Adsorption of Ni(II) onto Chemically Modified Spent Grated Coconut (Cocos Nucifera)

NASA Astrophysics Data System (ADS)

Hamzah, F. I.; Khalid, K.; Hanafiah, M. A. K. M.

2017-06-01

A new adsorbent of plant waste origin from coconut processing food factory was explored for removing Ni(II) from aqueous solutions. Several parameters such as pH, dosage, concentration and contact time were studied to obtain optimum conditions for treatment of Ni(II) contaminated wastewater. Spent grated coconut (Cocos nucifera) treated with sulfuric acid (SSGC) showed good adsorption capacity for Ni(II) ion. The amount adsorbed was affected by solution pH with the highest value achieved at pH 5. Other optimum conditions found were; dosage of 0.02 g, and 60 min of equilibrium time. Ni(II) adsorption obeyed the pseudo-second order kinetic model which suggested that chemisorption mechanism occurred in the adsorption process. The equilibrium data presented a better fitting to the Langmuir isotherm model, an indication that monolayer adsorption occurred onto a homogeneous surface. The maximum adsorption capacity, qmax was 97.09 mg g-1, thus SSGC can be classified as good and comparable with other plant waste adsorbents.

Comparative study on kinetic adsorption of Cu(II), Cd(II) and Ni(II) ions from aqueous solutions using activated sludge and dried sludge

NASA Astrophysics Data System (ADS)

Ong, Soon-An; Toorisaka, Eiichi; Hirata, Makoto; Hano, Tadashi

2013-03-01

The adsorption of Cu(II), Cd(II) and Ni(II) ions from aqueous solutions by activated sludge and dried sludge was investigated under laboratory conditions to assess its potential in removing metal ions. The adsorption behavior of metal ions onto activated sludge and dried sludge was analyzed with Weber-Morris intra-particle diffusion model, Lagergren first-order model and pseudo second-order model. The rate constant of intra-particle diffusion on activated sludge and dried sludge increased in the sequence of Cu(II) > Ni(II) > Cd(II). According to the regression coefficients, it was observed that the kinetic adsorption data can fit better by the pseudo second-order model compared to the first-order Lagergren model with R 2 > 0.997. The adsorption capacities of metal ions onto activated sludge and dried sludge followed the sequence Ni(II) ≈ Cu(II) > Cd(II) and Cu(II) > Ni(II) > Cd(II).

Kinetic and thermodynamic studies of the Co(II) and Ni(II) ions removal from aqueous solutions by Ca-Mg phosphates.

PubMed

Ivanets, A I; Srivastava, V; Kitikova, N V; Shashkova, I L; Sillanpää, M

2017-03-01

The aim of this work was to study the sorption kinetics and thermodynamics of Co(II) and Ni(II) from aqueous solutions by sorbents on the basis of hydrogen (PD-1) and tertiary (PD-2) Ca-Mg phosphates depending on the solution temperature and sorbents chemical composition. Kinetic studies of adsorption of Co(II) and Ni(II) ions onto samples of phosphate sorbents were performed in batch experiment at the temperatures 288, 303, 318 and 333 K. The sorbent dose was fixed at 10 g L -1 , initial pH value 2.6, and contact time varied from 5 to 600 min. The kinetics of Co(II) and Ni(II) adsorption were analyzed by using pseudo-first order, pseudo-second order and intraparticle diffusion models. Thermodynamic parameters (ΔG°, ΔH° and ΔS°) for the sorption of Co(II) and Ni(II) were determined using the Gibbs-Helmholtz equation. The calculated kinetic parameters and corresponding correlation coefficients revealed that Co(II) and Ni(II) uptake process followed the pseudo-second order rate expression. Thermodynamic studies confirmed the spontaneous and endothermic nature of removal process which indicate that sorption of Co(II) and Ni(II) ions onto both phosphate sorbents is favoured at higher temperatures and has the chemisorptive mechanism. The data thus obtained would be useful for practical application of the low cost and highly effective Ca-Mg phosphate sorbents. Copyright © 2016 Elsevier Ltd. All rights reserved.

The influence of Ni(II) on brushite structure stabilization

NASA Astrophysics Data System (ADS)

Guerra-López, J. R.; Güida, J. A.; Ramos, M. A.; Punte, G.

2017-06-01

Brushite samples doped with Ni(II) in different concentrations, from 5% to 20%, were prepared in aqueous solution at pH = 7 and at two temperatures: 25 and 37 °C. The solid samples were characterized by chemical analysis, infrared spectroscopy (FTIR) and x-ray powder diffraction (XRPD). Chemical analysis has shown Ni(II) almost complete incorporation to the solid phase up to 15%. X-ray diffraction patterns have allowed to identify brushite phase with almost no modification of the line breadth and only small shifts of lines positions with increasing Ni(II) incorporation up to 15%. For larger Ni(II) concentration, in solution, a mixture of phases has been detected. Infrared spectra have supported diffraction results. For Ni(II) 20% and over the characteristic bands of HPO42- anions tend to vanish, and the typical shaped PO43- bands are observed. These results have allowed to establish that the presence of low levels of Ni in the synthetic process not only helps brushite formation; but, also prevents brushite from apatite conversion and, in addition, preserves brushite crystallinity. According to these findings, it is possible to propose that nickel traces present in the urinary system might be a trigger to brushite stone formation and/or growth, rather than the expected brushite conversion to hydroxyapatite. This outcome would explain the recurrent detection of difficult to treat brushite stones, observed in the last three decades.

Effect of humic acid on nickel(II) sorption to Ca-montmorillonite by batch and EXAFS techniques study.

PubMed

Hu, Jun; Tan, Xiaoli; Ren, Xuemei; Wang, Xiangke

2012-09-21

The influence of humic acid (HA) on Ni(II) sorption to Ca-montmorillonite was examined by using a combination of batch sorption experiments and extended X-ray absorption fine structure (EXAFS) spectroscopy technique. The sorption of Ni(II) on HA-montmorillonite hybrids is strongly dependent on pH and temperature. At low pH, the sorption of Ni(II) is mainly dominated by Ni-HA-montmorillonite and outer-sphere surface complexation. The EXAFS results indicate that the first coordination shell of Ni(II) consists of ∼6 O atoms at the interatomic distances of ∼2.04 Å in an octahedral structure. At high pH, binary Ni-montmorillonite surface complexation is the dominant sorption mechanism. EXAFS analysis indicates the formation of mononuclear complexes located at the edges of Ca-montmorillonite platelets at pH 7.5, while a Ni-Al layered double hydroxide (LDH) phase at the Ca-montmorillonite surface formed with pH 8.5. At pH 10.0, the dissolved HA-Ni(II) complexation inhibits the precipitation of Ni hydroxide, and Ni-Al LDH phase forms. The rise of temperature increases the sorption capacity of Ni(II), and promotes Ni-Al LDH phase formation and the growth of crystallites. The results are important to evaluate the physicochemical behavior of Ni(II) in the natural environment.

Structural characterization and antioxidant properties of Cu(II) and Ni(II) complexes derived from dicyandiamide

NASA Astrophysics Data System (ADS)

Kertmen, Seda Nur; Gonul, Ilyas; Kose, Muhammet

2018-01-01

New Cu(II) and Ni(II) complexes derived from dicyandiamide were synthesized and characterised by spectroscopic and analytical methods. Molecular structures of the complexes were determined by single crystal X-ray diffraction studies. In the complexes, the Cu(II) or Ni(II) ions are four-coordinate with a slight distorted square planar geometry. The ligands (L-nPen and L-iPen) derived from dicyandiamide formed via nucleophilic addition of alcohol solvent molecule in the presence Cu(II) or Ni(II) ions. Complexes were stabilised by intricate array of hydrogen bonding interactions. Antioxidant activity of the complexes was evaluated by DPPH radical scavenging and CUPRAC methods. The complexes exhibit antioxidant activity, however, their activities were much lower than standard antioxidants (Vitamin C and trolox).

Synthesis and characterization of hydroxyapatite nanoparticles impregnated on apple pomace to enhanced adsorption of Pb(II), Cd(II), and Ni(II) ions from aqueous solution.

PubMed

Chand, Piar; Pakade, Yogesh B

2015-07-01

Hydroxyapatite nanoparticles were synthesized, characterized, and impregnated onto apple pomace surface (HANP@AP) for efficient removal of Pb(II), Cd(II), and Ni(II) ions from water. HANP@AP was characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDS), transmission electron microscope (TEM), X-ray diffraction (XRD), and surface area analysis. Batch sorption studies were carried out to investigate the influence of different parameters as amount of dose (g), pH, time (min), and initial concentration (mg L(-1)) on adsorption process. Experimental kinetic data followed pseudo-second-order model and equilibrium data well fitted to Langmuir adsorption model with maximum adsorption capacities of 303, 250, and 100 mg g(-1) for Pb(II), Cd(II), and Ni(II) ions, respectively. Competitive adsorption of Pb(II), Cd(II), and Ni(II) ions in presences of each other was studied to evaluate the removal efficiency of HANP@AP against multi metal-loaded water. HANP@AP was successfully applied to real industrial wastewater with 100 % removal of all three metal ions even at high concentration. HANP@AP could be recycled for four, four, and three cycles in case of Pb(II), Cd(II) and Ni(II), respectively. The study showed that HANP@AP is fast, cost effective, and environmental friendly adsorbent for removal of Pb(II), Cd(II), and Ni(II) ions from real industrial wastewater.

Speciation of aqueous Ni(II)-carboxylate and Ni(II)-fulvic acid solutions: Combined ATR-FTIR and XAFS analysis

NASA Astrophysics Data System (ADS)

Strathmann, Timothy J.; Myneni, Satish C. B.

2004-09-01

Aqueous solutions containing Ni(II) and a series of structurally related carboxylic acids were analyzed using attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) and Ni K-edge X-ray absorption fine structure spectroscopy (XAFS). XAFS spectra were also collected for solutions containing Ni 2+ and chelating ligands (ethylenediaminetetraacetic acid, nitrilotriacetic acid (NTA)) as well as soil fulvic acid. Limited spectral changes are observed for aqueous Ni(II) complexes with monocarboxylates (formate, acetate) and long-chain polycarboxylates (succinate, tricarballylate), where individual donor groups are separated by multiple bridging methylene groups. These spectral changes indicate weak interactions between Ni(II) and carboxylates, and the trends are similar to some earlier reports for crystalline Ni(II)-acetate solids, for which X-ray crystallography studies have indicated monodentate Ni(II)-carboxylate coordination. Nonetheless, electrostatic or outer-sphere coordination cannot be ruled out for these complexes. However, spectral changes observed for short-chain dicarboxylates (oxalate, malonate) and carboxylates that contain an alcohol donor group adjacent to one of the carboxylate groups (lactate, malate, citrate) demonstrate inner-sphere metal coordination by multiple donor groups. XAFS spectral fits of Ni(II) solutions containing soil fulvic acid are consistent with inner-sphere Ni(II) coordination by one or more carboxylate groups, but spectra are noisy and outer-sphere modes of coordination cannot be ruled out. These molecular studies refine our understanding of the interactions between carboxylates and weakly complexing divalent transition metals, such as Ni(II).

Performance of Spent Mushroom Farming Waste (SMFW) Activated Carbon for Ni (II) Removal

NASA Astrophysics Data System (ADS)

Desa, N. S. Md; Ghani, Z. Ab; Talib, S. Abdul; Tay, C. C.

2016-07-01

The feasibility of a low cost agricultural waste of spent mushroom farming waste (SMFW) activated carbon for Ni(II) removal was investigated. The batch adsorption experiments of adsorbent dosage, pH, contact time, metal concentration, and temperature were determined. The samples were shaken at 125 rpm, filtered and analyzed using ICP-OES. The fifty percent of Ni(II) removal was obtained at 0.63 g of adsorbent dosage, pH 5-6 (unadjusted), 60 min contact time, 50 mg/L Ni(II) concentration and 25 °C temperature. The evaluated SMFW activated carbon showed the highest performance on Ni(II) removal compared to commercial Amberlite IRC86 resin and zeolite NK3. The result indicated that SMFW activated carbon is a high potential cation exchange adsorbent and suitable for adsorption process for metal removal. The obtained results contribute toward application of developed SMFW activated carbon in industrial pilot study.

Ni(II) removal from aqueous solutions using cone biomass of Thuja orientalis.

PubMed

Malkoc, Emine

2006-09-21

The biomass of terrestrial-plant materials has high removal capacities for a number of heavy metal ions. The Ni(II) biosorption capacity of the cone biomass of Thuja orientalis was studied in the batch mode. The biosorption equilibrium level was determined as a function of contact time, pH, temperature, agitation speed at several initial metal ion and adsorbent concentrations. The removal of Ni(II) from aqueous solutions increased with adsorbent concentration, temperature and agitation speed of the solution were increased. The biosorption process was very fast; 90% of biosorption occurred within 3 min and equilibrium was reached at around 7 min. It is found that the biosorption of Ni(II) on the cone biomass was correlated well (R2 > 0.99) with the Langmuir equation as compared to Freundlich, BET Temkin and D-R isotherm equation under the concentration range studied. According to Langmuir isotherm, the monolayer saturation capacity (Q(o)) is 12.42 mg g(-1). The pseudo-first-order, pseudo-second-order and intraparticle diffusion kinetic models were applied to test the experimental data for initial Ni(II) and cone biomass concentrations. The pseudo-second-order kinetic model provided the best correlation of the used experimental data compared to the pseudo-first-order and intraparticle diffusion kinetic models. The activation energy of biosorption (E(a)) was determined as 36.85 kJ mol(-1) using the Arrhenius equation. This study indicated that the cone biomass of T. orientalis can be used as an effective and environmentally friendly adsorbent for the treatment of Ni(II) containing aqueous solutions.

Highly anisotropic exchange interactions in a trigonal bipyramidal cyanide-bridged Ni(II)3Os(III)2 cluster.

PubMed

Palii, Andrei V; Reu, Oleg S; Ostrovsky, Sergei M; Klokishner, Sophia I; Tsukerblat, Boris S; Hilfiger, Matthew; Shatruk, Michael; Prosvirin, Andrey; Dunbar, Kim R

2009-06-25

This article is a part of our efforts to control the magnetic anisotropy in cyanide-based exchange-coupled systems with the eventual goal to obtain single-molecule magnets with higher blocking temperatures. We give the theoretical interpretation of the magnetic properties of the new pentanuclear complex {[Ni(II)(tmphen)(2)](3)[Os(III)(CN)(6)](2)} x 6 CH(3)CN (Ni(II)(3)Os(III)(2) cluster). Because the system contains the heavy Os(III) ions, spin-orbit coupling considerably exceeds the contributions from the low-symmetry crystal field and exchange coupling. The magnetic properties of the Ni(II)(3)Os(III)(2) cluster are described in the framework of a highly anisotropic pseudo-spin Hamiltonian that corresponds to the limit of strong spin-orbital coupling and takes into account the complex molecular structure. The model provides a good fit to the experimental data and allows the conclusion that the trigonal axis of the bipyramidal Ni(II)(3)Os(III)(2) cluster is a hard axis of magnetization. This explains the fact that in contrast with the isostructural trigonal bipyramidal Mn(III)(2)Mn(II)(3) cluster, the Ni(II)(3)Os(III)(2) system does not exhibit the single-molecule magnetic behavior.

Effects of ball milling on the physicochemical and sorptive properties of biochar: Experimental observations and governing mechanisms.

PubMed

Lyu, Honghong; Gao, Bin; He, Feng; Zimmerman, Andrew R; Ding, Cheng; Huang, Hua; Tang, Jingchun

2018-02-01

With the goal of combining the advantages of ball-milling and biochar technologies, a variety of ball-milled biochars (BM-biochars) were synthesized, characterized, and tested for nickel (Ni(II)) removal from aqueous solution. Ball milling increased only the external surface area of low temperature biochars, but still dramatically enhanced their ability to sorb aqueous Ni(II). For higher temperature biochars with relatively low surface area, ball milling increased both external and internal surface area. Measurements of pH, zeta potential, stability, and Boehm titration demonstrated that ball milling also added oxygen-containing functional groups (e.g., carboxyl, lactonic, and hydroxyl) to biochar's surface. With these changed, all the BM-biochars showed much better Ni(II) removal efficiency than unmilled biochars. Ball-milled 600 °C bagasse biochar (BMBG600) showed the greatest Ni(II) adsorption capacity (230-650 compared to 26-110 mmol/kg for unmilled biochar) and the adsorption was dosage and pH dependent. Compared with the unmilled biochar, BMBG600 also displayed faster adsorption kinetics, likely due to an increase in rates of intra-particle diffusion in the latter. Experimental and modeling results suggest that the increase in BM-biochar's external and internal surface areas exposed its graphitic structure, thus enhancing Ni(II) adsorption via strong cation-π interaction. In addition, the increase in acidic surface functional groups enhanced Ni(II) adsorption by BM-biochar via electrostatic interaction and surface complexation. Ball milling thus has great potential to increase the efficiency of environmentally friendly biochar for various environmental applications. Copyright © 2017 Elsevier Ltd. All rights reserved.

Selective and sensitized spectrophotometric determination of trace amounts of Ni(II) ion using α-benzyl dioxime in surfactant media

NASA Astrophysics Data System (ADS)

Ghaedi, Mehrorang

2007-02-01

Highly sensitive and interference-free sensitized spectrophotometric method for the determination of Ni(II) ions is described. The method is based on the reaction between Ni(II) ion and benzyl dioxime in micellar media in the presence of sodium dodecyl sulfate (SDS). The absorbance is linear from 0.1 up to 25.0 μg mL -1 in aqueous solution with repeatability (RSD) of 1.0% at a concentration of 1 μg mL -1 and a detection limit of 0.12 ng mL -1 and molar absorption coefficient of 68,600 L mol -1 cm -1. The influence of reaction variables including type and amount of surfactant, pH, and amount of ligand and complexation time and the effect of interfering ions are investigated. The proposed procedure was applied to the determination of trace amounts of Ni(II) ion in tap water, river water, chocolate and vegetable without separation or organic solvent extraction.

