimum Mn(II) concentration. We propose an approximate electron transfer pathway in which MCO266 transfers only one electron to convert Mn(II) to Mn(III) and then cooperates with other COMC electron transporters to transfer the other electron required to oxidize Mn(III) to Mn(IV). PMID:26039669

  12. Binuclear and tetranuclear Mn(II) clusters in coordination polymers derived from semirigid tetracarboxylate and N-donor ligands: syntheses, new topology structures and magnetism

    Science.gov (United States)

    Li, Xiao-Ling; Liu, Guang-Zhen; Xin, Ling-Yun; Wang, Li-Ya

    2017-02-01

    Two topologically new Mn(II) coordination polymers, namely {[Mn2(H4ipca)(4,4‧-bpy)1.5(CH3CH2OH)0.5(H2O)1.5]·0.5CH3CH2OH·2.5H2O}n (1) and {Mn4(H4ipca)2(bze)(H2O)4}n (2) were prepared by the solvothermal reactions of Mn(II) acetate with 5-(2',3'-dicarboxylphenoxy)isophthalic acid (H4ipca) in the presence of different N-donor coligands (4,4‧-bpy=4,4‧-bipyridyl and bze=1, 4-bis(1-imidazoly)benzene). The single crystal X-ray diffractions reveal that two complexes display 3D metal-organic frameworks with binuclear and tetranuclear Mn(II) units, respectively. Complex 1 features a (3,4,6)-connected porous framework based on dinuclear Mn(II) unit with the (4.52)2(42.68.83.92)(52.8.92.10) new topology, and complex 2 possesses a (3,8)-connected network based on tetranuclear Mn(II) unit with the (42.6)2(44.614.77.82.9) new topology. Magnetic analyses indicate that both two compounds show weak antiferromagnetic interactions within binuclear and tetranuclear Mn(II) units.

  13. Mn(II) deposition on anodes and its effects on capacity fade in spinel lithium manganate-carbon systems.

    Science.gov (United States)

    Zhan, Chun; Lu, Jun; Jeremy Kropf, A; Wu, Tianpin; Jansen, Andrew N; Sun, Yang-Kook; Qiu, Xinping; Amine, Khalil

    2013-01-01

    Dissolution and migration of manganese from cathode lead to severe capacity fading of lithium manganate-carbon cells. Overcoming this major problem requires a better understanding of the mechanisms of manganese dissolution, migration and deposition. Here we apply a variety of advanced analytical methods to study lithium manganate cathodes that are cycled with different anodes. We show that the oxidation state of manganese deposited on the anodes is +2, which differs from the results reported earlier. Our results also indicate that a metathesis reaction between Mn(II) and some species on the solid-electrolyte interphase takes place during the deposition of Mn(II) on the anodes, rather than a reduction reaction that leads to the formation of metallic Mn, as speculated in earlier studies. The concentration of Mn deposited on the anode gradually increases with cycles; this trend is well correlated with the anodes rising impedance and capacity fading of the cell.

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

    Directory of Open Access Journals (Sweden)

    SULEKH CHANDRA

    2009-08-01

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

  15. A Mononuclear Mn(II) Pseudoclathrochelate Complex Studied by Multi-Frequency Electron-Paramagnetic-Resonance Spectroscopy.

    Science.gov (United States)

    Azarkh, Mykhailo; Penkova, Larysa V; Kats, Svitlana V; Varzatskii, Oleg A; Voloshin, Yan Z; Groenen, Edgar J J

    2014-03-06

    Knowledge of the correlation between structural and spectroscopic properties of transition-metal complexes is essential to deepen the understanding of their role in catalysis, molecular magnetism, and biological inorganic chemistry. It provides topological and, sometimes, functional insight with respect to the active site properties of metalloproteins. The electronic structure of a high-spin mononuclear Mn(II) pseudoclathrochelate complex has been investigated by electron-paramagnetic-resonance (EPR) spectroscopy at 9.5 and 275.7 GHz. A substantial, virtually axial zero-field splitting with D = -9.7 GHz (-0.32 cm(-1)) is found, which is the largest one reported to date for a Mn(II) complex with six nitrogen atoms in the first coordination sphere.

  16. Influence of the Mn(II) and CH 4 on the evolution of light induced radicals in chloroplasts

    Science.gov (United States)

    Trif, V.; Trif, Eleonora

    1995-06-01

    The photochemical activity of the leaves and chloroplasts of several species of plants developed in gaseous hydrocarbon environments (C nH 2 n+2 ) was investigated by the EPR method. The influence of different concentrations of paramagnetic ions [Mn(II), Cu(II) and VO(II), respectively] on the plants grown in dietary media containing these ions was also followed by EPR spectroscopy. The contents of paramagnetic ions, lower than 0.1%, in the nutritive solutions, are the most suitable in the biosynthesis of chlorophyll-like pigments containing paramagnetic ions in their porphyrine ring. The changes in the form, structure and photosensibility of the EPR signals corresponding to the free radicals, as well as the properties of the pheophytins containing paramagnetic ions, such as: Mn(II), Cu(II) and VO(II), were related to the photochemical synthesis in gaseous hydrocarbon environments.

  17. Influences of Mn(II) and V(IV) on Bacterial Surface Chemistry and Metal Reactivity

    Science.gov (United States)

    French, S.; Fakra, S.; Glasauer, S.

    2009-05-01

    Microorganisms in terrestrial and marine environments are typically bathed in solutions that contain a range of metal ions, toxic and beneficial. Bacteria such as Shewanella putrefaciens CN32 are metabolically versatile in their respiration, and the reductive dissolution of widely dispersed metals such as Fe(III), Mn(IV), or V(V) can present unique challenges if nearby bodies of water are used for irrigation or drinking. In redox transition zones, dissimilatory metal reduction (DMR) by bacteria can lead to generation of high concentrations of soluble metals. It has been shown that metals will associate with negatively charged bacterial membranes, and the mechanisms of metal reduction are well defined for many species of bacteria. The interaction of metals with the cell wall during DMR is, however, not well documented; very little is known about the interaction of respired transition metals with membrane lipids. Furthermore, bacterial surfaces tend to change in response to their immediate environments. Variations in conditions such as oxygen or metal presence may affect surface component composition, including availability of metal reactive sites. Our research seeks to characterize the biochemical nature of metal-membrane interactions, as well as identify the unique changes at the cell surface that arise as a result of metal presence in their environments. We have utilized scanning transmission X-ray microscopy (STXM) to examine the dynamics of soluble Mn(II) and V(IV) interactions with purified bacterial membranes rather than whole cells. This prevents intracellular interferences, and allows for near edge X-ray absorption fine structure (NEXAFS) spectroscopic analyses of cell surface and surface-associated components. NEXAFS spectra for carbon, nitrogen, and oxygen edges indicate that Mn(II) and V(IV) induce biological modifications of the cell membrane in both aerobic and anaerobic conditions. These changes depend not only on the metal, but also on the presence of

  18. Biological low pH Mn(II) oxidation in a manganese deposit influenced by metal-rich groundwater

    Science.gov (United States)

    Bohu, Tsing; Akob, Denise M.; Abratis, Michael; Lazar, Cassandre S.; Küsel, Kirsten

    2016-01-01

    The mechanisms, key organisms, and geochemical significance of biological low-pH Mn(II) oxidation are largely unexplored. Here, we investigated the structure of indigenous Mn(II)-oxidizing microbial communities in a secondary subsurface Mn oxide deposit influenced by acidic (pH 4.8) metal-rich groundwater in a former uranium mining area. Microbial diversity was highest in the Mn deposit compared to the adjacent soil layers and included the majority of known Mn(II)-oxidizing bacteria (MOB) and two genera of known Mn(II)-oxidizing fungi (MOF). Electron X-ray microanalysis showed that romanechite [(Ba,H2O)2(Mn4+,Mn3+)5O10] was conspicuously enriched in the deposit. Canonical correspondence analysis revealed that certain fungal, bacterial, and archaeal groups were firmly associated with the autochthonous Mn oxides. Eight MOB within the Proteobacteria, Actinobacteria, and Bacteroidetes and one MOF strain belonging to Ascomycota were isolated at pH 5.5 or 7.2 from the acidic Mn deposit. Soil-groundwater microcosms demonstrated 2.5-fold-faster Mn(II) depletion in the Mn deposit than adjacent soil layers. No depletion was observed in the abiotic controls, suggesting that biological contribution is the main driver for Mn(II) oxidation at low pH. The composition and species specificity of the native low-pH Mn(II) oxidizers were highly adapted to in situ conditions, and these organisms may play a central role in the fundamental biogeochemical processes (e.g., metal natural attenuation) occurring in the acidic, oligotrophic, and metalliferous subsoil ecosystems.

  19. Mn(II removal from aqueous solutions by Co/Mo layered double hydroxide: Kinetics and thermodynamics

    Directory of Open Access Journals (Sweden)

    A.A. Bakr

    2016-06-01

    Full Text Available This paper deals with the experimental investigation related to the Mn(II removal from aqueous solutions by the adsorption onto a synthesized Co/Mo layered double hydroxide (Co/Mo-LDH. The adsorption behavior was studied as a function of initial Mn(II concentration (40–145 mg/L, contact time (15–90 min, solution pH (2–9 and adsorbent mass (0.05–0.35 g per 1.0 L. All adsorption processes were rapidly carried out at different temperatures (298, 308 and 318 K and constant stirring rate 160 rpm. The results showed that the Co/Mo-LDH is a very promising material for removing of Mn(II from the aqueous solutions. Particularly, the solution pH range of 4–7 has the most significant effect on the adsorption capacity. The results revealed that the maximum adsorption capacities were 20.2, 26.75 and 38.1 mg/g from the initial Mn(II concentration (145 mg/L at pH 5, adsorbent mass (0.2 g/1.0 L, and contact time (60 min at different temperatures, 298, 308 and 318 K, respectively. The adsorption kinetics data are well fitted by the pseudo-second-order model, while the adsorption isotherms data were better fitted by the Langmuir equation. Also, this paper discusses the thermodynamic parameters of the adsorption and the results demonstrate that the adsorption process is spontaneous and endothermic.

  20. Microwave Assisted Synthesis Spectral and Antibacterial Investigations on Complexes of Mn(II) With Amide Containing Ligands

    OpenAIRE

    N. Bhojak; D. D. Gudasaria; N. Khiwani; Jain, R.

    2007-01-01

    The present research work describes the synthesis, spectral and antibacterial studies on the complexes of Mn(II) with amide group containing ligands. Synthesis of complexes has been carried out by conventional method as well as by microwave method. The complexes have been characterized on the basis of elemental analysis, infrared, electronic spectra and magnetic susceptibility studies. The diffuse reflectance spectrums of the complexes show bands in the region 20,000 cm-1 to 26,000 cm-1 ass...

  1. The effect of Ca2+ ions and ionic strength on Mn(II) oxidation by spores of the marine Bacillus sp. SG-1

    Science.gov (United States)

    Toyoda, Kazuhiro; Tebo, Bradley M.

    2013-01-01

    Manganese(IV) oxides, believed to form primarily through microbial activities, are extremely important mineral phases in marine environments where they scavenge a variety of trace elements and thereby control their distributions. The presence of various ions common in seawater are known to influence Mn oxide mineralogy yet little is known about the effect of these ions on the kinetics of bacterial Mn(II) oxidation and Mn oxide formation. We examined factors affecting bacterial Mn(II) oxidation by spores of the marine Bacillus sp. strain SG-1 in natural and artificial seawater of varying ionic conditions. Ca2+ concentration dramatically affected Mn(II) oxidation, while Mg2+, Sr2+, K+, Na+ and NO3- ions had no effect. The rate of Mn(II) oxidation at 10 mM Ca2+ (seawater composition) was four or five times that without Ca2+. The relationship between Ca2+ content and oxidation rate demonstrates that the equilibrium constant is small (on the order of 0.1) and the binding coefficient is 0.5. The pH optimum for Mn(II) oxidation changed depending on the amount of Ca2+ present, suggesting that Ca2+ exerts a direct effect on the enzyme perhaps as a stabilizing bridge between polypeptide components. We also examined the effect of varying concentrations of NaCl or KNO3 (0-2000 mM) on the kinetics of Mn(II) oxidation in solutions containing 10 mM Ca2+. Mn(II) oxidation was unaffected by changes in ionic strength (I) below 0.2, but it was inhibited by increasing salt concentrations above this value. Our results suggest that the critical coagulation concentration is around 200 mM of salt (I = ca. 0.2), and that the ionic strength of seawater (I > 0.2) accelerates the precipitation of Mn oxides around the spores. Under these conditions, the aggregation of Mn oxides reduces the supply of dissolved O2 and/or Mn2+ and inhibits the Mn(II) → Mn(III) step controlling the enzymatic oxidation of Mn(II). Our results suggest that the hardness and ionic strength of the aquatic environment

  2. Contributions of the S100A9 C-terminal tail to high-affinity Mn(II) chelation by the host-defense protein human calprotectin.

    Science.gov (United States)

    Brophy, Megan Brunjes; Nakashige, Toshiki G; Gaillard, Aleth; Nolan, Elizabeth M

    2013-11-27

    Human calprotectin (CP) is an antimicrobial protein that coordinates Mn(II) with high affinity in a Ca(II)-dependent manner at an unusual histidine-rich site (site 2) formed at the S100A8/S100A9 dimer interface. We present a 16-member CP mutant family where mutations in the S100A9 C-terminal tail (residues 96-114) are employed to evaluate the contributions of this region, which houses three histidines and four acidic residues, to Mn(II) coordination at site 2. The results from analytical size-exclusion chromatography, Mn(II) competition titrations, and electron paramagnetic resonance spectroscopy establish that the C-terminal tail is essential for high-affinity Mn(II) coordination by CP in solution. The studies indicate that His103 and His105 (HXH motif) of the tail complete the Mn(II) coordination sphere in solution, affording an unprecedented biological His6 site. These solution studies are in agreement with a Mn(II)-CP crystal structure reported recently (Damo, S. M.; et al. Proc. Natl. Acad. Sci. U.S.A. 2013, 110, 3841). Remarkably high-affinity Mn(II) binding is retained when either H103 or H105 are mutated to Ala, when the HXH motif is shifted from positions 103-105 to 104-106, and when the human tail is substituted by the C-terminal tail of murine S100A9. Nevertheless, antibacterial activity assays employing human CP mutants reveal that the native disposition of His residues is important for conferring growth inhibition against Escherichia coli and Staphylococcus aureus. Within the S100 family, the S100A8/S100A9 heterooligomer is essential for providing high-affinity Mn(II) binding; the S100A7, S100A9(C3S), S100A12, and S100B homodimers do not exhibit such Mn(II)-binding capacity.

  3. A Mn-54 Radiotracer Study of Mn Isotope Solid-Liquid Exchange during Reductive Transformation of Vernadite (δ-MnO₂) by Aqueous Mn(II)

    Energy Technology Data Exchange (ETDEWEB)

    Elzinga, Evert J.; Kustka, Adam B. [Rutgers

    2015-04-09

    We employed Mn-54 radiotracers to characterize the extent and dynamics of Mn atom exchange between aqueous Mn(II) and vernadite (δ-Mn(IV)O2) at pH 7.5 under anoxic conditions. Exchange of Mn atoms between the solid and liquid phase is rapid, reaching dynamic equilibrium in 2–4 days. We propose that during the initial stages of reaction, Mn atom exchange occurs through consecutive comproportionation-disproportionation reactions where interfacial electron transfer from adsorbed Mn(II) to lattice Mn(IV) generates labile Mn(III) cations that rapidly disproportionate to reform aqueous Mn(II) and solid-phase Mn(IV). Following nucleation of Mn(III)OOH phases, additional exchange likely occurs through electron transfer from aqueous Mn(II) to solid-phase Mn(III). Our results provide evidence for the fast and extensive production of transient Mn(III) species at the vernadite surface upon contact of this substrate with dissolved Mn(II). We further show that HEPES buffer is a reductant of lattice Mn(IV) in the vernadite structure in our experiments. The methods and results presented here introduce application of Mn-54 tracers as a facile tool to further investigate the formation kinetics of labile Mn(III) surface species and their impacts on Mn-oxide structure and reactivity over a range of environmentally relevant geochemical conditions.

  4. Semi- and thiosemicarbazide Mn(II) complexes: Characterization, DFT and biological studies

    Science.gov (United States)

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

    2016-09-01

    One NO and two NOS donor ligands have been prepared by addition ethanolic suspension of 2-hydrazino-2-oxo-N-phenyl-acetamide to phenyl isocyanate (H2PAPS), phenyl isothiocyanate (H2PAPT) and benzoyl isothiocyanate (H2PABT). The Mn (II) complexes were prepared from the chloride salt and characterized by conventional techniques. The isolated complexes were assigned the formulaes, [Mn(HPAPS)2], [Mn(HPAPT)Cl] and [Mn(HPABT)Cl(H2O)2], respectively. The IR study of ligands and their complexes shows that H2PAPS behaves as a mononegative tridentate via both CO of hydrazide moiety in keto and deprotonated enol form and CN (azomethine) due to enolization of CO cyanate moiety without deprotonation. H2PAPT behaves as mononegative tridentate via CO of hydrazide moiety, deprotonated thiol CS and NH group. Finally H2PABT behaves as mononegative tridentate via deprotonated enolized CO of hydrazide moiety, CO of benzoyl moiety and NH group. The IR spectra of ligands from DFT calculations are compared with those obtained experimentally. Also, HOMO, LUMO, the bond lengths, bond angles, and dipole moments have been calculated. The calculated HOMO-LUMO energy gap reveals that charge transfer occurs within the molecule. The binding energy values display the high stability of complexes. The kinetic and thermodynamic parameters were determined by Coats-Redfern and Horowitz-Metzger methods. The antibacterial activities were also tested against Bacillus subtilis and Escherichia coli bacteria. Finally, the antitumor activities of the Ligands and their Mn(II) complexes have been evaluated against liver (HePG2) and breast (MCF-7) cancer cells.

  5. Sorption behaviour of manganese-coated calcined-starfish and manganese-coated sand for Mn(II).

    Science.gov (United States)

    Lee, Seung-Mok; Kim, Won-Gee; Yang, Jae-Kyu; Tiwari, Diwakar

    2010-04-01

    The objective of the present investigation was to explore the sorption behaviour of manganese-coated samples of calcined starfish (MCCSF) (i.e. the impregnation of calcined starfish with manganese) for the removal of low levels of an important heavy metal toxic ion, Mn(II), from aqueous solutions. The suitability of this solid was further compared with two different samples of manganese-coated sands (MCS): MCS4 and MCS9 impregnated at pH 4.0 and pH 9.0, respectively. These comparative studies were performed in both batch and column experiments. Batch data indicated that a fairly good stability of the coating was obtained for these three samples in the pH region 2.5 to 10.0. The removal efficiency of MCCSF was fairly good in comparison with the MCS4 and MCS9 samples. These last two samples possessed similar Mn(II) removal capacities. Moreover, a small dose of sodium hypochlorite further enhanced the uptake of Mn(II) by these solids. The sorbate concentration dependence data fitted reasonably well to the Freundlich adsorption isotherm. The column data indicated that MCCSF possessed a relatively higher adsorption capacity compared with the MCS4 and MCS9 samples. The breakthrough curves obtained were then used to evaluate the apparent removal capacity of these solids under the dynamic conditions using the Thomas equation. The SEM images obtained for these manganese-coated solids along with the virgin base materials, i.e. sand and calcined starfish, showed that manganese oxides occupied the surfaces or pores of the base materials and formed clusters on the base surface.

  6. Enzymatic microbial Mn(II) oxidation and Mn biooxide production in the Guaymas Basin deep-sea hydrothermal plume

    Science.gov (United States)

    Dick, Gregory J.; Clement, Brian G.; Webb, Samuel M.; Fodrie, F. Joel; Bargar, John R.; Tebo, Bradley M.

    2009-11-01

    Microorganisms play important roles in mediating biogeochemical reactions in deep-sea hydrothermal plumes, but little is known regarding the mechanisms that underpin these transformations. At Guaymas Basin (GB) in the Gulf of California, hydrothermal vents inject fluids laden with dissolved Mn(II) (dMn) into the deep waters of the basin where it is oxidized and precipitated as particulate Mn(III/IV) oxides, forming turbid hydrothermal "clouds". Previous studies have predicted extremely short residence times for dMn at GB and suggested they are the result of microbially-mediated Mn(II) oxidation and precipitation. Here we present biogeochemical results that support a central role for microorganisms in driving Mn(II) oxidation in the GB hydrothermal plume, with enzymes being the primary catalytic agent. dMn removal rates at GB are remarkably fast for a deep-sea hydrothermal plume (up to 2 nM/h). These rapid rates were only observed within the plume, not in background deep-sea water above the GB plume or at GB plume depths (˜1750-2000 m) in the neighboring Carmen Basin, where there is no known venting. dMn removal is dramatically inhibited under anoxic conditions and by the presence of the biological poison, sodium azide. A conspicuous temperature optimum of dMn removal rates (˜40 °C) and a saturation-like (i.e. Michaelis-Menten) response to O 2 concentration were observed, indicating an enzymatic mechanism. dMn removal was resistant to heat treatment used to select for spore-forming organisms, but very sensitive to low concentrations of added Cu, a cofactor required by the putative Mn(II)-oxidizing enzyme. Extended X-ray absorption fine structure spectroscopy (EXAFS) and synchrotron radiation-based X-ray diffraction (SR-XRD) revealed the Mn oxides to have a hexagonal birnessite or δ-MnO 2-like mineral structure, indicating that these freshly formed deep-sea Mn oxides are strikingly similar to primary biogenic Mn oxides produced by laboratory cultures of bacteria

  7. Synthesis and Structural Studies of Cr(III, Mn(II and Fe(III Complexes of N(2-Benzimidazolylacetylacetohydrazone

    Directory of Open Access Journals (Sweden)

    G. H. Anuradha

    2011-01-01

    Full Text Available The ligand N(2-benzimidazolylacetylacetohydrazone (BAAH have been synthesized and characterized. Coordination complexes of Cr(III, Mn(II and Fe(III have been synthesized with the ligand BAAH. These complexes were characterized on the basis of analytical, conductance, thermal, magnetic data and infrared and electronic spectral data. The ligand BAAH is behaving as a neutral tridentate NNO donar employing two azomethine nitrogens (ring and side chain and carbonyl oxygen. The ligand and it's metal complexes were tested for anti microbial activity on the gram positive S. Aureus, E. coli and Proteus.

  8. Characterization of pH dependent Mn(II oxidation strategies and formation of a bixbyite-like phase by Mesorhizobium australicum T-G1

    Directory of Open Access Journals (Sweden)

    Tsing eBohu

    2015-07-01

    Full Text Available Despite the ubiquity of Mn oxides in natural environments, there are only a few observations of biological Mn(II oxidation at pH < 6. The lack of low pH Mn-oxidizing bacteria (MOB isolates limits our understanding of how pH influences biological Mn(II oxidation in extreme environments. Here, we report that a novel MOB isolate, Mesorhizobium australicum strain T-G1, isolated from an acidic and metalliferous uranium mining area, can oxidize Mn(II at both acidic and neutral pH using different enzymatic pathways. X-ray diffraction (XRD, Raman spectroscopy, and scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDS revealed that T-G1 initiated bixbyite-like Mn oxide formation at pH 5.5 which coincided with multi-copper oxidase (MCO expression from early exponential phase to late stationary phase. In contrast, reactive oxygen species (ROS, particularly superoxide, appeared to be more important for T-G1 mediated Mn(II oxidation at neutral pH. ROS was produced in parallel with the occurrence of Mn(II oxidation at pH 7.2 from early stationary phase. Solid phase Mn oxides did not precipitate, which is consistent with the presence of a high amount of H2O2 and lower activity of catalase in the liquid culture at pH 7.2. Our results show that M. australicum T-G1, an acid tolerant MOB, can initiate Mn(II oxidation by varying its oxidation mechanisms depending on the pH and may play an important role in low pH manganese biogeochemical cycling.

  9. Characterization of pH dependent Mn(II) oxidation strategies and formation of a bixbyite-like phase by Mesorhizobium australicum T-G1.

    Science.gov (United States)

    Bohu, Tsing; Santelli, Cara M; Akob, Denise M; Neu, Thomas R; Ciobota, Valerian; Rösch, Petra; Popp, Jürgen; Nietzsche, Sándor; Küsel, Kirsten

    2015-01-01

    Despite the ubiquity of Mn oxides in natural environments, there are only a few observations of biological Mn(II) oxidation at pH < 6. The lack of low pH Mn-oxidizing bacteria (MOB) isolates limits our understanding of how pH influences biological Mn(II) oxidation in extreme environments. Here, we report that a novel MOB isolate, Mesorhizobium australicum strain T-G1, isolated from an acidic and metalliferous uranium mining area, can oxidize Mn(II) at both acidic and neutral pH using different enzymatic pathways. X-ray diffraction, Raman spectroscopy, and scanning electron microscopy with energy dispersive X-ray spectroscopy revealed that T-G1 initiated bixbyite-like Mn oxide formation at pH 5.5 which coincided with multi-copper oxidase expression from early exponential phase to late stationary phase. In contrast, reactive oxygen species (ROS), particularly superoxide, appeared to be more important for T-G1 mediated Mn(II) oxidation at neutral pH. ROS was produced in parallel with the occurrence of Mn(II) oxidation at pH 7.2 from early stationary phase. Solid phase Mn oxides did not precipitate, which is consistent with the presence of a high amount of H2O2 and lower activity of catalase in the liquid culture at pH 7.2. Our results show that M. australicum T-G1, an acid tolerant MOB, can initiate Mn(II) oxidation by varying its oxidation mechanisms depending on the pH and may play an important role in low pH manganese biogeochemical cycling.

  10. Characterization of pH dependent Mn(II) oxidation strategies and formation of a bixbyite-like phase by Mesorhizobium australicum T-G1

    Science.gov (United States)

    Bohu, Tsing; Santelli, Cara M; Akob, Denise M.; Neu, Thomas R; Ciobota, Valerian; Rösch, Petra; Popp, Jürgen; Nietzsche, Sándor; Küsel, Kirsten

    2015-01-01

    Despite the ubiquity of Mn oxides in natural environments, there are only a few observations of biological Mn(II) oxidation at pH MOB) isolates limits our understanding of how pH influences biological Mn(II) oxidation in extreme environments. Here, we report that a novel MOB isolate, Mesorhizobium australicum strain T-G1, isolated from an acidic and metalliferous uranium mining area, can oxidize Mn(II) at both acidic and neutral pH using different enzymatic pathways. X-ray diffraction, Raman spectroscopy, and scanning electron microscopy with energy dispersive X-ray spectroscopy revealed that T-G1 initiated bixbyite-like Mn oxide formation at pH 5.5 which coincided with multi-copper oxidase expression from early exponential phase to late stationary phase. In contrast, reactive oxygen species (ROS), particularly superoxide, appeared to be more important for T-G1 mediated Mn(II) oxidation at neutral pH. ROS was produced in parallel with the occurrence of Mn(II) oxidation at pH 7.2 from early stationary phase. Solid phase Mn oxides did not precipitate, which is consistent with the presence of a high amount of H2O2 and lower activity of catalase in the liquid culture at pH 7.2. Our results show that M. australicum T-G1, an acid tolerant MOB, can initiate Mn(II) oxidation by varying its oxidation mechanisms depending on the pH and may play an important role in low pH manganese biogeochemical cycling.

  11. Characterization of pH dependent Mn(II) oxidation strategies and formation of a bixbyite-like phase by Mesorhizobium australicum T-G1

    Science.gov (United States)

    Bohu, Tsing; Santelli, Cara M.; Akob, Denise M.; Neu, Thomas R.; Ciobota, Valerian; Rösch, Petra; Popp, Jürgen; Nietzsche, Sándor; Küsel, Kirsten

    2015-01-01

    Despite the ubiquity of Mn oxides in natural environments, there are only a few observations of biological Mn(II) oxidation at pH < 6. The lack of low pH Mn-oxidizing bacteria (MOB) isolates limits our understanding of how pH influences biological Mn(II) oxidation in extreme environments. Here, we report that a novel MOB isolate, Mesorhizobium australicum strain T-G1, isolated from an acidic and metalliferous uranium mining area, can oxidize Mn(II) at both acidic and neutral pH using different enzymatic pathways. X-ray diffraction, Raman spectroscopy, and scanning electron microscopy with energy dispersive X-ray spectroscopy revealed that T-G1 initiated bixbyite-like Mn oxide formation at pH 5.5 which coincided with multi-copper oxidase expression from early exponential phase to late stationary phase. In contrast, reactive oxygen species (ROS), particularly superoxide, appeared to be more important for T-G1 mediated Mn(II) oxidation at neutral pH. ROS was produced in parallel with the occurrence of Mn(II) oxidation at pH 7.2 from early stationary phase. Solid phase Mn oxides did not precipitate, which is consistent with the presence of a high amount of H2O2 and lower activity of catalase in the liquid culture at pH 7.2. Our results show that M. australicum T-G1, an acid tolerant MOB, can initiate Mn(II) oxidation by varying its oxidation mechanisms depending on the pH and may play an important role in low pH manganese biogeochemical cycling. PMID:26236307

  12. Pecan nutshell as biosorbent to remove Cu(II), Mn(II) and Pb(II) from aqueous solutions.

    Science.gov (United States)

    Vaghetti, Julio C P; Lima, Eder C; Royer, Betina; da Cunha, Bruna M; Cardoso, Natali F; Brasil, Jorge L; Dias, Silvio L P

    2009-02-15

    In the present study we reported for the first time the feasibility of pecan nutshell (PNS, Carya illinoensis) as an alternative biosorbent to remove Cu(II), Mn(II) and Pb(II) metallic ions from aqueous solutions. The ability of PNS to remove the metallic ions was investigated by using batch biosorption procedure. The effects such as, pH, biosorbent dosage on the adsorption capacities of PNS were studied. Four kinetic models were tested, being the adsorption kinetics better fitted to fractionary-order kinetic model. Besides that, the kinetic data were also fitted to intra-particle diffusion model, presenting three linear regions, indicating that the kinetics of adsorption should follow multiple sorption rates. The equilibrium data were fitted to Langmuir, Freundlich, Sips and Redlich-Peterson isotherm models. Taking into account a statistical error function, the data were best fitted to Sips isotherm model. The maximum biosorption capacities of PNS were 1.35, 1.78 and 0.946mmolg(-1) for Cu(II), Mn(II) and Pb(II), respectively.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2009-07-01

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

  14. Synthesis, Structural Diversity and Mimic Superoxide Dismutase of Mn(II) Complexes Derived from N, O-donor Schiff bases.

    Science.gov (United States)

    Qin, Jie; Yin, Qiang; Zhao, Shan-Shan; Wang, Jun-Zheng; Qian, Shao-Song

    2016-01-01

    Two new potentially tetradentate Schiff base ligands N'-(pyridin-2-ylmethylene)nicotinohydrazide (L1), and N'-(pyridin-2-ylmethylene)isonicotinohydrazide (L(2)) were synthesized. Reactions of hydrazone ligands L(1) and L(2) with Mn(NO(3))(2) afford two mononuclear Mn(II) complexes, [Mn(L(1))(NO(3))(H(2)O)(2)]•(NO(3)) (1) and [Mn(L(2))(2)(NO(3))(H(2)O)]•(NO(3)) (2). For complexes 1 and 2, L(1) and L(2) act as pincer-like tridentate or bidentate ligands, respectively. The Mn(II) ions in the two compounds are both in heptacoordinated environment, while the two molecules display diverse solid-state supramolecular structures because of the different orientation of Npyridine and hydrogen bonding patterns of nitrate anions. Complex 1 features 2D supramolecular sheet, while complex 2 is double-chain supramolecular structure. Both of the two complexes exhibit moderate superoxide dismutase (SOD) mimetic activity.

  15. Pulse Electron Double Resonance Detected Multinuclear NMR Spectra of Distant and Low Sensitivity Nuclei and Its Application to the Structure of Mn(II) Centers in Organisms.

    Science.gov (United States)

    Bruch, Eduardo M; Warner, Melissa T; Thomine, Sébastien; Tabares, Leandro C; Un, Sun

    2015-10-29

    The ability to characterize the structure of metal centers beyond their primary ligands is important to understanding their chemistry. High-magnetic-field pulsed electron double resonance detected NMR (ELDOR-NMR) is shown to be a very sensitive approach to measuring the multinuclear NMR spectra of the nuclei surrounding Mn(II) ions. Resolved spectra of intact organisms with resonances arising from (55)Mn, (31)P, (1)H, (39)K, (35)Cl, (23)Na, and (14)N nuclei surrounding Mn(2+) centers were obtained. Naturally abundant cellular (13)C could be routinely measured as well. The amplitudes of the (14)N and (2)H ELDOR-NMR spectra were found to be linearly dependent on the number of nuclei in the ligand sphere. The evolution of the Mn(II) ELDOR-NMR spectra as a function of excitation time was found to be best described by a saturation phenomenon rather than a coherently driven process. Mn(II) ELDOR-NMR revealed details about not only the immediate ligands to the Mn(II) ions but also more distant nuclei, providing a view of their extended structures. This will be important for understanding the speciation and chemistry of the manganese complexes as well as other metals found in organisms.

  16. A polyoxometalate-based single-molecule magnet with a mixed-valent {Mn(IV)2Mn(III)6Mn(II)4} core.

    Science.gov (United States)

    Zhang, Zhi-Ming; Yao, Shuang; Li, Yang-Guang; Wu, Hai-Hong; Wang, Yong-Hui; Rouzières, Mathieu; Clérac, Rodolphe; Su, Zhong-Min; Wang, En-Bo

    2013-03-28

    A polyoxometalate (POM)-based {Mn(IV)2Mn(III)6Mn(II)4} complex with single-molecule magnet (SMM) behaviour was prepared, exhibiting the largest known Mn nuclearity and the most Mn valence states in the POM-based SMM family.

  17. Application of Local Adsorbant From Southeast Sulawesi Clay Immobilized Saccharomyces Cerevisiae Bread’s Yeast Biomass for Adsorption Of Mn(Ii) Metal Ion

    Science.gov (United States)

    R, Halimahtussaddiyah; Mashuni; Budiarni

    2017-05-01

    Southeast Sulawesi has a great stock of clay. It is probably to use as a source of adsorbent. The adsorbent capacity of clay can be largered with teratment using bread’s yeast as biomass. At this research, study of analysis adsorption of Mn(II) metal ion on clay immobilized Saccharomyces cerevisiae bread’s yeast biomass adsorbent has been conducted. The aims of this research were to determine the effects of contact time, pH and concentration of Mn(II) metal ion and to determine the adsorption capacity of clay immobilized S. cerevisiae biomass for adsorbtion of Mn(II) metal ion. Activated clay was synthesized by reaction of clay with KMnO4, H2SO4 and HCl. S. cerevisiae biomass was result by bread’s yeast mashed. Immobilization of S. cerevisiae biomass into clay was done by mixing of ratio of S. cerevisiae bread’s yeast biomass and clay equal to 1:3 (mass of biomassa : mass of clay). The adsorption capacity was determined by using Freundlich and Langmuir adsorption isoterms. The results of FTIR spectrums showed that the functional groups of clay immobilized S. cerevisiae biomass were Si-OH (wave number 1643 cm-1), Si-O-Si (wave number 1033 cm-1), N-H (wave number 2337 cm-1), O-H (wave number 3441cm-1), and C-H (wave number 2931 cm-1). The result of adsorption capacity from Mn(II) metal ion of contact time optimum 120 minutes, pH optimun at 7 and concentration optimum 50 mg/L were 1,816 mg/g; 0,509 mg/g and 2,624mg/g respectively. The adsorption capacity of Mn(II) metal ion with ratio 1:3 (biomass : clay) was 0,1045 mg/g. Type of isothermal adsorption followed the Freunlich adsorption.

  18. Synthesis, experimental and theoretical characterization of a Mn(II) complex of N,N‧-dipyridoxyl(1,2-diaminobenzene)

    Science.gov (United States)

    Toozandejani, Tina; Beyramabadi, S. Ali; Chegini, Hamed; Khashi, Maryam; Morsali, Ali; Pordel, Mehdi

    2017-01-01

    Herein, hopping to biological and catalytic applications, synthesis of a Mn(II) complex of the N,N‧-dipyridoxyl(1,2-diaminobenzene) [Hdbnd 2L] Schiff-base has been reported. The Mn complex was characterized experimentally and theoretically. The optimized geometry and vibrational frequencies of the complex were computed by using the density functional theory (DFT) methods. In the optimized geometry of the octahedral complex, the dianionic L2- acts as a tetradentate ligand. Four coordination positions of the square plane have been occupied with two azomethine nitrogens and two phenolic oxygens of the L2- ligand. Two coordinated methanol ligands are perpendicular to the square plane. Also, properties of the Mnsbnd N and Mnsbnd O bonds were explored investigated using the Atoms in molecules (AIM) analysis.

  19. Microwave Assisted Synthesis Spectral and Antibacterial Investigations on Complexes of Mn(II With Amide Containing Ligands

    Directory of Open Access Journals (Sweden)

    N. Bhojak

    2007-01-01

    Full Text Available The present research work describes the synthesis, spectral and antibacterial studies on the complexes of Mn(II with amide group containing ligands. Synthesis of complexes has been carried out by conventional method as well as by microwave method. The complexes have been characterized on the basis of elemental analysis, infrared, electronic spectra and magnetic susceptibility studies. The diffuse reflectance spectrums of the complexes show bands in the region 20,000 cm-1 to 26,000 cm-1 assignable to 6A1g → 4T2g and 6A1g → 4E1g transitions. These are also typical of tetrahedral environment around the manganese. The magnetic moment (5.80 BM of the complex indicates high spin tetrahedral environment. The microwave method of synthesis of complexes have been found easier, convenient and ecofriendly.

  20. [Pr2(pdc3(Hpdc(H2O4]n·n(H3hp·8n(H2O, a One-Dimensional Coordination Polymer Containing PrO6N3 Tri-Capped Trigonal Prisms and PrO8N Mono-Capped Square Anti-Prisms (H2pdc = Pyridine 2,6-Dicarboxylic Acid, C7H5NO4; 3hp = 3-Hydroxy Pyridine, C5H5NO

    Directory of Open Access Journals (Sweden)

    Shahzad Sharif

    2012-08-01

    Full Text Available The synthesis, structure and some properties of the one-dimensional coordination polymer, [Pr2(pdc3(Hpdc]n·n(H3hp·8n(H2O, (H2pdc = pyridine 2,6-dicarboxylic acid, C7H5NO4; 3hp = 3-hydroxypyridine, C5H5NO are described. One of the Pr3+ ions is coordinated by two O,N,O-tridentate pdc2− ligands and one tridentate Hpdc− anion to generate a fairly regular PrO6N3 tri-capped trigonal prism, with the N atoms acting as the caps. The second Pr3+ ion is coordinated by one tridentate pdc2− dianion, four water molecules and two monodentate bridging pdc2− ligands to result in a PrO8N coordination polyhedron that approximates to a mono-capped square-anti-prism. The ligands bridge the metal-atom nodes into a chain, which extends in the [100] direction. The H3hp+ cation and uncoordinated water molecules occupy the inter-chain regions and an N–HLO and numerous O–HLO hydrogen bonds consolidate the structure. The H3hp+ species appears to intercalate between pendant pdc rings to consolidate the polymeric structure. Crystal data: 1 (C33H43N5O29Pr2, Mr = 1255.54, triclinic,  (No. 2, Z = 2, a = 13.2567(1 Å, b = 13.6304(2 Å, c = 13.6409(2 Å, α = 89.695(1°, β = 63.049(1°, γ = 86.105(1°, V = 2191.16(5 Å3, R(F = 0.033, wR(F2 = 0.084.

  1. Electronic structure aspects of the complete O2 transfer reaction between Ni(II) and Mn(II) complexes with cyclam ligands.

    Science.gov (United States)

    Zapata-Rivera, Jhon; Caballol, Rosa; Calzado, Carmen J

    2015-01-28

    This work explores the electronic structure aspects involving the complete intermolecular O2 transfer between Ni(ii) and Mn(ii) complexes, both containing N-tetramethylated cyclams (TMC). The energy of the low-lying states of reactants, intermediates and products is established at the CASSCF level and also the DDCI level when possible. The orthogonal valence bond analysis of the wave functions obtained from CASSCF and DDCI calculations indicates the dominant superoxide nature of all the adducts participating in the reaction, and consequently that the whole reaction can be described as the transfer of the superoxide O2(-) between Ni(ii) and Mn(ii) complexes, without any additional change in the electronic structure of the fragments.

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

    Directory of Open Access Journals (Sweden)

    W. FERENC

    2005-09-01

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

  3. Treatment of groundwater containing Mn(II), Fe(II), As(III) and Sb(III) by bioaugmented quartz-sand filters.

    Science.gov (United States)

    Bai, Yaohui; Chang, Yangyang; Liang, Jinsong; Chen, Chen; Qu, Jiuhui

    2016-12-01

    High concentrations of iron (Fe(II)) and manganese (Mn(II)) often occur simultaneously in groundwater. Previously, we demonstrated that Fe(II) and Mn(II) could be oxidized to biogenic Fe-Mn oxides (BFMO) via aeration and microbial oxidation, and the formed BFMO could further oxidize and adsorb other pollutants (e.g., arsenic (As(III)) and antimony (Sb(III))). To apply this finding to groundwater remediation, we established four quartz-sand columns for treating groundwater containing Fe(II), Mn(II), As(III), and Sb(III). A Mn-oxidizing bacterium (Pseudomonas sp. QJX-1) was inoculated into two parallel bioaugmented columns. Long-term treatment (120 d) showed that bioaugmentation accelerated the formation of Fe-Mn oxides, resulting in an increase in As and Sb removal. The bioaugmented columns also exhibited higher overall treatment effect and anti-shock load capacity than that of the non-bioaugmented columns. To clarify the causal relationship between the microbial community and treatment effect, we compared the biomass of active bacteria (reverse-transcribed real-time PCR), bacterial community composition (Miseq 16S rRNA sequencing) and community function (metagenomic sequencing) between the bioaugmented and non-bioaugmented columns. Results indicated that the QJX1 strain grew steadily and attached onto the filter material surface in the bioaugmented columns. In general, the inoculated strain did not significantly alter the composition of the indigenous bacterial community, but did improve the relative abundances of xenobiotic metabolism genes and Mn oxidation gene. Thus, bioaugmentation intensified microbial degradation/utilization for the direct removal of pollutants and increased the formation of Fe-Mn oxides for the indirect removal of pollutants. Our study provides an alternative method for the treatment of groundwater containing high Fe(II), Mn(II) and As/Sb. Copyright © 2016 Elsevier Ltd. All rights reserved.

  4. Kinetics and Mechanism of Mn(II Catalyzed Periodate Oxidation of p-anisidine: Effect of pH

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    Rajneesh Dutt Kaushik

    2014-10-01

    Full Text Available The stoichiometry for the initial part of the reaction, Mn(II catalysed periodate oxidation of p-anisidine (PMA, has been found to be 1 mol of PMA consuming 2 mol of periodate ion. The kinetic-mechanistic study of reaction in acetone-water medium was made spectrophotometrically by noting the increase in the absorbance of reaction intermediate. Reaction is first order in reactants and catalyst each. A decrease in dielectric constant of the medium results in decrease in the rate of reaction suggesting an ion-dipole type interaction. Free radical scavengers do not affect the reaction rate. A special type of rate-pH profile shows a maximum at pH = 7.0. This pH effect also suggests the involvement of at least three differently reactive reactant species in the reaction and this fact has been considered by us while deriv-ing the rate law. Under pseudo first order conditions [IO4-] >> [PMA] and in agreement with the derived rate law, the 1/kcat versus [H+] plot passes through the minimum and the results can be fitted to the equation: 1/kcat = (K2 / k K3 K4 [H+] + {(Kw + Kb K2 / k K3 K4 Kw} + Kb [H+] / k K3 K4 Kw, where kK3K4 is the empirical composite rate constant, Kw is ionic product of water, K2 is acid dissociation constant of H4IO6- and Kb is base dissociation constant of PMA. The experimental value of [H+]min is in good agreement with the value calculated by using the derived rate law equation and is character-istic of the substrate involved relating to the base dissociation constant of PMA. The value of thermo-dynamic parameters have been evaluated. © 2014 BCREC UNDIP. All rights reservedReceived: 2nd May 2014; Revised: 2nd July 2014; Accepted: 5th July 2014How to Cite: Kaushik, R.D., Singh, J., Manila, M., Kaur, M., Singh, P. (2014. Kinetics and Mechanism of MnII Catalyzed Periodate Oxidation of p-anisidine: Effect of pH. Bulletin of Chemical Reaction En-gineering & Catalysis, 9(3: 182-191. (doi: 10.9767/bcrec.9.3.6823.182-191Permalink

  5. Growth and productivity of different Pleuritus ostreatus strains on sunflower seed hulls supplemented with N-NH{sub 4}{sup +} and/or Mn(II)

    Energy Technology Data Exchange (ETDEWEB)

    Curvetto, N.R.; Figlas, D.; Devalis, R.; Delmastro, S. [Universidad Nacional del Sur, Buenos Aires (Argentina). Departamento de Agronomia

    2002-09-01

    The mycelial growth rates in lineal growth assay, yield, and production rate of five Pleurotus ostreatus strains were evaluated in response to different levels of Mn(II) and/or NH{sub 4}{sup +} in a substrate containing sunflower seed hulls as a main energy and nutritional component. Each strain showed different basal values for mycelial growth rate and biological efficiency on sunflower seed-hull substrate. Adding growth limiting mineral nutrients increased the mycelial growth rate by 13-25%. Primordia initiation for the first flush appeared between day 24 and 28 and days to the second crop ranged from 39 to 51. Biological efficiency increased over control values and reached 60-112%, depending on the strain and the concentration of Mn(II) and NH{sub 4}{sup +}. This study demonstrated the advantage of selecting the most productive P. ostreatus strains in a substrate formulated with sunflower seed hulls to provide the main energy and nutritional ingredients and supplemented with Mn(II) and/or NH{sub 4}{sup +}. (author)

  6. Growth and productivity of different Pleurotus ostreatus strains on sunflower seed hulls supplemented with N-NH4+ and/or Mn(II).

    Science.gov (United States)

    Curvetto, N R; Figlas, D; Devalis, R; Delmastro, S

    2002-09-01

    The mycelial growth rates in lineal growth assay, yield, and production rate of five Pleurotus ostreatus strains were evaluated in response to different levels of Mn(II) and/or NH4+ in a substrate containing sunflower seed hulls as a main energy and nutritional component. Each strain showed different basal values for mycelial growth rate and biological efficiency on sunflower seed-hull substrate. Adding growth limiting mineral nutrients increased the mycelial growth rate by 13-25%. Primordia initiation for the first flush appeared between day 24 and 28 and days to the second crop ranged from 39 to 51. Biological efficiency increased over control values and reached 60-112%, depending on the strain and the concentration of Mn(II) and NH4+. This study demonstrated the advantage of selecting the most productive P. ostreatus strains in a substrate formulated with sunflower seed hulls to provide the main energy and nutritional ingredients and supplemented with Mn(II) and/or NH4+.

  7. A Multifunctional Mn(II) Phosphonate for Rapid Separation of Methyl Orange and Electron-Transfer Photochromism.

    Science.gov (United States)

    Gao, Chao-Ying; Yang, Yang; Ai, Jing; Tian, Hong-Rui; Li, Lei-Jiao; Yang, Weiting; Dang, Song; Sun, Zhong-Ming

    2016-08-08

    A Mn(II) phosphonate of the general formula [Mn(H2 L)2 (H2 O)2 (H2 bibp)] adopts a layered motif with protonated H2 bibp(2+) cations embedded in the channels (H4 L=thiophene-2-phosphonic acid; bibp=4,4'-bis(1-imidazolyl)biphenyl). The title compound exhibits excellent adsorptive removal of methyl orange (MO) dye from aqueous solution. Its advantageous features include fast adsorption, high uptake capacity, selective removal, and reusability, which are of great significance for practical application in wastewater treatment. Meanwhile, the compound displays rapid photochromism upon irradiation with visible light at room temperature. Extensive research has demonstrated that such behavior is based on a ligand-to-ligand charge-transfer (LLCT) mechanism. The irradiated sample possesses an ultra-long-lived charge-separated state. Moreover, not only is the compound the first Mn-based photochromic MOF, but it is also one of the very few examples showing LLCT with non-photochromic components. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Crystal Structures Reveal that the Reaction Mechanism of Imidazoleglycerol-Phosphate Dehydratase Is Controlled by Switching Mn(II) Coordination

    Science.gov (United States)

    Bisson, Claudine; Britton, K. Linda; Sedelnikova, Svetlana E.; Rodgers, H. Fiona; Eadsforth, Thomas C.; Viner, Russell C.; Hawkes, Tim R.; Baker, Patrick J.; Rice, David W.

    2015-01-01

    Summary Imidazoleglycerol-phosphate dehydratase (IGPD) catalyzes the Mn(II)-dependent dehydration of imidazoleglycerol phosphate (IGP) to 3-(1H-imidazol-4-yl)-2-oxopropyl dihydrogen phosphate during biosynthesis of histidine. As part of a program of herbicide design, we have determined a series of high-resolution crystal structures of an inactive mutant of IGPD2 from Arabidopsis thaliana in complex with IGP. The structures represent snapshots of the enzyme trapped at different stages of the catalytic cycle and show how substrate binding triggers a switch in the coordination state of an active site Mn(II) between six- and five-coordinate species. This switch is critical to prime the active site for catalysis, by facilitating the formation of a high-energy imidazolate intermediate. This work not only provides evidence for the molecular processes that dominate catalysis in IGPD, but also describes how the manipulation of metal coordination can be linked to discrete steps in catalysis, demonstrating one way that metalloenzymes exploit the unique properties of metal ions to diversify their chemistry. PMID:26095028

  9. Mn(II) complexes containing the polypyridylic chiral ligand (-)-pinene[5,6]bipyridine. Catalysts for oxidation reactions.

    Science.gov (United States)

    Rich, Jordi; Rodríguez, Montserrat; Romero, Isabel; Vaquer, Lydia; Sala, Xavier; Llobet, Antoni; Corbella, Montserrat; Collomb, Marie-Noëlle; Fontrodona, Xavier

    2009-10-14

    A series of mononuclear and dinuclear chiral manganese(II) complexes containing the neutral bidentate chiral nitrogen ligand (-)-pinene[5,6]bipyridine, (-)-L, were prepared from different manganese salts. The chirality in these complexes arises from the pinene ring that has been fused to the 5,6 positions of one pyridine group of the bipyridine ligand. These complexes have been characterized through analytical, spectroscopic (IR, UV/Vis, ESI-MS) and electrochemical techniques (cyclic voltammetry). Single X-ray structure analysis revealed a five-coordinated Mn(II) ion in [{MnCl((-)-L)}2(mu-Cl)2] (2), [{Mn((-)-L)}2(mu-OAc)3](PF6) (3) and [MnCl2(H2O)((-)-L)] (4) and a six-coordinated one in [MnCl2((-)-L)2] (5), [Mn(CF3SO3)2((-)-L)2] (6) and [Mn(NO3)(H2O)((-)-L)2)](NO3) (7). The magnetic properties of the binuclear compounds 2 and 3 have been studied. Both compounds show a weak antiferromagnetic coupling (2, J = -0.22 cm(-1); 3, J = -0.85 cm(-1)). The catalytic activity of the whole set of complexes has been tested with regard to the epoxidation of aromatic alkenes with peracetic acid. In the particular case of styrene, good selectivities and moderate enantioselectivities were obtained. Furthermore, total retention of the initial cis configuration was achieved when epoxidizing cis-beta-methylstyrene with the chloride complexes. In general, the epoxidation activity of these manganese complexes is strongly dependent on the steric encumbrance of the substrates employed.

  10. 1,1,1-Tris(hydroxymethyl)propane in manganese carboxylate chemistry: synthesis, structure and magnetic properties of a mixed-valence [MnIII4MnII4] cluster featuring the novel [MnIII4MnII4(mu3-OR)6(mu2-OR)8]6+ core.

    Science.gov (United States)

    Milios, Constantinos J; Fabbiani, Francesca P A; Parsons, Simon; Murugesu, Muralee; Christou, George; Brechin, Euan K

    2006-01-14

    The reaction between MnBr(2).4H(2)O with H(3)tmp (1,1,1-tris(hydroxymethyl)propane) in MeCN in the presence of Na(O(2)CCMe(3)) and NBu(4)Br produces the complex [Mn(8)(O(2)CCMe(3))(2)(tmp)(2)(Htmp)(4)Br(4)(H(2)O)(2)].2MeCN (1.2MeCN) in good yield. The centrosymmetric octanuclear molecule consists of four Mn(III) and four Mn(II) ions assembled together by fourteen alkoxo bridges to give a [Mn(III)(4)Mn(II)(4)(mu(3)-OR)(6)(mu(2)-OR)(8)](6+) rod-like core in which the metal centres are arranged in a planar zigzag fashion. Peripheral ligation is provided by a combination of bridging pivalate ions, terminal bromides and water molecules. Dc magnetic susceptibility measurements reveal the presence of dominant antiferromagnetic interactions leading to a spin ground state of S = 0. A rationalization of this result is attempted by structural comparison with previously reported tetranuclear manganese complexes containing the [Mn(III)(2)Mn(II)(2)(mu(3)-OR)(2)(mu(2)-OR)(4)] core in which the magnetic interactions are ferromagnetic.

  11. Synthesis and crystal structure of a novel Mn(II) coordination polymer with 3-(4-(1 H-benzo[d]imidazol-1-yl)-4-methoxyphenyl)-1-phenylprop-2-en-1-one ligands

    Science.gov (United States)

    Wang, G.-F.; Zhang, X.; Sun, S.-W.; Han, Q.-P.; Yang, X.; Li, H.; Ma, H.-X.; Yao, C.-Z.; Sun, H.; Dong, H.-B.

    2015-12-01

    3-(4-(1 H-Benzo[d]imidazol-1-yl)-4-methoxyphenyl)-1-phenylprop-2-en-1-one ( L 1 , 1) and its Mn(II) complex, [Mn( L 1 )2(SCN)2]∞ ( 2), were synthesized and characterized by elemental analyses, IR spectroscopy and single-crystal X-ray diffraction. The Mn(II) ion in 2 is six-coordinated to four nitrogen atoms of two L 1 ligands, two SCN-ligands, and two oxygen atoms of other two L 1 ligands to form a distorted octahedral geometry. Therefore, each L 1 links Mn ions through the O and N atoms to generate 2D sheet structure.

  12. Breakthrough Curve Analysis for Column Dynamics Sorption of Mn(II Ions from Wastewater by Using Mangostana garcinia Peel-Based Granular-Activated Carbon

    Directory of Open Access Journals (Sweden)

    Z. Z. Chowdhury

    2013-01-01

    Full Text Available The potential of granular-activated carbon (GAC derived from agrowaste of Mangostene (Mangostana garcinia fruit peel was investigated in batch and fixed bed system as a replacement of current expensive methods for treating wastewater contaminated by manganese, Mn(II cations. Batch equilibrium data was analyzed by Langmuir, Freundlich, and Temkin isotherm models at different temperatures. The effect of inlet metal ion concentration (50 mg/L, 70 mg/L, and 100 mg/L, feed flow rate (1 mL/min and 3 mL/min, and activated carbon bed height (4.5 cm and 3 cm on the breakthrough characteristics of the fixed bed sorption system were determined. The adsorption data were fitted with well-established column models, namely, Thomas, Yoon-Nelson, and Adams-Bohart. The results were best-fitted with Thomas and Yoon-Nelson models rather than Adams-Bohart model for all conditions. The column had been regenerated and reused consecutively for five cycles. The results demonstrated that the prepared activated carbon was suitable for removal of Mn(II ions from wastewater using batch as well as fixed bed sorption system.

  13. Effect of L-alanine, Mn(II) and glycine dopants on the structural, crystalline perfection, second harmonic generation (SHG), dielectric and mechanical properties of BTCA single crystals

    Energy Technology Data Exchange (ETDEWEB)

    Ganesh, V. [Department of Physics, Ganapathy Engineering College, Warangal 506005 (India); Bhaskar Rao, T.; Kishan Rao, K. [Department of Physics, Kakatiya University, Warangal 506009 India (India); Bhagavannarayana, G. [CSIR-National Physical Laboratory, Dr. K.S. Krishnan Road, New Delhi 110012 (India); Shkir, Mohd, E-mail: shkirphysics@gmail.com [Department. of Physics, Atma Ram Sanatan Dharma (ARSD) College, University of Delhi, New Delhi 110021 (India) and CSIR-National Physical Laboratory, Dr. K.S. Krishnan Road, New Delhi 110012 (India)

    2012-11-15

    Bis thiourea cadmium acetate (BTCA) single crystals were grown at room temperature with different dopants by aqueous solution technique. The crystal system of the grown crystals with all the dopants was confirmed by powder X-ray diffraction study which confirms that there is no extra phase due to doping of L-alanine (LA), Mn(II) and glycine (Gly). It was further confirmed by FT-IR as well as FT-Raman spectroscopy analysis. The effect of LA, Mn(II) and Gly doping on the crystalline perfection was assessed by high-resolution X-ray diffractometry (HRXRD) analysis which revealed that the grown crystals with Gly doping are more perfect in comparison of other dopants. The SHG efficiency was measured using the Kurtz powder technique and shows that the grown crystals with Gly doping are more efficient in comparison of other dopants which is in tune with crystalline perfection. The low values of dielectric constant and loss also revealed that the grown crystals are defect free. The hardness values were found to be increased by increasing the doping concentration. -- Highlights: Black-Right-Pointing-Pointer The strong effect on crystalline perfection was found in BTCA crystals due to glycine doping. Black-Right-Pointing-Pointer The SHG efficiency was found to be higher in case of glycine doped BTCA crystals. Black-Right-Pointing-Pointer The hardness value was found to be increase with doping.

  14. Preparation, Investigation and the Study of the Effect of Mn(II Complex of Catechol and 2-Aminopyridine on Seed Germination

    Directory of Open Access Journals (Sweden)

    F. I. El-Moshaty

    2011-01-01

    Full Text Available The formation of mixed ligand complex of Mn(II with catechol (L1 and 2-aminopyridine (L2 was determined by elemental analyses (C, H and N, molar conductance measurement, thermogravimetric analysis, infrared, electronic and electron paramagnetic resonance spectroscopies. The elemental analysis data show the formation of 1:1:1 [M: L1: L2] complex. The molar conductance measurement shows a non-electrolyte nature. The thermogravimetric analysis data of the complex display the existence of hydrated and coordinated water molecules. The infrared spectral data exhibit the coordination sites that are through -OH,-C=N and –NH2 groups. The electronic spectral data display the electronic transitions of the ligands and suggest an octahedral structure for the complex. The electron paramagnetic resonance spectrum of the complex reveals the existence of paramagnetic phenomena and supports its geometrical structure. Seed germination and root length of grass were also assayed under the effect of MnCl2.4H2O, catechol, 2-aminopyridine and its complex. Mn(II salt was the most effective on germination than its complex which possess the high test effect on root length, while the ligands are the least active of all.

  15. A [Mn18Dy] SMM resulting from the targeted replacement of the central MnII in the S = 83/2 [Mn19]-aggregate with DyIII.

    Science.gov (United States)

    Ako, Ayuk M; Mereacre, Valeriu; Clérac, Rodolphe; Wernsdorfer, Wolfgang; Hewitt, Ian J; Anson, Christopher E; Powell, Annie K

    2009-02-07

    Anisotropy can be introduced into the [Mn(19)]-aggregate, which currently has the highest known spin ground state of S = 83/2, by the targeted replacement of the central Mn(II) cation with Dy(III) leading to a [Mn(18)Dy] complex with the same core topology showing slow relaxation of the magnetisation.

  16. Mn(II) and Cu(II) complexes of a bidentate Schiff's base ligand: Spectral, thermal, molecular modelling and mycological studies

    Science.gov (United States)

    Tyagi, Monika; Chandra, Sulekh; Tyagi, Prateek

    2014-01-01

    Complexes of manganese(II) and copper(II) of general composition M(L)2X2 have been synthesized [L = 2-acetyl thiophene thiosemicarbazone and X = Cl- and NO3-]. The elemental analysis, molar conductance measurements, magnetic susceptibility measurements, mass, IR, UV, NMR and EPR spectral studies of the compounds led to the conclusion that the ligand acts as a bidentate manner. The Schiff's base ligand forms hexacoordinated complexes having octahedral geometry for Mn(II) and tetragonal geometry for Cu(II) complexes. The thermal studies suggested that the complexes are more stable as compared to ligand. In molecular modelling the geometries of Schiff's base and metal complexes were fully optimized with respect to the energy using the 6-31g(d,p) basis set. The mycological studies of the compounds were examined against the plant pathogenic fungi i.e. Rhizoctonia bataticola, Macrophomina phaseolina, Fusarium odum.

  17. Green microwave switching from oxygen rich yellow anatase to oxygen vacancy rich black anatase TiO₂ solar photocatalyst using Mn(II) as 'anatase phase purifier'.

    Science.gov (United States)

    Ullattil, Sanjay Gopal; Periyat, Pradeepan

    2015-12-07

    Green and rapid microwave syntheses of 'yellow oxygen rich' (YAT-150) and 'black oxygen vacancy rich' (BAT-150) anatase TiO2 nanoparticles are reported for the first time. YAT-150 was synthesized using only titanium(iv) butoxide and water as precursors. The in situ precursor modification by Mn(ii) acetate switched anatase TiO2 from YAT-150 to BAT-150. The entry of Mn(2+) into the crystal lattice of anatase TiO2 paved the way for peak texturing in the existing peak orientations along with the origin of three new anatase TiO2 peaks in the (103), (213) and (105) directions. The as synthesized ultra-small (∼5 nm) yellow and black anatase TiO2 nanoparticles were found to be two fold and four fold more photoactive than the commercially available photocatalyst Degussa-P25 under sunlight illumination.

  18. A rare 3D chloro-laced Mn(II) metal-organic framework to show sensitive probing effect to Hg2+

    Science.gov (United States)

    Ming, Mei; Bai, Na

    2017-10-01

    Two 3D Mn(II) metal-organic frameworks (MOFs), [Mn(L-Cl)(DMA)](H2O) (1) and Mn(L-CH3)(DMA) (2) (H2L-Cl = 2,2'-dichloro-4,4'-azodibenzoic acid, H2L-CH3 = 2,2'-dimethyl-4,4'-azodibenzoic acid) were synthesized under similar solvothermal condition. Both MOFs crystallize in the orthorhombic system and show the 3D rod-packing networks in 2-fold interpenetrated pattern with sra topology. Due to the different substituent laces of MOFs (-Cl vs -CH3), only MOF 1 shows highly selective and sensitive fluorescence sensing effect for detecting Hg2+ ion.

  19. Synthesis, Characterization and Antimicrobial Activities of 1,2,4-Triazole /Isatin Schiff bases and their Mn(II, Co(II complexes

    Directory of Open Access Journals (Sweden)

    Sunita Bajroliya

    2014-12-01

    Full Text Available Mn(II and Co(II metal complexes have been synthesized with newly synthesized Schiff bases derived from isatin/5-nitroisatin and 3-substituted-4-amino-5-mercapto-1,2,4-triazole by new environmental benign microwave irradiation method as well as conventional method. Reaction achieved by microwave irradiation technique, require drastically reduced reaction time and provide high yield with improved selectivity as compared to conventional method. The synthesized compounds were characterized by elemental analysis as well as spectral studies. The elemental analysis were clearly indicated that ML2 type complexes have 1:2 stoichiometry (M=metal, L=ligand. The synthesized Schiff bases and their metal complexes screened for antimicrobial activities against selected bacteria and fungi.

  20. Synthesis, spectral, thermal and magnetic studies of Mn(II), Ni(II) and Cu(II) complexes with some benzopyran-4-one Schiff bases.

    Science.gov (United States)

    el-Ansary, Aida L; Abdel-Fattah, Hussein M; Abdel-Kader, Nora S

    2011-08-01

    The Schiff bases of N(2)O(2) dibasic ligands, H(2)La and H(2)Lb are prepared by the condensation of ethylenediamine (a) and trimethylenediamine (b) with 6-formyl-7-hydroxy-5-methoxy-2-methylbenzopyran-4-one. Also tetra basic ligands, H(4)La and H(4)Lb are prepared by the condensation of aliphatic amines (a) and (b) with 6-formyl-5,7-dihydroxy-2-methylbenzopyran-4-one. New complexes of H(4)La and H(4)Lb with metal ions Mn(II), Ni(II) and Cu(II) are synthesized, in addition Mn(II) complexes with ligands H(2)La and H(2)Lb are also synthesized. Elemental and thermal analyses, infrared, ultraviolet-visible as well as conductivity and magnetic susceptibility measurements are used to elucidate the structure of the newly prepared metal complexes. The structures of copper(II) complexes are also assigned based upon ESR spectra study. All the complexes separated with the stoichiometric ratio (1:1) (M:L) except Mn-H(4)La and Mn-H(4)Lb with (2:1) (M:L) molar ratio. In metal chelates of the type 1:1 (M:L), the Schiff bases behave as a dinegative N(2)O(2) tetradentate ligands. Moreover in 2:1 (M:L) complexes, the Schiff base molecules act as mono negative bidentate ligand and binuclear complex is then formed. The Schiff bases were assayed by the disc diffusion method for antibacterial activity against Staphylococcus aureus and Escherichia coli. The antifungal activity of the Schiff bases was also evaluated against the fungi Aspergillus flavus and Candida albicans.

  1. Self-assembled decanuclear Na(I)2Mn(II)4Mn(III)4 complexes: from discrete clusters to 1-D and 2-D structures, with the Mn(II)4Mn(III)4 unit displaying a large spin ground state and probable SMM behaviour.

    Science.gov (United States)

    Langley, Stuart K; Chilton, Nicholas F; Moubaraki, Boujemaa; Murray, Keith S

    2011-12-07

    The synthesis, magnetic characterization and X-ray crystal structures are reported for five new manganese compounds, [Mn(III)(teaH(2))(sal)]·(1/2)H(2)O (1), [Na(I)(2)Mn(II)(4)Mn(III)(4)(teaH)(6)(sal)(4)(N(3))(2)(MeOH)(4)]·6MeOH (2), [Na(I)(2)Mn(II)(4)Mn(III)(4)(teaH)(6)(sal)(4)(N(3))(2)(MeOH)(2)](n)·7MeOH (3), [Na(I)(2)Mn(II)(4)Mn(III)(4)(teaH)(6)(sal)(4)(N(3))(2)(MeOH)(2)](n)·2MeOH·Et(2)O (4) and [K(I)(2)Mn(II)(4)Mn(III)(4)(teaH)(6)(sal)(4)(N(3))(2)(H(2)O)(2)](n)·5MeOH (5). Complex 1 is a mononuclear compound, formed via the reaction of Mn(NO(3))(2)·4H(2)O, triethanolamine (teaH(3)) and salicylic acid (salH(2)) in a basic methanolic solution. Compound 2 is a mixed-valent hetero-metallic cluster made up of a Mn(8)Na(2) decanuclear core and is formed via the reaction of sodium azide (NaN(3)) with 1. Compounds 3-5 are isolated as 1- or 2-D coordination polymers, each containing the decanuclear Mn(8)M(2) (M = Na(+) or K(+)) core building block as the repeating unit. Compound 3 is isolated when 1 is reacted with NaN(3) over a very short reaction time and forms a 1-D coordination polymer. Each unit displays inter-cluster bridges via the O-atoms of teaH(2-) ligands bonding to the sodium ions of an adjacent cluster. Increasing the reaction time appears to drive the formation of 4 which forms 2-D polymeric sheets and is a packing polymorph of 3. The addition of KMnO(4) and NaN(3) to 1 resulted in compound 5, which also forms a 1-D coordination polymer of the decanuclear core unit. The 1-D chains are now linked via inter-cluster potassium and salicylate bridges. Solid state DC susceptibility measurements were performed on compounds 1-5. The data for 1 are as expected for an S = 2 Mn(III) ion, with the isothermal M vs. H data being fitted by matrix diagonalization methods to give values of g and the axial (D) and rhombic (E) zero field splitting parameters of 2.02, -2.70 cm(-1) and 0.36 cm(-1) respectively. The data for 2-5, each with an identical Mn(II)(4)Mn(III)(4

  2. Synthesis, characterization, fluorescence and biological studies of Mn(II, Fe(III and Zn(II complexes of Schiff bases derived from Isatin and 3-substituted-4-amino-5-mercapto-1,2,4-triazoles

    Directory of Open Access Journals (Sweden)

    Sangamesh A. Patil

    2014-12-01

    Full Text Available A series of Mn(II, Fe(III and Zn(II complexes have been synthesized with Schiff bases derived from isatin and 3-substituted-4-amino-5-mercapto-1,2,4-triazole. The elemental, spectroscopic (Infrared, nuclear magnetic resonance, ultraviolet-visible, fast atom bombardment-mass, fluorescence and electrochemistry and magnetic studies suggested that the metal complexes possess octahedral geometry. The Schiff bases and their metal complexes exhibit fluorescent properties. The antimicrobial studies of Schiff bases and their metal complexes against various bacterial (Escherichia coli, Staphylococcus aureus, Pseudomonas aeruginosa and Bacillus subtilis and fungal (Aspergillus niger, and Penicillium chrysogenum species by the minimum inhibitory concentration method revealed that the metal complexes possess more healing antibacterial activities than the Schiff bases. DNA cleavage property of Mn(II, Fe(III and Zn(II complexes revealed the important role of metal ion in the biological system.

  3. Synthesis and crystal structure of a novel Mn(II) coordination polymer with 3-(4-(1H-benzo[d]imidazol-1-yl)-4-methoxyphenyl)-1-phenylprop-2-en-1-one ligands

    Energy Technology Data Exchange (ETDEWEB)

    Wang, G.-F., E-mail: wgf1979@126.com [Yuncheng University, Department of Applied Chemistry (China); Zhang, X., E-mail: zhangx@hit.edu.cn [Harbin Institute of Technology, Academy of Fundamental and Interdisciplinary Science (China); Sun, S.-W., E-mail: s-shuwen@163.com; Han, Q.-P.; Yang, X.; Li, H.; Ma, H.-X.; Yao, C.-Z.; Sun, H. [Yuncheng University, Department of Applied Chemistry (China); Dong, H.-B., E-mail: Donghb0622@126.com [Jilin Medical College, College of Pharmacy (China)

    2015-12-15

    3-(4-(1H-Benzo[d]imidazol-1-yl)-4-methoxyphenyl)-1-phenylprop-2-en-1-one (L{sup 1}, 1) and its Mn(II) complex, [Mn(L{sup 1}){sub 2}(SCN){sub 2}]{sub ∞} (2), were synthesized and characterized by elemental analyses, IR spectroscopy and single-crystal X-ray diffraction. The Mn(II) ion in 2 is six-coordinated to four nitrogen atoms of two L{sup 1} ligands, two SCN-ligands, and two oxygen atoms of other two L{sup 1} ligands to form a distorted octahedral geometry. Therefore, each L{sup 1} links Mn ions through the O and N atoms to generate 2D sheet structure.

  4. Synthesis and spectral studies of Cu(II, Ni(II, Co(II, Mn(II, Zn(II and Cd(II complexes of a new macroacyclic ligand N,N’-bis(2-benzothiazolyl-2,6-pyridinedicarboxamide

    Directory of Open Access Journals (Sweden)

    KALAGOUDA B. GUDASI

    2006-05-01

    Full Text Available A new macroacyclic amide ligand N,N’-bis(2-benzothiazolyl-2,6-pyridinedicarboxamide (BPD, formed by the condensation of 2,6-pyridinedicarbonyldichloride with 2-aminobenzothiazole, and its Cu(II, Ni(II, Co(II, Mn(II, Zn(II and Cd(II complexes were synthesized. Their structures were elucidated on the basis of elemental analyses, conductance measurements, magnetic moments, spectral (IR, NMR, UV-Visible, EPR and FAB and thermal studies. The complexes exhibit an octahedral geometry around the metal center. Conductance data of the complexes suggested them to be 1:1 electrolytes. The pentadentate behavior of the ligand was proposed on the basis of spectral studies. The X-band EPR spectra of the Cu(II and Mn(II complexes in the polycrystalline state at room (300 K and liquid nitrogen temperature (77 K were recorded and their salient features are reported.

  5. Synthesis and characterisation of Cu(II), Ni(II), Mn(II), Zn(II) and VO(II) Schiff base complexes derived from o-phenylenediamine and acetoacetanilide

    Indian Academy of Sciences (India)

    N Raman; Y Pitchaikani Raja; A Kulandaisamy

    2001-06-01

    Neutral tetradentate N2O2 type complexes of Cu(II), Ni(II), Mn(II), Zn(II) and VO(II) have been synthesised using a Schiff base formed by the condensation of -phenylenediamine with acetoacetanilide in alcohol medium. All the complexes were characterised on the basis of their microanalytical data, molar conductance, magnetic susceptibility, IR, UV-Vis 1H NMR and ESR spectra. IR and UV-Vis spectral data suggest that all the complexes are square-planar except the Mn(II) and VO(II) chelates, which are of octahedral and square pyramidal geometry respectively. The monomeric and neutral nature of the complexes was confirmed by their magnetic susceptibility data and low conductance values. The ESR spectra of copper and vanadyl complexes in DMSO solution at 300 K and 77 K were recorded and their salient features are reported.

  6. New Mn(II, Ni(II, Cd(II, Pb(II complexes with 2-methylbenzimidazole and other ligands. Synthesis, spectroscopic characterization, crystal structure, magnetic susceptibility and biological activity studies

    Directory of Open Access Journals (Sweden)

    Shayma A. Shaker

    2016-11-01

    Full Text Available Synthesis and characterization of Mn(II, Ni(II, Cd(II and Pb(II mixed ligand complexes of 2-methylbenzimidazole with other ligands have been reported. The structure of the ligands and their complexes was investigated using elemental analysis, IR, UV–Vis, (1H, 13C NMR spectroscopy, molar conductivity and magnetic susceptibility measurements. In all the studies of complexes, the 2-methylbenzimidazole behaves as a neutral monodentate ligand which is coordinated with the metal ions through the N atom. While benzotriazole behaves as a neutral bidentate ligand which is coordinated with the Ni(II ion through the two N atoms. Moreover, the N-acetylglycine behaves as a bidentate ligand which is coordinated with the Mn(II, Ni(II and Pb(II ions through the N atom and the terminal carboxyl oxygen atom. The magnetic and spectral data indicate the tetrahedral geometry for Mn(II complex, irregular tetrahedral geometry for Pb(II complex and octahedral geometry for Ni(II complex. The X-ray single crystal diffraction method was used to confirm a centrosymmetric dinuclear Cd(II complex as each two metal ions are linked by a pair of thiocyanate N = S bridge. Two 2-methylbenzimidazole N-atom donors and one terminal thiocyanate N atom complete a highly distorted square pyramid geometry around the Cd atom. Besides, different cell types were used to determine the inhibitory effect of Mn(II, Ni(II, Cd(II and Pb(II complexes on cell growth using MTT assay. Cd(II complex showed cytotoxic effect on various types of cancer cell lines with different EC50 values.

  7. Simultaneous determination of Mn(II), Cu(II) and Fe(III) as 2-(5'-bromo-2'-pyridylazo)-5-diethylaminophenol complexes by adsorptive cathodic stripping voltammetry at a carbon paste electrode.

    Science.gov (United States)

    Ghoneim, Enass M

    2010-07-15

    A simple and precise square-wave adsorptive cathodic stripping voltammetry (SW-AdCSV) method has been described for simultaneous determination of Mn(II), Cu(II) and Fe(III) in water samples using a carbon paste electrode. In 0.1 mol L(-1) acetate buffer (pH 5) containing 50 micromol L(-1) of 2-(5'-bromo-2'-pyridylazo)-5-diethylaminophenol (5-Br-PADAP), Mn(II), Cu(II) and Fe(III) were simultaneously determined as metal-complexes with 5-Br-PADAP following preconcentration onto the carbon paste electrode by adsorptive accumulation at +1.0V (vs. Ag/AgCl/3M KCl). Insignificant interference from various cations (K(+), Na(+), Mg(2+), Ca(2+), Al(3+), Bi(3+), Sb(3+), Se(4+), Zn(2+), Ni(2+), Co(2+), Cd(2+), Pb(2+), V(5+), Ti(4+) and NH(4)(+)), anions (HCO(3)(-), Cl(-), NO(3-), SO(4)(2-) and PO(4)(3-)) and ascorbic acid was noticed. Limits of detection of 0.066, 0.108 and 0.093 microg L(-1) and limits of quantitation of 0.22, 0.36 and 0.31 microg L(-1) Mn(II), Cu(II) and Fe(III), respectively, were achieved by the described method. The described stripping voltammetry method was successfully applied for simultaneous determination of Mn(II), Cu(II) and Fe(III) in ground, tap and bottled natural water samples. Copyright 2010 Elsevier B.V. All rights reserved.

  8. Solid phase extraction of Cu(II), Ni(II), Pb(II), Cd(II) and Mn(II) ions with 1-(2-thiazolylazo)-2-naphthol loaded Amberlite XAD-1180.

    Science.gov (United States)

    Tokalioğlu, Serife; Yilmaz, Vedat; Kartal, Senol

    2009-05-01

    A new method for separation and preconcentration of trace amounts of Cu(II), Ni(II), Pb(II), Cd(II) and Mn(II) ions in various matrices was proposed. The method is based on the adsorption and chelation of the metal ions on a column containing Amberlite XAD-1180 resin impregnated with 1-(2-thiazolylazo)-2-naphthol (TAN) reagent prior to their determination by flame atomic absorption spectrometry (FAAS). The effect of pH, type, concentration and volume of eluent, sample volume, flow rates of sample and elution solutions, and interfering ions have been investigated. The optimum pH for simultaneous retention of all the metal ions was 9. Eluent for quantitative elution was 20 ml of 2 mol l(-1) HNO(3). The optimum sample and eluent flow rates were found as 4 ml min(-1), and also sample volume was 500 ml, except for Mn (87% recovery). The sorption capacity of the resin was found to be 0.77, 0.41, 0.57, and 0.30 mg g(-1) for Cu(II), Ni(II), Cd(II), and Mn(II), respectively. The preconcentration factor of the method was 200 for Cu(II), 150 for Pb(II), 100 for Cd(II) and Ni(II), and 50 for Mn(II). The recovery values for all of the metal ions were > or = 95% and relative standard deviations (RSDs) were < or = 5.1%. The detection limit values were in the range of 0.03 and 1.19 microg l(-1). The accuracy of the method was confirmed by analysing the certified reference materials (TMDA 54.4 fortified lake water and GBW 07605 tea samples) and the recovery studies. This procedure was applied to the determination of Cu(II), Ni(II), Pb(II), Cd(II) and Mn(II) in waste water and lake water samples.

  9. Synthesis, characterization, DFT calculations and biological studies of Mn(II), Fe(II), Co(II) and Cd(II) complexes based on a tetradentate ONNO donor Schiff base ligand

    Science.gov (United States)

    Abdel-Rahman, Laila H.; Ismail, Nabawia M.; Ismael, Mohamed; Abu-Dief, Ahmed M.; Ahmed, Ebtehal Abdel-Hameed

    2017-04-01

    This study highlights synthesis and characterization of a tetradentate ONNO Schiff base ligand namely (1, 1‧- (pyridine-2, 3-dimethyliminomethyl) naphthalene-2, 2‧-diol) and hereafter denotes as "HNDAP″ and selected metal complexes including Mn(II), Fe(II), Co(II) and Cd(II) as a central metal. HNDAP was synthesized from 1:2 M ratio condensation of 2, 3-diaminopyridine and 2- hydroxy-1-naphthaldhyde, respectively. The stoichiometric ratios of the prepared complexes were estimated using complementary techniques such as; elemental analyses (-C, H, N), FT-IR, magnetic measurements and molar conductivity. Furthermore, their physicochemical studies were carried out using thermal TGA, DTA and kinetic-thermodynamic studies along with DFT calculations. The results of elemental analyses showed that these complexes are present in a 1:1 metal-to- ligand molar ratio. Moreover, the magnetic susceptibilities values at room temperature revealed that Mn(II), Fe(II) and Co(II) complexes are paramagnetic in nature and have an octahedral (Oh) geometry. In contrast, Cd(II) is diamagnetic and stabilizes in square planar sites. The molar conductivity measurements indicated that all complexes are nonelectrolytes in dimethyl formamide. Spectral data suggested that the ligand is as tetradentate and coordinated with Co(II) ion through two phenolic OH and two azomethine nitrogen. However, for Mn(II), Fe(II) and Cd(II) complexes, the coordination occurred through two phenolic oxygen and two azomethine nitrogen with deprotonation of OH groups. The proposed chemical structures have been validated by quantum mechanics calculations. Antimicrobial activities of both the HNDAP Schiff base ligand and its metal complexes were tested against strains of Gram (-ve) E. coli and Gram (+ve) B. subtilis and S. aureus bacteria and C. albicans, A. flavus and T. rubrum fungi. All the prepared compounds showed good results of inhibition against the selected pathogenic microorganisms. The investigated

  10. Cu(II), Fe(III) and Mn(II) combinations as environmental stress factors have distinguishing effects on Enterococcus hirae.

    Science.gov (United States)

    Vardanyan, Zaruhi; Trchounian, Armen

    2015-02-01

    Pollution by various heavy metals as environmental stress factors might affect bacteria. It was established that iron (Fe(III)), manganese (Mn(II)) and copper (Cu(II)) ion combinations caused effects on Enterococcus hirae that differed from the sum of the effects when the metals were added separately. It was shown that the Cu2+-Fe3+ combination decreased the growth and ATPase activity of membrane vesicles of wild-type E. hirae ATCC9790 and atpD mutant (with defective FoF1-ATPase) MS116. Addition of Mn2+-Fe3+ combinations within the same concentration range had no effects on growth compared to control (without heavy metals). ATPase activity was increased in the presence of Mn2+-Fe3+, while together with 0.2 mmol/L N,N'-dicyclohexylcarbodiimide (DCCD), ATPase activity was decreased compared to control (when only 0.2 mmol/L DCCD was present). These results indicate that heavy metals ion combinations probably affect the FOF1-ATPase, leading to conformational changes. Moreover the action may be direct or be mediated by environment redox potential. The effects observed when Fe3+ was added separately disappeared in both cases, which might be a result of competing processes between Fe3+ and other heavy metals. These findings are novel and improve the understanding of heavy metals ions effects on bacteria, and could be applied for regulation of stress response patterns in the environment.

  11. A density functional study on magnetic exchange interaction between Mn(II) ion and nitronyl nitroxide radical in trans- and cis-metal-radical complexes

    Institute of Scientific and Technical Information of China (English)

    WEI; Haiyan; WANG; Fan; CHEN; Zhida

    2005-01-01

    The magneto-structural correlation between a Mn(II) ion, coordinated in an octahedral environment, and two nitronyl nitroxide radical ligands in trans- and cis-metal-radical complexes is investigated by the broken symmetry (BS) approach within density functional theory (DFT). The dependences of coupling constants J on three structural parameters: (i) bond angle(∈) (Mn-O-N (nitroxide)); (ii) rotating angle(∈), defined by the nitronyl nitroxide radical plane rotating around the axial Mn-O (nitroxide); (iii) bond distance R (Mn-O (nitroxide)) are directly calculated. Our calculations showed that both trans- and cis-Mn(II)-radical complexes behave a stronger antiferromagnetic interaction, consistent with experiments. In view of molecular orbital theory, the direct exchanges, including σ-type and π-type exchanges, are responsible for the magnetic exchange pathways. There is a preferable linear correlation between the calculated coupling constants J and the overlap integral squares between the local magnetic orbitals at the various rotating angle(∈) at the fixed bond angle(∈) and bond distance R, in both trans- and cis-Mn(II)- radical complexes.

  12. The effects of some compounds of Mn(II and Zn(II on the multiplication of wine yeast and biosynthesis of carbohydrates in the biomass

    Directory of Open Access Journals (Sweden)

    Agafia USATÎI

    2010-11-01

    Full Text Available The aim of investigation was to establish the influence of sulphates, acetates and coordination compounds of Mn(II and Zn(II as stimulators of the multiplication and growth of wine yeasts strain Saccharomyces cerevisiae CNMN-Y-20 and inducers of carbohydrate biosynthesis in biomass with the following elaboration of new procedures for directed carbohydrate biosynthesis. The study has been revealed that compounds MnSO4•4H2O, [Mn2Ac(2PyTCH-1,5-Bis(piridintiocarbohidrazid-dimanganese-acetate] and ZnLP-2 in optimal concentrations can be recommended as effective regulators of the yeast Saccharomyces cerevisiae CNMN-Y-20 multiplications, as well as compounds [Mn(Gly2]Cl2, (CH3COO2Zn and ZnLP-2 in established concentrations - of the carbohydrates biosynthesis in the biomass of studied wine yeast strain. Stimulatory properties of studied compounds of Mn2+ and Zn2+ on carbohydrate biosynthesis in biomass of Saccharomyces cerevisiae CNMN-Y-20 can be explained both by the action of metal and by the nature of the ligand. The obtained biomass of wine yeast strain with high content of carbohydrates can be utilized for the obtaining of new bioproducts with the following application in the field of medicine and cosmetology.

  13. Electrochemical studies of DNA interaction and antimicrobial activities of MnII, FeIII, CoII and NiII Schiff base tetraazamacrocyclic complexes

    Science.gov (United States)

    Kumar, Anuj; Vashistha, Vinod Kumar; Tevatia, Prashant; Singh, Randhir

    2017-04-01

    Tetraazamacrocyclic complexes of MnII, FeIII, CoII and NiII have been synthesized by template method. These tetraazamacrocycles have been analyzed with various techniques like molar conductance, IR, UV-vis, mass spectral and cyclic voltammetric studies. On the basis of all these studies, octahedral geometry has been assigned to these tetraazamacrocyclic complexes. The DNA binding properties of these macrocyclic complexes have been investigated by electronic absorption spectra, fluorescence spectra, cyclic voltammetric and differential pulse voltammetric studies. The cyclic voltammetric data showed that ipc and ipa were effectively decreased in the presence of calf thymus DNA, which is a strong evidence for the interaction of these macrocyclic complexes with the calf thymus DNA (ct-DNA). The heterogeneous electron transfer rate constant found in the order: KCoII > KNiII > KMnII which indicates that CoII macrocyclic complex has formed a strong intercalated intermediate. The Stern-Volmer quenching constant (KSV) and voltammetric binding constant were found in the order KSV(CoII) > KSV(NiII) > KSV(MnII) and K+(CoII) > K+(NiII) > K+(MnII) which shows that CoII macrocyclic complex exhibits the high interaction affinity towards ct-DNA by the intercalation binding. Biological studies of the macrocyclic complexes compared with the standard drug like Gentamycin, have shown antibacterial activities against E. coli, P. aeruginosa, B. cereus, S. aureus and antifungal activity against C. albicans.

  14. Synthesis, Characterization and DNA-Binding Properties of The Novel Mononuclear Zn(II, Cd(II, and Mn(II Complexes with Pantoprazole.

    Directory of Open Access Journals (Sweden)

    Wessam N. El-Sayed

    2016-04-01

    Full Text Available A   novel   mononuclear   Mn(II,   Zn(II   and   Cd(II   complexes of pantoprazole   (PA   was synthesized  and characterized  by elemental analysis,  molar conductivity,  magnetic susceptibility   measurements,   IR,  UV-visible  spectral  studies,  and  thermal  analysis.  The electronic spectra along with magnetic data suggest octahedral geometry for Mn(II, Zn(II and Cd(II complexes.  PA acts as an anionic bi-dentate ligand being coordinated by (S=O oxygen and benzimdazolyl nitrogen atoms. The interaction of the complexes with calf thymus DNA (CT-DNA was monitored by blue shift and hyperchromism in the UV-vis spectra. The observed  intrinsic  binding  constants  together  with  structural  analysis  of  the  complexes indicate  the groove  binding. The binding constants were determined at 303°K, 308°K and 313°K.  A thermodynamic analysis showed that the reaction is spontaneous with ΔG being negative. The enthalpy ΔH and the entropy ΔS of reactions were all determined.

  15. Oscillatory oxidation of Mn(II) ions by hexacyanoferrates(III) and bistability in the reductions of MnO 2 by hexacyanoferrates(II) in a CSTR

    Science.gov (United States)

    Olexová, Anna; Melicherčík, Milan; Treindl, L'udovít

    1997-04-01

    A new transition metal oscillator based on the oxidation of Mn 2+ ions by Fe(CN) 3-6 ions in a CSTR has been found. As well as the oscillations of the absorbance of the Mn(IV) species, pH-oscillations have been observed. In the reduction of manganese dioxide by Fe(CN) 4-6 ions a kinetic bistability has been described. A skeleton mechanism described recently for Mn(II)H 2O 2 and Mn(II)Br 2 oscillators has been applied here and further developed by the idea of the catalytic activity of colloidal particles and of the assistance of the pH-value change of both main processes, i.e. of the Mn(II) oxidation by Fe(CN) 3-6 ions and of the Mn(IV) reduction by Fe(CN) 4-6 ions. This appears to be the first case where both sides of a reversible reaction are autocatalytic.

  16. Preparation and characterization of electrically conducting polypyrrole Sn(IV phosphate cation-exchanger and its application as Mn(II ion selective membrane electrode

    Directory of Open Access Journals (Sweden)

    A.A. Khan

    2011-10-01

    Full Text Available Polypyrrole Sn(IV phosphate, an organic–inorganic composite cation-exchanger was synthesized via sol-gel mixing of an organic polymer, polypyrrole, into the matrices of the inorganic precipitate of Sn(IV phosphate. The physico-chemical properties of the material were determined using Atomic Absorption Spectrometry (AAS, CHN elemental analysis (inductively coupled plasma mass spectrometry, ICP-MS, UV–VIS spectrophotometry, FTIR (Fourier Transform Infra-Red, SEM (Scanning Electron Microscopy, TGA–DTA (Thermogravimetric Analysis–Differential Thermal Analysis, and XRD (X-ray diffraction. Ion-exchange behavior was observed to characterize the material. On the basis of distribution studies, the material was found to be highly selective for toxic heavy metal ion Mn2+. Due to its selective nature, the material was used as an electroactive component for the construction of an ion-selective membrane electrode. The proposed electrode shows fairly good discrimination of mercury ion over several other inorganic ions. The analytical utility of this electrode was established by employing it as an indicator electrode in electrometric titrations for Mn(II in water.

  17. Zn(II, Mn(II and Sr(II Behavior in a Natural Carbonate Reservoir System. Part II: Impact of Geological CO2 Storage Conditions

    Directory of Open Access Journals (Sweden)

    Auffray B.

    2016-07-01

    Full Text Available Some key points still prevent the full development of geological carbon sequestration in underground formations, especially concerning the assessment of the integrity of such storage. Indeed, the consequences of gas injection on chemistry and petrophysical properties are still much discussed in the scientific community, and are still not well known at either laboratory or field scale. In this article, the results of an experimental study about the mobilization of Trace Elements (TE during CO2 injection in a reservoir are presented. The experimental conditions range from typical storage formation conditions (90 bar, supercritical CO2 to shallower conditions (60 and 30 bar, CO2 as gas phase, and consider the dissolution of the two carbonates, coupled with the sorption of an initial concentration of 10−5 M of Zn(II, and the consequent release in solution of Mn(II and Sr(II. The investigation goes beyond the sole behavior of TE in the storage conditions: it presents the specific behavior of each element with respect to the pressure and the natural carbonate considered, showing that different equilibrium concentrations are to be expected if a fluid with a given concentration of TE leaks to an upper formation. Even though sorption is evidenced, it does not balance the amount of TE released by the dissolution process. The increase in porosity is clearly evidenced as a linear function of the CO2 pressure imposed for the St-Emilion carbonate. For the Lavoux carbonate, this trend is not confirmed by the 90 bar experiment. A preferential dissolution of the bigger family of pores from the preexisting porosity is observed in one of the samples (Lavoux carbonate while the second one (St-Emilion carbonate presents a newly-formed family of pores. Both reacted samples evidence that the pore network evolves toward a tubular network type.

  18. The mechanism of paramagnetic NMR relaxation produced by Mn(II): role of orthorhombic and fourth-order zero field splitting terms.

    Science.gov (United States)

    Sharp, Robert

    2008-10-14

    Mn(II) is a spin-5/2 paramagnetic ion that mediates a characteristically large NMR paramagnetic relaxation enhancement (NMR-PRE) of nuclear spins in solution. In the range of high magnetic field strengths (above about 0.3 T), where the electronic Zeeman interaction provides the largest term of the electron spin Hamiltonian, NMR relaxation mechanism is well understood. In the lower field range, the physical picture is more complex because of the presence in the spin Hamiltonian of zero field splitting (ZFS) terms that are comparable to or greater than the Zeeman term. This work describes a systematic study of the relaxation mechanism in the low field range, particularly aspects involving the dependence of NMR-PRE on the orthorhombic (E) and fourth-order (a(q)(4), q=0,2,4) ZFS tensor components. It is shown that the fourfold (a(4)(4)) and twofold (a(2)(4)) fourth-order components exert large orientation-dependent influences on the NMR-PRE. Thus, fourth-order terms with magnitudes equal to only a few percent of the quadratic ZFS terms (D,E) produce large changes in the shape of the magnetic field profile of the PRE. Effects arising from the orthorhombic quadratic ZFS term (E) are much smaller than those of the fourth-order terms and can in most cases be neglected. However, effects due to a(4)(4) and a(2)(4) need to be included in simulations of low field data.

  19. Half-integer spin heptanuclear single-molecule magnet with an unusual Mn(III)6Mn(II) exchange-coupled core.

    Science.gov (United States)

    Chen, Siou-Yin; Beedle, Christopher C; Gan, Pei-Rung; Lee, Gene-Hsian; Hill, Stephen; Yang, En-Che

    2012-04-16

    The synthesis, X-ray crystallography, magnetic properties, and high-field electron paramagnetic resonance (HFEPR) of a new heptanuclear manganese complex [Mn(7)(heamp)(6)](ClO(4))(2)·4CH(2)Cl(2)·H(2)O (complex 2), in which heampH(3) is 2-[N,N-di(2-hydroxyethyl)aminomethyl]phenol (compound 1), is reported. Complex 2 has a hexagonal, disk-shaped topology and contains six Mn(III) ions and a central Mn(II) ion. It crystallizes in the monoclinic space group P2(1)/c with two molecular orientations. Consideration of the cluster topology, together with variable-temperature and variable-field DC magnetic susceptibility data, suggest that complex 2 exists in a half-integer, S = (19)/(2) ± 1 spin ground state, with appreciable uniaxial zero-field splitting (D = -0.16 cm(-1)). AC magnetic susceptibility measurements clearly show out-of-phase signals, which are frequency- and temperature-dependent, indicating slow magnetization relaxation behavior. An analysis of the relaxation data employing the Arrhenius formula yielded an effective relaxation barrier of 12.9 cm(-1). Simulations of HFEPR studies agree with the assignment of an S ≈ (19)/(2) spin ground state, with g = 1.96, D = -4.71 GHz (-0.16 cm(-1)), and a longitudinal fourth-order zero-field splitting parameter B(4)(0) = -2.7 × 10(-4) GHz (-9.0 × 10(-6) cm(-1)).

  20. Hierarchical Assembly of a {Mn(II)15Mn(III)4} Brucite Disc: Step-by-Step Formation and Ferrimagnetism.

    Science.gov (United States)

    Deng, Yong-Kai; Su, Hai-Feng; Xu, Jia-Heng; Wang, Wen-Guang; Kurmoo, Mohamedally; Lin, Shui-Chao; Tan, Yuan-Zhi; Jia, Jiong; Sun, Di; Zheng, Lan-Sun

    2016-02-03

    In search of functional molecular materials and the study of their formation mechanism, we report the elucidation of a hierarchical step-by-step formation from monomer (Mn) to heptamer (Mn7) to nonadecamer (Mn19) satisfying the relation 1 + Σn6n, where n is the ring number of the Brucite structure using high-resolution electrospray ionization mass spectrometry (HRESI-MS). Three intermediate clusters, Mn10, Mn12, and Mn14, were identified. Furthermore, the Mn19 disc remains intact when dissolved in acetonitrile with a well-resolved general formula of [Mn19(L)x(OH)y(N3)36-x-y](2+) (x = 18, 17, 16; y = 8, 7, 6; HL = 1-(hydroxymethyl)-3,5-dimethylpyrazole) indicating progressive exchange of N3(-) for OH(-). The high symmetry (R-3) Mn19 crystal structure consists of a well-ordered discotic motif where the peripheral organic ligands form a double calix housing the anions and solvent molecules. From the formula and valence bond sums, the charge state is mixed-valent, [Mn(II)15Mn(III)4]. Its magnetic properties and electrochemistry have been studied. It behaves as a ferrimagnet below 40 K and has a coercive field of 2.7 kOe at 1.8 K, which can be possible by either weak exchange between clusters through the anions and solvents or through dipolar interaction through space as confirmed by the lack of ordering in frozen CH3CN. The moment of nearly 50 NμB suggests Mn(II)-Mn(II) and Mn(III)-Mn(III) are ferromagnetically coupled while Mn(II)-Mn(III) is antiferromagnetic which is likely if the Mn(III) are centrally placed in the cluster. This compound displays the rare occurrence of magnetic ordering from nonconnected high-spin molecules.

  1. How to overcome inter-electrode variability and instability to quantify dissolved oxygen, Fe(II, mn(II, and S(−II in undisturbed soils and sediments using voltammetry

    Directory of Open Access Journals (Sweden)

    Slowey Aaron J

    2012-06-01

    Full Text Available Abstract Background Although uniquely capable of measuring multiple redox constituents nearly simultaneously with no or minimal sample pretreatment, voltammetry is currently underutilized in characterizing redox conditions in aquatic and terrestrial systems. Investigation of undisturbed media such as pore water requires a solid-state electrode, and such electrodes can be difficult to fabricate reproducibly. An approach to determine the concentrations of electroactive constituents using indirectly calibrated electrodes has been developed, but the protocol for and accuracy of this approach—the pilot ion method—has not been documented in detail. Results A detailed procedure for testing electrode quality is provided, and the application and limitations of the pilot ion method have been documented. To quantify Fe(II and Mn(II, subtraction of non-linear baseline functions from voltammetric signals produced better calibration curves than did linear baselines, enabled lower detection limits and reliable deconvolution of overlapping signals, and was successfully applied to sediment pore water signals. We observed that electrode sensitivities often vary by tens of percent, and that the sensitivity declines over time. The ratio of calibration slopes of Mn(II to Fe(II varied by no more than 11% from one Hg/Au electrode to another and Fe(II concentrations predicted by the Mn(II pilot ion were, on average, 13% different from their actual values. However, concentration predictions by the pilot ion method were worse for less than 15 μM Fe(II (46% different on average. The ratio of calibration slopes of Mn(II to S(−II varied by almost 20% from one Hg/Au electrode to another, and S(−II predicted concentrations were as much as 58% different from their actual values. These predictions of Fe(II and S(−II concentrations indicate that the accuracy of the pilot ion method depends on how independent calibration slope ratios are from the electrode used. At

  2. Synthesis, Spectral Characterization, Molecular Modeling, and Antimicrobial Studies of Cu(II, Ni(II, Co(II, Mn(II, and Zn(II Complexes of ONO Schiff Base

    Directory of Open Access Journals (Sweden)

    Padmaja Mendu

    2012-01-01

    Full Text Available A series of Cu(II, Ni(II, Co(II, Mn(II, and Zn(II complexes have been synthesized from the schiff base ligand L. The schiff base ligand [(4-oxo-4H-chromen-3-yl methylene] benzohydrazide (L has been synthesized by the reaction between chromone-3-carbaldehyde and benzoyl hydrazine. The nature of bonding and geometry of the transition metal complexes as well as schiff base ligand L have been deduced from elemental analysis, FT-IR, UV-Vis, 1HNMR, ESR spectral studies, mass, thermal (TGA and DTA analysis, magnetic susceptibility, and molar conductance measurements. Cu(II, Ni(II, Co(II, and Mn(II metal ions are forming 1:2 (M:L complexes, Zn(II is forming 1:1 (M:L complex. Based on elemental, conductance and spectral studies, six-coordinated geometry was assigned for Cu(II, Ni(II, Co(II, Mn(II, and Zn(II complexes. The complexes are 1:2 electrolytes in DMSO except zinc complex, which is neutral in DMSO. The ligand L acts as tridentate and coordinates through nitrogen atom of azomethine group, oxygen atom of keto group of γ-pyrone ring and oxygen atom of hydrazoic group of benzoyl hydrazine. The 3D molecular modeling and energies of all the compounds are furnished. The biological activity of the ligand and its complexes have been studied on the four bacteria E. coli, Edwardella, Pseudomonas, and B. subtilis and two fungi pencillium and tricoderma by well disc and fusion method and found that the metal chelates are more active than the free schiff base ligand.

  3. Synthesis, Characterization and Thermal Decomposition Studies of Cr(III, Mn(II and Fe(III Complexes of N, N '-Bis[1,3-benzodioxol-5-ylmethylene]butane-1,4-diamine

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    Prasad M. Alex

    2009-01-01

    Full Text Available A bidentate Schiff base ligand namely, N,N'-bis-1,3-benzodioxol-5-ylmethylene]butane-1,4-diamine was synthesised by condensing piperonal (3,4-dioxymethylenebenzaldehyde with butane-1,4-diamine. Cr(III, Mn(II, Fe(III complexes of this chelating ligand were synthesised using acetates, chlorides, bromides, nitrates and perchlorates of these metals. The ligand and the complexes were characterised by elemental analysis, 1H NMR, UV-Vis and IR spectra, conductance and magnetic susceptibility measurements and thermogravimetric analysis. The thermograms of three complexes were analysed and the kinetic parameters for the different stages of decompositions were determined.

  4. Cubane-type Cu(II)4 and Mn(II)2Mn(III)2 complexes based on pyridoxine: a versatile ligand for metal assembling.

    Science.gov (United States)

    Marino, Nadia; Armentano, Donatella; Mastropietro, Teresa F; Julve, Miguel; De Munno, Giovanni; Martínez-Lillo, José

    2013-10-21

    By using Vitamin B6 in its monodeprotonated pyridoxine form (PN-H) [PN = 3-hydroxy-4,5-bis(hydroxymethyl)-2-methylpyridine], two tetranuclear compounds of formula [Mn4(PN-H)4(CH3CO2)3Cl2]Cl·2CH3OH·2H2O (1) and [Cu4(PN-H)4Cl2(H2O)2]Cl2 (2) have been synthesized and magneto-structurally characterized. 1 crystallizes in the triclinic system with space group P1 whereas 2 crystallizes in the orthorhombic system with Fdd2 as space group. They exhibit Mn(II)2Mn(III)2 (1) and Cu(II)4 (2) cubane cores containing four monodeprotonated pyridoxine groups simultaneously acting as chelating and bridging ligands (1 and 2), three bridging acetate ligands in the syn-syn conformation (1), and two terminally bound chloride anions (1 and 2) plus two coordinated water molecules (2). The electroneutrality is achieved by the presence of chloride counterions in both compounds. Tri- [Mn(1) and Mn(3)] and divalent [Mn(2) and Mn(4)] manganese centers coexist in 1, all being six-coordinate with distorted Mn(1/3)O6 and Mn(2/4)O5Cl octahedral surroundings, respectively, the equatorial Mn-O bonds being about 0.2 Å shorter at the former ones. The two crystallographically independent copper(II) ions in 2 are five-coordinate in somewhat distorted CuO5 [Cu(1)] and CuO4Cl [Cu(2)] square pyramidal geometries. The values of the intracore metal-metal separation cover the ranges 3.144(1)-3.535(1) (1) and 2.922(6)-3.376(1) Å (2). The magnetic properties of 1 and 2 were investigated in the temperature range 1.9-300 K, and they correspond to an overall antiferromagnetic behavior with susceptibility maxima at 5.0 (1) and 65.0 K (2). The analysis of the magnetic susceptibility data showed the coexistence of intracore antiferro- and ferromagnetic interactions in the two compounds. Their values compare well with those existing in the literature for the parent systems.

  5. Crystal structure and spectroscopic analysis of a new oxalate-bridged MnII compound: catena-poly[guanidinium [[aquachloridomanganese(II]-μ2-oxalato-κ4O1,O2:O1′,O2′] monohydrate

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    Hiba Sehimi

    2016-05-01

    Full Text Available As part of our studies on the synthesis and the characterization of oxalate-bridged compounds M–ox–M (ox = oxalate dianion and M = transition metal ion, we report the crystal structure of a new oxalate-bridged MnII phase, {(CH6N3[Mn(C2O4Cl(H2O]·H2O}n. In the compound, a succession of MnII ions (situated on inversion centers adopting a distorted octahedral coordination and bridged by oxalate ligands forms parallel zigzag chains running along the c axis. These chains are interconnected through O—H...O hydrogen-bonding interactions to form anionic layers parallel to (010. Individual layers are held together via strong hydrogen bonds involving the guanidinium cations (N—H...O and N—H...Cl and the disordered non-coordinating water molecule (O—H...O and O—H...Cl, as well as by guanidinium π–π stacking. The structural data were confirmed by IR and UV–Visible spectroscopic analysis.

  6. Multi-reverse flow injection analysis integrated with multi-optical sensor for simultaneous determination of Mn(II), Fe(II), Cu(II) and Fe(III) in natural waters.

    Science.gov (United States)

    Youngvises, Napaporn; Suwannasaroj, Kittigan; Jakmunee, Jaroon; AlSuhaimi, Awadh

    2017-05-01

    Multi-reverse flow injection analysis (Mr-FIA) integrated with multi-optical sensor was developed and optimized for the simultaneous determination of multi ions; Mn(II), Fe(II), Cu(II) and Fe(III) in water samples. The sample/standard solutions were propelled making use of a four channels peristaltic pump whereas 4 colorimetric reagents specific for the metal ions were separately injected in sample streams using multi-syringe pump. The color zones that formed in the individual mixing coils were then streamed into multi-channels spectrometer, which comprised of four flows through cell and four pairs of light emitting diode and photodiode, whereby signals were measured concurrently. The linearity range (along with detection limit, µgL(-1)) was 0.050-3.0(16), 0.30-2.0 (11), 0.050-1.0(12) and 0.10-1.0(50)mgL(-1), for Mn(II), Fe(II), Cu(II) and Fe(III), respectively. In the interim, the correlation coefficients were 0.9924-0.9942. The percentages relative standard deviation was less than 3. The proposed system was applied successfully to determine targeted metal ions simultaneously in natural water with high sample throughput and low reagent consumption, thus it satisfies the criteria of Green Analytical Chemistry (GAC) and its goals.

  7. Synthesis, spectral characterization thermal stability, antimicrobial studies and biodegradation of starch–thiourea based biodegradable polymeric ligand and its coordination complexes with [Mn(II, Co(II, Ni(II, Cu(II, and Zn(II] metals

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    Nahid Nishat

    2016-09-01

    Full Text Available A biodegradable polymer was synthesized by the modification reaction of polymeric starch with thiourea which is further modified by transition metals, Mn(II, Co(II, Ni(II, Cu(II and Zn(II. All the polymeric compounds were characterized by (FT-IR spectroscopy, 1H NMR spectroscopy, 13C NMR spectroscopy, UV–visible spectra, magnetic moment measurements, thermogravimetric analysis (TGA and antibacterial activities. Polymer complexes of Mn(II, Co(II and Ni(II show octahedral geometry, while polymer complexes of Cu(II and Zn(II show square planar and tetrahedral geometry, respectively. The TGA revealed that all the polymer metal complexes are more thermally stable than their parental ligand. In addition, biodegradable studies of all the polymeric compounds were also carried out through ASTM-D-5338-93 standards of biodegradable polymers by CO2 evolution method which says that coordination decreases biodegradability. The antibacterial activity was screened with the agar well diffusion method against some selected microorganisms. Among all the complexes, the antibacterial activity of the Cu(II polymer–metal complex showed the highest zone of inhibition because of its higher stability constant.

  8. 4-nitrocatechol as a probe of a Mn(II)-dependent extradiol-cleaving catechol dioxygenase (MndD): comparison with relevant Fe(II) and Mn(II) model complexes.

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    Reynolds, Mark F; Costas, Miquel; Ito, Masami; Jo, Du-Hwan; Tipton, A Alex; Whiting, Adam K; Que, Lawrence

    2003-02-01

    Mn(II)-dependent 3,4-dihydroxyphenylacetate 2,3-dioxygenase (MndD) is an extradiol-cleaving catechol dioxygenase from Arthrobacter globiformis that has 82% sequence identity to and cleaves the same substrate (3,4-dihydroxyphenylacetic acid) as Fe(II)-dependent 3,4-dihydroxyphenylacetate 2,3-dioxygenase (HPCD) from Brevibacterium fuscum. We have observed that MndD binds the chromophoric 4-nitrocatechol (4-NCH(2)) substrate as a dianion and cleaves it extremely slowly, in contrast to the Fe(II)-dependent enzymes which bind 4-NCH(2) mostly as a monoanion and cleave 4-NCH(2) 4-5 orders of magnitude faster. These results suggest that the monoanionic binding state of 4-NC is essential for extradiol cleavage. In order to address the differences in 4-NCH(2) binding to these enzymes, we synthesized and characterized the first mononuclear monoanionic and dianionic Mn(II)-(4-NC) model complexes as well as their Fe(II)-(4-NC) analogs. The structures of [(6-Me(2)-bpmcn)Fe(II)(4-NCH)](+), [(6-Me(3)-TPA)Mn(II)(DBCH)](+), and [(6-Me(2)-bpmcn)Mn(II)(4-NCH)](+) reveal that the monoanionic catecholate is bound in an asymmetric fashion (Delta r(metal-O(catecholate))=0.25-0.35 A), as found in the crystal structures of the E(.)S complexes of extradiol-cleaving catechol dioxygenases. Acid-base titrations of [(L)M(II)(4-NCH)](+) complexes in aprotic solvents show that the p K(a) of the second catecholate proton of 4-NCH bound to the metal center is half a p K(a) unit higher for the Mn(II) complexes than for the Fe(II) complexes. These results are in line with the Lewis acidities of the two divalent metal ions but are the opposite of the trend observed for 4-NCH(2) binding to the Mn(II)- and Fe(II)-catechol dioxygenases. These results suggest that the MndD active site decreases the second p K(a) of the bound 4-NCH(2) relative to the HPCD active site.

  9. Zn(II, Mn(II and Sr(II Behavior in a Natural Carbonate Reservoir System. Part I: Impact of Salinity, Initial pH and Initial Zn(II Concentration in Atmospheric Conditions

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    Auffray B.

    2016-07-01

    Full Text Available The sorption of inorganic elements on carbonate minerals is well known in strictly controlled conditions which limit the impact of other phenomena such as dissolution and/or precipitation. In this study, we evidence the behavior of Zn(II (initially in solution and two trace elements, Mn(II and Sr(II (released by carbonate dissolution in the context of a leakage from a CO2 storage site. The initial pH chosen are either equal to the pH of the water-CO2 equilibrium (~ 2.98 or equal to the pH of the water-CO2-calcite system (~ 4.8 in CO2 storage conditions. From this initial influx of liquid, saturated or not with respect to calcite, the batch experiments evolve freely to their equilibrium, as it would occur in a natural context after a perturbation. The batch experiments are carried out on two natural carbonates (from Lavoux and St-Emilion with PCO2 = 10−3.5 bar, with different initial conditions ([Zn(II]i from 10−4 to 10−6 M, either with pure water or 100 g/L NaCl brine. The equilibrium regarding calcite dissolution is confirmed in all experiments, while the zinc sorption evidenced does not always correspond to the two-step mechanism described in the literature. A preferential sorption of about 10% of the concentration is evidenced for Mn(II in aqueous experiments, while Sr(II is more sorbed in saline conditions. This study also shows that this preferential sorption, depending on the salinity, is independent of the natural carbonate considered. Then, the simulations carried out with PHREEQC show that experiments and simulations match well concerning the equilibrium of dissolution and the sole zinc sorption, with log KZn(II ~ 2 in pure water and close to 4 in high salinity conditions. When the simulations were possible, the log K values for Mn(II and Sr(II were much different from those in the literature obtained by sorption in controlled conditions. It is shown that a new conceptual model regarding multiple Trace Elements (TE sorption is

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

    Science.gov (United States)

    Refat, Moamen S.

    2013-04-01

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

  11. Spiral Dinuclear Complexes of Tetradentate N(4) Diazine Ligands with Mn(II), Fe(II), Fe(III), Co(III), and Ni(II) Salts.

    Science.gov (United States)

    Xu, Zhiqiang; Thompson, Laurence K.; Miller, David O.; Clase, Howard J.; Howard, Judith A. K.; Goeta, Andrés E.

    1998-07-13

    A series of dinuclear complexes of the tetradentate dipyridyl-diazine ligand PAHAP with Mn(II), Fe(II), Fe(III), Co(III), and Ni(II) salts is reported in which three ligands wrap themselves around the six-coordinate metal centers in a rare spiral-like fashion. A similar Fe(II) complex is found for the dipyrazinyl-diazine ligand PZHPZ. The ligands are severely twisted with dihedral angles between the metal chelate ring mean planes on each ligand in the range 50-70 degrees, values close to the expected twist angle for orthogonality between the bridging nitrogen atom p orbitals. Full structures are reported for the dinuclear complexes [Mn(2)(PAHAP)(3)](ClO(4))(4).5H(2)O (1), [Fe(2)(PAHAP)(3)](NO(3))(4).3H(2)O (2), [Fe(2)(PZHPZ)(3)](NO(3))(4).5H(2)O (5), [Co(2)(PAHAP)(3)](NO(3))(6).5H(2)O (6), and [Ni(2)(PAHAP)(3)][Ni(H(2)O)(6)](NO(3))(6).4.5H(2)O (7). Other derivatives [Fe(2)(PAHAP)(3)](ClO(4))(4).4H(2)O (3), [Fe(2)(PAHAP)(3)](ClO(4))(6).4.5H(2)O (4), [Ni(2)(PAHAP)(3)](ClO(4))(4).5H(2)O (8), and [Fe(PHAAP-H)(H(2)O)(2)(NO(3))](NO(3))(2) (9) are also reported. Complex 1 crystallized in the monoclinic system, space group C2/c, with a = 13.4086(2) Å, b = 32.0249(1) Å, c = 14.3132(2) Å, alpha = 90 degrees, beta = 115.635(1) degrees, gamma = 90 degrees, and Z = 4. Complex 2 crystallized in the cubic system, space group Pa&thremacr;, with a = b = c = 21.0024(1) Å, alpha = beta = gamma = 90 degrees, and Z = 8. Complex 5 crystallized in the monoclinic system, space group P2/n, with a = 14.039(3) Å, b = 11.335(6) Å, c = 14.6517(15) Å, beta = 96.852(11) degrees, and Z = 1. Complex 6 crystallized in the trigonal system, space group R&thremacr;c(h), with a = b = 17.386(2) Å, c = 32.15(2) Å, alpha = beta = 90 degrees, gamma = 120 degrees, and Z = 4. Complex 7 crystallized in the trigonal system, space group R&thremacr;c, with a = b = 17.3737(3) Å, c = 33.235(6) Å, alpha = beta = 90 degrees, gamma = 120 degrees, and Z = 27. Weak ferromagnetic coupling was observed for 1

  12. mer-[Fe(pcq)(CN)3]-: a novel cyanide-containing building block and its application to assembling cyanide-bridged trinuclear FeIII2MnII complexes [pcq- = 8-(pyridine-2-carboxamido)quinoline anion].

    Science.gov (United States)

    Ni, Zhong-Hai; Kou, Hui-Zhong; Zhang, Li-Fang; Ni, Wei-Wei; Jiang, Yun-Bo; Cui, Ai-Li; Ribas, Joan; Sato, Osamu

    2005-12-26

    A new cyanide-containing building block K[Fe(pcq)(CN)(3)] [1; pcq(-) = 8-(pyridine-2-carboxamido)quinoline anion] containing a low-spin Fe(III) center with three cyanide groups in a meridional arrangement has been successfully designed and synthesized. Three cyanide-bridged trinuclear Fe(III)(2)Mn(II) complexes, [Fe(pcq)(CN)(3)](2)[Mn(CH(3)OH)(2)(H(2)O)(2)].2H(2)O (2), [Fe(pcq)(CN)(3)](2)[Mn(bipy)(2)].CH(3)OH.2H(2)O (3), and [Fe(pcq)(CN)(3)](2)[Mn(phen)(2)].CH(3)OH.2H(2)O (4), have been synthesized and structurally characterized. The magnetic susceptibilities of the three heterometallic complexes have been investigated.

  13. SERS and DFT investigation of 1-(2-pyridylazo)-2-naphthol and its metal complexes with Al(III), Mn(II), Fe(III), Cu(II), Zn(II) and Pb(II)

    Science.gov (United States)

    Szabó, László; Herman, Krisztian; Mircescu, Nicoleta E.; Fălămaş, Alexandra; Leopold, Loredana F.; Leopold, Nicolae; Buzumurgă, Claudia; Chiş, Vasile

    The development of surface-enhanced Raman scattering (SERS) as a prospective analytical methodology for detection of metal ions was shown in recent years by several studies on metal complexes. In this work, 1-(2-pyridylazo)-2-naphthol (PAN) and its Al(III), Mn(II), Fe(III), Cu(II), Zn(II) and Pb(II) complexes were studied by FTIR, FT-Raman and surface enhanced Raman spectroscopies. Molecular geometry optimization, molecular electrostatic potential (MEP) distribution and vibrational frequencies calculations were performed using the hybrid B3LYP exchange-correlation functional for the PAN molecule and its bidentate complexes. The calculated MEP distributions indicated the atoms with highest electronegativity, the adsorption to the silver surface occurring through these atoms. Based on experimental and theoretical data we were able to identify unique and representative features, useful for the identification of each PAN-metal complex.

  14. The crystal structure, luminescence and nitrobenzene-sensing properties of a two-dimensional Mn(II) coordination polymer based on 2,6-bis(imidazol-1-yl)pyridine.

    Science.gov (United States)

    Wang, Yin-Lin; Long, Ling-Liang; Zhang, Jin-Fang

    2015-06-01

    A two-dimensional Mn(II) coordination polymer (CP), poly[bis[μ2-2,6-bis(imidazol-1-yl)pyridine-κ(2)N(3):N(3')]bis(thiocyanato-κN)manganese] [Mn(NCS)2(C11H9N5)2]n, (I), has been obtained by the self-assembly reaction of Mn(ClO4)2·6H2O, NH4SCN and bent 2,6-bis(imidazol-1-yl)pyridine (2,6-bip). CP (I) was characterized by FT-IR spectroscopy, elemental analysis and single-crystal X-ray diffraction. The crystal structure features a unique two-dimensional (4,4) network with one-dimensional channels. The luminescence and nitrobenzene-sensing properties were explored in a DMF suspension, revealing that CP (I) shows a strong luminescence emission and is highly sensitive for nitrobenzene detection.

  15. A new bioactive Schiff base ligands derived from propylazo-N-pyrimidin-2-yl-benzenesulfonamides Mn(II) and Cu(II) complexes: synthesis, thermal and spectroscopic characterization biological studies and 3D modeling structures.

    Science.gov (United States)

    Tawfik, Abdelrazak M; El-Ghamry, Mosad A; Abu-El-Wafa, Samy M; Ahmed, Naglaa M

    2012-11-01

    New series of Schiff base ligand H(2)L and their Cu(II) and Mn(II) complexes derived from azosulfapyrimidine were synthesized and characterized by elemental and thermal studies conductance measurements IR, electronic and EPR spectra. 3D modeling of the ligand indicate that azo group does not participate in complex formation and surface potential on one of the ligand under study indicate that electron density around azomethine groups are much higher than the azo group therefore coordination takes place around azomethine groups. The variety in the geometrical structures depends on the nature of both the metal ions and the Schiff base ligands. The thermo kinetic parameters are calculated and discussed. The biological activities of the ligands and complexes have been screened in vitro against some bacteria and fungi to study their capacity to inhibit their growth and to study the toxicity of the compounds.

  16. Spectroscopic (FT-IR, FT-Raman, 1H, 13C NMR, UV/VIS), thermogravimetric and antimicrobial studies of Ca(II), Mn(II), Cu(II), Zn(II) and Cd(II) complexes of ferulic acid

    Science.gov (United States)

    Kalinowska, M.; Piekut, J.; Bruss, A.; Follet, C.; Sienkiewicz-Gromiuk, J.; Świsłocka, R.; Rzączyńska, Z.; Lewandowski, W.

    2014-03-01

    The molecular structure of Mn(II), Cu(II), Zn(II), Cd(II) and Ca(II) ferulates (4-hydroxy-3-methoxycinnamates) was studied. The selected metal ferulates were synthesized. Their composition was established by means of elementary and thermogravimetric analysis. The following spectroscopic methods were used: infrared (FT-IR), Raman (FT-Raman), nuclear magnetic resonance (13C, 1H NMR) and ultraviolet-visible (UV/VIS). On the basis of obtained results the electronic charge distribution in studied metal complexes in comparison with ferulic acid molecule was discussed. The microbiological study of ferulic acid and ferulates toward Escherichia coli, Bacillus subtilis, Candida albicans, Pseudomonas aeruginosa, Staphylococcus aureus and Proteus vulgaris was done.

  17. Identification of symmetry, structure and defects of dopant Mn(II) ions in Zn(C 3H 3O 4) 2(H 2O) 2 by single crystal EPR technique

    Science.gov (United States)

    Natarajan, B.; Mithira, S.; Sambasiva Rao, P.

    2008-12-01

    In order to understand the symmetry, structure and defects of Mn(II) impurity incorporated in diaquabis[malonato(1-)-κ 2O,O'] zinc(II), single crystal EPR studies have been carried out at X-band frequencies at room temperature. Angular variation in the three orthogonal planes shows the presence of two defects, having a relatively large and small zero-field splitting parameter ( D), with orthorhombic symmetry. The spin-Hamiltonian parameters, estimated from the three mutually orthogonal crystal rotations, are: Defect I:g xx = 1.959, g yy = 1.998, g zz = 2.011; A xx = -8.73, A yy = -8.55, A zz = -9.10 mT; D xx = 5.58, D yy = 1.33, D zz = -6.91 mT. Defect II:g xx = 2.015, g yy = 1.996, g zz = 2.004; A xx = -8.18, A yy = -8.00, A zz = -8.58 mT; D xx = 33.48, D yy = 6.92, D zz = -40.40 mT. The observed large zero-field tensor for Defect II is due to the steric effects caused by the two malonate rings. The location of the two interstitial defects has been determined from the X-ray data of the host lattice. The powder EPR spectrum also confirms the chemical inequivalence of the two defects. The optical absorption spectrum shows the characteristic of Mn(II) ions in distorted octahedral symmetry.

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

    Science.gov (United States)

    Al-Shaalan, Nora H

    2011-10-13

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

  19. Synthesis, Characterization and Biological Activities of Cu(II, Co(II, Mn(II, Fe(II, and UO2(VI Complexes with a New Schiff Base Hydrazone: O-Hydroxyacetophenone-7-chloro-4-quinoline Hydrazone

    Directory of Open Access Journals (Sweden)

    Nora H. Al-Shaalan

    2011-10-01

    Full Text Available The Schiff base hydrazone ligand HL was prepared by the condensation reaction of 7-chloro-4-quinoline with o-hydroxyacetophenone. The ligand behaves either as monobasic bidentate or dibasic tridentate and contain ONN coordination sites. This was accounted for be the presence in the ligand of a phenolic azomethine and imine groups. It reacts with Cu(II, Ni(II, Co(II, Mn(II, UO2 (VI and Fe(II to form either mono- or binuclear complexes. The ligand and its metal complexes were characterized by elemental analyses, IR, NMR, Mass, and UV-Visible spectra. The magnetic moments and electrical conductance of the complexes were also determined. The Co(II, Ni(II and UO2 (VI complexes are mononuclear and coordinated to NO sites of two ligand molecules. The Cu(II complex has a square-planar geometry distorted towards tetrahedral, the Ni(II complex is octahedral while the UO2 (VI complex has its favoured heptacoordination. The Co(II, Mn(II complexes and also other Ni(II and Fe(III complexes, which were obtained in the presence of Li(OH as deprotonating agent, are binuclear and coordinated via the NNNO sites of two ligand molecules. All the binuclear complexes have octahedral geometries and their magnetic moments are quite low compared to the calculated value for two metal ions complexes and thus antiferromagnetic interactions between the two adjacent metal ions. The ligand HL and metal complexes were tested against a strain of Gram +ve bacteria (Staphylococcus aureus, Gram −ve bacteria (Escherichia coli, and fungi (Candida albicans. The tested compounds exhibited high antibacterial activities.

  20. DNA interaction, antimicrobial, anticancer activities and molecular docking study of some new VO(II), Cr(III), Mn(II) and Ni(II) mononuclear chelates encompassing quaridentate imine ligand.

    Science.gov (United States)

    Abdel-Rahman, Laila H; Abu-Dief, Ahmed M; Aboelez, Moustafa O; Hassan Abdel-Mawgoud, Azza A

    2017-05-01

    The present study was conducted to synthesis of some new imine Cr(III), VO(II), Mn(II) and Ni(II) complexes derived from the condensation of 2-amino phenol with 2-hydroxynapthaldehyde were synthesized. The prepared HNPN imine ligand was analyzed by its melting point, IR, (1)H NMR and (13)C NMR spectroscopies. The investigated HNPN imine complexes were characterized by elemental analysis, FT IR, UV-vis and thermal analysis (TGA) under nitrogen atmosphere from ambient temperature to 750°C. The experimental results revealed that the investigated complexes contain hydrated water molecules. The molar conductance values of complexes are relatively low, indicating the non-electrolytic nature of these complexes. Magnetic susceptibility measurements show that the investigated complexes are paramagnetic. Moreover, the stability constants of the preparing complexes were determined spectrophotometrically. All the complexes were found to be monomeric 1:1 (M:L) stoichiometry in nature with octahedral geometry for Cr(III), tetrahedral for Mn(II), square planner for Ni(II) and square pyramidal for VO(II). Moreover, the prepared HNPN imine ligand and its complexes were evaluated for antimicrobial effect against some types of bacteria such as Bacillus subtilis (+ve), Escherichia coli(-ve) and Staphylococcus aureus (+ve) and some types of fungi such as Aspergillusniger, Candida glabrata and Trichophyton rubrum. The results of these studies indicate that the metal complexes exhibit a stronger antibacterial and antifungal efficiency compared to their corresponding imine ligand. Moreover, the interaction of the investigated complexes with CT-DNA was checked using spectral studies, viscosity measurements and gel electrophoreses. The absorption titration studies revealed that each of these complexes is an avid binder to calf thymus-DNA. Also, there was appreciable changes in the relative viscosity of DNA, which is consistent with enhanced hydrophobic interaction of the aromatic rings and

  1. catena-Poly[[di-μ2-aqua-hexaaquabis(μ3-4-oxidopyridine-2,6-dicarboxylato)trimanganese(II)] trihydrate]: a new one-dimensional coordination polymer based on a trinuclear Mn(II) complex of chelidamic acid.

    Science.gov (United States)

    Mirzaei, Masoud; Eshtiagh-Hosseini, Hossein; Karrabi, Zahra; Notash, Behrouz

    2013-10-01

    4-Hydroxypyridine-2,6-dicarboxylic acid (chelidamic acid, hypydc[H]H2) reacts with MnCl2·2H2O in the presence of piperazine in water to afford the title complex, {[Mn3(C7H2NO5)2(H2O)8]·3H2O}n or {[Mn3(hypydc)2(H2O)8]·3H2O}n. This compound is a one-dimensional coordination polymer, with the twofold symmetric repeat unit containing three metal centres. Two different coordination geometries are observed for the two independent Mn(II) metal centres, viz. a distorted pentagonal bipyramid and a distorted octahedron. The 4-oxidopyridine-2,6-dicarboxylate anions and two of the water molecules act as bridging ligands. The zigzag-like geometry of the coordination polymer is stabilized by hydrogen bonds. O-H···O and C-H···O hydrogen bonds and water clusters consolidate the three-dimensional network structure.

  2. Single-crystal electron paramagnetic resonance study of the interstitial position of Mn(II) in dipotassium diaquabis(malonato-κ2O,O') zincate(II) dihydrate

    Science.gov (United States)

    Natarajan, B.; Mithira, S.; Sambasiva Rao, P.

    2011-06-01

    A single-crystal electron paramagnetic resonance (EPR) spectroscopic investigation of Mn(II)-doped dipotassium diaquabis(malonato-κ2O,O') zincate dihydrate has been carried out at X-band frequencies at 300 K. The EPR spectrum at room temperature exhibits more than 30 lines along a crystallographic axis, suggesting the presence of two types of impurities in the lattice. Single crystals, rotated along the three mutually orthogonal axes, have yielded the spin-Hamiltonian parameters g, A and D as gxx=2.049, gyy=2.005, gzz=1.993; Axx=-9.17, Ayy=-8.36, Azz=-8.06 mT; Dxx=31.55, Dyy=7.13, Dzz=-38.68 mT, respectively. The other site, due to its low intensity, could not be followed during crystal rotations. The optical absorption spectrum contains characteristic bands of Mn(II) ions in distorted octahedral symmetry. From the observed optical spectrum, the crystal field parameters have been evaluated.

  3. Single-crystal electron paramagnetic resonance study of the interstitial position of Mn(II) in dipotassium diaquabis(malonato-{kappa}{sup 2}O,O') zincate(II) dihydrate

    Energy Technology Data Exchange (ETDEWEB)

    Natarajan, B; Mithira, S; Sambasiva Rao, P, E-mail: psr52in@yahoo.co.in [Department of Chemistry, Pondicherry University, Puducherry 605014 (India)

    2011-06-01

    A single-crystal electron paramagnetic resonance (EPR) spectroscopic investigation of Mn(II)-doped dipotassium diaquabis(malonato-{kappa}{sup 2}O,O') zincate dihydrate has been carried out at X-band frequencies at 300 K. The EPR spectrum at room temperature exhibits more than 30 lines along a crystallographic axis, suggesting the presence of two types of impurities in the lattice. Single crystals, rotated along the three mutually orthogonal axes, have yielded the spin-Hamiltonian parameters g, A and D as g{sub xx}=2.049, g{sub yy}=2.005, g{sub zz}=1.993; A{sub xx}=-9.17, A{sub yy}=-8.36, A{sub zz}=-8.06 mT; D{sub xx}=31.55, D{sub yy}=7.13, D{sub zz}=-38.68 mT, respectively. The other site, due to its low intensity, could not be followed during crystal rotations. The optical absorption spectrum contains characteristic bands of Mn(II) ions in distorted octahedral symmetry. From the observed optical spectrum, the crystal field parameters have been evaluated.

  4. Synthesis, structural, spectral (FT-IR, FT-Ra, and UV-Vis), thermal, and density functional studies on p-methylaniline complexes of Mn(II), Co(II), and Ni(II) bromides

    Science.gov (United States)

    Bardakçı, Tayyibe; Altun, Ahmet; Golcuk, Kurtulus; Kumru, Mustafa

    2015-11-01

    Transition metal complexes of the form MBr2L2, where M = Mn(II), Co(II) and Ni(II); L = p-methylaniline, were prepared and characterized by elemental and thermogravimetric analyses, magnetic moment measurements, and UV-vis, FT-IR and FT-Raman spectral studies. Geometries, spin-state energetics, and vibrational spectra of the complexes were obtained at the B3LYP/def2-TZVP level. The present experimental and theoretical data suggest 5-coordinate polymeric bromide bridged structure for the Mn complex, distorted tetrahedral structure for the Co complex, and distorted octahedral coordination site for the Ni complex. The experimental FT-IR and FT-Raman bands of the complexes were assigned based on the computational results expressed in terms of internal coordinates with percent potential energy distributions. The vibrational spectra suggest that the coordination occurs via nitrogen atom of p-methylaniline. The thermal characteristics of the complexes indicate that their decompositions start through p-methylaniline.

  5. Spectral, structural elucidation and coordination abilities of Co(II) and Mn(II) coordination entities of 2,6,11,15-tetraoxa-9,17-diaza-1,7,10,16-(1,2)-tetrabenzenacyclooctadecaphan-8,17-diene.

    Science.gov (United States)

    Rajiv, Kumar; Rajni, Johar

    2011-09-01

    Designing tactics were tailored and followed by synthetic and formulation methodologies to prepare 2,6,11,15-tetraoxa-9,17-diaza-1,7,10,16-(1,2)-tetrabenzenacyclooctadecaphan-8,17-diene. Spectral techniques (MS, infrared, 1H NMR, 13C NMR, electronic and EPR), physiochemical measurements (elemental analysis, molar conductance and magnetic susceptibility), electrochemistry (cyclic voltammetry) and classical mechanics (molecular modeling) were employed for structural elucidation of Co(II) and Mn(II) coordination entities having N2O4 chromophore. Comparative spectral analysis revealed legating nature of N2O4 donor macrocycle and confirmed host/guest connectivity between ligand and metal(s). Mass spectrometry (MS) determined 1:1 stoichiometry in CEs. Further electrochemical study confirmed change in oxidation and reduction patterns of CEs. Inhibiting potential (antifungal screened against Aspergillus flavus) showed enhanced antimicrobial properties of CEs as compared to ligand. Molecular modeling was employed to find out different molecular features along with their stabilization energies.

  6. Biodegradable coordination polymer: Polycondensation of glutaraldehyde and starch in complex formation with transition metals Mn(II, Co(II, Ni(II, Cu(II and Zn(II

    Directory of Open Access Journals (Sweden)

    Nahid Nishat

    2016-11-01

    Full Text Available Starch a biopolymer, possesses many unique characteristics features accompanied with some shortcoming simultaneously. Some synthetic compounds are of great help to these demerits of starch and so by an addition of all these alternatively may acquire the tailor made features of starch-based compounds. By combining the individual advantages of starch and some other compounds and elements, starch-based biodegradable polymers were prepared for potential applications in biomedical and environmental fields. In this research, the structural analysis and characterization studies of starch glutaraldehyde polycondensed polymer were undertaken, and then the formation of polymer metal complexes with transition metal in coordinated form are carried out. FT-IR spectroscopy and 1H NMR and 13C NMR spectroscopy were used to analyze the functionality of the synthesized compound. CHN of the synthesized compound was supported by FT-IR and NMR which again proved helpful for structural analysis. Electronic spectroscopy confirmed the geometry of the synthesized compounds. Thermal studies were carried out by thermogravimetric analysis (TGA and differential scanning calorimetry (DSC. Besides this the biodegradable studies were carried out by ASTM standards of biodegradable materials by CO2 evolution in respirometric titration method. All the polymers showed good thermal strength and reduced biodegradation on attachment of transition metals, Mn(II, Co(II, Ni(II, Cu(II and Zn(II.

  7. Solid-phase extraction of Mn(II), Co(II), Ni(II), Cu(II), Cd(II) and Pb(II) ions from environmental samples by flame atomic absorption spectrometry (FAAS)

    Energy Technology Data Exchange (ETDEWEB)

    Duran, Celal [Department of Chemistry, Faculty of Art and Science, Karadeniz Technical University, 61080 Trabzon (Turkey); Gundogdu, Ali [Department of Chemistry, Faculty of Art and Science, Karadeniz Technical University, 61080 Trabzon (Turkey); Bulut, Volkan Numan [Department of Chemistry, Giresun Faculty of Art and Science, Karadeniz Technical University, 28049 Giresun (Turkey); Soylak, Mustafa [Department of Chemistry, Faculty of Art and Science, Erciyes University, 38039 Kayseri (Turkey)]. E-mail: soylak@erciyes.edu.tr; Elci, Latif [Department of Chemistry, Faculty of Art and Science, Pamukkale University, 20020 Denizli (Turkey); Sentuerk, Hasan Basri [Department of Chemistry, Faculty of Art and Science, Karadeniz Technical University, 61080 Trabzon (Turkey); Tuefekci, Mehmet [Department of Chemistry, Faculty of Art and Science, Karadeniz Technical University, 61080 Trabzon (Turkey)

    2007-07-19

    A new method using a column packed with Amberlite XAD-2010 resin as a solid-phase extractant has been developed for the multi-element preconcentration of Mn(II), Co(II), Ni(II), Cu(II), Cd(II), and Pb(II) ions based on their complex formation with the sodium diethyldithiocarbamate (Na-DDTC) prior to flame atomic absorption spectrometric (FAAS) determinations. Metal complexes sorbed on the resin were eluted by 1 mol L{sup -1} HNO{sub 3} in acetone. Effects of the analytical conditions over the preconcentration yields of the metal ions, such as pH, quantity of Na-DDTC, eluent type, sample volume and flow rate, foreign ions etc. have been investigated. The limits of detection (LOD) of the analytes were found in the range 0.08-0.26 {mu}g L{sup -1}. The method was validated by analyzing three certified reference materials. The method has been applied for the determination of trace elements in some environmental samples.

  8. Synthesis, spectroscopic, molecular structure, antioxidant, antimicrobial and antitumor behavior of Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) complexes of O2N type tridentate chromone-2-carboxaldehyde Schiff's base ligand

    Science.gov (United States)

    Ammar, Reda A.; Alaghaz, Abdel-Nasser M. A.; Zayed, Mohamed E.; Al-Bedair, Lamia A.

    2017-08-01

    Tridentate Schiff's base (HL) ligand was synthesized via condensation of salicylaldehyde and 3-hydroxypyridin-2-yliminomethyl-4H-chromen-4-one and their corresponding Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) complexes have been synthesized. The isolated solid complexes were characterized by elemental analyses, molar conductance, spectral (IR, UV-Vis, 1H NMR), magnetic moment, EPR, and thermal measurements. The IR spectra showed that HL was coordinated to the metal ions in tridentate manner with O2N donor sites of the azomethine N, deprotonated phenolic-OH and carbonyl-O. The activation of thermodynamic parameters are calculated using Coast-Redfern and Horowitz-Metzger (HM). The octahedral geometry of the complexes is confirmed using DFT method from DMOL3 calculations, UV-Vis and magnetic moment measurements, ESR and ligand field parameters. Antioxidant activities have also been performed for all the compounds. The investigated ligand and metal complexes were screened for their in-vitro antimicrobial activities against different types of fungal and bacterial strains. The resulting data assert on the inspected compounds as a highly promising bactericides and fungicides. The antitumor activities of all inspected compounds were evaluated towards human liver Carcinoma (HepG2) cell line.

  9. Syntheses, structures, electrochemistry and catalytic oxidation degradation of organic dyes of two new coordination polymers derived from Cu(II) and Mn(II) and 1-(tetrazo-5-yl)-4-(triazo-1-yl)benzene

    Science.gov (United States)

    Song, Ming; Mu, Bao; Huang, Ru-Dan

    2017-02-01

    Two new coordination polymers (CPs), namely, [Cu2(ttbz)(H2btc)2(OH)]n (1) and [Mn(ttbz)2(H2O)2]n (2) (Httbz =1-(tetrazo-5-yl)-4-(triazo-1-yl)benzene, H3btc =1,3,5-benzenetricarboxylic acid), have been hydrothermally synthesized and structurally characterized. Complex 1 exhibits a (3,5,5,5)-connected 2D layer with a Schläfli symbol of {3·42}{3·440.520.63}{320.440.520.62}{320.440.530.6}, in which the ttbz- ligand can be described as μ5-bridge, linking Cu(II) ions into a 2D layer and H2btc- ions play a supporting role in complex 1. The ttbz- ligand in complex 2 represents the bridging coordination mode, connecting two Mn(II) ions to form the infinite 1D zigzag chains, respectively, which are further connected by two different types of hydrogen bonds to form a 3D supramolecular. Furthermore, catalytic oxidation activities toward organic dyes and electrochemical behaviors of the title complexes have been investigated at room temperature in aqueous solutions, indicating these complexes may be applicable to color removal in a textile wastewater stream and practical applications in areas of electrocatalytic reduction toward nitrite, respectively.

  10. Synthesis, spectroscopic characterization, DNA interaction and biological activities of Mn(II), Co(II), Ni(II) and Cu(II) complexes with [(1H-1,2,4-triazole-3-ylimino)methyl]naphthalene-2-ol

    Science.gov (United States)

    Gaber, Mohamed; El-Wakiel, Nadia A.; El-Ghamry, Hoda; Fathalla, Shaimaa K.

    2014-11-01

    Manganese(II), cobalt(II), nickel(II) and copper(II) complexes of [(1H-1,2,4-triazole-3-ylimino)methyl]naphthalene-2-ol have been synthesized. The structure of complexes have been characterized by elemental analysis, molar conductance, magnetic moment measurements and spectral (IR, 1H NMR, EI-mass, UV-Vis and ESR), and thermal studies. The results showed that the chloro and nitrato Cu(II) complexes have octahedral geometry while Ni(II), Co(II) and Mn(II) complexes in addition to acetato Cu(II) complex have tetrahedral geometry. The possible structures of the metal complexes have been computed using the molecular mechanic calculations using the hyper chem. 8.03 molecular modeling program to confirm the proposed structures. The kinetic and thermodynamic parameters of the thermal decomposition steps were calculated from the TG curves. The binding modes of the complexes with DNA have been investigated by UV-Vis absorption titration. The results showed that the mode of binding of the complexes to DNA is intercalative or non-intercalative binding modes. Schiff base and its metal complexes have been screened for their in vitro antimicrobial activities against Gram positive bacteria (Staphylococcus aureus), Gram negative bacteria (Escherichia coli and Pesudomonas aeruginosa), fungi (Asperigllus flavus and Mucer) and yeast (Candida albicans and Malassezia furfur).

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

    Science.gov (United States)

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

    2014-08-01

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

  12. Application of maghemite nanoparticles as sorbents for the removal of Cu(II), Mn(II) and U(VI) ions from aqueous solution in acid mine drainage conditions

    Science.gov (United States)

    Etale, Anita; Tutu, Hlanganani; Drake, Deanne C.

    2016-06-01

    The adsorptive removal of Cu(II), Mn(II) and U(VI) by maghemite nanoparticles (NPs) was investigated under acid mine drainage (AMD) conditions to assess NP potential for remediating AMD-contaminated water. The effects of time, NP and metal concentration, as well as manganese and sulphate ions were quantified at pH 3. Adsorption of all three ions was rapid, and equilibrium was attained in 5 min or less. 56 % of Cu, 53 % of Mn and 49 % of U were adsorbed. In addition, adsorption efficiencies were enhanced by ≥10 % in the presence of manganese and sulphate ions, although Cu sorption was reduced in 1:2 Cu-to-Mn solutions. Adsorption also increased with pH: 86 % Cu, 62 % Mn and 77 % U were removed from solution at pH 9 and increasing initial metal concentrations. Increasing NP concentrations did not, however, always increase metal removal. Kinetics data were best described by a pseudo-second-order model, implying chemisorption, while isotherm data were better fitted by the Freundlich model. Metal removal by NPs was then tested in AMD-contaminated surface and ground water. Removal efficiencies of up to 46 % for Cu and 54 % for Mn in surface water and 8 % for Cu and 50 % for Mn in ground water were achieved, confirming that maghemite NPs can be applied for the removal of these ions from AMD-contaminated waters. Notably, whereas sulphates may increase adsorption efficiencies, high Mn concentrations in AMD will likely inhibit Cu sorption.

  13. On-Line pre-concentration of Cr(III) and Mn(II) in FI-FAAS: A critical study involving interference effects and analytical use of an immobilized 8-hydroxyquinoline minicolumn

    Energy Technology Data Exchange (ETDEWEB)

    Bruhn, C.G.; Pino, F.E.; Campos, V.H. [Depto. de Analisis Instrumental, Facultad de Farmacia, Universidad de Concepcion, P.O. Box 237, Concepcion (Chile); Nobrega, J.A. [Departamento de Quimica, Universidade Federal de Sao Carlos, Caixa Postal 676, 13565-905, Sao Carlos, SP (Brazil)

    2002-09-01

    A flow injection system with a pre-concentration minicolumn based on a chelating resin was coupled to a flame atomic absorption spectrometer. The focus of this work was the investigation of interference effects and the analytical applicability of the azo-immobilized 8-hydroxyquinoline on controlled-pore glass for the determination of Cr and Mn in mussel and non-fat milk powder. All studied concomitants affected the retention of Cr(III). These effects are probably related to the formation of hydroxo-complexes at the optimum pH range 9.0-10. The positive effect caused by Ca(II) was exploited to increase the retention of Cr(III) species and to improve the slope by 70%. The interferences on Mn(II) retention were less severe. The quantification of Cr and Mn was performed by standard additions. The proposed methodology was validated by analysis of three certified reference materials of mussels (Cr and Mn) and non-fat milk powder (Mn) with a mean relative percent error of <6.5% and mean relative standard deviation of <13%. Chromium and Mn were determined in typical Chilean mussels samples, and Mn was determined in non-fat milk powder samples. Results agreed at the 95% confidence level with those obtained by electrothermal atomic absorption spectrometry (ETAAS) using graphite furnace atomization. The method detection limits for a 30 s pre-concentration time were 0.9 and 1.1 {mu}g L{sup -1} for Mn, and 2.2 and 2.5 {mu}g L{sup -1} for Cr in acid digested solutions of mussel and non-fat milk, respectively. The methodology is simple, fast (sampling frequency 60-72 h{sup -1}), reliable, of low cost, and can be applied to the determination of traces of Cr ({>=}0.18 {mu}g g{sup -1}) and Mn ({>=}0.6 {mu}g g{sup -1}) in mussel samples, and Mn ({>=}0.37 {mu}g g{sup -1}) in non-fat milk powder. (orig.)

  14. CATALYTIC SPECTROPHOTOMETRIC DETERMINATION OF Mn(II ...

    African Journals Online (AJOL)

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    procedures for trace metals analysis which offer high sensitivity and simplicity. ... distribution of volumes of reagent and working solutions of anionic and cationic ... the laboratory ware used for handling solutions were cleaned with detergent ...

  15. Spectral and thermodynamic properties of Ag(I), Au(III), Cd(II), Co(II), Fe(III), Hg(II), Mn(II), Ni(II), Pb(II), U(IV), and Zn(II) binding by methanobactin from Methylosinus trichosporium OB3b.

    Science.gov (United States)

    Choi, Dong W; Do, Young S; Zea, Corbin J; McEllistrem, Marcus T; Lee, Sung-W; Semrau, Jeremy D; Pohl, Nicola L; Kisting, Clint J; Scardino, Lori L; Hartsel, Scott C; Boyd, Eric S; Geesey, Gill G; Riedel, Theran P; Shafe, Peter H; Kranski, Kim A; Tritsch, John R; Antholine, William E; DiSpirito, Alan A

    2006-12-01

    Methanobactin (mb) is a novel chromopeptide that appears to function as the extracellular component of a copper acquisition system in methanotrophic bacteria. To examine this potential physiological role, and to distinguish it from iron binding siderophores, the spectral (UV-visible absorption, circular dichroism, fluorescence, and X-ray photoelectron) and thermodynamic properties of metal binding by mb were examined. In the absence of Cu(II) or Cu(I), mb will bind Ag(I), Au(III), Co(II), Cd(II), Fe(III), Hg(II), Mn(II), Ni(II), Pb(II), U(VI), or Zn(II), but not Ba(II), Ca(II), La(II), Mg(II), and Sr(II). The results suggest metals such as Ag(I), Au(III), Hg(II), Pb(II) and possibly U(VI) are bound by a mechanism similar to Cu, whereas the coordination of Co(II), Cd(II), Fe(III), Mn(II), Ni(II) and Zn(II) by mb differs from Cu(II). Consistent with its role as a copper-binding compound or chalkophore, the binding constants of all the metals examined were less than those observed with Cu(II) and copper displaced other metals except Ag(I) and Au(III) bound to mb. However, the binding of different metals by mb suggests that methanotrophic activity also may play a role in either the solubilization or immobilization of many metals in situ.

  16. Novel transition metal oxalatophosphates with a two-dimensional honeycomb structure: (H3TREN)[M2(HPO4)(C2O4)2.5] x 3H2O (M = Mn(II) and Fe(II), TREN = tris(2-aminoethyl)amine).

    Science.gov (United States)

    Jiang, Yau-Chen; Wang, Sue-Lein; Lee, Shang-Fan; Lii, Kwang-Hwa

    2003-10-06

    Two new layered transition metal oxalatophosphates, (H(3)TREN)[M(2)(HPO(4))(C(2)O(4))(2.5)].3H(2)O (M = Mn(II) and Fe(II)), have been synthesized by hydrothermal methods in the presence of a structure-directing organic amine, tris(2-aminoethyl)amine, and characterized by single-crystal X-ray diffraction and magnetic susceptibility. They are the first metal oxalatophosphates which adopt a two-dimensional honeycomb structure with the organic cations and water molecules intercalated in between. Within a layer, there are 12-membered pores made from 6 Mn, 1 phosphate, and 5 oxalate units. Measurements of field dependence of magnetization and variable-temperature susceptibilities under different fields were performed on a polycrystalline sample of the manganese compound. The results indicate a phase transition from a paramagnetic to an antiferromagnetic coupled state at about 12 K. Crystal data for the manganese compound follow: triclinic, space group Ponemacr; (No. 2), a = 8.8385(6) A, b = 9.0586(6) A, c = 16.020(1) A, alpha = 77.616(1) degrees, beta = 83.359(1) degrees, gamma = 68.251(1) degrees, and Z = 2. Crystal data for the iron compound are the same as those for the manganese compound except a = 8.7776(9) A, b = 8.9257(9) A, c = 15.884(2) A, alpha = 78.630(2) degrees, beta = 84.018(2) degrees, and gamma = 67.372(2) degrees.

  17. Cu(II), Co(II), Ni(II), Mn(II), and Fe(II) metal complexes containing N,N'-(3,4-diaminobenzophenon)-3,5-Bu(t)(2)-salicylaldimine ligand: Synthesis, structural characterization, thermal properties, electrochemistry, and spectroelectrochemistry.

    Science.gov (United States)

    Tas, E; Kilic, A; Durgun, M; Küpecik, L; Yilmaz, I; Arslan, S

    2010-02-01

    The synthesis, structure, spectroscopic and electro-spectrochemical properties of steric hindered Schiff-base ligand [N,N'-(3,4-benzophenon)-3,5-Bu(t)(2)-salicylaldimine (LH(2))] and its mononuclear Cu(II), Co(II), Ni(II), Mn(II) and Fe(II) complexes are described in this work. The new dissymmetric steric hindered Schiff-base ligand containing a donor set of NONO was prepared through reaction of 3,4-diaminobenzophenon with 3,5-Bu(t)(2)-salicylaldehyde. Certain metal complexes of this ligand were synthesized by treating an ethanolic solution of the ligand with an equimolar amount of metal salts. The ligand and its complexes were characterized by FT-IR, UV-vis, (1)H NMR, elemental analysis, molar conductivity and thermal analysis methods in addition to magnetic susceptibility, electrochemistry and spectroelectrochemistry techniques. The tetradentate and mononuclear metal complexes were obtained by reacting N,N'-(3,4-benzophenon)-3,5-Bu(t)(2)-salicylaldimine (LH(2)) with some metal acetate in a 1:1 mole ratio. The molar conductance data suggest metal complexes to be non-electrolytes.

  18. Novel thioarsenates {[Mn(2,2'-bipy)2(SCN)][Mn(2,2'-bipy)](As(V)S4)}2 and {[Mn(2,2'-bipy)2(SCN)]2[As(III)2(S2)2S2]}: introducing an anionic second ligand to modify MnII complex cations of 2,2'-bipyridine.

    Science.gov (United States)

    Liu, Guang-Ning; Guo, Guo-Cong; Wang, Ming-Sheng; Huang, Jin-Shun

    2014-03-14

    Two novel manganese thioarsenates, {[Mn(2,2'-bipy)2(SCN)][Mn(2,2'-bipy)](As(V)S4)}2 (1, 2,2'-bipy = 2,2'-bipyridine) and {[Mn(2,2'-bipy)2(SCN)]2[As(III)2(S2)2S2]} (2), containing thiocyanate-modified Mn-2,2'-bipy complex cations were synthesized. They feature two terminal [Mn(2,2'-bipy)2(SCN)](+) complex cations bridged by a polyanion {[Mn(2,2'-bipy)]2(As(V)S4)2}(2-) for 1 and a cyclic thioarsenate anion (As(III)2S6)(2-) for 2. In 2, the [As(III)2(S2)2S2](2-) anion can be described as two (As(III)S3)(3-) trigonal-pyramids interlinked through S-S bonds. The method to obtain new metal complex cations shown here, introducing an anionic second ligand to modify the number of coordination sites and the charges of the metal complex cations simultaneously, is different from the traditional methods, varying either the TM center or the organic ligand or employing mixed neutral organic ligands, and may open up a new route for preparing novel chalcogenidometalates. Compounds 1 and 2 exhibit wide optical gaps of 2.20 and 2.67 eV, respectively, and photoluminescence with the emission maxima occurring around 440 nm. Magnetic measurements show the presence of antiferromagnetic interactions between Mn(II) centers in the two compounds.