A Novel Nanocomposite as an Efficient Adsorbent for the Rapid Adsorption of Ni(II) from Aqueous Solution

PubMed Central

Wang, Ximing; Chen, Zhangjing

2017-01-01

A sulfhydryl-lignocellulose/montmorillonite (SLT) nanocomposite was prepared using a chemical intercalation reaction. The SLT nanocomposite was characterized by Fourier Transform Infrared Spectroscopy (FTIR), X-Ray Diffraction (XRD), Scanning Electron Microscope (SEM), and Transmission Electron Microscopy (TEM), the results demonstrated that an intercalated-exfoliated nanostructure was formed in the SLT nanocomposite. Batch experiments were conducted to optimize parameters such as SLT nanocomposite dosage, the initial concentration of Ni(II), solution pH, temperature, and time. The results indicated that the attractive adsorption capacity reached 1134.08 mg/g with 0.05 g of SLT at an initial concentration of Ni(II) of 700 mg/L, solution pH of 5.5, adsorption temperature of 50 °C, and adsorption time of 40 min, meanwhile, the Ni(II) adsorption capacity significantly decreased with the increase in ionic strength. The pseudo-second order kinetic model could describe the whole adsorption process well, and the isotherm adsorption equilibrium conformed to the Freundlich model. The adsorption mechanism of SLT was also discussed by means of FTIR and Energy-Dispersive X-Ray (EDX). Dramatically, the introduction of sulfhydryl achieves the increased activated functional groups content of SLT nanocomposite, leading to remarkably higher adsorption amount on Ni(II). The desorption capacity of SLT was dependent on parameters such as HNO3 concentration, desorption temperature, and ultrasonic desorption time. The satisfactory desorption capacity and desorption efficiency of 458.21 mg/g and 40.40% were obtained at an HNO3 concentration, desorption temperature, and ultrasonic desorption time of 0.4 mol/L, 40 °C, and 30 min, respectively. The regeneration studies showed that the adsorption capacity of SLT was consistent for four cycles without any appreciable loss and confirmed that the SLT was reusable. Owing to such outstanding features, the novel SLT nanocomposite proved the great potential in adsorption for Ni(II) removal from aqueous solution, and exhibited an extremely significant amount of Ni(II), compared to pristine lignocellulose/montmorillonite and the conventional spent adsorbents. PMID:28937606

Structural Investigations of the Nickel-Induced Inhibition of Truncated Constructs of the JMJD2 Family of Histone Demethylases Using X-ray Absorption Spectroscopy

PubMed Central

Giri, Nitai Charan; Passantino, Lisa; Sun, Hong; Zoroddu, Maria Antonietta; Costa, Max; Maroney, Michael J.

2013-01-01

Occupational and/or environmental exposure to nickel has been implicated in various types of cancer, and in vitro exposure to nickel compounds results in accumulation of Ni(II) ions in cells. One of the major targets of Ni(II) ions inside the cell is Fe(II)- and αKG-dependent dioxygenases. Using JMJD2A and JMJD2C as examples, we show that JMJD2 family of histone demethylases, which are products of putative oncogenes as well as Fe(II)- and αKG-dependent dioxygenases, are highly sensitive to inhibition by Ni(II) ions. In this work, X-ray absorption spectroscopy (XAS) has been used to investigate the Fe(II) active site of truncated JMJD2A and JMJD2C (1 – 350 aa) in the presence and absence of αKG and/or substrate to obtain mechanistic details of the early steps in catalysis that precede O2 binding in histone demethylation by the JMJD2 family of histone demethylases. Zinc K-edge XAS has been performed on the resting JMJD2A (with iron in the active site) to confirm the presence of the expected structural zinc site. XAS of the Ni(II)-substituted enzymes has also been performed to investigate the inhibition of these enzymes by Ni(II) ions. Our XAS results indicate that the five-coordinate Fe(II) center in the resting enzyme is retained in the binary and ternary complexes. In contrast, the Ni(II) center is six-coordinate in the resting enzyme, binary and ternary complexes. XAS results indicate that both Fe(II) and Ni(II) bind αKG in the binary and ternary complexes. The electron density build-up that is observed at the Fe(II) center in the presence of αKG and substrate is not observed at the Ni(II) center. Thus, both electronic and steric factors are responsible for Ni-induced inhibition of the JMJD2 family of histone demethylases. Ni-induced inhibition of these enzymes may explain the alteration of the epigenetic mechanism of gene expression that is responsible for Ni-induced carcinogenesis. PMID:23692052

Polymeric Cd(II), trinuclear and mononuclear Ni(II) complexes of 5-methyl-4-phenyl-1,2,4-triazole-3-thione: Synthesis, structural characterization, thermal behaviour, fluorescence properties and antibacterial activity

NASA Astrophysics Data System (ADS)

Bharty, M. K.; Paswan, S.; Dani, R. K.; Singh, N. K.; Sharma, V. K.; Kharwar, R. N.; Butcher, R. J.

2017-02-01

Syntheses of a polymeric Cd(II) complex, [Cd(mptt)2]n (1), a trinuclear Ni(II) complex, [Ni3(μ-mptt)4(μ-H2O)2(H2O)2(ttfa)2]·3H2O (2) and a mononuclear Ni(II) complex [Ni(mptt)2(en)2] (3) have been performed using the ligand 5-methyl-4-phenyl-1,2,4-triazole-3-thione (Hmptt) and nickel(II)/cadmium(II) salts {ttfa = thenoyltrifluroacetonate). The ligand and the complexes have been characterized by various physicochemical methods in addition to their single crystal X-ray structure. The Cd centre in complex 1 adopts a distorted tetrahedral geometry with one sulfur atom and two mptt ligands provide three nitrogen atoms from three triazole units. The sulfur atom of the ligand binds covalently and overall the ligand acts as uninigative N,S/N,N bidentate moiety. The polymeric structure of complex 1 results from the N atoms of the neighboring triazole units coordinating with the Cd(II) centre. The three Ni(II) centres in the trinuclear Ni(II) complex 2 form a linear arrangement and all have six coordinated arrangements. The middle Ni(II) binds with four deprotonated triazole ring nitrogens and two water molecules form two bridges. The terminal Ni(II) centres bind through two thenoyl oxygens, two triazole nitrogens and water molecules that formed bridges with the middle Ni centre. In complex 3, the nickel(II) centre is covalently bonded through two deprotonated triazole ring nitrogens from two ligand moieties and other four sites are occupied by four nitrogens from two bidentate en ligands. Thermogravimetric analyses (TGA) of the complexes indicated for NiO as the final residue. The bioefficacy of the ligand and complexes 2 and 3 have been examined against the growth of bacteria to evaluate their anti-microbial potential. Complex 2 showed high antibacterial activity as compared to the ligand and complex 3. Complexes 1, 2 and 3 are fluorescent materials with maximum emissions at 425, 421 and 396 nm at an excitation wavelength of 323, 348 and 322 nm, respectively.

Novel method of vulnerability assessment of simple landfills area using the multimedia, multipathway and multireceptor risk assessment (3MRA) model, China.

PubMed

Yuan, Ying; He, Xiao-Song; Xi, Bei-Dou; Wei, Zi-Min; Tan, Wen-Bing; Gao, Ru-Tai

2016-11-01

Vulnerability assessment of simple landfills was conducted using the multimedia, multipathway and multireceptor risk assessment (3MRA) model for the first time in China. The minimum safe threshold of six contaminants (benzene, arsenic (As), cadmium (Cd), hexavalent chromium [Cr(VI)], divalent mercury [Hg(II)] and divalent nickel [Ni(II)]) in landfill and waste pile models were calculated by the 3MRA model. Furthermore, the vulnerability indexes of the six contaminants were predicted based on the model calculation. The results showed that the order of health risk vulnerability index was As > Hg(II) > Cr(VI) > benzene > Cd > Ni(II) in the landfill model, whereas the ecology risk vulnerability index was in the order of As > Hg(II) > Cr(VI) > Cd > benzene > Ni(II). In the waste pile model, the order of health risk vulnerability index was benzene > Hg(II) > Cr(VI) > As > Cd and Ni(II), whereas the ecology risk vulnerability index was in the order of Hg(II) > Cd > Cr(VI) > As > benzene > Ni(II). These results indicated that As, Hg(II) and Cr(VI) were the high risk contaminants for the case of a simple landfill in China; the concentration of these in soil and groundwater around the simple landfill should be strictly monitored, and proper mediation is also recommended for simple landfills with a high concentration of contaminants. © The Author(s) 2016.

Uptake of Nickel by Synthetic Mackinawite

EPA Science Inventory

The uptake of aqueous Ni(II) by synthetic mackinawite (FeS) was examined in anaerobic batch experiments at near-neutral pH (5.2 to 8.4). Initial molar ratios of Ni(II) to FeS ranged from 0.008 to 0.83 and maximum Ni concentrations in mackinawite, expressed as the cation mol fract...

Polyethylene imine modified hydrochar adsorption for chromium (VI) and nickel (II) removal from aqueous solution.

PubMed

Shi, Yuanji; Zhang, Tao; Ren, Hongqiang; Kruse, Andrea; Cui, Ruofan

2018-01-01

An adsorbent hydrochar was synthesized from corn cobs and modified with polyethylene imine (PEI). The hydrochars before and after modification were characterized by scanning electron microscopy, Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and thermogravimetric analysis. FTIR and XPS revealed that the PEI was grafted onto the hydrochar via ether and imine bonds formed with glutaraldehyde. The maximum adsorption capacities for Cr(VI) (33.663mg/g) and Ni(II) (29.059mg/g) on the modified hydrochars were 365% and 43.7% higher, respectively, than those on the unmodified hydrochar. A pseudo-second-order model described the adsorption of Ni(II) and Cr(VI) on all the adsorbents. The adsorption of Cr(VI) was endothermic, spontaneous, increased disorder, and obeyed the Langmuir model. By contrast, the adsorption of Ni(II) was exothermic, spontaneous, decreased disorder, and obeyed the Freundlich model. XPS confirmed that the adsorption sites and mechanisms for Ni(II) and Cr(VI) on the modified hydrochars were different. Copyright © 2017 Elsevier Ltd. All rights reserved.

Toxicology and metabolism of nickel compounds. Progress report, December 1, 1974--November 30, 1975. [97433ONE

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sunderman, F.W. Jr.

1975-08-15

The toxicology and metabolism of nickel compounds (NiCl/sub 2/, Ni/sub 3/S/sub 2/, NiS, and Ni powder) were investigated in rats and hamsters. The new knowledge has included: demonstration that hyperglucagonemia is primarily responsible for the acute hyperglycemic effect of parenteral Ni(II) in rats; demonstration that parenteral injection of Ni(II) in rats produces acute nephropathy with proteinuria and amino aciduria, and with ultrastructural lesions of renal glomeruli and tubules; confirmation of the inhibitory effect of manganese upon the carcinogenicity of Ni/sub 3/S/sub 2/ after intramuscular injection in rats, and elucidation of the effects of manganese upon the rates of excretion ofmore » nickel, and upon the acute histological reactions produced by Ni/sub 3/S/sub 2/; discovery that the antidotal efficacy of triethylenetetramine (TETA) in acute Ni(II) poisoning in rats is substantially greater than that of other chelating agents, including ..cap alpha..-lipoic acid, diethyldithiocarbamate, d-penicillamine, and glycylglycyl-L-histidine-N-methylamide; observation that the acute renal toxicity of Ni(II) is suppressed by administration of TETA, but that the hyperglycemic and hyperglucagonemic responses to Ni(II) are not prevented by TETA; confirmation that marked erythrocytosis is induced in rats by a single intrarenal injection of Ni/sub 3/S/sub 2/, and elucidation of the time-response and dose-response relationships for the Ni-induced erythrocytosis. (auth)« less

Multisurface modeling of Ni bioavailability to wheat (Triticum aestivum L.) in various soils.

PubMed

Zhao, Xiaopeng; Jiang, Yang; Gu, Xueyuan; Gu, Cheng; Taylor, J Anita; Evans, Les J

2018-07-01

Continual efforts have been made to determine a simple and universal method of estimating heavy metal phytoavailability in terrestrial systems. In the present study, a mechanism-based multi-surface model (MSM) was developed to predict the partition of Ni(II) in soil-solution phases and its bioaccumulation in wheat (Triticum aestivum L.) in 19 Chinese soils with a wide range of soil properties. MSM successfully predicted the Ni(II) dissolution in 0.01 M CaCl 2 extracting solution (R 2  = 0.875). The two-site model for clay fraction improved the prediction, particularly for alkaline soils, because of the additional consideration of edge sites. More crucially, the calculated dissolved Ni(II) was highly correlated with the metal accumulation in wheat (R 2  = 0.820 for roots and 0.817 for shoots). The correlation coefficients for the MSM and various chemical extraction methods have the following order: soil pore water > MSM ≈ diffuse gradient technique (DGT) > soil total Ni > 0.43 M HNO 3  > 0.01 M CaCl 2 . The results suggested that the dissolved Ni(II) calculated using MSM can serve as an effective indicator of the bioavailability of Ni(II) in various soils; hence, MSM can be used as an supplement for metal risk prediction and assessment besides chemical extraction techniques. Copyright © 2018 Elsevier Ltd. All rights reserved.

Desenvolvimento de modelo clínico para predição da possibilidade de identificação da artéria de Adamkiewicz por angiotomografia

PubMed Central

Amato, Alexandre Campos Moraes; Parga, José Rodrigues; Stolf, Noedir Antônio Groppo

2018-01-01

Resumo Contexto Diferenças morfológicas da artéria de Adamkiewicz (AKA) entre a população portadora e não portadora de doença aórtica têm importância clínica, influenciando as complicações neuroisquêmicas da medula espinhal em procedimentos operatórios. Ainda não é conhecida a correlação entre parâmetros clínicos e a previsibilidade da identificação dessa artéria pela angiotomografia. Objetivo Desenvolver um modelo matemático que, através de parâmetros clínicos correlacionados com aterosclerose, possa prever a probabilidade de identificação da AKA em pacientes submetidos a angiotomografias. Método Estudo observacional transversal utilizando banco de imagens e dados de pacientes. Foi feita análise estatística multivariada e criado modelo matemático logit de predição para identificação da AKA. Variáveis significativas foram utilizadas na montagem da fórmula para cálculo da probabilidade de identificação. O modelo foi calibrado, e a discriminação foi avaliada pela curva receiver operating characteristic (ROC). A seleção das variáveis explanatórias foi guiada pela maior área na curva ROC (p = 0,041) e pela significância combinada das variáveis. Resultados Foram avaliados 110 casos (54,5% do sexo masculino, com idade média de 60,97 anos e etnia com coeficiente B -2,471, M -1,297, N -0,971), com AKA identificada em 60,9%. Índice de massa corporal: 27,06 ± 0,98 (coef. -0,101); fumantes: 55,5% (coef. -1,614/-1,439); diabéticos: 13,6%; hipertensos: 65,5% (coef. -1,469); dislipidêmicos: 58,2%; aneurisma aórtico: 38,2%; dissecção aórtica: 12,7%; e trombo mural: 24,5%. Constante de 6,262. Fórmula para cálculo da probabilidade de detecção: (e−(Coef. Etnia+(Coef. IMC×IMC)+Coef.fumante+Coef.HAS+Coef.dislip+Constante)+1)−1 . O modelo de predição foi criado e disponibilizado no link https://vascular.pro/aka-model . Conclusão Com as covariáveis etnia, índice de massa corporal, tabagismo, hipertensão arterial e dislipidemia, foi possível criar um modelo matemático de predição de identificação da AKA com significância combinada de nove coeficientes (p = 0,042). PMID:29930677

Direct Measurement of the Supernova Rate in Starburst Galaxies

NASA Technical Reports Server (NTRS)

Bregman, Jesse D.; Temi, Pasquale; Rank, David; DeVincenzi, Donald L. (Technical Monitor)

1999-01-01

Supernovae play a key role in the dynamics, structure, and chemical evolution of galaxies. The massive stars that end their lives as supernovae live for short times. Many are still associated with dusty star formation regions when they explode, making them difficult to observe at visible wavelengths. In active star forming regions (galactic nuclei and starburst regions), dust extintion is especially severe. Thus, determining the supernova rate in the active star forming regions of galaxies, where the supernova rate can be one or two orders of magnitude higher than the average, has proven to be difficult. From observations of SN1987A, we know that the [NiII] 6.63 micron emission line was the strongest line in the infrared spectrum for a period of a year and a half after the explosion. Since dust extintion is much less at 6.63 pm than at visible wavelengths (A(sub 6.63)/A(sub V) = 0.025), the NiII line can be used as a sensitive probe for the detection of recent supernovae. We have observed a sample of starburst galaxies at 6.63 micron using ISOCAM to search for the NiII emission line characteristic of recent supernovae. We did not detect any NiII line emission brighter than a 5sigma limit of 5 mJy. We can set upper limits to the supernova rate in our sample, scaled to the rate in M82, of less than 0.3 per year at the 90% confidence level using Bayesian methods. Assuming that a supernova would have a NiII with the same luminosity as observed in SN1987A, we find less than 0.09 and 0.15 per year at the 50% and 67% confidence levels. These rates are somewhat less if a more normal type II supernovae has a NiII line luminosity greater than the line in SN1987A.

A Paper-Based Analytical Device Based on Combination of Thin Film Microextraction and Reflection Scanometry for Sensitive Colorimetric Determination of Ni(II) in Aqueous Matrix.

PubMed

Allafchian, Ali Reza; Farajmand, Bahman; Koupaei, Amin Javaheri

2018-04-01

In this research, the thin film microextraction method was applied for the extraction of Ni(II) ion from aqueous matrixes. Chemically modified cellulosic filter paper with phosphorus was used as a thin film extractor. After extraction, the thin film was treated with a solution of dimethylglyoxime. The colored film was captured by flatbed scanner and the absorbance of the images was extracted by some suitable software. Under the optimum conditions and at the pH 7.0, with the sample volume of 100 mL, the stirring rate of 800 rpm, and the extraction time of 50 min, the calibration curve was obtained in the range of 0.05-5 mg/L Ni(II) (R 2  = 0.989). Limit and relative standard deviation were achieved to be 18 µg/L and less than 6.7%, respectively. Relative recoveries were obtained in the range of 87%-105%. Finally, the proposed method was found to be simple and cost-effective, with adequate analytical performance for the rapid detection of Ni(II) in river and wastewater samples.

Site preference of alloying elements in DO22-Ni3V phase: Phase-field and first-principles study

NASA Astrophysics Data System (ADS)

Zhang, Ding-Ni; Shangguan, Qian-Qian; Liu, Fu; Zhang, Ming-Yi

2015-07-01

Site preference of alloying elements in DO22-Ni3V phase was investigated using phase-field and first-principles method. The concentrations of alloying elements on sublattices of DO22-Ni3V phase were quantitatively studied using phase-field model based on microscopic diffusion equations. The phase-field computation results demonstrate that the concentration differences of alloying elements on the NiI and NiII site are attributed to the coordination environment difference. Host atoms Ni and substitutional ternary additions Al prefer to occupy NiI site. Antisite atoms V show site preference on the NiII site. Further reason of site preference of alloying elements on the two different Ni sites were studied using first-principles method to calculate the electronic structure of DO22-Ni3V phase. Calculation of density of states, orbitals population and charge population of the optimized Ni3V structure found that the electronic structures of NiI and NiII sites are different. Electronic structure difference, which is caused by coordination environment difference, is the essential reason for site selectivity behaviors of alloying elements on NiI and NiII sites.

NEW TECHNIQUE FOR OBESITY SURGERY: INTERNAL GASTRIC PLICATION TECHNIQUE USING INTRAGASTRIC SINGLE-PORT (IGS-IGP) IN EXPERIMENTAL MODEL.