  19. Schiff base ligand derived from (±trans-1,2-cyclohexanediamine and its Cu(II, Co(II, Zn(II and Mn(II complexes: Synthesis, characterization, styrene oxidation and hydrolysis study of the imine bond in Cu(II Schiff base complex

    Directory of Open Access Journals (Sweden)

    Sarkheil Marzieh

    2016-01-01

    Full Text Available A Schiff base ligand (H2L derived from 2´-hydroxypropiophenone and (±trans-1,2-cyclohexanediamine was synthesized. The reactions of MCl2.xH2O (M =Cu(II, Co(II, Zn(II and Mn(IIwith the di-Schiff base ligand (H2L were studied. This ligand when stirred with 1 equivalent of CuCl2.2H2O in the solution of ethanol and chloroform undergoes partial hydrolysis of the imino bond and the resultant tridentate ligand (HL′immediately forms complex[CuL´Cl]∙3/2CHCl3(1with N2O coordination sphere. Under the same condition, the reaction of H2L with MCl2.xH2O (M = Co(II (3, Zn(II (4 and Mn(II (5 gave complexes[ML]•1/2CHCl3∙3/2H2O (3-5with N2O2 coordination sphere and no hydrolytic cleavage was occurred. Also, the reaction of H2L with CuCl2.2H2O in THF gave the complex CuL (2with N2O2 coordination sphere. The ligand and complexes were characterized by FTIR, UV-Vis, 1H NMRand elemental analysis. The homogeneous catalytic activity of the complexes1, 3 and 5wasevaluated for the oxidation of styrene using tert-butyl hydroperoxide (TBHP as oxidant. Finally, the copper(II complex(1encapsulated in the nanopores of zeolite-Y by flexible ligand method (CuL´-Yand its encapsulation was ensured by different studies. The catalytic performance of heterogeneous catalyst in the styrene oxidation with TBHP was investigated. The catalytic tests showed that the homogenous and heterogeneous catalysts were active in the oxidation of styrene.

  20. (Dimethylformamide-κO(2-hydroxybenzoato-κ2O1,O1′[tris(1-methyl-1H-benzimidazol-2-ylmethyl-κN3amine-κN]manganese(II perchlorate dimethylformamide monosolvate

    Directory of Open Access Journals (Sweden)

    Baoliang Qi

    2010-10-01

    Full Text Available In the title complex, [Mn(C7H5O3(C27H27N7(C3H7NO]ClO4·C3H7NO, the MnII ion is coordinated in a slightly distorted monocapped trigonal-prismatic geometry. The tris(1-methyl-1H-benzimidazol-2-ylmethylamine (Mentb ligand coordinates in a tetradentate mode and the coordination is completed by a bis-chelating salicylate ligand and a dimethylformamide ligand. The hydroxy group and the ortho H atoms of the salicylate ligand were refined as disordered over two sites with occupancies of 0.581 (8 and 0.419 (8. Both disorder components of the hydroxy group form intramolecular O—H...O hydrogen bonds.

  1. 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.

    Science.gov (United States)

    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.

  2. High Turnover Catalysis of Water Oxidation by Mn(II) complexes of Monoanionic Pentadentate Ligands

    DEFF Research Database (Denmark)

    Seidler-Egdal, Rune Kirk; Nielsen, Anne; Bond, Andrew

    2011-01-01

    Capillary electrophoresis (CE) and electrospray ionisation (ESI) mass spectra of aqueous solutions of manganese(II) complexes of the monoanions of the pentadentate ligands N-methyl-N′-carboxymethyl-N,N′-bis(2-pyridylmethyl)ethane-1,2-diamine (mcbpen−) and N-benzyl-N′-carboxymethyl-N,N′-bis(2...

  3. High turnover catalysis of water oxidation by Mn(II) complexes of monoanionic pentadentate ligands

    DEFF Research Database (Denmark)

    Seidler-Egdal, Rune Kirk; Nielsen, Anne; Bond, Andrew

    2011-01-01

    Capillary electrophoresis (CE) and electrospray ionisation (ESI) mass spectra of aqueous solutions of manganese(II) complexes of the monoanions of the pentadentate ligands N-methyl-N'-carboxymethyl-N,N'-bis(2-pyridylmethyl)ethane-1,2-diamine (mcbpen(-)) and N-benzyl-N'-carboxymethyl-N,N'-bis(2...

  4. Effect of PVC and iron materials on Mn(II) deposition in drinking water distribution systems.

    Science.gov (United States)

    Cerrato, José M; Reyes, Lourdes P; Alvarado, Carmen N; Dietrich, Andrea M

    2006-08-01

    Polyvinyl chloride (PVC) and iron pipe materials differentially impacted manganese deposition within a drinking water distribution system that experiences black water problems because it receives soluble manganese from a surface water reservoir that undergoes biogeochemical cycling of manganese. The water quality study was conducted in a section of the distribution system of Tegucigalpa, Honduras and evaluated the influence of iron and PVC pipe materials on the concentrations of soluble and particulate iron and manganese, and determined the composition of scales formed on PVC and iron pipes. As expected, total Fe concentrations were highest in water from iron pipes. Water samples obtained from PVC pipes showed higher total Mn concentrations and more black color than that obtained from iron pipes. Scanning electron microscopy demonstrated that manganese was incorporated into the iron tubercles and thus not readily dislodged from the pipes by water flow. The PVC pipes contained a thin surface scale consisting of white and brown layers of different chemical composition; the brown layer was in contact with the water and contained 6% manganese by weight. Mn composed a greater percentage by weight of the PVC scale than the iron pipe scale; the PVC scale was easily dislodged by flowing water. This research demonstrates that interactions between water and the infrastructure used for its supply affect the quality of the final drinking water.

  5. Authentically radiolabelled Mn(II) complexes as bimodal PET/MR tracers

    Energy Technology Data Exchange (ETDEWEB)

    Vanasschen, Christian; Brandt, Marie; Ermert, Johannes [Institute of Neuroscience and Medicine, INM-5 - Nuclear Chemistry, Forschungszentrum Jülich (Germany); Neumaier, Bernd [Institute for Radiochemistry and Experimental Molecular Imaging, Medical Clinics, University of Cologne (Germany); Coenen, Heinz H [Institute of Neuroscience and Medicine, INM-5 - Nuclear Chemistry, Forschungszentrum Jülich (Germany)

    2015-05-18

    The development of small molecule bimodal PET/MR tracers is mainly hampered by the lack of dedicated preparation methods. Authentic radiolabelling of MR contrast agents ensures easy access to such probes: a ligand, chelating a paramagnetic metal ion (e.g. Mn2+) and the corresponding PET isotope (e.g. 52gMn), leads to a “cocktail mixture” where both imaging reporters exhibit the same pharmacokinetics. Paramagnetic [55Mn(CDTA)]2- shows an excellent compromise between thermodynamic stability, kinetic inertness and MR contrast enhancement. Therefore, the aim of this study was to develop new PET/MR tracers by labelling CDTA ligands with paramagnetic manganese and the β+-emitter 52gMn. N.c.a. 52gMn (t1/2: 5.6 d; Eβ+: 575.8 keV (29.6%)) was produced by proton irradiation of a natCr target followed by cation-exchange chromatography. CDTA was radiolabelled with n.c.a. 52gMn2+ in NaOAc buffer (pH 6) at RT. The complex was purified by RP-HPLC and its stability tested in PBS and blood plasma at 37°C. The redox stability was assessed by monitoring the T1 relaxation (20 MHz) in HEPES buffer (pH 7.4). A functionalized CDTA ligand was synthesized in 5 steps. [52gMn(CDTA)]2- was quantitatively formed within 30 min at RT. The complex was stable for at least 6 days in PBS and blood plasma at 37°C and no oxidation occurred within 7 months storage at RT. Labelling CDTA with an isotopic 52g/55Mn2+ mixture led to the corresponding bimodal PET/MR tracer. Furthermore, a functionalized CDTA ligand was synthesized with an overall yield of 18-25%. [52g/55Mn(CDTA)]2-, the first manganese-based bimodal PET/MR tracer prepared, exhibits excellent stability towards decomplexation and oxidation. This makes the functionalized CDTA ligand highly suitable for designing PET/MR tracers with high relaxivity or targeting properties.

  6. Cathodic stripping voltammetry of trace Mn(II) at carbon film electrodes

    OpenAIRE

    Filipe, Olga M. S.; Brett,Christopher M.A.

    2003-01-01

    A sensitive voltammetric method is presented for the determination of tract levels of Mn (II) using carbon film electrodes fabricated from carbon resistors of 2 [Omega]. Determination of manganese was made by square wave cathodic stripping voltammetry (CSV), with deposition of manganese as manganese dioxide. Chronoamperometric experiments were made to study MnO2 nucleation and growth. As a result, it was found to be necessary to perform electrode conditioning at a more positive potential to i...

  7. Structures, Photophysical Properties, and Growth Patterns of Methylurea Coordinated Ni(II and Mn(II Complexes

    Directory of Open Access Journals (Sweden)

    Wenting Wang

    2017-02-01

    Full Text Available Four coordinated complexes MnxNi(1−x(C2H6N2O6SO4 (x=0, 0.33, 0.75, 0.90 were synthesized and characterized. Single-crystal X-ray analysis revealed that the complexes belong to the trigonal crystal family, R-3c space group. Spiral and terraced nucleus growth modes were observed by atomic force microscopy (AFM in the crystals. Thermogravimetric analysis (TGA and differential thermal analysis (DTA measurements showed their excellent thermostability until 200 °C. UV–vis spectra revealed that the transmission peaks of these crystals have a slight bathochromic shift compared to nickel sulfate hexahydrate (NSH, and the transmittance in the UV range increased as the proportion of Mn2+ increased. With their photophysical properties remaining similar, the much higher heat endurance is rendering these crystals better suitable for UV light filter (ULF applications.

  8. Mn(ii) mediated degradation of artemisinin based on Fe3O4@MnSiO3-FA nanospheres for cancer therapy in vivo

    Science.gov (United States)

    Chen, Jian; Zhang, Weijie; Zhang, Min; Guo, Zhen; Wang, Haibao; He, Mengni; Xu, Pengping; Zhou, Jiajia; Liu, Zhenbang; Chen, Qianwang

    2015-07-01

    Artemisinin (ART) is a natural drug with potent anticancer activities related with Fe2+ mediated cleavage of the endoperoxide bridge in ART. Herein, we reported that Mn2+ could substitute for Fe2+ to react with ART and generate toxic products, inducing a much higher anticancer efficiency. On this basis, we prepared pH-responsive Fe3O4@MnSiO3-FA nanospheres which can efficiently deliver hydrophobic ART into tumors in mice models. Mn2+ was released in acidic tumor environments and intracellular lysosomes, interacting with ART to kill cancer cells. The ART-loaded nanocarriers could suppress tumor growth more efficiently than free ART, which could be further illustrated by magnetic resonance imaging (MRI). Histological analysis revealed that the drug delivery system had no obvious effect on the major organs of mice. ART has been reported to have lower toxicity than chemotherapeutics. The ART-loaded nanocarriers are promising to be used in improving the survival of chemotherapy patients, providing a novel method for clinical tumor therapy.Artemisinin (ART) is a natural drug with potent anticancer activities related with Fe2+ mediated cleavage of the endoperoxide bridge in ART. Herein, we reported that Mn2+ could substitute for Fe2+ to react with ART and generate toxic products, inducing a much higher anticancer efficiency. On this basis, we prepared pH-responsive Fe3O4@MnSiO3-FA nanospheres which can efficiently deliver hydrophobic ART into tumors in mice models. Mn2+ was released in acidic tumor environments and intracellular lysosomes, interacting with ART to kill cancer cells. The ART-loaded nanocarriers could suppress tumor growth more efficiently than free ART, which could be further illustrated by magnetic resonance imaging (MRI). Histological analysis revealed that the drug delivery system had no obvious effect on the major organs of mice. ART has been reported to have lower toxicity than chemotherapeutics. The ART-loaded nanocarriers are promising to be used in improving the survival of chemotherapy patients, providing a novel method for clinical tumor therapy. Electronic supplementary information (ESI) available: Iron mediated degradation mechanism for artemisinin, mechanism of alkylation of iron(ii)-heme or iron(ii)/heme dimethylester by artemisinin, mechanism of alkylation of the heme model MnIITPP by artemisinin, schematic illustration of the synthesis of ART-loaded Fe3O4@MnSiO3-FA nanospheres, further characterization such as XRD and EDX patterns, N2 adsorption and desorption isotherm and BJH pore distribution, FT-IR spectra, UV-vis spectra, DLS and parallel test results of flow cytometric detection are given in Fig. S1-S13, Fe2+ or Mn2+ release from Fe3O4@MnSiO3 nanospheres in PBS at different pHs is given in Table S1. See DOI: 10.1039/c5nr02402a

  9. Role of annealing on the structural and optical properties of nanostructured diaceto bis-benzimidazole Mn(II) complex thin films.

    Science.gov (United States)

    Praveen, P A; Babu, R Ramesh; Ramamurthi, K

    2017-02-15

    A coordination complex, manganese incorporated benzimidazole, thin films were prepared by chemical bath deposition method. Structural characterization of the deposited films, carried out by Fourier transform infrared spectroscopy, Raman and electron paramagnetic resonance spectral analyses, reveals the distorted tetrahedral environment of the metal ion with bis-benzimidazole ligand. Further the molecular composition of the deposited metal complex was estimated by energy-dispersive X-ray spectroscopy. The prepared thin films were thermally treated to study the effect of annealing temperature on the surface morphology and the results showed that the surface homogeneity of the films increased for thermally treated films up to 150°C. But distortion and voids were observed for the films annealed at 200°C. The Raman analysis reveals the molecular hydrogen bond distortion which leads to the evaporation of the metal complex from the thin film surface with respect to annealing temperature. The linear and nonlinear optical properties of the as prepared and annealed films were studied using ultraviolet-visible transmittance spectroscopy, second harmonic generation and Z-scan analyses. Films annealed at 150°C show a better linear transmittance in the visible region and larger SHG efficiency and third order nonlinear susceptibility when compared with the other samples. Further, the film annealed at 150°C was subjected to optical switching analysis and demonstrated to have an inverted switching behavior.

  10. Ab initio and coupled-perturbed density functional theory estimation of zero-field splittings in MnII transition metal complexes.

    Science.gov (United States)

    Zein, Samir; Neese, Frank

    2008-08-28

    The paper presents a method comparison for the prediction of zero-field splitting (ZFS) parameters in a series of Mn (II) coordination complexes. The test set consists of Mn (II) complexes that are experimentally well-characterized by X-ray diffraction and high-field electron paramagnetic resonance. Their ZFS parameters have been calculated using density functional theory (DFT) as well as complete active space self-consistent field (CASSCF) methods. It is shown that the recently introduced coupled-perturbed spin-orbit coupling (CP-SOC) approach [ Neese, F. J. Chem. Phys. 2007, 127, 164112 ] together with hybrid-DFT functionals leads to a slope of the correlation line (plot of experimental vs calculated D values) that is essentially unity provided that the direct spin-spin interaction is properly included in the treatment. This is different from our previous DFT study on the same series of complexes where a severe overestimation of the D parameter has been found [ Zein, S. ; Duboc, C. ; Lubitz, W. ; Neese, F. Inorg. Chem. 2008, 47, 134 ]. CASSCF methods have been used to evaluate the ZFS in an "ab initio ligand-field" type treatment. The study demonstrates that a substantial part of the relevant physics is lost in such a treatment since only excitations within the manganese d-manifold are accounted for. Thus, a severe underestimation of the D parameter has been found. Because the CASSCF calculations in combination with quasidegenerate perturbation theory treats the SOC to all orders, we have nevertheless verified that second-order perturbation theory is an adequate approximation in the case of the high-spin d (5) configuration.

  11. Theoretical approach to the magnetic properties of Mn(II), Cr(III), and Cu(II) complexes in the newly reported 12- and 15-membered macrocyclic ligands

    Indian Academy of Sciences (India)

    Ali Bayri; Mustafa Karkaplan

    2007-08-01

    The magnetic properties of Cu2+, Cr3+, and Mn2+ ions in the newly reported 12- and 15-membered macrocyclic complexes are analysed by a theoretical approach. The calculated magnetic moment and magnetic anisotropy for various situations, especially for Cu(II) ion, suggest that the magnetic properties may lead to a better interpretation about the geometry. It is also suggested that the zero-field splitting Hamiltonian may be used for magnetic properties of some metal ions, which have orbital singlet ground term in these complexes.

  12. Synthesis and Properties of New Molecule-Based Magnets Containing Mn(II, Cu(II and Nitronyl Nitroxide Radical Cation

    Directory of Open Access Journals (Sweden)

    Vaz Maria G. F.

    2002-01-01

    Full Text Available In this work, we describe the synthesis of two new copper(II compounds, (Pr-Rad2 [Cu(opba].H2O (1 and (Bu-Rad2[Cu(opba].2H2O (2 where opba stands for ortho-phenylenebis(oxamato and RRad+ are nitronyl nitroxide radical cations. From 1 and 2, two new molecule-based magnets [Pr-Rad]2[Mn2{Cu(opba}3 ].3.3DMSO.5H2O (3 and [Bu-Rad]2 [Mn2{Cu(opba}3].3DMSO.6H 2O (4 were obtained, respectively. The magnetic properties of precursors 1 and 2 show the presence of ferromagnetic interaction between the radical cations with copper(II, in the temperature range of 20-300 K. The magnets 3 and 4 exhibit spontaneous magnetization at critical temperatures, Tc, of 23 K and 24 K, respectively.

  13. Generation of a Mn(IV)-Peroxo or Mn(III)-Oxo-Mn(III) Species upon Oxygenation of Mono- and Binuclear Thiolate-Ligated Mn(II) Complexes.

    Science.gov (United States)

    Lee, Chien-Ming; Wu, Wun-Yan; Chiang, Ming-Hsi; Bohle, D Scott; Lee, Gene-Hsiang

    2017-09-05

    A thiolate-bridged binuclear complex [PPN]2[(Mn(II)((TMS)PS3))2] (1, PPN = bis(triphenylphosphine)iminium and (TMS)PS3H3 = (2,2',2″-trimercapto-3,3',3″-tris(trimethylsilyl)triphenylphosphine)), prepared from the reaction of MnCl2/[PPN]Cl and Li3[(TMS)PS3], converts into a mononuclear complex [PPN][Mn(II)((TMS)PS3)(DABCO)] (2) in the presence of excess amounts of DABCO (DABCO = 1,4-diazabicyclo[2.2.2]octane). Variable temperature studies of solution containing 1 and DABCO by UV-vis spectroscopy indicate that 1 and 2 exist in significant amounts in equilibrium and mononuclear 2 is favored at low temperature. Treatment of 1 or 2 with the monomeric O2-side-on-bound [PPN][Mn(IV)(O2)((TMS)PS3)] (3) produces the mono-oxo-bridged dimer [PPN]2[(Mn(III)((TMS)PS3))2(μ-O)] (4). The electrochemistry of 1 and 2 reveals anodic peak(s) for a Mn(III/)Mn(II) redox couple at shifted potentials against Fc/Fc(+), indicating that both complexes can be oxidized by dioxygen. The O2 activation mediated by 1 and 2 is investigated in both solution and the solid state. Microcrystals of 2 rapidly react with air or dry O2 to generate the Mn(IV)-peroxo 3 in high yield, revealing a solid-to-solid transformation and two-electron reduction of O2. Oxygenation of 1 or 2 in solution, however, is affected by diffusion and transient concentration of dioxygen in the two different substrates, leading to generation of 3 and 4 in variable ratios.

  14. Isomorphous substitution of Mn(II), Ni(II) and Zn(II) in AlPO-31 molecular sieves and study of their catalytic performance

    Indian Academy of Sciences (India)

    V Umamaheswari; C Kannan; Banumathi Arabindoo; M Palanichamy; V Murugesan

    2000-08-01

    Isomorphously substituted molecular sieves, MAPO-31, NAPO-31 and ZAPO-31, were prepared under mild hydrothermal conditions from gels containing sources of aluminium, phosphorus, appropriate metal and dipropylamine (DPA), presumably acting as a structure-directing template. They were characterized by XRD, FTIR, TGA, inductively coupled plasma (ICP), ESR, Brunauer, Emmett, Teller (BET) and diffusion reflectance spectroscopy (DRS) techniques. In the XRD, the peak at 2 = 16 7° of the metal substituted AlPO-31 is more intense than that of pure AlPO-31 suggesting preferential occupation of the plane corresponding to it as compared to other planes. The O-H stretch in the IR spectra of the metal-substituted molecular sieves is blue-shifted with respect to the parent AlPO-31 molecular sieves possibly due to metal substitution. The g values obtained from the ESR spectra of MAPO-31 and NAPO-31 also substantiate framework substitution. Ethylation of toluene was carried out between 300 and 450°C over the above catalysts as a model test reaction. The high toluene conversion over metal-substituted molecular sieves proves the isomorphic substitution of metal ions in the AlPO-31 framework.

  15. Separation of Mn(II) in presence of Al(III) in acid drainage from an Uranium mine with the use of chelating resins

    Energy Technology Data Exchange (ETDEWEB)

    Soares, Eliane Pavesi B., E-mail: pavesi@ien.gov.br [Instituto de Engenharia Nuclear (IEN/CNEN-RJ), Rio de Janeiro, RJ (Brazil); Gomes, Viviane T.; Vaitsman, Delmo S., E-mail: vgomes@iq.ufrj.br, E-mail: vaistman@iq.ufrj.br [Instituto de Quimica, Universidade Federal do Rio de Janeiro, UFRJ, RJ (Brazil)

    2011-07-01

    The acid drainage of Osamu Utsumi mine is the main environmental impact from mining activities in Pocos de Caldas - MG - Brazil. The water produced in this process is characterized by high acidity and heavy metal concentration. To minimize this environmental impact, new technologies directed towards treatment of acid drainage of mine (ADM) have been studied. However, due to the presence of Al{sup 3+} (which has a high charge) in the ADM, these resins get quickly saturated, preventing stripping of divalent cations like Mn{sup 2+}. This study proposes the synthesis of chelating resins that provide preferential retention of Mn{sup 2+} instead of Al{sup 3+}. It was synthesized resins functionalized with amidoxime and dithiocarbamate. The capacity of retention of Mn{sup 2+} e Al{sup 3+} ions at different pH values was assessed for each resin. The stripping of Mn{sup 2+} at 2, 3 and 4 (pH ADM range) by studied resins was not preferential for Mn{sup 2+} in relation to Al{sup 3+}, probably due to the strong electrostatic interaction between this last type of high charge density and the active sites from extractor agents and resins. However at pH 6 (stated by environmental norms for liquid effluents discharge) the synthesized resins had a good retention capacity for Mn{sup 2+}. So it is proposed that the extraction technique using chelating resins could be employed to strip Mn{sup 2+} from ADM at pH 6,0, since at this condition , Al{sup 3+} is precipitated as Al(OH){sub 3}. (author)

  16. Use of coal mining waste for the removal of acidity and metal ions Al(III), Fe(III) and Mn(II) in acid mine drainage

    Energy Technology Data Exchange (ETDEWEB)

    Geremias, R.; Laus, R.; Macan, J.M.; Pedrosa, R.C.; Laranjeira, M.C.M.; Silvan, J.; Favere, F.V. [Universidade Federal de Santa Catarina, Florianopolis (Brazil)

    2008-08-15

    The coal industry may generate acid mine drainage (AMD) and mining wastes, which may adversely affect the quality of the environment. In this study we propose the use of this waste in the removal of acidity and metal ions, as well as in the reduction of the toxicity of AMD. A physico-chemical analysis of the waste shows the presence of mainly SiO{sub 2}, Al{sub 2}O{sub 3} and Fe{sub 2}O{sub 3} and a superficial area of 4.316 m{sup 2} g{sup -1}. The treatment of AMD with the waste resulted in an increase in pH from 2.6 to 7.8 and removed 100% of the Al(III), 100% of the Fe(III) and 89% of the Mn (II). We also observed that the high toxicity of the AMD towards Daphnia magna (LC50 = 3.68%) and Artemia sp. (LC50 = 4.97%) was completely eliminated after treatment with the waste. The data obtained allow us to propose that the waste can be used in the treatment of AMD, providing an economic use for the waste.

  17. Spectroscopic investigation of new water soluble Mn(II)(2) and Mg(II)(2) complexes for the substrate binding models of xylose/glucose isomerases.

    Science.gov (United States)

    Patra, Ayan; Bera, Manindranath

    2014-01-30

    In methanol, the reaction of stoichiometric amounts of Mn(OAc)(2)·4H(2)O and the ligand H(3)hpnbpda [H(3)hpnbpda=N,N'-bis(2-pyridylmethyl)-2-hydroxy-1,3-propanediamine-N,N'-diacetic acid] in the presence of NaOH, afforded a new water soluble dinuclear manganese(II) complex, [Mn2(hpnbpda)(μ-OAc)] (1). Similarly, the reaction of Mg(OAc)(2)·4H(2)O and the ligand H3hpnbpda in the presence of NaOH, in methanol, yielded a new water soluble dinuclear magnesium(II) complex, [Mg2(hpnbpda)(μ-OAc)(H2O)2] (2). DFT calculations have been performed for the structural optimization of complexes 1 and 2. The DFT optimized structure of complex 1 shows that two manganese(II) centers are in a distorted square pyramidal geometry, whereas the DFT optimized structure of complex 2 reveals that two magnesium(II) centers adopt a six-coordinate distorted octahedral geometry. To understand the mode of substrate binding and the mechanistic details of the active site metals in xylose/glucose isomerases (XGI), we have investigated the binding interactions of biologically important monosaccharides d-glucose and d-xylose with complexes 1 and 2, in aqueous alkaline solution by a combined approach of FTIR, UV-vis, fluorescence, and (13)C NMR spectroscopic techniques. Fluorescence spectra show the binding-induced gradual decrease in emission of complexes 1 and 2 accompanied by a significant blue shift upon increasing the concentration of sugar substrates. The binding modes of d-glucose and d-xylose with complex 2 are indicated by their characteristic coordination induced shift (CIS) values in (13)C NMR spectra for C1 and C2 carbon atoms.

  18. Synthesis, thermogravimetric analysis, infrared, electronic and mass spectra of Mn(II), Co(II) and Fe(III) norfloxacin complexes

    Science.gov (United States)

    Sadeek, Sadeek A.

    2005-10-01

    The interactions of manganese acetate, ferric chloride and cobalt sulphate with norfloxacin (NOR) in acetone or methanol were studied. The isolated solid complexes were characterized by elemental analysis, infrared, electronic, mass spectra and thermal analysis. The results support the formation of complexes of the formula [Fe(NOR) 3]Cl 3·12H 2O and [M(NOR) 2]X 2·8H 2O (M=Mn(II) or Co(II) and X=(CH 3COO -) or SO4-2). The infrared spectra of the isolated solid complexes suggested, indicated that NOR act as bidentate ligands through one of the oxygen atoms of the carboxylic group and the ring carbonyl oxygen atom. The interpretation, mathematical analysis and evaluation of kinetic parameters of thermogravimetric (TGA) and its differential (DTG), such as entropy of activation, pre-exponential factors, activation energy evaluated by using Coats-Redfern and Horowitz-Metzger equations for two complexes are carried out. General mechanisms describing the decomposition of the solid complexes are suggested.

  19. Pyrazoles and imidazoles as ligands. X. electron paramagnetic resonance spectra of MnII in a tetragonal environment of four pyrazoles and two anions

    NARCIS (Netherlands)

    Dowsing, R.D.; Nieuwenhuijse, B.; Reedijk, J.

    1971-01-01

    Electron Paramagnetic Resonance Spectra have been recorded for some compounds of the type Mn(ligand)4- (anion)2, with pyrazole and 3(5)-methyl pyrazole as the ligands, and Cl−, Br−, I−, and NO3−, as the anions. The spectra show absorptions far from geff=2 for all compounds at both X- and Q-band fre

  20. Regulation of MntH by a dual Mn(II- and Fe(II-dependent transcriptional repressor (DR2539 in Deinococcus radiodurans.

    Directory of Open Access Journals (Sweden)

    Hongxing Sun

    Full Text Available The high intracellular Mn/Fe ratio observed within the bacteria Deinococcus radiodurans may contribute to its remarkable resistance to environmental stresses. We isolated DR2539, a novel regulator of intracellular Mn/Fe homeostasis in D. radiodurans. Electrophoretic gel mobility shift assays (EMSAs revealed that DR2539 binds specifically to the promoter of the manganese acquisition transporter (MntH gene, and that DR0865, the only Fur homologue in D. radiodurans, cannot bind to the promoter of mntH, but it can bind to the promoter of another manganese acquisition transporter, MntABC. β-galactosidase expression analysis indicated that DR2539 acts as a manganese- and iron-dependent transcriptional repressor. Further sequence alignment analysis revealed that DR2539 has evolved some special characteristics. Site-directed mutagenesis suggested that His98 plays an important role in the activities of DR2539, and further protein-DNA binding activity assays showed that the activity of H98Y mutants decreased dramatically relative to wild type DR2539. Our study suggests that D. radiodurans has evolved a very efficient manganese regulation mechanism that involves its high intracellular Mn/Fe ratio and permits resistance to extreme conditions.

  1. Estudo da labilidade de Cu(II, Cd(II, Mn(II e Ni(II em substâncias húmicas aquáticas utilizando-se membranas celulósicas organomodificadas Lability study of Cu(II, Cd(II, Mn(II and Ni(II complexed by aquatic humic substances using organomodified cellulose membranes

    Directory of Open Access Journals (Sweden)

    André Henrique Rosa

    2007-02-01

    Full Text Available In this work commercial filters papers were organomodified with tetraethylorthosilicate (TEOS and 3-aminopropyltriethoxysilane (3-APTS, aiming at the development of a new analytical procedure for in-situ speciation of labile and inert metal species in aquatic systems. Parameters that exert influence on the metal lability such as pH, chelating time, concentration and characteristics of the organic matter were studied in the laboratory using tests for metal recuperation. The results showed slower kinetics for Cu ion than for Ni, Mn and Cd in the absence of aquatic humic substances (AHS. The relative lability observed for complexed metals in aquatic humic substances using organomodified filter papers was Cu>>Cd>Ni>Mn. The pH values, structural characteristics and concentration of AHS exert strong influence on the lability of the metals. The results obtained showed that the utilization of organomodified filter papers can be an interesting and promising alternative for in situ characterization of metal lability in aquatic systems.

  2. Preparação de membranas de acetato de celulose organomodificadas para adsorção dos íons Cu(II, Cd(II, Mn(II e Ni(II Preparation of the orgamomodified cellulose acetate membranes for adsorption of the ions Cu(II, Cd(II, Mn(II AND Ni(II

    Directory of Open Access Journals (Sweden)

    Danielle Goveia

    2010-01-01

    Full Text Available Cellulose acetate polymeric membranes had been prepared by a procedure of two steps, combining the method of phase inversion and the technique of hydrolysis-deposition. The first step was the preparation of the membrane, and together was organomodified with tetraethylortosilicate and 3-aminopropyltrietoxysilane. Parameters that exert influence in the complexation of the metallic ion, as pH, time of complexation, metal concentration, had been studied in laboratory using tests of metal removal. The membranes had presented resistance mechanics and reactivity to cations, being able to be an alternative for the removal, daily pay-concentration or in the study of the lability of metals complexed.

  3. Manganese acquisition by Lactobacillus plantarum

    Energy Technology Data Exchange (ETDEWEB)

    Archibald, F.S.; Duong, M.N.

    1984-04-01

    Lactobacillus plantarum has an unusually high Mn(II) requirement for growth and accumulated over 30 mM intracellular Mn(II). The acquisition of Mn(II) by L. plantarum occurred via a specific active transport system powered by the transmembrane proton gradient. The Mn(II) uptake system has a K/sub m/ of 0.2 ..mu..M and a V/sub max/ of 24 nmol mg/sup -1/ of protein min/sup -1/. Above a medium Mn(II) concentration of 200 ..mu..M, the intracellular Mn(II) level was independent of the medium Mn(II) and unresponsive to oxygen stresses but was reduced by phosphate limitation. At a pH of 5.5, citrate, isocitrate, and cis-aconitate effectively promoted MN(II) uptake, although measurable levels of 1,5-(/sup 14/C)citrate were not accumulated. When cells were presented with equimolar Mn(II) and Cd(II), Cd(II) was preferentially taken up by the Mn(II) transport system. Both Mn(II) and Cd(II) uptake were greatly increased by Mn(II) starvation. Mn(II) uptake by Mn(II)-starved cells was subject to a negative feedback regulatory mechanism functioning less than 1 min after exposure of the cells to Mn(II) and independent of protein synthesis. When presented with a relatively large amount of exogenous Mn(II), Mn(II)-starved cells exhibited a measurable efflux of their internal Mn(II), but the rate was only a small fraction of the maximal Mn(II) uptake rate.

  4. How to overcome inter-electrode variability and instability to quantify dissolved oxygen, Fe(II), mn(II), and S(−II) in undisturbed soils and sediments using voltammetry

    Science.gov (United States)

    Slowey, Aaron J.; Marvin-DiPasquale, Mark

    2012-01-01

    Background - Although uniquely capable of measuring multiple redox constituents nearly simultaneously with no or minimal sample pretreatment, voltammetry is currently underutilized in characterizing redox conditions in aquatic and terrestrial systems. Investigation of undisturbed media such as pore water requires a solid-state electrode, and such electrodes can be difficult to fabricate reproducibly. An approach to determine the concentrations of electroactive constituents using indirectly calibrated electrodes has been developed, but the protocol for and accuracy of this approach—the pilot ion method—has not been documented in detail.

  5. Spectroscopic, thermal and biological studies of coordination compounds of sulfasalazine drug: Mn(II), Hg(II), Cr(III), ZrO(II), VO(II) and Y(III) transition metal complexes

    Indian Academy of Sciences (India)

    M G Abd El-Wahed; M S Refat; S M El-Megharbel

    2009-04-01

    The complexations of sulfasalazine (H3Suz) with some of transition metals have been investigated. Three types of complexes, [Mn(HSuz)-2(H2O)4].2H2O, [M(HSuz)-2(H2O)2].H2O (M = Hg(II), ZrO(II) and VO(II), = 4, 8 and 6, respectively) and [M(HSuz)-2(Cl)(H2O)3].H2O (M = Cr(III) and Y(III), = 5 and 6, respectively) were obtained and characterized by physicochemical and spectroscopic methods. The IR spectra of the complexes suggest that the sulfasalazine behaves as a monoanionic bidentate ligand. The thermal decomposition of the complexes as well as thermodynamic parameters ( *}, *, * and *) were estimated using Coats–Redfern and Horowitz–Metzger equations. In vitro antimicrobial activities of the H3Suz and the complexes were tested.

  6. Magnetic property and thermal analysis of a Mn(II) complex with [Mn(CO2)]n chains based on 4,4‧-bis(1H-imidazol-1-yl-methyl)biphenyl

    Science.gov (United States)

    Zhang, Ming-Dao; Zheng, Bao-Hui; Wang, Zhe; Jiao, Yan; Chen, Min-Dong

    2014-11-01

    Magnetic coordination polymers have attracted considerable interest due to their novel structures and potential applications. In this paper, one new 2D magnetic manganese coordination polymer {[Mn(bimb)(OBA)]}n (1) was synthesized under solvothermal conditions based on 4,4‧-bis(1H-imidazol-1-yl-methyl)biphenyl (bimb) and 4,4‧-oxybis(benzoate) (H2OBA). Complex 1 contains [Mn(CO2)]n 1D chains and magnetic susceptibility measurements indicate that compound 1 exhibits an antiferromagnetic coupling interaction. In addition, complex 1 exhibits solid-state photoluminescence and high thermal stability.

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

    Science.gov (United States)

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

    2009-11-01

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

  8. Syntheses, Characterization, and Antimicrobial Screening of N-(benzothiazol-2-ylbenzenesulphonamide and its Cu(I, Ni(II, Mn(II, Co(II, and Zn(II Complexes

    Directory of Open Access Journals (Sweden)

    N. L. Obasi

    2012-01-01

    Full Text Available N-(benzothiazol-2-ylbenzenesulphonamide (BS2ABT was synthesized by the condensation (by refluxing of 2-aminobenzothiazole and benzenesulphonylchloride in acetone at 140ºC. The resulting crude precipitates were recrystallized from dimethylformamide (DMF. Five metal complexes of copper(I, nickel(II, manganese(II, cobalt(II and zinc(II of the ligands were synthesized. The compounds were characterized using magnetic susceptibility measurements, UV/VIS spectrophotometry, infra red, proton and 13C nmr spectroscopies. The antimicrobial tests of the ligands and its metal complexes were carried out on both multi-resistant bacterial strains isolated under clinical conditions and cultured species using agar-well diffusion method. The multi-resistant bacterial strains used were Escherichia coli, Proteus species, Pseudomonas aeroginosa and Staphylococcus aureus which were isolated from dogs. The culture species were Pseudomonas aeruginosa (ATCC 27853, Escherichia Coli (ATCC 25922 Staphylococcus aureus (ATCC 25923, and the fungi, Candida krusei (ATCC 6258 and Candida albicans (ATCC 90028. The tests were both in vitro and in vivo. Thus the Inhibition Zone Diameter (IZD, the Minimum Inhibitory Concentration (MIC, and the Lethal and Effective Concentrations (LC50 and EC50 were determined. The antimicrobial activities of the compounds were compared with those of Ciprofloxacin and trimethoprim-sulphamethoxazole as antibacterial agents and Fluconazole as an antifungal drug. All the compounds showed varying activities against the cultured typed bacteria and fungi used. However, they were less active than the standard drugs used except Fluconazole which did not show any activity against Candida krusei (ATCC 6258 but most of the compounds synthesized were very active against it. The Lethal Concentration (LC50 ranged from 26.25±4.9-1833.88±186.92 ppm. These are within the permissible concentrations.

  9. How to overcome inter-electrode variability and instability to quantify dissolved oxygen, Fe(II), mn(II), and S(−II) in undisturbed soils and sediments using voltammetry

    OpenAIRE

    2012-01-01

    Abstract Background Although uniquely capable of measuring multiple redox constituents nearly simultaneously with no or minimal sample pretreatment, voltammetry is currently underutilized in characterizing redox conditions in aquatic and terrestrial systems. Investigation of undisturbed media such as pore water requires a solid-state electrode, and such electrodes can be difficult to fabricate reproducibly. An approach to determine the concentrations of electroactive constituents using indire...

  10. Isotypic Mn(II) and Fe(II) binuclear complexes of the ligand 5,6-bis-(pyridin-2-yl)-pyrazine-2,3-di-carb-oxy-lic acid.

    Science.gov (United States)

    Alfonso, Monserrat; Stoeckli-Evans, Helen

    2016-10-01

    The title isotypic complexes, bis-[μ-5,6-bis-(pyridin-2-yl)pyrazine-2,3-di-carboxylato]-κ(4)N(1),O(2),N(6):O(3);κ(4)O(3):N(1),O(2),N(6)-bis-[di-aqua-manganese(II)] tetra-hydrate, [Mn2(C16H8N4O4)2(H2O)4]·4H2O, (I), and bis-[μ-5,6-bis-(pyridin-2-yl)pyrazine-2,3-di-carboxyl-ato]-κ(4)N(1),O(2),N(6):O(3);κ(4)O(3):N(1),O(2),N(6)-bis-[di-aqua-iron(II)] tetrahydrate, [Fe2(C16H8N4O4)2(H2O)4]·4H2O, (II), are, respectively, the mangan-ese(II) and iron(II) complexes of the ligand 5,6-bis-(pyridin-2-yl)-pyrazine-2,3-di-carb-oxy-lic acid. The complete mol-ecule of each complex is generated by inversion symmetry. Each metal ion is coordinated by a pyrazine N atom, a pyridine N atom, two carboxyl-ate O atoms, one of which is bridging, and two water O atoms. The metal atoms have MN2O4 coordination geometries and the complexes have a cage-like structure. In the crystals of both compounds, the complexes are linked by O-H⋯O and O-H⋯N hydrogen bonds involving the coordinating water mol-ecules, forming chains along [100]. These chains are linked by O-H⋯O hydrogen bonds involving the non-coordinating water mol-ecules, forming layers parallel to (011). The layers are linked by pairs of C-H⋯O hydrogen bonds and offset π-π inter-actions, so forming a hydrogen-bonded three-dimensional framework.

  11. Synthesis, Characterization and Antibacterial Activity of Novel Schiff Bases Derived from 4-Phenyl-2-aminothiazole and their Mn(II, Fe(II, Co(II, Ni(II and Cu(II Metal complexes

    Directory of Open Access Journals (Sweden)

    A. S. Thakar

    2011-01-01

    Full Text Available Novel Schiff bases and their metal complexes were derived from some hetero cyclic β-diketones with 4-phenyl-2-aminothiazole. All the synthesized compounds were confirmed their structure by Elemental analysis, FT-IR, 1H NMR, 13C NMR, Mass spectra, TGA analysis and UV spectra. All the compounds were tested for their antibacterial activity. Spectroscopic measurements suggest that all Schiff base metal complexes are of type ML2.(H2O2 (M=Mn, Fe, Co, Ni and Cu and all the metal complexes shows moderate antibacterial activity in the agar cup assay method.

  12. A pure inorganic 1D chain based on {Mo8O28} clusters and Mn(II) ions: [Mn(H2O)2Mo8O28 ] n 6 n -

    Science.gov (United States)

    Zhang, Xiaofen; Yan, Yonghong; Wu, Lizhou; Yu, Chengxin; Dong, Xinbo; Hu, Huaiming; Xue, Ganglin

    2016-01-01

    A new pure inorganic polymer, (NH4)6n[Mn(H2O)2Mo8O28)]n(H2O)2n(1), has been synthesized and characterized by elemental analyses, IR spectrum, UV-vis absorption spectra, TG-DSC and electrochemical studies. In 1, [Mo8O28]8- anions act as tetradentate ligands and are alternately linked by Mn(H2O)2 2 + ions into a one-dimensional chain structure. It is interesting that 1 represents the first example of pure inorganic-inorganic hybrid based on octamolybdate and transition metal ions. Moreover, it was indicated that 1 had definite catalytic activities on the probe reaction of benzyl alcohol oxidation to benzaldehyde with H2O2.

  13. [2-(3,5-Dimethyl-1H-pyrazol-1-yl-κN2-1,10-phenanthroline-κ2N,N′]bis(nitrito-κ2O,O′cadmium(II

    Directory of Open Access Journals (Sweden)

    Jing Min Shi

    2010-08-01

    Full Text Available In the title complex, [Cd(NO22(C17H14N4], the CdII ion assumes a distorted monocapped octahedral coordination geometry defined by an N3O4 donor set. The crystal structure is stabilized by π–π stacking interactions [shortest centroid–centroid distance = 3.5537 (18 Å].

  14. Synthesis and Structural Determination of Binuclear Nine-Coordinate K4[Y2(Httha)2]·14H2O

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    A Y3+ complex with triethylenetetraaminehexaacetic acid was prepared and its composition and structure were determined as K4[Y2(Httha)2]*14H2O by elemental analysis and single-crystal X-ray four circle diffraction analysis. In the binuclear complex, the two YN3O6 parts all form nine-coordinate monocapped square anti prismatic structures. There are a lot of water molecules in the unit cell which form hydrogen bonds.

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

    Science.gov (United States)

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

    2012-08-01

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

  16. Oxygen Isotope Evidence for Mn(II)-Catalyzed Recrystallization of Manganite (γ-MnOOH).

    Science.gov (United States)

    Frierdich, Andrew J; Spicuzza, Michael J; Scherer, Michelle M

    2016-06-21

    Manganese is biogeochemically cycled between aqueous Mn(II) and Mn(IV) oxides. Aqueous Mn(II) often coexists with Mn(IV) oxides, and redox reactions between the two (e.g., comproportionation) are well known to result in the formation of Mn(III) minerals. It is unknown, however, whether aqueous Mn(II) exchanges with structural Mn(III) in manganese oxides in the absence of any mineral transformation (similar to what has been reported for aqueous Fe(II) and some Fe(III) minerals). To probe whether atoms exchange between a Mn(III) oxide and water, we use a (17)O tracer to measure oxygen isotope exchange between structural oxygen in manganite (γ-MnOOH) and water. In the absence of aqueous Mn(II), about 18% of the oxygen atoms in manganite exchange with the aqueous phase, which is close to the estimated surface oxygen atoms (∼11%). In the presence of aqueous Mn(II), an additional 10% (for a total of 28%) of the oxygen atoms exchange with water, suggesting that some of the bulk manganite mineral (i.e., beyond surface) is exchanging with the fluid. Exchange of manganite oxygen with water occurs without any observable change in mineral phase and appears to be independent of the rapid Mn(II) sorption kinetics. These experiments suggest that Mn(II) catalyzes manganese oxide recrystallization and illustrate a new pathway by which these ubiquitous minerals interact with their surrounding fluid.

  17. Indirect Manganese Removal by Stenotrophomonas sp. and Lysinibacillus sp. Isolated from Brazilian Mine Water

    Science.gov (United States)

    Barboza, Natália Rocha; Amorim, Soraya Sander; Santos, Pricila Almeida; Reis, Flávia Donária; Cordeiro, Mônica Mendes; Guerra-Sá, Renata; Leão, Versiane Albis

    2015-01-01

    Manganese is a contaminant in the wastewaters produced by Brazilian mining operations, and the removal of the metal is notoriously difficult because of the high stability of the Mn(II) ion in aqueous solutions. To explore a biological approach for removing excessive amounts of aqueous Mn(II), we investigated the potential of Mn(II) oxidation by both consortium and bacterial isolates from a Brazilian manganese mine. A bacterial consortium was able to remove 99.7% of the Mn(II). A phylogenetic analysis of isolates demonstrated that the predominant microorganisms were members of Stenotrophomonas, Bacillus, and Lysinibacillus genera. Mn(II) removal rates between 58.5% and 70.9% were observed for Bacillus sp. and Stenotrophomonas sp. while the Lysinibacillus isolate 13P removes 82.7%. The catalytic oxidation of Mn(II) mediated by multicopper oxidase was not properly detected; however, in all of the experiments, a significant increase in the pH of the culture medium was detected. No aggregates inside the cells grown for a week were found by electronic microscopy. Nevertheless, an energy-dispersive X-ray spectroscopy of the isolates revealed the presence of manganese in Stenotrophomonas sp. and Lysinibacillus sp. grown in K medium. These results suggest that members of Stenotrophomonas and Lysinibacillus genera were able to remove Mn(II) by a nonenzymatic pathway. PMID:26697496

  18. Oxidation of Alkenes with H2O2 by an in-Situ Prepared Mn(II)/Pyridine-2-carboxylic Acid Catalyst and the Role of Ketones in Activating H2O2

    NARCIS (Netherlands)

    Dong, Jia Jia; Saisaha, Pattama; Meinds, Tim G.; Alsters, Paul L.; Ijpeij, Edwin G.; van Summeren, Ruben P.; Mao, Bin; Fananas-Mastral, Martin; de Boer, Johannes W.; Hage, Ronald; Feringa, Ben L.; Browne, Wesley R.

    2012-01-01

    A simple, high yielding catalytic method for the multigram scale selective epoxidation of electron-rich alkenes using near-stoichiometric H2O2 under ambient conditions is reported. The system consists of a Mn(II) salt (

  19. Contribution of arginase to manganese metabolism of Aspergillus niger.

    Science.gov (United States)

    Keni, Sarita; Punekar, Narayan S

    2016-02-01

    Aspects of manganese metabolism during normal and acidogenic growth of Aspergillus niger were explored. Arginase from this fungus was a Mn[II]-enzyme. The contribution of the arginase protein towards A. niger manganese metabolism was investigated using arginase knockout (D-42) and arginase over-expressing (ΔXCA-29) strains of A. niger NCIM 565. The Mn[II] contents of various mycelial fractions were found in the order: D-42 strain niger mycelia harvested from acidogenic growth media contain substantially less Mn[II] as compared to those from normal growth media. Nevertheless, acidogenic mycelia harbor considerable Mn[II] levels and a functional arginase. Altered levels of mycelial arginase protein did not significantly influence citric acid production. The relevance of arginase to cellular Mn[II] pool and homeostasis was evaluated and the results suggest that arginase regulation could occur via manganese availability.

  20. Spectroscopic characterization of manganese minerals

    Science.gov (United States)

    Lakshmi Reddy, S.; Padma Suvarna, K.; Udayabhaska Reddy, G.; Endo, Tamio; Frost, R. L.

    2014-01-01

    Manganese minerals ardenite, alleghanyite and leucopoenicite originated from Madhya Pradesh, India, Nagano prefecture Japan, Sussex Country and Parker Shaft Franklin, Sussex Country, New Jersey respectively are used in the present work. In these minerals manganese is the major constituent and iron if present is in traces only. An EPR study of on all of the above samples confirms the presence of Mn(II) with g around 2.0. Optical absorption spectrum of the mineral alleghanyite indicates that Mn(II) is present in two different octahedral sites and in leucophoenicite Mn(II) is also in octahedral geometry. Ardenite mineral gives only a few Mn(II) bands. NIR results of the minerals ardenite, leucophoenicite and alleghanyite are due to hydroxyl and silicate anions which confirming the formulae of the minerals.

  1. Spectroscopic characterization of manganese minerals.

    Science.gov (United States)

    Lakshmi Reddy, S; Padma Suvarna, K; Udayabhaska Reddy, G; Endo, Tamio; Frost, R L

    2014-01-03

    Manganese minerals ardenite, alleghanyite and leucopoenicite originated from Madhya Pradesh, India, Nagano prefecture Japan, Sussex Country and Parker Shaft Franklin, Sussex Country, New Jersey respectively are used in the present work. In these minerals manganese is the major constituent and iron if present is in traces only. An EPR study of on all of the above samples confirms the presence of Mn(II) with g around 2.0. Optical absorption spectrum of the mineral alleghanyite indicates that Mn(II) is present in two different octahedral sites and in leucophoenicite Mn(II) is also in octahedral geometry. Ardenite mineral gives only a few Mn(II) bands. NIR results of the minerals ardenite, leucophoenicite and alleghanyite are due to hydroxyl and silicate anions which confirming the formulae of the minerals. Copyright © 2013 Elsevier B.V. All rights reserved.

  2. Investigation of the oxygen affinity of manganese(II, cobalt(II and nickel(II complexes with some tetradentate Schiff bases

    Directory of Open Access Journals (Sweden)

    Adel A.A. Emara

    2014-12-01

    Full Text Available Oxygen absorption–desorption processes for square planar Mn(II, Co(II and Mn(II complexes of tetradentate Schiff base ligands in DMF and chloroform solvents were investigated. The tetradentate Schiff base ligands were obtained by condensation reaction of ethylenediamine with salcyldehyde, o-hydroxyacetophenone or acetylacetone in the molar ratio 1:2. The square planar complexes were prepared by the reaction of the Schiff base ligands with Mn(II acetate, Co(II nitrate and Ni(II nitrate in dry ethanol under nitrogen atmosphere. The sorption processes were undertaken in the presence and absence of (pyridine axial-base in 1:1 M ratio of (pyridine:metal(II complexes. Complexes in DMF indicate significant oxygen affinity than in chloroform solvent. Cobalt(II complexes showed significant sorption processes compared to Mn(II and Ni(II complexes. The presence of pyridine axial base clearly increases oxygen affinity.

  3. Cobalt immobilization by manganese oxidizing bacteria from the Indian ridge system

    Digital Repository Service at National Institute of Oceanography (India)

    Antony, R.; Sujith, P.P.; Fernandes, S.O.; Verma, P.; Khedekar, V.D.; LokaBharathi, P.A.

    , Matrosova VY, Vasilenko A, Zhai M, Venkateswaran A, Hess M, Omelchenko MV, Kostandarithes HM., Makarova KS, Wackett LP, Fredrickson JK, Ghosal D (2004) Accumulation of Mn(II) in Deinococcus radiodurans facilitates gamma-radiation resistance. Science...

  4. catena-Poly[manganese(II-(μ2-3,5-di-2-pyridyl-1,2,4-triazolato-μ2-formato

    Directory of Open Access Journals (Sweden)

    Ya-Wen Zhang

    2008-08-01

    Full Text Available Owing to the presence of crystallographic twofold rotation axes (site symmetry 2, Wyckoff letters e and f, the asymmetric unit of the title compound, [Mn(C12H8N5(CHO2]n, contains one-half of an MnII cation, one-half of a bpt anion (Hbpt is 3,5-di-2-pyridyl-4H-1,2,4-triazole and one-half of a formate anion. The bpt and formate ligands occupy the same C2 symmetry, while the MnII ion resides on another crystallographic twofold rotation axis. Each bpt ligand acts as a cis-bis-chelate to ligate two MnII ions into a one-dimensional chain running along the crystallographic 41 screw axis. Adjacent MnII ions are further bridged by a μ2-formate ligand, completing the distorted octahedral coordination geometry of the cation.

  5. ADSORPTION BEHAVIOUR OF Mn(Ⅱ) AND Zn(Ⅱ) ON ATTAPULGITE WITH FAAS METHOD

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    Active attapulbgite as adsorptive reagent, the adsorptive behavior of Mn(II) and Zn(II) was studied with Flame atomic absorption spectroscopy (FAAS) method. The mainly factors of influencing the adsorption and desorption of Mn(II) and Zn(II) were discussed. The interference of coexisting ions was investigated, and the actual sample determination from adzuki beans, mung beans and phosphating waste water was conducted with good result.

  6. One-dimensional mu-chloromanganese(II)-tetrathiafulvalene (TTF) coordination compound.

    Science.gov (United States)

    Jia, Chunyang; Liu, Shi-Xia; Ambrus, Christina; Neels, Antonia; Labat, Gaël; Decurtins, Silvio

    2006-04-17

    A new tetrathiafulvalene derivative 1 bearing a single pyridine group and its coordination complex 2, with stoichiometry [Mn(mu-Cl)Cl(1)2(CH3OH)]n, have been synthesized and fully characterized. The complex 2 shows an extended chain structure, which is potentially favorable for electrical conductivity. Notably, this is the first monohalogen-bridged Mn(II) polymer exhibiting a moderate antiferromagnetic coupling between the Mn(II) centers.

  7. A unique manganese (II) complex of 4-methoxy-pyridine-2-carboxylate: Synthesis, crystal structure, FT-IR and UV-Vis spectra and DFT calculations

    Science.gov (United States)

    Tamer, Ömer

    2017-09-01

    The first metal complex of 4-Methoxy-pyridine-2-carboxylic acid, [Mn(4-mpic)2(H2O)2], has been synthesized, and its crystal structure has been determined by X-Ray diffraction method. The FT-IR spectrum for [Mn(4-mpic)2(H2O)2] complex has been presented in this paper, as compared with that of single 4-mpic ligand. The electronic absorption spectrum recorded in DMSO solvent revealed that the ligand metal charge transfer (LMCT) interactions occur in Mn(II) complex. In order to support experimental results, density functional theory (DFT) calculations have been also carried out with the hybrid B3LYP functional. The coordination sphere of central Mn(II) ion has been evaluated by using the hyperconjugative interactions between the lone pair electrons of metal and donor atoms (N and O). The natural charge of Mn(II) ion demonstrated that the electronic transitions from metal ion to 4-mpic are higher than those in reverse direction. The carboxylate group has been determined as the most reactive side of Mn(II) complex in chemical reactions. A comparison among Mulliken, NBO and APT charges has been carried out for Mn(II) complex system. The first static hyperpolarizability parameter for Mn(II) complex has been also investigated by using B3LYP level.

  8. A seven-coordinated manganese(II) complex with V-shaped ligand bis(N-benzylbenzimidazol-2-ylmethyl)benzylamine: synthesis, structure, DNA-binding properties and antioxidant activities.

    Science.gov (United States)

    Wu, Huilu; Yuan, Jingkun; Bai, Ying; Wang, Hua; Pan, Guolong; Kong, Jin

    2012-11-05

    A manganese(II) complex of the type, [MnL(pic)(2)]·H(2)O, was obtained by the reaction of the V-shaped ligand bis(N-benzylbenzimidazol-2-ylmethyl)benzylamine (L) with Mn(pic)(2) (pic=picrate). The ligand L and Mn(II) complex were confirmed on the basis of elemental analysis, molarconductivities, (1)H NMR, IR, UV-vis spectra and X-ray crystallography. Single-crystal X-ray revealed that central Mn(II) atom is seven-coordinate with a MnN(3)O(4) environment, in which ligand L acts as a tridentate N-donor. The remaining coordination sites were occupied by four O atoms afforded by two picrate anion. Interaction of the free ligand L and Mn(II) complex with DNA were investigated by spectrophotometric methods and viscosity measurements. The results suggested that both ligand L and Mn(II) complex bind to DNA in an intercalative binding mode, and DNA-binding affinity of the Mn(II) complex is stronger than that of ligand L. Moreover, antioxidant assay in vitro shows the Mn(II) complex possesses significant antioxidant activities.

  9. Oxidation of manganese(II) with ferrate: Stoichiometry, kinetics, products and impact of organic carbon.

    Science.gov (United States)

    Goodwill, Joseph E; Mai, Xuyen; Jiang, Yanjun; Reckhow, David A; Tobiason, John E

    2016-09-01

    Manganese is a contaminant of concern for many drinking water utilities, and future regulation may be pending. An analysis of soluble manganese (Mn(II)) oxidation by ferrate (Fe(VI)) was executed at the bench-scale, in a laboratory matrix, both with and without the presence of natural organic matter (NOM) and at two different pH values, 6.2 and 7.5. In the matrix without NOM, the oxidation of Mn(II) by Fe(VI) followed a stoichiometry of 2 mol Fe(VI) to 3 mol Mn(II). The presence of NOM did not significantly affect the stoichiometry of the oxidation reaction, indicating relative selectivity of Fe(VI) for Mn(II). The size distribution of resulting particles included significant amounts of nanoparticles. Resulting manganese oxide particles were confirmed to be MnO2 via X-ray photoelectron spectroscopy. The rate of the Mn(II) oxidation reaction was fast relative to typical time scales in drinking water treatment, with an estimated second order rate constant of approximately 1 × 10(4) M(-1) s(-1) at pH 9.2 and > 9 × 10(4) M(-1) s(-1) at pH 6.2. In general, ferrate is a potential option for Mn(II) oxidation in water treatment.

  10. Bis(μ-3,5-dinitrobenzoato-κ2O1:O1′bis(μ-3,5-dinitrobenzoato-κ3O1,O1′:O1;κ3O1:O1,O1′-bis[(3,5-dinitrobenzoato-κ2O1,O1′(1,10-phenanthroline-κ2N,Ndysprosium(III

    Directory of Open Access Journals (Sweden)

    Gai-Qing Xi

    2011-01-01

    Full Text Available In the binuclear title complex, [Dy2(C7H3N2O66(C12H8N22], the DyIII ions exhibit a distorted monocapped square-antiprismatic geometry and are coordinated by seven O atoms of four 3,5-dinitrobenzoate (DNBA anions and two N atoms of a phenanthroline ligand. The carboxylate groups of the DNBA anions exhibit three coordination modes: bidentate chelating, bidentate chelating–bridging and tridentate chelating–bridging. The center of the molecule is located on a crystallographic center of inversion.

  11. Nitrilotris(methylenephosphonato)potassium K[μ6-NH(CH2PO3)3H4]: Synthesis, structure, and the nature of the K-O chemical bond

    Science.gov (United States)

    Somov, N. V.; Chausov, F. F.; Zakirova, R. M.

    2016-07-01

    The crystal structure of nitrilotris(methylenephosphonato)potassium K[μ6-NH(CH2PO3)3H4]—a three-dimensional coordination polymer—was determined. The potassium atom is coordinated by seven oxygen atoms belonging to the six nearest ligand molecules, resulting in distorted monocapped octahedral coordination geometry. The complex contains the four-membered chelate ring K-O-P-O. The K-O chemical bond is predominantly ionic. Meanwhile, the bonds of the potassium atom with some oxygen atoms have a noticeable covalent component. In addition to coordination bonds, the molecules in the crystal packing are linked by hydrogen bonds.

  12. μ-Acetato-diacetato{μ-6,6′-dimethoxy-2,2′-[o-phenylenebis(nitrilomethanylylidene]diphenolato}gadolinium(IIIzinc

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    Fan Yang

    2011-09-01

    Full Text Available In the heterodinuclear title complex, [GdZn(C22H18N2O4(CH3COO3], the ZnII ion is five-coordinated in a square-pyramidal environment defined by two O atoms and two N atoms from the ligand, forming the square plane, and one acetate O atom serving as the apex, while the GdIII ion is nine-coordinated in an approximate mono-capped tetragonal–antiprismatic environment defined by four O atoms from the ligand and five acetate O atoms.

  13. Cs5Sn9(OH·4NH3

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    Ute Friedrich

    2014-06-01

    Full Text Available The title compound, pentacaesium nonastannide hydroxide tetraammonia, crystallized from a solution of CsSnBi in liquid ammonia. The Sn94− unit forms a monocapped quadratic antiprism. The hydroxide ion is surrounded by five caesium cations, which form a distorted quadratic pyramidal polyhedron. A three-dimensional network is formed by Cs—Sn [3.8881 (7 Å to 4.5284 (7 Å] and Cs—NH3 [3.276 (7–3.636 (7 Å] contacts.

  14. Eu{sub 2}(PO{sub 3}H){sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Foulon, J.D. [Ecole Nationale Superieure de Chimie, 34 - Montpellier (France). Lab. de Physicochimie des Materiaux; Durand, J. [Ecole Nationale Superieure de Chimie, 34 - Montpellier (France). Lab. de Physicochimie des Materiaux; Cot, L. [Ecole Nationale Superieure de Chimie, 34 - Montpellier (France). Lab. de Physicochimie des Materiaux; Tijani, N. [Laboratoire de Chimie Minerale Appliquee, Fes (Morocco). Faculte des Sciences; Rafiq, M. [Laboratoire de Chimie Minerale Appliquee, Fes (Morocco). Faculte des Sciences

    1995-03-15

    The structure of dieuropium tris(hydrogen phosphite), Eu{sub 2}(PO{sub 3}H){sub 3}, contains three independent phosphite anions. One Eu{sup 3+} cation is eight-coordinate whereas the other is only seven-coordinate. One [EuO{sub 8}] dodecahedron and one monocapped [EuO{sub 7}] trigonal prism alternate so that, by sharing one vertex, infinite layers are formed parallel to the [101] direction. The layers are held together by Eu-O interlayer bonds. (orig.).

  15. Bis(μ-2-methyl­quinolin-1-ium-8-olato-κ2 O:O′)bis­[(2-methyl­quinolin-1-ium-8-olato-κO)tris­(nitrato-κ2 O,O′)lanthanum(III)

    OpenAIRE

    Fazaeli, Yousef; Najafi, Ezzatollah; Mostafa M. Amini; Ng, Seik Weng

    2009-01-01

    The two independent N-heterocycles in the centrosymmetric title compound, [La2(C10H9NO)4(NO3)6], exist in the zwitterionic form. One of these binds to one metal center, whereas the other bridges two metal centers. The La atom is chelated by three nitrate groups and is surrounded by nine O atoms in a coordination environment based on a distorted monocapped square-anti­prism. The dinuclear structure is further stabilized by intra­molecular N—H⋯O(nitrate) hydrogen bonds.

  16. Bis(μ-2-methyl-quinolin-1-ium-8-olato-κO:O')bis-[(2-methyl-quinolin-1-ium-8-olato-κO)tris-(nitrato-κO,O')lanthanum(III)].

    Science.gov (United States)

    Fazaeli, Yousef; Najafi, Ezzatollah; Amini, Mostafa M; Ng, Seik Weng

    2009-06-06

    The two independent N-heterocycles in the centrosymmetric title compound, [La(2)(C(10)H(9)NO)(4)(NO(3))(6)], exist in the zwitterionic form. One of these binds to one metal center, whereas the other bridges two metal centers. The La atom is chelated by three nitrate groups and is surrounded by nine O atoms in a coordination environment based on a distorted monocapped square-anti-prism. The dinuclear structure is further stabilized by intra-molecular N-H⋯O(nitrate) hydrogen bonds.

  17. Bis({tris[2-(3,5-di-tert-butyl-2-oxidobenzylideneaminoethyl]amine}cerium(III diethyl ether solvate

    Directory of Open Access Journals (Sweden)

    Peter Dröse

    2010-11-01

    Full Text Available The title compound, 2[Ce(C51H75N4O3]·C4H10O, was obtained in high yield (92% by reduction of (TRENDSALCeIVCl [TRENDSAL is N,N′,N′′-tris(3,5-di-tert-butylsalicylidenatoaminotriethylamine] with potassium in THF. The bulky tripodal TRENDSAL ligand effectively encapsulates the central CeIII cation with a Ce—N(imine distance of 2.860 (2 Å and an average C—N(amine distance of 2.619 Å within a distorted monocapped octahedral coordination.

  18. Bis({tris[2-(3,5-di-tert-butyl-2-oxido-benzylideneamino)ethyl]amine}cerium(III)) diethyl ether solvate.

    Science.gov (United States)

    Dröse, Peter; Hrib, Cristian G; Edelmann, Frank T

    2010-10-13

    The title compound, 2[Ce(C(51)H(75)N(4)O(3))]·C(4)H(10)O, was obtained in high yield (92%) by reduction of (TRENDSAL)Ce(IV)Cl [TRENDSAL is N,N',N''-tris-(3,5-di-tert-butyl-salicyl-ide-natoamino)-triethyl-amine] with potassium in THF. The bulky tripodal TRENDSAL ligand effectively encapsulates the central Ce(III) cation with a Ce-N(imine) distance of 2.860 (2) Å and an average C-N(amine) distance of 2.619 Å within a distorted monocapped octahedral coordination.

  19. Sulfitos duplos contendo cobre (I e um metal de transição M(II tipo Cu2SO3.M(IISO3.2H 2O [M(II = Cu(II, Fe(II, Mn(II e Cd(II]: preparação e seletividade na incorporação de M(II Double sulfite containing copper (I and a metal transition M(II like Cu2SO3.M(IISO3.2H 2O [M(II = Cu(II, Fe(II, Mn(II and Cd(II]: synthesis and selectivity in M(II incorporation

    Directory of Open Access Journals (Sweden)

    Luciana Almeida Silva

    1998-04-01

    Full Text Available The metal-catalyzed autooxidation of S(IV has been studied for more than a century without a consensus being obtained as to reaction rates, rate laws or mechanisms. The main objective in this work was to explore the reaction between Cu(II and SO2 in the presence of M(II, paying special attention to the formation of double sulfites like Cu2SO3.M(IISO3.2H 2O. The two principal aspects studied were: i a new way to prepare double sulfites with high purity degree and the selectivity in the M(II incorporation during the salt formation.

  20. Elimination of manganese(II,III) oxidation in Pseudomonas putida GB-1 by a double knockout of two putative multicopper oxidase genes.

    Science.gov (United States)

    Geszvain, Kati; McCarthy, James K; Tebo, Bradley M

    2013-01-01

    Bacterial manganese(II) oxidation impacts the redox cycling of Mn, other elements, and compounds in the environment; therefore, it is important to understand the mechanisms of and enzymes responsible for Mn(II) oxidation. In several Mn(II)-oxidizing organisms, the identified Mn(II) oxidase belongs to either the multicopper oxidase (MCO) or the heme peroxidase family of proteins. However, the identity of the oxidase in Pseudomonas putida GB-1 has long remained unknown. To identify the P. putida GB-1 oxidase, we searched its genome and found several homologues of known or suspected Mn(II) oxidase-encoding genes (mnxG, mofA, moxA, and mopA). To narrow this list, we assumed that the Mn(II) oxidase gene would be conserved among Mn(II)-oxidizing pseudomonads but not in nonoxidizers and performed a genome comparison to 11 Pseudomonas species. We further assumed that the oxidase gene would be regulated by MnxR, a transcription factor required for Mn(II) oxidation. Two loci met all these criteria: PputGB1_2447, which encodes an MCO homologous to MnxG, and PputGB1_2665, which encodes an MCO with very low homology to MofA. In-frame deletions of each locus resulted in strains that retained some ability to oxidize Mn(II) or Mn(III); loss of oxidation was attained only upon deletion of both genes. These results suggest that PputGB1_2447 and PputGB1_2665 encode two MCOs that are independently capable of oxidizing both Mn(II) and Mn(III). The purpose of this redundancy is unclear; however, differences in oxidation phenotype for the single mutants suggest specialization in function for the two enzymes.

  1. Role of Reactive Intermediates in Manganese Oxide Formation By Filamentous Ascomycete Fungi

    Science.gov (United States)

    Zeiner, C. A.; Anderton, C.; Wu, S.; Purvine, S.; Zink, E.; Paša-Tolić, L.; Santelli, C. M.; Hansel, C. M.

    2014-12-01

    Biogenic manganese (Mn) oxide minerals are ubiquitous in the environment, and their high reactivity can profoundly impact the fate of contaminants and cycling of carbon and nutrients. In contrast to bacteria, the pathways utilized by fungi to oxidize Mn(II) to Mn(III,IV) oxides remain largely unknown. Here, we explore the mechanisms of Mn(II) oxidation by a phylogenetically diverse group of filamentous Ascomycete fungi using a combination of chemical assays and bulk and spatially-resolved mass spectrometry. We show that the mechanisms of Mn(II) oxidation vary with fungal species, over time during secretome compositional changes, and in the presence of other fungi. Specifically, our work implicates a dynamic transition in Mn(II) oxidation pathways that varies between species. In particular, while reactive oxygen species (ROS) produced via transmembrane NADPH oxidases are involved in initial oxidation, over time, secreted enzymes become important Mn(II) oxidation mediators for some species. In addition, the overall secretome oxidation capacity varies with time and fungal species. Secretome analysis reveals a surprising absence of enzymes currently considered to be Mn(II)-oxidizing enzymes in these organisms, and instead highlights a wide variety of redox-active enzymes. Furthermore, we implicate fungal cell defense mechanisms in the formation of distinct Mn oxide patterns when fungi are grown in head-to-head competition. The identification and regulation of these secreted enzymes are under current investigation within the bulk secretome and within the interaction zone of structured fungal communities. Overall, our findings illustrate that Ascomycete Mn(II) oxidation mechanisms are highly variable and are dictated by complex environmental and ecological interactions. Future work will explore the connection between Ascomycete Mn(II) oxidation and the ability to degrade cellulose, a key carbon reservoir for biofuel production.

  2. Unraveling the role of animal heme peroxidases in superoxide mediated Mn oxide formation

    Science.gov (United States)

    Learman, D. R.; Hansel, C. M.

    2013-12-01

    Manganese(III,IV) oxides are important in the environment as they can impact the fate of a broad range of nutrients (e.g. carbon and phosphate) and contaminates (e.g. lead and chromium). Bacteria play a valuable role in the production of Mn oxides, yet the mechanisms and physiological reasons remain unclear. Roseobacter sp. AzwK-3b, an organism within the abundant and ubiquitous Roseobacter clade, has recently been shown to oxidize Mn(II) via a novel pathway that involves enzymatic extracellular superoxide production. However, in reactions with only Mn(II) and abiotically generated superoxide, we find superoxide alone is not enough to produce Mn(III,IV) oxides. Scavenging of the byproduct hydrogen peroxide (via the addition of catalase) is required to generate Mn oxides via abiotic reaction of Mn(II) with superoxide. Thus, R. AzwK-3b must produce superoxide and also scavenge hydrogen peroxide to form Mn oxides. Further, in-gel Mn(II) oxidation assay revealed a protein band that could generate Mn oxides in the presence of soluble Mn(II). This Mn(II)-oxidizing protein band was excised from the gel and the peptides identified via mass spectrometry. An animal heme peroxidase (AHP) was the predominant protein found in this band. This protein is homologous to the AHPs previously implicated as a Mn(II)-oxidizing enzyme within the Alphaproteobacteria, Erythrobacter SD-21 and Aurantimonas manganoxydans strain SI85-9A1. Currently, protein expression of the AHPs in R. AzwK-3b is being examined to determine if expression is correlated with Mn(II) concentration or oxidative stress. Our data suggests that AHPs do not directly oxidize Mn(II) but rather plays a role in scavenging hydrogen peroxide and/or producing an organic Mn(III) ligand that complexes Mn(III) and likely aids in Mn oxide precipitation.

  3. Biological Superoxide In Manganese Oxide Formation

    Science.gov (United States)

    Hansel, C.; Learman, D.; Zeiner, C.; Santelli, C. M.

    2011-12-01

    Manganese (Mn) oxides are among the strongest sorbents and oxidants within the environment, controlling the fate and transport of numerous elements and the degradation of recalcitrant carbon. Both bacteria and fungi mediate the oxidation of Mn(II) to Mn(III/IV) oxides but the genetic and biochemical mechanisms responsible remain poorly understood. Furthermore, the physiological basis for microbial Mn(II) oxidation remains an enigma. We have recently reported that a common marine bacterium (Roseobacter sp. AzwK-3b) oxidizes Mn(II) via reaction with extracellular superoxide (O2-) produced during exponential growth. Here we expand this superoxide-mediated Mn(II) oxidation pathway to fungi, introducing a surprising homology between prokaryotic and eukaryotic metal redox processes. For instance, Stibella aciculosa, a common soil Ascomycete filamentous fungus, precipitates Mn oxides at the base of asexual reproductive structures (synnemata) used to support conidia (Figure 1). This distribution is a consequence of localized production of superoxide (and it's dismutation product hydrogen peroxide, H2O2), leading to abiotic oxidation of Mn(II) by superoxide. Disruption of NADPH oxidase activity using the oxidoreductase inhibitor DPI leads to diminished cell differentiation and subsequent Mn(II) oxidation inhibition. Addition of Cu(II) (an effective superoxide scavenger) leads to a concentration dependent decrease in Mn oxide formation. We predict that due to the widespread production of extracellular superoxide within the fungal and likely bacterial kingdoms, biological superoxide may be an important contributor to the cycling of Mn, as well as other metals (e.g., Hg, Fe). Current and future explorations of the genes and proteins involved in superoxide production and Mn(II) oxidation will ideally lend insight into the physiological and biochemical basis for these processes.

  4. STUDY ADSORPTION DESORPTION OF MANGANESE(II USING IMPREGNATED CHITIN-CELLULOSE AS ADSORBENT

    Directory of Open Access Journals (Sweden)

    Aldes Lesbani

    2015-03-01

    Full Text Available Abstract- Study adsorption desorption of manganese(II using impregnated chitin-cellulose as adsorbent has been carried out. Chitin was extracted from snail shell and cellulose isolated from rice straw. Chitin and cellulose were impregnated using thiourea as impregnant agent. Characterization of chitin and cellulose was performed using FTIR spectroscopy, determination of water content, and ash content, while impregnated chitin-cellulose was characterized using FTIR spectrophotometer and X-Ray diffractometer. The adsorption of Mn(II on impregnated chitin-cellulose was studied through determination of adsorption time and the influence of Mn(II concentration, while desorption was carried out sequentially using various reagents. The results shown that chitin and cellulose from extraction processes are has similar FTIR spectrum compared to chitin and cellulose standard. The FTIR spectrum of impregnated chitin-cellulose shows both vibration of chitin and cellulose appeared and indicated successfully impregnate. These results were also equal to XRD pattern analysis. The water and ash contents of chitin are 0.038% and 0.043 while for cellulose are 0.184% and 0.165%, respectively. The adsorption of Mn(II on chitin and cellulose are quite similar kinetically, while adsorption of Mn(II on impregnated chitin-cellulose is higher at the same time with chitin and cellulose. In the low concentration of Mn(II, adsorption phenomena are similar on chitin, cellulose, and impregnated chitin-cellulose. Desorption process of Mn(II on the adsorbents shows sodium etilenediamine tetra acetate able to desorp Mn(II up to 68% higher than other reagents. Keywords: Manganese(II, Chitin, Cellulose, Impregnated Chitin-Cellulose

  5. Self-assembled silver polyhedra with embedded acetylide dianion stabilized by perfluorocarboxylate and 4-hydroxyquinoline ligands.

    Science.gov (United States)

    Zhao, Xiao-Li; Wang, Quan-Ming; Mak, Thomas C W

    2003-12-01

    Four new silver(I) double salts (L(2)H)(4)[Ag(10)(C(2))(CF(3)CO(2))(12)(L)(2)].5H(2)O (1), [Ag(8)(C(2))(CF(3)CO(2))(6)(L)(6)] (2), [(Ag(2)C(2))(AgC(2)F(5)CO(2))(6)(L)(3)(H(2)O)].H(2)O (3), and (L.H(3)O)(2)[Ag(11)(C(2))(2)(C(2)F(5)CO(2))(9)(H(2)O)(2)].H(2)O (4) incorporating the hitherto unexplored ligand 4-hydroxyquinoline (L) have been synthesized by the hydrothermal method. Compound 1 features an unprecedented bicapped square-antiprismatic Ag(10) silver cage with an embedded C(2)(2-) moiety, whereas the discrete supermolecule 2 bears a rhombohedral Ag(8) core similar to that previously found in Ag(2)C(2).6AgNO(3). Compound 3 contains a discrete supramolecular complex whose core is a (C(2))(2)@Ag(16) double cage constructed from the edge-sharing of two monocapped square antiprisms, which is completely surrounded by 12 pentafluoropropionate, 6 4-hydroxyquinoline, and 2 aqua ligands. The layer structure in 4 is constructed from a sinuous anionic silver column composed of fused irregular monocapped trigonal antiprisms each encapsulating a C(2)(2-) dianion, with L.H(3)O(+) species serving as hydrogen-bond connectors to adjacent columns.