PubMed

Müller, Verena; Fikatas, Panagiotis; Gül, Safak; Noesser, Maximilian; Fuehrer, Kirs Ten; Sauer, Igor; Pratschke, Johann; Zorron, Ricardo

2017-01-01

Bariatric surgery is currently the most effective method to ameliorate co-morbidities as consequence of morbidly obese patients with BMI over 35 kg/m2. Endoscopic techniques have been developed to treat patients with mild obesity and ameliorate comorbidities, but endoscopic skills are needed, beside the costs of the devices. To report a new technique for internal gastric plication using an intragastric single port device in an experimental swine model. Twenty experiments using fresh pig cadaver stomachs in a laparoscopic trainer were performed. The procedure was performed as follow in ten pigs: 1) volume measure; 2) insufflation of the stomach with CO2; 3) extroversion of the stomach through the simulator and installation of the single port device (Gelpoint Applied Mini) through a gastrotomy close to the pylorus; 4) performance of four intragastric handsewn 4-point sutures with Prolene 2-0, from the gastric fundus to the antrum; 5) after the performance, the residual volume was measured. Sleeve gastrectomy was also performed in further ten pigs and pre- and post-procedure gastric volume were measured. The internal gastric plication technique was performed successfully in the ten swine experiments. The mean procedure time was 27±4 min. It produced a reduction of gastric volume of a mean of 51%, and sleeve gastrectomy, a mean of 90% in this swine model. The internal gastric plication technique using an intragastric single port device required few skills to perform, had low operative time and achieved good reduction (51%) of gastric volume in an in vitro experimental model. A cirurgia bariátrica é atualmente o método mais efetivo para melhorar as co-morbidades decorrentes da obesidade mórbida com IMC acima de 35 kg/m2. Técnicas endoscópicas foram desenvolvidas para tratar pacientes com obesidade leve e melhorar as comorbidades, mas habilidades endoscópicas são necessárias, além dos custos. Relatar uma nova técnica para a plicatura gástrica interna utilizando um dispositivo intragástrico de portal único em modelo experimental de suínos. Foram realizados 20 experimentos utilizando estômagos de cadáver de porco fresco em um instrutor laparoscópico. O procedimento foi realizado da seguinte forma em dez porcos: 1) medida de volume; 2) insuflação do estômago com CO2; 3) extroversão do estômago através do simulador e instalação do dispositivo de uma única via (Gelpoint Applied Mini) através de uma gastrotomia próxima ao piloro; 4) realização de quatro suturas de quatro pontos intra-gástricas com Prolene 2-0, desde o fundo gástrico até o antro; 5) medição do volume residual. A gastrectomia vertical foi também realizada em mais dez suínos e o volume gástrico pré e pós-procedimento foi medido. A técnica de plicatura gástrica interna foi realizada com sucesso nos dez experimentos com suínos. O tempo médio do procedimento foi de 27±4 min. Produziu redução do volume gástrico em média de 51%, e a gastrectomia vertical em média de 90% neste modelo suíno. A técnica de plicatura gástrica interna, utilizando um dispositivo intragástrico de uma única via, exigiu poucas habilidades para ser realizada, teve baixo tempo operatório e obteve boa redução (51%) do volume gástrico em um modelo experimental in vitro.

Catalytic reduction of pralidoxime in pharmaceuticals by macrocyclic Ni(II) compounds derived from orthophthalaldehyde.

PubMed

Reddy, P Muralidhar; Prasad, Adapa V S S; Rohini, Rondla; Ravinder, Vadde

2008-08-01

Efficient catalytic method for the reduction of pralidoxime to its amine derivative by macrocyclic Ni(II) compounds has been developed. Ten macrocyclic Schiff base Ni(II) compounds were synthesized via non-template synthesis by treating the corresponding macrocycles with nickel chloride in 1:1 ratio. The resulting compounds were characterized by elemental, IR, (1)H NMR, (13)C NMR, mass, electronic spectra, conductance, magnetic, thermal studies and their structures have been proposed. These compounds were used as catalysts for the reduction of pralidoxime to its amino derivative. The reduced pralidoxime was also characterized by spectral analysis and catalytic cycle has been established. The reduced product was determined spectrophotometrically by treating with ninhydrin reagent and the percent yields were found to be in the range of 75.12-82.36%.

Glutamate Ligation in the Ni(II)- and Co(II)-Responsive Escherichia coli Transcriptional Regulator, RcnR

DOE Office of Scientific and Technical Information (OSTI.GOV)

Carr, Carolyn E.; Musiani, Francesco; Huang, Hsin-Ting

Escherichia coli RcnR (resistance to cobalt and nickel regulator, EcRcnR) is a metal-responsive repressor of the genes encoding the Ni(II) and Co(II) exporter proteins RcnAB by binding to PRcnAB. The DNA binding affinity is weakened when the cognate ions Ni(II) and Co(II) bind to EcRcnR in a six-coordinate site that features a (N/O)5S ligand donor-atom set in distinct sites: while both metal ions are bound by the N terminus, Cys35, and His64, Co(II) is additionally bound by His3. On the other hand, the noncognate Zn(II) and Cu(I) ions feature a lower coordination number, have a solvent-accessible binding site, and coordinatemore » protein ligands that do not include the N-terminal amine. A molecular model of apo-EcRcnR suggested potential roles for Glu34 and Glu63 in binding Ni(II) and Co(II) to EcRcnR. The roles of Glu34 and Glu63 in metal binding, metal selectivity, and function were therefore investigated using a structure/function approach. X-ray absorption spectroscopy was used to assess the structural changes in the Ni(II), Co(II), and Zn(II) binding sites of Glu → Ala and Glu → Cys variants at both positions. The effect of these structural alterations on the regulation of PrcnA by EcRcnR in response to metal binding was explored using LacZ reporter assays. These combined studies indicate that while Glu63 is a ligand for both metal ions, Glu34 is a ligand for Co(II) but possibly not for Ni(II). The Glu34 variants affect the structure of the cognate metal sites, but they have no effect on the transcriptional response. In contrast, the Glu63 variants affect both the structure and transcriptional response, although they do not completely abolish the function of EcRcnR. The structure of the Zn(II) site is not significantly perturbed by any of the glutamic acid variations. The spectroscopic and functional data obtained on the mutants were used to calculate models of the metal-site structures of EcRcnR bound to Ni(II), Co(II), and Zn(II). The results are interpreted in terms of a switch mechanism, in which a subset of the metal-binding ligands is responsible for the allosteric response required for DNA release.« less

A Trinuclear Ni(II) Enediolate Complex: Synthesis, Characterization, and O2 Reactivity

PubMed Central

Arif, Atta M.; Berreau, Lisa M.

2009-01-01

Using a new N4-donor chelate ligand having a mixture of hydrophobic phenyl and hydrogen bond donor appendages, a trinuclear Ni(II) complex of the doubly deprotonated form of 2-hydroxy-1,3-diphenylpropane-1,3-dione was isolated, characterized (X-ray crystallography, elemental analysis, UV-vis, 1H NMR, FTIR, magnetic moment measurement), and evaluated for O2 reactivity. This complex, [(6-NA-6-Ph2TPANi)2(μ-PhC(O)C(O)C(O)Ph)2Ni](ClO4)2 (4), has two terminal pseudo octahedral Ni(II) centers supported by the tetradentate chelate ligand, and a central square planar Ni(II) ion ligated by oxygen atoms of two bridging enediolate ligands. In CH3CN, 4 exhibits a deep orange/brown color and λmax = 463 nm (ε = 16,000 M-1cm-1). The room temperature magnetic moment of 4, determined by Evans method, is μeff = 5.3(2) μB. This is consistent with the presence of two non-interacting high-spin Ni(II) centers, a diamagnetic central Ni(II) ion, and an overall quintet ground state. Exposure of a CH3CN solution of 4 to O2 results in the rapid loss of the orange/brown color to give a green solution. The products identified from this reaction are [(κ3-6-NA-6-Ph2TPA)Ni(O2Ph)(H2O)]ClO4 (5), benzil (PhC(O)C(O)Ph), and CO. Identification of 5 was achieved via its independent synthesis and comparison of its 1H NMR and mass spectral features with those of the 6-NA-6-Ph2TPA-containing product generated upon reaction of 4 with O2. The independently prepared sample of 5 was characterized by X-ray crystallography, elemental analysis, UV-vis, mass spectrometry, and FTIR. The O2 reactivity of 4 has relevance to the active site chemistry of Ni(II)-containing acireductone dioxygenase (Ni(II)-ARD). PMID:18959363

Process development for recovery of vanadium and nickel from an industrial solid waste by a leaching-solvent extraction technique.

PubMed

Barik, S P; Park, K H; Nam, C W

2014-12-15

A process for recovering V(V) and Ni(II) from an industrial solid waste using sulfuric acid leaching, solvent extraction, precipitation and crystallization has been developed. The leaching parameters investigated were time, temperature and H2SO4 concentration. To quantify the linear and interaction coefficients a 2(3) full factorial experimental design was used. Regression equations for the extraction of V(V) and Ni(II) were determined and the adequacy of these equations was tested by Student's t-Test. More than 98% of both V(V) and Ni(II) were extracted in 90 min using 1.35 M H2SO4 at 40 °C. In addition, solvent extraction of V(V) with LIX 84-I in kerosene from the acidic leach liquor bearing 10.922 g/L V(V) and 18.871 g/L of Ni(II) was investigated. V(V) was extracted selectively using 40% LIX 84-I followed by stripping with NH4OH solution. McCabe-Thiele plots at O:A = 2:3 with 40% LIX 84-I and O:A = 3:1 with 15% (v/v) NH4OH showed two and three theoretical stages are needed for quantitative extraction and stripping of V(V), respectively. Ni(II) was selectively recovered from the V(V) free raffinate by adding ammonium oxalate at 60 °C. The purity of different products such as ammonium vanadate, nickel oxalate and nickel oxide obtained during the processes were analyzed and confirmed from the XRD studies. Copyright © 2014 Elsevier Ltd. All rights reserved.

Mycobacterium tuberculosis NmtR harbors a nickel sensing site with parallels to Escherichia coli RcnR†

PubMed Central

Reyes-Caballero, Hermes; Lee, Chul Won; Giedroc, David P.

2011-01-01

Mycobacterium tuberculosis NmtR is a Ni(II)/Co(II)-sensing metalloregulatory protein from the extensively studied ArsR/SmtB family. Two Ni(II) ions bind to the NmtR dimer to form octahedral coordination complexes with stepwise binding affinities of KNi1=1.2 (±0.1) × 1010 and KNi2=0.7 (±0.4) × 1010 M-1 (pH 7.0). A glutamine scanning mutagenesis approach reveals that Asp91, His93, His104 and His107, all contained within the C-terminal α5 helix, and His3 as part of the conserved α-NH2-Gly2-His3-Gly4 motif at the N-terminus make significant contributions to the magnitude of KNi. In contrast, substitution of residues from the C-terminal region, His109, Asp114 and His116, previously implicated in Ni(II) binding and metalloregulation in cells, gives rise to wild-type KNi and Ni(II)-dependent allosteric coupling free energies. Interestingly, deletion of residues 112-120 in the C-terminal region (Δ111 NmtR) reduces the Ni(II) binding stoichiometry to one per dimer and greatly reduces Ni(II) responsiveness. H3Q and Δ111 NmtRs also show clear perturbations in the rank order of metal responsiveness to Ni(II), Co(II) and Zn(II) that is distinct from wild-type NmtR. 15N relaxation experiments with apo-NmtR reveal that both N-terminal (residues 2-14) and C-terminal (residues 110-120) regions are unstructured in solution, and this property likely dictates the metal specificity profile characteristic of the Ni(II)-sensor NmtR relative to other ArsR family regulators. PMID:21819125

Amorphous silica as a versatile supermolecular ligand for Ni(II) amine complexes: toward interfacial molecular recognition.

PubMed

Boujday, Souhir; Lambert, Jean-François; Che, Michel

2004-07-19

Selective adsorption of Ni(II) amine complexes used as precursors for supported catalysts was studied on amorphous silica surfaces. The nature of the adsorption sites was probed by [Ni(en)(dien) (H2O)]2+, [Ni(en)2(H2O)2]2+, and [Ni(dien)(H2O)3]2+ (en = ethylenediamine, dien = diethylenetriamine), which respectively contain one, two, and three labile aqua ligands. The silica surface acts as a mono- or polydentate ligand that can substitute the aqua ligands of the Ni(II) complexes in an inner-sphere adsorption mechanism. Room-temperature adsorption isotherms indicate that each nickel complex selects a limited number of adsorption sites; different sites are recognised by the three complexes, even though they have the same charge and comparable sizes. Several spectroscopic techniques (UV/Vis/NIR, EXAFS, and 29Si NMR) were used to confirm the selective character of the interaction of Ni(II) amine complexes with the silica surface. The specific sites include both silanol/silanolate groups in the same number as the original labile ligands and other surface groups that probably act as hydrogen-bond acceptors. These two types of groups cooperate to result in interfacial molecular-recognition phenomena with interactional complementarity.

Extraction and separation of Co(II) and Ni(II) from acidic sulfate solutions using Aliquat 336.

PubMed

Nayl, A A

2010-01-15

Extraction and separation of Co(II) and Ni(II) from acidic sulfate solutions by solvent extraction technique were studied using different forms of Aliquat 336 diluted with kerosene. The extraction percent of each metal ion was found to increase with increasing pH and extractant concentration. Co(II) was preferentially extracted by different forms of Aliquat 336 over Ni(II) under the same extraction conditions. From analysis of the experimental results, the extraction mechanism of R(4)N-forms was proposed with Co(II). It was found that the highest separation factor (S(Co/Ni)) value of 606.7 was obtained with 0.36 M R(4)N-SCN in kerosene from 2.0M H(2)SO(4) solution at pH 4.8 and shaking time of 20 min. Stripping of the two metal ions from the organic phase was also investigated. Based on the experimental results, a separation method was developed and tested to separate high purity Co(II), Ni(II) and Ln(III) from Ni-MH batteries leached by 2.0M H(2)SO(4). Based on the experimental results, a flow sheet was developed and tested and 0.34 g Co, 1.39 g Ln and 5.2g Ni were obtained from the leaching process.

Observations of localized NiII emission in M82: Evidence for supernovae activity in the molecular cloud east of the nucleus

NASA Technical Reports Server (NTRS)

Rank, David M.; Temi, Pasquale; Bregman, Jesse D.; Dunham, Edward W.; Harker, David

1995-01-01

Narrow band images of M82 at wavelengths of 6.63 microns (NiII) and 6.8 microns (continuum) are discussed in terms of new evidence for supernova activity in the nuclear region of the M82 starburst galaxy. Data were recorded using a 128x128 Si:Ga array in an infrared camera on the KAO Southern Expedition in April '94.

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

NASA Astrophysics Data System (ADS)

Sharma, Amit Kumar; Chandra, Sulekh

2011-10-01

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

The Co(II), Ni(II) and Cu(II) complexes with herbicide 2,4-dichlorophenoxyacetic acid - Synthesis and structural studies

NASA Astrophysics Data System (ADS)

Drzewiecka-Antonik, Aleksandra; Ferenc, Wiesława; Wolska, Anna; Klepka, Marcin T.; Cristóvão, Beata; Sarzyński, Jan; Rejmak, Paweł; Osypiuk, Dariusz

2017-01-01

The Co(II), Ni(II) and Cu(II) complexes with herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) were synthesized and structurally characterized. The geometry of metal-ligand interaction was refined using XAFS and DFT studies. The Co(2,4-D)2·6H2O and Ni(2,4-D)2·4H2O complexes have octahedral geometry with two carboxylate groups of 2,4-D anions and four water molecules in the coordination sphere. The square planar geometry around metal cations formed by the carboxylate groups from two monodentate ligands and two water molecules, is observed for Cu(2,4-D)2·4H2O complex. In the recrystallized Ni(II) complex dinuclear 'Chinese lantern' structures with bridging carboxylate groups of 2,4-D were observed.

Asymmetric synthesis of α-amino acids via homologation of Ni(II) complexes of glycine Schiff bases. Part 2: aldol, Mannich addition reactions, deracemization and (S) to (R) interconversion of α-amino acids.

PubMed

Sorochinsky, Alexander E; Aceña, José Luis; Moriwaki, Hiroki; Sato, Tatsunori; Soloshonok, Vadim

2013-11-01

This review provides a comprehensive treatment of literature data dealing with asymmetric synthesis of α-amino-β-hydroxy and α,β-diamino acids via homologation of chiral Ni(II) complexes of glycine Schiff bases using aldol and Mannich-type reactions. These reactions proceed with synthetically useful chemical yields and thermodynamically controlled stereoselectivity and allow direct introduction of two stereogenic centers in a single operation with predictable stereochemical outcome. Furthermore, new application of Ni(II) complexes of α-amino acids Schiff bases for deracemization of racemic α-amino acids and (S) to (R) interconversion providing additional synthetic opportunities for preparation of enantiomerically pure α-amino acids, is also reviewed. Origin of observed diastereo-/enantioselectivity in the aldol, Mannich-type and deracemization reactions, generality and limitations of these methodologies are critically discussed.

A causa das estações do ano: modelos mentais

NASA Astrophysics Data System (ADS)

de Campos, J. A. S.; de Araujo, J. F. S.

2003-08-01

A década de 70 do século passado foi marcada pelo estudo das concepções alternativas que os alunos trazem para a sala de aula. A identificação destas concepções foi o ponto de partida para promover a mudança conceitual, onde as pré-concepções seriam trocadas pelas concepções científicas. Na década seguinte, surgiram muitas propostas de estratégias educacionais para facilitar esta troca, na sua maioria baseadas na idéia do conflito cognitivo, proposta por Piaget. Entretanto, os resultados pouco animadores conduziram à percepção de que a mudança conceitual é um processo mais complexo. Pelas idéias da Ciência Cognitiva, a mudança conceitual é uma mudança progressiva dos modelos mentais que o aluno tem sobre o mundo físico, através de enriquecimento e revisão. A causa das Estações do Ano é um tópico sobre o qual a maioria dos estudantes apresenta concepções alternativas. Os autores fizeram um levantamento sobre as pré-concepções encontradas em trabalhos sobre o tema (16 referências), procurando encontrar elementos comuns que indicassem a presença de modelos mentais específicos. As pré-concepções encontradas na literatura foram obtidas usando-se diversas metodologias (desde entrevistas clínicas até questionários de múltipla escolha) e envolvendo alunos e professores de diferentes regiões geográficas. A partir de uma análise aprofundada de cada trabalho, e utilizando-se a técnica das Redes Sistêmicas, chegou-se a conclusão que as diversas pré-concepções identificadas (em torno de 50), poderiam ser representadas por 6 modelos mentais, onde a explicação da causa das estações do ano tem um mecanismo causal responsável. Os mecanismos causais identificados foram: a dependência da distância, a dependência da orientação, a dependência conjunta da distância e orientação, a dependência da obstrução, a dependência da velocidade e a dependência da inclinação dos raios solares. Foram ainda identificadas associações alternativas, que são um conjunto de pré-concepções, onde não existe a idéia de um modelo científico completo mas, sim, fragmentos de observação do dia a dia das pessoas.