  6. CotA, a multicopper oxidase from Bacillus pumilus WH4, exhibits manganese-oxidase activity.

    Directory of Open Access Journals (Sweden)

    Jianmei Su

    Full Text Available Multicopper oxidases (MCOs are a family of enzymes that use copper ions as cofactors to oxidize various substrates. Previous research has demonstrated that several MCOs such as MnxG, MofA and MoxA can act as putative Mn(II oxidases. Meanwhile, the endospore coat protein CotA from Bacillus species has been confirmed as a typical MCO. To study the relationship between CotA and the Mn(II oxidation, the cotA gene from a highly active Mn(II-oxidizing strain Bacillus pumilus WH4 was cloned and overexpressed in Escherichia coli strain M15. The purified CotA contained approximately four copper atoms per molecule and showed spectroscopic properties typical of blue copper oxidases. Importantly, apart from the laccase activities, the CotA also displayed substantial Mn(II-oxidase activities both in liquid culture system and native polyacrylamide gel electrophoresis. The optimum Mn(II oxidase activity was obtained at 53°C in HEPES buffer (pH 8.0 supplemented with 0.8 mM CuCl2. Besides, the addition of o-phenanthroline and EDTA both led to a complete suppression of Mn(II-oxidizing activity. The specific activity of purified CotA towards Mn(II was 0.27 U/mg. The Km, Vmax and kcat values towards Mn(II were 14.85±1.17 mM, 3.01×10(-6±0.21 M·min(-1 and 0.32±0.02 s(-1, respectively. Moreover, the Mn(II-oxidizing activity of the recombinant E. coli strain M15-pQE-cotA was significantly increased when cultured both in Mn-containing K liquid medium and on agar plates. After 7-day liquid cultivation, M15-pQE-cotA resulted in 18.2% removal of Mn(II from the medium. Furthermore, the biogenic Mn oxides were clearly observed on the cell surfaces of M15-pQE-cotA by scanning electron microscopy. To our knowledge, this is the first report that provides the direct observation of Mn(II oxidation with the heterologously expressed protein CotA, Therefore, this novel finding not only establishes the foundation for in-depth study of Mn(II oxidation mechanisms, but also offers

  7. Determination of chromium, cadmium and manganese in water and fish samples after preconcentration using penicillium digitatum immobilized on pumice Stone

    Energy Technology Data Exchange (ETDEWEB)

    Baytak, Sitki [Nevsehir University, Science and Art Faculty, Chemistry Department, Nevsehir (Turkey); Tuerker, A.R. [Gazi University, Science and Art Faculty, Chemistry Department, Ankara (Turkey)

    2009-04-15

    This study presents a procedure for preconcentration of Cr(III), Cd(II) and Mn(II) from water and biological samples using Penicillium digitatum immobilized on pumice stone. Optimum conditions such as pH, flow rate were evaluated. The recoveries of Cr(III), Cd(II) and Mn(II) under optimum conditions were found to be 98{+-}2%, 100{+-}2%, and 97{+-}2%, respectively, at a 95% confidence level. Detection limits were 2.0, 1.6 and 1.5 ng/mL for Cr(III), Cd(II) and Mn(II), respectively. The proposed procedure was successfully applied for the determination of chromium, cadmium and manganese in dam water, spring water and fish (Carp) samples. The accuracy was evaluated through the analysis of the certified standard reference fish tissue samples (IAEA-407) and spiked fish and water samples. (Abstract Copyright [2009], Wiley Periodicals, Inc.)

  8. Bis(2-methoxybenzylammonium diaquabis(dihydrogen diphosphato-κ2O,O′manganate(II dihydrate

    Directory of Open Access Journals (Sweden)

    Adel Elboulali

    2013-11-01

    Full Text Available The asymmetric unit of the title compound, (C8H12NO2[Mn(H2P2O72(H2O2]·2H2O, consists of half an MnII complex anion, a 2-methoxybenylammonium cation and a solvent water molecule. The MnII complex anion lies across an inversion center, and has a slightly distorted octahedral coordination environment for the MnII ion, formed by two bidentate dihydrogendiphosphate ligands and two water molecules. In the crystal, the components are linked by O—H...O and N—H...O hydrogen bonds, forming layers parallel to (100. An intramolecular N—H...O hydrogen bond is also observed.

  9. Determinação de manganês em material particulado atmosférico de ambientes de trabalho utilizando eletrodo de diamante dopado com boro e voltametria de onda quadrada com redissolução catódica

    Directory of Open Access Journals (Sweden)

    Felix Fabiana da Silva

    2005-01-01

    Full Text Available A boron-doped diamond electrode is used for determination of Mn(II in atmospheric particulate matter by square wave cathodic stripping voltammetry. The analytical curve was linear for Mn(II concentrations between 5.0 and 37.5 µg L-1, with quantification limit of 3.6 µg L-1. The precision was evaluated by the relative standard deviation, with values between 5.1% and 9.3%. The electrode is free of adsorption, minimizing memory effects. Samples collected in the workplace atmosphere of a foundry had Mn(II concentrations between 0.4 and 4 µg m-3. No significant differences were observed between the proposed method and inductively coupled plasma optical emission spectroscopy.

  10. Studies on the reduction of birnessite thin layers: Influence of medium

    Energy Technology Data Exchange (ETDEWEB)

    Ndjeri, Marthe [CNRS - Universite d' Evry - CEA, ' Laboratoire Analyse et Modelisation pour la Biologie et l' Environnement' , UMR 8587, Universite d' Evry Val d' Essonne, Boulevard Francois Mitterrand, 91025 Evry (France); Peulon, Sophie, E-mail: sophie.peulon@univ-evry.fr [CNRS - Universite d' Evry - CEA, ' Laboratoire Analyse et Modelisation pour la Biologie et l' Environnement' , UMR 8587, Universite d' Evry Val d' Essonne, Boulevard Francois Mitterrand, 91025 Evry (France); Bach, Stephane, E-mail: stephane.bach@univ-evry.fr [Universite d' Evry Val d' Essonne, Bd F. Mitterrand, Departement Chimie, 91025 Evry, Cedex (France); Institut de Chimie et des Materiaux Paris Est, ICMPE/GESMAT, UMR 7182 CNRS (France); Chausse, Annie [CNRS - Universite d' Evry - CEA, ' Laboratoire Analyse et Modelisation pour la Biologie et l' Environnement' , UMR 8587, Universite d' Evry Val d' Essonne, Boulevard Francois Mitterrand, 91025 Evry (France)

    2011-10-01

    Highlights: > Determination of compounds during reduction of birnessite layer. > Importance of Mn(II) ions in solution on the nature of resulting compounds. > Proposition of reduction mechanisms of birnessite thin films. > Interests of XRD characterisation coupled to electrochemistry. - Abstract: This paper describes studies on the reduction of birnessite thin layers electrodeposited onto a cheap transparent semiconductor substrate, tin dioxide (SnO{sub 2}), in neutral sulphate solutions. A coupled approach based on electrochemical measurements (cyclic voltammetry and chronoamperometry) and X-ray diffraction (XRD) characterisation allowed us to give information about reduction mechanism of birnessite in presence or absence of Mn(II) in solution. In absence of Mn(II), birnessite is reduced only at low potential (E = -0.6 V) into {beta}-MnOOH (feitkneichtite), if Q{sub reduction} is lower than Q{sub synthesis}, and in amorphous Mn(II) compound, if Q{sub reduction} is equal to Q{sub synthesis}. In presence of Mn(II) in solution, hausmannite (Mn{sub 3}O{sub 4}) was detected, and even at high potentials (E = 0.15 V). These results signify that a complex between Mn(III), coming from the reduction of Mn(IV) species, and Mn(II) present in solution, can be formed near the surface and leads to the formation of Mn{sub 3}O{sub 4}, a very resistive compound. These results are important for studies devoted to environmental applications, chemical sensors and also for energy storage.

  11. Mechanistic insight into chromium(VI) reduction by oxalic acid in the presence of manganese(II)

    Energy Technology Data Exchange (ETDEWEB)

    Wrobel, Katarzyna; Corrales Escobosa, Alma Rosa; Gonzalez Ibarra, Alan Alexander; Mendez Garcia, Manuel; Yanez Barrientos, Eunice; Wrobel, Kazimierz, E-mail: kazimier@ugto.mx

    2015-12-30

    Over the past few decades, reduction of hexavalent chromium (Cr(VI)) has been studied in many physicochemical contexts. In this research, we reveal the mechanism underlying the favorable effect of Mn(II) observed during Cr(VI) reduction by oxalic acid using liquid chromatography with spectrophotometric diode array detector (HPLC–DAD), nitrogen microwave plasma atomic emission spectrometry (HPLC–MP-AES), and high resolution mass spectrometry (ESI–QTOFMS). Both reaction mixtures contained potassium dichromate (0.67 mM Cr(VI)) and oxalic acid (13.3 mM), pH 3, one reaction mixture contained manganese sulfate (0.33 mM Mn(II)). In the absence of Mn(II) only trace amounts of reaction intermediates were generated, most likely in the following pathways: (1) Cr(VI) → Cr(IV) and (2) Cr(VI) + Cr(IV) → 2Cr(V). In the presence of Mn(II), the active reducing species appeared to be Mn(II) bis-oxalato complex (J); the proposed reaction mechanism involves a one-electron transfer from J to any chromium compound containing Cr=O bond, which is reduced to Cr−OH, and the generation of Mn(III) bis-oxalato complex (K). Conversion of K to J was observed, confirming the catalytic role of Mn(II). Since no additional acidification was required, the results obtained in this study may be helpful in designing a new, environmentally friendly strategy for the remediation of environments contaminated with Cr(VI).

  12. A novel [Mn2(μ-(C6H5)2CHCOO)2(bipy)4](bipy)(ClO4)2 complex loaded solid lipid nanoparticles: synthesis, characterization and in vitro cytotoxicity on MCF-7 breast cancer cells.

    Science.gov (United States)

    Guney Eskiler, G; Cecener, G; Dikmen, G; Kani, I; Egeli, U; Tunca, B

    2016-09-01

    Manganese (Mn)-based complexes have been drawing attention due to the fact that they are more effective than other metal complexes. However, the use of Mn(II)-based complexes in medicine remains limited because of certain side effects. The aim of this study was to investigate the cytotoxic and apoptotic effects of a novel Mn(II) complex [Mn2(μ-(C6H5)2CHCOO)2(bipy)4](bipy)(ClO4)2 and Mn(II) complex loaded solid lipid nanoparticles (SLNs) on MCF-7 and HUVEC control cells. The average diameter of Mn(II) complex was about 1120 ± 2.43 nm, while the average particle size of Mn(II) complex-SLNs was ∼340 ± 2.27 nm. The cytotoxic effects of Mn(II) complex and Mn(II)-SLNs were 86.8 and 66.4%, respectively (p complex (39.25%) and Mn(II)-SLNs (38.05%) induced apoptosis and increased the arrest of G0/G1 phase. However, Mn(II) complex exerted toxic effects on the HUVEC control cell (63.4%), whereas no toxic effects was observed when treated with Mn(II)-SLNs at 150 μM. As a consequence, SLNs might be potentially used for metal-based complexes in the treatment of cancer due to reducing size and toxic effects of metal-based complexes.

  13. Electronic structure study of seven-coordinate first-row transition metal complexes derived from 1,10-diaza-15-crown-5: a successful marriage of theory with experiment.

    Science.gov (United States)

    Platas-Iglesias, Carlos; Vaiana, Lea; Esteban-Gómez, David; Avecilla, Fernando; Real, José Antonio; de Blas, Andrés; Rodríguez-Blas, Teresa

    2005-12-26

    A detailed study of the electronic structure of seven-coordinate Mn(II), Co(II), and Ni(II) complexes with the lariat ether N,N'-bis(2-aminobenzyl)-1,10-diaza-15-crown-5 (L(1)) is presented. These complexes represent new examples of structurally characterized seven-coordinate (pentagonal bipyramidal) complexes for the Mn(II), Co(II), and Ni(II) ions. The X-ray crystal structures of the Mn(II) and Co(II) complexes show C(2) symmetries for the [M(L(1))](2+) cations, whereas the structures of the Ni(II) complexes show a more distorted coordination environment. The magnetic properties of the Mn(II) complex display a characteristic Curie law, whereas those of the Co(II) and Ni(II) ions show the occurrence of zero-field splitting of the S = 3/2 and 1 ground states, respectively. Geometry optimizations of the [M(L(1))](2+) systems (M = Mn, Co, or Ni) at the DFT (B3LYP) level of theory provide theoretical structures in good agreement with the experimental data. Electronic structure calculations predict a similar ordering of the metal-based beta spin frontier MO for the Mn(II) and Co(II) complexes. This particular ordering of the frontier MO leads to a pseudodegenerate ground state for the d(8) Ni(II) ion. The distortion of the C(2) symmetry in [Ni(L(1))](2+) is consistent with a Jahn-Teller effect that removes this pseudodegeneracy. Our electronic structure calculations predict that the binding strength of L(1) should follow the trend Co(II) approximately Mn(II) > Ni(II), in agreement with experimental data obtained from spectrophotometric titrations.

  14. Formation of manganese phosphate and manganese carbonate during long-term sorption of Mn(2+) by viable Shewanella putrefaciens: effects of contact time and temperature.

    Science.gov (United States)

    Chubar, Natalia; Avramut, Cristina; Visser, Tom

    2015-04-01

    The influence of temperature (5, 10, 22 and 30 °C) on the long-term (30 days) sorption of Mn(2+) by viable Shewanella putrefaciens was studied by FTIR and EXAFS. The additional Mn-removal capacity of these bacteria was found to result from the surface precipitation of Mn-containing inorganic phases. The chemical composition of the Mn-containing precipitates is temperature and contact-time dependent. Mn(ii) phosphate and Mn(ii) carbonate were the two major precipitates formed in 1000 mL batches at 10, 22 and 30 °C. The ratio of Mn(ii) phosphate to Mn(ii) carbonate was a function of the contact time. After 30 days, MnCO3 was the dominant phase in the precipitates at 10, 22 and 30 °C; however, MnCO3 did not form at 5 °C. Mn(ii) phosphate was the only precipitate formed at 5 °C over 30 days. The biosynthesis of Extracellular Polymeric Substances (EPS) was much greater at the lowest temperature (5 °C); however, these polymeric sugars did not contribute to the additional removal of Mn(ii) under the experimental conditions. This work is one of the first reports demonstrating the ability of microbes to bioprecipitate manganese phosphate and manganese carbonate. Because of the focus on interfacial processes, this is the first report showing a molecular-level mechanism for manganese carbonate formation (in contrast to the traditionally studied aged minerals).

  15. Diazidobis[4,4,5,5-tetramethyl-2-(1,3-thiazol-2-yl-2-imidazoline-1-oxyl-3-oxide-κ2O,N]manganese(II

    Directory of Open Access Journals (Sweden)

    Kai Jiang

    2009-02-01

    Full Text Available In the crystal structure of the title compound, [Mn(N32(C10H14N3O2S2], the Mn(II atom exhibits a roughly octahedral coordination geometry. The Mn(II atom lies on an inversion centre, thus the asymmetric unit comprises one half-molecule. The metal center is six-coordinated by two azide anions and by two chelating 4,4,5,5-tetramethyl-2-(1,3-thiazol-2-yl-2-imidazoline-1-oxyl-3-oxide nitronyl nitroxide radical ligands, leading to two six-membered chelate rings.

  16. Syntheses and Structural Researches of Yb3+ Complexes with Nitrilotriacetic Acids--Nine-coordinate K3[Yb(nta)2(H2O)]·5H2O and Eight-coordinate Na3[Yb(nta)2]·6H2O Complexes

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    Yb3+ complexes with two nitrilotriacetic acid molecules were prepared and their compositions were determined as K3[Yb(nta)2(H2O)]*5H2O and Na3[Yb(nta)2]*6H2O by elemental analyses. Their structures were characterized by single-crystal X-ray diffraction analyses. In complex K3[Yb(nta)2(H2O)]*5H2O, the YbN2O7 part forms a nine-coordinate monocapped square antiprismatic structure. In complex Na3[Yb(nta)2]*6H2O, the YbN2O6 part forms an eight-coordinate square antiprismatic structure. It can be seen that the outer cations (K+ and Na+) greatly affect the coordination number and coordinate structure from these results.

  17. Poly[mu-aqua-diaqua-mu4-malonato-mu3-malonato-barium(II)nickel(II)].

    Science.gov (United States)

    Guo, Ming-Lin; Zhang, Hou-Ying

    2008-01-01

    The title complex, [BaNi(C3H2O4)2(H2O)3]n, is polymeric, with two non-equivalent malonate dianions bridging one Ni atom and five different Ba atoms. The Ni atoms have a distorted octahedral (NiO6) environment, and are coordinated by four malonate O atoms in a planar arrangement and two water molecules in axial positions. The Ba atom may be described as a BaO9 polyhedron in a monocapped square-antiprismatic environment, which involves two water molecules and seven O atoms from different malonate ligands. The three-dimensional structure is further maintained and stabilized by hydrogen bonds.

  18. catena-Poly[[[pentaaquaeuropium(III]-μ-5-sulfonatoisophthalato-κ4O1,O1′:O3,O3′] 4,4'-bipyridine N,N′-dioxide hemisolvate trihydrate

    Directory of Open Access Journals (Sweden)

    Ai-Zhi Wu

    2010-11-01

    Full Text Available In the crystal structure of the title compound, {[Eu(C8H3O7S(H2O5]·0.5C10H8N2O2·3H2O}n, the EuIII coordination polymer displays a ribbon motif as the 5-sulfoisopthalate anion uses one of carboxyl –CO2 units to chelate to a Eu atom and the other to bind to other two Eu atoms; the sulfonyl –SO3 unit is not involved in coordination. Adjacent ribbons are linked by O—H...O hydrogen bonds, generating a three-dimensional network. The 4,4′-bipyridine-N,N′-dioxide molecule lies on an inversion centre and is hydrogen-bonded to the complex network. The coordination geometry of the Eu atom is a monocapped square antiprism.

  19. The lanthanum(III molybdate(VI La4Mo7O27

    Directory of Open Access Journals (Sweden)

    Petra Becker

    2009-08-01

    Full Text Available Crystals of the orthorhombic phase La4Mo7O27 (lanthanum molybdenum oxide were obtained from a non-stoichiometric melt in the pseudo-ternary system La2O3–MoO3–B2O3. In the crystal structure, distorted square-antiprismatic [LaO8] and monocapped square-antiprismatic [LaO9] polyhedra are connected via common edges and faces into chains along [010]. These chains are arranged in layers that alternate with layers of [MoO4] and [MoO5] polyhedra parallel to (001. In the molybdate layers, a distorted [MoO5] trigonal bipyramid is axially connected to two [MoO4] tetrahedra, forming a [Mo3O11] unit.

  20. Redetermination of Ba2CdTe3 from single-crystal X-ray data

    Directory of Open Access Journals (Sweden)

    Min Yang

    2012-10-01

    Full Text Available The previous structure determination of the title compound, dibarium tritelluridocadmate, was based on powder X-ray diffraction data [Wang & DiSalvo (1999. J. Solid State Chem. 148, 464–467]. In the current redetermination from single-crystal X-ray data, all atoms were refined with anisotropic displacement parameters. The previous structure report is generally confirmed, but with some differences in bond lengths. Ba2CdTe3 is isotypic with Ba2MX3 (M = Mn, Cd; X = S, Se and features 1∞[CdTe2/2Te2/1]4− chains of corner-sharing CdTe4 tetrahedra running parallel [010]. The two Ba2+ cations are located between the chains, both within distorted monocapped trigonal–prismatic coordination polyhedra. All atoms in the structure are located on a mirror plane.

  1. Synthesis and Crystal Structure of the Binuclear Complex [Pr2(C10H8N2O4)2(C10H9N2O4)2(H2O)4]·3H2O·C6H6

    Institute of Scientific and Technical Information of China (English)

    WU Wang-Ting; CHEN Feng-Ying; HE Shui-Yang; HU Huai-Ming; YANG Meng-Lin; WANG Yao-Yu

    2006-01-01

    The binuclear praseodymium(Ⅲ) complex with N-(1-carboxyethylidene)-salicylhydrazide (C10H10N2O4, H2L)determined by X-ray single crystal diffraction. The crystal complex crystallizes in the triclinic system with spacegroup P-1, and in the structure each Pr atom is 9-coordinated by carboxyl O and acyl O and azomethine N atoms oftwo tridentate ligands to form two stable five-membered rings sharing one side in keto-mode and two water mole-cules. The coordination polyhedron around Pr3+ was described as a monocapped square antiprism geometry. In anindividual molecule, four tridentate ligands were coordinated by two negative univalent (HL) and two bivalentforms (L) respectively. Two negative univalent ligands were coordinated via μ2-bridging mode.

  2. Syntheses and Structural Researches of Yb3+ Complexes with Nitrilotriacetic Acids—Nine—coordinate K3[Yb(nta)2(H2O)]·5H2O and Eight—coordinate Na3[Yb(nta)2]·6H2O complexes

    Institute of Scientific and Technical Information of China (English)

    WANGJun; ZHANGXiang-dong; JIAWei-guo; LIHui-fang

    2003-01-01

    Yb3+ complexes with two nitrilotriacetic acid molecules were prepared and their compositions were determined as K3[Yb(nta)2(H2O)]·5H2O and Na3[Yb(nta)2]·6H2O by elemental analyses.Their structures were characterized by single-crystal X-ray diffraction analyses.In complex K3[Yb(nta)2(H2O)]·5H2O,the YbN2O7 part forms a nine-coordinate monocapped square antiprismatic structure.In comples Na3[Yb(nta)2]·6H2O,the YbN2O6 part forms an eight-coordinate square antiprismatic structure.It can be seen that the outer cations(K+ and Na+)greatly affect the coordination number and coordinate structure from these results.

  3. La{sub 4.27}Mg{sub 2.89}Zn{sub 30}, a new structure type with strong positional disorder

    Energy Technology Data Exchange (ETDEWEB)

    Pavlyuk, Volodymyr; Rozycka-Sokolowska, Ewa; Marciniak, Bernard [Jan Dlugosz Univ., Inst. of Chemistry, Environmental Protection and Biotechnology, Czrstochowa (Poland)

    2011-03-15

    Ternary tetralanthanum trimagnesium tricontazinc, La{sub 4.27}Mg{sub 2.89}Zn{sub 30}, crystallizes as a new structure type. It belongs to the structural family that may be derived from the hexagonal CaCu{sub 5} and Th{sub 2}Ni{sub 17} structure types by combination of internal deformation and multiple substitution. The triangular 3{sub 6} and hexagonal 6{sub 3} nets are alternately stacked with Kagome 3636 nets. The atoms with the largest radius (La) are enclosed in 18- vertex polyhedra (distorted pseudo-Frank-Kasper polyhedra). The coordination polyhedra of the two Mg atoms are bicapped and monocapped hexagonal antiprisms, with coordination numbers of 14 and 13, respectively. For all the Zn atoms, the typical icosahedral coordination is observed. In the direction of the six- and threefold axes, strong positional disorder is observed as a result of partial substitutions of La atoms by pairs of Mg atoms. (orig.)

  4. Crystal structure of (Bi0.94Sb1.06)S-3 and reconsideration of cation distribution over mixed sites in the bismuthinitestibnite solid-solution series

    DEFF Research Database (Denmark)

    Poleti, Dejan; Karanovic, Ljiljana; Balic Zunic, Tonci;

    2012-01-01

    -3 obtained by crystal structure analysis. The crystal structure was refined to the R-factors: R-1 = 0.0288 for I > 2 sigma(I) and wR(2) = 0.0542 for all data. (Bi0.94Sb1.06)S-3 has orthorhombic symmetry with space group Pnma (No. 62). The asymmetric unit contains two independent mixed cation sites......, both coordinated to seven S atoms in a form of mono-capped trigonal prism. They combine into infinite (M4S6)(n) rods parallel to the [010] direction with only weak interactions between rods where the lone electron pairs are directed. Our data and the revaluation of previous data resolve a controversy...

  5. Synthesis and Characterization of Some Lanthanide(Ⅲ) Complexes with 4-[N-(2-methoxybenzylimine)formyl]-2, 3-dimethyl-1-phenyl-3-pyazolin-5-one

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    A series of seven novel lanthanide(Ⅲ) nitrato complexes with 4-[N-(2-methoxybenzylimine)formyl]l-2, 3-dimethyl-1-phenyl-3-pyazolin-5-one (2mbfa), were synthesized.These complexes were characterized by elemental analysis, molecular mass determination, conductance and magnetic moment measurements, IR, UV-visible, and 13CNMR spectral studies.In these complexes, the Schiff base, 2mbfa, acts as neutral bidentate ligand by utilizing the carbonyl oxygen and azomethine nitrogen as donor sites.All the three nitrate ions are also coordinated unidentately with 7 coordination for the lanthanide(Ⅲ) ions with a tentative monocapped octahedral geometry for the complexes.All the seven lanthanide(Ⅲ) complexes have a general formula, [Ln(2mbfa)2(NO3)3].

  6. Dipotassium hydrogencarbonate fluoride monohydrate

    Directory of Open Access Journals (Sweden)

    Volker Kahlenberg

    2013-04-01

    Full Text Available Single crystals of the title compound, K2(HCO3F·H2O, were obtained as a secondary product after performing flux synthesis experiments aimed at the preparation of potassium rare earth silicates. The basic building unit of the structure is an [(HCO3(H2OF]2− zigzag chain running parallel to [001]. Both types of anions as well as the water molecules reside on mirror planes perpendicular to [010] at y = 0.25 and y = 0.75, respectively. Linkage between the different constituents of the chains is provided by O—H...O and O—H...F hydrogen bonding. The K+ cations are located between the chains and are coordinated by two F and five O atoms in form of a distorted monocapped trigonal prism.

  7. Synthesis and Crystal Structure of Lanthanide Heteropolymolybdate Complex(NH4)11Gd[Gd4Mo29O100(H2O)23]·25.75H2O

    Institute of Scientific and Technical Information of China (English)

    黄金凤; 王世铭; 林深; 蔡秀真; 林祥

    2000-01-01

    The title complex crystallizes in the triclinic system, space group P1with a = 16.9568(5), b = 18.8631(6), c =24. 1640(8) (A。), α = 100. 110(1), β=92.330(1), γ=113.368(1)°, V=7602.54(4) (A。)3, Dc =3.002 g/crn3, F(000) =5893, Mr=6245.25, μ(MoKα)=5.010mm-1, Z=2andfinalR=0.0722and wR = 0. 1960 for 16015 observed reflections with Ⅰ≥2σ(Ⅰ). The Gd( Ⅲ ) ion is coordinated by nine oxygen atoms, forming a distorted mono-capped square antiprism, while the Mo( Ⅵ ) ions have their different coordination numbers such as 4, 5 and 6 with different configurations such as tetrahedron, squar e pyramid and octahedron, respectively.

  8. Poly[[μ-aqua-aqua-[μ(4)-ethyl (dichloro-methyl-ene)diphospho-nato]sesqui-calcium(II)] acetone hemisolvate 4.5-hydrate].

    Science.gov (United States)

    Jokiniemi, Jonna; Peräniemi, Sirpa; Vepsäläinen, Jouko; Ahlgrén, Markku

    2009-03-25

    The title compound, {[Ca(1.5)(C(3)H(5)Cl(2)O(6)P(2))(H(2)O)(2)]·0.5CH(3)COCH(3)·4.5H(2)O}(n), has a two-dimensional polymeric structure. The asymmetric unit contains two crystallographically independent Ca(2+) cations connected by a chelating and bridging ethyl (dichloro-methyl-ene)diphos-pho-n-ate(3(-)) ligand and an aqua ligand. One of the Ca atoms, lying on a centre of symmetry, has a slightly distorted octa-hedral geometry, while the other Ca atom is seven-coordinated in a distorted monocapped trigonal-prismatic geometry. The polymeric layers are further connected by extensive O-H⋯O hydrogen bonding into a three-dimensional supra-molecular network. The acetone solvent mol-ecule and one uncoordin-ated water mol-ecule are located on twofold rotation axes.

  9. Mechanism of Alkene, Alkane, and Alcohol Oxidation with H2O2 by an in Situ Prepared Mn-II/Pyridine-2-carboxylic Acid Catalyst

    NARCIS (Netherlands)

    Saisaha, Pattama; Dong, Jia Jia; Meinds, Tim G.; de Boer, Johannes W.; Hage, Ronald; Mecozzi, Francesco; Kasper, Johann B.; Browne, Wesley R.

    2016-01-01

    The oxidation of alkenes, alkanes, and alcohols with H2O2 is catalyzed efficiently using an in situ prepared catalyst comprised of a MnII salt and pyridine-2-carboxylic acid (PCA) together with a ketone in a wide range of solvents. The mechanism by which these reactions proceed is elucidated, with a

  10. Impact of Mn(II)-Manganese Oxide Reactions on Ni and Zn Speciation.

    Science.gov (United States)

    Hinkle, Margaret A G; Dye, Katherine G; Catalano, Jeffrey G

    2017-03-01

    Layered Mn oxide minerals (phyllomanganates) often control trace metal fate in natural systems. The strong uptake of metals such as Ni and Zn by phyllomanganates results from adsorption on or incorporation into vacancy sites. Mn(II) also binds to vacancies and subsequent comproportionation with structural Mn(IV) may alter sheet structures by forming larger and distorted Mn(III)O6 octahedra. Such Mn(II)-phyllomanganate reactions may thus alter metal uptake by blocking key reactive sites. Here we investigate the effect of Mn(II) on Ni and Zn binding to phyllomanganates of varying initial vacancy content (δ-MnO2, hexagonal birnessite, and triclinic birnessite) at pH 4 and 7 under anaerobic conditions. Dissolved Mn(II) decreases macroscopic Ni and Zn uptake at pH 4 but not pH 7. Extended X-ray absorption fine structure spectroscopy demonstrates that decreased uptake at pH 4 corresponds with altered Ni and Zn adsorption mechanisms. These metals transition from binding in the interlayer to sheet edges, with Zn increasing its tetrahedrally coordinated fraction. These effects on metal uptake and binding correlate with Mn(II)-induced structural changes, which are more substantial at pH 4 than 7. Through these structural effects and the pH-dependence of Mn(II)-metal competitive adsorption, system pH largely controls metal binding to phyllomanganates in the presence of dissolved Mn(II).

  11. Poly[hexa-aqua-(μ9-cyclo-hexane-1,2,3,4,5,6-hexa-carboxyl-ato)trimanganese(II)].

    Science.gov (United States)

    Sun, Weixuan; Zang, Hu; Quan, Chengshi

    2013-01-01

    The asymmetric unit of the title compound, [Mn3(C12H6O12)(H2O)6] n , comprises one Mn(II) ion, one third of a cyclo-hexane-1,2,3,4,5,6-hexa-carboxyl-ate anion and two aqua ligands. The anion is completed by application of a -3 axis. The Mn(II) ion is six-coordinated by six O atoms from two aqua ligands and three different cyclo-hexa-carboxyl-ate anions in an octa-hedral geometry. The six carboxyl-ate groups adopt a bridging bidentate mode to ligate the Mn(II) ions. Thus, each cyclo-hexane-1,2,3,4,5,6-hexa-carboxyl-ate anion adopts a μ9-connected mode, ligating nine different Mn(II) ions and forming a three-dimensional framework. In the framework, there are strong O-H⋯O hydrogen-bonding inter-actions, which further stabilize the crystal structure.

  12. Sorption and precipitation of Mn2+ by viable and autoclaved Shewanella putrefaciens: Effect of contact time

    NARCIS (Netherlands)

    Chubar, N.; Visser, T.; Avramut, C.; de Waard, H.C.

    2013-01-01

    The sorption of Mn(II) by viable and inactivated cells of Shewanella putrefaciens, a non-pathogenic, facultative anaerobic, gram-negative bacterium characterised as a Mn(IV) and Fe(III) reducer, was studied under aerobic conditions, as a function of pH, bacterial density and metal loading. During

  13. Testing of the KRIA Ionizing Water Treatment System for Waters Contaminated with Diesel, PCBs, and Nutrients (Nitrogen Forms)

    Science.gov (United States)

    2016-02-01

    other technical reports published by ERDC, visit the ERDC online library at http://acwc.sdp.sirsi.net/client/default. ERDC/EL TR-16-3 February...Water and Wastewater Technology. 2nd Edition. New York, NY: Wiley . Hanse1, C. M., C. A. Zeiner, C. M. Santelli, and S. M. Webb. 2012. Mn(II

  14. Browse Title Index

    African Journals Online (AJOL)

    Items 201 - 250 of 444 ... ... and Functionality in Dye-sensitized Solar Cells, Abstract PDF ... Parameters in preparing Multinanoporous TiO2 Thin Films by the Anodic ... Vol 65 (2012), Pb(II) and Mn(II) Supermolecular Polymers of Bipy and ...

  15. Calix[4]arene supported clusters: a dimer of [Mn(III)Mn(II)] dimers

    DEFF Research Database (Denmark)

    Taylor, Stephanie M; McIntosh, Ruaraidh D; Beavers, Christine M;

    2011-01-01

    Phosphinate ligands allow for the transformation of a calix[4]arene supported [Mn(III)(2)Mn(II)(2)] tetramer cluster motif into an unusual [Mn(III)Mn(II)](2) dimer of dimers; the clusters self-assemble in the crystal to form bi-layer arrays reminiscent of the typical packing of calixarene solvates....

  16. Significant in vivo anti-inflammatory activity of Pytren4Q-Mn a superoxide dismutase 2 (SOD2 mimetic scorpiand-like Mn (II complex.

    Directory of Open Access Journals (Sweden)

    Carolina Serena

    Full Text Available The clinical use of purified SOD enzymes has strong limitations due to their large molecular size, high production cost and immunogenicity. These limitations could be compensated by using instead synthetic SOD mimetic compounds of low molecular weight.We have recently reported that two SOD mimetic compounds, the Mn(II complexes of the polyamines Pytren2Q and Pytren4Q, displayed high antioxidant activity in bacteria and yeast. Since frequently molecules with antioxidant properties or free-radical scavengers also have anti-inflammatory properties we have assessed the anti-inflammatory potential of Pytren2Q and Pytren4Q Mn(II complexes, in cultured macrophages and in a murine model of inflammation, by measuring the degree of protection they could provide against the cellular injury produced by lipopolisacharide, a bacterial endotoxin.In this report we show that the Mn(II complex of Pytren4Q but not that of Pytren2Q effectively protected human cultured THP-1 macrophages and whole mice from the inflammatory effects produced by LPS. These results obtained with two molecules that are isomers highlight the importance of gathering experimental data from animal models of disease in assessing the potential of candidate molecules.The effective anti-inflammatory activity of the Mn(II complex of Pytren4Q in addition to its low toxicity, water solubility and ease of production would suggest it is worth taking into consideration for future pharmacological studies.

  17. A one-dimensional chain structure based on unusual tetranuclear manganese(II) clusters.

    Science.gov (United States)

    Che, Guang Bo; Wang, Jian; Liu, Chun Bo; Li, Xiu Ying; Liu, Bo

    2008-11-01

    The title coordination polymer, poly[bis(mu(4)-biphenyl-2,2'-dicarboxylato)(dipyrido[3,2-a:2',3'-c]phenazine)manganese(II)], [Mn(2)(C(14)H(8)O(4))(2)(C(18)H(10)N(4))](n), was obtained through the reaction of MnCl(2).4H(2)O, biphenyl-2,2'-dicarboxylic acid (H(2)dpdc) and dipyrido[3,2-a:2',3'-c]phenazine (L) under hydrothermal conditions. The asymmetric unit contains two crystallographically unique Mn(II) ions, one unique L ligand and two unique dpdc ligands. One Mn ion is six-coordinated by four O atoms from three different dpdc ligands and two N atoms from one L ligand, adopting a distorted octahedral coordination geometry. The distortions from ideal octahedral geometry are largely due to the presence of chelating ligands and the resulting acute N-Mn-N and O-Mn-O angles. The second Mn ion is coordinated in a distorted trigonal bipyramidal fashion by five O atoms from four distinct dpdc ligands. Four Mn(II) ions are bridged by the carboxylate groups of the dpdc ligands to form an unusual tetranuclear Mn(II) cluster. Clusters are further connected by the aromatic backbone of the dicarboxylate ligands, forming a one-dimensional chain structure along the b axis. The title compound is the first example of a chain structure based on a tetranuclear Mn(II) cluster.

  18. COMPLEXES WITH TRIDENTATE N2,O-DONOR LIGAND

    African Journals Online (AJOL)

    been investigated towards several transition metal ions. .... high-spin Mn(II) complex with d5 configuration (S = 5/2) and shows an octahedral ... at short wavelengths, between 290 and 405 nm, may be assigned to ligand-metal ion charge.

  19. Influence of amino acids Shiff bases on irradiated DNA stability in vivo.

    Science.gov (United States)

    Karapetyan, N H; Malakyan, M H; Bajinyan, S A; Torosyan, A L; Grigoryan, I E; Haroutiunian, S G

    2013-01-01

    To reveal protective role of the new Mn(II) complexes with Nicotinyl-L-Tyrosinate and Nicotinyl-L-Tryptophanate Schiff Bases against ionizing radiation. The DNA of the rats liver was isolated on 7, 14, and 30 days after X-ray irradiation. The differences between the DNA of irradiated rats and rats pre-treated with Mn(II) complexes were studied using the melting, microcalorimetry, and electrophoresis methods. The melting parameters and the melting enthalpy of rats livers DNA were changed after the X-ray irradiation: melting temperature and melting enthalpy were decreased and melting interval was increased. These results can be explained by destruction of DNA molecules. It was shown that pre-treatment of rats with Mn(II) complexes approximates the melting parameters to norm. Agarose gel electrophoresis data confirmed the results of melting studies. The separate DNA fragments were revealed in DNA samples isolated from irradiated animals. The DNA isolated from animals pre-treated with the Mn(II) chelates had better electrophoretic characteristics, which correspond to healthy DNA. Pre-treatment of the irradiated rats with Mn(II)(Nicotinil-L-Tyrosinate) and Mn(II)(Nicotinil-L-Tryptophanate)2 improves the DNA characteristics.

  20. Download this PDF file

    African Journals Online (AJOL)

    Magashi

    2013-06-01

    Jun 1, 2013 ... ABSTRACT. The complex of Mn(II) with schiff base derived from 2-aminophenol and 2-hydroxybenzaldehyde has been ... vibration thus confirming participation of oxygen in the coordination. Further ... ions bonded to biologically active compounds may ... and other transformations of organic and inorganic.

  1. Development of a Reliable Method for the Spectrophotometric ...

    African Journals Online (AJOL)

    NICO

    2014-12-02

    Dec 2, 2014 ... The palladium(II)-OMePT complex was stable for more than. 72 h. .... analysis of catalyst. 23. 2-(2-quinolylazo)-5-diethylaminobenzoic acid. HCl ..... Tolerance limit/mg. Mn(II). MnCl2.6H2O. 12.0. Ba(II). BaCl2.6H2O. 50.0.

  2. The Role of Oxygen Radicals in Biology and Medicine 7-11 February 1983, Ventura, California,

    Science.gov (United States)

    1983-02-11

    Center, Durham, NC 27710 Oxygen tolerant organisms usually contain superoxide dismutase (SOD). Lactobacillus plantarum was an apparent exception. We...prevented from accumulating Mn(II) by a phosphate deficiency, L. plantarum becomes oxygen intolerant and very sensitive to the lethality of

  3. Structural and biological evaluation of some metal complexes of vanillin-4N-(2-pyridyl) thiosemicarbazone

    Science.gov (United States)

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

    2013-12-01

    The synthesis and characterization of Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II), Hg(II) and U(VI)O2 complexes of vanillin-4N-(2-pyridyl) thiosemicarbazone (H2PVT) are reported. Theoretical calculations have been performed to obtain IR spectra of ligand and its complexes using AM1, Zindo/1, MM+ and PM3, methods. The Schiff base and its metal complexes have been screened for antibacterial Pseudomonas aeruginosa, Escherichia coli, Bacillus subtilis and Staphylococcus saprophyticus. H2VPT shows no apparent digestion effect on the egg albumin while Mn(II), Hg(II) and Cu(II) complexes exhibited a considerable digestion effect following the order Cu(II) > Mn(II) > Hg(II). Moreover, Ni(II) and Co(II) complexes revealed strong digestion effect. Fe(II), Mn(II), Cu(II), Zn(II) and Ni(II) acted as metal co- SOD enzyme factors, which are located in different compartments of the cell.

  4. Acetylacetonate anchors for robust functionalization of TiO2 nanoparticles with Mn(II)-terpyridine complexes.

    Science.gov (United States)

    McNamara, William R; Snoeberger, Robert C; Li, Gonghu; Schleicher, James M; Cady, Clyde W; Poyatos, Macarena; Schmuttenmaer, Charles A; Crabtree, Robert H; Brudvig, Gary W; Batista, Victor S

    2008-10-29

    A novel class of derivatized acetylacetonate (acac) linkers for robust functionalization of TiO2 nanoparticles (NPs) under aqueous and oxidative conditions is reported. The resulting surface adsorbate anchors are particularly relevant to engineering photocatalytic and photovoltaic devices since they can be applied to attach a broad range of photosensitizers and photocatalytic complexes and are not affected by humidity. Acac is easily modified by CuI-mediated coupling reactions to provide a variety of scaffolds, including substituted terpy complexes (terpy = 2,2':6,2''-terpyridine), assembled with ligands coordinated to transition-metal ions. Since Mn-terpy complexes are known to be effective catalysts for oxidation chemistry, functionalization with Mn(II) is examined. This permits visible-light sensitization of TiO2 nanoparticles due to interfacial electron transfer, as evidenced by UV-vis spectroscopy of colloidal thin films and aqueous suspensions. The underlying ultrafast interfacial electron injection is complete on a subpicosecond time scale, as monitored by optical pump-terahertz probe transient measurements and computer simulations. Time-resolved measurements of the Mn(II) EPR signal at 6 K show that interfacial electron injection induces Mn(II) --> Mn(III) photooxidation, with a half-time for regeneration of the Mn(II) complex of ca. 23 s.

  5. Structure of poly[diaqua[μ-1,2-bis(pyridin-4-ylethane-κ2N:N′]bis(μ3-cyclobutane-1,1-dicarboxylato-κ3O,O′:O′′:O′′′dimanganese(II

    Directory of Open Access Journals (Sweden)

    Do Nam Lee

    2015-08-01

    Full Text Available In the title compound, [Mn(C6H6O4(C12H12N2(H2O]n, the cyclobutane-1,1-dicarboxylate (cbdc ligands bridge three MnII ions, forming layers parallel to the ac plane. These layers are additionally connected by 1,2-bis(pyridin-4-ylethane ligands to form a three-dimensional polymeric framework. An inversion centre is located at the mid-point of the central C—C bond of the 1,2-bis(pyridin-4-ylethane ligand. The coordination geometry of the MnII ion is distorted octahedral and is built up by four carboxylate O atoms, one water O atom and a pyridyl N atom. The pyridine ligand and the coordinating water molecule are in a trans configuration. One carboxylate group of the cbdc ligand acts as a chelating ligand towards one MnII atom, whereas the second carboxylate group coordinates two different MnII atoms.

  6. Manganese binding properties of human calprotectin under conditions of high and low calcium: X-ray crystallographic and advanced electron paramagnetic resonance spectroscopic analysis.

    Science.gov (United States)

    Gagnon, Derek M; Brophy, Megan Brunjes; Bowman, Sarah E J; Stich, Troy A; Drennan, Catherine L; Britt, R David; Nolan, Elizabeth M

    2015-03-04

    The antimicrobial protein calprotectin (CP), a hetero-oligomer of the S100 family members S100A8 and S100A9, is the only identified mammalian Mn(II)-sequestering protein. Human CP uses Ca(II) ions to tune its Mn(II) affinity at a biologically unprecedented hexahistidine site that forms at the S100A8/S100A9 interface, and the molecular basis for this phenomenon requires elucidation. Herein, we investigate the remarkable Mn(II) coordination chemistry of human CP using X-ray crystallography as well as continuous-wave (CW) and pulse electron paramagnetic resonance (EPR) spectroscopies. An X-ray crystallographic structure of Mn(II)-CP containing one Mn(II), two Ca(II), and two Na(I) ions per CP heterodimer is reported. The CW EPR spectrum of Ca(II)- and Mn(II)-bound CP prepared with a 10:0.9:1 Ca(II):Mn(II):CP ratio is characterized by an unusually low zero-field splitting of 485 MHz (E/D = 0.30) for the S = 5/2 Mn(II) ion, consistent with the high symmetry of the His6 binding site observed crystallographically. Results from electron spin-echo envelope modulation and electron-nuclear double resonance experiments reveal that the six Mn(II)-coordinating histidine residues of Ca(II)- and Mn(II)-bound CP are spectroscopically equivalent. The observed (15)N (I = 1/2) hyperfine couplings (A) arise from two distinct classes of nitrogen atoms: the coordinating ε-nitrogen of the imidazole ring of each histidine ligand (A = [3.45, 3.71, 5.91] MHz) and the distal δ-nitrogen (A = [0.11, 0.18, 0.42] MHz). In the absence of Ca(II), the binding affinity of CP for Mn(II) drops by two to three orders of magnitude and coincides with Mn(II) binding at the His6 site as well as other sites. This study demonstrates the role of Ca(II) in enabling high-affinity and specific binding of Mn(II) to the His6 site of human calprotectin.

  7. Sorption and precipitation of Mn2+ by viable and autoclaved Shewanella putrefaciens: Effect of contact time

    Science.gov (United States)

    Chubar, Natalia; Visser, Tom; Avramut, Cristina; de Waard, Helen

    2013-01-01

    The sorption of Mn(II) by viable and inactivated cells of Shewanella putrefaciens, a non-pathogenic, facultative anaerobic, gram-negative bacterium characterised as a Mn(IV) and Fe(III) reducer, was studied under aerobic conditions, as a function of pH, bacterial density and metal loading. During a short contact time (3-24 h), the adsorptive behaviour of live and dead bacteria toward Mn(II) was sufficiently similar, an observation that was reflected in the studies on adsorption kinetics at various metal loadings, effects of pH, bacteria density, isotherms and drifting of pH during adsorption. Continuing the experiment for an additional 2-30 days demonstrated that the Mn(II) sorption by suspensions of viable and autoclaved cells differed significantly from one another. The sorption to dead cells was characterised by a rapid equilibration and was described by an isotherm. In contrast, the sorption (uptake) to live bacteria exhibited a complex time-dependent uptake. This uptake began as adsorption and ion exchange processes followed by bioprecipitation, and it was accompanied by the formation of polymeric sugars (EPS) and the release of dissolved organic substances. FTIR, EXAFS/XANES and XPS demonstrated that manganese(II) phosphate was the main precipitate formed in 125 ml batches, which is the first evidence of the ability of microbes to synthesise manganese phosphates. XPS and XANES spectra did not detect Mn(II) oxidation. Although the release of protein-like compounds by the viable bacteria increased in the presence of Mn2+ (and, by contrast, the release of carbohydrates did not change), electrochemical analyses did not indicate any aqueous complexation of Mn(II) by the organic ligands.

  8. Diverse Ligand-Functionalized Mixed-Valent Hexamanganese Sandwiched Silicotungstates with Single-Molecule Magnet Behavior.

    Science.gov (United States)

    Xue, Han; Zhao, Jun-Wei; Pan, Rui; Yang, Bai-Feng; Yang, Guo-Yu; Liu, Hong-Sheng

    2016-08-22

    Under hydrothermal conditions, replacement of the water molecules in the [Mn(III) 4 Mn(II) 2 O4 (H2 O)4 ](8+) cluster of mixed-valent Mn6 sandwiched silicotungstate [(B-α-SiW9 O34 )2 Mn(III) 4 Mn(II) 2 O4 (H2 O)4 ](12-) (1 a) with organic N ligands led to the isolation of five organic-inorganic hybrid, Mn6 -substituted polyoxometalates (POMs) 2-6. They were all structurally characterized by IR spectroscopy, elemental analysis, thermogravimetric analysis, diffuse-reflectance spectroscopy, and powder and single-crystal X-ray diffraction. Compounds 2-6 represent the first series of mixed-valent {Mn(III) 4 Mn(II) 2 O4 (H2 O)4-n (L)n } sandwiched POMs covalently functionalized by organic ligands. The preparation of 1-6 not only indicates that the double-cubane {Mn(III) 4 Mn(II) 2 O4 (H2 O)4-n (L)n } clusters are very stable fragments in both conventional aqueous solution and hydrothermal systems and that organic functionalization of the [Mn(III) 4 Mn(II) 2 O4 (H2 O)4 ](8+) cluster by substitution reactions is feasible, but also demonstrates that hydrothermal environments can promote and facilitate the occurrence of this substitution reaction. This work confirms that hydrothermal synthesis is effective for making novel mixed-valent POMs substituted with transition-metal (TM) clusters by combining lacunary Keggin precursors with TM cations and tunable organic ligands. Furthermore, magnetic measurements reveal that 3 and 6 exhibit single-molecule magnet behavior.

  9. Mn(II,III) oxidation and MnO2 mineralization by an expressed bacterial multicopper oxidase

    Science.gov (United States)

    Butterfield, Cristina N.; Soldatova, Alexandra V.; Lee, Sung-Woo; Spiro, Thomas G.; Tebo, Bradley M.

    2013-07-01

    Reactive Mn(IV) oxide minerals are ubiquitous in the environment and control the bioavailability and distribution of many toxic and essential elements and organic compounds. Their formation is thought to be dependent on microbial enzymes, because spontaneous Mn(II) to Mn(IV) oxidation is slow. Several species of marine Bacillus spores oxidize Mn(II) on their exosporium, the outermost layer of the spore, encrusting them with Mn(IV) oxides. Molecular studies have identified the mnx (Mn oxidation) genes, including mnxG, encoding a putative multicopper oxidase (MCO), as responsible for this two-electron oxidation, a surprising finding because MCOs only catalyze single-electron transfer reactions. Characterization of the enzymatic mechanism has been hindered by the lack of purified protein. By purifying active protein from the mnxDEFG expression construct, we found that the resulting enzyme is a blue (absorption maximum 590 nm) complex containing MnxE, MnxF, and MnxG proteins. Further, by analyzing the Mn(II)- and (III)-oxidizing activity in the presence of a Mn(III) chelator, pyrophosphate, we found that the complex facilitates both electron transfers from Mn(II) to Mn(III) and from Mn(III) to Mn(IV). X-ray absorption spectroscopy of the Mn mineral product confirmed its similarity to Mn(IV) oxides generated by whole spores. Our results demonstrate that Mn oxidation from soluble Mn(II) to Mn(IV) oxides is a two-step reaction catalyzed by an MCO-containing complex. With the purification of active Mn oxidase, we will be able to uncover its mechanism, broadening our understanding of Mn mineral formation and the bioinorganic capabilities of MCOs.

  10. Antimony oxidation and adsorption by in-situ formed biogenic Mn oxide and Fe-Mn oxides.

    Science.gov (United States)

    Bai, Yaohui; Jefferson, William A; Liang, Jinsong; Yang, Tingting; Qu, Jiuhui

    2017-04-01

    Antimony (Sb), which can be toxic at relatively low concentrations, may co-exist with Mn(II) and/or Fe(II) in some groundwater and surface water bodies. Here we investigated the potential oxidation and adsorption pathways of Sb (III and V) species in the presence of Mn(II) and Mn-oxidizing bacteria, with or without Fe(II). Batch experiments were conducted to determine the oxidation and adsorption characteristics of Sb species in the presence of biogenic Mn oxides (BMOs), which were formed in-situ via the oxidation of Mn(II) by a Mn-oxidizing bacterium (Pseudomonas sp. QJX-1). Results indicated that Sb(III) ions could be oxidized to Sb(V) ions by BMO, but only Sb(V) originating from Sb(III) oxidation was adsorbed effectively by BMO. Introduced Fe(II) was chemically oxidized to FeOOH, the precipitates of which mixed with BMO to form a new compound, biogenic Fe-Mn oxides (BFMO). The BMO part of the BFMO mainly oxidized and the FeOOH of the BFMO mainly adsorbed the Sb species. In aquatic solutions containing both As(III) and Sb(III), the BFMO that formed in-situ preferentially oxidized Sb over As but adsorbed As more efficiently. Chemical analysis and reverse transcription real-time polymerase chain reaction revealed that the presence of Fe(II), As(III) and Sb(III) accelerated the oxidation of Mn(II) but inhibited the activity of Mn-oxidizing bacteria. These results provide significant insights into the biogeochemical pathways of Sb, Mn(II) in aquatic ecosystems, with or without Fe(II). Copyright © 2016. Published by Elsevier B.V.

  11. Sorption and precipitation of Mn2+ by viable and autoclaved Shewanella putrefaciens: Effect of contact time

    KAUST Repository

    Chubar, Natalia

    2013-01-01

    The sorption of Mn(II) by viable and inactivated cells of Shewanella putrefaciens, a non-pathogenic, facultative anaerobic, gram-negative bacterium characterised as a Mn(IV) and Fe(III) reducer, was studied under aerobic conditions, as a function of pH, bacterial density and metal loading. During a short contact time (3-24h), the adsorptive behaviour of live and dead bacteria toward Mn(II) was sufficiently similar, an observation that was reflected in the studies on adsorption kinetics at various metal loadings, effects of pH, bacteria density, isotherms and drifting of pH during adsorption. Continuing the experiment for an additional 2-30days demonstrated that the Mn(II) sorption by suspensions of viable and autoclaved cells differed significantly from one another. The sorption to dead cells was characterised by a rapid equilibration and was described by an isotherm. In contrast, the sorption (uptake) to live bacteria exhibited a complex time-dependent uptake. This uptake began as adsorption and ion exchange processes followed by bioprecipitation, and it was accompanied by the formation of polymeric sugars (EPS) and the release of dissolved organic substances. FTIR, EXAFS/XANES and XPS demonstrated that manganese(II) phosphate was the main precipitate formed in 125ml batches, which is the first evidence of the ability of microbes to synthesise manganese phosphates. XPS and XANES spectra did not detect Mn(II) oxidation. Although the release of protein-like compounds by the viable bacteria increased in the presence of Mn2+ (and, by contrast, the release of carbohydrates did not change), electrochemical analyses did not indicate any aqueous complexation of Mn(II) by the organic ligands. © 2012 Elsevier Ltd.

  12. Multicomutation flow system for manganese speciation by solid phase extraction and flame atomic absorption spectrometry

    Science.gov (United States)

    Tobiasz, Anna; Sołtys, Monika; Kurys, Ewa; Domagała, Karolina; Dudek-Adamska, Danuta; Walas, Stanisław

    2017-08-01

    In the paper an application of solid phase extraction technique for speciation analysis of manganese in water samples with the use of flame atomic absorption spectrometry is presented. Two types of sorbents, activated silica gel and Dowex 1 × 4, were used respectively for simultaneously Mn2 + and MnO42 - retention and preconcentration. The whole procedure was realized in multicomutation flow system. Different conditions like: type and concentration of eluent, sample pH and loading time were tested during the study. Under appropriate conditions, it was possible to obtained enrichment factors of 20 and 16 for Mn(II) and Mn(VII), respectively. Precision of the procedure was close to 4% (measured as relative standard deviation), whereas the detection limit (3σ) was 1.4 μg·L- 1 for Mn(II) and 4.8 μg·L- 1 for Mn(VII).

  13. Spectral, magnetic and biological studies of 1,4-dibenzoyl-3-thiosemicarbazide complexes with some first row transition metal ions

    Indian Academy of Sciences (India)

    Nand K Singh; Saty B Singh; Anuraag Shrivastav; Sukh M Singh

    2001-08-01

    The ligand 1,4-dibenzoyl-3-thiosemicarbazide (DBtsc) forms complexes [M(DBtsc-H)(SCN)] [M = Mn(II), Co(II) or Zn(II)], [M(DBtscH)(SCN)(H2O)] [M = Ni(II) or Cu(II)], [M(DBtsc-H)Cl] [M = Co(II), Ni(II), Cu(II) or Zn(II)] and [Mn(DBtsc)Cl2], which have been characterized by elemental analyses, magnetic susceptibility measurements, UV/Vis, IR, 1H and 13C NMR and FAB mass spectral data. Room temperature ESR spectra of the Mn(II) and Cu(II) complexes yield values, characteristic of tetrahedral and square planar complexes respectively. DBtsc and its soluble complexes have been screened against several bacteria, fungi and tumour cell lines.

  14. Spectroscopic and structural studies of the Schiff base 3-methoxy-N-salicylidene-o-amino phenol complexes with some transition metal ions and their antibacterial, antifungal activities

    Science.gov (United States)

    Abo-Aly, M. M.; Salem, A. M.; Sayed, M. A.; Abdel Aziz, A. A.

    2015-02-01

    Spectroscopic (IR, Raman, NMR, UV-visible, and ESR), and structural studies of the ligand 3-methoxy-N-salicylidene-o-amino phenol (H2L) and its synthesized complexes with some transition metal ions (Mn(II), Co(II), Ni(II)), Cu(II) and Zn(II)) were recorded and analyzed. The magnetic properties and thermal gravimetric analysis (TGA and DTA) were also measured for the complexes. The metal complexes were found to have The structural formula MLṡH2O and the metal ions Mn(II), Co(II), Ni(II)) and Zn(II) were found to form tetrahedral complexes with the ligand whereas Cu(II) formed a square planar one. Antimicrobial activity of the ligand and its complexes were also investigated and discussed.

  15. Manganese (II) Chelate Functionalized Copper Sulfide Nanoparticles for Efficient Magnetic Resonance/Photoacoustic Dual-Modal Imaging Guided Photothermal Therapy.

    Science.gov (United States)

    Liu, Renfa; Jing, Lijia; Peng, Dong; Li, Yong; Tian, Jie; Dai, Zhifei

    2015-01-01

    The integration of diagnostic and therapeutic functionalities into one nanoplatform shows great promise in cancer therapy. In this research, manganese (II) chelate functionalized copper sulfide nanoparticles were successfully prepared using a facile hydrothermal method. The obtained ultrasmall nanoparticles exhibit excellent photothermal effect and photoaoustic activity. Besides, the high loading content of Mn(II) chelates makes the nanoparticles attractive T1 contrast agent in magnetic resonance imaging (MRI). In vivo photoacoustic imaging (PAI) results showed that the nanoparticles could be efficiently accumulated in tumor site in 24 h after systematic administration, which was further validated by MRI tests. The subsequent photothermal therapy of cancer in vivo was achieved without inducing any observed side effects. Therefore, the copper sulfide nanoparticles functionalized with Mn(II) chelate hold great promise as a theranostic nanomedicine for MR/PA dual-modal imaging guided photothermal therapy of cancer.

  16. Effect of manganese on the secretion of manganese-peroxidase by the basidiomycete Ceriporiopsis subvermispora.

    Science.gov (United States)

    Mancilla, Rodrigo A; Canessa, Paulo; Manubens, Augusto; Vicuña, Rafael

    2010-07-01

    The ligninolytic machinery of the widely used model fungus Ceriporiopsis subvermispora includes the enzymes manganese-peroxidase (MnP) and laccase (Lcs). In this work the effect of Mn(II) on the secretion of MnP was studied. Cultures grown in the absence of Mn(II) showed high levels of mnp transcripts. However, almost no MnP enzyme was detected in the extracellular medium, either by enzymatic activity assays or Western blot hybridizations. In the corresponding mycelia, immuno-electron microscopy experiments showed high levels of MnP enzyme within intracellular compartments. These results suggest that in addition to its well-known effect on transcription regulation of mnp genes, manganese influences secretion of MnP to the extracellular medium. Experiments carried out in the presence of cycloheximide confirmed that the metal is required to secrete MnP already synthesized and retained within the cell.

  17. Bis[(2-methylbenzylbis(pyridin-2-ylmethyl-κNamine-κN]manganese(II bis(perchlorate

    Directory of Open Access Journals (Sweden)

    Ray J. Butcher

    2014-03-01

    Full Text Available In the title complex, [Mn(C20H21N32](ClO42, two tridentate (2-methylbenzylbis(pyridin-2-ylmethylamine (L ligands form the MnII complex [MnL2](ClO42. The MnII ion lies on a twofold axis and the complex cation is significantly distorted from regular octahedral geometry. The packing is stabilized by weak C—H...O interactions between the cations and anions, which link them into a zigzag ribbon along [101]. The perchlorate anion is disordered and was constrained to be tetrahedral with two orientations having occupancies of 0.768 (4 and 0.232 (4. The 2-methylbenzyl moiety is also disordered over two sets of sites, with occupancies of 0.508 (15 and 0.492 (15.

  18. VizieR Online Data Catalog: Atomic transition probabilities of Mn (Den Hartog+, 2011)

    Science.gov (United States)

    den Hartog, E. A.; Lawler, J. E.; Sobeck, J. S.; Sneden, C.; Cowan, J. J.

    2011-08-01

    The goal of the present work is to produce transition probabilities with very low uncertainties for a selected set of multiplets of MnI and MnII. Multiplets are chosen based upon their suitability for stellar abundance analysis. We report on new radiative lifetime measurements for 22 levels of MnI from the e8D, z6P, z6D, z4F, e8S, and e6S terms and six levels of MnII from the z5P and z7P terms using time-resolved laser-induced fluorescence on a slow atom/ion beam. New branching fractions for transitions from these levels, measured using a Fourier-transform spectrometer, are reported. (2 data files).

  19. The extrinsic PsbO protein modulates the oxidation/reduction rate of the exogenous Mn cation at the high-affinity Mn-binding site of Mn-depleted PSII membranes.

    Science.gov (United States)

    Semin, Boris K; Podkovirina, Tatiana E; Davletshina, Lira N; Timofeev, Kirill N; Ivanov, Il'ya I; Rubin, Andrei B

    2015-08-01

    The oxidation of exogenous Mn(II) cations at the high-affinity (HA) Mn-binding site in Mn-depleted photosystem II (PSII) membranes with or without the presence of the extrinsic PsbO polypeptide was studied by EPR. The six-lines EPR spectrum of Mn(II) cation disappears in the absence of the PsbO protein in membranes under illumination, but there was no effect when PSII preparations bound the PsbO protein. Our study demonstrates that such effect is determined by significant influence of the PsbO protein on the ratio between the rates of Mn oxidation and reduction at the HA site when the membranes are illuminated.

  20. New manganese(II) and nickel(II) coordination compounds with N,O-polydentate ligands obtained from pyridoxal and tripodal units

    Science.gov (United States)

    Ebani, Patrícia Regina; Fontana, Liniquer Andre; Campos, Patrick Teixeira; Rosso, Eduardo F.; Piquini, Paulo C.; Iglesias, Bernardo Almeida; Back, Davi Fernando

    2016-09-01

    We have reported the synthesis involving the condensation of pyridoxal with tris(2-aminoethyl)amine obtained a tripodal ligand, as well as its subsequent complexation with the manganese(II) and nickel(II) ions. The structural analysis revealed, in the case of complex 1, the formation of a monomeric complex with Mn(II) species. In the complex 2, with Ni(II) metal ion, we describe the probable mechanism for the formation of hemiacetal in these complexes. Only the complex 1 catalyze the dismutation of superoxide efficiently with IC50 equal to 3.38 μM, evaluated through the nitro blue tetrazolium photoreduction inhibition superoxide dismutase assay, in aqueous solution of pH 7.8. Density functional theory calculations are done to characterize and compare the molecular frontier orbitals of the Mn(II) and Ni(II) complexes.

  1. Computational and instrumental methods in EPR

    CERN Document Server

    Bender, Christopher J

    2006-01-01

    Computational and Instrumental Methods in EPR Prof. Bender, Fordham University Prof. Lawrence J. Berliner, University of Denver Electron magnetic resonance has been greatly facilitated by the introduction of advances in instrumentation and better computational tools, such as the increasingly widespread use of the density matrix formalism. This volume is devoted to both instrumentation and computation aspects of EPR, while addressing applications such as spin relaxation time measurements, the measurement of hyperfine interaction parameters, and the recovery of Mn(II) spin Hamiltonian parameters via spectral simulation. Key features: Microwave Amplitude Modulation Technique to Measure Spin-Lattice (T1) and Spin-Spin (T2) Relaxation Times Improvement in the Measurement of Spin-Lattice Relaxation Time in Electron Paramagnetic Resonance Quantitative Measurement of Magnetic Hyperfine Parameters and the Physical Organic Chemistry of Supramolecular Systems New Methods of Simulation of Mn(II) EPR Spectra: Single Cryst...

  2. Poly[(μ4-biphenyl-3,3′-dicarboxylatobis[μ2-1,1′-(butane-1,4-diyldiimidazole](μ2-oxalatodimanganese(II

    Directory of Open Access Journals (Sweden)

    Bao-Yong Zhu

    2010-10-01

    Full Text Available In the title coordination compound, [Mn2(C14H8O4(C2O4(C10H14N42]n, the biphenyl-3,3′-dicarboxylate and oxalate anions, both situated on inversion centres, function in a bridging mode, linking the dinuclear MnII atoms into wave-like layers. Each 1,1′-(1,4-butane-1,4-diyldiimidazole ligand coordinates to two MnII atoms located in adjacent layers via Mn—N coordination bonds, giving a three-dimensional network. As the methylene groups can bend freely relative to each other due to the C atoms connected via single bonds, the 1,1′-(butane-1,4-diyldiimidazole ligand forms an S-shaped conformation, which makes the void in the three-dimensional network distorted.

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

    Science.gov (United States)

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

    2016-05-01

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

  4. Accelerated Oxygen Atom Transfer and C-H Bond Oxygenation by Remote Redox Changes in Fe3 Mn-Iodosobenzene Adducts.

    Science.gov (United States)

    de Ruiter, Graham; Carsch, Kurtis M; Gul, Sheraz; Chatterjee, Ruchira; Thompson, Niklas B; Takase, Michael K; Yano, Junko; Agapie, Theodor

    2017-03-24

    We report the synthesis, characterization, and reactivity of [LFe3 (PhPz)3 OMn((s) PhIO)][OTf]x (3: x=2; 4: x=3), where 4 is one of very few examples of iodosobenzene-metal adducts characterized by X-ray crystallography. Access to these rare heterometallic clusters enabled differentiation of the metal centers involved in oxygen atom transfer (Mn) or redox modulation (Fe). Specifically, (57) Fe Mössbauer and X-ray absorption spectroscopy provided unique insights into how changes in oxidation state (Fe(III)2 Fe(II) Mn(II) vs. Fe(III)3 Mn(II) ) influence oxygen atom transfer in tetranuclear Fe3 Mn clusters. In particular, a one-electron redox change at a distal metal site leads to a change in oxygen atom transfer reactivity by ca. two orders of magnitude.

  5. Speciation and thermodynamic properties of manganese(II) chloride complexes in hydrothermal fluids: In situ XAS study

    Science.gov (United States)

    Tian, Yuan; Etschmann, Barbara; Mei, Yuan; Grundler, Pascal V.; Testemale, Denis; Hazemann, Jean-Louis; Elliott, Peter; Ngothai, Yung; Brugger, Joël

    2014-03-01

    The speciation of Mn(II) in acidic brines under a wide range of conditions (30-550 °C, 600 bar, 0.100-10.344 m chloride and 0.110-2.125 m bromide) was investigated using in situ X-ray Absorption Spectroscopy (XAS). Increasing temperature and/or salinity results in a structural change of the Mn(II) complexes from octahedral to (distorted) tetrahedral. Octahedral species predominate at room temperature within the whole salinity range and persist up to ∼400 °C in low salinity solutions (mCl 3 m, Cl:Mn ratio > 53) is MnCl3(H2O)-, and that a lower order chlorocomplex, MnCl2(H2O)2(aq), is the predominant species in low salinity solutions (mCl UV-Vis spectroscopic studies.

  6. Ionic immobilization, diversification, and release: application to the generation of a library of methionine aminopeptidase inhibitors.

    Science.gov (United States)

    Vedantham, Punitha; Guerra, Jennifer M; Schoenen, Frank; Huang, Min; Gor, Parul J; Georg, Gunda I; Wang, Jenna L; Neuenswander, Benjamin; Lushington, Gerald H; Mitscher, Lester A; Ye, Qi-Zhuang; Hanson, Paul R

    2008-01-01

    Development of an ionic immobilization, diversification, and release method for the generation of methionine aminopeptidase inhibitors is reported. This method involves the immobilization of 5-bromofuran-2-carboxylic acid and 5-bromothiophene-2-carboxylic acid onto PS-BEMP, followed by Suzuki reaction on a resin-bound intermediate and subsequent release to provide products in moderate yields and excellent purities. Compound potencies were evaluated on the Co(II), Mn(II), Ni(II), and Fe(II) forms of Escherichia coli MetAP1. The furoic-acid analogs were found to be Mn(II) selective with IC 50 values in the low micromolar range. Qualitative SAR analysis, supplemented by molecular modeling studies, provides valuable information on structural elements responsible for potency and selectivity.

  7. Poly[[bis(μ-4,4′-bipyridyl-κ2N:N′bis(thiocyanato-κNmanganese(II] diethyl ether disolvate

    Directory of Open Access Journals (Sweden)

    Mario Wriedt

    2010-07-01

    Full Text Available In the title compound, {[Mn(NCS2(C10H8N22]·2C4H10O}n, the MnII ion is coordinated by four N-bonded 4,4′-bipyridine (bipy ligands and two N-bonded thiocyanate anions in a distorted octahedral coordination geometry. The asymmetric unit consists of one MnII ion and two bipy ligands each located on a twofold rotation axis, as well as one thiocyanate anion and one diethyl ether molecule in general positions. In the crystal structure, the metal centers with terminally bonded thicyanate anions are bridged by the bipy ligands into layers parallel to (001. The diethyl ether solvent molecules occupy the voids of the structure.

  8. The role of chemical speciation, chemical fractionation and calcium disruption in manganese-induced developmental toxicity in zebrafish (Danio rerio) embryos.

    Science.gov (United States)

    Hernández, R B; Nishita, M I; Espósito, B P; Scholz, S; Michalke, B

    2015-10-01

    Manganese (Mn) is an essential nutrient that can be toxic in excess concentrations, especially during early development stages. The mechanisms of Mn toxicity is still unclear, and little information is available regarding the role of Mn speciation and fractionation in toxicology. We aimed to investigate the toxic effects of several chemical forms of Mn in embryos of Danio rerio exposed during different development stages, between 2 and 122h post fertilization. We found a stage-specific increase of lethality associated with hatching and removal of the chorion. Mn(II), ([Mn(H2O)6](2+)) appeared to be the most toxic species to embryos exposed for 48h, and Mn(II) citrate was most toxic to embryos exposed for 72 and/or 120h. Manganese toxicity was associated with calcium disruption, manganese speciation and metal fractionation, including bioaccumulation in tissue, granule fractions, organelles and denaturated proteins.

  9. Improved Understanding of In Situ Chemical Oxidation. Technical Objective 2: Soil Reactivity

    Science.gov (United States)

    2009-05-01

    sample by irradiation with neutrons. The primary source of neutrons for irradiation is usually a nuclear reactor. Each element which is activated...generally considered to be a major reductant. One possible explanation is that TOC is related to NODmax (as indicated by Eq. 26) and its primary ...e.g., goethite, magnetite, and hematite ) or other transition metals (Mn(II, IV), Ti(III)) in a peroxide system can significantly facilitate

  10. Metallic complexes with glyphosate: a review; Complexos metalicos com o herbicida glifosato: revisao

    Energy Technology Data Exchange (ETDEWEB)

    Coutinho, Claudia F.B.; Mazo, Luiz Henrique [Sao Paulo Univ., Sao Carlos, SP (Brazil). Inst. de Quimica]. E-mail: claudiabreda@iqsc.usp.br

    2005-11-15

    We present studies involving metallic ions and the herbicide glyphosate. The metallic complexes of Cu(II), Zn(II), Mn(II), Ni(II), Cd(II), Pb(II), Cr(III), Fe(III), Co(III), ammonium, sodium, Ag(I), alkaline earth metals and of some lanthanides ions are described. The complexes are discussed in terms of their synthesis, identification, stability and structural properties, based on data from the current literature. (author)

  11. Crystal structure of hexakis(dimethyl sulfoxide-κOmanganese(II diiodide

    Directory of Open Access Journals (Sweden)

    Mathias Glatz

    2016-07-01

    Full Text Available The asymmetric unit of the title salt, [Mn(C2H6OS6]I2, consists of one MnII ion, six O-bound dimethyl sulfoxide (DMSO ligands and two I− counter-anions. The isolated complex cations have an octahedral configuration and are grouped in hexagonally arranged rows extending parallel to [100]. The two I− anions are located between the rows and are linked to the cations through two weak C—H...I interactions.

  12. Constraints on superoxide mediated formation of manganese oxides

    Directory of Open Access Journals (Sweden)

    Deric R. Learman

    2013-09-01

    Full Text Available Manganese (Mn oxides are among the most reactive sorbents and oxidants within the environment, where they play a central role in the cycling of nutrients, metals, and carbon. Recent discoveries have identified superoxide (O2- (both of biogenic and abiogenic origin as an effective oxidant of Mn(II leading to the formation of Mn oxides. Here we examined the conditions under which abiotically produced superoxide led to oxidative precipitation of Mn and the solid-phases produced. Oxidized Mn, as both aqueous Mn(III and Mn(III/IV oxides, was only observed in the presence of active catalase, indicating that hydrogen peroxide, a product of the reaction of O2- with Mn(II, inhibits the oxidation process presumably through the reduction of Mn(III. Citrate and pyrophosphate increased the yield of oxidized Mn but decreased the amount of Mn oxide produced via formation of Mn(III-ligand complexes. While complexing ligands played a role in stabilizing Mn(III, they did not eliminate the inhibition of net Mn(III formation by H2O2. The Mn oxides precipitated were highly disordered colloidal hexagonal birnessite, similar to those produced by biotically generated superoxide. Yet, in contrast to the large particulate Mn oxides formed by biogenic superoxide, abiotic Mn oxides did not ripen to larger, more crystalline phases. This suggests that the deposition of crystalline Mn oxides within the environment requires a biological, or at least organic, influence. This work provides the first direct evidence that, under conditions relevant to natural waters, oxidation of Mn(II by superoxide can occur and lead to formation of Mn oxides. For organisms that oxidize Mn(II by producing superoxide, these findings may also point to other microbially mediated processes, in particular enzymatic hydrogen peroxide degradation and/or production of organic ligand metabolites, that allow for Mn oxide formation.

  13. The oxidation capacity of Mn3O4 nanoparticles is significantly enhanced by anchoring them onto reduced graphene oxide to facilitate regeneration of surface-associated Mn(III).

    Science.gov (United States)

    Duan, Lin; Wang, Zhongyuan; Hou, Yan; Wang, Zepeng; Gao, Guandao; Chen, Wei; Alvarez, Pedro J J

    2016-10-15

    Metal oxides are often anchored to graphene materials to achieve greater contaminant removal efficiency. To date, the enhanced performance has mainly been attributed to the role of graphene materials as a conductor for electron transfer. Herein, we report a new mechanism via which graphene materials enhance oxidation of organic contaminants by metal oxides. Specifically, Mn3O4-rGO nanocomposites (Mn3O4 nanoparticles anchored to reduced graphene oxide (rGO) nanosheets) enhanced oxidation of 1-naphthylamine (used here as a reaction probe) compared to bare Mn3O4. Spectroscopic analyses (X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy) show that the rGO component of Mn3O4-rGO was further reduced during the oxidation of 1-naphthylamine, although rGO reduction was not the result of direct interaction with 1-naphthylamine. We postulate that rGO improved the oxidation efficiency of anchored Mn3O4 by re-oxidizing Mn(II) formed from the reaction between Mn3O4 and 1-naphthylamine, thereby regenerating the surface-associated oxidant Mn(III). The proposed role of rGO was verified by separate experiments demonstrating its ability to oxidize dissolved Mn(II) to Mn(III), which subsequently can oxidize 1-naphthylamine. The role of dissolved oxygen in re-oxidizing Mn(II) was ruled out by anoxic (N2-purged) control experiments showing similar results as O2-sparged tests. Opposite pH effects on the oxidation efficiency of Mn3O4-rGO versus bare Mn3O4 were also observed, corroborating the proposed mechanism because higher pH facilitates oxidation of surface-associated Mn(II) even though it lowers the oxidation potential of Mn3O4. Overall, these findings may guide the development of novel metal oxide-graphene nanocomposites for contaminant removal. Copyright © 2016 Elsevier Ltd. All rights reserved.

  14. Synchrotron-Based Techniques Shed Light on Mechanisms of Plant Sensitivity and Tolerance to High Manganese in the Root Environment1[OPEN

    Science.gov (United States)

    Blamey, F. Pax C.; Hernandez-Soriano, Maria C.; Cheng, Miaomiao; Tang, Caixian; Paterson, David J.; Lombi, Enzo; Wang, Wei Hong; Scheckel, Kirk G.; Kopittke, Peter M.