Synthesis, spectral, antitumor, antioxidant and antimicrobial studies on Cu(II), Ni(II) and Co(II) complexes of 4-[(1H-Benzoimidazol-2-ylimino)-methyl]-benzene-1,3-diol.

PubMed

El-wakiel, Nadia; El-keiy, Mai; Gaber, Mohamed

2015-08-05

A new Schiff base of 2-aminobenzimidazole with 2,4-dihydroybezaldehyde (H₃L), and its Cu(II), Ni(II) and Co(II) complexes have been synthesized and characterized by elemental analyses, molar conductance, thermal analysis (TGA), inductive coupled plasma (ICP), magnetic moment measurements, IR, EI-mass, UV-Vis. and ESR spectral studies. On the basis of spectral studies and analytical data, it is evident that the Schiff base acts as dibasic tridentate ligand coordinating via deprotonated OH, NH and azomethine nitrogen atom. The results showed that Co(II) and Ni(II) complexes have tetrahedral structure while Cu(II) complexes has octahedral geometry. The kinetic and thermodynamic parameters of the thermal decomposition stages have been evaluated. The studied complexes were tested for their in vitro antimicrobial activities against some bacterial strains. The anticancer activity of the ligand and its metal complexes is evaluated against human liver Carcinoma (HEPG2) cell. These compounds exhibited a moderate and weak activity against the tested HEPG2 cell lines with IC₅₀ of 9.08, 18.2 and 19.7 μg/ml for ligand, Cu(II) and Ni(II) complexes, respectively. In vitro antioxidant activity of the newly synthesized compounds has also been evaluated. Copyright © 2015 Elsevier B.V. All rights reserved.

Adsorption and Desorption of Nickel(II) Ions from Aqueous Solution by a Lignocellulose/Montmorillonite Nanocomposite

PubMed Central

Zhang, Xiaotao; Wang, Ximing

2015-01-01

A new and inexpensive lignocellulose/montmorillonite (LNC/MMT) nanocomposite was prepared by a chemical intercalation of LNC into MMT and was subsequently investigated as an adsorbent in batch systems for the adsorption-desorption of Ni(II) ions in an aqueous solution. The optimum conditions for the Ni(II) ion adsorption capacity of the LNC/MMT nanocomposite were studied in detail by varying parameters such as the initial Ni(II) concentration, the solution pH value, the adsorption temperature and time. The results indicated that the maximum adsorption capacity of Ni(II) reached 94.86 mg/g at an initial Ni(II) concentration of 0.0032 mol/L, a solution pH of 6.8, an adsorption temperature of 70°C, and adsorption time of 40 min. The represented adsorption kinetics model exhibited good agreement between the experimental data and the pseudo-second-order kinetic model. The Langmuir isotherm equation best fit the experimental data. The structure of the LNC/MMT nanocomposite was characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM), whereas the adsorption mechanism was discussed in combination with the results obtained from scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), and Fourier-transform infrared spectroscopy analyses (FTIR). The desorption capacity of the LNC/MMT nanocomposite depended on parameters such as HNO3 concentration, desorption temperature, and desorption time. The satisfactory desorption capacity of 81.34 mg/g was obtained at a HNO3 concentration, desorption temperature, and desorption time of 0.2 mol/L, 60 ºC, and 30 min, respectively. The regeneration studies showed that the adsorption capacity of the LNC/MMT nanocomposite was consistent for five cycles without any appreciable loss in the batch process and confirmed that the LNC/MMT nanocomposite was reusable. The overall study revealed that the LNC/MMT nanocomposite functioned as an effective adsorbent in the detoxification of Ni(II)-contaminated wastewater. PMID:25647398

Solution structure of Mycobacterium tuberculosis NmtR in the apo-state: Insights into Ni(II)-mediated allostery

PubMed Central

Lee, Chul Won; Chakravorty, Dhruva K.; Chang, Feng-Ming James; Reyes-Caballero, Hermes; Ye, Yuzhen; Merz, Kenneth M.; Giedroc, David P.

2012-01-01

Mycobacterium tuberculosis is an obligate human respiratory pathogen that encodes approximately ten arsenic repressor (ArsR) family regulatory proteins that allow the organism to respond to a wide range of changes in its immediate microenvironment. How individual ArsR repressors have evolved to respond to selective stimuli is of intrinsic interest. The Ni(II)/Co(II)-specific repressor NmtR and related actinomycete nickel sensors harbor a conserved N-terminal αNH2-Gly2-His3-Gly4 sequence. Here, we present the solution structure of homodimeric apo-NmtR and show that the core of the molecule adopts a typical winged-helix ArsR repressor (α1-α2-α3-αR-β1-β2-α5) “open conformation” that is similar to the related zinc sensor Staphylococcus aureus CzrA, but harboring long, flexible N-terminal (residues 2-16) and C-terminal (residues 109-120) extensions. Ni(II) binding to the regulatory sites induces strong paramagnetic broadening of the α5 helical region and the extreme N-terminal tail to residue 10. Ratiometric pulse chase amidination mass spectrometry reveals that the rate of amidination of the Gly2 α-amino group is strongly attenuated in the Ni(II) complex relative to the apo-state and non-cognate Zn(II) complex. Ni(II) binding also induces dynamic disorder in the μs-ms timescale of key DNA interacting regions that likely contributes to the negative regulation of DNA binding by Ni(II). Molecular dynamics simulations and quantum chemical calculations reveal that NmtR readily accommodates a distal Ni(II) hexacoordination model involving the α-amine and His3 of the N-terminal region and α5 residues Asp91′, His93′, His104 and His107, which collectively define a new metal sensing site configuration in ArsR family regulators. PMID:22394357

A robust Ni(II) α-diimine catalyst for high temperature ethylene polymerization.

PubMed

Rhinehart, Jennifer L; Brown, Lauren A; Long, Brian K

2013-11-06

Sterically demanding Ni(II) α-diimine precatalysts were synthesized utilizing 2,6-bis(diphenylmethyl)-4-methyl aniline. When activated with methylaluminoxane, the catalyst NiBr2(ArN═C(Me)-C(Me)═NAr) (Ar = 2,6 bis(diphenylmethyl)-4-methylbenzene) was highly active, produced well-defined polyethylene at temperatures up to 100 °C (Mw/Mn = 1.09-1.46), and demonstrated remarkable thermal stability at temperatures appropriate for industrially used gas-phase polymerizations (80-100 °C).

Comparison of nickel biosorption properties of living and dead Rhizopus arrhizus biosorbent

NASA Astrophysics Data System (ADS)

Silah, Hülya; Gül, Ülküye Dudu

2017-04-01

The passive removal of commonly used heavy metal Ni(II), from aqueous solutions by inexpensive biomaterial, fungi Rhizopus arrhizus biomass, termed biosorption, was studied in this study. The effects of biomass type (living and dead) and pH (2-6) on metal removal by fungus were investigated. The dead biomass (44.2%) exhibited higher uptake ability of Ni(II) than living biomass (40.5%) at 100 mg/L heavy metal after 6 h. Optimal pH for biosorption was 6.

Sorption kinetics of zinc and nickel on modified chitosan.

PubMed

Tripathi, Nimisha; Choppala, Girish; Singh, Raj S; Srivastava, Prashant; Seshadri, Balaji

2016-09-01

This study was conducted to evaluate the effect of equilibration time on adsorption of zinc [Zn(II)] and nickel [Ni(II)] on pure and modified chitosan beads. The initial adsorption of Zn(II) was high on molybdenum (Mo)-impregnated chitosan beads (MoCB) during the initial 60 min. However, after 240 min, Zn(II) adsorption occurred more on single super phosphate chitosan beads (SSPCB), followed by monocalcium phosphate chitosan beads (MCPCB), untreated pure chitosan beads (UCB), and MoCB. Similarly, Ni(II) adsorption was greatest on MoCB during the initial 60 min. At the conclusion of the experiment (at 240 min), the greatest adsorption was occurred on MCPCB, followed by MoCB, UCB, and SSPCB. Chemical sorption and intra-particle diffusion were probably the dominant processes responsible for Zn(II) and Ni(II) sorption onto chitosan beads. The results demonstrated that modified chitosan beads were effective in adsorbing Zn and Ni and hence, could be used for the removal of these toxic metals from soil.

Nickel(II) Inhibits Tet-Mediated 5-Methylcytosine Oxidation by High Affinity Displacement of the Cofactor Iron(II).

PubMed

Yin, Ruichuan; Mo, Jiezhen; Dai, Jiayin; Wang, Hailin

2017-06-16

Ten-eleven translocation (Tet) family proteins are Fe(II)- and 2-oxoglutarate-dependent dioxygenases that regulate the dynamics of DNA methylation by catalyzing the oxidation of DNA 5-methylcytosine (5mC). To exert physiologically important functions, redox-active iron chelated in the catalytic center of Tet proteins directly involves the oxidation of the multiple substrates. To understand the function and interaction network of Tet dioxygenases, it is interesting to obtain high affinity and a specific inhibitor. Surprisingly, here we found that natural Ni(II) ion can bind to the Fe(II)-chelating motif (HXD) with an affinity of 7.5-fold as high as Fe(II). Consistently, we further found that Ni(II) ion can displace the cofactor Fe(II) of Tet dioxygenases and inhibit Tet-mediated 5mC oxidation activity with an estimated IC 50 of 1.2 μM. Essentially, Ni(II) can be used as a high affinity and selective inhibitor to explore the function and dynamics of Tet proteins.

Effect of the type of metal on the electrical conductivity and thermal properties of metal complexes: The relation between ionic radius of metal complexes and electrical conductivity

NASA Astrophysics Data System (ADS)

Morgan, Sh. M.; El-Ghamaz, N. A.; Diab, M. A.

2018-05-01

Co(II) complexes (1-4) and Ni(II) complexes (5-8) were prepared and characterized by elemental analysis, IR spectra and thermal analysis data. Thermal decomposition of all complexes was discussed using thermogravimetric analysis. The dielectric properties and alternating current conductivity were investigated in the frequency range 0.1-100 kHz and temperature range 300-660 K. The thermal activation energies of electrical conductivity (ΔE1 and ΔE2) values for complexes were calculated and discussed. The values of ΔE1 and ΔE2 for complexes (1-8) were found to decrease with increasing the frequency. Ac electrical conductivity (σac) values increases with increasing temperatures and the values of σac for Co(II) complexes are greater than Ni(II) complexes. Co(II) complexes showed a higher conductivity than other Ni(II) complexes due to the higher crystallinity as confirmed by X-ray diffraction analysis.

Anticancer, antibacterial and antifungal activity of new ni (ii) and cu (ii) complexes of imidazole-phenanthroline derivatives.

PubMed

Moghadam, Mahboube Eslami; Divsalar, Adeleh; Zare, Marziye Shahraki; Gholizadeh, Roghayeh; Mahalleh, Doran; Saghatforosh, Lotfali; Sanati, Soheila

2017-11-02

Two new nickel(II) and copper(II) complexes of 2-(Furan-2-yl)-1H-Imidazo[4,5-f][1,10]Phenanthroline (FIP) and 2-(thiophen-2-yl)-1H-imidazo[4,5-f][1,10]phenanthroline (TIP), imidazophen derivatives were synthesized. The structures of the compounds were determined by UV-visible and FT-IR spectroscopic methods and elemental analysis. The biological activities of Ni and Cu complexes, as anticancer agents, were tested against chronic myelogenous leukemia cell line, K562, at micromolar concentration. The MTT studies showed Cc 50 values are 21 and 160 µM for Cu and Ni(II) complexes, respectively; suggesting that Ni (II) complex has Cc 50 almost seven times of that obtained for cisplatin. Biological activity of the Ni(II) and Cu(II) complexes were also assayed against selective microorganisms by disc diffusion method. These results showed that the Cu(II) complex is antifungal agent but Ni(II) complex has antibacterial activity.

Synthesis, characterization and anti-microbial evaluation of Cu(II), Ni(II), Pt(II) and Pd(II) sulfonylhydrazone complexes; 2D-QSAR analysis of Ni(II) complexes of sulfonylhydrazone derivatives

NASA Astrophysics Data System (ADS)

Özbek, Neslihan; Alyar, Saliha; Alyar, Hamit; Şahin, Ertan; Karacan, Nurcan

2013-05-01

Copper(II), nickel(II), platinum(II) and palladium(II) complexes with 2-hydroxy-1-naphthaldehyde-N-methylpropanesulfonylhydrazone (nafpsmh) derived from propanesulfonic acid-1-methylhydrazide (psmh) were synthesized, their structure were identified, and antimicrobial activity of the compounds was screened against three Gram-positive and three Gram-negative bacteria. The results of antimicrobial studies indicate that Pt(II) and Pd(II) complexes showed the most activity against all bacteria. The crystal structure of 2-hydroxy-1-naphthaldehyde-N-methylpropanesulfonylhydrazone (nafpsmh) was also investigated by X-ray analysis. A series of Ni(II) sulfonyl hydrazone complexes (1-33) was synthesized and tested in vitro against Escherichia coli and Staphylococcus aureus. Their antimicrobial activities were used in the QSAR analysis. Four-parameter QSAR models revealed that nucleophilic reaction index for Ni and O atoms, and HOMO-LUMO energy gap play key roles in the antimicrobial activity.

Metal (II) Complexes Derived from Naphthofuran-2-carbohydrazide and Diacetylmonoxime Schiff Base: Synthesis, Spectroscopic, Electrochemical, and Biological Investigation

PubMed Central

Sumathi, R. B.; Halli, M. B.

2014-01-01

A new Schiff base and a new series of Co(II), Ni(II), Cu(II), Cd(II), and Hg(II) complexes were synthesized by the condensation of naphthofuran-2-carbohydrazide and diacetylmonoxime. Metal complexes of the Schiff base were prepared from their chloride salts of Co(II), Ni(II), Cu(II), Cd(II), and Hg(II) in ethanol. The ligand along with its metal complexes have been characterized on the basis of analytical data, IR, electronic, mass, 1HNMR, ESR spectral data, thermal studies, magnetic susceptibility, and molar conductance measurements. The nonelectrolytic behaviour of the complexes was assessed from the measured low conductance data. The elemental analysis of the complexes confirm the stoichiometry of the type CuL2Cl2 and MLCl2 where M = Ni(II), Co(II), Cd(II), and Hg(II) and L = Schiff base. The redox property of the Cu(II) complex was investigated by electrochemical method using cyclic voltammetry. In the light of these results, Co(II), Ni(II), and Cu(II) complexes are assigned octahedral geometry, Cd(II), and Hg(II) complexes tetrahedral geometry. In order to evaluate the effect of metal ions upon chelation, both the ligand and its metal complexes were screened for their antibacterial and antifungal activities by minimum inhibitory concentration (MIC) method. The DNA cleaving capacity of all the complexes was analysed by agarose gel electrophoresis method. PMID:24592203

Synthesis, characterization and physicochemical studies of new chelating resin 1, 8-(3, 6-dithiaoctyl)-4-polyvinylbenzenesulphonate (dpvbs) and its metallopolymer Cu(II), Ni(II), Co(II) and Fe(III) complexes

NASA Astrophysics Data System (ADS)

Khalil, Tarek E.; Elbadawy, Hemmat A.; El-Dissouky, Ali

2018-02-01

A new chelating resin, 1,8-(3,6-dithiaoctyl)-4-polyvinylbenzenesulphonate (dpvbs) has been synthesized by coupling Amberlite XAD-16 with (2,2‧-ethylenedithio) diethanol using pyridine/CH2Cl2 mixture as a solvent. The chelating resin and its metallopolymer Cu(II), Ni(II), Co(II) and Fe(III) complexes have been synthesized and characterized by EDS, SEM, XPS, elemental analysis, spectral (IR, UV/Vis, EPR). The thermal analysis of the resin and its metallopolymer complexes indicated an endothermic spontaneous sorption mechanism with the liberation of water of hydration of the metal ions and that adsorbed by the free resin. At the solid liquid interface, the degrees of freedom increased during the sorption of the metal ions onto the resin. The surface area of polymer support and its metallopolymer complexes are estimated by (BJH) method. The batch equilibrium method was used for studying the metal sorption and selectivity at different pH values and different contact times at room temperature. ICP-AES was used to estimate the metal capacity of the resin for sorption of Cu(II), Ni(II), Co(II) and Fe(III) from aqueous solutions utilizing the batch equilibrium method. The sorption tendency of the metal ions by the resin was found to be: Cu(II) > Fe(III) > Co(II) > Ni(II). Adsorption kinetics was found to be fit the pseudo-second order model.

Macroscopic and microscopic investigation of Ni(II) sequestration on diatomite by batch, XPS, and EXAFS techniques.

PubMed

Sheng, Guodong; Yang, Shitong; Sheng, Jiang; Hu, Jun; Tan, Xiaoli; Wang, Xiangke

2011-09-15

Sequestration of Ni(II) on diatomite as a function of time, pH, and temperature was investigated by batch, XPS, and EXAFS techniques. The ionic strength-dependent sorption at pH < 7.0 was consistent with outer-sphere surface complexation, while the ionic strength-independent sorption at pH = 7.0-8.6 was indicative of inner-sphere surface complexation. EXAFS results indicated that the adsorbed Ni(II) consisted of ∼6 O at R(Ni-O) ≈ 2.05 Å. EXAFS analysis from the second shell suggested that three phenomena occurred at the diatomite/water interface: (1) outer-sphere and/or inner-sphere complexation; (2) dissolution of Si which is the rate limiting step during Ni uptake; and (3) extensive growth of surface (co)precipitates. Under acidic conditions, outer-sphere complexation is the main mechanism controlling Ni uptake, which is in good agreement with the macroscopic results. At contact time of 1 h or 1 day or pH = 7.0-8.0, surface coprecipitates occur concurrently with inner-sphere complexes on diatomite surface, whereas at contact time of 1 month or pH = 10.0, surface (co)precipitates dominate Ni uptake. Furthermore, surface loading increases with temperature increasing, and surface coprecipitates become the dominant mechanism at elevated temperature. The results are important to understand Ni interaction with minerals at the solid-water interface, which is helpful to evaluate the mobility of Ni(II) in the natural environment.

Synthesis, spectroscopic characterization, first order nonlinear optical properties and DFT calculations of novel Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) complexes with 1,3-diphenyl-4-phenylazo-5-pyrazolone ligand

NASA Astrophysics Data System (ADS)

Abdel-Latif, Samir A.; Mohamed, Adel A.

2018-02-01

Novel Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) metal ions with 1,3-diphenyl-4-phenylazo-5-pyrazolone (L) have been prepared and characterized using different analytical and spectroscopic techniques. 1:1 Complexes of Mn(II), Co(II) and Zn(II) are distorted octahedral whereas Ni(II) complex is square planar and Cu(II) is distorted trigonal bipyramid. 1:2 Complexes of Mn(II), Co(II), Cu(II) and Zn(II) are distorted trigonal bipyramid whereas Ni(II) complex is distorted tetrahedral. All complexes behave as non-ionic in dimethyl formamide (DMF). The electronic structure and nonlinear optical parameters (NLO) of the complexes were investigated theoretically at the B3LYP/GEN level of theory. Molecular stability and bond strengths have been investigated by applying natural bond orbital (NBO) analysis. The geometries of the studied complexes are non-planner. DFT calculations have been also carried out to calculate the global properties; hardness (η), global softness (S) and electronegativity (χ). The calculated small energy gap between HOMO and LUMO energies shows that the charge transfer occurs within the complexes. The total static dipole moment (μtot), the mean polarizability (<α>), the anisotropy of the polarizability (Δα) and the mean first-order hyperpolarizability (<β>) were calculated and compared with urea as a reference material. The complexes show implying optical properties.

Complexes of ditopic carbo- and thio-carbohydrazone ligands--mononuclear, 1D chain, dinuclear and tetranuclear examples.

PubMed

Tandon, Santokh S; Dul, Marie-Claire; Lee, John L; Dawe, Louise N; Anwar, Muhammad U; Thompson, Laurence K

2011-04-14

Ligands based on carbo- and thio-carbohydrazone cores, modified with pyridine, carboxylate and oxime ends, have been examined. They display a tautomeric versatility based on the flexible nature of the hydrazone linkages, leading to varied coordination motifs. Examples of mononuclear (Co(II), Ni(II)), dinuclear (Co(III)), 1D chain (Cu(II)) and square [2 × 2] grid (Ni(II)) complexes are obtained. Ferromagnetic (Cu(II)) and antiferromagnetic (Ni(II)) exchange is observed, with spin coupling in the Ni(II)(4) square grids propagated through the μ-O and μ-S bridges. Weak antiferromagnetic exchange (J = -6.0 cm(-1)) is observed for the μ-O bridged grid, despite the large Ni-O-Ni angles (137-141°), while for the μ-S bridged grids much stronger exchange is observed (J = -148 cm(-1), -198 cm(-1)). This is much larger than expected based on the Ni-S-Ni bridge angles (151-169°), and is associated with the soft (less polarizing than oxygen) nature of the sulfur bridge, which would allow for much more efficient transmission of spin exchange than observed in the μ-O bridged case. Structures and variable temperature magnetic data are included, and spin exchange is analyzed using normal Heisenberg exchange models. No examples involving oxime (NO) bridging are reported, which reflects the positioning of the N,O and N,S donor combinations in each ligand, and the preferred coordination through these donor atoms. © The Royal Society of Chemistry 2011

Synthesis and characterization of homoleptic group 10 dithiocarbamate complexes and heteroleptic Ni(II) complexes, and the use of the homoleptic Ni(II) for the preparation of nickel sulphide nanoparticles

NASA Astrophysics Data System (ADS)

Bobinihi, Felicia F.; Onwudiwe, Damian C.; Hosten, Eric C.

2018-07-01

A series of new dithiocarbamate complexes of Ni(II), Pd(II) and Pt(II) of the form [NiL2], [PdL2] and [PtL2] (where L = N-ethyl-N-ethanoldithiocarbamate) have been synthesized and characterized by elemental analysis, FTIR, and 1H and 13C NMR spectroscopy. The nickel complex was utilized to prepare heteroleptic complexes bearing triphenylphosphino (PPh3) and isothiocyanate (sbnd NCS) or isocyanide (sbnd NC) molecules. Furthermore, the structures of the palladium complex and the heteroleptic nickel with PPh3 and NC molecules have been confirmed by X-ray diffraction. The Pd(II) complex indicated a trans arrangement with a distorted square planar geometry around the Pd atom, while the Ni(II) complex revealed a highly distorted geometry with another molecule of triphenylphosphine moiety, held by hydrogen bonding, within the crystal structure. The thermal stability studies of all the complexes conducted by using thermogravimetric analyser (TGA) showed they all have good stability above 200 °C. The nanoparticles synthesized using the homoleptic nickel complex yielded platelets of pure Heazlewoodite phase of Ni3S2 with average size of 7.60 nm. The optical properties of the nanoparticles studied by using UV-vis spectroscopy showed band gap energy of 4.0 eV (355 nm), which was a blue shift of 1.90 eV compared to the bulk and a consequence of quantum confinement effect.

Theoretical study of the magnetic behavior of hexanuclear Cu(II) and Ni(II) polysiloxanolato complexes.

PubMed

Ruiz, Eliseo; Cano, Joan; Alvarez, Santiago; Caneschi, Andrea; Gatteschi, Dante

2003-06-04

A theoretical density functional study of the exchange coupling in hexanuclear polysiloxanolato-bridged complexes of Cu(II) and Ni(II) is presented. By calculating the energies of three different spin configurations, we can obtain estimates of the first-, second-, and third-neighbor exchange coupling constants. The study has been carried out for the complete structures of the Cu pristine cluster and of the chloroenclathrated Ni complex as well as for the hypotethical pristine Ni compound and for magnetically dinuclear analogues M(2)Zn(4) (M = Cu, Ni).

Efficient removal of nickel(II) from high salinity wastewater by a novel PAA/ZIF-8/PVDF hybrid ultrafiltration membrane.

PubMed

Li, Ting; Zhang, Weiming; Zhai, Shu; Gao, Guandao; Ding, Jie; Zhang, Wenbin; Liu, Yang; Zhao, Xin; Pan, Bingcai; Lv, Lu

2018-06-15

The development of highly efficient membranes, especially those aimed at the removal of trace (ppm, 10 -6 ) heavy metals from high salinity wastewater, is one of the principal challenges in the wastewater treatment field. In this study, a new metal-organic frameworks-based hybrid ultrafiltration membrane (PAA/ZIF-8/PVDF membrane) was prepared, which outperformed some other adsorption materials and owned the first and highest reported nickel ion (Ni(II)) adsorption capacity (219.09 mg/g) in high salinity ([Na + ] = 15000 mg/L) wastewater. Novel and highly efficient hybrid ultrafiltration membrane was facilely fabricated by physically immobilizing zeolitic imidazolate framework-8 (ZIF-8) particles onto the surface of trimesoyl chloride (TMC)-modified polyvinylidene fluoride (PVDF) membrane under the protection of polyacrylic acid (PAA) layer, and possessed a relatively high water flux of ∼460 L m -2 h -1 . The XPS studies revealed that the Ni(II) uptake was mainly attributed to the specific hydrogen bonding interaction between Ni(II) and hydroxyl on ZIF-8 frameworks as well as the electrostatic adsorption by carboxyl groups in PAA layer. Especially, compared to PAA, ZIF-8 could selectively bind with Ni(II) effectively, which was almost not affected by concentrated sodium ion. The filtration study showed that the membrane with an area of 12.56 cm 2 could treat 5.76 L of Ni(II)-contained high salinity wastewater ([Ni(II) = 2 mg/L, [Na + ] = 15000 mg/L) to meet the maximum contaminant level of 0.1 mg/L Ni(II). Moreover, the hybrid membrane can be regenerated several times by HCl-NaCl solution (pH = 5.5) for repeated use under direct current electric field. Thus, the newly developed ZIF-8 hybrid ultrafiltration membrane showed a promising potential for heavy metals containing wastewater treatment. This work provides a worthy reference for designing highly efficient ultrafiltration membranes modified by metal-organic frameworks. Copyright © 2018 Elsevier Ltd. All rights reserved.

Application of mucilage from Dicerocaryum eriocarpum plant as biosorption medium in the removal of selected heavy metal ions.

PubMed

Jones, Bassey O; John, Odiyo O; Luke, Chimuka; Ochieng, Aoyi; Bassey, Bridget J

2016-07-15

The ability of mucilage from Dicerocaryum eriocarpum (DE) plant to act as biosorption medium in the removal of metals ions from aqueous solution was investigated. Functional groups present in the mucilage were identified using Fourier transform infrared spectroscopy (FTIR). Mucilage was modified with sodium and potassium chlorides. This was aimed at assessing the biosorption efficiency of modified mucilage: potassium mucilage (PCE) and sodium mucilage (SCE) and comparing it with non-modified deionised water mucilage (DCE) in the uptake of metal ions. FTIR results showed that the functional groups providing the active sites in PCE and SCE and DCE include: carboxyl, hydroxyl and carbonyl groups. The chloride used in the modification of the mucilage did not introduce new functional groups but increased the intensity of the already existing functional groups in the mucilage. Results from biosorption experiment showed that DE mucilage displays good binding affinity with metals ions [Zn(II), Cd(II) Ni(II), Cr(III) and Fe(II)] in the aqueous solution. Increase in the aqueous solution pH, metal ions initial concentration and mucilage concentration increased the biosorption efficiency of DE mucilage. The maximum contact time varied with each species of metal ions. Optimum pH for [Zn(II), Cd(II) Ni(II) and Fe(II)] occurred at pH 4 and pH 6 for Cr(III). Kinetic models result fitted well to pseudo-second-order with a coefficient values of R(2) = 1 for Cd(II), Ni(II), Cr(III), Fe(II) and R(2) = 0.9974 for Zn(II). Biosorption isotherms conforms best with Freundlich model for all the metal ions with correlation factors of 0.9994, 0.9987, 0.9554, 0.9621 and 0.937 for Zn(II), Ni(II), Fe(II), Cr(III) and Cd(II), respectively. Biosorption capacity of DE mucilage was 0.010, 2.387, 4.902, 0688 and 0.125 for Zn(II), Cr(III), Fe(II), Cd(II) and Ni(II) respectively. The modified mucilage was found to be highly efficient in the removal of metal ions than the unmodified mucilage. Copyright © 2016 Elsevier Ltd. All rights reserved.

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

PubMed

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

2013-03-01

The chelating behavior of ligands based on carbohydrazone core modified with pyridine end towards Co(II), Ni(II) and Cu(II) ions have been examined. The ligands derived from the condensation of carbohydrazide with 2-acetylpyridine (H(2)APC) and 4-acetylpyridine (H(2)APEC). The (1)H NMR, IR data and the binding energy calculations of H(2)APC revealed the presence of two stereoisomers syn and anti in the solid state and in the solution. The (1)H NMR, IR data and the binding energy calculations confirmed the presence of H(2)APEC in one keto form only in the solid state and in the solution. The spectroscopic data confirmed that H(2)APC behaves as a monobasic pentadentate in Co(II) and Cu(II) complexes and as mononegative tetradentate in Ni(II) complex. On the other hand, H(2)APEC acts as a mononegative tridentate in Co(II) complex, neutral tridentate in Ni(II) complex and neutral bidentate in Cu(II) complex. The electronic spectra and the magnetic measurements of complexes as well as the ESR of the copper complexes suggested the octahedral geometry. The bond length and bond angles were evaluated by DFT method using material studio program. The thermal behavior and the kinetic parameters of degradation were determined using Coats-Redfern and Horowitz-Metzger methods. The antioxidant (DDPH and ABTS methods), anti-hemolytic and in vitro Ehrlich ascites of the compounds have been screened. Copyright © 2012 Elsevier B.V. All rights reserved.

Thermodynamic Analysis of Nickel(II) and Zinc(II) Adsorption to Biochar.

PubMed

Alam, Md Samrat; Gorman-Lewis, Drew; Chen, Ning; Flynn, Shannon L; Ok, Yong Sik; Konhauser, Kurt O; Alessi, Daniel S

2018-05-21

While numerous studies have investigated metal uptake from solution by biochar, few of these have developed a mechanistic understanding of the adsorption reactions that occur at the biochar surface. In this study, we explore a combined modeling and spectroscopic approach for the first time to describe the molecular level adsorption of Ni(II) and Zn(II) to five types of biochar. Following thorough characterization, potentiometric titrations were carried out to measure the proton (H + ) reactivity of each biochar, and the data was used to develop protonation models. Surface complexation modeling (SCM) supported by synchrotron-based extended X-ray absorption fine structure (EXAFS) was then used to gain insights into the molecular scale metal-biochar surface reactions. The SCM approach was combined with isothermal titration calorimetry (ITC) data to determine the thermodynamic driving forces of metal adsorption. Our results show that the reactivity of biochar toward Ni(II) and Zn(II) directly relates to the site densities of biochar. EXAFS along with FT-IR analyses, suggest that Ni(II) and Zn(II) adsorption occurred primarily through proton-active carboxyl (-COOH) and hydroxyl (-OH) functional groups on the biochar surface. SCM-ITC analyses revealed that the enthalpies of protonation are exothermic and Ni(II) and Zn(II) complexes with biochar surface are slightly exothermic to slightly endothermic. The results obtained from these combined approaches contribute to the better understanding of molecular scale metal adsorption onto the biochar surface, and will facilitate the further development of thermodynamics-based, predictive approaches to biochar removal of metals from contaminated water.

Vínculos sobre um modelo de quartessência de Chaplygin usando observações do satélite chandra da fração de massa de gás em aglomerados de galáxias

NASA Astrophysics Data System (ADS)

de Souza, R. S.

2003-08-01

Observações de Supernovas do tipo Ia mostram que a expansão do Universo está acelerando. Segundo as equações de Einstein uma componente com pressão negativa (energia escura) é necessária para explicar a aceleração cósmica. Além da energia escura é usualmente admitido que no Universo há também uma matéria exótica com pressão zero, que é chamada de matéria escura. Essa componente possui um papel fundamental na formação de estruturas no Universo. Recentemente tem se explorado a possibilidade de que matéria e energia escura poderiam ser unificadas através de uma única componente, que tem sido denominada de quartessência. Um exemplo de fluido com essas características é o Gás de Chaplygin Generalizado, que possui uma equação de estado da forma p = -A/ra. Inicialmente consideramos o caso especial a = 1 (gás de Chaplygin) e vinculamos parâmetros do modelo utilizando observações em raios-X do satélite Chandra da fração de massa de gás em aglomerados de galáxias. Uma comparação dos vínculos obtidos com esse teste com outros testes, tais como supernovas e idade do Universo, mostra que esse teste é bastante restritivo. Exibiremos ainda resultados para o caso em que a curvatura é nula e o parâmetro a está compreendido no intervalo -1 < a 1.

Synthesis, characterization and antimicrobial studies of Schiff base complexes

NASA Astrophysics Data System (ADS)

Zafar, Hina; Ahmad, Anis; Khan, Asad U.; Khan, Tahir Ali

2015-10-01

The Schiff base complexes, MLCl2 [M = Fe(II), Co(II), Ni(II), Cu(II) and Zn(II)] have been synthesized by the template reaction of respective metal ions with 2-acetylpyrrole and 1,3-diaminopropane in 1:2:1 M ratio. The complexes have been characterized by elemental analyses, ESI - mass, NMR (1H and 13C), IR, XRD, electronic and EPR spectral studies, magnetic susceptibility and molar conductance measurements. These studies show that all the complexes have octahedral arrangement around the metal ions. The molar conductance measurements of all the complexes in DMSO indicate their non-electrolytic nature. The complexes were screened for their antibacterial activity in vitro against Gram-positive (Streptococcus pyogenes) and Gram-negative (Klebsiella pneumoniae) bacteria. Among the metal complexes studied the copper complex [CuLCl2], showed highest antibacterial activity nearly equal to standard drug ciprofloxacin. Other complexes also showed considerable antibacterial activity. The relative order of activity against S. Pyogenes is as Cu(II) > Zn(II) > Co(II) = Fe(II) > Ni(II) and with K. Pneumonia is as Cu(II) > Co(II) > Zn(II) > Fe(II) > Ni(II).

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

NASA Astrophysics Data System (ADS)

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

2015-02-01

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

2,4-Dinitrophenylhydrazine functionalized sodium dodecyl sulfate-coated magnetite nanoparticles for effective removal of Cd(II) and Ni(II) ions from water samples.

PubMed

Sobhanardakani, Soheil; Zandipak, Raziyeh

2015-07-01

2,4-Dinitrophenylhydrazine immobilized on sodium dodecyl sulfate (SDS)-coated magnetite and was used for removal of Cd(II) and Ni(II) ions from aqueous solution. The prepared product was characterized by X-ray diffraction (XRD) analysis, Fourier transform infrared spectroscopy (FT-IR), and scanning electron microscopy (SEM). The size of the nanoparticles according to SEM was obtained around 20-35 nm. In batch tests, the effects of pH, contact time, initial metal concentration, and temperature were studied. The kinetic and equilibrium data were modeled with recently developed models. The adsorption kinetics and isotherms were well fitted by the fractal-like pseudo-second-order model and Langmuir-Freundlich model, respectively. Maximum adsorption capacity by this adsorbent is 255.1 mg g(-1) for Cd(II) ion and 319.6 mg g(-1) for Ni(II) ion at pH 7.0 and 25 °C. The method was successfully applied to the removal of metal cations in real samples (tap water, river water, and petrochemical wastewater).

Coordination behavior of tetraaza [N4] ligand towards Co(II), Ni(II), Cu(II), Cu(I) and Pd(II) complexes: Synthesis, spectroscopic characterization and anticancer activity

NASA Astrophysics Data System (ADS)

El-Boraey, Hanaa A.

2012-11-01

Novel eight Co(II), Ni(II), Cu(II), Cu(I) and Pd(II) complexes with [N4] ligand (L) i.e. 2-amino-N-{2-[(2-aminobenzoyl)amino]ethyl}benzamide have been synthesized and structurally characterized by elemental analysis, spectral, thermal (TG/DTG), magnetic, and molar conductivity measurements. On the basis of IR, mass, electronic and EPR spectral studies an octahedral geometry has been proposed for Co(II), Ni(II) complexes and Cu(II) chloride complex, square-pyramidal for Cu(I) bromide complex. For Cu(II) nitrate complex (6), Pd(II) complex (8) square planar geometry was proposed. The EPR data of Cu(II) complexes in powdered form indicate dx2-y2 ground state of Cu(II) ion. The antitumor activity of the synthesized ligand and some selected metal complexes has been studied. The palladium(II) complex (8) was found to display cytotoxicity (IC50 = 25.6 and 41 μM) against human breast cancer cell line MCF-7 and human hepatocarcinoma HEPG2 cell line.