    2015-01-01

    Plant species differ in response to high available manganese (Mn), but the mechanisms of sensitivity and tolerance are poorly understood. In solution culture, greater than or equal to 30 µm Mn decreased the growth of soybean (Glycine max), but white lupin (Lupinus albus), narrow-leafed lupin (Lupin angustifolius), and sunflower (Helianthus annuus) grew well at 100 µm Mn. Differences in species’ tolerance to high Mn could not be explained simply by differences in root, stem, or leaf Mn status, being 8.6, 17.1, 6.8, and 9.5 mmol kg–1 leaf fresh mass at 100 µm Mn. Furthermore, x-ray absorption near edge structure analyses identified the predominance of Mn(II), bound mostly to malate or citrate, in roots and stems of all four species. Rather, differences in tolerance were due to variations in Mn distribution and speciation within leaves. In Mn-sensitive soybean, in situ analysis of fresh leaves using x-ray fluorescence microscopy combined with x-ray absorption near edge structure showed high Mn in the veins, and manganite [Mn(III)] accumulated in necrotic lesions apparently through low Mn sequestration in vacuoles or other vesicles. In the two lupin species, most Mn accumulated in vacuoles as either soluble Mn(II) malate or citrate. In sunflower, Mn was sequestered as manganite at the base of nonglandular trichomes. Hence, tolerance to high Mn was ascribed to effective sinks for Mn in leaves, as Mn(II) within vacuoles or through oxidation of Mn(II) to Mn(III) in trichomes. These two mechanisms prevented Mn accumulation in the cytoplasm and apoplast, thereby ensuring tolerance to high Mn in the root environment. PMID:26395840

  15. Dual function photocatalysis of cyano-bridged heteronuclear metal complexes for water oxidation and two-electron reduction of dioxygen to produce hydrogen peroxide as a solar fuel.

    Science.gov (United States)

    Aratani, Yusuke; Suenobu, Tomoyoshi; Ohkubo, Kei; Yamada, Yusuke; Fukuzumi, Shunichi

    2017-03-25

    The photocatalytic production of hydrogen peroxide from water and dioxygen under visible light irradiation was made possible by using polymeric cyano-bridged heteronuclear metal complexes (M(II)[Ru(II)(CN)4(bpy)]; M(II) = Ni(II), Fe(II) and Mn(II)), where the photocatalytic two-electron reduction of O2 and water oxidation were catalysed by the Ru and M(II) moieties, respectively.

  16. Purification and Characterization of the Manganese(II) Oxidizing Protein from Erythrobacter sp. SD-21

    Science.gov (United States)

    Nakama, K. R.; Lien, A.; Johnson, H. A.

    2013-12-01

    The manganese(II) oxidizing protein (Mop) found in the alpha-proteobacterium Erythrobacter sp. SD-21 catalyzes the formation of insoluble Mn(III/IV) oxides from soluble Mn(II). These Mn(III/IV) oxides formed are one of the strongest naturally occurring oxides, next to oxygen, and can be used to adsorb and oxidize toxic chemicals from the surrounding environment. Because of the beneficial use in the treatment of contaminated sources, the mechanism and biochemical properties of this novel enzyme are being studied. Due to low expression levels in the native host strain, purification of Mop has been problematic. To overcome this problem the gene encoding Mop, mopA, was cloned from the native host into a C-terminal histidine tag vector and expressed in Escherichia coli cells. Affinity chromatography under denaturing conditions have been applied in attempts to purify an active Mop. Western blots have confirmed that the protein is being expressed and is at the expected size of 250 kDa. Preliminary characterization on crude extract containing Mop has shown a Km and vmax value of 2453 uM and 0.025 uM min-1, respectively. Heme and pyrroloquinoline quinone can stimulate Mn(II) oxidizing activity, but hydrogen peroxide does not affect activity, despite the sequence similarity to animal heme peroxidase proteins. Research has been shown that calcium is essential for Mop activity. Purifying an active Mn(II) oxidizing protein will allow for a better understanding behind the enigmatic process of Mn(II) oxidation.

  17. SYNTHESIS AND CHARACTERIZATION OF SALICYLALDAZINE AND ITS METAL (II) COMPLEXES DERIVED FROM METAL (II) CHLORIDES

    OpenAIRE

    Jamila wazir

    2016-01-01

    The salicylaldazine (ligand) and its metal (II) complexes like copper (II), nickel (II), zinc (II), cobalt (II) and manganese (II) complexes has been synthesized and characterized by different techniques using FTIR, UV-VIS spectroscopy. The ligand (salicylaldazine) is synthesized by the condensation reaction of salicylaldehyde and hydrazine sulfate. The salicylaldazine metal (II) complexes like Cu (II) , Ni(II), Zn (II), Co(II), Mn(II) were prepared by using metal (II) chloride in dioxane. Th...

  18. (μ-Ethane-1,1,2,2-tetracarboxylatobis[tetraaquamanganese(II

    Directory of Open Access Journals (Sweden)

    Meng-Wei Xue

    2011-04-01

    Full Text Available In the centrosymmetric title molecule, [Mn2(C6H2O8(H2O8], the MnII atom is in an octahedral environment coordinated by six O-atom donors from water molecules and ethane-1,1,2,2-tetracarboxylate ligands. The crystal structure features a three-dimensional hydrogen-bonding network based on a strong and distinctive pattern of O—H...O hydrogen-bonding interactions.

  19. The use of Agrobacterium tumefacients immobilized on Amberlite XAD-4 as a new biosorbent for the column preconcentration of iron(III), cobalt(II), manganese(II) and chromium(III).

    Science.gov (United States)

    Baytak, Sıtkı; Türker, A Rehber

    2005-02-28

    A microorganism Agrobacterium tumefacients as an immobilized cell on a solid support was presented as a new biosorbent for the enrichment of Fe(III), Co(II), Mn(II) and Cr(III) prior to flame atomic absorption spectrometric analysis. Amberlite XAD-4 was used as a support material for column preconcentration. Various parameters such as pH, amount of adsorbent, eluent type and volume, flow rate of sample solution, volume of sample solution and matrix interference effect on the retention of the metal ions have been studied. The optimum pH for the sorption of above mentioned metal ions were about 6, 8, 8 and 6, respectively. The loading capacity of adsorbent for Co(II) and Mn(II) were found to be 29 and 22mumolg(-1), respectively. The recoveries of Fe(III), Co(II), Mn(II) and Cr(III), under the optimum conditions were found to be 99 +/- 3, 99 +/- 2, 98 +/- 3 and 98 +/- 3%, respectively, at the 95% confidence level. The limit of detection was 3.6, 3.0, 2.8 and 3.6ngml(-1) for Fe(III), Co(II), Mn(II) and Cr (III), respectively, by applying a preconcentration factor of 25. The proposed enrichment method was applied for metal ion determination from water samples, alloy samples, infant foods and certified samples such as whey powder (IAEA-155) and aluminum alloy (NBS SRM 85b). The analytes were determined with a relative error lower than 10% in all samples.

  20. Biogeochemical cycling of manganese in Oneida Lake, New York: whole lake studies of manganese

    Science.gov (United States)

    Aguilar, C.; Nealson, K. H.

    1998-01-01

    Oneida Lake, New York is a eutrophic freshwater lake known for its abundant manganese nodules and a dynamic manganese cycle. Temporal and spatial distribution of soluble and particulate manganese in the water column of the lake were analyzed over a 3-year period and correlated with other variables such as oxygen, pH, and temperature. Only data from 1988 are shown. Manganese is removed from the water column in the spring via conversion to particulate form and deposited in the bottom sediments. This removal is due to biological factors, as the lake Eh/pH conditions alone can not account for the oxidation of the soluble manganese Mn(II). During the summer months the manganese from microbial reduction moves from the sediments to the water column. In periods of stratification the soluble Mn(II) builds up to concentrations of 20 micromoles or more in the bottom waters. When mixing occurs, the soluble Mn(II) is rapidly removed via oxidation. This cycle occurs more than once during the summer, with each manganese atom probably being used several times for the oxidation of organic carbon. At the end of the fall, whole lake concentrations of manganese stabilize, and remain at about 1 micromole until the following summer, when the cycle begins again. Inputs and outflows from the lake indicate that the active Mn cycle is primarily internal, with a small accumulation each year into ferromanganese nodules located in the oxic zones of the lake.

  1. Synthesis and Structural Studies of Some Inorganic Polymers of Succinoyl Carboxymethyl Cellulose

    Directory of Open Access Journals (Sweden)

    H. D. Juneja

    2011-01-01

    Full Text Available The inorganic polymers containing transition metals such as Mn(II, Co(II, Ni(II, Cu(II and Zn(II were synthesized by using succinoyl carboxymethyl cellulose (SCMC in aqueous media. The newly synthesized polymers were characterized by elemental analysis, IR spectroscopy, TG analysis, UV reflectance spectra and magnetic moment. On the basis of these studies, the composition of the polymeric unit was found to be [M(IIL]n, [Mʼ(IIL.2H2 O]n, {[Mˮ(IIL.2H2O]n H2O}, where M= Zn(II, Mʼ = Mn(II, Ni(II and Cu(II and Mˮ = Co(II, L = SCMC ligand. On the basis of instrumental techniques, it has been found that the [Zn(II(SCMC]n inorganic polymer has tetrahedral geometry, whereas {[Cu(II(SCMC].2H2O}n has square planar geometry and [Mn(II(SCMC.2H2O]n, {[Co(II(SCMC.2H2O].H2O}n and [Ni(II (SCMC.2H2O]n have octahedral geometry. The decomposition temperatures of the inorganic polymers have been determined by TGA. The TGA reveal that the Mn(II polymer of SCMC is highly thermally stable than rest of the polymers and these polymers can be used as thermal resisting materials.

  2. On the role of Mn(IV) vacancies in the photoreductive dissolution of hexagonal birnessite

    Energy Technology Data Exchange (ETDEWEB)

    Kwon, K.D.; Refson, K.; Sposito, G.

    2009-06-01

    Photoreductive dissolution of layer type Mn(IV) oxides (birnessite) under sunlight illumination to form soluble Mn(II) has been observed in both field and laboratory settings, leading to a consensus that this process is a key driver of the biogeochemical cycling of Mn in the euphotic zones of marine and freshwater ecosystems. However, the underlying mechanisms for the process remain unknown, although they have been linked to the semiconducting characteristics of hexagonal birnessite, the ubiquitous Mn(IV) oxide produced mainly by bacterial oxidation of soluble Mn(II). One of the universal properties of this biogenic mineral is the presence of Mn(IV) vacancies, long-identified as strong adsorption sites for metal cations. In this paper, the possible role of Mn vacancies in photoreductive dissolution is investigated theoretically using quantum mechanical calculations based on spin-polarized density functional theory (DFT). Our DFT study demonstrates unequivocally that Mn vacancies significantly reduce the band-gap energy for hexagonal birnessite relative to a hypothetical vacancy-free MnO{sub 2} and thus would increase the concentration of photo-induced electrons available for Mn(IV) reduction upon illumination of the mineral by sunlight. Calculations of the charge distribution in the presence of vacancies, although not fully conclusive, show a clear separation of photo-induced electrons and holes, implying a slow recombination of these charge-carriers that facilitates the two-electron reduction of Mn(IV) to Mn(II).

  3. EVALUATING ARSENIC AND MANGANESE REMOVAL FROM WATER BY CHLORINE OXIDATION FOLLOWED BY CLARIFICATION

    Directory of Open Access Journals (Sweden)

    V. G. R. Pires

    2015-06-01

    Full Text Available AbstractThis paper investigates the simultaneous removal of arsenic [As(V or As(III] and manganese [Mn(II] from natural waters of low and high turbidity by clarification (with polyaluminum chloride and aluminum sulfate as primary coagulants associated or not with chlorine pre-oxidation. The results showed that the clarification process exhibited low Mn(II removal, that varied from 6% to 18% and from 19% to 27% for natural waters of low and high turbidity, respectively. The use of chlorine as pre-oxidant increased Mn(II removal up to 77% and was associated with the formation of birnessite. Regarding As(V removal by clarification, particularly for high turbidity water, a concentration lower than that established by the National Drinking Water Quality Standards (10 μg.L-1 was achieved in almost all tests. Oxidation preceding the clarification led to AsIII removal efficiencies from 80% to 90% for both coagulants and types of water.

  4. Permanganate-based synthesis of manganese oxide nanoparticles in ferritin

    Science.gov (United States)

    Olsen, Cameron R.; Smith, Trevor J.; Embley, Jacob S.; Maxfield, Jake H.; Hansen, Kameron R.; Peterson, J. Ryan; Henrichsen, Andrew M.; Erickson, Stephen D.; Buck, David C.; Colton, John S.; Watt, Richard K.

    2017-05-01

    This paper investigates the comproportionation reaction of MnII with {{{{MnO}}}4}- as a route for manganese oxide nanoparticle synthesis in the protein ferritin. We report that {{{{MnO}}}4}- serves as the electron acceptor and reacts with MnII in the presence of apoferritin to form manganese oxide cores inside the protein shell. Manganese loading into ferritin was studied under acidic, neutral, and basic conditions and the ratios of MnII and permanganate were varied at each pH. The manganese-containing ferritin samples were characterized by transmission electron microscopy, UV/Vis absorption, and by measuring the band gap energies for each sample. Manganese cores were deposited inside ferritin under both the acidic and basic conditions. All resulting manganese ferritin samples were found to be indirect band gap materials with band gap energies ranging from 1.01 to 1.34 eV. An increased UV/Vis absorption around 370 nm was observed for samples formed under acidic conditions, suggestive of MnO2 formation inside ferritin.

  5. Synthesis, structural characterization and antimicrobial activity evaluation of metal complexes of sparfloxacin

    Science.gov (United States)

    El-Gamel, Nadia E. A.; Zayed, M. A.

    2011-11-01

    The synthesis and characterization of binary Cu(II)- ( 1), Co(II)- ( 2), Ni(II)- ( 3), Mn(II)- ( 4), Cr(III)- ( 5), Fe(III)- ( 6), La(III)- ( 7), UO 2(VI)- ( 8) complexes with sparfloxacin ( HL1) and ternary Cu(II)- ( 9), Co(II)- ( 10), Ni(II)- ( 11), Mn(II)- ( 12), Cr(III)- ( 13), Fe(III)- ( 14), La(III)- ( 15), UO 2(VI)- ( 16) complexes with sparfloxacin ( HL1) and DL-alanine ( H2L2) complexes are reported using elemental analysis, molar conductance, magnetic susceptibility, IR, UV-Vis, thermal analysis and 1H-NMR spectral studies. The molar conductance measurements of all the complexes in DMF solution correspond to non-electrolytic nature. All complexes were of the high-spin type and found to have six-coordinate octahedral geometry except the Cu(II) complexes which were four coordinate, square planar and U- and La-atoms in the uranyl and lanthanide have a pentagonal bipyramidal coordination sphere. The antimicrobial activity of these complexes has been screened against two Gram-positive and two Gram-negative bacteria. Antifungal activity against two different fungi has been evaluated and compared with reference drug sparfloxacin. All the binary and ternary complexes showed remarkable potential antimicrobial activity higher than the recommended standard agents. Ni(II)- and Mn(II) complexes exhibited higher potency as compared to the parent drug against Gram-negative bacteria.

  6. Manganese(II)-catalyzed and clay-minerals-mediated reduction of chromium(VI) by citrate.

    Science.gov (United States)

    Sarkar, Binoy; Naidu, Ravi; Krishnamurti, Gummuluru S R; Megharaj, Mallavarapu

    2013-01-01

    Unlike lower valent iron (Fe), the potential role of lower valent manganese (Mn) in the reduction of hexavalent chromium (Cr(VI)) in soil is poorly documented. In this study, we report that citrate along with Mn(II) and clay minerals (montmorillonite and kaolinite) reduce Cr(VI) both in aqueous phase and in the presence of dissolved organic carbon (SDOC) extracted from a forest soil. The reduction was favorable at acidic pH (up to pH 5) and followed the pseudo-first-order kinetic model. The citrate (10 mM) + Mn(II) (182.02 μM) + clay minerals (3% w/v) system in SDOC accounted for complete reduction of Cr(VI) (192.32 μM) in about 72 h at pH 4.9. In this system, citrate was the reductant, Mn(II) was a catalyst, and the clay minerals acted as an accelerator for both the reductant and catalyst. The clay minerals also serve as a sink for Cr(III). This study reveals the underlying mechanism of the Mn(II)-induced reduction of Cr(VI) by organic ligand in the presence of clay minerals under certain environmental conditions.

  7. Synthesis and Structural Studies of Transition Metal Complexes with Bidentate Schiff Base Derived from 3-Acetyl-6-methyl-(2H-pyran-2,4(3H-dione

    Directory of Open Access Journals (Sweden)

    Praveen S. Mane

    2011-01-01

    Full Text Available The solid complexes of Cu(II, Ni(II, Co(II, Mn(II and Fe(III with Schiff base ligands derived from heterocyclic compounds 3-acetyl-6-methyl-(2H-pyran-2,4(3H-dione (Dehydroacetic acid and o-chloroaniline were synthesized and characterized by elemental analysis, conductance, magnetic, thermal, UV-Vis and 1H-NMR spectroscopy. The ligand field parameters have been evaluated for Cu(II, Ni(II, Co(II, Mn(II and Fe(III complexes which suggest an octahedral geometry for each of them. The magnetic moment and spectral data suggest the dimeric nature of Mn(II complexes with octahedral geometry. The fungicidal activities of the ligands and their metal complexes have been screened in vitro against Aspergillus niger and the percentage inhibition of the metal complexes is found to be increased considerably then that of their corresponding ligands and the order is Cu>Ni>Fe>Mn>Co.

  8. Effect of Mn(IV) on the biodegradation of polycyclic aromatic hydrocarbons under low-oxygen condition in mangrove sediment slurry.

    Science.gov (United States)

    Li, Chun-Hua; Ye, Chun; Wong, Yuk-Shan; Tam, Nora Fung-Yee

    2011-06-15

    This study investigated the effect of manganese [Mn(IV)] amendment on the anaerobic biodegradation of four mixed PAHs, namely fluorene (Fl), phenanthrene (Phe), fluoranthene (Flua) and pyrene (Pyr) under low-oxygen condition, with and without the inoculation of enriched PAH-degrading bacterial consortia, in mangrove sediment slurries. The results revealed that the addition of Mn(IV) significantly inhibited PAH biodegradation, the rate of which was about 31-70% lower than the one of the groups without Mn(IV) addition. The amendment of Mn(IV) also showed adverse effect on the population size of enriched PAH-degrading bacteria and bacterial activity. The analysis results on the concentrations of Mn(II) and Mn(IV) indicated that Mn(IV) was converted to Mn(II) fast, the latter was the predominate manganese form in the mangrove sediment slurries through the whole experimental period. The Mn(II) toxicity to microorganisms was considered the main reason for inhibition of the PAH-biodegradation. On the other hand, the inoculation of the enriched PAH-degrading consortia significantly enhanced the biodegradation rates of all four PAHs, and the biodegradation rates of 3-rings (Fl, Phe) and 4-rings (Flua, Pyr) PAHs were enhanced by 14-15% and 21-34%, respectively.

  9. (μ-2,2′-Bipyrimidine-κ4 N 1,N 1′:N 3,N 3′)bis­[triaqua­(sulfato-κO)manganese(II)

    Science.gov (United States)

    Ha, Kwang

    2011-01-01

    The title complex, [Mn2(SO4)2(C8H6N4)(H2O)6], is the second monoclinic polymorph [De Munno et al. (1995 ▶). Inorg. Chem. 34, 408–411; Hong et al. (1996 ▶). Polyhedron, 15, 447–452]. The asymmetric unit contains two crystallographically independent half-mol­ecules of the binuclear MnII complex; an inversion centre is located at the centroid of each complex. The two MnII atoms in each complex mol­ecules are bridged by a bis-chelating 2,2′-bipyrimidine (bpym) ligand and each MnII atom is six-coordinated in a considerably distorted octa­hedral environment defined by two N atoms of the bridging bpym ligand and four O atoms from one sulfato anionic ligand and three water mol­ecules. In the crystal, the complex mol­ecules are linked by O—H⋯O hydrogen bonds between the water and sulfato ligands, forming a three-dimensional network. PMID:22064892

  10. (μ-2,2′-Bipyrimidine-κ4N1,N1′:N3,N3′bis[triaqua(sulfato-κOmanganese(II

    Directory of Open Access Journals (Sweden)

    Kwang Ha

    2011-10-01

    Full Text Available The title complex, [Mn2(SO42(C8H6N4(H2O6], is the second monoclinic polymorph [De Munno et al. (1995. Inorg. Chem. 34, 408–411; Hong et al. (1996. Polyhedron, 15, 447–452]. The asymmetric unit contains two crystallographically independent half-molecules of the binuclear MnII complex; an inversion centre is located at the centroid of each complex. The two MnII atoms in each complex molecules are bridged by a bis-chelating 2,2′-bipyrimidine (bpym ligand and each MnII atom is six-coordinated in a considerably distorted octahedral environment defined by two N atoms of the bridging bpym ligand and four O atoms from one sulfato anionic ligand and three water molecules. In the crystal, the complex molecules are linked by O—H...O hydrogen bonds between the water and sulfato ligands, forming a three-dimensional network.

  11. Crystal structure of hexakis(dimethylformamide-κOmanganese(II decakis(dimethylformamide-1κ5O,2κ5O-[μ-octadecatungstodiphosphato(V-κO:κO′]dimanganate(II dimethylformamide disolvate

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    Fatma Dhifallah

    2016-06-01

    Full Text Available The crystal structure of the title compound, [Mn(C3H7NO6][{Mn(C3H7NO5}2(μ-P2W18O62]·2C3H7NO, reveals that the Wells–Dawson-type polyanion [P2W18O62]6−, through terminal O atoms from the belts, bridges two MnII octahedral complexes. In the complex anion [{Mn(dmf5}2(μ-P2W18O62]2−, located around a twofold rotation axis, the MnII ions are coordinated by five O atoms from dimethylformamide (dmf ligands and to a terminal O atom from the [P2W18O62]6− polyanion. Another MnII ion, located on an inversion centre, is coordinated by six O atoms from the dmf ligands and forms the [Mn(dmf6]2+ cation. The crystal components are connected through numerous weak C—H...O hydrogen bonds to construct a three-dimensional network.

  12. Biosorption of Cr(VI)_ and Cr(III)_Arthrobacter species

    CERN Document Server

    Gelagutashvili, E; Gurielidze, M

    2011-01-01

    The biosorption of Cr(VI)_ and Cr(III)_ Arthrobacter species (Arthrobacter globiformis and Arthrobacter oxidas) was studied simultaneous application dialysis and atomic absorption analysis. Also biosorption of Cr(VI) in the presence of Zn(II) during growth of Arthrobacter species and Cr(III) in the presence of Mn(II) were discussed. Comparative Cr(VI)_ and Cr(III)_ Arthrobacter species shown, that Cr(III) was more effectively adsorbed by both bacterium than Cr(VI). The adsorption capacity is the same for both the Chromium-Arthrobacter systems. The biosorption constants for Cr(III) is higher than for Cr(VI) 5.7-5.9- fold for both species. Comparative Freundlich biosorption characteristics Cr(VI) Arthrobacter species of living and dry cells shown, that capacity(n) is in both cases the same(1.25,1.35). Dry cells have larger biosorption constant for both species, than living cells. Biosorption characteristics (K) and (n) for A. oxidas are without Mn(II) and in the presence of Mn(II) 2.6 x 10-4 (K), 1.37 (n) and 2...

  13. Manganese-enhanced MRI of rat brain based on slow cerebral delivery of manganese(II) with silica-encapsulated Mn x Fe(1-x) O nanoparticles.

    Science.gov (United States)

    Chen, Wei; Lu, Fang; Chen, Chiao-Chi V; Mo, Kuan-Chi; Hung, Yann; Guo, Zhi-Xuan; Lin, Chia-Hui; Lin, Ming-Huang; Lin, Yu-Hsuan; Chang, Chen; Mou, Chung-Yuan

    2013-09-01

    In this work, we report a monodisperse bifunctional nanoparticle system, MIO@SiO2 -RITC, as an MRI contrast agent [core, manganese iron oxide (MIO); shell, amorphous silica conjugated with rhodamine B isothiocyanate (RITC)]. It was prepared by thermal decomposition and modified microemulsion methods. The nanoparticles with varying iron to manganese ratios displayed different saturated magnetizations and relaxivities. In vivo MRI of rats injected intravenously with MIO@SiO2-RITC nanoparticles exhibited enhancement of the T1 contrast in brain tissue, in particular a time-delayed enhancement in the hippocampus, pituitary gland, striatum and cerebellum. This is attributable to the gradual degradation of MIO@SiO2-RITC nanoparticles in the liver, resulting in the slow release of manganese(II) [Mn(II)] into the blood pool and, subsequently, accumulation in the brain tissue. Thus, T1-weighted contrast enhancement was clearly detected in the anatomic structure of the brain as time progressed. In addition, T2*-weighted images of the liver showed a gradual darkening effect. Here, we demonstrate the concept of the slow release of Mn(II) for neuroimaging. This new nanoparticle-based manganese contrast agent allows one simple intravenous injection (rather than multiple infusions) of Mn(II) precursor, and results in delineation of the detailed anatomic neuroarchitecture in MRI; hence, this provides the advantage of the long-term study of neural function. Copyright © 2013 John Wiley & Sons, Ltd.

  14. Direct observation of structurally encoded metal discrimination and ether bond formation in a heterodinuclear metalloprotein.

    Science.gov (United States)

    Griese, Julia J; Roos, Katarina; Cox, Nicholas; Shafaat, Hannah S; Branca, Rui M M; Lehtiö, Janne; Gräslund, Astrid; Lubitz, Wolfgang; Siegbahn, Per E M; Högbom, Martin

    2013-10-22

    Although metallocofactors are ubiquitous in enzyme catalysis, how metal binding specificity arises remains poorly understood, especially in the case of metals with similar primary ligand preferences such as manganese and iron. The biochemical selection of manganese over iron presents a particularly intricate problem because manganese is generally present in cells at a lower concentration than iron, while also having a lower predicted complex stability according to the Irving-Williams series (Mn(II) Zn(II)). Here we show that a heterodinuclear Mn/Fe cofactor with the same primary protein ligands in both metal sites self-assembles from Mn(II) and Fe(II) in vitro, thus diverging from the Irving-Williams series without requiring auxiliary factors such as metallochaperones. Crystallographic, spectroscopic, and computational data demonstrate that one of the two metal sites preferentially binds Fe(II) over Mn(II) as expected, whereas the other site is nonspecific, binding equal amounts of both metals in the absence of oxygen. Oxygen exposure results in further accumulation of the Mn/Fe cofactor, indicating that cofactor assembly is at least a two-step process governed by both the intrinsic metal specificity of the protein scaffold and additional effects exerted during oxygen binding or activation. We further show that the mixed-metal cofactor catalyzes a two-electron oxidation of the protein scaffold, yielding a tyrosine-valine ether cross-link. Theoretical modeling of the reaction by density functional theory suggests a multistep mechanism including a valyl radical intermediate.

  15. Evidence for the biogenic origin of manganese-enriched layers in Lake Superior sediments.

    Science.gov (United States)

    Palermo, Christine; Dittrich, Maria

    2016-04-01

    Manganese (Mn) and iron (Fe)-enriched sediment layers were discovered in Lake Superior within, above and below the oxic-anoxic interface. While the role of bacteria in redox reactions with Mn is known to be significant, little information exists about indigenous microbial communities in many freshwater environments. This study examined the bacterial communities of Mn-enriched layers in Lake Superior to identify the potential Mn(II) oxidizers responsible for the formation of Mn oxides. Anaerobic Mn(II) oxidation occurring in the Mn-enriched layers at the oxic-anoxic interface was investigated using Mn(II)-enriched cultures. High-resolution microscopic and spectroscopic investigations provided evidence of the biogenic formation of Mn oxides on cell surfaces. Spectroscopic mapping confirmed high levels of Mn in structures resembling biogenic Mn oxides. These structures were observed in enrichment cultures and in Mn-enriched layer sediment samples, indicating the significance of biogenic Mn oxidation occurring in situ. 16S ribosomal DNA pyrosequencing was used to identify the bacteria potentially responsible for Mnoxide formation in the enrichment cultures and Mn-enriched layers, revealing that the Mn-enriched layer contains classes with known Mn(II)-oxidizing members. Pyrosequencing of bacterial cultures suggested that these bacteria may be Bacillus strains, and that anaerobic microbial-mediated Mn(II) oxidation contributes to the formation of the layers.

  16. Synthesis, characterization and thermal study of some transition metal complexes of an asymmetrical tetradentate Schiff base ligand

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    ACHUT S. MUNDE

    2010-03-01

    Full Text Available Complexes of Cu(II, Ni(II, Co(II, Mn(II and Fe(III with an asymmetric tetradentate Schiff base ligand derived from dehydroacetic acid, 4-methyl-o-phenylenediamine and salicylic aldehyde were synthesized and characterized by elemental analysis, conductometry, magnetic susceptibility, UV–Vis, IR, 1H-NMR spectroscopy, X-ray diffraction analysis of powdered samples and thermal analysis, and screened for antimicrobial activity. The IR spectral data suggested that the ligand behaves as a dibasic tetadentate ligand towards the central metal ion with an ONNO donor atoms sequence. From the microanalytical data, the stoichiometry of the complexes 1:1 (metal:ligand was found. The physico-chemical data suggested square planar geometry for the Cu(II and Ni(II complexes and octahedral geometry for the Co(II, Mn(II and Fe(III complexes. The thermal behaviour (TGA/DTA of the complexes was studied and kinetic parameters were determined by Horowitz–Metzger and Coats–Redfern methods. The powder X-ray diffraction data suggested a monoclinic crystal system for the Co(II, Mn(II and Fe(III complexes. The ligand and their metal complexes were screened for antibacterial activity against Staphylococcus aureus and Escherichia coli and fungicidal activity against Aspergillus niger and Trichoderma viride.

  17. Syntheses, structures and magnetic properties of four-spin Mn-Imino nitroxide radical complexes

    Science.gov (United States)

    Lv, Xue-Hui; Yang, Shuai-Liang; Li, Yuan-Xia; Zhang, Chen-Xi; Wang, Qing-Lun

    2017-04-01

    Based on the nitroxide radicals, four-spin complexes [Mn(hfac)2(IMpPhCl)]2·NITpPhCl (1) and [Mn(hfac)2(IMmPhCl)]2·NITmPhCl (2) (IMpPhCl = 2-(4'-chlorophenyl)-4,4,5,5-tetramethylimidazoline-1-oxyl, IMmPhCl = 2-(3'-chlorophenyl)-4,4,5,5-tetramethylimidazoline-1-oxyl, hfac = hexafluoroacetylacetonate) have been synthesized and characterized by single-crystal X-ray diffraction. The X-ray crystal structure analyses show that the structures of the two compounds are similar and the imino nitroxide radical ligand acts as a bridge ligand linking two Mn(II) ions through the oxygen atom of the N-O group to form a four-spin system. Two kinds of nitroxide radicals: nitronyl nitroxide and imino nitroxide radicals coexist in the cyclic Mn(II) complexes. The magnetic studies show that there exists an antiferromagnetic interaction between Mn(II) ions and the imino nitroxide radical ligands, which is explained by spin polarization mechanism. The antiferromagnetic interaction of Mn-Rad in complex 2 (J1 = -9.36 cm-1) is stronger than that in complex 1 (J1 = -9.19 cm-1), which is consistent with crystal structure of complexes (The bond length of the shortest Mn-O in complex 2 (2.1625 Å) is smaller than complex 1 (2.1898 Å)).

  18. Synthesis and Structure of a Mn(II)-triazolyl Coordination Polymer Consisting of Dinuclear Units%Synthesis and Structure of a Mn(II)-triazolyl Coordination Polymer Consisting of Dinuclear Units

    Institute of Scientific and Technical Information of China (English)

    WU Tao; XU Hong-Yan; KONG Fan-Zhen; YU Zhang-Yu; WANG Rui-Hu

    2012-01-01

    The reaction of bis(1,2,4-triazolyl-4-yl) (btr) and MnClO4-6H20 gave rise to a Mn(II) complex comprised of unprecedented dinuclear Mn(II) units, {[Mn2(btr)s(H20)5]- (ClO4)4(H20)2]n (1). Single-crystal X-ray diffraction analysis revealed that 1 crystallizes in the monoclinic space group C2/c. btr adopts two types of bridging modes. One serves as μ-N1 :N2 bridge through one triazolyl ring of btr forming a dinuclear Mn(II) unit, and the other adopts an exo-bidentate mode using two nitrogen atoms from each triazolyl ring and links the dinuclear units into a 2D cationic layer. ClO4 acts as a counter anion and does not take part in coordination. Interestingly, 2D layers are packed in an ABCABC mode. ClO4- and uncoordinated water molecules locate between the adjacent layers, and extensive hydrogen bonds further stabilize the whole framework.

  19. Role of extracellular polymeric substances (EPS from Pseudomonas putida strain MnB1 in dissolution of natural rhodochrosite

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    H. Wang

    2014-05-01

    Full Text Available Microbially mediated oxidation of Mn(II to Mn oxides have been demonstrated in previous studies, however, the mechanisms of bacteria how to dissolve and oxidize using a solid Mn(II origin are poorly understood. In this study, we examined the role of extracellular polymeric substances (EPS from P. putida strain MnB1 in enhancing dissolution of natural rhodochrosite. The results showed that P. putida strain MnB1 cell can effectively dissolve and oxidize natural rhodochrosite to generate Mn oxides, and EPS were found to play an important role in increasing dissolution of natural rhodochrosite. Compared with EPS-free treatment, dissolution rate of natural rhodochrosite in the presence of bacterial EPS was significantly increased with decreasing initial pH and increasing EPS concentration, ionic strength and rhodochrosite dosage (p < 0.05. The fourier-transform infrared spectroscopy (FTIR analysis implies that the functional groups like N-H, C=O and C-H in EPS contributed to the dissolution of natural rhodochrosite. This study is helpful for understanding the mechanisms of the formation of biogenic Mn oxides using a solid Mn(II origin.

  20. Synthesis, crystal structure, spectroscopic characterization and nonlinear optical properties of manganese (II) complex of picolinate: A combined experimental and computational study

    Science.gov (United States)

    Tamer, Ömer; Avcı, Davut; Atalay, Yusuf; Çoşut, Bünyemin; Zorlu, Yunus; Erkovan, Mustafa; Yerli, Yusuf

    2016-02-01

    A novel manganese (II) complex with picolinic acid (pyridine 2-carboxylic acid, Hpic), namely, [Mn(pic)2(H2O)2] was prepared and its crystal structure was fully characterized by using single crystal X-ray diffraction. Picolinate (pic) ligands were coordinated to the central manganese(II) ion as bidentate N,O-donors through the nitrogen atoms of pyridine rings and the oxygen atoms of carboxylate groups forming five-membered chelate rings. The spectroscopic characterization of Mn(II) complex was performed by the applications of FT-IR, Raman, UV-vis and EPR techniques. In order to support these studies, density functional theory (DFT) calculations were carried out by using B3LYP level. IR and Raman spectra were simulated at B3LYP level, and obtained results indicated that DFT calculations generally give compatible results to the experimental ones. The electronic structure of the Mn(II) complex was predicted using time dependent DFT (TD-DFT) method with polarizable continuum model (PCM). Molecular stability, hyperconjugative interactions, intramolecular charge transfer (ICT) and bond strength were investigated by applying natural bond orbital (NBO) analysis. Nonlinear optical properties of Mn(II) complex were investigated by the determining of molecular polarizability (α) and hyperpolarizability (β) parameters.

  1. Microbial manganese oxide formation and interaction with toxic metal ions.

    Science.gov (United States)

    Miyata, Naoyuki; Tani, Yukinori; Sakata, Masahiro; Iwahori, Keisuke

    2007-07-01

    Diverse bacteria and fungi oxidize Mn(II) enzymatically and produce insoluble Mn(III, IV) oxides, and these organisms are considered to be the primal agents for the occurrence of natural Mn oxide phases in most environments. Biogenic Mn oxides have a high sorption capacity for metal cations and an ability to oxidize numerous inorganic and organic compounds, owing to their structural and redox features. Thus, the microbial process is of significance in both biogeochemical and biotechnological contexts. In this article we summarize the enzymatic Mn(II) oxidation and interactions of biogenic Mn oxides with toxic metal and metalloid ions. Although Mn oxide formation by fungi has not been fully characterized yet, recent researches with ascomycetes emphasize the similarity between the bacterial and fungal Mn(II) oxidation with respect to the involved catalyst (i.e., multicopper oxidase-type enzymes) and the reaction product [i.e., layer-type Mn(IV) oxides]. Laboratory cultures of bacterial and fungal Mn oxidizers are expected to provide fundamental knowledge in their potential use for remediation of environments and effluents contaminated with toxic metal(loid) ions.

  2. The Zintl Chemistry of the Heavy Tetrel Elements

    Energy Technology Data Exchange (ETDEWEB)

    John D. Corbett

    2002-12-31

    Exploration of the alkali metal/alkaline-earth metal/heavy tetrel (Sn or Pb) systems has revealed a vast array of new chemistry and novel structure types. The structures and properties of these new materials have been studied in an attempt to understand the chemistry of these and other related systems. The first phase reported is Rb{sub 4}Pb{sub 9} (K{sub 4}Pb{sub 9} type). The compound contains two different types of Pb{sub 9}{sup 4-} deltahedra, a monocapped square pyramid and a distorted tricapped trigonal prism. Both cluster geometries correspond to a nido assignment even though the tricapped trigonal prism is not the classic Wade's rules nido deltahedron expected for a monocapped square antiprism. Also, a series of compounds that contain square pyramidal Tt{sub 5} polyanions of tin and lead has been obtained in alkaline-earth or rare-earth metal-tetrel systems by direct fusion of the elements to yield Sr{sub 3}Sn{sub 5}, Ba{sub 3}Pb{sub 5}, and La{sub 3}Sn{sub 5}. These phases contain square pyramidal clusters of the tetrel elements that are weakly interlinked into chains via two types of longer intercluster interactions that are mediated by bridging cations and substantially influenced by cation size and the free electron count. Attempts at incorporating another main-group element to form heteroatomic clusters were also successful. In the case of A{sub 5}InPb{sub 8} (A = K, Rb), the compounds contain clusters composed of two Pb{sub 4} tetrahedra that are interbridged by a lone {micro}{sub 6}-In atom. The InPb{sub 8} units are weakly interlinked into sheets in the ab plane by long intercluster Pb-Pb interactions. Using As led to the formation of the compound K{sub 5}As{sub 3}Pb{sub 3} which is made up of As{sub 3}Pb{sub 3}{sup 5-} crown clusters that can be likened to a 6-atom hypho-cluster based on the tricapped trigonal parent as the closo structure. These crowns are connected via intercluster bonds to form infinite chains down the b axis. This work

  3. Structure and magnetic exchange in heterometallic 3d-3d transition metal triethanolamine clusters.

    Science.gov (United States)

    Langley, Stuart K; Chilton, Nicholas F; Moubaraki, Boujemaa; Murray, Keith S

    2012-01-21

    Synthetic methods are described that have resulted in the formation of seven heterometallic complexes, all of which contain partially deprotonated forms of the ligand triethanolamine (teaH(3)). These compounds are [Mn(III)(4)Co(III)(2)Co(II)(2)O(2)(teaH(2))(2)(teaH)(0.82)(dea)(3.18)(O(2)CMe)(2)(OMe)(2)](BF(4))(2)(O(2)CMe)(2)·3.18MeOH·H(2)O (1), [Mn(II)(2)Mn(III)(2)Co(III)(2)(teaH)(4)(OMe)(2)(acac)(4)](NO(3))(2)·2MeOH (2), [Mn(III)(2)Ni(II)(4)(teaH)(4)(O(2)CMe)(6)]·2MeCN (3), [Mn(III)(2)Co(II)(2)(teaH)(2)(sal)(2)(acac)(2)(MeOH)(2)]·2MeOH (4), [Mn(II)(2)Fe(III)(2)(teaH)(2)(paa)(4)](NO(3))(2)·2MeOH·CH(2)Cl(2) (5), [Mn(II)Mn(III)(2)Co(III)(2)O(teaH)(2)(dea)(Iso)(OMe)(F)(2)(Phen)(2)](BF(4))(NO(3))·3MeOH (6) and [Mn(II)(2)Mn(III)Co(III)(2)(OH)(teaH)(3)(teaH(2))(acac)(3)](NO(3))(2)·3CH(2)Cl(2) (7). All of the compounds contain manganese, combined with 3d transition metal ions such as Fe, Co and Ni. The crystal structures are described and examples of 'rods', tetranuclear 'butterfly' and 'triangular' Mn(3) cluster motifs, flanked in some cases by diamagnetic cobalt(III) centres, are presented. Detailed DC and AC magnetic susceptibility and magnetization studies, combined with spin Hamiltonian analysis, have yielded J values and identified the spin ground states. In most cases, the energies of the low-lying excited states have also been obtained. The features of note include the 'inverse butterfly' spin arrangement in 2, 4 and 5. A S = 5/2 ground state occurs, for the first time, in the Mn(III)(2)Mn(II) triangular moiety within 6, the many other reported [Mn(3)O](6+) examples having S = ½ or 3/2 ground states. Compound 7 provides the first example of a Mn(II)(2)Mn(III) triangle, here within a pentanuclear Mn(3)Co(2) cluster.

  4. Microbial Manganese Oxidation in Saltmarsh Surface Sediments Using a Leuco Crystal Violet Manganese Oxide Detection Technique

    Science.gov (United States)

    Spratt, Henry G.; Siekmann, Ellen C.; Hodson, Robert E.

    1994-01-01

    Microbial manganese (Mn) oxide production in surface sediments of a Georgia saltmarsh was directly measured using an assay involving the oxidation of 4,4',4″-methylidynetris (N,N-dimethylaniline), leuco crystal violet (LCV), by Mn oxides to produce crystal violet. The assay exhibits high specificity for Mn oxides without interference by Mn(II) and is sufficiently sensitive to determine rates of Mn oxidation in surface sediment or saltmarsh creek water suspensions. Sample salinity affects crystal violet absorbance in the 0-25 salinity range and must be corrected for in Mn oxide determinations for estuarine samples of variable salinity. Other oxidants found to oxidize LCV slowly included Cl(I), Cr(III), I(V), Fe(III), and Mn(III), although the sensitivity of the assay for Mn(IV) oxides was found to be seven times greater than for Mn(III), and at least 100 times greater than for any of the other oxidants. Rates of abiotic Mn oxide production in sediment suspensions treated with either sodium azide or formalin, or autoclaved, were much slower than rates determined for untreated sediments. Sodium azide (7·7 mM) inhibited Mn oxide production in these sediment suspensions to rates between 5 and 10% of the rates of Mn oxidation determined for unamended suspensions. Manganese oxidation was highly temperature dependent, with maximal rates on a dry weight basis (8·9 nmol mg dwt -1 h -1), occurring at 60°C, and negligible activity at 100 and 0°C. Rates were also dependent on sample pH, with maximal rates at pH 6·7, decreasing to near 0 as the pH was lowered to approximately 3·0. For Mn(II) concentrations ranging from 9 to 91 μM, rates of Mn oxide production were independent of Mn(II) concentration, while Mn oxide production was inhibited at concentrations greater than 91 μM (e.g. by 25-40% at 450 μM). Rates of microbial Mn oxide production in surface sediment/saltmarsh creek water suspensions incubated under natural conditions of temperature, pH, and Mn(II

  5. High Tc ferrimagnetic organic-inorganic hybrid materials with MnII-L-MnII and MnII-NC-NbIV linkages (L=pyrazine, pyrazine-N,N'-dioxide, bipyrimidine).

    Science.gov (United States)

    Podgajny, Robert; Pinkowicz, Dawid; Korzeniak, Tomasz; Nitek, Wojciech; Rams, Michał; Sieklucka, Barbara

    2007-11-26

    A series of heterobimetallic, cyano-bridged 3D inorganic-organic hybrid networks with MnII-L-MnII and MnII-NC-NbIV linkages are reported. Reaction of [Mn(H2O)6]2+ with [Nb(CN)8]4- in the presence of organic linker L (pyrazine (pyz), pyrazine-N,N'-dioxide (pzdo), and 2,2'-bipyrimidine (bpym)) in H2O affords {MnII2(pz)2(H2O)4[NbIV(CN)8]}.pz.3H2O (1), {MnII2(pzdo)(H2O)4[NbIV(CN)8]}.5H2O (2), and {MnII2(bpym)(H2O)2[NbIV(CN)8]} (3), respectively. 1-3 were examined by X-ray crystallography and vibrational and magnetochemical studies. 1 is characterized by the coexistence of 3D inorganic cyano-bridged and 1D organic [Mn-(micro-pyz)]n2n+ sublattices along with the presence of monocoordinated and crystallization molecules of pyrazine. Assemblies 2 and 3 exhibit dimeric {MnII2-(micro-L)}4+ coordination motifs. The magnetic behavior of heterobimetallic 1-3 complexes is dominated by antiferromagnetic coupling between MnII and NbIV centers mediated by cyano bridges, resulting in long-range ferrimagnetic ordering with a high TC of 27 (1), 37 (2), and 50 K (3). The magneto-structural correlation leads to the conclusion that the magnitude of TC is related to the type of coordination polyhedra of [Nb(CN)8] moieties (SAPR (1), intermediate between SAPR and DD (2), and DD (3)), the relative number of cyano bridges per Mn2Nb unit, and coexistence of inorganic and organic connectivity. FC/ZFC responses appear to be sensitive to the degree of organic connectivity. The discussion of magneto-structural correlation is based on the spin-density properties of adequate heterobimetallic systems containing octacyanometalates.

  6. Understanding the Development and Stabilization of Mn(III) Intermediates during Microbial Manganese Reduction

    Science.gov (United States)

    Johnson, J. E.; Savalia, P.; Kocar, B. D.; Webb, S. M.; Nealson, K. H.; Fischer, W. W.

    2014-12-01

    The dominant products of Mn(II) oxidation are manganese(IV)-oxide phases, which act as important environmental oxidants and sorbents in soils, freshwater, and marine sediments. Mn(IV) oxides also provide favorable electron acceptors for metal-reducing microbes, but the intermediates and final products formed are highly dependent on environmental conditions, and challenging to predict thermodynamically. We engineered a flow-through reactor system to study the Mn phases during microbial Mn(IV) reduction by Shewanella oneidensis MR-1 in real time, using synchrotron X-ray absorption spectroscopy (XAS) to monitor redox and mineralogical changes. These 10-20 hour experiments capture Mn XAS spectra every 20 minutes and thus we can observe both transient phases and stable products under different experimental conditions. We also record the pH, collect solution and filtered solid samples throughout the experiments for later solute measurements, and confirm mineral identifications with synchrotron x-ray diffraction measurements. With excess organic carbon and high (mM) phosphate (like in a soil), Mn(IV) oxides are reduced to Mn(II) and immediately form Mn(II) phosphate in a clearly binary system. This experiment demonstrates that while there may be two successive single-electron transfer reactions from outer membrane cytochromes (Lin et al, 2012), the microbial reduction of Mn(IV) oxides is effectively a two-electron process. However, with minimal phosphate, a transient Mn(III) oxyhydroxide forms before all manganese is reduced to Mn(II) in solution and precipitates a final Mn(II)-carbonate product. We propose this Mn(III) intermediate phase forms due to reaction of Mn2+ in solution with Mn(IV)-oxide surfaces to form Mn(III)OOH, similar to experimental results from this abiotic comproportionation reaction (Elzinga, 2011). Recently, we stabilized this Mn(III) intermediate by limiting the organic carbon available to S. oneidensis, producing Mn(III)OOH and Mn(II) phases

  7. Structure-redox-relaxivity relationships for redox responsive manganese-based magnetic resonance imaging probes.

    Science.gov (United States)

    Gale, Eric M; Mukherjee, Shreya; Liu, Cynthia; Loving, Galen S; Caravan, Peter

    2014-10-06

    A library of 10 Mn-containing complexes capable of switching reversibly between the Mn(II) and Mn(III) oxidation states was prepared and evaluated for potential usage as MRI reporters of tissue redox activity. We synthesized N-(2-hydroxybenzyl)-N,N',N'-ethylenediaminetriacetic acid (HBET) and N-(2-hydroxybenzyl-N,N',N'-trans-1,2-cyclohexylenediaminetriacetic acid (CyHBET) ligands functionalized (-H, -OMe, -NO2) at the 5-position of the aromatic ring. The Mn(II) complexes of all ligands and the Mn(III) complexes of the 5-H and 5-NO2 functionalized ligands were synthesized and isolated, but the Mn(III) complexes with the 5-OMe functionalized ligands were unstable. (1)H relaxivity of the 10 isolable complexes was measured at pH 7.4 and 37 °C, 1.4 T. Thermodynamic stability, pH-dependent complex speciation, hydration state, water exchange kinetics of the Mn(II) complexes, and pseudo-first order reduction kinetics of the Mn(III) complexes were studied using a combination of pH-potentiometry, UV-vis spectroscopy, and (1)H and (17)O NMR measurements. The effects of ligand structural and electronic modifications on the Mn(II/III) redox couple were studied by cyclic voltammetry. The Mn(II) complexes are potent relaxation agents as compared to the corresponding Mn(III) species with [Mn(II)(CyHBET)(H2O)](2-) exhibiting a 7.5-fold higher relaxivity (3.3 mM(-1) s(-1)) than the oxidized form (0.4 mM(-1) s(-1)). At pH 7.4, Mn(II) exists as a mixture of fully deprotonated (ML) and monoprotonated (HML) complexes and Mn(II) complex stability decreases as the ligands become more electron-releasing (pMn for 10 μM [Mn(II)(CyHBET-R')(H2O)](2-) decreases from 7.6 to 6.2 as R' goes from -NO2 to -OMe, respectively). HML speciation increases as the electron-releasing nature of the phenolato-O donor increases. The presence of a water coligand is maintained upon conversion from HML to ML, but the water exchange rate of ML is faster by up to 2 orders of magnitude (k(ex)(310) for H

  8. Two actinide-organic frameworks constructed by a tripodal flexible ligand: Occurrence of infinite {(UO2)O2(OH)3}4n and hexanuclear {Th6O4(OH)4} motifs

    Science.gov (United States)

    Liang, Lingling; Zhang, Ronglan; Zhao, Jianshe; Liu, Chiyang; Weng, Ng Seik

    2016-11-01

    Two new actinide metal-organic frameworks were constructed by using a tripodal flexible ligand tris (2-carboxyethyl) isocyanurate (H3tci) under hydrothermal condition. The combination of H3tci and uranyl nitrate hexahydrate in aqueous solution leads to the isolation of [(UO2)2(H2O)4]0.5(tci)2(UO2)4(OH)4·18H2O (1), which contains two distinct UO22+ coordination environments. Four uranyl cations, linked through μ3-OH respectively, result in the edge-sharing ribbons. Then, the layer structure is constructed by U-O clusters linked through other eight-coordinated uranyl unions, giving rise to a porous structure in the space. Topological analysis reveals that complex 1 belongs to a (4, 8)-connected net with a schläfli symbol of (34.26.3)2(34.46.56.68.73.8). Th3(tci)2O2(OH)2(H2O)3·12H2O (2) generated by the reaction of H3tci and thorium nitrate tetrahydrate, possesses nine-fold coodinated Th(IV) centers with a monocapped square antiprismatic geometry. The hexamers "Th6O4(OH)4" motifs are connected together by the carboxylate groups, showing a three-dimensional structures. Complex 2 takes on an 8-connected architecture and the point symbol is (424.64).

  9. Synthesis and Structural Determination of Nine-Coordinate K[GdIII(edta)(H2O)3]·5H2O

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    The title complex K[GdIII(edta)(H2O)3]·5H2O was synthesized, where edta denotes ethylenediamine-tetraacetic acid. The crystal and molecular structure of the complex were determined by single-crystal X-ray structure analysis. The crystal belongs to an orthorhombic crystal system and an Fdd2 space group. The complex anion [GdIII(edta)(H2O)3]- has a pseudo-monocapped square antiprismatic nine-coordinate structure in which six coordinate atoms (two N and four O) are from an edta ligand and three water molecules coordinate to GdIII ion directly. It can be predicted that GdIII ion can also form a nine-coordinate complex with ttha (triethylenetetraminehexaacetic acid) ligand, so the GdIII complex anion [GdIII(Httha)]2- can supply a free non-coordinate carboxyl group used for molecular embellishment in some biological molecules to form a contrast agent of Magnetic Resonance Imagine (MRI) with targeting function.

  10. Poly[[diaqua-μ3-citrato-praseodymium(III] monohydrate

    Directory of Open Access Journals (Sweden)

    Li-Jun Han

    2011-07-01

    Full Text Available In the coordination polymer, {[Pr(C6H5O7(H2O2]·H2O}n, seven of the nine coordination sites of the monocapped square-antiprismatic geometry are occupied by three O atoms of the same citrate trianion (an O atom of the hydroxy unit and the formally single-bond O atoms from two carboxyl units. Two other coordination sites are occupied by the O atoms of a chelating carboxyl unit of another citrate; one of these atoms is additionally involved in bridging. The seventh coordination site is occupied by the O atom of the formally double-bond O atom of a neighboring citrate. The remaining two coordination sites are occupied by water molecules. The citrate functions in a μ3-bridging mode, connecting the metal atoms into a ribbon structure parallel to [010]. The structure is consolidated into a three-dimensional network by O—H...O hydrogen bonds.

  11. Crystal structures of Na2SeO4·1.5H2O and Na2SeO4·10H2O

    Directory of Open Access Journals (Sweden)

    Matthias Weil

    2014-08-01

    Full Text Available The crystal structures of Na2SeO4·1.5H2O (sodium selenate sesquihydrate and Na2SeO4·10H2O (sodium selenate decahydrate are isotypic with those of Na2CrO4·1.5H2O and Na2XSeO4·10H2O (X = S, Cr, respectively. The asymmetric unit of the sesquihydrate contains two Na+ cations, one SeO4 tetrahedron and one and a half water molecules, the other half being generated by twofold rotation symmetry. The coordination polyhedra of the cations are a distorted monocapped octahedron and a square pyramid; these [NaOx] polyhedra are linked through common edges and corners into a three-dimensional framework structure, the voids of which are filled with the Se atoms of the SeO4 tetrahedra. The structure is consolidated by O—H...O hydrogen bonds between coordinating water molecules and framework O atoms. The asymmetric unit of the decahydrate consists of two Na+ cations, one SeO4 tetrahedron and ten water molecules. Both Na+ cations are octahedrally surrounded by water molecules and by edge-sharing condensed into zigzag chains extending parallel to [001]. The SeO4 tetrahedra and two uncoordinating water molecules are situated between the chains and are connected to the chains through an intricate network of medium-strength O—H...O hydrogen bonds.

  12. Ferromagnetic coupling in the three-dimensional malonato-bridged gadoliniumIII complex [Gd2(mal)3(H2O)6] (H2mal = malonic acid).

    Science.gov (United States)

    Hernández-Molina, María; Ruiz-Pérez, Catalina; López, Trinidad; Lloret, Francesc; Julve, Miguel

    2003-09-08

    The novel gadolinium(III) complex of formula [Gd(2)(mal)(3)(H(2)O)(6)] (1) (H(2)mal = 1,3-propanedioic acid) has been prepared and characterized by X-ray diffraction analysis. Crystal data for 1: monoclinic, space group I2/a, a = 11.1064(10) A, b = 12.2524(10) A, c =13.6098(2) A, beta = 92.925(10) degrees, U = 1849.5(3) A(3), Z = 4. Compound 1 is a three-dimensional network made up of malonate-bridged gadolinium(III) ions where the malonate exhibits two bridging modes, eta(5)-bidentate + unidentate and eta(3):eta(3) + bis(unidentate). The gadolinium atom is nine-coordinate with three water molecules and six malonate oxygen atoms from three malonate ligands forming a distorted monocapped square antiprism. The shortest metal-metal separations are 4.2763(3) A [through the oxo-carboxylate bridge] and 6.541(3) A [through the carboxylate in the anti-syn coordination mode]. The value of the angle at the oxo-carboxylate atom is 116.8(2) degrees. Variable-temperature magnetic susceptibility measurements reveal the occurrence of a significant ferromagnetic interaction through the oxo-carboxylate pathway (J = +0.048(1) cm(-1), H = -JS(Gd(1)) x S(Gd(1a))).

  13. Structural rearrangement through lanthanide contraction in dinuclear complexes.

    Science.gov (United States)

    Hutchings, Amy-Jayne; Habib, Fatemah; Holmberg, Rebecca J; Korobkov, Ilia; Murugesu, Muralee

    2014-02-17

    A new series of lanthanide complexes was synthesized, and the geometry and preliminary magnetic measurements of the complexes were explored. The specific ligand used (N'-(2-hydroxy-3-methoxybenzylidene)benzhydrazide) (H2hmb) was synthesized using a Schiff-base approach and was employed due to the presence of a coordination pocket that is able to accommodate magnetically selective lanthanide ions. The series can be divided into two groups that are categorized by a drastic structural rearrangement. The first group, Type I, contains six analogous complexes with the formula [M(III)2(Hhmb)3(NCS)3]·2MeOH·py (M = Y 1, Eu 2, Gd 3, Tb 4, Dy 5, Ho 6), while the second group, Type II, contains two dinuclear complexes with formula [M(III)2(Hhmb)2(NCS)4(MeOH)2] (M = Er 7, and Yb 8). Single-crystal X-ray analysis revealed that all M(III) ions in Type I exhibit monocapped distorted square antiprismatic geometries, while those of Type II exhibit distorted dodecahedron geometry. The direct current and alternating current magnetic measurements were carried out on all complexes, with 5, 7, and 8 exhibiting slow relaxation of the magnetization under an applied optimum dc field. Furthermore, complex 8 is the first example of a dinuclear Yb-based single-molecule magnet showing field-dependent multiple relaxation processes.

  14. Cristallochimie de Tl III6Te VIO 12 et Tl I6Te VIO 6E 6: un exemple original de l'activitéstéréochimique de la paireélectronique 6s 2(E) du thallium(I)

    Science.gov (United States)

    Frit, Bernard; Roult, Georges; Galy, Jean

    1983-07-01

    Both crystal structures of Tl 6TeO 12 and Tl 6TeO 6E 6 compounds have been determined, the former by X-ray single crystal techniques, the latter by powder neutron diffraction techniques. They crystallize in the trigonal system, space group R3¯ the corresponding hexagonal cell parameters are a = 9.645(2) Å, c = 9.421(2) Å, and a = 9.5722(3) Å, c = 9.3494(4) Å, respectively, with Z = 3. In both compounds tellurium(VI) is octahedrally coordinated to oxygen atoms with Te sbnd O distances of 1.936Åfor the Tl(III)-containing compound, i.e., Tl 6TeO 12, and 1.946Åfor Tl 6TeO 6 (Tl(I)). Tl(III) is surrounded by seven oxygen atoms sitting at the summits of a distorted monocapped trigonal prism. Tl(I) is linked to three oxygen atoms, forming a distorted TlO 3 pyramid. The lone pairs brought by Tl(I) are in the positions precedingly occupied by oxygen atoms in the crystal structure of Tl 6TeO 12. This is an outstanding example of the crystallochemical role of the lone pairs E which act like oxygen atoms, making Tl I6Te VIO 6E 6 isostructural with Tl IIITe VIO 12. Structural relationships with fluorite type network are discussed.

  15. Tris(2-ethylamino)amine ( tren) as template for the elaboration of fluorides: synthesis and crystal structures of [(C 2H 4NH 3) 3NH]·[Zr 3F 16(H 2O)], [(C 2H 4NH 3) 3N] 2·[ZrF 6]·[Zr 2F 12] and [(C 2H 4NH 3) 3N]·[TaF 7]·F

    Science.gov (United States)

    Goreshnik, E.; Leblanc, M.; Maisonneuve, V.

    2004-11-01

    Using tris(2-ethylamino)amine ( tren) as a template, three new fluorides are obtained by solvothermal synthesis: [(C 2H 4NH 3) 3NH]·[Zr 3F 16(H 2O)] ( I), [(C 2H 4NH 3) 3N] 2·[ZrF 6]·[Zr 2F 12] ( II) and [(C 2H 4NH 3) 3N]·[TaF 7]·F ( III). The structure determinations are performed by single crystal technique. The structure of I consists of infinite spiral-like [Zr 3F 16(H 2O)] 4- chains connected by tetraprotonated [ trenH 4] 4+ cations which possess a plane configuration. In II, isolated [ZrF 6] octahedra or [Zr 2F 12] dimers are linked to organic cations by a tridimensional hydrogen bond network. In III, [TaF 7] 2- monocapped trigonal prisms and "isolated" fluoride ions are connected by hydrogen bonds to template moieties. In II and III, every organic moiety is triprotonated [ trenH 3] 3+ with a "spider" configuration. In the tantalum phase, the hydrogen bond network leads to the formation of a layered structure.

  16. Poly[tetra-μ-aqua-diaquatetrakis[μ-(E-2-nitrocinnamato]tetrarubidium

    Directory of Open Access Journals (Sweden)

    Graham Smith

    2011-11-01

    Full Text Available In the structure of the title compound, [Rb4(C9H6NO44(H2O6]n, the asymmetric unit comprises four rubidium cations, two of which have an RbO7 coordination polyhedron with a monocapped distorted octahedral stereochemistry and two of which have a distorted RbO6 octahedral coordination. The bonding about both the seven-coordinate cations is similar, comprising one monodentate water molecule together with three bridging water molecules and three carboxylate O-atom donors, two of which are bridging. The environments around the six-coordinate cations are also similar, comprising a monodentate nitro O-atom donor, a bridging water molecule and four bridging carboxylate O-atom donors [overall Rb—O range = 2.849 (2–3.190 (2 Å]. The coordination leads to a two-dimensional polymeric structure extending parallel to (001, which is stabilized by interlayer water O—H...O hydrogen-bonding associations to water, carboxyl and nitro O-atom acceptors, together with weak inter-ring π–π interactions [minimum ring centroid–centroid separation = 3.5319 (19 Å].

  17. Characterization of structure and dynamics of an aqueous scandium(III) ion by an extended ab initio QM/MM molecular dynamics simulation.

    Science.gov (United States)

    Vchirawongkwin, Viwat; Kritayakornupong, Chinapong; Tongraar, Anan; Rode, Bernd M

    2012-10-14

    Hydration structure and dynamics of an aqueous Sc(III) solution were characterized by means of an extended ab initio quantum mechanical/molecular dynamical (QM/MM) molecular dynamics simulation at Hartree-Fock level. A monocapped trigonal prismatic structure composed of seven water molecules surrounding scandium(III) ion was proposed by the QM/MM simulation including the quantum mechanical effects for the first and second hydration shells. The mean Sc(III)-O bond length of 2.14 Å was identified for six prism water molecules with one capping water located at around 2.26 Å, reproducing well the X-ray diffraction data. The Sc(III)-O stretching frequency of 432 cm(-1) corresponding to a force constant of 130 N m(-1), evaluated from the enlarged QM/MM simulation, is in good agreement with the experimentally determined value of 430 cm(-1) (128 N m(-1)). Various water exchange processes in the second hydration shell of the hydrated Sc(III) ion predict a mean ligand residence time of 7.3 ps.

  18. catena-Poly[lead(II-[μ-2,4-diamino-6-(piperidin-1-ylpyrimidine N-oxide-κ2O:O]di-μ-iodido

    Directory of Open Access Journals (Sweden)

    Maryam Ranjbar

    2009-07-01

    Full Text Available The N-oxide O atom of the minoxidil unit in the 1/1 adduct with lead(II iodide, [PbI2(C9H15N5O]n, bridges two PbII atoms, as do each of the I atoms. The bridging interactions give rise to a linear chain motif that propagates along the a axis of the orthorhombic unit cell. The coordination sphere around the six-coordinate PbII atom is a distorted ψ-monocapped octahedron in which the stereochemically active lone pair caps one of the faces defined by the O and I atoms forming the longer Pb—O or Pb—I bonds. The PbII atom lies on a mirror plane; the mirror plane is perpendicular to the pyrimidine ring and it bisects the piperidine ring. The aromatic ring is disordered about the mirror plane with respect to the 1-nitrogen and 5-carbon atoms.

  19. Synthesis, Characterization and Crystal Structure of Quaternary Complex of Gadolinium (Ⅲ)

    Institute of Scientific and Technical Information of China (English)

    朱龙观; 蔡国强; 王国平; 北川进; 正冈重行

    2003-01-01

    A new quaternary mixed anion complex of gadolinium(Ⅲ), [Gd(CH3CH2COO)2(NO3)(phen)]2, was synthesized and structurally characterized. The ESR spectrum of the complex with effective g values of 5.314, 2.473 and 1.880 in polycrystalline powder at room temperature is quite different from the U spectrum. The coordination number of Gd3+ is nine with a monocapped square antiprism geometry. And the stacking effect was observed in the complex. The crystal of the complex belongs to triclinic with space group P 1, a=0.9626(4) nm, b=0.9732(4) nm, c=1.1758(5) nm, α=102.45(1)°, β=108.16(1)°, γ=96.68(2)°, V=1.0018(7) nm3, Z=2, Dc=1.80 g*cm-3, μ(MoKα)=33.63 mm-1, F(000)=530, GOF=1.80, R=0.023 and Rw=0.027.

  20. Synthesis, Crystal Structure, Fluorescent and Thermal Properties of Sodium Tridecafluorodizirconate Na5Zr2F13 Compound

    Institute of Scientific and Technical Information of China (English)

    MAO Shao-Yu; KANG You-Jun; MI Jin-Xiao; LI Man-Rong; WEI Zan-Bin; WU Xue-Yan; ZHAO Jing-Tai

    2006-01-01

    Crystals of sodium tridecafluorodizirconate Na5Zr2F13 were synthesized under mild hydrothermal conditions, and the structure was refined by single-crystal X-ray diffraction. The compound crystallizes in monoclinic with crystallographic data: Mr = 544.39, C2/m (No.12), a = 11.5600(9), b = 5.4759(4), c = 8.3989(6)(A), β= 97.361(10)°, V = 527.28(7)(A)3, Z = 2, Dc = 3.429 g/cm3, λ = 0.71073(A), μ = 23.48 cm-1, F(000) = 504, T = 295 K, R1 = 0.0173 and wR2 = 0.0449 for 55 variables and 682 contributing unique reflections. The crystal structure is constituted with six- and eight-fold sodium atoms, forming irregular trigonal prisms and irregular cubes, respectively. Here, the zirconium atoms are connected with seven fluorine atoms to form a mono-capped trigonal prism. [Zr2F13]5- complex ions formed by corner-shared [ZrF7]3- are corner- and edge- shared to [Na4F22] and [Na3F8] cages, leading to the network structure. Thermal analysis, X-ray excited luminescence and photoluminescence under UV light measurements were conducted on Na5Zr2F13 crystals.

  1. Synthesis and Structural Studies on Transition Metal Complexes Derived from 4-Hydroxy-4-methyl–2-pentanone-1H-benzimidazol-2-yl-hydrazone

    Directory of Open Access Journals (Sweden)

    M. Neelamma

    2011-01-01

    Full Text Available Transition metal complexes of Cr(III, Fe(III, Mn(II, Co(II, Ni(II, Cu(II and Zn(II with a tridentate ligand, 4-hydroxy-4-methyl-2-pentanone-1H-benzimidazole-2yl-hydrazone (H-HPBH derived from the condensation of 2-hydrazinobenzimidazole and diacetone alcohol was synthesized. Characterization has been done on the basis of analytical, conductance, thermal and magnetic data, infrared, 1H NMR, electronic, mass and ESR spectral data. From analytical and thermal data, the stoichiometry of the complexes has been found to be 1:1 (metal: ligand. Divalent complexes have the general formula [M(HPBHCl(H2O2] in octahedral geometry, [M(HPBHCl] in tetrahedral and square planar stereochemistries and trivalent complexes [M(HPBHCl2(H2O] in octahedral disposition. Infrared spectral data suggest that the ligand HPBH behaves as a monobasic tridentate ligand with N: N: O donor sequence towards the metal ions. On the basis of the above physicochemical data, octahedral, tetrahedral and square planar geometries were assigned for the complexes. The ligand and metal complexes were screened for their physiological activities against E. coli and S. aureus. The order of physiological activity has been found to be Cu(II > Ni(II > Zn(II > Co(II > Cr(III > Mn(II > Fe (III > ligand against E.coli and Ni(II > Cu(II > Zn(II > Mn(II > Cr(III > Fe(III > Co(II > ligand against S. aureus.

  2. The structure of the homogeneous oxidation catalyst, Mn(II)(Br(-1))x, in supercritical water: an X-ray absorption fine-structure study.

    Science.gov (United States)

    Chen, Yongsheng; Fulton, John L; Partenheimer, Walter

    2005-10-12

    Extended X-ray absorption fine structure (EXAFS) and X-ray absorption near edge structure (XANES) spectroscopies were used to probe the first-shell coordination structure about Mn(II) and Br(-1) ions that exist as contact ion pairs in supercritical water. This work was performed to clarify why solutions of MnBr2 in supercritical water are known to effectively catalyze the aerobic oxidative synthesis of terephthalic acid from p-xylene as well as a number of other methylaromatic compounds. The Mn and Br K-edge spectra were collected at the bending magnet beamline (sector 20) at the Advanced Photon Source, Argonne National Laboratory. The first-shell coordination structure about the Mn(II) ion changes from octahedral at ambient conditions to tetrahedral at supercritical conditions. Under supercritical conditions, the measured bond distances of Mn-OH2 and Mn-Br are 2.14 and 2.46 A, respectively. Direct contact ion pairs form with about 2 Br(-1) ions present in the first coordination shell of the Mn(II) ion. The structure of dissolved MnBr2, below 1.0 m, changes from essentially [Mn(II)(H2O)6]+2 to [Mn(II)(H2O)2(Br(-1))2] in supercritical water (scH2O). When an excess of Br(-1) ion is added, the bromide coordination number increases and the number of water molecules decreases. The results show that the initial MnBr2 catalyst in scH2O is tetrahedral with two Mn-Br contact ion pairs. The presence of the acetate anion deactivates the catalyst by formation of insoluble MnO.

  3. The structure of the homogeneous oxidation catalyst, Mn(II)-Br(-I)x, in supercritical water: An x-ray absorption fine structure study

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Yongsheng; Fulton, John L.; Partenheimer, Walt

    2005-10-12

    Extended x-ray absorption fine structure (EXAFS) and x-ray absorption near edge structure (XANES) spectroscopies were used to probe the first-shell coordination structure of Mn(II) and Br(-I) ion pairs in supercritical water. This work was performed to clarify why solutions of MnBr2 in supercritical water are known to effectively catalyze the aerobic oxidative synthesis of terephthalic acid from p-xylene. The Mn and Br K-edge spectra were collected at the bending magnet beamline (sector 20) at the Advanced Photon Source, Argonne. The first-shell coordination structure about the Mn(II) ion changes from octahedral at ambient conditions to tetrahedral at supercritical conditions. Under supercritical conditions, the measured bond distances of Mn-OH2 and Mn-Br are 2.11 and 2.46 ?, respectively. Direct contact ion pairs form with about 2 Br(-I) ions present in the first coordination shell of the Mn(II) ion. The structure of dissolved MnBr2, below 1.0 m, changes from essentially [Mn(II)(H2O)6]+2 to [Mn(II)(H2O)2(Br)2] in supercritical water (scH2O). When an excess of a Br(-I) ion is added, the bromide coordination increases and the number of water molecules decreases. The results show that the initial MnBr2 catalyst in scH2O is tetrahedral with two Mn-Br contact ion pairs. The presence of the acetate anion deactivates the catalyst by formation of insoluble MnO.

  4. The Structure of the Homogeneous Oxidation Catalyst, Mn(II)(Br[superscript -1])[subscript x], in Supercritical Water: An X-ray Absorption Fine-Structure Study

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Yongsheng; Fulton, John L.; Partenheimer, Walter (PNNL)

    2008-09-25

    Extended X-ray absorption fine structure (EXAFS) and X-ray absorption near edge structure (XANES) spectroscopies were used to probe the first-shell coordination structure about Mn(II) and Br{sup -1} ions that exist as contact ion pairs in supercritical water. This work was performed to clarify why solutions of MnBr{sub 2} in supercritical water are known to effectively catalyze the aerobic oxidative synthesis of terephthalic acid from p-xylene as well as a number of other methylaromatic compounds. The Mn and Br K-edge spectra were collected at the bending magnet beamline (sector 20) at the Advanced Photon Source, Argonne National Laboratory. The first-shell coordination structure about the Mn(II) ion changes from octahedral at ambient conditions to tetrahedral at supercritical conditions. Under supercritical conditions, the measured bond distances of Mn-OH{sub 2} and Mn-Br are 2.14 and 2.46 {angstrom}, respectively. Direct contact ion pairs form with about 2 Br{sup -1} ions present in the first coordination shell of the Mn(II) ion. The structure of dissolved MnBr{sub 2}, below 1.0 m, changes from essentially [Mn(II)(H{sub 2}O){sub 6}]{sup +2} to [Mn(II)(H{sub 2}O){sub 2}(Br{sup -1}){sub 2}] in supercritical water (scH{sub 2}O). When an excess of Br{sup -1} ion is added, the bromide coordination number increases and the number of water molecules decreases. The results show that the initial MnBr{sub 2} catalyst in scH{sub 2}O is tetrahedral with two Mn-Br contact ion pairs. The presence of the acetate anion deactivates the catalyst by formation of insoluble MnO.

  5. A nano-structured material for reliable speciation of chromium and manganese in drinking waters, surface waters and industrial wastewater effluents.

    Science.gov (United States)

    Abdolmohammad-Zadeh, H; Sadeghi, G H

    2012-05-30

    A simple solid phase extraction system based on the applying the nickel-aluminum layered double hydroxide (Ni-Al LDH) as a nano-sorbent was developed for the speciation analysis of chromium and manganese by flame atomic absorption spectrometry (FAAS). The method is based on the fact that Cr(VI) and Mn(VII) oxyanions could be adsorbed on the Ni-Al(NO(3)(-)) LDH and/or exchanged with LDH interlayer NO(3)(-) ions at pH 6.0, whereas Cr(III) and Mn(II) cations pass through the LDH-packed column without retention. The determinations of total Cr and Mn, and hence indirectly Cr(III) and Mn(II), involve the pre-oxidations of Cr(III) and Mn(II) to Cr(VI) and Mn(VII) with H(2)O(2) and acidic solution of KIO(4), respectively. Several important factors affecting the retention efficiency were investigated and optimized. In the optimum experimental conditions, the limits of detection (3S(b)/m) for Cr(VI) and Mn(VII) were 0.51 and 0.47 ng mL(-1), and the relative standard deviations were 2.5 and 3.2% (C=30.0 ng mL(-1), n=6), respectively. The presented method was validated by the analysis of a certified reference material, and applied to the speciation of Cr and Mn in drinking waters, surface waters and industrial wastewater effluents. Copyright © 2012 Elsevier B.V. All rights reserved.

  6. As(III) oxidation by MnO2 during groundwater treatment.

    Science.gov (United States)

    Gude, J C J; Rietveld, L C; van Halem, D

    2017-03-15

    The top layer of natural rapid sand filtration was found to effectively oxidise arsenite (As(III)) in groundwater treatment. However, the oxidation pathway has not yet been identified. The aim of this study was to investigate whether naturally formed manganese oxide (MnO2), present on filter grains, could abiotically be responsible for As(III) oxidation in the top of a rapid sand filter. For this purpose As(III) oxidation with two MnO2 containing powders was investigated in aerobic water containing manganese(II) (Mn(II)), iron(II) (Fe(II)) and/or iron(III) (Fe(III)). The first MnO2 powder was a very pure - commercially available - natural MnO2 powder. The second originated from a filter sand coating, produced over 22 years in a rapid filter during aeration and filtration. Jar test experiments showed that both powders oxidised As(III). However, when applying the MnO2 in aerated, raw groundwater, As(III) removal was not enhanced compared to aeration alone. It was found that the presence of Fe(II)) and Mn(II) inhibited As(III) oxidation, as Fe(II) and Mn(II) adsorption and oxidation were preferred over As(III) on the MnO2 surface (at pH 7). Therefore it is concluded that just because MnO2 is present in a filter bed, it does not necessarily mean that MnO2 will be available to oxidise As(III). However, unlike Fe(II), the addition of Fe(III) did not hinder As(III) oxidation on the MnO2 surface; resulting in subsequent effective As(V) removal by the flocculating hydrous ferric oxides. Copyright © 2016 Elsevier Ltd. All rights reserved.

  7. The role of biogenic Fe-Mn oxides formed in situ for arsenic oxidation and adsorption in aquatic ecosystems.

    Science.gov (United States)

    Bai, Yaohui; Yang, Tingting; Liang, Jinsong; Qu, Jiuhui

    2016-07-01

    As(III&V), Mn(II), and Fe(II) may occur simultaneously in some groundwater and surface water. Studying their redox reactions and interactions is essential to unravel the biogeochemical cycles of these metal ions in aquatic ecosystems and to find effective methods to remove them simultaneously in drinking water treatment. Here, the formation of biogenic Fe-Mn oxides (BFMO, defined as a mixture of biogenic Mn oxide (BMO) and Fe oxide) as well as its oxidation and adsorption of As in a Fe(II)-Mn(II)-As(III&V)-Mn-oxidizing microbe (Pseudomonas sp. QJX-1) system were investigated. Batch experiments and structure characterization revealed that the BFMO was formed via a sequential precipitation of Fe oxide and BMO. The first formed Fe oxide was identified as FeOOH (lepidocrocite) and the latter formed BMO was identified as MnO2 (similar to hexagonal birnessite). In the BFMO mixture, the BMO part was mainly responsible for As(III) oxidation, and the Fe oxide part dominated As adsorption. Remarkably, the BMO could oxidize Fe(II) to form FeOOH, which may improve As adsorption. The optimum Mn(II)/Fe(II) ratio for As removal was approximately 1:3 (mol/mol). Taken together, in Fe(II)-Mn(II)-As(III&V)-Mn-oxidizing microbe ecosystems, the in situ formation of BFMO could eliminate or decrease Fe(II), Mn(II), and As(III&V) species simultaneously. Therefore, based on this study, new approaches may be developed for As removal from water containing high concentrations of Fe(II) and Mn(II). Copyright © 2016 Elsevier Ltd. All rights reserved.

  8. Spectral, thermal, kinetic, molecular modeling and eukaryotic DNA degradation studies for a new series of albendazole (HABZ) complexes

    Science.gov (United States)

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

    2011-01-01

    This work represents the elaborated investigation for the ligational behavior of the albendazole ligand through its coordination with, Cu(II), Mn(II), Ni(II), Co(II) and Cr(III) ions. Elemental analysis, molar conductance, magnetic moment, spectral studies (IR, UV-Vis and ESR) and thermogravimetric analysis (TG and DTG) have been used to characterize the isolated complexes. A deliberate comparison for the IR spectra reveals that the ligand coordinated with all mentioned metal ions by the same manner as a neutral bidentate through carbonyl of ester moiety and NH groups. The proposed chelation form for such complexes is expected through out the preparation conditions in a relatively acidic medium. The powder XRD study reflects the amorphous nature for the investigated complexes except Mn(II). The conductivity measurements reflect the non-electrolytic feature for all complexes. In comparing with the constants for the magnetic measurements as well as the electronic spectral data, the octahedral structure was proposed strongly for Cr(III) and Ni(II), the tetrahedral for Co(II) and Mn(II) complexes but the square-pyramidal for the Cu(II) one. The thermogravimetric analysis confirms the presence or absence of water molecules by any type of attachments. Also, the kinetic parameters are estimated from DTG and TG curves. ESR spectrum data for Cu(II) solid complex confirms the square-pyramidal state is the most fitted one for the coordinated structure. The albendazole ligand and its complexes are biologically investigated against two bacteria as well as their effective effect on degradation of calf thymus DNA.

  9. Recovery of MnO2 from a spent alkaline battery leach solution via ozone treatment

    Science.gov (United States)

    Cruz-Díaz, Martín R.; Arauz-Torres, Yennifer; Caballero, Francisco; Lapidus, Gretchen T.; González, Ignacio

    2015-01-01

    This work investigates the reaction rate of Mn(II) to generate solid manganese dioxide (MnO2) as a function of the gaseous ozone mass flow rate (27.5-77 g h-1). The experimental studies were carried out in a semi-continuous reactor, using a synthetic solution (300 mL of 1 M H2SO4 with 6000 ppm of Mn(II) added as MnSO4) that simulated the composition of an acid leaching solution from spent alkaline battery material (SBM). It was observed that at 1.3-1.45 V/SHE and pH < 1.0 a selective formation of MnO2 powder was obtained; at values greater than 1.45 V/SHE, permanganate ion (MnO41-) was formed. On the other hand, a linear relation was perceived between the volumetric mass transfer coefficient (kLa) and the ozone mass flow rate (19.3-77 g h-1 in 600 mL of the 1 M H2SO4 solution). The rate constant (k) was determined in the presence and absence of nonporous plastic spheres (D = 3 mm). In both cases the rate of Mn(II) conversion increased proportionally with the ozone mass flow rate, although the conversions obtained with non-porous plastic spheres (x = 82%) were always higher than those without non-porous plastic spheres (x = 72%). A pseudo-homogenous mass transfer model adequately approximated the experimental data.

  10. Single molecule magnet behavior of a pentanuclear Mn-based metallacrown complex: solid state and solution magnetic studies.

    Science.gov (United States)

    Zaleski, Curtis M; Tricard, Simon; Depperman, Ezra C; Wernsdorfer, Wolfgang; Mallah, Talal; Kirk, Martin L; Pecoraro, Vincent L

    2011-11-21

    The magnetic behavior of the pentanuclear complex of formula Mn(II)(O(2)CCH(3))(2)[12-MC(Mn(III)(N)shi)-4](DMF)(6), 1, was investigated using magnetization and magnetic susceptibility measurements both in the solid state and in solution. Complex 1 has a nearly planar structure, made of a central Mn(II) ion surrounded by four peripheral Mn(III) ions. Solid state variable-field dc magnetic susceptibility experiments demonstrate that 1 possesses a low value for the total spin in the ground state; fitting appropriate expressions to the data results in antiferromangetic coupling both between the peripheral Mn(III) ions (J = -6.3 cm(-1)) and between the central Mn(II) ion and the Mn(III) ones (J' = -4.2 cm(-1)). In order to obtain a reasonable fit, a relatively large single ion magnetic anisotropy (D) value of 1 cm(-1) was necessary for the central Mn(II) ion. The single crystal magnetization measurements using a microsquid array display a very slight opening of the hysteresis loop but only at a very low temperature (0.04 K), which is in line with the ac susceptibility data where a slow relaxation of the magnetization occurs just around 2 K. In frozen solution, complex 1 displays a frequency dependent ac magnetic susceptibility signal with an energy barrier to magnetization reorientation (E) and relaxation time at an infinite temperature (τ(o)) of 14.7 cm(-1) and 1.4 × 10(-7) s, respectively, demonstrating the single molecule magnetic behavior in solution.

  11. Study of the manganese (II) manganese (III) complexes with quinaldic acid in aprotic medium, mononuclear and binuclear species produced under these conditions and possible formation of radical species upon oxidation or reduction of the ligand

    Energy Technology Data Exchange (ETDEWEB)

    Bodini, E.M.; Funes, M.M.; Valle, M.A. del; Arancibia, V. [Departamento de Quimica Analitica y Electroquimica, Facultad de Quimica, Universidad Catolica de Chile (Switzerland)

    1996-11-01

    The redox chemistry of the ligand Quinaldic acid (2-QA), its monoanion and its complexes with manganese (II) and manganese (III) has studied in dimethylsulphoxide using electrochemical, spectroscopic and magnetic measurements. The protonated ligand is reduce at -1.28 V vs SCE with the transfer of one equivalent of charge the resulting solution presents oxidation peaks at -0.02 V, +0.32 V and +1.14 V vs SCE which is indicative that both radical and dimeric species are involved in the oxidation processes. The combination of the monoanion of the ligand with Mn(II) in a 1:2 mole ratio forms a stable complex which presents a magnetic susceptibility of 5.90B.M. and conditional formation constant of 1.71 x 10``8 M``-2. Its oxidation at +0.76 V vs SCE yields a brown complex of Mn(III) with a magnetic susceptibility of 4.80 B.M. The voltammetric behaviour of the latter species indicates that is probably binuclear. This complex is reduced at +0.60 V vs SCE generating a Mn(II)-Mn(III) mixed-valance complex, and a second reduction at -0.40 V vs SCE regenerating the mononuclear Mn(II) complex. The mixed-valance complex decomposes quickly generating the corresponding Mn(II) and Mn(III) monomers. On the other hand, in the presence of this metal ion as counter-ion, both its +2 or +3 oxidation state, the monoanion of the ligand shows reduction processes that might lead to the stabilization of radical species. the voltammetric and spectroscopic characterization if these species is described. The results may be useful to the understanding of the charge transfer mechanism in biological systems. (Author) 26 refs.

  12. The Role of Paraquat (1,1-dimethyl-4,4-bipyridinium chloride and Glyphosate (n-phosphonomethyl glycine in Translocation of Metal Ions to Subsurface Soils.

    Directory of Open Access Journals (Sweden)

    Rhoda O. Mbuk

    2009-12-01

    Full Text Available We investigated the role of paraquat (1,1’-Dimethyl-4,4’-bipyridinium dichloride and glyphosate (N-(phosphonomethyl glycine, on the translocation of some metals (K, Mg(II, Mn(II, Fe(II, Pb(II, Cu(II and Cd(II in soil, using a topsoil (Aquic Ustifluvent: USDA Soil Taxonomy, 2000 sampled at the University of Agriculture Makurdi Crop Farm, in Central Nigeria (7o 47’N, 8o 32’E. Employing column leaching experiments with water only on native soil and soil spiked with the metals and different levels of glyphosate or paraquat treatment, leachates were collected and analyzed for their metal contents. Results showed that in the presence of paraquat the transport of Fe(II and Mn(II by leaching in the soil was suppressed while that of Cu(II, K and Pb(II was enhanced. Glyphosate, similarly suppressed Mn(II and to some extent Fe(II translocation in the soil; however, it enhanced the mobility of Cd(II, Cu(II, Mg(II, Pb(II and K under similar treatment. While paraquat seemed to enhance the translocation of Mg(II at low application rates of the herbicide, glyphosate promoted its transport only at high application rates; there was no evidence that paraquat affected the movement of Cd(II in the soil. Our results show that the long-term use of these pesticides in the field may result in the depletion of Cu(II, K and Mg(II in agricultural soils, and that the use of glyphospate may present the additional risk of possible groundwater contamination with Cd(II and Pb(II.

  13. Diaquabis[5-(1-oxidopyridin-1-ium-2-yl-1,2,3,4-tetrazolido]manganese(II dihydrate

    Directory of Open Access Journals (Sweden)

    Feng Gao

    2011-02-01

    Full Text Available In the title compound, [Mn(C6H4N5O2(H2O2]·2H2O, the MnII ion is situated on an inversion centre and is coordinated by the O and N atoms of two bis-chelating 5-(2-pyridyl-1-oxidetetrazolate ligands and two O atoms of two water molecules in a distorted octahedral geometry. All the water H atoms are involved in O—H...N and O—H...O hydrogen bonds with uncoordinated water O atoms and tetrazole N atoms, which link the molecules into a three-dimensional network.

  14. Designer ligands. Part 15. Synthesis and characterisation of novel Mn(lI), Ni(II) and Zn(II) complexes of 1,10-phenanthroline-derived ligands

    CSIR Research Space (South Africa)

    Wellington, Kevin W

    2009-01-01

    Full Text Available ions such as Mn, Co or Ni31,32 are also known. As part of our research on the development of complexes that mimic the active site of the enzyme tyrosinase,33 we also explored the phenolase and catecholase activity of the Mn(II) complexes 2a-c and 3.... For a model to successfully mimic the enzyme tyrosinase it must be capable of oxidizing a phenol and/or catechol. For this study, 3,5-di-t-butylphenol (3,5- DTBP) 8 and 3,5-di-t-butylcatechol (3,5-DTBC) 9 were selected as substrates since...

  15. catena-Poly[[[aqua(formato-κO(1,10-phenanthroline-κ2N,N′manganese(II]-μ-formato-κ2O:O′] monohydrate

    Directory of Open Access Journals (Sweden)

    Wei Xu

    2011-07-01

    Full Text Available The title compound, {[Mn(HCOO2(C12H8N2(H2O]·H2O}n, consists of polymeric chains of the complex [Mn(HCOO2(phen(H2O]∞ (phen is 1,10-phenanthroline with solvent water molecules. The chains contain six-coordinate MnII ions bridged by formate anions. They are further extended into a three-dimensional network via O—H...O hydrogen-bonding interactions and interchain π–π stacking interactions, with a centroid–centroid distance of 3.679 (4 Å.

  16. trans-Diaquabis[5-carboxy-2-(3-pyridyl-1H-imidazole-4-carboxylato-κ2N3,O4]manganese(II

    Directory of Open Access Journals (Sweden)

    Li-Zhuang Chen

    2008-10-01

    Full Text Available In the title compound, [Mn(C10H6N3O42(H2O2], synthesized by hydrothermal reaction, the MnII ion lies on an inversion centre and displays a distorted octahedral coordination geometry defined by the two imidazole N atoms and two carboxylate O atoms of the two trans-standing chelate ligands, and two O atoms of the water molecules. A two-dimensional supramolecular architecture is formed via N—H...O, O—H...N and O—H...O hydrogen-bonding interactions.

  17. Crystal structure of hexa-kis-(dimethyl sulfoxide-κO)manganese(II) diiodide.

    Science.gov (United States)

    Glatz, Mathias; Schroffenegger, Martina; Weil, Matthias; Kirchner, Karl

    2016-07-01

    The asymmetric unit of the title salt, [Mn(C2H6OS)6]I2, consists of one Mn(II) ion, six O-bound dimethyl sulfoxide (DMSO) ligands and two I(-) counter-anions. The isolated complex cations have an octa-hedral configuration and are grouped in hexa-gonally arranged rows extending parallel to [100]. The two I(-) anions are located between the rows and are linked to the cations through two weak C-H⋯I inter-actions.

  18. In Situ Immobilization on the Silica Gel Surface and Adsorption Capacity of Poly[ N-(4-carboxyphenyl)methacrylamide] on Toxic Metal Ions

    Science.gov (United States)

    Yanovska, Elina; Savchenko, Irina; Sternik, Dariusz; Kychkiruk, Olga; Ol'khovik, Lidiya; Buriachenko, Iana

    2017-04-01

    In situ immobilization of poly[ N-(4-carboxyphenyl)methacrylamide] has been performed on silica gel surface. Infrared (IR) and mass spectroscopies as well as thermogravimetry (TG) analysis have been used to elucidate the structure of immobilized polymer. An adsorption capacity of the synthesized composite towards Cu(II), Pb(II), Mn(II), Fe(III), Co(II), and Ni(II) ions has been estimated. Adsorption activity to microquantities of Pb(II), Cu(II), and Ni(II) in a neutral aqueous medium has been observed.

  19. Diaquabis[2-(5-isopropyl-5-methyl-4-oxo-4,5-dihydro-1H-imidazol-2-yl-κN3nicotinato-κN]manganese(II

    Directory of Open Access Journals (Sweden)

    Peng Gao

    2010-12-01

    Full Text Available In the title compound, [Mn(C13H14N3O32(H2O2], the MnII ion is coordinated by four N atoms from two (±-2-(5-isopropyl-5-methyl-4-oxo-4,5-dihydro-1H-imidazol-2-ylnicotinate ligands and two water molecules in a distorted octahedral environment. Intermolecular O—H...O hydrogen bonds lead to a chain along [010]. Intramolecular N—H...O and O—H...O hydrogen bonds are observed.

  20. Synthesis, Characterization, and Biological Activity of Some Transition Metal Complexes of N-Benzoyl-N′-2-thiophenethiocarbohydrazide

    Directory of Open Access Journals (Sweden)

    Mahendra Yadav

    2012-01-01

    Full Text Available In the present study, Mn(II, Fe(II, Ni(II, and Cu(II complexes of N-benzoyl -N′-2-thiophenethiocarbohydrazide (H2 BTTH have been synthesized and characterized by elemental analysis, magnetic susceptibility measurements, infrared, NMR, electronic, and ESR spectral studies. The complexes were found to have compositions [Mn(H BTTH2], [Ni(BTTH(H2O2], [Cu(BTTH], and [Fe(H BTTH2EtOH]. The antibacterial and antifungal properties of H2 BTTH and its metal complexes have been screened against several bacteria and fungi.

  1. Speciation study on the interaction of some divalent transition metal ions with succinic acid dihydrazide in aqueous medium.

    Science.gov (United States)

    Satyanarayana, Atreyapurapu; Kenie, Dunkana Negussa; Shyamala, Pulipaka

    2013-01-01

    The interaction of succinic acid dihydrazide with Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) was investigated in aqueous medium at 303K and ionic strength of 0.1 mol dm-3. The speciation and stability constants of the metal complexes formed were determined by pH-metric method. Mononuclear and homo binuclear species in different protonation and deprotonation states were identified, the corresponding formation constants calculated using MINIQUAD-75 computer program, and species distribution diagrams produced using the HYSS computer program. Selection of the best-fit chemical models was based on statistical parameters.

  2. Magnetic spongelike behavior of 3D ferrimagnetic {[Mn(II)(imH)]2[Nb(IV)(CN)8]}n with Tc = 62 K.

    Science.gov (United States)

    Pinkowicz, Dawid; Podgajny, Robert; Bałanda, Maria; Makarewicz, Magdalena; Gaweł, Bartłomiej; Łasocha, Wiesław; Sieklucka, Barbara

    2008-11-03

    Fully reversible room temperature dehydration of 3D {Mn(II)2(imH)2(H2O)4[Nb(IV)(CN)8] x 4 H2O}n (1; imH = imidazole) of Tc = 25 K results in the formation of 3D ferrimagnet {[Mn(II)(imH)]2[Nb(IV)(CN)8]}n (2), with Tc = 62 K, the highest ever known for octacyanometalate-based compounds. The dramatic magnetostructural modifications in 2 provide the first example of magnetic spongelike behavior in an octacyanometallate-based assembly.

  3. Reverse Transcription-PCR Analysis of the Regulation of the Manganese Peroxidase Gene Family

    OpenAIRE

    Gettemy, Jessica M.; Ma, Biao; Alic, Margaret; Gold, Michael H.

    1998-01-01

    Manganese peroxidase (MnP) gene expression in the lignin-degrading fungus Phanerochaete chrysosporium is regulated by nutrient nitrogen levels and by Mn(II), the substrate for the enzyme, as well as by heat shock and other factors. Reverse transcription-PCR (RT-PCR) of total RNA can distinguish the mRNAs of each of the three sequenced P. chrysosporium mnp genes, i.e., mnp1, mnp2, and mnp3. Quantitative RT-PCR demonstrates that each of the three transcripts is present at a similar low basal le...

  4. Heat Shock Induction of Manganese Peroxidase Gene Transcription in Phanerochaete chrysosporium

    OpenAIRE

    Brown, Julie A.; Li, Dan; Alic, Margaret; Gold, Michael H.

    1993-01-01

    The expression of manganese peroxidase (MnP) in nitrogen-limited cultures of Phanerochaete chrysosporium is regulated by heat shock at the level of gene transcription. Nitrogen limitation and manganous ion [Mn(II)] previously have been shown to regulate mnp gene transcription. Northern (RNA) blot analysis demonstrates that 45°C heat shock results in the accumulation of mnp mRNA, even in cells grown in the absence of Mn. Heat shock induces mnp gene transcription in 4- or 5-day-old cells, and m...

  5. Transition Metal Complexes of Isonicotinoyl–hydrazone-4-diphenylaminobenzaldehyde: Synthesis, Characterization and Antimicrobial Studies

    Directory of Open Access Journals (Sweden)

    L. Mitu

    2012-01-01

    Full Text Available A series of complexes of Cu(II, Ni(II, Co(II, Mn(II and Cd(II with Isonicotinoylhydrazone-4-diphenylaminobenzaldehyde (INHDAB has been reported. The complexes have been characterized by analytical data, IR, UV-Vis, NMR spectra, magnetic susceptibility values, thermal analysis and for the Cu(II complex the ESR spectrum has been registered. The biological activity of these complexes were investigated against Staphylococcus aureus, Escherichia coli, Pseudomonas aeruginosa, Salmonella enteritidis and Shigella flexneri bacteria. The INHDAB ligand is coordinate at the metallic ions by oxygen amide (O=C and the azomethine nitrogen.

  6. Synthesis, identification and thermal decomposition of double sulfites like Cu2SO3·MSO3·2H2O (M=Cu, Fe, Mn or Cd)

    OpenAIRE

    2000-01-01

    Texto completo: acesso restrito. p.17–27 Double sulfites with empirical formula Cu2SO3·MSO3·2H2O (where M is Cu, Fe, Mn, or Cd) were obtained by saturation with sulfur dioxide gas of an aqueous mixture of MII sulfate and copper sulfate at room temperature. The salts obtained were identified by infrared spectra, X-ray powder diffraction and elemental analysis. The compounds studied are isostructural with the CuII replacement by MnII, FeII, and CdII in Chevreul’s salt (Cu2SO3·CuSO3·2H2O). Th...

  7. Synthesis and Characterization of Metallic Gel Complexes Derived from Carboxymethyl Cellulose

    Directory of Open Access Journals (Sweden)

    H. D. Juneja

    2013-01-01

    Full Text Available The oxaloyl carboxymethyl cellulose (OCMC complexes of Mn(II, Co(II, Ni(II, Cu(II, and Zn(II metal ions have been synthesized and the coordination of OCMC in these complexes has been investigated through IR spectra, reflectance spectra, and thermal analysis. On the basis of spectral and thermal data an octahedral geometry was assigned to [Mn(IIOCMC(H2O2]n and [Co(IIOCMC(H2O2]n, square planar geometry was assigned to [Cu(IIOCMC]n, and tetrahedral geometry was assigned to [Ni(IIOCMC]n and [Zn(IIOCMC]n Metallic Gel complexes.

  8. Lability of heavy metal species in aquatic humic substances characterized by ion exchange with cellulose phosphate.

    Science.gov (United States)

    Rocha, J C; Toscano, I A; Burba, P

    1997-01-01

    Labile metal species in aquatic humic substances (HSs) were characterized by ion exchange on cellulose phosphate (CellPhos) by applying an optimized batch procedure. The HSs investigated were pre-extracted from humic-rich waters by ultrafiltration and a resin XAD 8 procedure. The HS-metal species studied were formed by complexation with Cd(II), Ni(II), Cu(II), Mn(II) and Pb(II) as a function of time and the ratio ions to HSs. The kinetics and reaction order of this exchange process were studied. At the beginning ( Pb > Mn > Ni > Cd. The required metal determinations were carried out by atomic absorption spectrometry.

  9. Flow-injection sample preconcentration for ion-pair chromatography of trace metals in waters.

    Science.gov (United States)

    Pobozy, Ewa; Halko, Radoslav; Krasowski, Marcin; Wierzbicki, Tomasz; Trojanowicz, Marek

    2003-05-01

    Selected trace transition metal ions have been determined in an FIA/HPLC hyphenated system using on-line preconcentration on cellulose functionalised sorbent Cellex P. For HPLC separation ion-pair chromatography was employed with spectrophotometric detection at 510 nm using post-column derivatisation with PAR. Favourable kinetic conditions of sorption and elution as well as optimisation of hyphenated system allowed to obtain detection limits at sub-microgL(-1) level at 25 min preconcentration time. The developed method was employed for determination of Co(II), Ni(II), Cd(II) and Mn(II) in river water with reasonable agreement of obtained results with electrothermal AAS determination.

  10. EPR, UV-Visible, and Near-Infrared Spectroscopic Characterization of Dolomite

    OpenAIRE

    S. Lakshmi Reddy; Frost, R. L.; G. Sowjanya; Reddy, N. C. G.; G. Siva Reddy; Reddy, B. J.

    2008-01-01

    Dolomite mineral samples having white and light green colors of Indian origin have been characterized by EPR, optical, and NIR spectroscopy. The optical spectrum exhibits a number of electronic bands due to presence of Fe(III) ions in the mineral. From EPR studies, the parameters of g for Fe(III) and g,A, and D for Mn(II) are evaluated and the data confirm that the ions are in distorted octahedron. Optical absorption studies reveal that Fe(III) is in distorted octahedron. The bands in NIR spe...

  11. Complexometric assay for water hardness: an interactive lab experiment.

    OpenAIRE

    Milla González, Miguel

    2011-01-01

    Water hardness is due to the presence of multivalent metal ions. In natural waters, the most abundant ions are calcium(II) and, in less amount, magnesium(II). Cations such as Fe(III), Al(III), Mn(II) and other metal ions also contribute to hardness, although their concentration level is much below the concentration level of calcium. Water hardness is a parameter of interest in water analysis, since it has adverse consequences in a great deal of human activities related to the use of this natu...

  12. Ferro and paramagnetic resonance studies of natural volcanic glasses - Teotihuacan obsidians

    Science.gov (United States)

    Chavez-Rivas, F.; Zamorano-Ulloa, R.; Galland, D.; Regnard, J. R.; Chappert, J.

    1991-11-01

    Teotihuacan black obsidians have been experimentally studied and found to be very heterogeneous magnetically. Isolated high-spin Fe(III) and Mn(II) free ions are readily identified. The well-defined first-derivative Q-band singlet at g = 2.00 is assigned to superparamagnetic centers. A strong grain-size dependence of the overall line shape is observed at X-band. Other properties of the spectral lines indicate the presence of superparamagnetic clusters of magnetite and a range order in these obsidians larger than the common short-range order of the glassy state.

  13. Light-induced pH change and its application to solid phase extraction of trace heavy metals by high-magnetization Fe3O4@SiO2@TiO2 nanoparticles followed by inductively coupled plasma mass spectrometry detection.

    Science.gov (United States)

    Zhang, Nan; Peng, Hanyong; Hu, Bin

    2012-05-30

    We report here the preparation of high-magnetization Fe(3)O(4)@SiO(2)@TiO(2) nanoparticles for solid phase extraction of trace amounts of Cd(II), Cr(III), Mn(II) and Cu(II) from environmental waters. The prepared nanoparticles were characterized by scanning electron micrograph (SEM) and transmission electron microscopy (TEM). The high-magnetization nanoparticles carrying the target metals could be easily and fast separated from the aqueous solution simply by applying an external magnetic field while no filtration or centrifugation was necessary. A light-induced hydroxide ion emitter, molecular malachite green carbinol base (MGCB) was applied to adjust pH value of solution for quantitative adsorption instead of the conventional used buffer. In the presence of UV light, MGCB gives out OH(-) ions, and this leads to an increase in the pH value without the aid of buffer solution. Using high-magnetization Fe(3)O(4)@SiO(2)@TiO(2) nanoparticles as the extraction material and the light-induced MGCB for pH adjustment, we developed an efficient and convenient two-step method for separation/preconcentration trace amounts of Cd(II), Cr(III), Mn(II) and Cu(II) in environmental water samples followed by inductively coupled plasma mass spectrometry (ICP-MS) detection. The parameters affecting the extraction such as MGCB concentration, exposal time, sample volume, eluent condition, and interfering ions have been investigated in detail. Under the optimized conditions, the limits of detection for Cd(II), Cr(III), Mn(II) and Cu(II) were 4.0, 2.6, 1.6 and 2.3 ng L(-1), respectively, and the relative standard deviations (RSDs, c=1 μg L(-1), n=7) were 3.6%, 4.5%, 4.0 and 4.1%, respectively. The proposed method has been validated using certified reference materials, and it has been successfully applied in the determination of trace Cd(II), Cr(III), Mn(II) and Cu(II) in environmental water samples. Copyright © 2012 Elsevier B.V. All rights reserved.

  14. Root-induced cycling of lead in salt marsh sediments.

    Science.gov (United States)

    Sundby, Bjørn; Caetano, Miguel; Vale, Carlos; Gobeil, Charles; George, Luther W; Nuzzio, Donald B

    2005-04-01

    A gold-mercury amalgam microelectrode was used in situ to measure Pb(II) by anodic stripping voltammetry and O2, Fe(II), Mn(II), and HS- by square-wave voltammetry in sediment pore water in a Haliomione portulacoides stand in a Tagus estuary salt marsh. The measurements were made in spring, summer, and fall, and were supplemented with analysis of Pb in solid phases and stable isotope analysis of Pb. In spring, the pore water was anoxic, Fe(II) reached concentrations as high as 1700 micromol/L, and Pb(II) was undetectable (Tagus Estuary salt marshes.

  15. One-dimensional manganese coordination polymers composed of polynuclear cluster blocks and polypyridyl linkers: structures and properties.

    Science.gov (United States)

    Baca, Svetlana G; Malaestean, Iurii L; Keene, Tony D; Adams, Harry; Ward, Michael D; Hauser, Jürg; Neels, Antonia; Decurtins, Silvio

    2008-12-01

    The synthesis, crystal structures and magnetic properties of five new manganese compounds are reported. These include a linear trinuclear cluster [Mn(II)(3)(O(2)CCHMe(2))(6)(dpa)(2)].2MeCN (1) (dpa = 2,2'-dipyridylamine), a tetranuclear cluster [Mn(II)(2)Mn(III)(2)O(2)(O(2)CCMe(3))(6)(bpy)(2)] (3) (bpy = 2,2'-bipyridine), and chain coordination polymers composed of cluster blocks such as Mn(3), Mn(3)O, and Mn(4)O(2) bridged by 2,2'-bipyrimidine (bpm) or hexamethylentetramine (hmta) ligands to give ([Mn(II)(3)(O(2)CCHMe(2))(6)(bpm)].2EtOH)(n) (2), [Mn(II)(2)Mn(III)(2)O(2)(O(2)CCHMe(2))(6)(bpm)(EtOH)(4)](n) (4), and (([Mn(II)Mn(III)(2)O(O(2)CCHMe(2))(6)(hmta)(2)].EtOH)(n) (5). The magnetic analysis of the compounds was achieved using a combination of vector coupling and full-matrix diagonalization methods. Susceptibility data for compound 1 was fitted using a vector coupling model to give g = 2.02(1) and 2J/k(B) = -5.38(2) K. To model the trimer chain, we used vector coupling for initial values of J(1) and then diagonalization techniques to estimate J(2) to give g = 1.98(1), 2J(1)/k(B) = -3.3(1) K and 2J(2)/k(B) = -1.0(1) K by approximating the system to a dimer of trimers. The analysis of 3 was made difficult by the mixture of polymorphs and the difficulties of a three-J model, while for 4 an analysis was not possible because of the size of the computation and the relative magnitudes of the three couplings. Compound 5 was modeled using the same techniques as 2 to give g = 1.99(1), 2J(1)/k(B) = +32.5(2) K, 2J(2)/k(B) = -16.8(1) K, and 2J(3)/k(B) = +0.4(1) K. The combination of techniques has worked well for compounds 2 and 5 and thus opens up a method of modeling complex chains.

  16. Synthesis and structural studies of first row transition metal complexes of N-(2-nitro-benzilidine-3-hydrazino quinoxaline-2-one

    Directory of Open Access Journals (Sweden)

    P.V. Anantha Lakshmi

    2008-12-01

    Full Text Available Cr(III, Mn(II, Fe(III, Co(II, Ni(II and Cu(II complexes of N-(2-nitro-benzilidene-3-hydrazino quinoxaline-2-one (NBHQO have been synthesized and characterized by elemental analysis, conductance, thermal, spectral and magnetic data. NBHQO acts as a bidentate ON donor in all the complexes except in Ni(II complex in which it acts as a tridentate ONO donor. Octahedral geometries have been proposed for all the complexes except for Cu(II complex to which the square planar geometry is assigned.

  17. A One-Dimensional Magnet Based on [Mo(III)(CN)7](4.).

    Science.gov (United States)

    Wei, Xiao-Qin; Qian, Kun; Wei, Hai-Yan; Wang, Xin-Yi

    2016-06-01

    Self-assembly of the [Mo(III)(CN)7](4-) anion and the Mn(II) unit with a macrocyclic ligand results in the first example of a one-dimensional (1D) chain compound based on the heptacyanomolybdate, [Mn(LN5C10)]2[Mo(CN)7]·2H2O (LN5C10 = 1,4,7,10,13-pentaazacyclopentadecane). Because of the existence of the interchain magnetic coupling, long-rang magnetic ordering was observed in this compound.

  18. Reactivity of biogenic manganese oxide for metal sequestration and photochemistry: Computational solid state physics study

    Energy Technology Data Exchange (ETDEWEB)

    Kwon, K.D.; Sposito, G.

    2010-02-01

    Many microbes, including both bacteria and fungi, produce manganese (Mn) oxides by oxidizing soluble Mn(II) to form insoluble Mn(IV) oxide minerals, a kinetically much faster process than abiotic oxidation. These biogenic Mn oxides drive the Mn cycle, coupling it with diverse biogeochemical cycles and determining the bioavailability of environmental contaminants, mainly through strong adsorption and redox reactions. This mini review introduces recent findings based on quantum mechanical density functional theory that reveal the detailed mechanisms of toxic metal adsorption at Mn oxide surfaces and the remarkable role of Mn vacancies in the photochemistry of these minerals.

  19. Rapid and selective chelatometric titration of aluminium in non-ferrous alloys.

    Science.gov (United States)

    Nan, Z; Yuan-Xiang, G; Zhi-Ren, L; Eei-Yong, C

    1985-12-01

    A rapid chelatometric method for the determination of Al (4-20%) in magnesium, copper and chromium-aluminium-iron alloys is proposed. HEDTA is used as titrant and Zn solution as back-titrant, with hydrazidazol as indicator. Mn(II), Cu(II), Cd, Zn, Pb, Co(II), Ni, Hg(II), Fe(III), Bi, Cr(III), Sb(III), Ce(III), La, Sn(IV), Ti(IV), Zr and Mo(VI) do not interfere. High selectivity is achieved by a combination of group separation, masking and interference correction. The coefficient of variation varies from 0.2 to 1%.

  20. Protein Oxidation Implicated as the Primary Determinant of Bacterial Radioresistance

    Science.gov (United States)

    2007-04-01

    the facultative anaerobic, radio- resistant bacterium Lactobacillus plantarum [1,22] accumulates 20–25 mM Mn(II) [23]. For an irradiated cell...in dH2O at 0 8C and pre-conditioned to be anaerobic, H2O2 was released by D. radiodurans (;23 105 M) and L. plantarum (;6 3 105 M), in which the...non-irradiated D. radiodurans or L. plantarum control samples, nor by irradiated S. oneidensis (Figure 5A), which accumulates substantially more Fe

  1. Diaquabis(4-chlorobenzoato-κObis(N,N-diethylnicotinamide-κN1manganese(II

    Directory of Open Access Journals (Sweden)

    Hacali Necefoğlu

    2008-03-01

    Full Text Available The title compound, [Mn(C7H4ClO22(C10H14N2O2(H2O2], is a monomeric complex with the MnII atom lying on an inversion center. It contains two 4-chlorobenzoate and two diethylnicotinamide ligands and two water molecules, all of which are monodentate. The four O atoms in the equatorial plane around the Mn atom form a slightly distorted square-planar arrangement, while the distorted octahedral geometry is completed by two N atoms in the axial positions. In the crystal structure, O—H...O hydrogen bonds link the molecules into an infinite chain.

  2. The Zintl Chemistry of the Heavy Tetrel Elements

    Energy Technology Data Exchange (ETDEWEB)

    Klem, Michael Thomas [Iowa State Univ., Ames, IA (United States)

    2002-12-31

    Exploration of the alkali metal/alkaline-earth metal/heavy tetrel (Sn or Pb) systems has revealed a vast array of new chemistry and novel structure types. The structures and properties of these new materials have been studied in an attempt to understand the chemistry of these and other related systems. The first phase reported is Rb4Pb9 (K4Pb9 type). The compound contains two different types of Pb94- deltahedra, a monocapped square pyramid and a distorted tricapped trigonal prism. Both cluster geometries correspond to a nido assignment even though the tricapped trigonal prism is not the classic Wade's rules nido deltahedron expected for a monocapped square antiprism. Also, a series of compounds that contain square pyramidal Tt5 polyanions of tin and lead has been obtained in alkaline-earth or rare-earth metal-tetrel systems by direct fusion of the elements to yield Sr3Sn5, Ba3Pb5, and La3Sn5. These phases contain square pyramidal clusters of the tetrel elements that are weakly interlinked into chains via two types of longer intercluster interactions that are mediated by bridging cations and substantially influenced by cation size and the free electron count. Attempts at incorporating another main-group element to form heteroatomic clusters were also successful. In the case of A5InPb8 (A = K, Rb), the compounds contain clusters composed of two Pb4 tetrahedra that are interbridged by a lone μ6-In atom. The InPb8 units are weakly interlinked into sheets in the ab plane by long intercluster Pb-Pb interactions. Using As led to the formation of the compound K5As3Pb3 which is made up of As3Pb35- crown clusters that can be likened to a 6-atom hypho-cluster based on the tricapped trigonal parent as the closo

  3. Adsorption behavior of some metal ions on hydrated amorphous titanium dioxide surface

    Directory of Open Access Journals (Sweden)

    Panit Sherdshoopongse

    2005-09-01

    Full Text Available Titanium dioxide was prepared from titanium tetrachloride and diluted ammonia solution at low temperature. The product obtained was characterized by XRD, EDXRF, TGA, DSC, and FT-IR techniques. It was found that the product was in the form of hydrated amorphous titanium dioxide, TiO2·1.6H2O (ha- TiO2. Ha-TiO2 exhibits high BET surface area at 449 m2/g. Adsorptions of metal ions onto the ha-TiO2 surface were investigated in the batch equilibrium experiments, using Mn(II, Fe(III, Cu(II, and Pb(II solutions. The concentrations of metal ions were determined by atomic absorption spectrometer. The adsorption isotherms of all metal ions were studied at pH 7. The adsorption of Mn(II, Cu(II, and Pb(II ions on ha-TiO2 conformed to the Langmuir isotherm while that of Fe(III fit equally well to both Langmuir and Freundlich isotherms.

  4. Synthesis and structure of linear hexanuclear manganese (II) benzoate cluster

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    From a reaction system including benzoic acid and Mn(NO3)2 in alkali medium, two hexanuclear manganese benzoate cluster compounds have been synthesized. A compound [Et4N]2[Mn6(PhCOO)14] has been structurally characterized, which contains hexanuclear MnII moie-ties extending unlimitedly to form one-dimensional linear structure. Carboxyl oxygen atoms are bridged in variety of modes to the Mn atoms, forming an arrangement like a sinusoid for the Mn atoms. The structural parameters of these compounds were compared with the data obtained from EXAFS determination for the Mn cluster in the OEC of PSII, supporting that the coordination sphere of the Mn site in the OEC may contain carboxyl bridges. The possible combination modes between the carboxyl group and the Mn atoms have been suggested. The NMR signals exhibit widening and shift produced by the influence of the paramagnetic MnII sites. The red-shift of the absorption in IR spectrum was observed to be attributed to the coordination of the carboxyl group to the Mn atom, supporting the result of the study on crystal structure.

  5. Protonation constant of salicylidene (N-benzoyl)glycyl hydrazone and its coordination behaviour towards some bivalent metal ions

    Indian Academy of Sciences (India)

    R K Lonibala; T R Rao; R K Babita Devia

    2006-07-01

    Protonation constant of an unsymmetrical Schiff base, salicylidene(N-benzoyl)glycyl hydrazone (SalBzGH), and formation constants of its complexes have been determined potentiometrically at different temperatures in aqueous dioxane medium. Complexes of SalBzGH with VO(IV), Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Hg(II) have been prepared. Elemental analyses, pH-metric, molar conductance, magnetic susceptibility, electronic, IR, ESR, XRD (powder) and NMR studies have been carried out to study the coordination behaviour of SalBzGH toward these metal ions. pH-metric and 1H NMR studies show the presence of two dissociable protons in the ligand. IR and NMR spectra suggest the tridentate nature of the ligand, coordinating as a uninegative species in the Mn(II) complex and as a dinegative species in all the other complexes. Presence of two different conformers of the ligand at room temperature and stabilization of a single conformer upon complex formation have been established from 1H NMR spectra of the metal-free ligand, Zn(II) and Hg(II) complexes recorded at 296 K. Electronic and ESR spectra indicate highly distorted tetragonal geometry for VO(IV) and Cu(II) complexes. XRD powder patterns of the Zn(II) complexes are indexed for an orthorhombic crystal system.

  6. Manganese oxide phases and morphologies: A study on calcination temperature and atmospheric dependence

    Directory of Open Access Journals (Sweden)

    Matthias Augustin

    2015-01-01

    Full Text Available Manganese oxides are one of the most important groups of materials in energy storage science. In order to fully leverage their application potential, precise control of their properties such as particle size, surface area and Mnx+ oxidation state is required. Here, Mn3O4 and Mn5O8 nanoparticles as well as mesoporous α-Mn2O3 particles were synthesized by calcination of Mn(II glycolate nanoparticles obtained through an economical route based on a polyol synthesis. The preparation of the different manganese oxides via one route facilitates assigning actual structure–property relationships. The oxidation process related to the different MnOx species was observed by in situ X-ray diffraction (XRD measurements showing time- and temperature-dependent phase transformations occurring during oxidation of the Mn(II glycolate precursor to α-Mn2O3 via Mn3O4 and Mn5O8 in O2 atmosphere. Detailed structural and morphological investigations using transmission electron microscopy (TEM and powder XRD revealed the dependence of the lattice constants and particle sizes of the MnOx species on the calcination temperature and the presence of an oxidizing or neutral atmosphere. Furthermore, to demonstrate the application potential of the synthesized MnOx species, we studied their catalytic activity for the oxygen reduction reaction in aprotic media. Linear sweep voltammetry revealed the best performance for the mesoporous α-Mn2O3 species.

  7. Spectroscopic characterization of manganese-doped alkaline earth lead zinc phosphate glasses

    Indian Academy of Sciences (India)

    S Sreehari Sastry; B Rupa Venkateswara Rao

    2015-04-01

    Alkaline earth lead zinc phosphate glasses doped with Mn(II) are characterized by spectroscopic techniques like X-ray diffraction (XRD), UV–visible, differential scanning calorimetry (DSC), electron paramagnetic resonance (EPR), Fourier transform infrared (FTIR) and Raman. Optical absorption spectrum exhibits four bands which are characteristic of Mn(II) in distorted octahedral site symmetry. The crystal field parameter Dq and Racah interelectronic-repulsion parameters and have been evaluated. All investigated samples exhibit EPR signals which are characteristic to the Mn2+ ions. The shapes of spectra are also changed with varying alkaline earth ions content. FTIR spectra show specific vibrations of phosphate units. The characteristic Raman bands of these glasses due to stretching and bending vibrations were identified and analysed by varying alkaline earth content. The intensity and frequency variations for the characteristic phosphate group vibrations have been correlated with the changes of the structural units present in these glasses. Depolymerization of the phosphate chains in all the glasses is observed with replacement of alkaline earth content by spectroscopic studies. This leads to a strong decrease of the average chain length and a small decrease of the average P–O–P bridging angle with replacement of alkaline earth content.

  8. Diaquabis(4-bromobenzoato-κObis(N,N-diethylnicotinamide-κN1manganese(II

    Directory of Open Access Journals (Sweden)

    Hacali Necefoğlu

    2011-09-01

    Full Text Available In the crystal structure of the title MnII complex, [Mn(C7H4BrO22(C10H14N2O2(H2O2], the MnII cation is located on an inversion center and coordinated by two diethylnicotinamide (DENA ligands, two 4-bromobenzoate (PBB anions and two water molecules in a distorted octahedral geometry. The dihedral angle between the carboxylate group and the adjacent benzene ring is 3.25 (14°. In the molecule, the pyridine ring and the benzene ring are oriented at a dihedral angle of 77.24 (5°. In the crystal, intermolecular C—H...O hydrogen bonds link the molecules into a two-dimensional network. Weak intermolecular C—H...O hydrogen bonds and π–π interactions between the pyridine rings of neighbouring molecules [centroid–centroid distance = 3.537 (1 Å] further consolidate the crystal packing.

  9. Cu(II), Zn(II) andMn(II) complexes of poly(methyl vinyl ether-alt-maleic anhydride). Synthesis, characterization and thermodynamic parameters

    Indian Academy of Sciences (India)

    Hidayet Mazi; Ali Gulpinar

    2014-01-01

    The complexes of poly(methyl vinyl ether-alt-maleic anhydride) (poly(MVE-alt-MA)) with Zn(II), Mn(II) and Cu(II) ions were synthesized from the reaction of the aqueous solution of copolymer and metal(II) chlorides at different temperatures ranging from 25° to 40°C. Elemental analysis of themetal-polymer complexes suggests that the metal to ligand ratio is 1:1. The formation constants of each complex were determined by the mol-ratio method. UV-Vis studies showed that the complex formation tendency increased in the following order: Zn(II) > Cu(II) > Mn(II). This order was confirmed by the Irving-William series and Pearson’s classification. The IR spectral data indicated the metal ions to be coordinated through the hydroxyl groups of the hydrolysed maleic anhydride. The intrinsic viscosity and thermal properties of the copolymer and metal-polymer complexes and their thermal stability are discussed.

  10. Structural Characterization of Biogenic Manganese Oxides Produced in Sea Water

    Science.gov (United States)

    Webb, S. M.; Bargar, J. R.; Tebo, B. M.

    2003-12-01

    Manganese oxides have been coined as the "scavengers of the sea" and play important roles in both marine and freshwater systems. Natural manganese oxide nanoparticles and grain coatings are ubiquitous in the environment and profoundly impact the quality of sediments via their ability to degrade and sequester contaminants. These oxides are believed to form dominantly via oxidation of Mn(II) by marine and freshwater bacteria and have extremely high sorptive capacities for heavy metals. We have used XANES, EXAFS, and synchrotron (SR)-XRD techniques to study biogenic manganese oxides produced by spores of the marine Bacillus sp., strain SG-1 in seawater as a function of reaction time under fully in-situ conditions. The primary biogenic solid-phase Mn oxide product is a hexagonal layered phyollomanganate with an oxidation state similar to that in delta-MnO2. XRD data show the biooxides to have a phyllomanganate 10 basal plane spacing, suggesting the interlayer is hydrated and contains calcium. As the experiment continues, the initial biooxide changes to show triclinic symmetry. Fits to these EXAFS spectra suggest the octahedral layers have low Mn octahedral site vacancies in the lattice and the latyers bend to accommodate Jahn-Teller distortions creating the change in symmetry. The oxides observed in this study as models of Mn(II) bio-oxidation may be representative of the most abundant manganese oxide phase suspended in the oxic and sub-oxic zones of the oceanic water column.

  11. Coordination Modes of a Schiff Base Derived from Substituted 2-Aminothiazole with Chromium(III, Manganese(II, Iron(II, Cobalt(II, Nickel(II and Copper(II Metal Ions: Synthesis, Spectroscopic and Antimicrobial Studies

    Directory of Open Access Journals (Sweden)

    Ambit Thakar

    2011-01-01

    Full Text Available Transition metal complexes of Cr(III, Mn(II, Fe(II, Co(II, Ni(II and Cu(II metal ions with general stoichiometry [ML2.2H2O] and [ML3], where M= Mn(II, Cr(III, Fe(II, Co(II, Ni(II and Cu(II, L= Schiff base derived from the condensation of 2-amino-4(4’-phenyl/methylphenyl-5-methyl-thiazole with 4-acetyl-1(3-chloro phenyl-3-methyl-2-pyrazoline-5-ones, have been synthesized and structurally characterized by elemental analysis, molar conductance measurements, magnetic susceptibility measurements and spectral techniques like IR, UV, 1H NMR, 13C NMR and Mass Spectra. All the complexes were found to be octahedral geometry. The ligand and its complexes have been screened for their antifungal and antibacterial activities against three fungi, i.e. Alternaria brassicae, Aspergillus niger and Fesarium oxysporum and two bacteria, i.e. Xanthomonas compestris and Pseudomonas aeruginosa.

  12. Stability Constants of Mixed Ligand Complexes of Transition Metal(II Ions with Salicylidene-4-methoxyaniline as Primary Ligand and 5-Bromosalicylidene-4-nitroaniline as Secondary Ligand

    Directory of Open Access Journals (Sweden)

    N. G. Nadkarni

    2011-01-01

    Full Text Available Binary and ternary complexes of the type M-Y and M-X-Y [M = Mn(II, Ni(II, Cu(II and Zn(II; X = salicylidene-4-methoxyaniline and Y=5-bromosalicylidene-4-nitroaniline] have been examined pH-metrically at 27±0.5 °C and at constant ionic strength, μ= 0.1 M (KCl in 75 : 25(v/v 1,4-dioxne-water medium. The stability constants for binary (M-Y and ternary (M-X-Y systems were calculated. The relative stability (Δ log KT values of the ternary complexes with corresponding binary complexes for all the metal(II ions in the present study found to be negative indicating that ternary 1:1:1 (M-X-Y complexes are less stable than binary 1:1 (M-Y complexes. In the ternary system studied, the order of stability constants of mixed ligand complexes with respect to the metal ions was found to be Cu(II > NI(II > Mn(II > Zn(II; which is same as in the corresponding binary (M-Y systems.

  13. Bis(μ-2-carboxymethyl-2-hydroxybutanedioatobis[diaquamanganese(II]–1,2-bis(pyridin-4-ylethene–water (1/1/2

    Directory of Open Access Journals (Sweden)

    In Hong Hwang

    2012-12-01

    Full Text Available The asymmetric unit of the title compound, [Mn2(C6H6O72(H2O4]·C12H10N2·2H2O, contains half of the centrosymmetric Mn complex dimer, half of a 1,2-bis(pyridin-4-ylethene molecule, which lies across an inversion center, and one water molecule. Two citrate ligands bridge two MnII ions, and each MnII atom is coordinated by four O atoms from the citrate ligands (one from hydroxy and three from carboxylate groups and two water O atoms, forming a distorted octahedral environment. In the crystal, O—H...O and O—H...N hydrogen bonds link the centrosymmetric dimers and lattice water molecules into a three-dimensional structure which is further stabilized by intermolecular π–π interactions [centroid–centroid distance = 3.959 (2 Å]. Weak C—H...O hydrogen bonding interactions are also observed.

  14. Resting eggs as new biosorbent for preconcentration of trace elements in various samples prior to their determination by FAAS.

    Science.gov (United States)

    Saçmacı, Serife; Yılmaz, Yakup; Kartal, Senol; Kaya, Murat; Duman, Fatih

    2014-06-01

    In this study, the resting eggs of aquatic creatures living in freshwater (Daphnia, Cladocera, Crustacean) ecosystems were used as a novel biosorbent extractant for synchronous preconcentration of trace Cd(II), Co(II), Cu(II), Mn(II), and Ni(II) previous to measurement by flame atomic absorpiton spectrometry (FAAS). Using column procedures, optimization studies were conducted to realize the effective adsorption of the analyte ions such as the solution pH, amount of the biosorbent, volume of the sample, interfering ions, etc. A high preconcentration factor of 67 and low relative standard deflection of ≤4.1% (n=8) were obtained. The invention constrains based on the 3 s/b criterion were 2.4 for Cd(II), 41.4 for Co(II), 4.2 for Cu(II), 3.0 for Mn(II), and 9.6 μg L(-1) for Ni(II). The accuracy of the method was verified by analysis of a certified standard reference material. The used procedure was applied to the definition of the analytes in diverse environmental samples with convincing results. Consequently, the resting eggs of Daphnia can be used as a biosorbent for preconcentration and biosorption studies.

  15. Ternary complexes of albumin-Mn(II)-bilirubin and Electron Spin Resonance studies of gallstones

    CERN Document Server

    Chikvaidze, E N; Kirikashvili, I N; Mamniashvili, G I

    2009-01-01

    The stability of albumin-bilirubin complex was investigated depending on pH of solution. It was shown that the stability of complex increases in presence of Mn(II) ions. It was also investigated the paramagnetic composition of gallstones by the electron spin resonance (ESR) method. It turned out that all investigated gallstones contain a free bilirubin radical-the stable product of its radical oxidation. Accordingly the paramagnetic composition gallstones could be divided on three main types: cholesterol, brown pigment and black pigment stones. ESR spectra of cholesterol stones is singlet with g=2.003 and splitting between components 1.0 mT. At the same time the brown gallstones, besides aforementioned signal contain the ESR spectrum which is characteristics for Mn(II) ion complexes with inorganic compounds and, finally, in the black pigment stones it was found out Fe(III) and Cu(II) complexes with organic compounds and a singlet of bilirubin free radical. It is supposed that crystallization centers of gallst...

  16. Crystal structure of bis-(2,2'-bi-pyridine-κ(2) N,N')bis-(thio-cyanato-κN)mang-anese(II) 2,2'-bi-pyridine monosolvate.

    Science.gov (United States)

    Suckert, Stefan; Jess, Inke; Näther, Christian

    2015-01-01

    In the crystal structure of the mononuclear title compound, [Mn(NCS)2(C10H8N2)2]·C10H8N2, the Mn(II) cation is coordin-ated in an all-cis configuration by two N-bound thio-cyanate anions and two 2,2'-bi-pyridine ligands within a slightly distorted octa-hedral environment. The asymmetric unit consists of one Mn(II) cation, two thio-cyanate anions and two 2,2'-bi-pyridine ligands, as well as two non-coordinating 2,2'-bi-pyridine ligands that are each located on centres of inversion. In the crystal structure, the discrete [Mn(NCS)2(C10H8N2)2] complex mol-ecules are arranged in such a way that cavities are formed, in which the solvent 2,2'-bi-pyridine mol-ecules are located. Apart from van der Waals forces, there are no remarkable inter-molecular inter-actions present in the crystal structure.

  17. Speciation analysis of Mn(II)/Mn(VII) using Fe3O4@ionic liquids-β-cyclodextrin polymer magnetic solid phase extraction coupled with ICP-OES.

    Science.gov (United States)

    Chen, Songqing; Qin, Xingxiu; Gu, Weixi; Zhu, Xiashi

    2016-12-01

    Ionic liquids-β-cyclodextrin polymer (ILs-β-CDCP) was attached on Fe3O4 nanoparticles to prepare magnetic solid phase extraction agent (Fe3O4@ILs-β-CDCP). The properties and morphology of Fe3O4@ILs-β-CDCP were characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction(XRD), size distribution and magnetic analysis. A new method of magnetic solid phase extraction (MSPE) coupled to ICP-OES for the speciation of Mn(II)/Mn(VII) in water samples was established. The results showed that Mn(VII) and total manganese [Mn(II)+Mn(VII)] were quantitatively extracted after adjusting aqueous sample solution to pH 6.0 and 10.0, respectively. Mn(II) was calculated by subtraction of Mn(VII) from total manganese. Fe3O4@ILs-β-CDCP showed a higher adsorption capacity toward Mn(II) and Mn(VII). Several factors, such as the pH value, extraction temperature and sample volume, were optimized to achieve the best extraction efficiency. Moreover, the adsorption ability of Fe3O4@ILs-β-CDCP would not be significantly lower after reusing of 10 times. The accuracy of the developed method was confirmed by analyzing certified reference materials (GSB 07-1189-2000), and by spiking spring water, city water and lake water samples. Copyright © 2016 Elsevier B.V. All rights reserved.

  18. Influence of the nature and environment of manganese in Mn-BEA zeolites on NO conversion in selective catalytic reduction with ammonia.

    Science.gov (United States)

    Baran, R; Valentin, L; Krafft, J-M; Grzybek, T; Glatzel, P; Dzwigaj, S

    2017-05-31

    Manganese-containing BEA zeolites, MnxSiBEA (x = 1-4 wt%) and Mn(I.E.)AlBEA, were prepared by a two-step post-synthesis method and a conventional wet ion-exchange, respectively, and applied as catalysts in the selective catalytic reduction of NO with ammonia (NH3-SCR). The physicochemical analysis of zeolite properties by high-energy-resolution fluorescence-detected XANES (HERFD-XANES) and X-ray emission spectroscopy (XES) uncovered that the coordination, geometry and oxidation state of Mn species are strongly related to the preparation method. Additionally, the study of catalyst acidity by FTIR spectroscopy with CO and pyridine probe molecules provided important insight into the number and type of acidic centres present on the catalyst surface. The catalytic results revealed that NO conversion depended on the state and content of Mn. The zeolites obtained by the two-step post-synthesis method and with a low Mn content were very active in the medium temperature range (NO conversion ∼100%) with simultaneous high selectivity to N2 due to the presence of isolated, framework Mn(iii) and Mn(ii) species. The N2O formation was especially high in the case of catalysts containing extra-framework polynuclear Mn species and negligible in the case of Mn(I.E.)AlBEA containing predominantly isolated, extra-framework Mn(ii) species.

  19. Synthesis, spectral characterization and thermal aspects of coordination polymers of some transition metal ions with adipoyl bis(isonicotinoylhydrazone)

    Science.gov (United States)

    Haque, Mahejabeen Azizul; Paliwal, L. J.

    2017-04-01

    A series of metal coordination polymers of Mn(II), Fe(II), Co(II), Ni(II), Cu(II), and Zn(II), obtained by the reaction of metal acetate with newly synthesized adipoyl bis(isonicotinoylhydrazone) (ADBI) have been investigated. The ligand has been characterized by 1H NMR, 13C NMR, FTIR, and ESI mass spectra. Structural and spectroscopic characterization of the coordination polymers have been carried out using elemental analysis, XRD, SEM, infrared and diffused reflectance spectra, magnetic susceptibility measurements and thermogravimetric analytical techniques. Each metal ion is coordinated to the ligand through oxygen of carbonyl group and the nitrogen of azomethine group of ligand forming a stable 5-membered heterocyclic ring. The synthesized ligand coordinates in an octadentate manner. Magnetic and diffused reflectance spectral studies reveal octahedral geometry of Co(II), Cu(II), Fe(II) and Ni(II) coordination polymers and tetrahedral geometry of Mn(II) and Zn(II) coordination polymers. The thermal stability and decomposition steps of all coordination polymers have been studied using TG, DTG and DTA techniques. Moreover, the kinetic parameters such as activation energy (Ea*), order of reaction (n), Arrhenius factor (A), change in entropy (ΔS*), change in enthalpy (ΔH*) and free energy change (ΔG*) were evaluated at each stage of decomposition curve using Coats-Redfern method.

  20. Synthesis, characterization, antibacterial and antifungal studies of some transition and rare earth metal complexes of N-benzylidene-2-hydroxybenzohydrazide

    Directory of Open Access Journals (Sweden)

    T.K. Chondhekar

    2011-12-01

    Full Text Available The solid complexes of Cu(II, Co(II, Mn(II, La(III and Ce(III were prepared from bidentate Schiff base, N-benzylidene-2-hydroxybenzohydrazide. The Schiff base ligand was synthesized from 2-hyhdroxybenzohydrazide and benzaldehyde. These metal complexes were characterized by molar conductivity, magnetic susceptibility, thermal analysis, X-ray diffraction, FTIR, 1H-NMR, UV-Vis and mass spectroscopy. The analytical data of these metal complexes showed metal:ligand ratio of 1:2. The physico-chemical study supports the presence of square planar geometry around Cu(II and octahedral geometry around Mn(II, Co(II, La(III and Ce(III ions. The IR spectral data reveal that the ligand behaves as bidentate with ON donor atom sequence towards central metal ion. The molar conductance values of metal complexes suggest their non-electrolyte nature. The X-ray diffraction data suggest monoclinic crystal system for these complexes. Thermal behavior (TG/DTA and kinetic parameters calculated by Coats-Redfern method are suggestive of more ordered activated state in complex formation. The ligand and their metal complexes were screened for antibacterial activity against Staphylococcus aureus and Escherichia coli and fungicidal activity against Aspergillus niger and Trichoderma.

  1. Crystal structure of bis(2,2′-bipyridine-κ2N,N′bis(thiocyanato-κNmanganese(II 2,2′-bipyridine monosolvate

    Directory of Open Access Journals (Sweden)

    Stefan Suckert

    2015-01-01

    Full Text Available In the crystal structure of the mononuclear title compound, [Mn(NCS2(C10H8N22]·C10H8N2, the MnII cation is coordinated in an all-cis configuration by two N-bound thiocyanate anions and two 2,2′-bipyridine ligands within a slightly distorted octahedral environment. The asymmetric unit consists of one MnII cation, two thiocyanate anions and two 2,2′-bipyridine ligands, as well as two non-coordinating 2,2′-bipyridine ligands that are each located on centres of inversion. In the crystal structure, the discrete [Mn(NCS2(C10H8N22] complex molecules are arranged in such a way that cavities are formed, in which the solvent 2,2′-bipyridine molecules are located. Apart from van der Waals forces, there are no remarkable intermolecular interactions present in the crystal structure.

  2. Equilibrium and spectral studies on ligational behaviour of N,N'-diformylhydrazine

    Indian Academy of Sciences (India)

    G Bhargavi; B Sireesha; Ch Sarala Devi

    2003-02-01

    The ligand N,N'-diformylhydrazine (DFH) is a resonance hybrid of its keto- and enol-forms. The resonance structures indicate enolisation of one as well as both the carbonyl groups. This indicates the presence of dissociable protons in the molecule. Equilibrium studies carried out with DFH indicate the presence of one dissociable proton. The solid complexes of Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II) and Pb(II) with DFH have been synthesized, and have been characterized by elemental analysis, magnetic susceptibility, IR, Far-IR, 1H NMR, TGA, FAB and reflectance spectra. IR and 1H NMR spectra of the complexes indicate deprotonation of both the enol protons upon complexation. Elemental and TG analyses of Mn(II), Ni(II), Zn(II) DFH complexes indicate 1 : 1 metal to ligand composition. The dimeric nature of the Mn(II)-DFH complex is supported by its FAB spectrum.

  3. Synthesis, Characterization and Antimicrobial Studies of N1-[(1E-1-(2-Hydroxyphenyl ethylidene]-2-oxo-2H-chromene-3-carbohydrazide and its Metal Complexes

    Directory of Open Access Journals (Sweden)

    K. Siddappa

    2009-01-01

    Full Text Available A new complexes of the type ML, MʹL and M″L [where M=Cu(II, Co(II, Ni(II and Mn(II, Mʹ=Fe(III and M″=Zn(II, Cd(II and Hg(II and L=N1-[(1E-1-(2-hydroxyphenylethylidene]-2-oxo-2H-chromene- 3-carbohydrazide (HL] Schiff base have been synthesized and characterized by elemental analysis, magnetic susceptibility, molar conductance, IR, 1H NMR, UV-Visible and ESR data. The studies indicate the HL acts as doubly monodentate bridge for metal ions and form mononuclear complexes. The complexes Ni(II, Co(II, Cu(II Mn(II and Fe(III complexes are found to be octahedral, where as Zn(II, Cd(II and Hg(II complexes are four coordinated with tetrahedral geometry. The synthesized ligand and its metal complexes were screened for their antimicrobial activity.

  4. Synthesis, Spectroscopic, Anticancer, and Antimicrobial Properties of Some Metal(II Complexes of (Substituted Nitrophenol Schiff Base

    Directory of Open Access Journals (Sweden)

    Aderoju A. Osowole

    2012-01-01

    Full Text Available The Schiff base, 2-[(2,3-dihydro-1H-inden-4-yliminomethyl]-5-nitrophenol coordinates to Mn(II, Cu(II, Zn(II, and Pd(II ions through the phenolic O and imine N atoms. The complexes are characterized by physicochemical and spectroscopic methods. The metal complexes formed as [ML2]xH2O with exception of the Cu(II complex which is anhydrous. Spectroscopic data corroborate the adoption of a four-coordinate, tetrahedral geometry for the Mn(II, and Zn(II complexes, and a four-coordinate, square planar geometry for the Cu(II and Pd(II complexes. None is an electrolyte in DMSO. The in vitro anticancer activities of the metal free ligand, Cu(II, Zn(II, and Pd(II complexes against MCF-7 (human breast adenocarcinoma and HT-29 (colon carcinoma cells reveal that the Pd(II complex has the best cytotoxic activity against MCF-7 cells with an IC50 of 5.94 μM, which is within the same order of activity as cisplatin. Furthermore, the ligand and the Zn(II complex exhibit broad-spectrum activity against two gram-positive bacteria, three gram-negative bacteria, and a fungus with inhibitory zones range of 10.0–20.0 and 10.0–17.0 mm, respectively.

  5. Process for treating alkaline wastes for vitrification

    Science.gov (United States)

    Hsu, Chia-lin W.

    1994-01-01

    According to its major aspects and broadly stated, the present invention is a process for treating alkaline waste materials, including high level radioactive wastes, for vitrification. The process involves adjusting the pH of the wastes with nitric acid, adding formic acid (or a process stream containing formic acid) to reduce mercury compounds to elemental mercury and MnO{sub 2} to the Mn(II) ion, and mixing with class formers to produce a melter feed. The process minimizes production of hydrogen due to noble metal-catalyzed formic acid decomposition during, treatment, while producing a redox-balanced feed for effective melter operation and a quality glass product. An important feature of the present invention is the use of different acidifying and reducing, agents to treat the wastes. The nitric acid acidifies the wastes to improve yield stress and supplies acid for various reactions; then the formic acid reduces mercury compounds to elemental mercury and MnO{sub 2}) to the Mn(II) ion. When the pH of the waste is lower, reduction of mercury compounds and MnO{sub 2}) is faster and less formic acid is needed, and the production of hydrogen caused by catalytically-active noble metals is decreased.

  6. Biosorption of Cadmium and Manganese Using Free Cells of Klebsiella sp. Isolated from Waste Water.

    Directory of Open Access Journals (Sweden)

    Yunnan Hou

    Full Text Available In the present study, we evaluated a bacterium that was isolated from waste water for its ability to take up cadmium and manganese. The strain, identified both biochemically and by its 16S rRNA gene sequence as Klebsiella, was named Yangling I2 and was found to be highly resistant to heavy metals. Surface characterization of the bacterium via SEM revealed gross morphological changes, with cells appearing as biconcave discs after metal exposure rather than their typical rod shape. The effects of pH, temperature, heavy metal concentration, agitation and biomass concentration on the uptake of Cd(II and Mn(II was measured using atomic absorption spectrophotometry. The results showed that the biosorption was most affected by pH and incubation temperature, being maximized at pH 5.0 and 30°C, with absorption capacities of 170.4 and 114.1 mg/g for Cd(II and Mn(II, respectively. Two models were investigated to compare the cells' capacity for the biosorption of Cd and Mn, and the Langmuir model based on fuzzy linear regression was found to be close to the observed absorption curves and yield binding constants of 0.98 and 0.86 for Cd and Mn, respectively. This strain of Klebsiella has approximately ten times the absorption capacity reported for other strains and is promising for the removal of heavy metals from waste water.

  7. Inhibition of nitrification in soil by metal diethyldithiocarbamates.

    Science.gov (United States)

    Arora, A; Singh, Bijay; Sud, Dhiraj; Srivastava, T; Arora, C L

    2003-09-01

    Nitrification acts as a key process in determining fertilizer use efficiency by crops as well as nitrogen losses from soils. Metal dithiocarbamates in addition to their pesticidal properties can also inhibit biological oxidation of ammonium(nitrification) in soil. Metal [M = V(III), Cr(III), Mn(II), Fe(III), Ni(II), Cu(II), Zn(II) and Co(II)] diethyldithiocarbamates (DEDTC) were synthesized by the reaction of sodium diethyldithiocarbamate with metal chloride in dichloromethane/water mixture. These metal diethyldithiocarbamates were screened for their ability to inhibit nitrification at different concentrations( 10 microg/g soil, 50 microg/g soil and 100 microg/g soil). With increasing concentration of the complex, capacity to retard nitrification increased but the extent of increase varied for different metals. At 100 microg/g soil, different complexes showed nitrification inhibition from 22.36% to 46.45% . Among the diethyldithiocarbamates tested, Zn(DEDTC)2 proved to be the most effective nitrification inhibitor at 100 microg/g soil. Manganese, iron and chromium diethyldithiocarbamates also proved to be effective nitrification inhibitors than the others at 100 microg/g soil. The order of percent nitrification inhibition in soil by metal diethyldithiocarbamates was: Zn(II) > Mn(II) > Fe(III) > Cr(III) > V(III) > Co(II) > Ni(II) > Cu(II).

  8. Electronic Spectra of Chevreul's Salts

    Directory of Open Access Journals (Sweden)

    Silva Luciana A. da

    2002-01-01

    Full Text Available The isomorphic series of double sulfites with empirical formula Cu2SO3.MSO3.2H 2O (where M is Cu, Fe, Mn, or Cd have been prepared from the Cu(II replacement by transition metal ions such as Mn(II, Fe(II and Cd(II ions in Chevreul's salt, Cu2SO3.CuSO3.2H 2O. As a consequence, the isomorphic species present distinct colors. Molecular modeling calculations were carried out for the dimeric [CuI2(SO3 2(SO32]6- center. The electronic spectra of the Chevreul's salt consist of a charge-transfer band around 425 nm associated with the [CuI2(SO3 2(SO32]6- chromophore and two ligand field transitions at 785 and 1000 nm involving the Jahn-Teller splitting of the Cu(II levels. An additional intervalence-transfer band, responsible for its characteristic red color, can be found at 500 nm. The replacement of the Cu(II ions for Fe(II, Mn(II and Cd(II does not eliminate the absorption band at 425 nm, supporting its assignment as a charge-transfer transition centered on the Cu(I sites; while the original band at 500 nm disappears, in agreement with its intervalence transfer nature.

  9. Synthesis, X-Ray crystal structure, photophysical characterization and nonlinear optical properties of the unique manganese complex with picolinate and 1,10 phenantroline: toward the designing of new high NLO response crystal

    Science.gov (United States)

    Tamer, Ömer; Avcı, Davut; Atalay, Yusuf

    2016-12-01

    The first manganese complex of picolinic acid (also known as 2-pyridinecarboxylic acid) and 1,10 phenantroline has been synthesized, and its structure has been fully characterized by means of X-Ray diffraction method as well as FT-IR, Raman and UV-vis spectroscopies. In order to provide a deep understanding about the relation among the nonlinear optical properties, structural, spectroscopic and electronic behaviors, density functional theory (DFT) calculations have been performed by using hybrid B3LYP level. The intensive interactions between the bonding orbitals of donor O/N atoms and antibonding orbitals of Mn(II) lone pairs confirm the X-Ray diffraction results. Each of the conditions such as small energy gap between HOMO and LUMO, high energy second order perturbation interaction, elongation of conjugated π system and high spin Mn(II) ion induce the first static hyperpolarizability (β) parameter of investigated complex. The β parameter for [Mn(pic)2(phen)]·H2O complex has been found to be approximately 22 times higher than p-nitroaniline.

  10. Synthesis of M(II Complexes with Clioquinol and their Evaluation of Antimicrobial, Antioxidant and Anti-tubercular Activity

    Directory of Open Access Journals (Sweden)

    Chaudhari VR

    2015-12-01

    Full Text Available Co(II, Ni(II, Cu(II and Mn(II complexes synthesized by reflux of 6-bromo-3-(3-(4-chlorophenylacryloyl-2H-chromen-2-one, Ciprofloxacin and various transition metal. 1H, 13C, IR and ESI Mass confirm the formation of ligand. The metal complexes were characterized on the basis of various spectroscopic techniques like IR studies and elemental analysis while the geometry of complexes was octahedral which is confirmed by electronic spectra and thermogravimetric analysis. The compounds were subjected to antimicrobial, antioxidant and anti-tubercular activity screening using serial broth dilution method and Minimum Inhibitory Concentration (MIC is determined. Mn(II complex has shown significant antifungal activity with an MIC of 6.25µg/mL while Cu(II complex is noticeable for antibacterial activity at the same concentration. Anti-TB activity of the ligand has enhanced on complexation with Ni(II and Co(II ions. While Ni(II complex shows superior antioxidant activity than other complexes.

  11. Preconcentration and determination of trace metal ions from aqueous samples by newly developed gallic acid modified Amberlite XAD-16 chelating resin.

    Science.gov (United States)

    Sharma, R K; Pant, Parul

    2009-04-15

    Gallic acid was immobilized on Amberlite XAD-16 by coupling it through -N=N group. The resulting chelating resin Amberlite XAD-16 gallic acid, characterized by thermogravimetric analysis (TGA), infrared (IR) spectra and BET analysis, was used to preconcentrate Cr(III), Mn(II),Fe(III),Co(II), Ni(II) and Cu(II)ions. The resin was employed for the preconcentration of the metal ions present in river water and industrial area aqueous samples. Several parameters like effect of pH, effect of time, effect of sample volume and flow rate of sample were investigated. The sorption capacities for the resin were 216 micromol g(-1), 180 micromol g(-1), 403 micromol g(-1), 281 micromol g(-1), 250 micromol g(-1) and 344 micromol g(-1) for Cr(III), Mn(II), Fe(III), Co(II), Ni(II) and Cu(II) respectively. The preconcentration factors for Cr(III), Mn(II), Fe(III), Ni(II), Co(II) and Cu(II) were found out to be 300, 200, 400, 285.7, 300 and 400 respectively. The effect of various interfering ions was also studied. Results were validated by using standard addition method for river water sample.

  12. Crystal structure of trans-diaquabis(nicotinamide-κN1bis(4-nitrobenzoato-κOmanganese(II

    Directory of Open Access Journals (Sweden)

    Gülçin Şefiye Aşkın

    2016-05-01

    Full Text Available The asymmetric unit of the title compound, [Mn(C7H4NO42(C6H6N2O2(H2O2], contains one MnII atom, one 4-nitrobenzoate (NB anion, one nicotinamide (NA ligand and one water molecule; NA and NB each act as a monodentate ligand. The MnII atom, lying on an inversion centre, is coordinated by four O atoms and two pyridine N atoms in a distorted octahedral geometry. The water molecules are hydrogen bonded to the carboxylate O atoms. The dihedral angle between the carboxylate group and the adjacent benzene ring is 24.4 (3°, while the benzene and pyridine rings are oriented at a dihedral angle of 86.63 (11°. In the crystal, O—H...O and N—H...O hydrogen bonds link the molecules, forming a layer parallel to the ab plane. The layers are further linked via weak C—H...O hydrogen bonds, a π–π stacking interaction [centroid–centroid distance = 3.868 (2 Å] and a weak C—H...π interaction, resulting in a three-dimensional network.

  13. Inhibition of nitrification in soil by metal diethyldithiocarbamates

    Institute of Scientific and Technical Information of China (English)

    A. Arora; Bijay Singh; Dhiraj Sud; T.Srivastava; C. L. Arora

    2003-01-01

    Nitrification acts as a key process in determining fertilizer use efficiency by crops as well as nitrogen losses from soils. Metal dithiocarbamates in addition to their pesticidal properties can also inhibit biological oxidation of ammonium(nitrification) in soil. Metal [M=V(III), Cr(III), Mn(II), Fe(III), Ni(II), Cu(II), Zn(II) and Pt(IV)] diethyldithiocarbamates (DEDTC) were synthesized by the reaction of sodium diethyldithiocarbamate with metal chloride in dichloromethane/water mixture. These metal diethyldithiocarbamates were screened for their ability to inhibit nitrification at different concentrations(10 μg/g soil, 50 μg/g soil and 100 μg/g soil). With increasing concentration of the complex, capacity to retard nitrification increased but the extent of increase varied for different metals. At 100 μg/g soil, different complexes showed nitrification inhibition from 22.36% to 46.45%. Among the diethyldithiocarbamates tested, Zn(DEDTC)2 proved to be the most effective nitrification inhibitor at 100 μg/g soil. Manganese, iron and chromium diethyldithiocarbamates also proved to be effective nitrification inhibitors than the others at 100 μg/g soil. The order of percent nitrification inhibition in soil by metal diethyldithiocarbamates was: Zn(II) > Mn(II) > Fe(III) > Cr(III) >V(III) > Co(II) > Ni(II) > Cu(II).

  14. Polyhedral C2@Agn cages distorted by ancillary pyridine N-oxide ligands in silver-acetylenediide complexes.

    Science.gov (United States)

    Zhao, Xiao-Li; Zhang, Lin-Ping; Mak, Thomas C W

    2006-07-01

    Reactions of the pyridine N-oxide ligands L, L2 and L3 with the silver acetylenediide-containing system under hydrothermal conditions gave rise to four silver-acetylenediide complexes bearing interesting C2@Agn motifs: (Ag2C2)2(AgCF3CO2)8(L1)3.5 (1), (Ag2C2)2(AgCF3CO2)8(L2)2 (2), (Ag2C2)(AgCF3CO2)4(L3) (3) and [(Ag7(C2)(CF3SO3)3(L3)2(H2O)2] x 2CF3SO3 (4) (L = nicotinic acid N-oxide, L(1) = pyridine N-oxide, L2 = 1,2-bis(4-pyridyl)ethane N,N'-dioxide, L3 = 1,3-bis(4-pyridyl)propane N,N'-dioxide), which exhibit new distorted polyhedral C2@Agn cage motifs. Complex 1 has a pair of acetylenediide dianions encapsulated in a Ag(14) aggregate composed of three polyhedral parts, whereas 2 contains an irregular (C2)2@Ag13 double cage. In 3, the basic building unit is a centrosymmetric (C2)2@Ag12 double cage with each component single cage taking the shape of a highly distorted triangulated dodecahedron with one missing vertex. As to complex 4, the core is a C2@Ag7 single cage in the form of a slightly distorted monocapped trigonal prism with four cleaved edges that include all three vertical sides. Furthermore, in the silver-rich environment, the pyO-type ligands are induced to exhibit unprecedented coordination modes, such as the mu(5)-O,O,O,O',O' ligation mode of L2 in 2 and the mu4-O,O,O',O' mode of L3 in 3 and 4.