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

PubMed

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

2015-02-25

The metal complexes of Co(II), Ni(II) and Cu(II) have been synthesized from 6-formyl-7,8-dihydroxy-4-methylcoumarin with o-toluidine/3-aminobenzotrifluoride. The synthesized Schiff bases and their metal complexes were structurally characterized based on IR, (1)H NMR, (13)C NMR, UV-visible, ESR, magnetic, thermal, fluorescence, mass and ESI-MS studies. The molar conductance values indicate that complexes are non-electrolytic in nature. Elemental analysis reveals ML2·2H2O [M = Co(II), Ni(II) and Cu(II)] stoichiometry, where 'L' stands for a singly deprotonated ligand. The presence of co-ordinated water molecules were confirmed by thermal studies. The spectroscopic studies suggest the octahedral geometry. Redox behavior of the complexes were confirmed by cyclic voltammetry. All the synthesized compounds were screened for their antibacterial (Escherichia coli, Pseudomonas auregenosa, klebsiella, Proteus, Staphylococcus aureus and salmonella) antifungal (Candida, Aspergillus niger and Rhizopus), anthelmintic (Pheretima posthuma) and DNA cleavage (Calf Thymus DNA) activity. Copyright © 2014 Elsevier B.V. All rights reserved.

Dye-doped nanostructure polypyrrole film for electrochemically switching solid-phase microextraction of Ni(II) and ICP-OES analysis of waste water.

PubMed

Shamaeli, Ehsan; Alizadeh, Naader

2012-01-01

A nanostructure fiber based on conducting polypyrrole synthesized by an electrochemical method has been developed, and used for electrochemically switching solid-phase microextraction (ES-SPME). The ES-SPME was prepared by the doping of eriochrome blue in polypyrrole (PPy-ECB) and used for selectively extracting the Ni(II) cation in the presence of some transition and heavy metal ions. The cation-exchange behavior of electrochemically prepared polypyrrole on stainless-steel with and without eriochrome blue (ECB) dye was characterized using ICP-OES analysis. The effects of the scan rate for electrochemical synthesis, uptake and the release potential on the extraction behavior of the PPy-ECB conductive fiber were studied. Uptake and release time profiles show that the process of electrically switched cation exchange could be completed within 250 s. The results of the present study point concerning the possibility of developing a selective extraction process for Ni(II) from waste water was explored using such a nanostructured PPy-ECB film through an electrically switched cation exchange. 2012 © The Japan Society for Analytical Chemistry

Synthesis, structural studies and antimicrobial activity of N'-((2Z, 3E)-3-(hydroxyimino)butan-2-ylidene)-2-phenylacetohydrazide and its Co(II), Ni(II) complexes

NASA Astrophysics Data System (ADS)

Karadeniz, Şeyma; Ataol, Cigdem Yuksektepe; Şahin, Onur; İdil, Önder; Bati, Hümeyra

2018-06-01

A new aroylhydrazoneoxime, N'-((2Z, 3E)-3-(hydroxyimino)butan-2-ylidene)-2-phenylacetohydrazide ligand (LH2) and its Ni(II) and Co(II) complexes, have been synthesized and characterized by elemental and thermal analyses, IR and UV-vis spectroscopy, magnetic moment and X-ray diffraction. The antimicrobial activities of these compounds were tested by using minimal inhibitory concentration method (MIC). The ligand-containing aroylhydrazone and oxime groups and its Ni complex crystallize in the triclinic system and P 1 - space group, while its Co complex crystallizes in the monoclinic system and the C 2/c space group. X-ray results show that the ligand in the keto form is transformed into enolic form when it forms coordination. From elemental analysis data, the stoichiometry of Co(II) complex was found to be 1:2 (metal/ligand), but 1:1 for Ni(II). IR spectra indicate that the ligand acts as monoanionic NNO- tridentate and coordination takes place form through the oxime nitrogen, imine nitrogen, and enolate oxygen atoms.

Coordination-driven self-assembly of a novel carbonato-bridged heteromolecular neutral nickel(II) triangle by atmospheric CO2 fixation.

PubMed

Mukherjee, Pampa; Drew, Michael G B; Estrader, Marta; Ghosh, Ashutosh

2008-09-01

Formation of a quasi-symmetrical mu 3-carbonato-bridged self-assembled heteromolecular triangle of Ni(II), [(mu 3-CO 3){Ni 2(salmeNH) 2(NCS) 2}{Ni(salmeNH 2) 2].Et 2O.H 2O (HsalmeNH = 2-[(3-methylamino-propylimino)-methyl]-phenol) involves atmospheric CO 2 uptake in a neutral medium, by spontaneous self-reorganization of the starting mononuclear Ni(II)-Schiff-base complex, [Ni(salmeNH) 2]. The environment around Ni(II) in two of the subunits is different from the third one. The starting complex, [Ni(salmeNH) 2], and one of the possible intermediate species, [Ni(salmeNH 2) 2(NCS) 2], which has a very similar coordination environment to that in the third Ni(II) center, have been characterized structurally. A plausible mechanism for the formation of such a triangle has also been proposed. The compound shows a very strong antiferromagnetic coupling. Fit as a regular triangular arrangement gave J = -53.1, g = 2.24, and R = 1.5 x 10 (-4).

Adsorption of Cu(II), Hg(II), and Ni(II) ions by modified natural wool chelating fibers.

PubMed

Monier, M; Ayad, D M; Sarhan, A A

2010-04-15

The graft copolymerization of ethyl acrylate (EA) onto natural wool fibers initiated by potassium persulphate and Mohr's salt redox initiator system in limited aqueous medium was carried out in heterogeneous media. Ester groups of the grafted copolymers were partially converted into hydrazide function groups followed by hydrazone formation through reaction with isatin. Also the application of the modified fibers for metal ion uptake was studied using Cu(II), Hg(II) and Ni(II). The modified chelating fibers were characterized using FTIR spectroscopy, SEM and X-ray diffraction. 2009 Elsevier B.V. All rights reserved.

EPR, UV-vis, magnetic, spectral studies and electrochemical behaviour of mononuclear transition metal complexes derived from novel hexa-aza-macrotricyclic ligand

NASA Astrophysics Data System (ADS)

Chandra, Sulekh; Gupta, Nidhi; Gupta, Rachna; Bawa, Sukhwant Singh

2005-11-01

Aza-macrocyclic complexes have gained importance because of their pharmacological properties [N.K. Singh, Srivastava, Trans. Met. Chem. 25 (2000) 133]. Hexa-aza-macrocyles containing glutarimide efficiently coordinate as hexa-dentate ligand, to give complexes of Cu(II) possessing tetragonal structure and Mn(II), Co(II) and Ni(II) metal ions that are essentially octahedral. Spectroscopic, and chemical characterizations of these systems are presented in this article. For Ni(II) complexes results on electron transfer processes measured by cyclic voltammetry and colourimetry have been studied.

Synthesis of first row transition metal selenomaltol complexes.

PubMed

Spiegel, Michael T; Hoogerbrugge, Amanda; Truksa, Shamus; Smith, Andrew G; Shuford, Kevin L; Klausmeyer, Kevin K; Farmer, Patrick J

2018-06-21

We report an efficient, one-step synthesis of the chelator 3-hydroxy-2-methyl-4-selenopyrone (selenomaltol). Complexes of selenomaltol with Fe(iii), Ni(ii), Cu(ii) and Zn(ii) have been prepared and studied by NMR, X-ray crystallography, cyclic voltammetry, EPR and electronic absorption. The Ni(ii) and Cu(ii) complexes show chemically reversible oxidations which are suggested to be ligand-based. Nuclear independent chemical shifts (NICS) analysis is used to compare aromaticity of the heterocyclic rings of selenomaltol and its chelates. The compounds described here should significantly expand the scope and utility of unusual O,Se-donor chelates.

Relationship between Ni(II) and Zn(II) Coordination and Nucleotide Binding by the Helicobacter pylori [NiFe]-Hydrogenase and Urease Maturation Factor HypB*

PubMed Central

Sydor, Andrew M.; Lebrette, Hugo; Ariyakumaran, Rishikesh; Cavazza, Christine; Zamble, Deborah B.

2014-01-01

The pathogen Helicobacter pylori requires two nickel-containing enzymes, urease and [NiFe]-hydrogenase, for efficient colonization of the human gastric mucosa. These enzymes possess complex metallocenters that are assembled by teams of proteins in multistep pathways. One essential accessory protein is the GTPase HypB, which is required for Ni(II) delivery to [NiFe]-hydrogenase and participates in urease maturation. Ni(II) or Zn(II) binding to a site embedded in the GTPase domain of HypB modulates the enzymatic activity, suggesting a mechanism of regulation. In this study, biochemical and structural analyses of H. pylori HypB (HpHypB) revealed an intricate link between nucleotide and metal binding. HpHypB nickel coordination, stoichiometry, and affinity were modulated by GTP and GDP, an effect not observed for zinc, and biochemical evidence suggests that His-107 coordination to nickel toggles on and off in a nucleotide-dependent manner. These results are consistent with the crystal structure of HpHypB loaded with Ni(II), GDP, and Pi, which reveals a nickel site distinct from that of zinc-loaded Methanocaldococcus jannaschii HypB as well as subtle changes to the protein structure. Furthermore, Cys-142, a metal ligand from the Switch II GTPase motif, was identified as a key component of the signal transduction between metal binding and the enzymatic activity. Finally, potassium accelerated the enzymatic activity of HpHypB but had no effect on the other biochemical properties of the protein. Altogether, this molecular level information about HpHypB provides insight into its cellular function and illuminates a possible mechanism of metal ion discrimination. PMID:24338018

Relationship between Ni(II) and Zn(II) coordination and nucleotide binding by the Helicobacter pylori [NiFe]-hydrogenase and urease maturation factor HypB.

PubMed

Sydor, Andrew M; Lebrette, Hugo; Ariyakumaran, Rishikesh; Cavazza, Christine; Zamble, Deborah B

2014-02-14

The pathogen Helicobacter pylori requires two nickel-containing enzymes, urease and [NiFe]-hydrogenase, for efficient colonization of the human gastric mucosa. These enzymes possess complex metallocenters that are assembled by teams of proteins in multistep pathways. One essential accessory protein is the GTPase HypB, which is required for Ni(II) delivery to [NiFe]-hydrogenase and participates in urease maturation. Ni(II) or Zn(II) binding to a site embedded in the GTPase domain of HypB modulates the enzymatic activity, suggesting a mechanism of regulation. In this study, biochemical and structural analyses of H. pylori HypB (HpHypB) revealed an intricate link between nucleotide and metal binding. HpHypB nickel coordination, stoichiometry, and affinity were modulated by GTP and GDP, an effect not observed for zinc, and biochemical evidence suggests that His-107 coordination to nickel toggles on and off in a nucleotide-dependent manner. These results are consistent with the crystal structure of HpHypB loaded with Ni(II), GDP, and Pi, which reveals a nickel site distinct from that of zinc-loaded Methanocaldococcus jannaschii HypB as well as subtle changes to the protein structure. Furthermore, Cys-142, a metal ligand from the Switch II GTPase motif, was identified as a key component of the signal transduction between metal binding and the enzymatic activity. Finally, potassium accelerated the enzymatic activity of HpHypB but had no effect on the other biochemical properties of the protein. Altogether, this molecular level information about HpHypB provides insight into its cellular function and illuminates a possible mechanism of metal ion discrimination.

Simulation of water solutions of Ni 2+ at infinite dilution

NASA Astrophysics Data System (ADS)

Natália, M.; Cordeiro, D. S.; Ignaczak, Anna; Gomes, José A. N. F.

1993-10-01

A new ab initio pair potential is developed to describe the nickel—water interactions in Ni(II) aqueous solutions. Results of Monte Carlo simulations for the Ni(II)(H 2O) 200 system are presented for this pair potential with and without three-body classical polarization terms (the water—water interaction is described by the ab initio MCY potential). The structure of the solution around Ni(II) is discussed in terms of radial distribution functions, coordination numbers and thermal ellipsoids. The results show that the three-body terms have a non-negligible effect on the simulated solution. In fact, the experimental coordination number of six is reproduced with the full potential while a higher value is predicted when the simple pairwise-additive potential is used. The equilibrium NiO distance for the first hydration shell is also dependent on the use of the three-body terms. Comparison of our distribution functions with those obtained by neutron-diffraction experiments shows a reasonable quantitative agreement. Statistical pattern recognition analysis has also been applied to our simulations in order to better understand the local thermal motion of the water molecules around the metal ion. In this way, thermal ellipsoids have been computed (and graphically displayed) for each atom of the water molecules belonging to the Ni(II) first hydration shell. This analysis revealed that the twisting and bending motions are greater than the radial motion, and that the hydrogens have a higher mobility than the oxygens. In addition, a thermodynamic perturbation method has been incorporated in our Monte Carlo procedure in order to compute the free energy of hydration for the Ni(II) ion. Agreement between these results and the experimental ones is also sufficiently reasonable to demonstrate the feasibility of this new potential for the nickel—water interactions.

Synthesis, spectroscopic characterization, DFT calculations and biological evaluation of benzothiazole derivative bearing Mn(II) and Ni(II) metal ions

NASA Astrophysics Data System (ADS)

El-Gamel, Nadia E. A.; Ali, Korany A.

2017-11-01

N-(benzo[d]thiazol-2-yl)-3-oxo-3-phenylpropanamide ligand and its Nickel and Manganese complexes have been synthesized and characterized by elemental and thermal analyses, IR, diffuse reflectance, mass and UV-Vis spectra, molar conductance and magnetic moment measurements. The decomposition mechanism and thermal stability of the investigated complexes are interpreted in terms of their structures. The thermal behaviour of the complexes has been studied and different thermodynamic parameters are calculated using Coats-Redfern method. N-(benzo[d]thiazol-2-yl)-3-oxo-3-phenylpropanamide is a neutral bidentate ligand coordinating metal ions via thiazole ring nitrogen and amide carbonyl O forming high spin octahedral complexes with Mn(II) (2) and distorted square planar in case of Ni(II) (1). Natural bond orbital analysis and geometry optimization were carried out at DFT/B3LYP/6-31G(d) level of theory for the ligand and the mentioned complexes. Ab inito computations at the HF/6-31G(d) level of the theory is conducted in order to detect any probability of a hydrogen bond formation in the ligand. The dipole moment of the Ni(II) and Mn(II) complexes is recorded to be 9.69 and 7.39 Debye, respectively, indicating that the complexes are more polarized than the ligand 2.39 Debye. The in vitro biological activity of the metal chelates is screened against the Gram-positive bacteria (Staphylococcus aureus) and Gram-negative bacteria (Escherichia coli), fungus (Aspergillus flavus, Candida albicans). Ni(II) complexes displayed the highest activity against Candida albicans and Staphylococcus aureus with MIC values of 13, 30 μg/cm3, respectively.

Synthesis, characterization and anti-microbial activity of a novel macrocyclic ligand derived from the reaction of 2,6-pyridinedicarboxylic acid with homopiperazine and its Co(II), Ni(II), Cu(II), and Zn(II) complexes

NASA Astrophysics Data System (ADS)

Soleimani, Esmaiel

2011-05-01

The preparation of a novel macrocyclic ligand ( 1), N,N'-diethylhomopiperazinyl,2,6-pyridinedicarboxylate and its Co(II), Ni(II), Cu(II), and Zn(II) complexes are described. The ligand was prepared in EtOH from the reaction of dipotassium salt of 2,6-pyridinedicarboxylic acid with 1,2-dibromoethane in the presence of homopiperazine. Reaction of macrocyclic ligand ( 1) in EtOH with CoCl 2.6H 2O, NiCl 2.6H 2O, CuCl 2.2H 2O, and ZnCl 2·2H 2O yielded the complexes with the general formula [M(L)Cl 2] {where M = Co(II) ( 2), Ni(II) ( 3), Cu(II) ( 4), Zn ( 5), respectively}. The analysis of IR, 1H and 13C NMR spectral data of macrocyclic ligand ( 1) and its Zn(II) complex ( 5) together with their molar conductivity values, and the magnetic moments of the complexes suggest that the macrocyclic ligand ( 1) is bonded to metal(II) ions through two oxygen atoms of ester moiety and the two nitrogen atoms of homopiperazine ring. The electronic spectral data of these complexes in DMSO are in good agreement with the octahedral coordination of M(II) ions. The ligand field parameters for these complexes, i.e. splitting energy and Racah parameter were calculated to be 14,945 and 673 cm -1 for the Co(II) ( 2), 16,260 and 774 cm -1 for the Ni(II) ( 3) complexes respectively. The spliting energy of 17,262 cm -1 was obtained for the Cu(II) complex ( 4).

Life-cycle optimization model for distributed generation in buildings

NASA Astrophysics Data System (ADS)

Safaei, Amir

O setor da construcao e responsavel por uma grande parte do consumo de energia e emissoes na Uniao Europeia. A Geracao Distribuida (GD) de energia, nomeadamente atraves de sistemas de cogeracao e tecnologias solares, representa um papel importante no futuro energetico deste setor. A otimizacao do funcionamento dos sistemas de cogeracao e uma tarefa complexa, devido as diversas variaveis em jogo, designadamente: os diferentes tipos de necessidades energeticas (eletricidade, aquecimento e arrefecimento), os precos dinamicos dos combustiveis (gas natural) e da eletricidade, e os custos fixos e variaveis dos diferentes sistemas de GD. Tal torna-se mais complexo considerando a natureza flutuante das tecnologias solares termicas e fotovoltaicas. Ao mesmo tempo, a liberalizacao do mercado da eletricidade permite exportar para a rede, a electricidade gerada localmente. Adicionalmente, a operacao estrategica de um sistema de GD deve atender aos quadros politicos nacionais, se tiver como objetivo beneficiar de tais regimes. Alem disso, considerando os elevados impactes ambientais do setor da construcao, qualquer avaliacao energetica de edificios rigorosa deve tambem integrar aspetos ambientais, utilizando uma abordagem de Ciclo de Vida (CV). Uma avaliacao de Ciclo de Vida (ACV) completa de um sistema de GD deve incluir as fases relativas a operacao e construcao do sistema, bem como os impactes associados a producao dos combustiveis. Foram analisadas as emissoes da producao de GN, as quais variam de acordo com a origem, tipo (convencional ou nao-convencional), e estado (na forma de GN Liquefeito (GNL) ou gas). Do mesmo modo, o impacte dos sistemas solares e afetado pela meteorologia e radiacao solar, de acordo com a sua localizacao geografica. Sendo assim, uma avaliacao adequada dos sistemas de GD exige um modelo de ACV adequado a localizacao geografica (Portugal), integrando tambem a producao de combustivel (GN), tendo em conta as suas diferentes fontes de abastecimento. O principal objetivo desta tese de doutoramento foi desenvolver um modelo para otimizar o desenho e operacao de sistemas de GD para o setor da construcao de edificios comerciais em Portugal, considerando os respetivos Impactes de Ciclo de Vida (IAVC) e Custos de Ciclo de Vida (CCV), de modo a satisfazer as necessidades energeticas do edificio. Tres tipos de tecnologias de cogeracao (Micro-Turbinas, Motores de combustao interna, e Celulas combustiveis de Oxido solido), e dois tipos de tecnologias de energia solar, solar termica e fotovoltaica, constituem os sistemas de GD que sao acoplados aos sistemas convencionais. Foi desenvolvido um modelo de CV, tendo em conta todos os impactes relacionados com a construcao e operacao dos sistemas de energia, bem como os processos a montante relacionados com a producao do GN. Em particular, o mix de GN consumido em Portugal em 2011 foi identificado (60% da Nigeria, 40% da Argelia) e os impactes relativos a cada uma das vias de abastecimento foram avaliados separadamente para quatro categorias de impacte ambiental: Consumo de Energia Primaria (CEP), Gases com Efeito de Estufa (GEE), acidificacao, e eutrofizacao. Devido a importancia das emissoes de GEE na formulacao de politicas, foi tambem realizada uma analise de incerteza as emissoes de GEE do GN fornecido a Portugal. Foi desenvolvido um modelo matematico, em linguagem de Programacao General Algebraic Modeling System (GAMS), que utiliza os resultados da ACV dos sistemas de energia e as suas implicacoes economicas para minimizar o CCV e IACV ao longo de um horizonte de planeamento definido pelo decisor. Foram derivadas fronteiras otimas de Pareto, representando as relacoes entre o tipo de IACV (CEP, GEE, acidificacao, eutrofizacao) e CCV decorrentes da satisfacao das necessidades energeticas do edificio. Para aumentar a robustez do modelo, dada a incerteza dos precos dos combustiveis (GN e eletricidade), foi desenvolvido um modelo de custos robusto para os sistemas de GD, que e menos afetado por perturbacoes relativas aos custos de combustivel. A aplicacao do modelo proposto foi testada num caso de estudo real, um edificio comercial localizado na cidade de Coimbra, em Portugal.