  15. Investigation on the syntheses and structures of YIII complexes with aminopolycarboxylic acids (IV)

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    This paper deals with the structure of the YIII complex with aminopolycarboxylic acids, synthesis and structural determination of the complex (NH4)[YIII(edta)(H2O)3]3H2O (edta = ethylenediaminetetraacetic acid). The crystal and molecular structures of the (NH4)[YIII(edta)(H2O)3]3H2O complex have been determined by single-crystal X-ray structure analysis. The crystal of the complex (NH4)[YIII(edta)(H2O)3]3H2O belongs to orthorhombic crystal system and fdd2 space group. The crystal data are as follows: a = 1.944 1(9) nm, b = 3.545 9(18) nm, c = 1.219 6(6) nm, V = 8.407(7) nm3, Z = 16, Mr = 503.25, Dc = 1.590 gcm 3,  = 2.844 mm 1 and F(000) = 4 160. The final R and Rw are 0.048 6 and 0.133 2 for 3 388 (I>2 (I)) unique reflections, respectively. The complex anion [YIII(edta)(H2O)3]  has a pseudo-monocapped square antiprismatic nine-coordinate structure in which the six coordinate atoms (two N and four O) are from an edta ligand and three water molecules coordinate to the central YIII ion directly. From the results it can be predicted that the YIII ion can also form a nine-coordinate complex with ttha (=triethylenetetraminehexaacetic acid) ligand, so the radioactive complex anion [90YIII(Httha)]2  can supply a free carboxyl group ( CH2COOH) being used for molecular embellishment to form the TDDS for the treatment of cancers.

  16. Mixed europium valence in Eu0.937Ba8[BN2]6 - Structure and spectroscopic behavior

    Science.gov (United States)

    Dierkes, Tobias; Seidel, Stefan; Benndorf, Christopher; Heletta, Lukas; de Oliveira Junior, Marcos; Holtkamp, Michael; Karst, Uwe; Block, Theresa; Jüstel, Thomas; Eckert, Hellmut; Pöttgen, Rainer

    2017-08-01

    Polycrystalline samples of Sr0.95Eu0.05Ba8[BN2]6 and Eu0.937Ba8[BN2]6 were synthesized via conventional solid-state reaction from the binary precursor compounds Sr3N2, EuN, Ba3N2 and BN at 1000 °C. The structure of Eu0.937Ba8[BN2]6 was refined from single crystal X-ray diffractometer data: Eu0.937Ba8[BN2]6 type, Fd 3 barm, a = 1594.54(9) pm, wR2 = 0.0654, 380 F2 values and 23 variables. The 8a europium site shows an occupancy of only 93.7(9) % suggesting partial oxidation of europium to fulfil an electron-precise description, i. e. EuII0.81EuIII0.13Ba8[BN2]6. The mixed europium valence was confirmed by magnetic susceptibility measurements (reduced magnetic moment of 7.28 μB per europium atom) and 151Eu Mössbauer spectroscopy (EuII: EuIII = 82: 18). The nitridoborate anions are coordinated by slightly distorted, mono-capped (europium) square prisms formed by the barium atoms. All metal cations are hexa-coordinated by nitrogen atoms. The EPR spectra of EuxSr1-xBa8[BN2]6 samples (0.001 ≤ x ≤ 0.01) suggest close to cubic local symmetry of the Eu2+ dopant ions and reveal some highly unusual features: Magnetic hyperfine splitting is only observed with one of the Eu nuclear isotopes, and the coupling constant of 243.6 MHz is extremely large compared to values (90-100 MHz) typically observed in the literature for Eu2+ doped crystalline materials.

  17. Synthesis, Characterization and Properties of Bis{oxo-bis[heteroaromatic carboxylatodibenzyltin(Ⅳ)]} and Crystal Structure of Bis{oxo-bis[2-furylcarboxylatodibenzyltin(Ⅳ)]}

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    A series of bis{oxo-bis[heteroaromatic carboxylatodibenzyltin(Ⅳ)]} complexes {[(PhCH2)2Sn*(O2CR)]2O}2[where R=2-furyl, 2-(2-furyl)vinyl, 2-(5-tert-butyl)furyl, 2-thiophenyl, 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-indolyl, 3-indolylmethyl, 3-indolylpropyl] was synthesized by the reactions of heteroaromatic carboxylic acids with dibenzyltin(Ⅳ) oxide. All the complexes were characterized by elemental analysis, IR, and NMR spectra. The complexes were tested against two human tumour cell lines: MCF-7 and WiDr. The results show that they have higher activities in vitro. The crystal structure of bis{oxo-bis[2-furylcarboxylatodibenzyltin(Ⅳ)]}(1) was determined by X-ray diffraction. The crystal belongs to monoclinic space group P21/n, a=1.6641(2) nm, b=1.25073(18) nm, c=1.7193(3) nm, β=101.951(2)°, Z=2, R1=0.0446, wR2=0.1100. Complex 1 is of a centrosymmetric dimer structure with a four-membered central endo-cyclic Sn2O2 unit in which the bridged oxygen atoms are tri-coordinated. Each bridged oxygen atom also connects with an exo-cyclic tin atom. The tin atoms are six-coordinated and have a coordination geometry of a distorted octahedron. The exo-cyclic tin atoms are five-coordinated and have a coordination geometry of a monocapped trigonal bipyramid with a very similarly distorted mode. Four carboxylate ligands are divided into two types. The two of the four carboxylate ligands are bidentate and bridged to each pair of exo- and endo-cyclic tin atoms by using both the oxygen atoms. The other two are monodentate and bridged to each pair of exo- and endo-cyclic tin atoms but each utilizes one O atom only.

  18. Synthesis,Characterization and Properties of Bis{oxo—bis[heteroaromatic carboxylatodibenzyltin(Ⅳ)]}and Crystal Structure of Bis{oxo—bis[2—furylcarboxylatodibenzyltin(Ⅳ)]}

    Institute of Scientific and Technical Information of China (English)

    YINHan-dong; WANGChuan-hua; WANGYong; MAChun-lin

    2003-01-01

    A series of bis{oxo-bis[heteroaromatic carboxylatodibenzyltin(Ⅳ)]}complexes {[(PhCH2)2Sn·(O2CR)]2O}2[where R=2-furyl,2-(2-furyl)vinyl.2-(5-tert-butyl)furyl.2-thiophenyl,2-pyridinyl,2-pyridinyl,3-pyridinyl,4-pyridinyl,3-indolyl,3-indolylmethyl,3-indolylpropyl]was synthesizde by the reactions of heteroaromatic carboxylic acids with dibenzyltin(Ⅳ) oxide.All the complexes were characterized by elemental analysis,IR,and NMR spectra.The complexes were tested against two human tumour cell lines:MCF-7 and WiDr.The results show that they have higher activities in vitro.The crystal structure of bis{oxo-bis[2-furylcarboxylatodibenzyltin(Ⅳ)]}(1)was determined by X-ray diffraction.The crystal structure of bis{ox-bis [2-furylcarboxylatodibenzyltin(Ⅳ)]}(1) was determined by X-ray diffraction.The crystal belongs to monoclinic space group P21/n,a=1.6641(2)nm,b=1.25073(18)nm,c=1.7193(3)nm,β=101.951(2)°,Z=2.R1=0.0446,ωR2=0.1100,Complex 1 is of a centrosymmetric dimer structre with a four-membered central endo-cyclic Sn2O2 unit in which the bridged oxygen atoms are tri-coordinated.Each bridgde oxygen atom also connects with an exo-cyclic tin atom.The tin atoms are six-coordinated and have a coordination geometry of a monocapped trigonal bipyramid with a very similarly distorted mode.Four carboxylate ligands are divided into two types.The two of the four carboxylate ligands are bidentate and bridged to each pair of exoeach pair of exo-and endo-cyclic tin atoms but each utilized one O atom only.

  19. Cyanomethylene-bis(phosphonate)-based lanthanide complexes: structural, photophysical, and magnetic investigations.

    Science.gov (United States)

    Maxim, Catalin; Branzea, Diana G; Tiseanu, Carmen; Rouzières, Mathieu; Clérac, Rodolphe; Andruh, Marius; Avarvari, Narcis

    2014-03-01

    The syntheses, structural investigations, magnetic and photophysical properties of a series of 10 lanthanide mononuclear complexes, containing the heteroditopic ligand cyanomethylene-bis(5,5-dimethyl-2-oxo-1,3,2λ(5)-dioxa-phosphorinane) (L), are described. The crystallographic analyses indicate two structural types: in the first one, [Ln(III)(L)3(H2O)2]·H2O (Ln = La, Pr, Nd), the metal ions are eight-coordinated within a square antiprism geometry, while the second one, [Ln(III)(L)3(H2O)]·8H2O (Ln = Sm, Eu, Gd, Tb, Dy, Ho, Er), contains seven-coordinated Ln(III) ions within distorted monocapped trigonal prisms. Intermolecular hydrogen bonding between nitrogen atoms of the cyano groups, crystallization, and coordination water molecules leads to the formation of extended supramolecular networks. Solid-state photophysical investigations demonstrate that Eu(III) and Tb(III) complexes possess intense luminescence with relatively long excited-state lifetimes of 530 and 1370 μs, respectively, while Pr(III), Dy(III), and Ho(III) complexes have weak intensity luminescence characterized by short lifetimes ranging between a few nanoseconds to microseconds. The magnetic properties for Pr(III), Gd(III), Tb(III), Dy(III), and Ho(III) complexes are in agreement with isolated Ln(III) ions in the solid state, as suggested by the single-crystal X-ray analyses. Alternating current (ac) susceptibility measurements up to 10 kHz reveal that only the Ho(III) complex shows a frequency-dependent ac response, with a relaxation mode clearly observed at 1.85 K around 4500 Hz.

  20. Synthesis, Crystal Structure and Thermal Stability of a Saturated Dimeric Ce(Ⅲ)-chelated Complex Based on Benzoate and 1,10-Phenanthroline Ligands

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    The title complex, [Ce(BA)3phen]2 (BA = benzoate, phen = 1,10-phenanthroline),was prepared by the reaction of Ce(NO3)3·6H2O, benzoic acid and 1,10-phenanthroline. The complex was characterized by single-crystal X-ray diffraction, elemental analysis, IR spectra and TG-DTG techniques. The results show that the crystal is of triclinic, space group P(1) with a =10.912(2), b = 11.962(3), c = 12.474(3)(A), a = 104.889(3), β = 93.523(3), γ = 113.332(3)°,C66H46Ce2N4O12, Mr = 1366.90, V= 1420.2(6) (A)3, Z = 1, Dc = 1.598 g/cm3,μ = 1.652 mm-1, S =1.024 and F(000) = 682. The final R = 0.0391 and wR = 0.0947 for 4878 observed reflections with I > 2σ(1). The structure of the title complex consists of two Ce(C6H5COO)3(C12H8N2) units,forming a binuclear molecule. Each Ce(Ⅲ) is coordinated by two O atoms of one bidentate chelating carboxylate group, five O atoms of two bidentate bridging and two tridentate chelating-bridging carboxylate groups, and two N atoms of one 1,10-phenanthroline molecule to complete a distorted monocapped square antiprism geometry. Its thermogravimetric analysis was determined by TG-DTG techniques.

  1. Synthesis, structure, magnetism, and optical properties of theordered mixed-lanthanide sulfides gamma-LnLn'S3 (Ln=La, Ce; Ln'=Er, Tm,Yb)

    Energy Technology Data Exchange (ETDEWEB)

    Jin, G.B.; Choi, E.S.; Guertin, R.P.; Brooks, J.S.; Bray, T.H.; Booth, C.H.; Albrecht-Schmitt, T.E.

    2006-12-12

    {gamma}-LnLn{prime}S{sub 3} (Ln = La, Ce; Ln{prime} = Er, Tm, Yb) have been prepared as dark red to black single crystals by the reaction of the respective lanthanides with sulfur in a Sb{sub 2}S{sub 3} flux at 1000 C. This isotypic series of compounds adopts a layered structure that consists of the smaller lanthanides (Er, Tm, and Yb) bound by sulfide in six- and seven-coordinate environments that are connected together by the larger lanthanides (La and Ce) in eight- and nine-coordinate environments. The layers can be broken down into three distinct one-dimensional substructures containing three crystallographically unique Ln{prime} centers. The first of these is constructed from one-dimensional chains of edge-sharing [Ln{prime}S{sub 7}] monocapped trigonal prisms that are joined to equivalent chains via edge-sharing to yield ribbons. There are parallel chains of [Ln{prime}S{sub 6}] distorted octahedra that are linked to the first ribbons through corner-sharing. These latter units also share corners with a one-dimensional ribbon composed of parallel chains of [Ln{prime}S{sub 6}] polyhedra that edge-share both in the direction of chain propagation and with adjacent identical chains. Magnetic susceptibility measurements show Curie-Weiss behavior from 2 to 300 K with antiferromagnetic coupling, and no evidence for magnetic ordering. The {theta}{sub p} values range from -0.4 to -37.5 K, and spin-frustration may be indicated for the Yb-containing compounds. All compounds show magnetic moments substantially reduced from those calculated for the free ions. The optical band gaps for {gamma}-LaLn{prime}S{sub 3} (Ln{prime} = Er, Tm, Yb) are approximately 1.6 eV, whereas {gamma}-CeLn{prime}S{sub 3} (Ln{prime} = Er, Tm, Yb) are approximately 1.3 eV.

  2. Synthesis, characterization, and ligand exchange reactivity of a series of first row divalent metal 3-hydroxyflavonolate complexes.

    Science.gov (United States)

    Grubel, Katarzyna; Rudzka, Katarzyna; Arif, Atta M; Klotz, Katie L; Halfen, Jason A; Berreau, Lisa M

    2010-01-01

    A series of divalent metal flavonolate complexes of the general formula [(6-Ph(2)TPA)M(3-Hfl)]X (1-5-X; X = OTf(-) or ClO(4)(-); 6-Ph(2)TPA = N,N-bis((6-phenyl-2-pyridyl)methyl)-N-((2-pyridyl)methyl)amine; M = Mn(II), Co(II), Ni(II), Cu(II), Zn(II); 3-Hfl = 3-hydroxyflavonolate) were prepared and characterized by X-ray crystallography, elemental analysis, FTIR, UV-vis, (1)H NMR or EPR, and cyclic voltammetry. All of the complexes have a bidentate coordinated flavonolate ligand. The difference in M-O distances (Delta(M-O)) involving this ligand varies through the series, with the asymmetry of flavonolate coordination increasing in the order Mn(II) approximately Ni(II) pi*) of the coordinated flavonolate ligand in 1-5-OTf (relative to that in free anion) increases in the order Ni(II) metals fit well with this ordering. (1)H NMR studies indicate that the 3-Hfl complexes of Co(II), Ni(II), and Zn(II) exhibit a pseudo-octahedral geometry in solution. EPR studies suggest that the Mn(II) complex 1-OTf may form binuclear structures in solution. The mononuclear Cu(II) complex 4-OTf has a distorted square pyramidal geometry. The oxidation potential of the flavonolate ligand depends on the metal ion present and/or the solution structure of the complex, with the Mn(II) complex 1-OTf exhibiting the lowest potential, followed by the pseudo-octahedral Ni(II) and Zn(II) 3-Hfl complexes, and the distorted square pyramidal Cu(II) complex 4-OTf. The Mn(II) complex [(6-Ph(2)TPA)Mn(3-Hfl)]OTf (1-OTf) is unique in the series in undergoing ligand exchange reactions in the presence of M(ClO(4))(2).6H(2)O (M = Co, Ni, Zn) in CD(3)CN to produce [(6-Ph(2)TPA)M(CD(3)CN)(n)](X)(2), [Mn(3-Hfl)(2).0.5H(2)O], and MnX(2) (X = OTf(-) or ClO(4)(-)). Under similar conditions, the 3-Hfl complexes of Co(II), Ni(II), and Cu(II) undergo flavonolate ligand exchange to produce [(6-Ph(2)TPA)M(CD(3)CN)(n)](X)(2) (M = Co, Ni, Cu; n = 1 or 2) and [Zn(3-Hfl)(2).2H(2)O]. An Fe(II) complex of 3-Hfl, [(6-Ph(2)TPA

  3. Adsorption of methyl orange and salicylic acid on a nano-transition metal composite: Kinetics, thermodynamic and electrochemical studies.

    Science.gov (United States)

    Arshadi, M; Mousavinia, F; Amiri, M J; Faraji, A R

    2016-12-01

    In this work synthesis of Mn-nanoparticles (MnNPs) supported on the Schiff base modified nano-sized SiO2Al2O3 mixed-oxides (Si/Al) and its implementation as an adsorbent for the removal of organic pollutions such as methyl orange (MO) and salicylic acid (SA) was investigated. Si/Al were functionalized by grafting Schiff base ligand and in the next step, MnNPs were prepared over the modified nano sol-gel Si/Al. Structures and adsorption characteristics of the obtained organometallic-modified SiO2/Al2O3 mixed oxide were studied by several methods such as elemental analysis, diffuse reflectance UV-vis spectroscopy, FT-IR spectroscopy, nitrogen adsorption/desorption, scanning electron microscope (SEM), transmission electron microscope (TEM), energy dispersive X-ray (EDX), inductively coupled plasma (ICP-AES), Electron Paramagnetic Resonance (EPR), electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). EPR data of the immobilized manganese ions resulted that the transition state of active sites in the nano-adsorbent are in the form of Mn(II) ions at the surface. The adsorption properties of heterogeneous Mn(II) ions showed that this nano-adsorbent has very good potential to remove MO and SA ions from aqueous solution. The removal efficiency of the SAPAS@MnNPs towards MO reached out to 89.3 and 29.1% and for SA approached to 54.6 and 18.9% at 150 and 500mg/dm(3) initial organic pollution concentrations, respectively. To investigate the adsorption kinetic of Mn(II) ions onto the nano-sized support, pseudo first and pseudo second order kinetics, and the Freundlich, Langmuir and Langmuir-Freundlich isotherm models have also been applied to the equilibrium adsorption data. The contact time to obtain equilibrium for maximum adsorption capacity was 45min. The adsorption process was spontaneous and endothermic in nature and it was well explained with pseudo-second-order kinetic model. No remarkable loss of removal capacity even after 8th times regeneration

  4. A solvent-controlled switch of manganese complex assemblies with a beta-diketonate-based ligand.

    Science.gov (United States)

    Aromí, Guillem; Gamez, Patrick; Roubeau, Olivier; Berzal, Paula Carrero; Kooijman, Huub; Spek, Anthony L; Driessen, Willem L; Reedijk, Jan

    2002-07-15

    The coordination properties of the new polynucleating ligand H(3)L1 (1,3-bis(3-oxo-3-phenylpropionyl)-2-hydroxy-5-methylbenzene) with Mn(II/III) are described. Depending on the solvent used, the reaction of H(3)L1 with Mn(OAc)(2) yields either of the two new multinuclear assemblies [Mn(2)(HL1)(2)(py)(4)] (1) and [Mn(3)(HL1)(3)] (2), as revealed by X-ray crystallography. The structure of 2 is remarkable in that it shows a unique asymmetric triple-stranded helicate. Complexes 1 and 2 can be interconverted by controlling the solvent of the reaction system, and therefore, this ensemble constitutes an interesting externally addressable switch. In the presence of Mn(III)/pyridine, partial degradation of H(3)L1 occurs via oxidative cleavage, and the new complex [Mn(2)(L2)(2)(py)(4)] (3) is formed. The crystal structure of this complex has shown the fully deprotonated form of the new donor H(3)L2 (3-(3-oxo-3-phenylpropionyl)-5-methylsalicylic acid). From the same reaction, the Mn(II) complex 1 is also obtained. A rational synthesis of H(3)L2 is reported, and this has been used to prepare 3 in high yields, directly from its components. Variable-temperature magnetic susceptibility (chi(m)) measurements were performed on complexes 1-3 under a magnetic field of 1 kG. The data for each complex were fit to the appropriate chi(m) vs T theoretical equation, respectively. In 1, the Mn(II) ions are uncoupled, with g = 2.01. The data from 2 were fit by assuming the presence of an exchange coupled Mn(II)...Mn(II) pair next to a magnetically isolated Mn(II) center. The fit gave J = -2.75 cm(-1), g(12) = 1.97, and g(3) = 1.92, respectively. In 3, two models fit the experimental data. In the most satisfactory, the Mn(III) ions are coupled antiferromagnetically with J = -1.48 cm(-1) and g = 1.98 and a term for weak ferromagnetic intermolecular exchange is included with zJ' = 0.39 cm(-1). The other model contemplates the presence of two uncoupled zero field split Mn(III) ions.

  5. High-spin Mn wheels.

    Science.gov (United States)

    Manoli, Maria; Prescimone, Alessandro; Bagai, Rashmi; Mishra, Abhudaya; Murugesu, Muralee; Parsons, Simon; Wernsdorfer, Wolfgang; Christou, George; Brechin, Euan K

    2007-08-20

    The syntheses, structures, and magnetic properties of the complexes [MnIV4MnIII10MnII2O2(OCH3)12(tmp)8(O2CCH3)10].3Et2O (1.3Et2O), [MnIV2MnIII18MnII2O6(OCH3)14(O2CCH3)16(tmp)8(HIm)2].2CH3OH (2.2CH3OH), and [MnIV2MnIII18MnII2O6(OCH3)14(O2CCH3)16(Br-mp)8(HIm)2].2C6H14.5CH3OH (3.2C6H14.5CH3OH) are reported. The unusual wheel-like complexes were prepared by the treatment of [Mn3O(O2CCH3)6(HIm)3](O2CCH3) (HIm = imidazole) with 1,1,1-tris-(hydroxymethyl)propane (H3tmp) (1 and 2) or 2-(bromomethyl)-2-(hydroxymethyl)-1,3-propanediol (Br-mpH3) (3) in the presence of sodium methoxide (NaOCH3, 2, and 3) in CH3OH. Complex 1.3Et2O crystallizes in the triclinic space group P, while complexes 2.2CH3OH and 3.2C6H14.5CH3OH crystallize in the orthorhombic space group Pbca. Direct current magnetic susceptibility data, collected for 1-3 in the respective 1.8-300 K and 0.1-7 T temperature and magnetic-field ranges, afford spin ground-state values of S = 14 +/- 1 for complex 1 and S = 9 +/- 1 for complexes 2 and 3. Alternating current susceptibility measurements performed on all three complexes in the 1.8-10 K temperature range in a 3.5 G oscillating field at frequencies between 50 and 1000 Hz reveal out-of-phase chi"M signals below approximately 3 K. Single-crystal hysteresis loop and relaxation measurements confirm single-molecule magnetism behavior.

  6. Production of Manganese Oxide Nanoparticles by Shewanella Species

    Science.gov (United States)

    Farooqui, Saad M.; White, Alan R.

    2016-01-01

    ABSTRACT Several species of the bacterial genus Shewanella are well-known dissimilatory reducers of manganese under anaerobic conditions. In fact, Shewanella oneidensis is one of the most well studied of all metal-reducing bacteria. In the current study, a number of Shewanella strains were tested for manganese-oxidizing capacity under aerobic conditions. All were able to oxidize Mn(II) and to produce solid dark brown manganese oxides. Shewanella loihica strain PV-4 was the strongest oxidizer, producing oxides at a rate of 20.3 mg/liter/day and oxidizing Mn(II) concentrations of up to 9 mM. In contrast, S. oneidensis MR-1 was the weakest oxidizer tested, producing oxides at 4.4 mg/liter/day and oxidizing up to 4 mM Mn(II). Analysis of products from the strongest oxidizers, i.e., S. loihica PV-4 and Shewanella putrefaciens CN-32, revealed finely grained, nanosize, poorly crystalline oxide particles with identical Mn oxidation states of 3.86. The biogenic manganese oxide products could be subsequently reduced within 2 days by all of the Shewanella strains when culture conditions were made anoxic and an appropriate nutrient (lactate) was added. While Shewanella species were detected previously as part of manganese-oxidizing consortia in natural environments, the current study has clearly shown manganese-reducing Shewanella species bacteria that are able to oxidize manganese in aerobic cultures. IMPORTANCE Members of the genus Shewanella are well known as dissimilatory manganese-reducing bacteria. This study shows that a number of species from Shewanella are also capable of manganese oxidation under aerobic conditions. Characterization of the products of the two most efficient oxidizers, S. loihica and S. putrefaciens, revealed finely grained, nanosize oxide particles. With a change in culture conditions, the manganese oxide products could be subsequently reduced by the same bacteria. The ability of Shewanella species both to oxidize and to reduce manganese indicates

  7. A new three-dimensional manganese(II) coordination polymer based on the 1,3,5-tris[(1H-imidazol-1-yl)methyl]benzene ligand.

    Science.gov (United States)

    Lu, Xin Hua; Zhong, Kai Long

    2016-11-01

    The self-assembly of coordination polymers and the crystal engineering of metal-organic coordination frameworks have attracted great interest, but it is still a challenge to predict and control the compositions and structures of the complexes. Employing multidentate organic ligands and suitable metal ions to construct inorganic-organic hybrid materials through metal-ligand coordination and hydrogen-bonding interactions has become a major strategy. Recently, imidazole-containing multidentate ligands that contain an aromatic core have received much attention. A new three-dimensional Mn(II) coordination polymer based on 1,3,5-tris[(1H-imidazol-1-yl)methyl]benzene, namely poly[(ethane-1,2-diol-κO)(μ-sulfato-κ(2)O:O'){μ3-1,3,5-tris[(1H-imidazol-1-yl)methyl]benzene-κ(3)N:N':N''}manganese(II)], [Mn(SO4)(C18H18N6)(C2H6O2)]n, was synthesized and characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction. Crystal structural analysis shows that there are two kinds of crystallographically independent Mn(II) centres, each lying on a centrosymmetric position and having a similar six-coordinated octahedral structure. One is coordinated by four N atoms from four 1,3,5-tris[(1H-imidazol-1-yl)methyl]benzene (timb) ligands and two O atoms from two different bridging sulfate anions. The second is surrounded by two timb N atoms and four O atoms, two from sulfate anions and two from two ethane-1,2-diol ligands. The tripodal timb ligand bridges neighbouring Mn(II) centres to generate a two-dimensional layered structure running parallel to the ab plane. Adjacent layers are further bridged by sulfate anions, resulting in a three-dimensional structure with 3,4,6-c topology. Thermogravimetric analysis of the title polymer shows that it is stable up to 533 K. The first weight loss between 533 and 573 K corresponds to the release of coordinated ethane-1,2-diol molecules, and further decomposition occurred at 648 K.

  8. Manganese reduction and its stabilization in the rock record

    Science.gov (United States)

    Johnson, J. E.; Savalia, P.; Kocar, B. D.; Webb, S. M.; Nealson, K. H.; Fischer, W. W.

    2013-12-01

    Manganese oxides are abundant and highly reactive electron acceptors present within many environments. Their occurance is intimately tied to the availability of oxygen, as only O2 and oxygen-derived species such as superoxide and peroxide can oxidize reduced Mn(II). Because Mn2+ is soluble and Mn3+ and Mn4+ readily undergo hydrolysis to form insoluble precipitates, the record of manganese in sedimentary deposits can yield interesting insights into the history of atmospheric oxygen--the largest manganese deposits in Earth history (approximately 2.2 billion years ago) are associated with the rise of oxygen. From studying modern environments, we understand that manganese is concentrated in sediments by the oxidation and deposition of Mn(IV) minerals; however, our observations of the geologic record show diagenetic stabilization of only Mn(II) carbonate or mixed Mn(II)-Mn(III) oxide minerals--all Mn(IV)-oxide phases in ancient samples are associated with modern weathering and oxidation processes. Reduction is a key element within the manganese cycle, yet the (bio)geochemical processes responsible for the formation of mixed Mn(II)-Mn(III) minerals have not been fully elucidated. To better understand how manganese is converted from insoluble Mn(IV) oxide to these Mn(II/III)-bearing phases, we investigated secondary mineral precipitates which form during and after Mn(IV)-oxide reduction using a well-studied metal-reducing bacteria, Shewanella oneidensis MR-1. To examine changes in Mn mineralogy and oxidation state during the progression of Mn(IV) reductive dissolution/transformation by S. oneidensis, we utilized a flow through reactor system allowing for in-situ and real time x-ray absorption spectroscopy (XAS) measurements. We also confirmed mineral phases using XRD and FTIR spectrometry. Our experiments reveal that when solution phosphate concentrations are high, a Mn(II) phosphate phase quickly forms as a secondary precipitate during complete reduction of Mn(IV) oxides

  9. Adsorption of some metal complexes derived from acetyl acetone on activated carbon and purolite S-930

    Directory of Open Access Journals (Sweden)

    Salam A.H. Al-Ameri

    2014-12-01

    Full Text Available A new Schiff base (HL derived from condensation of p-anisidine and acetyl acetone has been prepared and used as a chelating ligand to prepare Cr(III, Mn(II, Co(II, Ni(II and Cu(II complexes. The study of the nature of these complexes formed in ethanol solution following the mole ratio method (2:1, L:M gave results which were compared successfully with these obtained from isolated solid state studies. These studies revealed that the complexes having square planner geometry of the type (ML2, M = Co(II, Ni(II and Cu(II, and octahedral geometry of the type [CrIIIL2(H2O2]Cl and [MNIIL2(H2O2]. The adsorption studies of three complexes Cr(III, Mn(II, and Co(II on activated carbon, H and Na-forms of purolite S-930 resin show high adsorption percentage for Cr(III on purolite S-930 due to ion exchange interaction compared with high adsorption of neutral Mn(II, Co(II complexes on activated charcoal. Linear plot of log Qe versus log Ce showed that the adsorption isotherm of these three complexes on activated carbon, H and Na-forms of purolite S-930 surface obeys Freundlich isotherm and was similar to S-curve type according to Giles classification which investigates heterogeneous adsorption. The regression values indicate that the adsorption data for these complexes fitted well within the Freundlich isothermal plots for the concentration studied. The accuracy and precision of the concentration measurements of these complexes were determined by preparing standard laboratory samples, the results show relative error ranging from ±1.08 to 5.31, ±1.04 to 4.82 and ±0.28 to 3.09 and the relative standard deviation did not exceed ±6.23, ±2.77 and ±4.38% for A1, A2 and A3 complexes, respectively.

  10. Use of Manganese(II)-Schiff Base Complexes for Carrying Polar Organometallics and Inorganic Ion Pairs.

    Science.gov (United States)

    Gallo, Emma; Solari, Euro; Floriani, Carlo; Chiesi-Villa, Angiola; Rizzoli, Corrado

    1997-05-07

    This report concerns the carrier properties of [Mn(acacen)]-derived compounds toward polar organometallics, inorganic ion pairs, and salts. Such properties are the consequence of Mn(II) behaving as a Lewis acid and the O&arcraise;O bite of the bidentate Schiff base ligand toward alkali cations. The starting compounds, which occur in a dimeric form, [Mn(acac-L-en)](2) [L' = CH(2)CH(2) (1); L" = C(6)H(10) (2); L"' = R,R-C(6)H(10) (3)] have been synthesized either via a metathesis reaction from MnCl(2) or using [Mn(3)Mes(6)]. The reaction of 1-3 with lithium organometallics allowed the isolation of [Mn(acac-L-en)(R)Li(DME)] [R = Me, L = L' (4); R = Ph, L = L' (5); R = Mes, L = L' (6); R = Me, L = L" (7); R = Me, L = L"' (8)] as metalated forms, where the alkyl or aryl group is sigma-bonded to Mn(II), while the lithium cation is anchored to the Schiff base ligand. The metalated forms 4-8 react with PhCHO to give the corresponding lithium alkoxide, which remains bound in its ion-pair form to the [Mn(acacen)] skeleton in [Mn(2)(acac-L'-en)(2)Li(2)(OCH(Ph)Me)(2)](n)() (9). The use of 8, which has a chiral bridge across two nitrogen atoms, did not lead to a significant asymmetric induction in the reaction with PhCHO, because of the long separation between the lithium cation and the stereogenic center. The metalated form 4 was able to transfer the methyl group to the nitrile function to give the corresponding lithium-imide which then remains bonded to [Mn(acacen)] as the ion pair in a dimeric structure, as revealed for [Mn(2)(acac-L'-en)(2)Li(2)(DME){N=C(Ph)Me}(2)](n)() (10). Their reaction with 1 appears to depend on the steric bulkiness of the alkyl group in NaOR, resulting in either monomeric adducts, i.e. in [Mn(acac-L'-en)(2,6-Bu(t)(2)C(6)H(3)O)Na(DME)(2)] (11.2DME), or polymeric structures, like in [Mn(acac-L'-en)Na(DME)(&mgr;-OEt)](n)() (13). All the dimeric units reported in this paper show a slight antiferromagnetic coupling between the two Mn(II) assisted by

  11. Biogenic precipitation of manganese oxides and enrichment of heavy metals at acidic soil pH

    Science.gov (United States)

    Mayanna, Sathish; Peacock, Caroline L.; Schäffner, Franziska; Grawunder, Anja; Merten, Dirk; Kothe, Erika; Büchel, Georg

    2014-05-01

    The precipitation of biogenic Mn oxides at acidic pH is rarely reported and poorly understood, compared to biogenic Mn oxide precipitation at near neutral conditions. Here we identified and investigated the precipitation of biogenic Mn oxides in acidic soil, and studied their role in the retention of heavy metals, at the former uranium mining site of Ronneburg, Germany. The site is characterized by acidic pH, low carbon content and high heavy metal loads including rare earth elements. Specifically, the Mn oxides were present in layers identified by detailed soil profiling and within these layers pH varied from 4.7 to 5.1, Eh varied from 640 to 660 mV and there were enriched total metal contents for Ba, Ni, Co, Cd and Zn in addition to high Mn levels. Using electron microprobe analysis, synchrotron X-ray diffraction and X-ray absorption spectroscopy, we identified poorly crystalline birnessite (δ-MnO2) as the dominant Mn oxide in the Mn layers, present as coatings covering and cementing quartz grains. With geochemical modelling we found that the environmental conditions at the site were not favourable for chemical oxidation of Mn(II), and thus we performed 16S rDNA sequencing to isolate the bacterial strains present in the Mn layers. Bacterial phyla present in the Mn layers belonged to Firmicutes, Actinobacteria and Proteobacteria, and from these phyla we isolated six strains of Mn(II) oxidizing bacteria and confirmed their ability to oxidise Mn(II) in the laboratory. The biogenic Mn oxide layers act as a sink for metals and the bioavailability of these metals was much lower in the Mn layers than in adjacent layers, reflecting their preferential sorption to the biogenic Mn oxide. In this presentation we will report our findings, concluding that the formation of natural biogenic poorly crystalline birnessite can occur at acidic pH, resulting in the formation of a biogeochemical barrier which, in turn, can control the mobility and bioavailability of heavy metals in

  12. Manganese(III)-containing Wells-Dawson sandwich-type polyoxometalates: comparison with their manganese(II) counterparts.

    Science.gov (United States)

    Lebrini, Mounim; Mbomekallé, Israël M; Dolbecq, Anne; Marrot, Jérôme; Berthet, Patrick; Ntienoue, Joseline; Sécheresse, Francis; Vigneron, Jacky; Etcheberry, Arnaud

    2011-07-18

    We present the synthesis and structural characterization, assessed by various techniques (FTIR, TGA, UV-vis, elemental analysis, single-crystal X-ray diffraction for three compounds, magnetic susceptibility, and electrochemistry) of five manganese-containing Wells-Dawson sandwich-type (WDST) complexes. The dimanganese(II)-containing complex, [Na(2)(H(2)O)(2)Mn(II)(2)(As(2)W(15)O(56))(2)](18-) (1), was obtained by reaction of MnCl(2) with 1 equiv of [As(2)W(15)O(56)](12-) in acetate medium (pH 4.7). Oxidation of 1 by Na(2)S(2)O(8) in aqueous solution led to the dimanganese(III) complex [Na(2)(H(2)O)(2)Mn(III)(2)(As(2)W(15)O(56))(2)](16-) (2), while its trimanganese(II) homologue, [Na(H(2)O)(2)Mn(II)(H(2)O)Mn(II)(2)(As(2)W(15)O(56))(2)](17-) (3), was obtained by addition of ca. 1 equiv of MnCl(2) to a solution of 1 in 1 M NaCl. The trimanganese(III) and tetramanganese(III) counterparts, [Mn(III)(H(2)O)Mn(III)(2)(As(2)W(15)O(56))(2)](15-) (4) and [Mn(III)(2)(H(2)O)(2)Mn(III)(2)(As(2)W(15)O(56))(2)](12-) (6), are, respectively, obtained by oxidation of aqueous solutions of 3 and [Mn(II)(2)(H(2)O)(2)Mn(II)(2)(As(2)W(15)O(56))(2)](16-) (5) by Na(2)S(2)O(8). Single-crystal X-ray analyses were carried out on 2, 3, and 4. BVS calculations and XPS confirmed that the oxidation state of Mn centers is +II for complexes 1, 3, and 5 and +III for 2, 4, and 6. A complete comparative electrochemical study was carried out on the six compounds cited above, and it was possible to observe the distinct redox steps Mn(IV/III) and Mn(III/II). Magnetization measurements, as a function of temperature, confirm the presence of antiferromagnetic interactions between the Mn ions in these compounds in all cases with the exception of compound 2.

  13. Heterometallic Rings: Their Physics and use as Supramolecular Building Blocks.

    Science.gov (United States)

    McInnes, Eric J L; Timco, Grigore A; Whitehead, George F S; Winpenny, Richard E P

    2015-11-23

    An enormous family of heterometallic rings has been made. The first were Cr7 M rings where M = Ni(II), Zn(II), Mn(II), and rings have been made with as many as fourteen metal centers in the cyclic structure. They are bridged externally by carboxylates, and internally by fluorides or a penta-deprotonated polyol. The size of the rings is controlled through templates which have included a range of ammonium or imidazolium ions, alkali metals and coordination compounds. The rings can be functionalized to act as ligands, and incorporated into hybrid organic-inorganic rotaxanes and into molecules containing up to 200 metal centers. Physical studies reported include: magnetic measurements, inelastic neutron scattering (including single crystal measurements), electron paramagnetic resonance spectroscopy (including measurements of phase memory times), NMR spectroscopy (both solution and solid state), and polarized neutron diffraction. The rings are hence ideal for understanding magnetism in elegant exchange-coupled systems.

  14. A one-dimensional double-chain coordination polymer: [Mn(C12H13NO6S)(C10H8N2)]n.

    Science.gov (United States)

    Liang, Fu-Pei; Chen, Man-Sheng; Hu, Rui-Xiang; Chen, Zi-Lu

    2004-06-01

    In the title compound, poly[[(2,2'-bipyridine-kappa(2)N,N')manganese(II)]-micro(3)-N-tosyl-L-glutamato-kappa(4)O,O':O":O"'], [Mn(tsgluo)(bipy)](n), where tsgluo is N-tosyl-L-glutamate (C(12)H(13)NO(6)S) and bipy is 2,2'-bipyridine (C(10)H(8)N(2)), the Mn atoms are octahedrally coordinated by two N atoms of one bipy ligand and by four O atoms of three tsgluo(2-) anions. The gamma-carboxyl group coordinates to the Mn(II) atom in a chelating mode, while the alpha-carboxyl group coordinates in a bidentate-bridging mode. The complex displays a one-dimensional double-chain structure.

  15. Synthesis and transition metal coordination chemistry of a novel hexadentate bispidine ligand.

    Science.gov (United States)

    Comba, Peter; Rudolf, Henning; Wadepohl, Hubert

    2015-02-14

    Reported is the new bispidine-derived hexadentate ligand (L = 3-(2-methylpyridyl)-7-(bis-2-methylpyridyl)-3,7-diazabicyclo[3.3.1]nonane) with two tertiary amine and four pyridine donor groups. This ligand can form heterodinuclear and mononuclear complexes and, in the mononuclear compounds discussed here, the ligand may coordinate as a pentadentate ligand, with one of the bispyridinemethane-based pyridine groups un- or semi-coordinated, or as a hexadentate ligand, leading to a pentagonal pyramidal coordination geometry or, with an additional monodentate ligand, to a heptacoordinate pentagonal bipyramidal structure. The solution and solid state data presented here indicate that, with the relatively small Cu(II) and high-spin Fe(II) ions the fourth pyridine group is only semi-coordinated for steric reasons and, with the larger high-spin Mn(II) ion genuine heptacoordination is observed but with a relatively large distortion in the pentagonal equatorial plane.

  16. Molecular structure, natural bond analysis, vibrational and electronic spectra, surface enhanced Raman scattering and Mulliken atomic charges of the normal modes of [Mn(DDTC)2] complex

    Science.gov (United States)

    Téllez S., Claudio A.; Costa, Anilton C.; Mondragón, M. A.; Ferreira, Glaucio B.; Versiane, O.; Rangel, J. L.; Lima, G. Müller; Martin, A. A.

    2016-12-01

    Theoretical and experimental bands have been assigned for the Fourier Transform Infrared and Raman spectra of the bis(diethyldithiocarbamate)Mn(II) complex, [Mn(DDTC)2]. The calculations have been based on the DFT/B3LYP method, second derivative spectra and band deconvolution analysis. The UV-vis experimental spectra were measured in acetonitrile solution, and the calculated electronic spectrum was obtained using the TD/B3LYP method with 6-311G(d, p) basis set for all atoms. Charge transfer bands and those d-d spin forbidden were assigned in the UV-vis spectrum. The natural bond orbital analysis was carried out using the DFT/B3LYP method and the Mn(II) hybridization leading to the planar geometry of the framework was discussed. Surface enhanced Raman scattering (SERS) was also performed. Mulliken charges of the normal modes were obtained and related to the SERS enhanced bands.

  17. Study of Stability Constants of Fe (Iii And Mn (Ii with Chloramphenicol by Paper Electrophoretic Technique

    Directory of Open Access Journals (Sweden)

    Arvind Singh

    2014-12-01

    Full Text Available Stabilty constant of binary complexes of Fe(III and Mn(II with medicinally important ligand chloramphenicol antibiotics in solution were determined by paper electrophoretic technique. Stability constant of the complexes were determined at 25°C temperature and 0.1M (HClO4 ionic strength. Our study is based upon the migration of a spot of metal ions on a paper strip at different pH against mobility gives information about the binary complexes and permits to calculate their stability constant. The stability constant data revealed that chloramphenicol may be used as chelating agent in chelation for medical treatment of metal overload or poisoning.

  18. Layered transition metal carboxylates: efficient reusable heterogeneous catalyst for epoxidation of olefins.

    Science.gov (United States)

    Sen, Rupam; Bhunia, Susmita; Mal, Dasarath; Koner, Subratanath; Miyashita, Yoshitaro; Okamoto, Ken-Ichi

    2009-12-01

    Layered metal carboxylates [M(malonato)(H(2)O)(2)](n) (M = Ni(II) and Mn(II)) that have a claylike structure have been synthesized hydrothermally and characterized. The interlayer separation in these layered carboxylates is comparable to that of the intercalation distance of the naturally occurring clay materials or layered double hydroxides (LDHs). In this study, we have demonstrated that, instead of intercalating the metal complex into layers of the clay or LDH, layered transition metal carboxylates, [M(malonato)(H(2)O)(2)](n), as such can be used as a recyclable heterogeneous catalyst in olefin epoxidation reaction. Metal carboxylates [M(malonato)(H(2)O)(2)](n) exhibit excellent catalytic performance in olefin epoxidation reaction.

  19. Structural transition induced by charge-transfer in RbMn[Fe(CN) sub 6]. Investigation by synchrotron-radiation X-ray powder analysis

    CERN Document Server

    Moritomo, Y; Sakata, M; Kato, K; Kuriki, A; Tokoro, H; Ohkoshi, S I; Hashimoto, K

    2002-01-01

    Temperature dependence of atomic coordinates is determined for RbMn[Fe(CN) sub 6] by means of synchrotron-radiation (SR) X-ray powder structural analysis. We observed a structural transition from the cubic (F4-bar3m; Z=4) to the tetragonal (I4-barm2; Z=2) phase at approx. =210K in the cooling run and at approx. =300K in the warming run. In the low-temperature tetragonal phase, we found Jahn-Tellar type distortion of the MnN sub 6 octahedra and compression of the averaged Fe-C bond distance. These structural data suggest that the structural transition is triggered by the inter-metallic charge-transfer from the Mn(II) site to the Fe(III) site.

  20. Bis(μ-5-carboxylato-1-carboxylatomethyl-2-oxidopyridinium-κ2O5:O1;κ2O1:O5-[diaqua(phenanthroline-κ2N,N′manganese(II] dihydrate

    Directory of Open Access Journals (Sweden)

    Mei-Xiang Jiang

    2009-06-01

    Full Text Available The centrosymmetric binuclear title complex, [Mn2(C8H5NO52(C12H8N22(H2O4]·2H2O, was obtained by the reaction of manganese chloride with 5-carboxy-1-carboxymethyl-2-oxidopyridinium and 1,10-phenanthroline. The MnII atom is coordinated by two N atoms from the 1,10-phenanthroline ligand, two O atoms from two 5-carboxylato-1-carboxylatomethyl-2-oxidopyridinium ligands and two water molecules, leading to a distorted octahedral MnN2O4 environment. Intermolecular O—H...O hydrogen bonds link neighbouring molecules into a layer structure parallel to (001.

  1. Diaquabis[4-(dimethylaminobenzoato-κO](isonicotinamide-κN1manganese(II

    Directory of Open Access Journals (Sweden)

    Tuncer Hökelek

    2009-09-01

    Full Text Available The title MnII complex, [Mn(C9H10NO22(C6H6N2O(H2O2], contains two 4-(dimethylaminobenzoate (DMAB anions, one isonicotinamide (INA ligand and two coordinated water molecules. One of the DMAB anions acts as a bidentate ligand, while the other is monodentate. The four O atoms in the equatorial plane around the Mn atom form a highly distorted square-planar arrangement, while the distorted octahedral coordination geometry is completed by the N atom of the INA ligand and the O atom of the second water molecule in the axial positions. In the crystal structure, strong intermolecular O—H...O, O—H...N and N—H...O hydrogen bonds link the molecules into a two-dimensional network parallel to (010. Two weak C—H...π interactions are also found.

  2. Diaqua(trifluoroacetato-κ2O,O′[2,4,6-tri-2-pyridyl-1,3,5-triazine-κ3N2,N1,N6]manganese(II trifluoroacetate

    Directory of Open Access Journals (Sweden)

    Seik Weng Ng

    2009-05-01

    Full Text Available The MnII atom in the two independent ion-pairs of the title salt, [Mn(C2F3O2(C18H12N6(H2O2]C2F3O2, is N,N′,N′′-chelated by the neutral N-heterocycle and O,O′-chelated by the carboxylate ion, the five atoms involved in chelation comprising a pentagon around it. The apical sites of the trans-pentagonal bipyramidal coordination geometry are occupied by two water molecules. The cations and lattice anions are linked by O—H...O and O—H...N hydrogen bonds into a three-dimensional network.

  3. Diaquabis(N,N-diethylnicotinamide-κN1bis(4-formylbenzoato-κO1manganese(II

    Directory of Open Access Journals (Sweden)

    2009-03-01

    Full Text Available The title compound, [Mn(C8H5O32(C10H14N2O2(H2O2], contains one MnII atom lying on an inversion centre, two 4-formylbenzoate and two diethylnicotinamide ligands and two coordinated water molecules. All ligands are monodentate. The four O atoms around the Mn atom form a slightly distorted equatorial plane, while the distorted octahedral coordination is completed by the two N atoms in the axial positions. An intramolecular O—H...O hydrogen bond occurs in the complex. In the crystal structure, O—H...O hydrogen bonds link the molecules through an R22(16 ring motif, forming a one-dimensional chain along the a axis. The π–π contact between the pyridyl rings [centroid–centroid distance = 3.629 (2 Å] may further stabilize the structure.

  4. Poly[[[(1-ethyl-6-fluoro-4-oxo-7-(piperazin-1-yl-1,4-dihydroquinoline-3-carboxylatomanganese(II]-μ3-4,4′-oxydibenzoato] monohydrate

    Directory of Open Access Journals (Sweden)

    Jun Hong

    2008-01-01

    Full Text Available In the title compound, {[Mn(C16H18N3O3(C14H8O5]·H2O}n, the unique MnII ion is coordinated by two O atoms from a chelating 1-ethyl-6-fluoro-4-oxo-7-(piperazin-1-yl-1,4-dihydroquinoline-3-carboxylate ligand and three O atoms from three 4,4′-oxydibenzoate ligands, forming a distorted square-pyramidal coordination environment. In the crystal structure, centrosymmetric dinuclear manganese units are linked via 4,4′-oxydibenzoate ligands into one-dimensional chains; these chains are, in turn, connected via intermolecular N—H...O and O—H...O hydrogen bonds to form a two-dimensional supramolecular network. The O atom of the solvent water molecule is disordered over two sites with equal occupancies; the attached H atoms are common to both sites.

  5. Bis(acetato-κ2O,O′(2,2′:6′,2′′-terpyridine-κ3N,N′,N′′manganese(II dihydrate

    Directory of Open Access Journals (Sweden)

    Kwang Ha

    2012-02-01

    Full Text Available The MnII ion in the title compound, [Mn(CH3CO22(C15H11N3]·2H2O, is seven-coordinated in a considerably distorted pentagonal–bipyramidal geometry by three N atoms of the tridentate 2,2′:6′,2′′-terpyridine ligand and four O atoms from two acetate anions which chelate the Mn atom via two O atoms. The lateral pyridine rings are slightly inclined to the central pyridine ring, making dihedral angles of 13.6 (2 and 5.7 (2°. The complex and solvent water molecules are linked by intermolecular O—H...O hydrogen bonds into a three-dimensional network.

  6. Bacterial killing in macrophages and amoeba: do they all use a brass dagger?

    Science.gov (United States)

    German, Nadezhda; Doyscher, Dominik; Rensing, Christopher

    2013-10-01

    Macrophages are immune cells that are known to engulf pathogens and destroy them by employing several mechanisms, including oxidative burst, induction of Fe(II) and Mn(II) efflux, and through elevation of Cu(I) and Zn(II) concentrations in the phagosome ('brass dagger'). The importance of the latter mechanism is supported by the presence of multiple counteracting efflux systems in bacteria, responsible for the efflux of toxic metals. We hypothesize that similar bacteria-killing mechanisms are found in predatory protozoa/amoeba species. Here, we present a brief summary of soft metal-related mechanisms used by macrophages, and perhaps amoeba, to inactivate and destroy bacteria. Based on this, we think it is likely that copper resistance is also selected for by protozoan grazing in the environment.

  7. Synthesis and Crystal Structure of the First Hybrid Manganese Phosphate with 1-D Framework of Dinuclear Structure

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    A novel hybrid manganese phosphate, [(bipy)Mn(H2PO4)2] (bipy = 2,2'-bipyridine) 1, was synthesized, and its structure is characteristic of 1-D framework involving a dinuclear structure made up of edge-sharing Mn(II) octahedra. 1 crystallizes in the monoclinic system, space group C2/c with a = 12.230(2), b = 17.800(4), c = 13.530(3)(A), β = 105.00(3)o, V = 2845.0(10)(A)3, Z = 8. Dc = 1.892 g/cm3, F(000) = 1640, Mr = 405.10, μ(MoKα) = 1.198 mm-1, R = 0.0306 and wR = 0.0657 for 2093 observed reflections (I > 2σ(I)).

  8. Development of Comparative Toxicity Potentials of 14 cationic metals in freshwater

    DEFF Research Database (Denmark)

    Dong, Yan; Gandhi, Nilima; Hauschild, Michael Zwicky

    2014-01-01

    Site-dependent and site-generic Comparative Toxicity Potentials (CTPs) (also known as Characterization Factors (CFs)) were calculated for 14 cationic metals (Al(III), Ba, Be, Cd, Co, Cr(III), Cs, Cu(II), Fe(II), Fe(III), Mn(II), Ni, Pb, Sr and Zn), to be applied in Life Cycle Impact Assessment....... CTPs were calculated for 7 EUarchetypes, taking bioavailability and speciation pattern into account. The resulting site-dependent CTPs showed up to 2.4–6.5 orders of magnitude variation across archetypes for those metals that form stable hydroxyl compounds in slightly alkaline waters (Al(III), Be, Cr......(III), Cu(II) and Fe(III)), emphasizing the importance of using site-dependent CTPs for these metals where possible. For the other metals, CTPs stayed within around 0.9 orders of magnitude, making spatial differentiation less important. In acidic waters (pH

  9. Diaqua-2κ2O-bis(μ-1-oxido-2-naphthoato-1:2κ3O1,O2:O2′;2:3κ3O2:O1,O2′-bis(1-oxido-2-naphthoato-1κ1O2,O2;3κ2O1,O2-hexapyridine-1κ2N,2κ2N,3κ2N-trimanganese(II/III pyridine disolvate dihydrate

    Directory of Open Access Journals (Sweden)

    Daqi Wang

    2008-12-01

    Full Text Available The title complex, [Mn3(C11H6O34(C5H5N6(H2O2]·2H2O·2C5H5N, is a trinuclear mixed oxidation state complex of overline1 symmetry. The three Mn atoms are six-coordinated in the shape of distorted octahedra, each coordinated with an O4N2 set of donor atoms, where the ligands exhibit mono- and bidentate modes. However, the coordination of the MnII ion located on the inversion centre involves water molecules at two coordination sites, whereas that of the two symmetry-related MnIII ions involves an O4N2 set of donor atoms orginating from the organic ligands. Intramolecular C—H...π interactions between neighbouring pyridine ligands stabilize this arrangement. A two-dimensional network parallel to (001 is formed by intermolecular O—H...O hydrogen bonds.

  10. EPR, UV-Visible, and Near-Infrared Spectroscopic Characterization of Dolomite

    Directory of Open Access Journals (Sweden)

    S. Lakshmi Reddy

    2008-01-01

    Full Text Available Dolomite mineral samples having white and light green colors of Indian origin have been characterized by EPR, optical, and NIR spectroscopy. The optical spectrum exhibits a number of electronic bands due to presence of Fe(III ions in the mineral. From EPR studies, the parameters of g for Fe(III and g,A, and D for Mn(II are evaluated and the data confirm that the ions are in distorted octahedron. Optical absorption studies reveal that Fe(III is in distorted octahedron. The bands in NIR spectra are due to the overtones and combinations of water molecules. Thus EPR and optical absorption spectral studies have proven useful for the study of the solid state chemistry of dolomite.

  11. Laccases of prokaryotic origin: enzymes at the interface of protein science and protein technology.

    Science.gov (United States)

    Martins, Lígia O; Durão, Paulo; Brissos, Vânia; Lindley, Peter F

    2015-03-01

    The ubiquitous members of the multicopper oxidase family of enzymes oxidize a range of aromatic substrates such as polyphenols, methoxy-substituted phenols, amines and inorganic compounds, concomitantly with the reduction of molecular dioxygen to water. This family of enzymes can be broadly divided into two functional classes: metalloxidases and laccases. Several prokaryotic metalloxidases have been described in the last decade showing a robust activity towards metals, such as Cu(I), Fe(II) or Mn(II) and have been implicated in the metal metabolism of the corresponding microorganisms. Many laccases, with a superior efficiency for oxidation of organic compounds when compared with metals, have also been identified and characterized from prokaryotes, playing roles that more closely conform to those of intermediary metabolism. This review aims to present an update of current knowledge on prokaryotic multicopper oxidases, with a special emphasis on laccases, anticipating their enormous potential for industrial and environmental applications.

  12. Synthesis, spectroscopic characterisation, biological and DNA cleavage properties of complexes of nicotinamide

    Directory of Open Access Journals (Sweden)

    C. Surendra Dilip

    2016-09-01

    Full Text Available Transition metal complexes of nicotinamide with metal precursors such as Cr(III, Mn(II, Fe(III, Co(II, Ni(II, Cu(II and Cd(II, were synthesized and characterised by physico-chemical and spectroscopic techniques. Based on analytical, spectral and magnetic moments, all the complexes are identified as distorted octahedral in structure. All the complexes are of the ML14L22 type. The shifts of the ν (CN (azomethine and ν (CO (amide stretches have been monitored in order to find out the donor sites of the ligands. Antibacterial and antifungal activities of the complexes were studied and the complexes were screened against bacteria and fungi. The activity data show that the metal complexes are more potent than the parent nicotinamide.

  13. Spectral and in vitro antimicrobial properties of 2-oxo-4-phenyl-6-styryl-1,2,3,4-tetrahydro-pyrimidine-5-carboxylic acid transition metal complexes

    Science.gov (United States)

    Dhankar, Raksha P.; Rahatgaonkar, Anjali M.; Chorghade, Mukund S.; Tiwari, Ashutosh

    2-oxo-4-phenyl-6-styryl-1,2,3,4-tetrahydro-pyrimidine-5-carboxylic acid (ADP) was complexed with acetates of Mn(II), Ni(II), Cu(II) and Zn(II). The structures of the ligand and its metal complexes were characterized by microanalysis, IR, NMR, UV-vis spectroscopy, magnetic susceptibility and TGA-DTA analyses. Octahedral and square planar geometries were suggested for the complexes in which the central metal ion coordinated with sbnd O donors of ligand and acetate ions. Each ligand binds the metal using carboxylate oxygens. The ligand and complexes were evaluated for their antimicrobial activities against different species of pathogenic bacteria and fungi. The present novel pyrimidine containing complexes could constitute a new group of antibacterial and antifungal agents.

  14. Chelating fibers prepared with a wet spinning technique using a mixture of a viscose solution and a polymer ligand for the separation of metal ions in an aqueous solution.

    Science.gov (United States)

    Kagaya, Shigehiro; Miyazaki, Hiroyuki; Inoue, Yoshinori; Kato, Toshifumi; Yanai, Hideyuki; Kamichatani, Waka; Kajiwara, Takehiro; Saito, Mitsuru; Tohda, Koji

    2012-02-15

    Chelating fibers containing polymer ligands such as carboxymethylated polyallylamine, carboxymethylated polyethyleneimine, and a copolymer of diallylamine hydrochloride/maleic acid were prepared with a wet spinning technique using mixtures of a viscose solution and the polymer ligands. The chelating fibers obtained effectively adsorbed various metal ions, including Cd(II), Co(II), Cr(III), Cu(II), Fe(III), Mn(II), Ni(II), Pb(II), Ti(IV), and Zn(II). The metal ions adsorbed could be readily desorbed using 0.1 or 0.5 mol L(-1) HNO(3). The chelating fiber containing carboxymethylated polyallylamine was available for the separation of some metal ions in synthetic wastewater containing a large amount of Na(2)SO(4). The wet spinning technique using a solution containing a base polymer and a polymer ligand was quite simple and effective and would be applicable for preparing various chelating fibers.

  15. Two-dimensional supramolecular networks via C-H$\\cdots$Cl and N-H$\\cdots$Cl interactions utilizing bidentate neutral pyridine amide coordinated MnIICl2 tectons

    Indian Academy of Sciences (India)

    Wilson Jacob; Rabindranath Mukherjee

    2008-09-01

    Reaction of -(phenyl)-2-pyridinecarboxamide (HL1) and -(-tolyl)-2-pyridinecarboxamide (HL2) ligands with MnCl2.4H2O affords complexes [(HL1)2MnCl2] 1 and [(HL2)2MnCl2] 2. The structures of 1 and 2 were determined by three-dimensional X-ray crystallography revealing that the MnII ions assume distorted octahedral geometry with coordination by two HL1/HL2 ligands providing two pyridine N and two amide O and two chloride ions. Notably, secondary interactions [C-H$\\cdots$Cl (pyridine 3-H hydrogen) and N-H$\\cdots$Cl (amide NH hydrogen)] triggered by MnII-coordinated chloride ions acting as hydrogen bonding acceptors generate self-complementary dimeric tectons, which lead to 2D supramolecular architectures.

  16. Bis(2-meth­oxy­benzyl­ammonium) di­aqua­bis­(di­hydrogen diphosphato-κ2 O,O′)cobaltate(II) dihydrate

    Science.gov (United States)

    Elboulali, Adel; Selmi, Ahmed; Ratel-Ramond, Nicolas; Rzaigui, Mohamed; Akriche, Samah Toumi

    2014-01-01

    The title compound, (C8H12NO)2[Co(H2P2O7)2(H2O)2]·2H2O, crystallizes isotypically with its MnII analogue. It consists of alternating layers of organic cations and inorganic complex anions, extending parallel to (100). The complex cobaltate(II) anion exhibits -1 symmetry. Its Co2+ atom has an octa­hedral coordination sphere, defined by two water mol­ecules in apical positions and two H2P2O7 2− ligands in equatorial positions. The cohesion between inorganic and organic layers is accomplished by a set of O—H⋯O and N—H⋯O hydrogen bonds involving the organic cation, the inorganic anion and the remaining lattice water mol­ecules. PMID:24826105

  17. Metal ion promoted synthesis of pentaazamacrocyclic complexes of a few first row transition metal series derived from 2,6-diaminopyridine

    Directory of Open Access Journals (Sweden)

    TAHIR ALI KHAN

    2005-11-01

    Full Text Available A new series of dichloro/dinitrato (2,6,9,13,18-pentaazacbicyclo [12.3.1]octadeca-1(18,14,16-triene metal (II [MLX2] (M = Mn(II, Co(II, Ni(II and Zn(II; X = Cl or NO3 and (2,6,9,13,18-pentaazacyclo[12.3.1]octadeca-1(18,14,16-triene copper(II dichloride/dinitrate [CuL]X2 (X = Cl or NO3 have been synthesized by the template condensation reaction of 2,6-diaminopyridine with 1,2-diaminoethane and 1,3-dibromopropane. The complexes were studied by elemental analysis, magnetic susceptibility and conductivity measurements. Various spectroscopic techniques, viz. IR, 1H-NMR, EPR, UV/Vis, were used to establish their structures. Except for the complexes of copper(II, which are square planar, all other complexes have octahedral structures.

  18. Synthesis and surface modification of uniform MFe{sub 2}O{sub 4} (M = Fe, Mn, and Co) nanoparticles with tunable sizes and functionalities

    Energy Technology Data Exchange (ETDEWEB)

    Cabrera, Lourdes I., E-mail: lourisa_cabrera@yahoo.com [Universita degli Studi di Firenze, LA.M.M. c/o dipartimento di Chimica (Italy); Somoza, Alvaro [Faculty of Science Module C-IX, Instituto Madrileno de Estudios Avanzados-Nanociencia (Spain); Marco, Jose F. [Instituto de Quimica-Fisica ' ROCASOLANO' , CSIC (Spain); Serna, Carlos J.; Puerto Morales, M. [Instituto de Ciencia de Materiales de Madrid, CSIC (Spain)

    2012-06-15

    Cubic monodisperse MFe{sub 2}O{sub 4} ferrite nanoparticles (M = Fe, Co, and Mn) with tunable sizes between 7 and 20 nm and a narrow size distribution have been achieved in a one step synthesis by thermal decomposition of Fe(III), Co (II), and Mn(II) oleates. These nanoparticles have been functionalized with dimercaptosuccinic acid (DMSA), 11-mercaptoundecanoic acid (MUA), and bis(carboxymethyl)(2-maleimidylethyl)ammonium 4-toluenesulfonate (MATS) to grant them aqueous stability and the possibility for further functionalization with different biomolecules. Their structural, magnetic, and colloidal properties have also been studied to determine their chemical and physical properties and the degree of stability under physiological conditions that will determine their future use in biomedical applications.

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

    Science.gov (United States)

    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.

  20. Thermochimica Acta Volume 360, Issue 1, 31 August 2000, Pages 17–27 Cover image Synthesis, identification and thermal decomposition of double sulfites like Cu2SO3·MSO3·2H2O (M=Cu, Fe, Mn or Cd)

    OpenAIRE

    2000-01-01

    p.17–27 Double sulfites with empirical formula Cu2SO3•MSO3•2H2O (where M is Cu, Fe, Mn, or Cd) were obtained by saturation with sulfur dioxide gas of an aqueous mixture of MII sulfate and copper sulfate at room temperature. The salts obtained were identified by infrared spectra, X-ray powder diffraction and elemental analysis. The compounds studied are isostructural with the CuII replacement by MnII, FeII, and CdII in Chevreul’s salt (Cu2SO3•CuSO3•2H2O). The thermal behavior of the double ...

  1. Bioactivities of Novel Metal Complexes Involving B Vitamins and Glycine

    Directory of Open Access Journals (Sweden)

    Fazary Ahmed E.

    2016-01-01

    Full Text Available In this work twelve novel mixed ligand complexes were synthesized. The complexes were formed between a metal ion (Cu(II, Cd(II, Mn(II, Fe(III, Ni(II, Pb(II and vitamins (B 3 and B 9 as primary ligands, and glycine as secondary ligand. Melting points, conductivities, and magnetic susceptibilities of the synthesized complexes were determined and the complexes were subjected to elemental analyses. The presence of coordination water molecules in the complex was also supported by TG/DTG thermal analysis. Full elucidation of the molecular structures for the synthesized mixed ligand complexes were confirmed using detailed spectroscopic IR, 1H-, 13C-NMR, and XRD techniques. In addition, cytotoxic and antioxidant activities of the twelve synthesized solid complexes were tested to evaluate their bioactivities.

  2. Investigating the role of metal chelation in HIV-1 integrase strand transfer inhibitors.

    Science.gov (United States)

    Bacchi, Alessia; Carcelli, Mauro; Compari, Carlotta; Fisicaro, Emilia; Pala, Nicolino; Rispoli, Gabriele; Rogolino, Dominga; Sanchez, Tino W; Sechi, Mario; Sinisi, Valentina; Neamati, Nouri

    2011-12-22

    HIV-1 integrase (IN) has been validated as an attractive target for the treatment of HIV/AIDS. Several studies have confirmed that the metal binding function is a crucial feature in many of the reported IN inhibitors. To provide new insights on the metal chelating mechanism of IN inhibitors, we prepared a series of metal complexes of two ligands (HL1 and HL2), designed as representative models of the clinically used compounds raltegravir and elvitegravir. Potentiometric measurements were conducted for HL2 in the presence of Mg(II), Mn(II), Co(II), and Zn(II) in order to delineate a metal speciation model. We also determined the X-ray structures of both of the ligands and of three representative metal complexes. Our results support the hypothesis that several selective strand transfer inhibitors preferentially chelate one cation in solution and that the metal complexes can interact with the active site of the enzyme.

  3. Transition Metal Complexes of 1, 4(2'-Hydroxyphenyl-1-yl di-imino azine: Synthesis, Characterization and Antimicrobial Studies

    Directory of Open Access Journals (Sweden)

    M. Revanasiddappa

    2008-01-01

    Full Text Available The synthesis and characterization of first row transition metal complexes of the 1, 4(2'-hydroxyphenyl-1-yl di-imino azine {1,4(2'HPDA} are reported. The complexes have been characterized by elemental analysis, molar conductance, magnetic studies, IR, 1H NMR and UV-visible studies. They have the stoichiometry of the type [M{1,4(2'HPDA}2 2H2O ] and [M'L2] where M= Mn(II, Fe(III, Co(II, Ni(II and Cu(II, and M' = ZrO(II, VO(II, Zn(II, Cd(II, and Hg(II. The antibacterial and antifungal activity of the metal complexes has been investigated. Both ligand and complexes have shown good antibacterial and antifungal activity.

  4. Trithiocyanurate Complexes of Iron, Manganese and Nickel and Their Anticholinesterase Activity

    Directory of Open Access Journals (Sweden)

    Pavel Kopel

    2014-04-01

    Full Text Available The complexes of Fe(II, Mn(II and Ni(II with a combination of a Schiff base, nitrogen-donor ligand or macrocyclic ligand and trithiocyanuric acid (ttcH3 were prepared and characterized by elemental analysis and spectroscopies. Crystal and molecular structures of the iron complex of composition [Fe(L1](ttcH2(ClO4·EtOH·H2O (1, where L1 is Schiff base derived from tris(2-aminoethylamine and 2-pyridinecarboxaldehyde, were solved. It was found that the Schiff base is coordinated to the central iron atom by six nitrogens forming deformed octahedral arrangement, whereas trithiocyanurate(1- anion, perchlorate and solvent molecules are not coordinated. The X-ray structure of the Schiff base sodium salt is also presented and compared with the iron complex. The anticholinesterase activity of the complexes was also studied.

  5. Bis(μ-pyridinium-2-carboxylato-κ2O:O′bis[triaqua(sulfato-κOmanganese(II

    Directory of Open Access Journals (Sweden)

    Hossein Ali Rasekh

    2012-01-01

    Full Text Available The asymmetric unit of the title compound, [Mn2(SO42(C6H5NO22(H2O6], comprises half of a centrosymmetric dimer. The MnII atom is coordinated by two O atoms of the monodentate carboxylate ligand, an O atom of the sulfate anion in axial position and three water molecules in a distorted octahedral geometry. In the crystal, molecules are connected through N—H...O and O—H...O hydrogen bonds, forming a three-dimensional network. The crystal structure is further stabilized by intermolecular π–π interactions [centroid–centroid distance = 3.842 (2 Å].

  6. The metamorphosis of heterometallic trinuclear antiferromagnetic complexes into nano-sized superparamagnetic spinels.

    Science.gov (United States)

    Vasylenko, Inna V; Gavrylenko, Konstiantyn S; Il'yin, Vladimir G; Golub, Vladimir; Goloverda, Galina; Kolesnichenko, Vladimir; Addison, Anthony W; Pavlishchuk, Vitaly V

    2010-05-15

    Thermal decomposition of the trinuclear heterometallic oxoacetates [Fe(2)M(μ(3)-O)(CH(3)COO)(6)(H(2)O)(3)] has been used as a single-precursor method for synthesis of the spinel-structured ternary oxides MFe(2)O(4) (M = Mn(II), Co(II), and Ni(II)). This facile process occurring at 320 °C results in the formation of nanocrystalline, (7-20 nm) highly pure stoichiometric ferrites in quantitative yield. The magnetic properties of these nanoparticulate ferrites were studied in the 10-300 K temperature range, revealing superparamagnetic behaviour for the Ni and Mn particles and ferromagnetic behavior for the Co ones at room temperature. Their blocking temperatures follow the order: CoFe(2)O(4) > MnFe(2)O(4) > NiFe(2)O(4).

  7. DNA binding, anti-inflammatory and analgesic evaluation of metal complexes of N/S/O donor ligands; Synthesis, spectral characterization

    Science.gov (United States)

    Kumar Naik, K. H.; Ashok, B.; Naik, Nagaraja; Mulla, Jameel Ahmed S.; Prakasha, Avinash

    2015-04-01

    Transition metal complexes containing tri-dentate NSN donor ligands i.e., 5-((1(aminomethyl)cyclohexyl)methyl)-1,3,4-thiadiazol-2-amine (AMTA) (2) and 5-(2-aminophenyl)-1,3,4-thiadiazol-2-amine (ATA) (4i-ii) have been synthesized. The newly synthesized ligands and their respective complexes were characterized by elemental analysis, molar conductance measurement and various spectral studies [infrared (IR), electronic, and NMR (for ligands only)]. Metal complexes are like [M(AMTA)2], [M(ATA)2] type, where M = Mn(II), Co(II) and Cu(II). The proposed geometries of the complexes are octahedral in nature. The synthesized ligands and their complexes were exhibits effective anti-inflammatory, analgesic and DNA binding activities. All the tested compounds exhibited significant analgesic activity, whereas the compound 4i, 4(ia) and 4(iib) is equipotent with Diclofenac sodium.

  8. Complexes of some 3d-metals with a Schiff base derived from 5-acetamido-1,3,4-thiadiazole-2-sulphonamide and their biological activity

    Directory of Open Access Journals (Sweden)

    Mitu Liviu

    2011-01-01

    Full Text Available Using a bidentate ligand, a Schiff base of 5-acetamido-1,3,4- thiadiazole-2-sulphonamide, complexes of transition metals having the general formula ML2, where M = Mn(II, Fe(II, Ni(II and Cu(II, were synthesized. The complexes were characterized by elemental analysis, molar conductivity, magnetic moment, electronic, ESR and IR spectroscopy, and particle size analysis. The conductivity data of the complexes suggests their non-electrolytic nature. The stability constants and free energy change for the complexes were calculated. Spectral studies and magnetic susceptibility measurements revealed an octahedral geometry for all the complexes. The ligand and its complexes were screened for their fungicidal activity against Aspergillus niger and A. flavus.

  9. An unusual binodal (6,8)-connected 3D supramolecular network with twofold self-penetration

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    A dicarboxylate ligand,5-carboxyl-1-carboxymethyl-2-oxidopyridinium (H2L),was utilized to form four complexes with the general formula [M(HL)2(H2O)]·2H2O,M = CuII (1),ZnII (2),MnII (3),CdII (4).The crystals were isomorphous,belonging to the monoclinic C2/c space group.They were constructed from 1D chains and further linked by hydrogen bonds into a novel binodal (6,8)-connected 3D supramolecular network with twofold self-penetration.Photoluminescence studies revealed that complexes 2-4 displayed intense structure-related fluorescent emission bands.

  10. Crystalline, mixed-valence manganese analogue of prussian blue: magnetic, spectroscopic, X-ray and neutron diffraction studies.

    Science.gov (United States)

    Franz, Patrick; Ambrus, Christina; Hauser, Andreas; Chernyshov, Dmitry; Hostettler, Marc; Hauser, Jürg; Keller, Lukas; Krämer, Karl; Stoeckli-Evans, Helen; Pattison, Philip; Bürgi, Hans-Beat; Decurtins, Silvio

    2004-12-22

    The compound of stoichiometry Mn(II)3[Mn(III)(CN)6]2.zH2O (z = 12-16) (1) forms air-stable, transparent red crystals. Low-temperature single crystal optical spectroscopy and single crystal X-ray diffraction provide compelling evidence for N-bonded high-spin manganese(II), and C-bonded low-spin manganese(III) ions arranged in a disordered, face-centered cubic lattice analogous to that of Prussian Blue. X-ray and neutron diffraction show structured diffuse scattering indicative of partially correlated (rather than random) substitutions of [Mn(III)(CN)6] ions by (H2O)6 clusters. Magnetic susceptibility measurements and elastic neutron scattering experiments indicate a ferrimagnetic structure below the critical temperature Tc = 35.5 K.

  11. Studies on Co-Ordination Polymers of 5,5’-(6-(4-Methoxy Phenoxy-1,3,5-Triazine- 2,4-DiylBis(AzanediylDiquinolin-8-Ol

    Directory of Open Access Journals (Sweden)

    Talaviya P

    2013-06-01

    Full Text Available A novel is ligand namely 5,5'-(6-(4-methoxyphenoxy-1,3,5-triazine-2,4-diylbis (azanediyldiquinolin-8-ol (PBDQ-6 has been prepared and characterized. This ligand was characterized by IR, 1H-NMR,and elemental analysis. Coordination polymers of this bis-ligand (NBDQ were prepared with Cu(II,Ni(II, Co(II, Mn(II, and Zn(II metal ions. All of these coordination polymers were characterized byelemental analyses, IR spectral and diffuse reflectance spectral studies. The thermal stability wasevaluated by thermo gravimetric analyses (TGA. In addition, all of the coordination polymers havebeen characterized by their magnetic susceptibilities. All the novel synthesized compounds werescreened for their antibacterial and antifungal activities.

  12. Synthesis of a Dehydroabietyl Derivative Bearing a 2-(2′-Hydroxyphenyl Benzimidazole Unit and Its Selective Cu2+ Chemosensing

    Directory of Open Access Journals (Sweden)

    Ying-Ming Pan

    2010-12-01

    Full Text Available A dehydroabietyl derivative 2 bearing a 2-(2′-hydroxyphenylbenzimidazole unit was synthesized and its sensing behaviors toward metal ions were investigated by UV-Vis and fluorescence spectroscopy methods. In THF solution, compound 2 exhibited excellent selectivity for Cu(II over miscellaneous other metal ions including Cr(II, Mn(II, Co(II, Ni(II, Zn(II, Cd(II, Al(III, Mg(II, Pb(II, Hg(II, Na(I, Li(I and K(I evidenced through the quenching of the fluorescence of the benzimidazole fragment. The reaction between 2 and Cu2+ was found to be stoichiometric with the formation of a 1:1 complex.

  13. Bis[6-(3,5-dimethyl-1H-pyrazol-1-yl-κN2picolinato-κ2N,O]manganese(II bis(3,5-dinitrobenzoic acid solvate

    Directory of Open Access Journals (Sweden)

    Cui-Wu Lin

    2008-07-01

    Full Text Available In the title complex, [Mn(C11H10N3O22]·2C7H4N2O6, the MnII atom has a disorted octahedral coordination formed by four N and two O atoms of two mer-6-(3,5-dimethyl-1H-pyrazol-1-ylpicolinate ligands (DMPP. Each of the two symmetry-independent 3,5-dinitrobenzoic acid molecules is linked to the molecule of the complex via a hydrogen bond involving its carboxylic H atom and one of the DMPP ligands of the complex. However, in one of the DMPP ligands, the non-coordinated carbonyl O atom serves as the hydrogen-bond acceptor, whereas in the second ligand it is the Mn-coordinated O atom which is involved in the hydrogen bonding.