2,6-Diiminopiperidin-1-ol: an overlooked motif relevant to uranyl and transition metal binding on poly(amidoxime) adsorbents

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kennedy, Zachary C.; Cardenas, Allan Jay P.; Corbey, Jordan F.

2016-01-01

Glutardiamidoxime, a structural motif on sorbents used in uranium extraction from seawater, was discovered to cyclize in situ at room temperature to 2,6-diimino-piperidin-1-ol in the presence of uranyl nitrate. The new diimino motif was also generated when exposed to competing transition metals Cu(II) and Ni(II). Multinuclear μ-O bridged U(VI), Cu(II), and Ni(II) complexes featuring bound diimino ligands were isolated. A Cu(II) complex with the historically relevant cyclic imide dioxime motif is also reported for structural comparison to the reported diimino complexes.

Selective adsorption of Pb(II), Cd(II), and Ni(II) ions from aqueous solution using chitosan-MAA nanoparticles.

PubMed

Heidari, Aghdas; Younesi, Habibollah; Mehraban, Zahra; Heikkinen, Harri

2013-10-01

Chitosan-MAA nanoparticles (CS-MAA) with an average size of 10-70 nm were prepared by polymerizing chitosan with methacrylic acid in aqueous solution. The physicochemical properties of nanoparticles were investigated using Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), dynamic light scattering (DLS) and nuclear magnetic resonance (NMR). The adsorption of Pb(II), Cd(II) and Ni(II) from aqueous solution on CS-MAA was studied in a batch system. The effects of the solution pH, initial metal concentration, contact time, and dosage of the adsorbent on the adsorption process were examined. The experimental data were analyzed using the pseudo-second-order kinetic equations and the Langmuir, Freundlich and Redlish-Peterson isotherms. The maximum adsorption capacity was 11.30, 1.84, and 0.87 mg/g for Pb(II), Cd(II) and Ni(II) ions, respectively, obtained by the Langmuir isotherm. However, the adsorption isotherm was better explained by the Freundlich rather than by the Langmuir model, as the high correlation coefficients (R(2)>0.99) were obtained at a higher confidence level. Copyright © 2013 Elsevier B.V. All rights reserved.

Oxidative Stress Level in the Testes of Mice and Rats during Nickel Intoxication

PubMed Central

Murawska-Ciałowicz, Eugenia; Bal, Wojciech; Januszewska, Lidia; Zawadzki, Marcin; Rychel, Joanna; Zuwała-Jagiełło, Jolanta

2012-01-01

The genotioxic and carcinogenic effect of nickel probably results from its capacity to produce reactive oxygen species (ROS) and disturb the redox balance. The aim of the study was to find out if rats lacking spermatic protamine 2 are less susceptible to Ni(II) than mice. Consequently, the levels of malondialdehyde + 4 hydroxynonenal (MDA+4HDA) − markers of lipid peroxidation, as well as the level of reduced glutathione (GSH) were measured within the rat and mouse testes. Our results showed that the levels of lipid peroxidation markers were elevated in testicular homogenates of intoxicated mice without any changes in rats. GSH level was lower in the group of intoxicated mice comparing to the control without statistically significant changes in rats' homogenates. Moreover, the level of GSH in the testes of intoxicated mice was lower than in rats. On the basis of our results, it appears that Ni(II) can initiate oxidative stress in the testes of mice but not of rats and can reduce GSH level. Consequently, the antioxidative defense of the testes is reduced. Ni(II) that causes oxidative stress in the testes may also contribute to infertility. PMID:22448131

Removal of copper and nickel from water using nanocomposite of magnetic hydroxyapatite nanorods

NASA Astrophysics Data System (ADS)

Thanh, Dong Nguyen; Novák, Pavel; Vejpravova, Jana; Vu, Hong Nguyen; Lederer, Jaromír; Munshi, Tasnim

2018-06-01

A nanocomposite of magnetic hydroxyapatite was synthesized and tested as an adsorbent for the removal of copper (Cu (II)) and nickel (Ni(II)) from aqueous solution. The adsorbent was investigated using Transmission Electron Microscopy (TEM), Scanning Electron Microscopy equipped with an Energy Dispersive Spectrometer (SEM/EDS), X-ray powder diffraction (XRD) and the Brunauer-Elmet-Teller nitrogen adsorption technique (BET-N2 adsorption). Batch experiments were carried out to determine and compare the adsorption parameters of Fe3O4 and its composite with hydroxyapatite. It was found that the adsorbent is nanostructured and has a specific surface area of 101.2 m2 g-1. The Langmuir adsorption isotherm was found to be an appropriate model to describe the adsorption processes, showing the adsorption capacities of Cu(II) and Ni(II) of 48.78 mg g-1 and 29.07 mg g-1, respectively. In addition to the high adsorption capacity, the fully-adsorbed material could be easily separated from aqueous media using an external magnetic field. These results suggested that the utilization of new hydroxyapatite - Fe3O4 nanocomposite for the removal of Cu(II) and Ni(II) is a promising method in water technology.

Synthesis, structural and fungicidal studies of hydrazone based coordination compounds

NASA Astrophysics Data System (ADS)

Sharma, Amit Kumar; Chandra, Sulekh

2013-02-01

The coordination compounds of the Co(II), Ni(II) and Cu(II) metal ions derived from imine based ligand, benzil bis(carbohydarzone) were structurally and pharmaceutically studied. The compounds have the general stoichiometry [M(L)]X2 and [Co(L)X2], where M = Ni(II) and Cu(II), and X=NO3- and Cl- ions. The analytical techniques like elemental analyses, molar conductance measurements, magnetic susceptibility measurements, IR, UV/Visible, NMR, ESI mass and EPR were used to study the compounds. The key IR bands, i.e., amide I, amide II and amide III stretching vibrations accounts for the tetradentate metal binding nature of the ligand. The electronic and EPR spectral results suggest the square planar Ni(II) and Cu(II) complexes (giso = 2.11-2.22) and tetragonal geometry Co(II) complexes (giso = 2.10-2.17). To explore the compounds in the biological field, they were examined against the opportunistic pathogens, i.e., Alternaria brassicae, Aspergillus niger and Fusarium oxysporum. The partial covalent character of metal-ligand bond is supported by the orbital reduction factor k (0.62-0.92) and nephalauxetic parameter β (0.55-0.57).

Rates of nickel(II) capture from complexes with NTA, EDDA, and related tetradentate chelating agents by the hexadentate chelating agents EDTA and CDTA: Evidence of a "semijunctive" ligand exchange pathway

NASA Astrophysics Data System (ADS)

Boland, Nathan E.; Stone, Alan T.

2017-09-01

Many siderophores and metallophores produced by soil organisms, as well as anthropogenic chelating agent soil amendments, rely upon amine and carboxylate Lewis base groups for metal ion binding. UV-visible spectra of metal ion-chelating agent complexes are often similar and, as a consequence, whole-sample absorbance measurements are an unreliable means of monitoring the progress of exchange reactions. In the present work, we employ capillary electrophoresis to physically separate Ni(II)-tetradentate chelating agent complexes (NiL) from Ni(II)-hexadentate chelating agent complexes (NiY) prior to UV detection, such that progress of the reaction NiL + Y → NiY + L can be conveniently monitored. Rates of ligand exchange for Ni(II) are lower than for other +II transition metal ions. Ni(II) speciation in environmental media is often under kinetic rather than equilibrium control. Nitrilotriacetic acid (NTA), with three carboxylate groups all tethered to a central amine Lewis base group, ethylenediamine-N,N‧-diacetic acid (EDDA), with carboxylate-amine-amine-carboxylate groups arranged linearly, plus four structurally related compounds, are used as tetradentate chelating agents. Ethylenediaminetetraacetic acid (EDTA) and the structurally more rigid analog trans-cyclohexaneethylenediaminetetraacetic acid (CDTA) are used as hexadentate chelating agents. Effects of pH and reactant concentration are explored. Ni(II) capture by EDTA was consistently more than an order of magnitude faster than capture by CDTA, and too fast to quantify using our capillary electrophoresis-based technique. Using NiNTA as a reactant, Ni(II) capture by CDTA is independent of CDTA concentration and greatly enhanced by a proton-catalyzed pathway at low pH. Using NiEDDA as reactant, Ni(II) capture by CDTA is first order with respect to CDTA concentration, and the contribution from the proton-catalyzed pathway diminished by CDTA protonation. While the convention is to assign either a disjunctive pathway or adjunctive pathway to multidentate ligand exchange reactions, our results indicate that a third "semijunctive" pathway is necessary to account for slow reactions progressing through Lsbnd Nisbnd Y ternary complexes. Ligand exchange pathways with NTA-type chelating agents are assigned a disjunctive pathway, while pathways with EDDA-type chelating agents are assigned a semijunctive pathway. Based upon operative mechanism(s), magnitudes of exchange rates and effects of ambient geochemical conditions can be predicted.

Synthesis, characterization, and ligand exchange reactivity of a series of first row divalent metal 3-hydroxyflavonolate complexes.

PubMed

Grubel, Katarzyna; Rudzka, Katarzyna; Arif, Atta M; Klotz, Katie L; Halfen, Jason A; Berreau, Lisa M

2010-01-04

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) < Cu(II) < Zn(II) < Co(II). The hypsochromic shift of the absorption band I (pi-->pi*) of the coordinated flavonolate ligand in 1-5-OTf (relative to that in free anion) increases in the order Ni(II) < Mn(II) < Cu(II) < Zn(II), Co(II). Previously reported 3-Hfl complexes of divalent 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)Fe(3-Hfl)]ClO(4) (8), was isolated and characterized by elemental analysis, FTIR, UV-vis, (1)H NMR, cyclic voltammetry, and a magnetic moment measurement. This complex reacts with O(2) to produce the diiron(III) mu-oxo compound [(6-Ph(2)TPAFe(3Hfl))(2)(mu-O)](ClO(4))(2) (6).

Thermodynamic Characteristics of Reactions of the Formation of Complexes between Triglycine and Ni2+ Ions in Aqueous Solution

NASA Astrophysics Data System (ADS)

Gorboletova, G. G.; Metlin, A. A.; Bychkova, S. A.

2018-05-01

Thermal effects of reactions of the formation of complexes between Ni(II) and triglycine are determined via direct calorimetry in aqueous solutions at 298.15 K and ionic strengths of 0.2, 0.5, and 1.0 (KNO3). Standard thermodynamic characteristics (Δr H°, Δr G°, Δr S°) of complexing processes in the investigated systems are calculated. The structures of triglycinate complexes NiL+, NiH-1L, NiL2, NiH-2L2- 2, NiL- 3, and NiH-3L4- 3 are introduced to compare the obtained values and data on the thermodynamics of triglycinate complexes of Ni(II).

Synthesis and Adsorption Properties of 4-Vinylpyridine and Styrene Copolymer In Situ Immobilized on Silica Surface

NASA Astrophysics Data System (ADS)

Yanovska, E. S.; Vretik, L. O.; Nikolaeva, O. A.; Polonska, Y.; Sternik, D.; Kichkiruk, O. Yu.

2017-03-01

Copolymer of 4-vinylpyridine with styrene was in situ immobilized on silica gel surface via the heterogeneous radical polymerization. Anchorage of the copolymer on the surface layer was confirmed by IR spectroscopy. The quantity of copolymer on the silica gel surface was evaluated as 25.73 wt.% by TG and DSC-MS analysis. "Islet" location of polymer layer on the silica surface was confirmed by the scanning electron microscopy. A high adsorption activity of silica gel with immobilized copolymer towards microquantitatives of Cu(II), Cd(II), Pb(II), Fe(III), and Ni(II) ions in steady state conditions as well as of Ni(II) ions in dynamic regime was found.

Synthesis and Adsorption Properties of 4-Vinylpyridine and Styrene Copolymer In Situ Immobilized on Silica Surface.

PubMed

Yanovska, E S; Vretik, L O; Nikolaeva, O A; Polonska, Y; Sternik, D; Kichkiruk, O Yu

2017-12-01

Copolymer of 4-vinylpyridine with styrene was in situ immobilized on silica gel surface via the heterogeneous radical polymerization. Anchorage of the copolymer on the surface layer was confirmed by IR spectroscopy. The quantity of copolymer on the silica gel surface was evaluated as 25.73 wt.% by TG and DSC-MS analysis. "Islet" location of polymer layer on the silica surface was confirmed by the scanning electron microscopy. A high adsorption activity of silica gel with immobilized copolymer towards microquantitatives of Cu(II), Cd(II), Pb(II), Fe(III), and Ni(II) ions in steady state conditions as well as of Ni(II) ions in dynamic regime was found.

Structural and Biological Behaviour of Co(II), Cu(II) and Ni(II) Metal Complexes of Some Amino Acid Derived Schiff-Bases

PubMed Central

Chohan, Zahid H.; Praveen, M.; Ghaffar, A.

1997-01-01

Biologically active tridentate amino acid (Alanine, Glycine & Tyrosine) derived Schiff-bases and their Co(II), Cu(II) & Ni(II) complexes have been synthesised and characterised on the basis of their conductance and magnetic measurements, elemental analysis and 13C-NMR, 1H-NMR, IR and electronic spectral data. These Schiff-bases and their complexes have been evaluated for their antibacterial activity against bacterial species such as Staphylococcus aureus, Escherichia coli, Klebsiella pneumonae, Proteus vulgarus and Pseudomonas aeruginosa and this activity data show the metal complexes to be more antibacterial than the Schiff-bases against one or more bacterial species. PMID:18475798

Synthesis, Spectroscopic, and Antimicrobial Studies on Bivalent Nickel and Copper Complexes of Bis(thiosemicrbazone)

PubMed Central

Chandra, Sulekh; Raizada, Smriti; Tyagi, Monika; Gautam, Archana

2007-01-01

A series of metal complexes of Cu(II) and Ni(II) having the general composition [M(L)X2] with benzil bis(thiosemicarbazone) has been prepared and characterized by element chemical analysis, molar conductance, magnetic susceptibility measurements, and spectral (electronic, IR, EPR, mass) studies. The IR spectral data suggest the involvement of sulphur and azomethane nitrogen in coordination to the central metal ion. On the basis of spectral studies, an octahedral geometry has been assigned for Ni(II) complexes but a tetragonal geometry for Cu(II) complexes. The free ligand and its metal complexes have been tested in vitro against a number of microorganisms in order to assess their antimicrobial properties. PMID:18273385

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

NASA Astrophysics Data System (ADS)

Chandra, Sulekh; Kumar, Anil

2007-12-01

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

Synthesis, spectroscopic, anticancer, antibacterial and antifungal studies of Ni(II) and Cu(II) complexes with hydrazine carboxamide, 2-[3-methyl-2-thienyl methylene

NASA Astrophysics Data System (ADS)

Chandra, Sulekh; Vandana; Kumar, Suresh

2015-01-01

Schiff's base ligand(L) hydrazine carboxamide, 2-[3-methyl-2-thienyl methylene] and its metal complexes have been synthesized and characterized by elemental analysis, molar conductance, various spectroscopic techniques such as electronic, IR, 1H NMR, mass, EPR. Molar conductance of complexes in DMF solution corresponds to non-electrolyte. Complexes have general composition [M(L)2X2], where M = Ni(II) and Cu(II), X = Cl-, NO3-, CH3COO- and ½SO42-. On the basis of above spectral studies, an octahedral geometry has been assigned for Ni(II) complexes and tetragonal geometry for Cu(II) complexes except [Cu(L)2SO4] which possesses five coordinated trigonal bipyramidal geometry. These metal complexes were also tested for their anticancer, antibacterial and antifungal activities to assess their inhibition potential. Anticancer activity of ligand and its metal complexes were evaluated using SRB fluorometric assay and Adriamycin (ADR) was applied as positive control. Schiff's base ligand and its metal complexes were screened for their antibacterial and antifungal activity against Escherichia coli, Bacillus cereus and Aspergillus niger, Aspergillus flavus, respectively. Kirby-Bauer single disk susceptibility test was used for antibacterial activity and well diffusion method for antifungal activity of the compounds on the used fungi.

Effects of metal on the biochemical properties of Helicobacter pylori HypB, a maturation factor of [NiFe]-hydrogenase and urease.

PubMed

Sydor, Andrew M; Liu, Jenny; Zamble, Deborah B

2011-03-01

The biosyntheses of the [NiFe]-hydrogenase and urease enzymes in Helicobacter pylori require several accessory proteins for proper construction of the nickel-containing metallocenters. The hydrogenase accessory proteins HypA and HypB, a GTPase, have been implicated in the nickel delivery steps of both enzymes. In this study, the metal-binding properties of H. pylori HypB were characterized, and the effects of metal binding on the biochemical behavior of the protein were examined. The protein can bind stoichiometric amounts of Zn(II) or Ni(II), each with nanomolar affinity. Mutation of Cys106 and His107, which are located between two major GTPase motifs, results in undetectable Ni(II) binding, and the Zn(II) affinity is weakened by 2 orders of magnitude. These two residues are also required for the metal-dependent dimerization observed in the presence of Ni(II) but not Zn(II). The addition of metals to the protein has distinct impacts on GTPase activity, with zinc significantly reducing GTP hydrolysis to below detectable levels and nickel only slightly altering the k(cat) and K(m) of the reaction. The regulation of HypB activities by metal binding may contribute to the maturation of the nickel-containing enzymes.