  14. Dual Heterogeneous Catalyst Pd-Au@Mn(II)-MOF for One-Pot Tandem Synthesis of Imines from Alcohols and Amines.

    Science.gov (United States)

    Chen, Gong-Jun; Ma, Hui-Chao; Xin, Wen-Ling; Li, Xiao-Bo; Jin, Fa-Zheng; Wang, Jing-Si; Liu, Ming-Yang; Dong, Yu-Bin

    2017-01-03

    A new Mn(II) metal-organic framework (MOF) 1 was synthesized by the combination of 4,4,4-trifluoro-1-(4-(pyridin-4-yl)phenyl)butane-1,3-dione (L) and Mn(OAc)2 in solution. 1 features a threefold-interpenetrating NbO net containing honeycomb-like channels, in which the opposite Mn(II)···Mn(II) distance is 23.5075(10) Å. Furthermore, 1 can be an ideal platform to support Pd-Au bimetallic alloy nanoparticles to generate a composite catalytic system of Pd-Au@Mn(II)-MOF (2). 2 can be a highly active bifunctional heterogeneous catalyst for the one-pot tandem synthesis of imines from benzyl alcohols and anilines and from benzyl alcohols and benzylamines.

  15. Characterizing the Catalytic Potential of Deinococcus, Arthrobacter and other Robust Bacteria in Contaminated Subsurface Environments of the Hanford Site

    Energy Technology Data Exchange (ETDEWEB)

    Fredrickson, Jim K.; Daly, Michael J.

    2006-06-01

    Until recently, there have been no clear physiologic predictors of a cell's ability to recover from ionizing radiation (IR), desiccation, and other DOE-relevant oxidative stress conditions. In general, the most resistant bacteria have been Gram-positive (e.g., Deinococcus, Arthrobacter, Lactobacillus & Enterococcus spp.) and the most sensitive have been Gram-negative (e.g., Pseudomonas, Shewanella & Neisseria spp.). However, there are several reported exceptions to this paradigm, the Gram-negative cyanobacterium Chroococcidiopsis is extremely resistant to IR, whereas the Gram-positive Micrococcus luteus is sensitive. We have identified biomolecular signatures for radiation sensitivity and resistance which are independent of phylogeny, where very high and very low intracellular Mn/Fe concentration ratios correlated with very high and very low resistances, respectively; and restricting Mn(II) in the famously resistant Deinococcus radiodurans sensitized this eubacterium to IR (http://cfyn.ifas.ufl.edu/radiation.pdf).

  16. Reminiscences From a Career in Geomicrobiology

    Science.gov (United States)

    Ehrlich, Henry L.

    2012-05-01

    This is a memoir relating how the author became a geomicrobiologist and how he practiced his specialty. Born in Germany and receiving his early schooling in Berlin, he completed his secondary education, followed by college and graduate school training, after emigration to the United States in 1940. After attaining a PhD degree in 1951, he spent his entire professional career as a faculty member of the Department of Biology at Rensselaer Polytechnic Institute (RPI) in Troy, New York. He was introduced to geomicrobiology in 1959 by a question from a colleague in the Department of Geology at RPI concerning the recent discovery of acidophilic iron-oxidizing, autotrophic bacteria in acid coal mine drainage. This led him to investigate bacterial interaction with metal sulfides, Mn(II) and Mn(IV) on land and in the sea, chromate, and bauxite; to teach a course in geomicrobiology; and to write a textbook on the subject, first published in 1981.

  17. Bis(2-methoxybenzylammonium diaquabis(dihydrogen diphosphato-κ2O,O′cobaltate(II dihydrate

    Directory of Open Access Journals (Sweden)

    Adel Elboulali

    2014-04-01

    Full Text Available The title compound, (C8H12NO2[Co(H2P2O72(H2O2]·2H2O, crystallizes isotypically with its MnII analogue. It consists of alternating layers of organic cations and inorganic complex anions, extending parallel to (100. The complex cobaltate(II anion exhibits -1 symmetry. Its Co2+ atom has an octahedral coordination sphere, defined by two water molecules in apical positions and two H2P2O72− ligands in equatorial positions. The cohesion between inorganic and organic layers is accomplished by a set of O—H...O and N—H...O hydrogen bonds involving the organic cation, the inorganic anion and the remaining lattice water molecules.

  18. Adsorption of manganese(II) ions by EDTA-treated activated carbons

    Energy Technology Data Exchange (ETDEWEB)

    Khan, A.Y.; Mazyck, D.W. [Jones Edmunds & Associates, Gainesville, FL (United States)

    2009-07-01

    The adsorption of manganese(II) ions from aqueous solution onto three different granular activated carbons treated with ethylenediamine tetraacetic acid (EDTA) and its sodium salt was investigated. Characterization of the chelate-treated carbons showed that EDTA altered the physical and chemical properties of the sorbents relative to their untreated counterparts. Furthermore, the modified sorbents exhibited a heightened capacity towards the adsorption of Mn(II) ions from aqueous media. Manganese(II) ion removal increased from 0 to 6.5 mg/g for the lignite coal-based sorbent, from 3.5 to 14.7 mg/g for the wood-based sorbent and from 1.3 to 7.9 mg/g for the bituminous coal-based sorbent. The increased removal is attributed, in part, to the creation of Lewis base sites that participate in covalent interactions and hydrolysis reactions.

  19. A Neutrally Charged Trimethylmanganese(III) Complex: Synthesis, Characterization, and Disproportionation Chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Stalzer, Madelyn M.; Telser, Joshua; Krzystek, Jurek; Motta, Alessandro; Delferro, Massimiliano; Marks, Tobin J.

    2016-08-22

    The synthesis and properties of an unusual, neutrally charged and volatile N,N,N',N'-tetramethylethylenediamine trimethyl manganese(III) complex, (TMEDA)MnMe3, are described, along with its facile disproportionation to the corresponding Mn(II) and Mn(IV) complexes. Characterization by single-crystal XRD, UV-vis spectroscopy, high-frequency and -field EPR (HFEPR), magnetic susceptibility, and density functional theory (DFT) computations indicate that the (TMEDA)MnMe3 electronic structure can be described as largely square pyramidal Mn(III) centered. The paucity of manganese(III) polyalkyls and the simplicity and reactivity of this compound implicate it as a potentially useful synthetic building block.

  20. Conversion of core oxos to water molecules by 4e-/4H+ reductive dehydration of the Mn4O2(6+) core in the manganese-oxo cubane complex Mn4O4(Ph2PO2)6: a partial model for photosynthetic water binding and activation.

    Science.gov (United States)

    Ruettinger, W F; Dismukes, G C

    2000-03-06

    Reaction of the Mn4O4(6+) "cubane" core complex, Mn4O4L6 (1) (L = diphenylphosphinate, Ph2PO2-), with a hydrogen atom donor, phenothiazine (pzH), forms the dehydrated cluster Mn4O2L6 (2), which has lost two mu-oxo bridges by reduction to water (H2O). The formation of 2 was established by electrospray mass spectrometry, whereas FTIR spectroscopy confirmed the release of water molecules into solution during the reduction of 1. UV-vis and EPR spectroscopies established the stoichiometry and chemical form of the pzH product by showing the production of 4 equiv of the neutral pz radical. By contrast, the irreversible decomposition of 1 to individual Mn(II) ions occurs if the reduction is performed using electrons provided by various proton-lacking reductants, such as cobaltocene or electrochemical reduction. Thus, cubane 1 undergoes coupled four-electron/four-proton reduction with the release of two water molecules, a reaction formally analogous to the reverse sequence of the steps that occur during photosynthetic water oxidation leading to O2 evolution. 1H NMR of solutions of 2 reveal that all six of the phosphinate ligands exhibit paramagnetic broadening, due to coordination to Mn ions, and are magnetically equivalent. A symmetrical core structure is thus indicated. We hypothesize that this structure is produced by the dynamic averaging of phosphinato ligand coordination or exchange of mu-oxos between vacant mu-oxo sites. The paramagnetic 1H NMR of water molecules in solution shows that they are able to freely exchange with water molecules that are bound to the Mn ion(s) in 2, and this exchange can be inhibited by the addition of coordinating anions, such as chloride. Thus, 2 possesses open or labile coordination sites for water and anions, in contrast to solutions of 1, which reveal no evidence for water coordination. Complex 2 exhibits greater paramagnetism than that of 1, as seen by 1H NMR, and it possesses a broad (440 G wide) EPR absorption, centered at g = 2

  1. Perfluorinated quaternary ammonium salts of polyoxometalate anions: Fluorous biphasic oxidation catalysis with and without fluorous solvents

    Energy Technology Data Exchange (ETDEWEB)

    Maayan, Galia; Fish, Richard H.; Neumann, Ronny

    2003-05-28

    Perfluorinated quaternary ammonium cations, [CF{sub 3}(CF{sub 2}){sub 7}(CH{sub 2}){sub 3}]{sub 3}CH{sub 3}N{sup +} (RFN{sup +}), were synthesized and used as counter cations for the [WZnM{sub 2}(H{sub 2}O){sub 2}(ZnW{sub 9}O{sub 34}){sub 2}]{sup 12-} (M = Mn(II), Zn(II)), polyoxometalate. The (RFN{sup +}){sub 12}[WZnM{sub 2}(H{sub 2}O){sub 2}(ZnW9O{sub 34}){sub 2}] compounds were fluorous biphasic catalysts for alcohol and alkenol oxidation, and alkene epoxidation with aqueous hydrogen peroxide. Reaction protocols with or without a fluorous solvent were tested. The catalytic activity and selectivity was affected both by the hydrophobicity of the solvent and the substrate.

  2. Synthesis, XAFS and X-ray structural studies of mono- and binuclear metal-chelates of N,O,O(N,O,S) tridentate Schiff base pyrazole derived ligands

    Science.gov (United States)

    Burlov, Anatolii S.; Uraev, Ali I.; Garnovskii, Dmitrii A.; Lyssenko, Konstantin A.; Vlasenko, Valery G.; Zubavichus, Yan V.; Murzin, Vadim Yu.; Korshunova, Eugenie V.; Borodkin, Gennadii S.; Levchenkov, Sergey I.; Vasilchenko, Igor S.; Minkin, Vladimir I.

    2014-05-01

    The syntheses of a series of novel N,O,O and N,O,S donor tridentate Schiff base ligands H2L1 and H2L2via the condensation of 1-phenyl-3-methyl-4-formylpyrazol-5-ol(thiol) with 2-hydroxymethylaniline and their Co(II), Ni(II), Cu(II), Fe(III), and Mn(II) complexes are reported. The compounds are characterized by the C, H, N, S, metal elemental analysis, IR spectroscopy; 1H NMR data for ligands, low-temperature magnetic measurements, X-ray absorption spectroscopy. The crystal structures for Ni(II) and Cu(II) coordination compounds with the compositions NiL21 and Cu2L21 are established by X-ray crystallography.

  3. (4-Carboxy-2-sulfonatobenzoato-κ2O1,O2bis(1,10-phenanthroline-κ2N,N′manganese(II

    Directory of Open Access Journals (Sweden)

    Qiong-Fang Wu

    2010-07-01

    Full Text Available In the title complex, [Mn(C8H4O7S(C12H8N22], the MnII atom is chelated by one 4-carboxy-2-sulfonatobenzoate anion and two phenathroline (phen ligands in a distorted octahedral MnN4O2 geometry. The benzene ring of the 4-carboxy-2-sulfonatobenzoate anion is twisted with respect to the two phen ring systems at dihedral angles of 66.38 (9 and 53.56 (9°. In the crystal, intermolecular O—H...O and C—H...O hydrogen bonding links the molecules into chains running parallel to [100]. Intermolecular π–π stacking is also observed between parallel phen ring systems, the face-to-face distance being 3.432 (6 Å.

  4. catena-Poly[[[diaqua(1,10-phenanthrolinemanganese]-μ-3-[3-(carboxylatomethoxyphenyl]acrylato] monohydrate

    Directory of Open Access Journals (Sweden)

    Jun Ji

    2012-07-01

    Full Text Available The title compound, [Mn(C11H8O5(C12H8N2(H2O2]·H2O, was obtained under hydrothermal conditions. The coordination environment of the Mn(II atom is a distorted MnN2O4 octahedron defined by two N atoms from 1,10-phenanthroline, two water O atoms and two carboxylate O atoms from two acrylate anions. The bis-monodentate coordination mode of the anion leads to the formation of chains propagating in [010]. Intermolecular O—H...O hydrogen bonds link the chains into a two-dimensional network parallel to (100. In the voids of this arrangement, disordered lattice water molecules are present.

  5. Synthesis, spectral elucidation, electrochemistry and DFT interpretation of manganese(II)-thioalkyl-arylazoimidazole complex

    Science.gov (United States)

    Nandi, Soumendranath; Das, Kuheli; Datta, Amitabha; Banerjee, Debashis; Roy, Suman; Mondal, Tapan Kumar; Mandal, Debashree; Nanda, Prasanta Kumar; Akitsu, Takashiro; Tanaka, Shinnosuke; Sinha, Chittaranjan

    2017-04-01

    One new Mn(II) thioalkyl-arylazoimidazole complex (1), [Mn(SRaaiNR/)2(SCN)2] (SRaaiNR/ = 1-alkyl-2-{(o-thioalkyl)phenylazo}imidazole and R = Me, R/ = Et) is afforded and systematically characterized by FT-IR, UV-Vis and EPR spectroscopy. The single crystal X-ray diffraction technique reveals that in complex 1, the central Mn atom possesses a tetrahedral environment of MnN4 sphere; coordinated by a pair of monodentate orientation of Nimidazolyl and NSCN atoms. Variable temperature magnetic moment confirms that in complex 1, there exists an antiferromagnetic coupling in tetrahedral symmetry. Cyclic voltammogram study of complex 1 evidenced the presence of a Mn(III)/Mn(II) redox response at 1.25 V alongwith azo reductions at -0.8 V. DFT computational using optimized geometry clearly explains the electronic and redox properties which is in accordance with the experimental evidence.

  6. Synthesis and Spectral Investigations of Manganese(II, Cobalt(II, Nickel(II, Copper(II and Zinc(II Complexes of New Polydentate Ligands Containing a 1,8-Naphthyridine Moiety

    Directory of Open Access Journals (Sweden)

    Sunkari Jyothi

    2006-12-01

    Full Text Available 2-(o-Hydroxyphenyl-1,8-naphthyridine (HN, 2-(4-hydroxy-6-methylpyran-2-one-3-yl-1,8-naphthyridine (HMPN and 2-(benzimidazol-2-yl-1,8-naphthyridine(BN react with acetates of Mn(II, Co(II, Ni(II, Cu(II and Zn(II to yield metal ioncomplexes of definite composition. These compounds were characterized by elementalanalyses, molar conductivity, magnetic susceptibility measurements, thermal studies, IR,UV-visible, NMR and mass spectral investigations. The complexes are found to have theformulae [M(HN2(H2O2], [M(HMPN2(H2O2] and [M(BN2(OAc2], respectively.

  7. Crystal structure of hexakis(dimethyl sulfoxide-κO)manganese(II) tetraiodide

    KAUST Repository

    Haque, Md Azimul

    2016-11-15

    The title salt, [Mn(C2H6OS)6]I4, is made up from discrete [Mn(DMSO)6]2+ (DMSO is dimethyl sulfoxide) units connected through non-classical hydrogen bonds to linear I4 2- tetraiodide anions. The MnII ion in the cation, situated on a position with site symmetry -3., is octahedrally coordinated by O atoms of the DMSO molecule with an Mn - O distance of 2.1808(12)Å. The I4 2- anion contains a neutral I2 molecule weakly coordinated by two iodide ions, forming a linear centrosymmetric tetraiodide anion. The title compound is isotypic with the Co, Ni, Cu, and Zn analogues.

  8. Synthesis, characterization and biocidal activities of Schiff base polychelates containing polyurethane links in the main chain

    Science.gov (United States)

    Hasnain, Sumaiya; Nishat, Nahid

    The concept of combining metallo-polymers with urethanes offers a versatile approach for the synthesis of new polymeric materials. Polyurethane containing transition metals was synthesized by the reaction of Schiff base metal complex with toluene 2,4 diisocyanate. The proposed structures were confirmed by elemental analysis, 1H NMR, 13C NMR and FT-IR. The geometry is determined by UV-Visible spectra and magnetic moment measurements, which reveals that the Mn(II), Co(II) and Ni(II) complexes have octahedral geometry while square planer geometry is reported for Cu(II) and tetrahedral for Zn(II) complex. The antimicrobial activities are determined using the agar well diffusion method with Staphylococcus aureus, Escherichia coli, Bacillus subtilis (bacteria), Aspergillus niger, Candida albicans and Aspergillus flavus (yeast). All the polymeric metal complexes show comparatively good biocidal activity, which is further enhanced after polymerization.

  9. Synthesis and characterization of ligational behavior of curcumin drug towards some transition metal ions: Chelation effect on their thermal stability and biological activity

    Science.gov (United States)

    Refat, Moamen S.

    2013-03-01

    Complexes of Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II) and Zn(II) with curcumin ligand as antitumor activity were synthesized and characterized by elemental analysis, conductometry, magnetic susceptibility, UV-Vis, IR, Raman, ESR, 1H-NMR spectroscopy, X-ray diffraction analysis of powdered samples and thermal analysis, and screened for antimicrobial activity. The IR spectral data suggested that the ligand behaves as a monobasic bidentate ligand towards the central metal ion with an oxygen's donor atoms sequence of both sbnd OH and Cdbnd O groups under keto-enol structure. From the microanalytical data, the stoichiometry of the complexes 1:2 (metal:ligand) was found. The ligand and their metal complexes were screened for antibacterial activity against Escherichia Coli, Staphylococcus aureus, Bacillus subtilis and Pseudomonas aeruginosa and fungicidal activity against Aspergillus flavus and Candida albicans.

  10. Effective optical Faraday rotations of semiconductor EuS nanocrystals with paramagnetic transition-metal ions.

    Science.gov (United States)

    Hasegawa, Yasuchika; Maeda, Masashi; Nakanishi, Takayuki; Doi, Yoshihiro; Hinatsu, Yukio; Fujita, Koji; Tanaka, Katsuhisa; Koizumi, Hitoshi; Fushimi, Koji

    2013-02-20

    Novel EuS nanocrystals containing paramagnetic Mn(II), Co(II), or Fe(II) ions have been reported as advanced semiconductor materials with effective optical rotation under a magnetic field, Faraday rotation. EuS nanocrystals with transition-metal ions, EuS:M nanocrystals, were prepared by the reduction of the Eu(III) dithiocarbamate complex tetraphenylphosphonium tetrakis(diethyldithiocarbamate)europium(III) with transition-metal complexes at 300 °C. The EuS:M nanocrystals thus prepared were characterized using X-ray diffraction (XRD), transmission electron microscopy (TEM), inductively coupled plasma atomic emission spectroanalysis (ICP-AES), and a superconducting quantum interference device (SQUID) magnetometer. Enhanced Faraday rotations of the EuS:M nanocrystals were observed around 550 nm, and their enhanced spin polarization was estimated using electron paramagnetic resonance (EPR) measurements. In this report, the magneto-optical relationship between the Faraday rotation efficiency and spin polarization is discussed.

  11. Synthesis, characterization, theoretical treatmentand antitubercular activity evaluation of (E-N’-(2,5-dimethoxylbenzylidene nicotinohydrazide and some of its transition metal complexes against Mycobacterium tuberculosis, H37Rv

    Directory of Open Access Journals (Sweden)

    Ogunniran Kehinde

    2016-03-01

    Full Text Available (E-N’-(2,5-dimethoxylbenzylidene nicotinohydrazide (HL was synthesized by condensing nicotinic acid hydrazide and 2,5-dimethoxylbenzaldehyde with ONO coordination pattern. The structure of the hydrazone was elucidated by using CHN analyzer, ESI mass spectrometry, IR, 1H NMR, 13C NMR and 2D NMR (COSY and HSQC. The hydrazone was used to synthesized five metal complexes [Mo(V, VO(II, Mn(II Ni(II and Cu(II] which werecharacterized by several physicochemical methods, namely elemental analysis, electronic spectra, infrared, EPR, molar conductivity and magnetic susceptibility measurements. An octahedral geometry was suggested for Mo(V, Ni(II and Cu(II complexes while tetrahedral was proposed for Mn(II complex. VO(II complex conformed with tetrahedral pyramidal. Structural geometries of these compounds were also suggested in gas phase by using Hyper Chem-8 program for the molecular mechanics and semi-empirical calculations. The energy (E and eV for homo and lumo state for the prepared compounds were calculated by using PM3 method. In vitroantimycobacterial activity study of the compounds was evaluated against Mycobacterium tuberculosis, H37Rv, by using micro-diluted method. Some of the metal complexes displayed higher activity than the ligand (HL and isoniazid (INH.Also some of the complexes showed moderate activity when compared to isoniazid. Generally, the results obtained revealed that the compounds exhibited promising antitubercular activity. However, the metal complexes were found to be more toxic than isoniazid drug.

  12. Synthesis, magnetic and spectral studies on polystyrene-anchored coordination complexes of bi-, tri-, tetra- and hexavalent metal ions with unsymmetrical dibasic tetradentate ONNO donor Schiff base derived from 3-formylsalicylic acid, ethylenediamine and 2-benzoylacetanilide

    Indian Academy of Sciences (India)

    Dinesh Kumar; Arun Syamal; Jaipal; Lalit Kumar Sharma

    2009-01-01

    Polystyrene-anchored Cu(II), Zn(II), Cd(II), Ni(II), Mn(II), MoO2(II), UO2(II), Fe(III) and Zr(IV), complexes of the unsymmetrical dibasic tetradentate ONNO donor Schiff base derived from the condensation of chloromethylated polystyrene, 3-formylsalicylic acid, ethylenediamine and 2-benzoylacetanilide (PS-LH2) has been synthesized. The polystyrene anchored complexes have the formulae: PS-LM (where M = Cu, Zn, Cd, Ni, MoO2, UO2), PS-LFeCl.DMF, PS-LMn.2DMF and PS-LZr(OH)2.DMF. The polystyrene-anchored coordination compounds have been characterized by elemental analysis, IR, reflectance, ESR and magnetic susceptibility measurements. The per cent reaction conversion of polystyrene anchored Schiff base to polystyrene supported coordination compounds lies between 28.98 and 85.9. The coordinated dimethylformamide is completely lost on heating the complexes. The shifts of the ν(C=N)(azomethine) and ν(C-O)(phenolic) stretches have been monitored in order to find out the donor sites of the ligands. The Cu(II) complex is paramagnetic with square planar structure; the Ni(II) complex is diamagnetic with square planar structure; the Zn(II) and Cd(II) complexes are diamagnetic and have tetrahedral structure; the Mn(II) and Fe(III) complexes are paramagnetic and have octahedral structure; the MoO2(II) and UO2(II) complexes are diamagnetic and have octahedral structure and the Zr(IV) complexes are diamagnetic and have pentagonal bipyramidal structure.

  13. Assessment of heavy metal tolerance and hexavalent chromium reducing potential of Corynebacterium paurometabolum SKPD 1204 isolated from chromite mine seepage

    Directory of Open Access Journals (Sweden)

    Amal Kanti Paul

    2016-07-01

    Full Text Available Corynebacterium paurometabolum SKPD 1204 (MTCC 8730, a heavy metal tolerant and chromate reducing bacterium isolated from chromite mine seepage of Odisha, India has been evaluated for chromate reduction under batch culture. The isolate was found to tolerate metals like Co(II, Cu(II, Ni(II, Mn(II, Zn(II, Fe(III and Hg(II along with Cr(VI and was resistant to different antibiotics as evaluated by disc-diffusion method. The isolate, SKPD 1204 was found to reduce 62.5% of 2 mM Cr(VI in Vogel Bonner broth within 8 days of incubation. Chromate reduction capability of SKPD 1204 decreased with increase in Cr(VI concentration, but increased with increase in cell density and attained its maximum at 1010 cells/mL. Chromate reducing efficiency of SKPD 1204 was promoted in the presence of glycerol and glucose, while the highest reduction was recorded at pH 7.0 and 35 °C. The reduction process was inhibited by divalent cations Zn(II, Cd(II, Cu(II, and Ni(II, but not by Mn(II. Anions like nitrate, phosphate, sulphate and sulphite was found to be inhibitory to the process of Cr(VI reduction. Similarly, sodium fluoride, carbonyl cyanide m-chlorophenylhydrazone, sodium azide and N, N,-Di cyclohexyl carboiimide were inhibitory to chromate reduction, while 2,4-dinitrophenol appeared to be neither promotive nor inhibitory to the process.

  14. Natural Monocrystalline Pyrite as Sensor for Potentiometric Redox Titrations. Part I. Titrations with Permanganate

    Directory of Open Access Journals (Sweden)

    B. V. Vukanovic

    2002-04-01

    Full Text Available Results obtained in potentiometric titrations of Fe(II, Mn(II, Fe(CN64-, C2O42- and As(III with standard potassium permanganate solution, are presented. The titration end point (TEP was detected with a universal electrode whose sensor is natural crystalline pyrite. The titrations of As(III were carried out in HCl (1.2 M and H2SO4 solutions (0.1- 4.5 M, whereas oxalate was determined in H2SO4 (0.1-4.5 M. Iron(II and hexacyanoferrate(II were titrated in H2SO4 and also in H3PO4 solutions (0.1-4.5 M. The titrations of Mn(II were performed in H2P2O72- media at pH 4.0, 5.0, 6.0 and 7.0. The results obtained by using the pyrite electrode were compared with those obtained by the application of a Pt-electrode, and good agreement, reproducibility and accuracy were obtained. The potentials in the course of the titration and at the end-point (TEP are rapidly established. The potential changes at the TEP ranged from 90 to 330 mV/0.1 mL, depending on the titrated system. The highest changes were observed in titrations of Fe(II in H3PO4 (240-330 mV/0.1 mL. Reversed titrations were also performed and accurate and reproducible results were obtained.

  15. Influence of foreign metal ions on crystal growth and morphology of brushite (CaHPO 4, 2H 2O) and its transformation to octacalcium phosphate and apatite

    Science.gov (United States)

    Lundager Madsen, Hans E.

    2008-05-01

    Brushite, forming tabular crystals, has been precipitated at 25 °C in the presence of each of 14 different di- and trivalent metal ions. The influence of these ions at micromolar concentrations on the solvent-mediated phase transformation of brushite to more basic calcium phosphates has been studied as well. The effect of additives on brushite crystallization was pH-dependent, which could be related to the presence or absence of amorphous precipitate. In the latter case the course of the crystallization process could be followed by recording pH as function of time. For half of the additives kinetic analysis was possible and showed that the crystal growth mechanism is surface nucleation. Edge free energy is lowered in the presence of an additive. Zn favoured aggregates, and the transition metals with the exceptions of Mn(II), Co(II) and Cu(II) favoured irregular growth. Zn inhibited lateral growth, as did Cd and Cr(III) at low and Cu(II) at high pH. Most of the ions have a marked effect on the transformation to octacalcium phosphate (OCP) and hydroxyapatite (HAP) as well. In both cases Cu(II) and Zn are strong inhibitors, whereas Pb(II) is a moderate promotor. Fe in both oxidation states, Co(II), Mn(II) and Sr are intermediate in effect on phase transformation. Inhibition may be caused by adsorbed foreign ions impeding growth of nuclei or by poisoning of the substrate for heterogeneous nucleation, i.e. brushite crystals. Promotion is explained by the formation of nuclei with suitable crystal structure, e.g. apatite/pyromorphite (Ca,Pb) 5OH(PO 4) 3 in the case of Pb.

  16. From a Dy(III) single molecule magnet (SMM) to a ferromagnetic [Mn(II)Dy(III)Mn(II)] trinuclear complex.

    Science.gov (United States)

    Bhunia, Asamanjoy; Gamer, Michael T; Ungur, Liviu; Chibotaru, Liviu F; Powell, Annie K; Lan, Yanhua; Roesky, Peter W; Menges, Fabian; Riehn, Christoph; Niedner-Schatteburg, Gereon

    2012-09-17

    The Schiff base compound 2,2'-{[(2-aminoethyl)imino]bis[2,1-ethanediyl-nitriloethylidyne]}bis-2-hydroxy-benzoic acid (H(4)L) as a proligand was prepared in situ. This proligand has three potential coordination pockets which make it possible to accommodate from one to three metal ions allowing for the possible formation of mono-, di-, and trinuclear complexes. Reaction of in situ prepared H(4)L with Dy(NO(3))(3)·5H(2)O resulted in the formation of a mononuclear complex [Dy(H(3)L)(2)](NO(3))·(EtOH)·8(H(2)O) (1), which shows SMM behavior. In contrast, reaction of in situ prepared H(4)L with Mn(ClO(4))(2)·6H(2)O and Dy(NO(3))(3)·5H(2)O in the presence of a base resulted in a trinuclear mixed 3d-4f complex (NHEt(3))(2)[Dy{Mn(L)}(2)](ClO(4))·2(H(2)O) (2). At low temperatures, compound 2 is a weak ferromagnet. Thus, the SMM behavior of compound 1 can be switched off by incorporating two Mn(II) ions in close proximity either side of the Dy(III). This quenching behavior is ascribed to the presence of the weak ferromagnetic interactions between the Mn(II) and Dy(III) ions, which at T > 2 K act as a fluctuating field causing the reversal of magnetization on the dysprosium ion. Mass spectrometric ion signals related to compounds 1 and 2 were both detected in positive and negative ion modes via electrospray ionization mass spectrometry. Hydrogen/deuterium exchange (HDX) reactions with ND(3) were performed in a FT-ICR Penning-trap mass spectrometer.

  17. Manganese and the Evolution of Photosynthesis.

    Science.gov (United States)

    Fischer, Woodward W; Hemp, James; Johnson, Jena E

    2015-09-01

    Oxygenic photosynthesis is the most important bioenergetic event in the history of our planet-it evolved once within the Cyanobacteria, and remained largely unchanged as it was transferred to algae and plants via endosymbiosis. Manganese plays a fundamental role in this history because it lends the critical redox behavior of the water-oxidizing complex of photosystem II. Constraints from the photoassembly of the Mn-bearing water-oxidizing complex fuel the hypothesis that Mn(II) once played a key role as an electron donor for anoxygenic photosynthesis prior to the evolution of oxygenic photosynthesis. Here we review the growing body of geological and geochemical evidence from the Archean and Paleoproterozoic sedimentary records that supports this idea and demonstrates that the oxidative branch of the Mn cycle switched on prior to the rise of oxygen. This Mn-oxidizing phototrophy hypothesis also receives support from the biological record of extant phototrophs, and can be made more explicit by leveraging constraints from structural biology and biochemistry of photosystem II in Cyanobacteria. These observations highlight that water-splitting in photosystem II evolved independently from a homodimeric ancestral type II reaction center capable of high potential photosynthesis and Mn(II) oxidation, which is required by the presence of homologous redox-active tyrosines in the modern heterodimer. The ancestral homodimer reaction center also evolved a C-terminal extension that sterically precluded standard phototrophic electron donors like cytochrome c, cupredoxins, or high-potential iron-sulfur proteins, and could only complete direct oxidation of small molecules like Mn(2+), and ultimately water.

  18. Characterization of Microbial Communities in Coal Mine Drainage Treatment Systems With Elevated Manganese

    Science.gov (United States)

    Tan, H.; Zhang, G.; Burgos, W.

    2007-12-01

    Sediment samples were collected from two coal mine drainage treatment sites in western Pennsylvania. Both of the sites use constructed limestone beds to passively treat acidic coal mine drainage containing elevated manganese (Mn). Site #1 has influent manganese of 150 mg/L and effluent manganese between 40-100 mg/L. Site #2 has influent manganese of 20 mg/L and effluent manganese of less than 0.5 mg/L. Large quantities of black crusts were deposited throughout the beds at both sites. X-ray diffraction showed these crusts constituted of buserite, which is a layered structure manganese oxide mineral. Both culture-dependent and nucleic acid- based techniques were used to characterize the bacterial and fungal communities in these beds. 16S rRNA gene analysis showed that bacterial communities were very diverse and included Cyanobacter, Proteobacteria, Bacteroidete, Planctomyceta, Acidobacter, Actinobacter and Gemmatimonade taxa. The archaeal diversity was lower and most sequences were related to uncultivated species. Two Mn-oxidizing fungi strains were isolated from one of the sites. One of the fungi is capable of oxidizing Mn(II) at both low and netural pH (3-7) while the other fungi can only oxidze Mn(II) at circumneutral pH. 18S rRNA gene analysis showed the low pH Mn-oxidizing fungus was closely related to Menispora tortuosa, Chaetosphaeria curvispora and Kionochaeta spissa, and the circumneutral Mn-oxidizing fungus was closely related to Myrothecium verrucaria, Didymostilbe echinofibrosa and Myrothecium roridum.

  19. Photo-oxidation of tyrosine in a bio-engineered bacterioferritin 'reaction centre'-a protein model for artificial photosynthesis.

    Science.gov (United States)

    Hingorani, Kastoori; Pace, Ron; Whitney, Spencer; Murray, James W; Smith, Paul; Cheah, Mun Hon; Wydrzynski, Tom; Hillier, Warwick

    2014-10-01

    The photosynthetic reaction centre (RC) is central to the conversion of solar energy into chemical energy and is a model for bio-mimetic engineering approaches to this end. We describe bio-engineering of a Photosystem II (PSII) RC inspired peptide model, building on our earlier studies. A non-photosynthetic haem containing bacterioferritin (BFR) from Escherichia coli that expresses as a homodimer was used as a protein scaffold, incorporating redox-active cofactors mimicking those of PSII. Desirable properties include: a di-nuclear metal binding site which provides ligands for bivalent metals, a hydrophobic pocket at the dimer interface which can bind a photosensitive porphyrin and presence of tyrosine residues proximal to the bound cofactors, which can be utilised as efficient electron-tunnelling intermediates. Light-induced electron transfer from proximal tyrosine residues to the photo-oxidised ZnCe6(•+), in the modified BFR reconstituted with both ZnCe6 and Mn(II), is presented. Three site-specific tyrosine variants (Y25F, Y58F and Y45F) were made to localise the redox-active tyrosine in the engineered system. The results indicate that: presence of bound Mn(II) is necessary to observe tyrosine oxidation in all BFR variants; Y45 the most important tyrosine as an immediate electron donor to the oxidised ZnCe6(•+) and that Y25 and Y58 are both redox-active in this system, but appear to function interchangebaly. High-resolution (2.1Å) crystal structures of the tyrosine variants show that there are no mutation-induced effects on the overall 3-D structure of the protein. Small effects are observed in the Y45F variant. Here, the BFR-RC represents a protein model for artificial photosynthesis. Crown Copyright © 2014. Published by Elsevier B.V. All rights reserved.

  20. Approach combining on-line metal exchange and tangential-flow ultrafiltration for in-situ characterization of metal species in humic hydrocolloids

    Energy Technology Data Exchange (ETDEWEB)

    Goveia, Danielle [UNESP - Universidade Estadual Paulista, Departamento de Engenharia Ambiental, Sorocaba, SP (Brazil); UNESP - Universidade Estadual Paulista, Instituto de Quimica de Araraquara, Araraquara, SP (Brazil); Lobo, Fabiana Aparecida; Fraceto, Leonardo Fernandes; Rosa, Andre Henrique [UNESP - Universidade Estadual Paulista, Departamento de Engenharia Ambiental, Sorocaba, SP (Brazil); Burba, Peter [ISAS - Institute for Analytical Sciences, Dortmund (Germany); Dias Filho, Newton Luiz [UNESP - Universidade Estadual Paulista, Departamento de Fisica e Quimica, Ilha Solteira, SP (Brazil)

    2010-05-15

    This paper deals with the development and optimization of an analytical procedure using ultrafiltration and a flow-injection system, and its application in in-situ experiments to characterize the lability and availability of metal species in humic-rich hydrocolloids. The on-line system consists of a tangential flow ultrafiltration device equipped with a 3-kDa filtration membrane. The concentration of free ions in the filtrate was determined by atomic-absorption spectrometry, assuming that metals not complexed by aquatic humic substances (AHS) were separated from the complexed species (M-AHS) retained by the membrane. For optimization, exchange experiments using Cu(II) solutions and AHS solutions doped with the metal ions Ni(II), Mn(II), Fe(III), Cd(II), and Zn(II) were carried out to characterize the stability of the metal-AHS complexes. The new procedure was then applied in-situ at a tributary of the Ribeira do Iguape river (Iguape, Sao Paulo State, Brazil) and evaluated using the ions Fe(III) and Mn(II), which are considered to be essential constituents of aquatic systems. From the exchange between metal-natural organic matter (M-NOM) and the Cu(II) ions it was concluded that Cu(II) concentrations >485 {mu}g L{sup -1} were necessary to obtain maximum exchange of the complexes Mn-NOM and Fe-NOM, corresponding to 100% Mn and 8% Fe. Moreover, the new analytical procedure is simple and opens up new perspectives for understanding the complexation, transport, stability, and lability of metal species in humic-rich aquatic environments. (orig.)

  1. Approach combining on-line metal exchange and tangential-flow ultrafiltration for in-situ characterization of metal species in humic hydrocolloids.

    Science.gov (United States)

    Goveia, Danielle; Lobo, Fabiana Aparecida; Burba, Peter; Fraceto, Leonardo Fernandes; Dias Filho, Newton Luiz; Rosa, André Henrique

    2010-05-01

    This paper deals with the development and optimization of an analytical procedure using ultrafiltration and a flow-injection system, and its application in in-situ experiments to characterize the lability and availability of metal species in humic-rich hydrocolloids. The on-line system consists of a tangential flow ultrafiltration device equipped with a 3-kDa filtration membrane. The concentration of free ions in the filtrate was determined by atomic-absorption spectrometry, assuming that metals not complexed by aquatic humic substances (AHS) were separated from the complexed species (M-AHS) retained by the membrane. For optimization, exchange experiments using Cu(II) solutions and AHS solutions doped with the metal ions Ni(II), Mn(II), Fe(III), Cd(II), and Zn(II) were carried out to characterize the stability of the metal-AHS complexes. The new procedure was then applied in-situ at a tributary of the Ribeira do Iguape river (Iguape, São Paulo State, Brazil) and evaluated using the ions Fe(III) and Mn(II), which are considered to be essential constituents of aquatic systems. From the exchange between metal-natural organic matter (M-NOM) and the Cu(II) ions it was concluded that Cu(II) concentrations >485 microg L(-1) were necessary to obtain maximum exchange of the complexes Mn-NOM and Fe-NOM, corresponding to 100% Mn and 8% Fe. Moreover, the new analytical procedure is simple and opens up new perspectives for understanding the complexation, transport, stability, and lability of metal species in humic-rich aquatic environments.

  2. Structural, photophysical and magnetic properties of transition metal complexes based on the dipicolylamino-chloro-1,2,4,5-tetrazine ligand.

    Science.gov (United States)

    Nazarenko, Iuliia; Pop, Flavia; Sun, Qinchao; Hauser, Andreas; Lloret, Francesc; Julve, Miguel; El-Ghayoury, Abdelkrim; Avarvari, Narcis

    2015-05-21

    The ligand 3-chloro-6-dipicolylamino-1,2,4,5-tetrazine (Cl-TTZ-dipica) , prepared by the direct reaction between 3,6-dichloro-1,2,4,5-tetrazine and di(2-picolyl)-amine, afforded a series of four neutral transition metal complexes formulated as [Cl-TTZ-dipica-MCl2]2, with M = Zn(II), Cd(II), Mn(II) and Co(II), when reacted with the corresponding metal chlorides. The dinuclear structure of the isostructural complexes was disclosed by single crystal X-ray analysis, clearly indicating the formation of [M(II)-(μ-Cl)2M(II)] motifs and the involvement of the amino nitrogen atom in semi-coordination with the metal centers, thus leading to distorted octahedral coordination geometries. Moreover, the chlorine atoms, either coordinated to the metal or as a substituent on the tetrazine ring, engage respectively in specific anion-π intramolecular and intermolecular interactions with the electron-poor tetrazine units in the solid state, thus controlling the supramolecular architecture. Modulation of the emission properties is observed in the case of the Zn(II) and Cd(II) complexes when compared to the free ligand. A striking difference is observed in the magnetic properties of the Mn(II) and Co(II) complexes. An antiferromagnetic coupling takes place in the dimanganese(II) compound (J = -1.25 cm(-1)) while the Co(II) centers are ferromagnetically coupled in the corresponding complex (J = +0.55 cm(-1)), the spin Hamiltonian being defined as H = -JSA·SB.

  3. Reusable manganese compounds containing pyrazole-based ligands for olefin epoxidation reactions.

    Science.gov (United States)

    Manrique, Ester; Poater, Albert; Fontrodona, Xavier; Solà, Miquel; Rodríguez, Montserrat; Romero, Isabel

    2015-10-28

    We describe the synthesis of new manganese(ii) and manganese(iii) complexes containing the bidentate ligands 2-(3-pyrazolyl)pyridine, pypz-H, and 3(5)-(2-hydroxyphenyl)pyrazole, HOphpz-H, with formula [MnX2(pypz-H)2] (X = Cl(-), 1, CF3SO3(-), 2, OAc(-), 3 or NO3(-) (4)), [MnCl2(pypz-H)(H2O)2], 5, or [MnCl(Ophpz-H)2], 6. All the complexes have been characterized through analytical, spectroscopic and electrochemical techniques. Single X-ray structure analysis revealed a six-coordinated Mn(ii) ion in complexes 1-5, and a five-coordinated Mn(iii) ion in complex 6. Compound 5 is the first co-crystal of Mn(ii) containing Cl and H2O ligands together with bidentate nitrogen ligands. The catalytic activity of complexes 1-6 has been tested with regard to the epoxidation of styrene and, in the case of 1, 5 and 6, other alkenes have been epoxidized using peracetic acid as oxidant in different media, among which glycerol, a green solvent never used in epoxidation reactions using peracetic acid as oxidant. The catalysts show moderate to high conversions and selectivities towards the corresponding epoxides. For complexes 1, 5 and 6, a certain degree of cis→trans isomerization is observed in the case of cis-β-methylstyrene. These observations have been explained through computational calculations. The reutilization of catalysts 1 and 6 for the epoxidation of alkenes has been evaluated in [bmim] : acetonitrile mixture (bmim = 1-butyl-3-methylimidazolium), allowing the effective recyclability of the catalytic system and keeping high conversion and selectivity values up to 12 successive runs, in all cases.

  4. Synthesis, structural elucidation, microbial, antioxidant and nuclease activities of some novel divalent M(II complexes derived from 5-fluorouracil and l-tyrosine

    Directory of Open Access Journals (Sweden)

    Jeyaprakash Dharmaraja

    2017-01-01

    Full Text Available Novel N2O2 sequence of mononuclear amino acid metal(II complexes (1a–1e was synthesized from 5-fluorouracil (5-FU: A and l-tyrosine (tyr: B with Mn(II, Co(II, Ni(II, Cu(II and Zn(II ions. The synthesized complexes were structurally characterized by analytical, spectral (FT-IR, UV–vis, 1H NMR, FAB-Mass, TGA/DTA and EPR as well as molar conductance and magnetic studies. From spectral studies, both the ligands act as bidentate and they bind metal(II ions through deprotonated-N3 and C4O atoms and amino-N and deprotonated carboxylato-O atoms, respectively, to form a stable metal chelate. The observed low molar conductance values suggest a non-electrolytic nature. Calculated g tensor values of Cu(II complex (1d at 77 and 300 K confirm their geometry. Thermal behavior of metal(II complexes (1a–1c shows loss of coordinated water molecules in the first step followed by decomposition of ligand moieties in a respective manner and leads to form air stable metal oxide as final residues. Powder X-ray diffraction and SEM studies illustrate that all the complexes have uniform microcrystalline with homogenous morphology. Mn(II, Ni(II and Cu(II complexes show significant in vitro antimicrobial and antioxidant activities than 5-fluorouracil(A. Moreover, the nuclease studies of Ni(II and Cu(II complexes (1c and 1d show considerable DNA binding and oxidative DNA cleavage activities than other complexes.

  5. Versatile chemical transformations of benzoxazole based ligands on complexation with 3d-metal ions.

    Science.gov (United States)

    Iasco, Olga; Novitchi, Ghenadie; Jeanneau, Erwann; Tommasino, Jean Bernard; Roques, Nans; Luneau, Dominique

    2012-02-20

    Two benzoxazoles derivative ligands were synthesized from the condensation of 3,5-di-tert-butyl-o-benzoquinone (DTBBQ) with ethanolamine or 1,3-diamino-2-hydroxypropane in methanol. Condensation of DTBBQ with ethanolamine gives the expected 5,7-di-tert-butyl-2-methylenhydroxylbenzoxazole (HL1) while with 1,3-diamino-2-hydroxypropane it gives (2-hydroxyethyl-2-{2,4-bis(1,1-dimethylethyl)-1-phenol-6 amino}-2{5,7-di-tert-butyl-benzoxazole}) (H(2)L2) with only one benzoxazole ring instead of the symmetric bis-benzoxazole derivative. The structure of HL1 and H(2)L2 were confirmed by NMR-spectroscopy and X-ray diffraction on a single crystal for HL1. The reaction of HL1 with CuCl(2) gives a mononuclear [Cu(II)(HL1)(2)Cl(2)] (1) complex for which the crystal structure shows that HL1 is preserved. In contrast, upon reaction with nickel(II), cobalt(II), and manganese(II) H(2)L2 is further oxidized and transformed in new ligands HL3 in mononuclear complexes [M(II)(L3)(2)] (M = Ni(II) (2); M = Co(II) (3)) and H(2)L4 in tetranuclear complex [Mn(II)(4)(HL4)(4)Cl(4)] (4) as found from the crystal structures of complexes 2-4. Electrochemical studies for complexes 2 and 3 evidence complicated redox properties. [Mn(II)(4)(HL4)(4)Cl(4)] (4) has a cubane-like structure with a "4 + 2" fashion The magnetic susceptibility of 4 is well fitted considering one Mn---Mn interaction J(a)(Mn(II)-Mn(II)) = -0.50(1) cm(-1) with g = 2.00(7).

  6. A novel dipeptidyl aminopeptidase in rat brain membranes. Its isolation, purification, and characterization.

    Science.gov (United States)

    Hui, K S

    1988-05-15

    A new type of dipeptidyl aminopeptidase, which releases basic aminoacyl dipeptides from the NH2-terminal end of oligopeptides, was purified about 2100-fold with 6.8% recovery from rat brain membranes by column chromatography on Cellex D, Arg-Tyr-AH-Sepharose 4B, hydroxylapatite, and Sephadex G-75, after the membranes were solubilized with Nonidet P-40. Activity was assayed by high performance liquid chromatography (HPLC) using Arg0-Met5-enkephalin (Arg0-enk)* as substrate in the presence of bestatin, thiorphan, and captopril. In sodium dodecyl sulfate-polyacrylamide gel electrophoresis, the purified enzyme is apparently homogeneous with a mass of 64,000 daltons. This thiol enzyme is optimally active at pH 7 and is selectively activated by Mn(II). It loses 94% of its activity after EDTA treatment and can be reactivated by Mn(II), Co(II), and Zn(II). It splits Arg0-enk into equimolar amounts of Arg-Tyr and Gly-Gly-Phe-Met with a Km of 100 microM, and Vmax of 3.8 mumol/mg of protein/min. Dipeptidyl aminopeptidase does not hydrolyze model substrates for dipeptidyl aminopeptidases I, II, III, and IV, aminoacyl beta-naphthylamides, actin, desmin, tubulin, glial fibrillary acidic protein, and cytoskeletal neurofilament proteins. The enzyme is insensitive to puromycin, but is inhibited by several neuropeptides. Angiotensin III is the most potent with a Ki of 0.3 microM. Substrate specificity, pH optimum, molecular weight, activators, and catalytic site demonstrate that this enzyme is distinct from dipeptidyl aminopeptidases previously described.

  7. Three two-dimensional coordination polymers constructed from transition metals and 2,3-norbornanedicarboxylic acid: Hydrothermal synthesis, crystal structures and photocatalytic properties

    Science.gov (United States)

    Zhang, Jia; Wang, Chong-Chen

    2017-02-01

    Three novel coordination polymers based on transition metals like Co(II), Cu(II) and Mn(II), namely [Co2(bpy)2(nbda)2(H2O)2]·2H2O (denoted as BUC-1), [Cu2(bpy)2(nbda)2(H2O)2]·2H2O (BUC-2), [Mn2(bpy)2(nbda)2(H2O)2]·2H2O (BUC-3), (where bpy = 4,4‧-bipyridine, H2nbda = 2,3-norbornanedicarboxylic acid, BUC = Beijing University of Civil Engineering and Architecture), were synthesized under hydrothermal conditions, and characterized by CNH elemental analyses (EA), Fourier Transform infrared spectroscopy (FTIR), and single crystal X-ray diffraction (SCXRD). BUC 1-3 were isostructural and crystallized in the monoclinic space group C2/c, in which the corresponding metal atoms were linked by typical bidentate bpy ligands into two adjacent 1D [M1(bpy)]n2n+ and [M2(bpy)]n2n+ (M = Co(II), Cu(II), Mn(II)), further joined by versatile nbda2- ligands into 2D [M2(bpy)2(nbda)2]n sheets. Finally, three-dimensional supramolecular frameworks were constructed with the aid of the intermolecular hydrogen bonding interactions. BUC 1-3 exhibited different photocatalytic degradation ability to decompose methylene blue (MB) and methyl orange (MO) under UV light irradiation. Additionally, a possible photocatalytic mechanism HOMO-LUMO was proposed and discussed, which was further confirmed by radicals trapping experiments using isopropanol as radical scavenger.

  8. Oxidative removal of aqueous steroid estrogens by manganese oxides.

    Science.gov (United States)

    Xu, Lei; Xu, Chao; Zhao, Meirong; Qiu, Yuping; Sheng, G Daniel

    2008-12-01

    This study investigated the oxidative removal of steroid estrogens from water by synthetic manganese oxide (MnO2) and the factors influencing the reactions. Using 1 x 10(-5)M MnO2 at pH 4, estrone (E1), 17beta-estradiol (E2), estriol (E3) and 17alpha-ethinylestradiol (EE2), all at 4 x 10(-6)M, were rapidly removed within 220 min, indicating the effectiveness of MnO2 as an oxidizing agent towards estrogens. E2 removal increased with decreasing pH over the tested range of 4-8, due most likely to increased oxidizing power of MnO2 and a cleaner reactive surface in acidic solutions. Coexisting metal ions of 0.01 M (Cu(II), Zn(II), Fe(III) and Mn(II)) and Mn(II) released from MnO2 reduction competed with E2 for reactive sites leading to reduced E2 removal. Observed differential suppression on E2 removal may be related to different speciations of metals, as suggested by the MINTEQ calculations, and hence their different adsorptivities on MnO2. By suppressing the metal effect, humic acid substantially enhanced E2 removal. This was attributed to complexation of humic acid with metal ions. With 0.01 M ZnCl2 in solutions containing 1 mg l(-1) humic acid, the binding of humic acid for Zn(II) was determined at 251 mmol g(-1). An in vitro assay using human breast carcinoma MCF-7 cells indicated a near elimination of estrogenic activities without secondary risk of estrogen solutions treated with MnO2. Synthetic MnO2 is therefore a promising chemical agent under optimized conditions for estrogen removal from water. Metal chelators recalcitrant to MnO2 oxidation may be properly used to further enhance the MnO2 performance.

  9. Solvent-mediated secondary building units (SBUs) diversification in a series of MnII-based metal-organic frameworks (MOFs)

    Science.gov (United States)

    Niu, Yan-Fei; Cui, Li-Ting; Han, Jie; Zhao, Xiao-Li

    2016-09-01

    The role of auxiliary solvents in the formation of MOFs has been investigated for a series of MnII-based framework systems. Reactions of 4,4‧,4″-nitrilotribenzoic acid (H3L) with MnII through varying auxiliary solvents of the medium resulted in the formation of diversified multinuclear MnII subunits in four new coordination polymers: [Mn3(L)(HCOO)3(DEF)3] (1), [Mn3(L)2(EtOH)2]·DMF (2), [Mn5(L)4(H2O)2]·2(H2NMe2)+·4DMF·2H2O (3), and [Mn3(L)2(py)4(H2O)]·H2O (4) (H3L=4,4‧,4‧-nitrilotribenzoic acid, DMF=dimethylformamide, DEF=N,N-diethylformamide, py=pyridine). These four compounds were fully characterized by single-crystal X-ray diffraction, showing interesting SBUs variations. For compound 1, it displays a (3,6)-connected kgd net with wheel [Mn6] cluster serving as SBU, whereas in 2, the sequence of Mn3(COO)9(EtOH)2 is repeated by inversion centers located between Mn1 and Mn3 to form an infinite Mn-carboxylate chain, which are further interlinked by L3- ligands to form a 3D architecture. In 3, the pentanuclear Mn5(CO2)12 clusters are interlinked to form a layer, which are further pillared by L3- to generate a 3D network. Compound 4 has a (3,6)-connected network in which the SBU is a linear trimeric Mn3(COO)6(py)4(H2O) cluster. In addition, the thermal stabilities, X-ray powder diffraction of all the compounds were studied, photoluminescence behaviors of compounds 1, 3 and 4 are discussed.

  10. Synthesis, characterization, biological evaluation and docking studies of macrocyclic binuclear manganese(II) complexes containing 3,5-dinitrobenzoyl pendant arms.

    Science.gov (United States)

    Arthi, P; Shobana, S; Srinivasan, P; Mitu, L; Kalilur Rahiman, A

    2015-05-15

    A series of bis(phenoxo) bridged binuclear manganese(II) complexes of the type [Mn2L(1-3)](ClO4)2 (1-3) containing 3,5-dinitrobenzoyl pendant-arms have been synthesized by cyclocondensation of 2,6-diformyl-4-R-phenols (where R=CH3, C(CH3)3 or Br) with 2,2'-3,5-dinitrobenzoyliminodi(ethylamine) trihydrochloride in the presence of manganese(II) perchlorate. The IR spectra of complexes indicate the presence of uncoordinated perchlorate anions. The UV-Vis spectra of complexes suggest the distorted octahedral geometry around manganese(II) nuclei. The EPR spectra of Mn(II) complexes show a broad signal with g value 2.03-2.04, which is characteristic for octahedral high spin Mn(2+) complex. The observed room temperature magnetic moment values of the Mn(II) complexes (5.60-5.62B.M.) are less than the normal value (5.92B.M.), indicating weak antiferromagnetic coupling interaction between the two metal ions. Electrochemical studies of the complexes show two distinct quasi-reversible one electron transfer processes in the cathodic (E(1)pc=-0.73 to -0.76V, E(2)pc=-1.30 to -1.36V), and anodic (E(1)pa=1.02-1.11V, E(2)pa=1.32-1.79V) potential regions. Antibacterial efficacy of complexes have been screened against four Gram (-ve) and two Gram (+ve) bacterial strains. The DNA interaction studies suggest that these complexes bind with CT-DNA by intercalation, giving the binding affinity in the order 1>2>3. All the complexes display significant cleavage activity against circular plasmid pBR322 DNA. Docking simulation was performed to insert complexes into the crystal structure of EGFR tyrosine kinase and B-DNA at active site to determine the probable binding mode.

  11. 2-{[1-(3,4-Dihydroxyphenyl)methylidene]amino}benzoic acid immobilized Amberlite XAD-16 as metal extractant.

    Science.gov (United States)

    Venkatesh, Gopalan; Singh, Ajai K

    2005-07-15

    2-{[1-(3,4-Dihydroxyphenyl)methylidene]amino}benzoic acid (DMABA) was loaded on Amberlite XAD-16 (AXAD-16) via azo linker and the resulting resin AXAD-16-DMABA explored for enrichment of Zn(II), Mn(II), Ni(II), Pb(II), Cd(II), Cu(II), Fe(III) and Co(II). The optimum pH values for extraction are 6.5-7.0, 5.0-6.0, 5.5-7.5, 5.0-6.5, 6.5-8.0, 5.5-7.0, 4.0-5.0 and 6.0-7.0, respectively. The sorption capacity was found between 97 and 515mumolg(-1) and the preconcentration factors from 100 to 450. Tolerance limits for foreign species are reported. The kinetics of sorption is fast as t(1/2) is Mn(II), Ni(II), Pb(II), Cd(II), Cu(II), Fe(III) and Co(II), respectively. The enrichment on AXAD-16-DMABA coupled with monitoring by flame atomic absorption spectrometry (FAAS) is used to determine all the metal ion ions in river and synthetic water samples, Co in vitamin tablets and Zn in milk samples.

  12. Thermodynamics of complexes formation by ITC in methanol/water = 9/1 (v/v) solution: A case study

    Energy Technology Data Exchange (ETDEWEB)

    Fisicaro, Emilia, E-mail: emilia.fisicaro@unipr.it [University of Parma, Department of Pharmacy, Parco Area delle Scienze, 27/A, 43124 Parma (Italy); Compari, Carlotta; Bacciottini, Franco; Contardi, Laura [University of Parma, Department of Pharmacy, Parco Area delle Scienze, 27/A, 43124 Parma (Italy); Carcelli, Mauro; Rispoli, Gabriele; Rogolino, Dominga [University of Parma, Department of Chemistry, Parco Area delle Scienze, 17/A, 43124 Parma (Italy)

    2014-06-01

    Graphical abstract: Integrase strand transfert inhibitors chelate the metal ions in the active site of HIV integrase. - Highlights: • Development of inhibitors acting against those viral enzymes operating via a cooperative two-metal ion mechanism, such as HIV integrase (IN), requires optimizing the binding affinity to the target. • We have defined an experimental procedure for obtaining reliable thermodynamic data by ITC in methanol/water = 9/1 (v/v) as solvent. • Formation heats in mixed solvent of the complexes formed by a ligand, model of Raltegravir, with Mg(II), Mn(II), Co(II) and Zn(II) are here reported. - Abstract: Most enzymes that participate in the biochemistry of nucleic acids require divalent metal ion cofactors to promote activity. Development of potent inhibitors, acting against those viral enzymes operating via a cooperative two-metal ion mechanism, such as HIV integrase (IN) and RNase H, hepatitis C virus polymerase and influenza endonuclease, requires optimizing the binding affinity to the target, which is dictated by the binding free energy composed of both enthalpic and entropic contributions. They can be obtained by using isothermal titration microcalorimetry. We have defined an experimental procedure for obtaining reliable thermodynamic data in methanol/water = 9/1 0.1 M KCl as solvent, used to overcome solubility problems. In this way we have measured the heats of formation of the complexes formed by N-(4-fluorobenzyl)-5-hydroxy-2-isopropyl-1-methyl-6-oxo-1, 6-dihydroxypyrimidine-4-carboxylate (HL, a model of Raltegravir, the antiretroviral drug produced by Merck and Co.), and a series of divalent metal ions of biological interest (Mg(II), Mn(II), Co(II) and Zn(II)), whose speciation was previously determined by potentiometry.

  13. Diaqua-bis{[1-hydr-oxy-2-(1H-imidazol-3-ium-1-yl)ethane-1,1-di-yl]bis-(hydrogen phospho-nato)}manganese(II).

    Science.gov (United States)

    Zhang, Zai-Chao; Li, Rong-Qing; Zhang, Yu

    2009-11-28

    In the title compound, [Mn(C(5)H(9)N(2)O(7)P(2))(2)(H(2)O)(2)], the Mn(II) atom (site symmetry ) is coordinated by four phos-pho-n-ate O atoms from a pair of partially deprotonated 1-hydr-oxy-2-(imidazol-3-yl)ethane-1,1-bis-phophonic acid ligands (imhedpH(3) (-)) and two water mol-ecules, resulting in a slightly distorted trans-MnO(6) octa-hedral geometry for the metal ion. In the ligands, the imidazole units are protonated and two of the hydr-oxy O atoms of the phospho-nate groups are deprotonated and chelate the Mn(II), thus forming the neutral mol-ecule of the title compound. The two protonated O atoms within the phospho-nate groups of one imhedpH(3) (-) ligand act as hydrogen-bond acceptors for a bifurcated hydrogen bond originating from the coordinated water mol-ecule. The phospho-nate units of neigboring mol-ecules are connected with their equivalents in neighboring mol-ecules via two types of inversion-symmetric hydrogen-bonding arrangements with four and two strong O-H⋯O hydrogen bonds, respectively. The two inter-actions connect mol-ecules into infinite chains along [111] and [110], in combination forming a tightly hydrogen-bonded three-dimensional supra-molecular network. This network is further stabilized by additional hydrogen bonds between the protonated imidazole units and one of the coordinated P-O O atoms and by additional O-H⋯O hydrogen bonds between the water mol-ecules and the P=O O atoms of neigboring mol-ecules.

  14. Single crystal structures of thallium (I) thorium fluorides and crystal chemistry of monovalent tetravalent cation pentafluorides

    Science.gov (United States)

    Oudahmane, Abdelghani; El-Ghozzi, Malika; Jouffret, Laurent; Avignant, Daniel

    2015-12-01

    Two thallium (I) thorium (IV) fluorides, TlTh3F13 and TlThF5 were obtained by solid state synthesis and their crystal structures determined from single crystal X-ray diffraction data recorded at room temperature with an APEX-II CCD diffractometer. TlTh3F13 is orthorhombic, space group Pmc21, with a=8.1801(2) Å, b=7.4479(2) Å, c=8.6375(2) Å, V=526.24(2) Å3, Z=2 and TlThF5 is monoclinic, space group P21/n, with a=8.1128(5) Å, b=7.2250(4) Å, c=8.8493(6) Å, β=116.683(3)°, V=463.46(5) Å3, Z=4. The structure of TlTh3F13 comprises layers of corner and edge-sharing ThF9 polyhedra further linked by chains of trans connected tricapped trigonal prisms ThF9 through corners and edges. The three dimensional thorium frameworks delimits channels parallel to [0 0 1] where the 11-coordinated Tl+ ions are arranged into double columns located in mirror planes of the structure. TlTh3F13 is isotypic with RbTh3F13, RbU3F13 and with one of the two polymorphs of CsTh3F13. The structure of TlThF5 may be regarded as a layer structure built up from the regular succession of 2∞[ M ‧F5 ] - corrugated layers further held by the Tl+ ions along the [1 0 1 ̅] direction. The layers are built up from edge and corner-sharing thorium polyhedra where each (ThF9)5- monocapped square antiprism is connected to five others by sharing three edges and two corners. TlThF5 is isostructural with β-NH4UF5 and with one of the polymorphs of CsThF5. A comparison of the different structural types of MM‧F5 pentafluorides is presented and a diagram of repartition of their structures is given. From the comparison of the Tl structures with their Rb or Cs homologs, where very similar monovalent cation environments are observed it should be concluded to a stereochemically inactivity of the 6s2 lone pair of Tl(I) in both TlTh3F13 and TlThF5, contrary to what is observed in richer Tl(I) content Tl3ThF7 fluorothorate.

  15. Bis(dimethylformamidepentakis(μ-N,2-dioxidobenzene-1-carboximidatotetrakis(1-methylimidazoledi-μ-propionato-pentamanganese(IIImanganese(II–dimethylformamide–methanol (1/0.24/1.36

    Directory of Open Access Journals (Sweden)

    Jacob C. Lutter

    2013-09-01

    Full Text Available The title compound [Mn6(C7H4NO35(C3H5O22(C4H6N24.17(C3H7NO1.83]·0.24C3H7NO·1.36CH3OH or Mn(II(C3H5O22[15-MCMn(IIIN(shi-5](Me—Im4.17(DMF1.83·0.24DMF·1.36MeOH (where MC is metallacrown, shi3− is salicylhydroximate, Me—Im is 1-methylimidazole, DMF is N,N-dimethylformamide, and MeOH is methanol, contains an MnII ion in the central cavity and five MnIII ions in the MC ring. The central MnII ion is seven coordinate and has a geometry best described as distorted face-capped trigonal prismatic with Φ angles of 6.13, 10.36, and 11.73° and an estimated average s/h ratio of 1.03±0.11. Four of the ring MnIII ions are six coordinate with distorted octahedral geometries. Two of the MnIII ions have Λ absolute stereoconfiguration, while the other two MnIII ions have a planar configuration. The fifth MnIII ion is five coordinate and has a distorted square pyramidal geometry with τ = 0.20. Three of the MnIII ions bind one 1-methylimidazole ligand. Two of the ring MnIII ions have a 1-methylimidazole and a DMF disordered over a coordination site. For one of the ring MnIII ions, the occupancy ratio of the ligands refines to 0.51 (1:0.49 (1 in favor of the DMF. For the other ring MnIII ion, the occupancy ratio of the ligands refines to 0.68 (1:0.32 (1 in favor of the 1-methylimidazole. Two propionate anions serve to bridge the central MnII ion between two different MnIII ions. The methyl groups of the bridging propionate anions are disordered over two positions. The methyl group disorder also induces disorder in the H atoms of the adjacent methylene C atom to the same degree. For one of the propionate anions, the occupancy ratio refines to 0.752 (8:0.248 (8 and for the second, the occupancy ratio refines to 0.604 (6:0.396 (6. In addition, the disorder of the methyl group of the latter propionate anion is correlated with a partially occupied [0.604 (6] methanol molecule. Furthermore, a methanol molecule and a DMF molecule are

  16. Removal of manganese from waste water by complexation-ultrafiltration using copolymer of maleic acid and acrylic acid%马来酸-丙烯酸共聚物络合超滤处理含锰废水

    Institute of Scientific and Technical Information of China (English)

    邱运仁; 毛廉君; 王伟华

    2014-01-01

    Copolymer of maleic acid and acrylic acid (PMA-100), combining with polyvinyl butyral (PVB) ultrafiltration membrane was used for the removal of Mn(II) from waste water by complexation-ultrafiltration. The carboxylic group content of PMA-100 and the rate of complexation reaction were measured. Effects of the mass ratio of PMA-100 to Mn(II) (n), pH, background electrolyte, etc on the rejection rate (R) and permeate flux (J) were investigated. The results show that carboxylic group content of PMA-100 is 9.5 mmol/g. The complexation of Mn(II) with PMA-100 is rapid and completed within 5 min at pH 6.0. Both R and J increase with pH increasing in the range of 2.5-7.0, and R increases with the increase of n at pH 6.0 while J is little affected. The background electrolyte leads to the decrease of R, and CaCl2 has much greater effect on R than NaCl at the same ionic strength.%用马来酸-丙烯酸共聚物(PMA-100)作络合剂,采用PVB中空纤维膜,研究络合-超滤处理含锰废水。测定了高聚物的羧基含量以及Mn(II)与PMA-100的络合反应速率,研究聚合物与重金属质量比(P/M)、pH、外加盐浓度等因素对锰离子截留率(R)和膜通量(J)的影响。结果表明:高聚物中羧基含量为9.5 mmol/g,对Mn(II)质量浓度为10 mg/L的模拟废水,在pH=6.0时,Mn(II)与PMA-100的络合在5 min内基本可完成,络合率达99.6%。在一定P/M下,pH在2.5~7.0范围内,截留率和膜通量均随着pH的增加而增大;在一定pH下,截留率随着P/M的增加而增加,但膜通量基本不变。外加盐的存在使截留率下降,在同样离子强度下,CaCl2的影响远大于NaCl的。

  17. Coordination Polymers Derived from Non-Steroidal Anti-Inflammatory Drugs for Cell Imaging and Drug Delivery.

    Science.gov (United States)

    Paul, Mithun; Dastidar, Parthasarathi

    2016-01-18

    A new series of Mn(II) coordination polymers, namely, [{Mn(L)(H2 O)2 }⋅2 Nap]∞ (CP1), [{Mn(L)(Ibu)2 (H2 O)2 }]∞ (CP2), [{Mn(L)(Flr)2 (H2 O)2 }]∞ (CP3), [{Mn(L)(Ind)2 (H2 O)2 }⋅H2 O]∞ (CP4), [{Mn2 (L)2 (μ-Flu)4 (H2 O)}⋅L]∞ (CP5), [{Mn2 (L)2 (μ-Tol)4 (H2 O)2 }]∞ (CP6) and [{Mn2 (L)2 (μ-Mef)4 (H2 O)2 }]∞ (CP7) (Nap=naproxen, Ibu=ibuprofen, Flr=flurbiprofen, Ind=indometacin, Flu=flufenamic acid, Tol=tolfenamic acid and Mef=mefenamic acid) derived from various non-steroidal anti-inflammatory drugs (NSAIDs) and the organic linker 1,2-bis(4-pyridyl)ethylene (L) have been synthesized with the aim of being used for cell imaging and drug delivery. Single-crystal X-ray diffraction (SXRD) studies revealed that the NSAID molecules were part of the coordination polymeric network either through coordination to the metal center (in the majority of the cases) or through hydrogen bonding. Remarkably, all the Mn(II) coordination polymers were found to be soluble in DMSO, thereby making them particularly suitable for the desired biological applications. Two of the coordination polymers (namely, CP1 and CP3) reported herein, were found to be photoluminescent both in the solid as well as in the solution state. Subsequent experiments (namely, MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide), and PGE2 (prostaglandin E2 ) assays) established their biocompatibility and anti-inflammatory response. In vitro studies by using a macrophage cell line (i.e., RAW 264.7) revealed that both CP1 and CP3 were excellent cell imaging agents. Finally, biodegradability studies under simulated physiological conditions in phosphate-buffered saline (PBS) at pH 7.6 showed that slow and sustained release of the corresponding NSAID was indeed possible from both CP1 and CP3.

  18. Enzymes involved in DNA ligation and end-healing in the radioresistant bacterium Deinococcus radiodurans

    Directory of Open Access Journals (Sweden)

    Shevelev Igor V

    2007-08-01

    Full Text Available Abstract Background Enzymes involved in DNA metabolic events of the highly radioresistant bacterium Deinococcus radiodurans are currently examined to understand the mechanisms that protect and repair the Deinococcus radiodurans genome after extremely high doses of γ-irradiation. Although several Deinococcus radiodurans DNA repair enzymes have been characterised, no biochemical data is available for DNA ligation and DNA endhealing enzymes of Deinococcus radiodurans so far. DNA ligases are necessary to seal broken DNA backbones during replication, repair and recombination. In addition, ionizing radiation frequently leaves DNA strand-breaks that are not feasible for ligation and thus require end-healing by a 5'-polynucleotide kinase or a 3'-phosphatase. We expect that DNA ligases and end-processing enzymes play an important role in Deinococcus radiodurans DNA strand-break repair. Results In this report, we describe the cloning and expression of a Deinococcus radiodurans DNA ligase in Escherichia coli. This enzyme efficiently catalyses DNA ligation in the presence of Mn(II and NAD+ as cofactors and lysine 128 was found to be essential for its activity. We have also analysed a predicted second DNA ligase from Deinococcus radiodurans that is part of a putative DNA repair operon and shows sequence similarity to known ATP-dependent DNA ligases. We show that this enzyme possesses an adenylyltransferase activity using ATP, but is not functional as a DNA ligase by itself. Furthermore, we identified a 5'-polynucleotide kinase similar to human polynucleotide kinase that probably prepares DNA termini for subsequent ligation. Conclusion Deinococcus radiodurans contains a standard bacterial DNA ligase that uses NAD+ as a cofactor. Its enzymatic properties are similar to E. coli DNA ligase except for its preference for Mn(II as a metal cofactor. The function of a putative second DNA ligase remains unclear, but its adenylyltransferase activity classifies it as a

  19. Biological potential study of metal complexes of sulphonylurea glibenclamide on the house fly, Musca domestica (Diptera—Muscidae): Preparation, spectroscopic and thermal characterization

    Science.gov (United States)

    Mohamed, Gehad G.; Abdallah, S. M.; Zayed, M. A.; Nassar, M. M. I.

    2009-10-01

    The ligatation behaviour of sulphonylurea glibenclamide drug is studied in order to give an idea about its potentiality towards some transition metals in vitro systems. Metal complexes of glibenclamide (GCA; H 3L) drug are prepared and characterized based on elemental analyses, IR, diffused reflectance, magnetic moment, molar conductance and thermal analysis (TG and DTG) techniques. From the elemental analyses data, the complexes are proposed to have the general formulae [M(H 3L)Cl n(H 2O) m]· yH 2O (where M = Cr(III) ( n = 3, m = 1, y = 3); Mn(II) ( n = 2, m = 0, y = 1); Fe(III) ( n = 3, m = 1, y = 0), Co(II) ( n = 2, m = 2, y = 0); Ni(II) ( n = 2, m = 2, y = 3); Cu(II) ( n = 2, m = 2, y = 2) and Zn(II) ( n = 2, m = 0, y = 0). The molar conductance data reveal that all the metal chelates are non-electrolytes. IR spectra show that GCA is coordinated to the metal ions in a neutral bidentate manner with OO donor sites of the amide- O and sulphone -O. From the magnetic and solid reflectance spectra, it is found that the geometrical structures of these complexes are octahedral except Mn(II) and Zn(II) complexes which have tetrahedral structure. The thermal behaviour of these chelates is studied using thermogravimetric analysis (TG and DTG) technique. The activation thermodynamic parameters are calculated using Coats-Redfern method. The GCA drug, in comparison to its metal complexes also is screened for its biological activity against house fly, Musca domestica (Diptera—Muscidae). Dose of 5 μg/insect of GCA is topically applied against 3 days old larval instar of M. domestica. Survival of pupal and adult stages has been affected by the complexes of GCA more than larval instars. Morphogenic abnormalities of larvae, pupae and adults are studied. On the other hand pupation and adult emergence program is deteriorated by the effect of different chemicals.

  20. On metal diagenesis in contaminated sediments of the Deule river (northern France)

    Energy Technology Data Exchange (ETDEWEB)

    Lesven, L. [Universite Lille 1 (USTL), FRE CNRS 3298 Geosystemes, Equipe de Chimie Analytique et Marine, 59655 Villeneuve d' Ascq cedex (France); Lourino-Cabana, B. [Universite Lille 1 (USTL), FRE CNRS 3298 Geosystemes, Equipe de Chimie Analytique et Marine, 59655 Villeneuve d' Ascq cedex (France)] [Faculty of Natural Sciences and Technology, Department of Chemistry, 7491 Trondheim (Norway); Billon, G.; Recourt, P. [Universite Lille 1 (USTL), FRE CNRS 3298 Geosystemes, Equipe de Chimie Analytique et Marine, 59655 Villeneuve d' Ascq cedex (France); Ouddane, B., E-mail: baghdad.ouddane@univ-lille1.fr [Universite Lille 1 (USTL), FRE CNRS 3298 Geosystemes, Equipe de Chimie Analytique et Marine, 59655 Villeneuve d' Ascq cedex (France); Mikkelsen, O. [Faculty of Natural Sciences and Technology, Department of Chemistry, 7491 Trondheim (Norway); Boughriet, A. [Universite d' Artois, I.U.T. de Bethune Departement de Chimie, Rue de l' Universite, B.P. 819, 62408 Bethune cedex (France)

    2010-09-15

    Research highlights: {yields} Behaviour and fate of metal contaminants in sediments (remobilisation, dredging ...). {yields} Implication of metal contaminations on biogeochemical processes in anoxic sediments. {yields} Impacts on the distribution of anthropogenic metal in sediments. - Abstract: The objective of the present work was to assess depth-related variations in the (bio)geochemical processes involved in anoxic sediments from the Deule river, and to examine particularly their impacts on the distribution of anthropogenically sourced metals. Anoxic sediment samples were sliced and analyzed to determine total concentrations vs. depth of elements and corresponding pore waters were analyzed to determine concentration profiles with depth of pH, Eh, alkalinity, O{sub 2}, dissolved organic carbon (DOC), and main inorganic anions and cations present in the medium. It was shown that rapid depletions of O{sub 2}, NO{sub 3}{sup -} and SO{sub 4}{sup 2-}, accompanied with HCO{sub 3}{sup -} generation and a sharp decrease in the redox potential occurred within the first centimeters of the surface sediment as a consequence of early diagenesis. Bacterial reductive dissolution of Mn(III and IV) and Fe(III) oxides/hydroxides to Mn(II) and Fe(II) accompanied by microbial degradation of organic matter took place as well, and resulted in trace metal increases in the pore water at levels that raised the possibility of mineral generation. Thermodynamic calculations predicted removal of metals from interstitial waters through combinations with carbonates and/or sulfides. These took place either by direct precipitation to form pure crystals, or by coprecipitation/sorption with/into calcite and with pyritic compounds. Chemical sequential extraction data were useful in this work to support, at least partially, some thermodynamic predictions concerning the existence of interactions between trace metals and carbonate and sulfide ions to generate (co)precipitates. Electron paramagnetic