Protein Tunnels: The Case of Urease Accessory Proteins.

PubMed

Musiani, Francesco; Gioia, Dario; Masetti, Matteo; Falchi, Federico; Cavalli, Andrea; Recanatini, Maurizio; Ciurli, Stefano

2017-05-09

Transition metals are both essential micronutrients and limited in environmental availability. The Ni(II)-dependent urease protein, the most efficient enzyme known to date, is a paradigm for studying the strategies that cells use to handle an essential, yet toxic, metal ion. Urease is a virulence factor of several human pathogens, in addition to decreasing the efficiency of soil organic nitrogen fertilization. Ni(II) insertion in the urease active site is performed through the action of three essential accessory proteins: UreD, UreF, and UreG. The crystal structure of the UreD-UreF-UreG complex from the human pathogen Helicobacter pylori (HpUreDFG) revealed the presence of tunnels that cross the entire length of both UreF and UreD, potentially able to deliver Ni(II) ions from UreG to apo-urease. Atomistic molecular dynamics simulations performed on the HpUreDFG complex in explicit solvent and at physiological ionic conditions demonstrate the stability of these protein tunnels in solution and provide insights on the trafficking of water molecules inside the tunnels. The presence of different alternative routes across the identified tunnels for Ni(II) ions, water molecules, and carbonate ions, all involved in urease activation, is highlighted here, and their potential role in the urease activation mechanism is discussed.

Kinetic and structural studies reveal a unique binding mode of sulfite to the nickel center in urease.

PubMed

Mazzei, Luca; Cianci, Michele; Benini, Stefano; Bertini, Leonardo; Musiani, Francesco; Ciurli, Stefano

2016-01-01

Urease is the most efficient enzyme known to date, and catalyzes the hydrolysis of urea using two Ni(II) ions in the active site. Urease is a virulence factor in several human pathogens, while causing severe environmental and agronomic problems. Sporosarcina pasteurii urease has been used extensively in the structural characterization of the enzyme. Sodium sulfite has been widely used as a preservative in urease solutions to prevent oxygen-induced oxidation, but its role as an inhibitor has also been suggested. In the present study, isothermal titration microcalorimetry was used to establish sulfite as a competitive inhibitor for S. pasteurii urease, with an inhibition constant of 0.19mM at pH7. The structure of the urease-sulfite complex, determined at 1.65Å resolution, shows the inhibitor bound to the dinuclear Ni(II) center of urease in a tridentate mode involving bonds between the two Ni(II) ions in the active site and all three oxygen atoms of the inhibitor, supporting the observed competitive inhibition kinetics. This coordination mode of sulfite has never been observed, either in proteins or in small molecule complexes, and could inspire synthetic coordination chemists as well as biochemists to develop urease inhibitors based on this chemical moiety. Copyright © 2015 Elsevier Inc. All rights reserved.

On the biosorption, by brown seaweed, Lobophora variegata, of Ni(II) from aqueous solutions: equilibrium and thermodynamic studies.

PubMed

Basha, Shaik; Jaiswar, Santlal; Jha, Bhavanath

2010-09-01

The biosorption equilibrium isotherms of Ni(II) onto marine brown algae Lobophora variegata, which was chemically-modified by CaCl(2) were studied and modeled. To predict the biosorption isotherms and to determine the characteristic parameters for process design, twenty-three one-, two-, three-, four- and five-parameter isotherm models were applied to experimental data. The interaction among biosorbed molecules is attractive and biosorption is carried out on energetically different sites and is an endothermic process. The five-parameter Fritz-Schluender model gives the most accurate fit with high regression coefficient, R (2) (0.9911-0.9975) and F-ratio (118.03-179.96), and low standard error, SE (0.0902-0.0.1556) and the residual or sum of square error, SSE (0.0012-0.1789) values to all experimental data in comparison to other models. The biosorption isotherm models fitted the experimental data in the order: Fritz-Schluender (five-parameter) > Freundlich (two-parameter) > Langmuir (two-parameter) > Khan (three-parameter) > Fritz-Schluender (four-parameter). The thermodynamic parameters such as DeltaG (0), DeltaH (0) and DeltaS (0) have been determined, which indicates the sorption of Ni(II) onto L. variegata was spontaneous and endothermic in nature.

Highly planar diarylamine-fused porphyrins and their remarkably stable radical cations† †Electronic supplementary information (ESI) available. CCDC 1469154–1469160. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c6sc02721k Click here for additional data file. Click here for additional data file.

PubMed Central

Fukui, Norihito; Cha, Wonhee; Shimizu, Daiki; Oh, Juwon

2017-01-01

Oxidative fusion reactions of meso-phenoxazino Ni(ii) porphyrin were found to be temperature dependent, giving rise to either a doubly phenylene-fused product at room temperature or a singly phenoxazine-fused product at 70 °C. The latter was further oxidized to a doubly phenoxazine-fused Ni(ii) porphyrin, which was subsequently converted to the corresponding free base porphyrin and Zn(ii) porphyrin. Compared to previously reported diphenylamine-fused porphyrins that displayed a molecular twist, doubly phenoxazine-fused porphyrins exhibited distinctly different properties owing to their highly planar structures, such as larger fluorescence quantum yields, formation of an offset face-to-face dimer both in solution and the solid state, and the generation of a mixed-valence π-radical cation dimer upon electrochemical oxidation. One-electron oxidation of the phenoxazine-fused Ni(ii) porphyrin with Magic Blue gave the corresponding radical cation, which was certainly stable and could be isolated by separation over a silica gel column but slowly chlorinated at the reactive β-positions in the solid state. This finding led to us to examine β,β′-dichlorinated phenoxazine-fused and diphenylamine-fused Ni(ii) porphyrins, which, upon treatment with Magic Blue, provided remarkably stable radical cations to an unprecedented level. It is actually possible to purify these radical cations by silica gel chromatography, and they can be stored for over 6 months without any sign of deterioration. Moreover, they exhibited no degradation even after the CH2Cl2 solution was washed with water. However, subtle structural differences (planar versus partly twisted) led to different crystal packing structures and solid-state magnetic properties. PMID:28451165

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

NASA Astrophysics Data System (ADS)

El-Behery, Mostafa; El-Twigry, Haifaa

2007-01-01

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

The Effects of Select Histidine to Cysteine Mutations on Transcriptional Regulation by E. coli RcnR‡

PubMed Central

Higgins, Khadine A.; Hu, Heidi Q.; Chivers, Peter T.; Maroney, Michael J.

2013-01-01

The RcnR metalloregulator represses the transcription of the Co(II) and Ni(II) exporter, RcnAB. Previous studies have shown that Co(II) and Ni(II) bind to RcnR in six-coordinate sites, resulting in de-repression. Here, the roles of His60, His64, and His67 in specific metal recognition are examined. His60 and His64 correspond to ligands that are important for Cu(I) binding in the homologous Cu(I)-responsive metalloregulator, CsoR. These residues are known to be functionally important in RcnR transcriptional regulation. XAS was used to examine the structure of bound cognate and non-cognate metal ions, and lacZ reporter assays were used to assess the transcription of rcnA in response to metal binding in the three His → Cys mutations, H60C, H64C and H67C. These studies confirm that both Ni(II) and Co(II) use His64 as a ligand. H64C-RcnR is also the only known mutation that retains a Co(II) response while eliminating the response to Ni(II) binding. XAS data indicate that His60 and His67 are potential Co(II) ligands. The effects of the mutations of His60, His64, and His67 residues on the structures of the non-cognate metal ions (Zn(II) and Cu(I)) reveals that these residues have distinctive roles in binding non-cognate metals. None of the His → Cys mutants in RcnR confer any response to Cu(I) binding, including H64C-RcnR, where the ligands involved in Cu(I) binding in CsoR are present. These data indicate that while the secondary, tertiary and quaternary structures of CsoR and RcnR are quite similar, small changes in primary sequence reveal that the specific mechanisms involved in metal recognition are quite different. PMID:23215580

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

NASA Astrophysics Data System (ADS)

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

2015-02-01

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

Thermodynamic Modeling of Poorly Complexing Metals in Concentrated Electrolyte Solutions: An X-Ray Absorption and UV-Vis Spectroscopic Study of Ni(II) in the NiCl2-MgCl2-H2O System

PubMed Central

Zhang, Ning; Brugger, Joël; Etschmann, Barbara; Ngothai, Yung; Zeng, Dewen

2015-01-01

Knowledge of the structure and speciation of aqueous Ni(II)-chloride complexes is important for understanding Ni behavior in hydrometallurgical extraction. The effect of concentration on the first-shell structure of Ni(II) in aqueous NiCl2 and NiCl2-MgCl2 solutions was investigated by Ni K edge X-ray absorption (XAS) and UV-Vis spectroscopy at ambient conditions. Both techniques show that no large structural change (e.g., transition from octahedral to tetrahedral-like configuration) occurs. Both methods confirm that the Ni(II) aqua ion (with six coordinated water molecules at R Ni-O = 2.07(2) Å) is the dominant species over the whole NiCl2 concentration range. However, XANES, EXAFS and UV-Vis data show subtle changes at high salinity (> 2 mol∙kg-1 NiCl2), which are consistent with the formation of small amounts of the NiCl+ complex (up to 0.44(23) Cl at a Ni-Cl distance of 2.35(2) Å in 5.05 mol∙kg-1 NiCl2) in the pure NiCl2 solutions. At high Cl:Ni ratio in the NiCl2-MgCl2-H2O solutions, small amounts of [NiCl2]0 are also present. We developed a speciation-based mixed-solvent electrolyte (MSE) model to describe activity-composition relationships in NiCl2-MgCl2-H2O solutions, and at the same time predict Ni(II) speciation that is consistent with our XAS and UV-Vis data and with existing literature data up to the solubility limit, resolving a long-standing uncertainty about the role of chloride complexing in this system. PMID:25885410

Structural, spectroscopic and thermal characterization of 2-tert-butylaminomethylpyridine-6-carboxylic acid methylester and its Fe(III), Co(II), Ni(II), Cu(II), Zn(II) and UO(2)(II) complexes.

PubMed

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

2005-04-01

Fe(III), Co(II), Ni(II), Cu(II), Zn(II) and UO(2)(II) complexes with the ligand 2-tert-butylaminomethylpyridine-6-carboxylic acid methylester (HL(2)) have been prepared and characterized by elemental analyses, molar conductance, magnetic moment, thermal analysis and spectral data. 1:1 M:HL(2) complexes, with the general formula [M(HL(2))X(2)].nH(2)O (where M = Co(II) (X = Cl, n = 0), Ni(II) (X = Cl, n = 3), Cu(II) (grey colour, X = AcO, n = 1), Cu(II) (yellow colour, X = Cl, n = 0) and Zn(II) (X = Br, n = 0). In addition, the Fe(III) and UO(2)(II) complexes of the type 1:2 M:HL(2) and with the formulae [Fe(L(2))(2)]Cl and [UO(2)(HL(2))(2)](NO(3))(2) are prepared. From the IR data, it is seen that HL(2) ligand behaves as a terdentate ligand coordinated to the metal ions via the pyridyl N, carboxylate O and protonated NH group; except the Fe(III) complex, it coordinates via the deprotonated NH group. This is supported by the molar conductance data, which show that all the complexes are non-electrolytes, while the Fe(III) and UO(2)(II) complexes are 1:1 electrolytes. IR and H1-NMR spectral studies suggest a similar behaviour of the Zn(II) complex in solid and solution states. From the solid reflectance spectral data and magnetic moment measurements, the complexes have a trigonal bipyramidal (Co(II), Ni(II), Cu(II) and Zn(II) complexes) and octahedral (Fe(III), UO(2)(II) complexes) geometrical structures. The thermal behaviour of the complexes is studied and the different dynamic parameters are calculated applying Coats-Redfern equation.

X-ray absorption spectroscopic evidence for binding of the competitive inhibitor 2-mercaptoethanol to the nickel sites of Jack bean urease. A new Ni-Ni interaction in the inhibited enzyme

DOE Office of Scientific and Technical Information (OSTI.GOV)

Clark, P.A.; Wilcox, D.E.; Scott, R.A.

The enzyme Jack bean urease has been identified as the first nickel-containing metalloenzyme to catalyze the hydrolysis of urea to carbon dioxide and ammonia. Competitive inhibitors such as 2-mercaptoethanol (2-ME) have been shown to dramatically affect the ground-state electronic properties of the urease Ni(II) ions. Results of preliminary structural investigations using x-ray absorption spectroscopy of the nickel salts of urease in its native and 2-ME bound forms are presented. The binding of 2-ME to Ni(II) through the thiolate sulfur is confirmed by the results of this study. 17 refs., 2 figs., 2 tabs.

Bio-important antipyrine derived Schiff bases and their transition metal complexes: Synthesis, spectroscopic characterization, antimicrobial, anthelmintic and DNA cleavage investigation

NASA Astrophysics Data System (ADS)

Manjunath, M.; Kulkarni, Ajaykumar D.; Bagihalli, Gangadhar B.; Malladi, Shridhar; Patil, Sangamesh A.

2017-01-01

Spectroscopic (IR, NMR, UV-vis, ESR, ESI-mass), magnetic and TGA studies suggests octahedral geometry for all the CoII, NiII and CuII complexes of the Schiff bases, derived from 4-aminoantipyrine and 8-formyl-7-Hydroxy-4-methylcoumarin/5-formyl-6-hydroxycoumarin, coordinated through ONO donor sites. Antibacterial (Escherichia coli, Staphylococcus aureus, Pseudomonas aeruginosa and Salmonella typhi), antifungal (Aspergillus niger, Aspergillus flavus and Cladosporium) and DNA cleavage properties of the metal complexes are investigated. The results suggested that some of the synthesized compounds are potential antimicrobials. The synthesized compounds tested for their anthelmintic activities and it was found that CoII and NiII complexes exhibited good anthelmintic properties.

Novelmetal-organic photocatalysts: Synthesis, characterization and decomposition of organic dyes

NASA Astrophysics Data System (ADS)

Gopal Reddy, N. B.; Murali Krishna, P.; Kottam, Nagaraju

2015-02-01

An efficient method for the photocatalytic degradation of methylene blue in an aqueous medium was developed using metal-organic complexes. Two novel complexes were synthesized using, Schiff base ligand, N‧-[(E)-(4-ethylphenyl)methylidene]-4-hydroxybenzohydrazide (HL) and Ni(II) (Complex 1)/Co(II) (Complex 2) chloride respectively. These complexes were characterized using microanalysis, various spectral techniques. Spectral studies reveal that the complexes exhibit square planar geometry with ligand coordination through azomethine nitrogen and enolic oxygen. The effects of catalyst dosage, irradiation time and aqueous pH on the photocatalytic activity were studied systematically. The photocatalytic activity was found to be more efficient in the presence of Ni(II) complexes than the Co(II) complex. Possible mechanistic aspects were discussed.

Two novel macroacyclic schiff bases containing bis-N 2O 2 donor set and their binuclear complexes: synthesis, spectroscopic and magnetic properties

NASA Astrophysics Data System (ADS)

Karaoglu, Kaan; Baran, Talat; Serbest, Kerim; Er, Mustafa; Degirmencioglu, Ismail

2009-03-01

Herein, we report two novel macroacyclic Schiff bases derived from tetranaphthaldehyde derivative compound and their binuclear Mn(II), Ni(II), Cu(II) and Zn(II) complexes. The structures of the compounds have been proposed by elemental analyses, spectroscopic data i.e. IR, 1H and 13C NMR, UV-Vis, electrospray ionisation mass spectra, molar conductivities and magnetic susceptibility measurements. The stoichiometries of the complexes derived from mass and elemental analysis correspond to the general formula [M 2L(ClO 4) n](ClO 4) 4-n, (where M is Mn(II), Ni(II), Cu(II), Zn(II) and L represents the Schiff base ligands).

Preparation of thiol-functionalized activated carbon from sewage sludge with coal blending for heavy metal removal from contaminated water.

PubMed

Li, Juan; Xing, Xing; Li, Jiao; Shi, Mei; Lin, Aijun; Xu, Congbin; Zheng, Jianzhong; Li, Ronghua

2018-03-01

Sewage sludge produced from wastewater treatment is a pressing environmental issue. Mismanagement of the massive amount of sewage sludge would threat our valuble surface and shallow ground water resources. Use of activated carbon prepared from carbonization of these sludges for heavy metal removal can not only minimize and stabilize these hazardous materials but also realize resources reuse. In this study, thiol-functionalized activated carbon was synthesized from coal-blended sewage sludge, and its capacity was examined for removing Cu(II), Pb(II), Cd(II) and Ni(II) from water. Pyrolysis conditions to prepare activated carbons from the sludge and coal mixture were examined, and the synthesized material was found to achieve the highest BET surface area of 1094 m 2 /g under 500 °C and 30 min. Batch equilibrium tests indicated that the thiol-functionalized activated carbon had a maximum sorption capacity of 238.1, 96.2, 87.7 and 52.4 mg/g for Pb(II), Cd(II), Cu(II) and Ni(II) removal from water, respectively. Findings of this study suggest that thiol-functionalized activated carbon prepared from coal-blended sewage sludge would be a promising sorbent material for heavy metal removal from waters contaminated with Cu(II), Pb(II), Cd(II) and Ni(II). Copyright © 2017 Elsevier Ltd. All rights reserved.

Binding ability of impromidine, a potent H2 agonist of histamine

NASA Astrophysics Data System (ADS)

Anouar, A.; Lhadi, E.; Decock, P.; Kozlowskyinst4, H.

1999-09-01

Impromidine (fig.1) is a potent and selective histamine H2 receptor agonist and its structure comprises a strongly basic guanidine group containing two different imidazole-containing side chains. The present work deals with the study of coordination equilibria between impromidine and Cu(II) and Ni(II) in aqueous solution at 25 circC. Potentiometric, UV-Visible and EPR studies on Cu(II) complexes with impromidine have shown that this anti-ulcerogenic drug is a very potent chelating agent. This drug is found to be a very effective ligand for Ni(II) ions also. The effective coordination of impromidine to metal ions may have significant biological implications. L'impromidine est un agoniste H2 de l'histamine, sa structure possède un groupement guanidinique de forte basicité et dont l'environne ment des deux groupements imidazoliques est différent. Le présent travail consiste en l'étude de la coordination de l'impromidine avec le Cu(II) et le Ni(II) en milieu aqueux à 25 circC. La potentiométrie, LíUV-Visible et la RPE montrent que le cuivre se coordine très fortement avec l'impromidine. Nous avons trouvé que ce médicament se coordine aussi fortement avec le nickel(II). La coordination de l'impromidine avec les métaux pourrait avoir des applications importantes en médecine.

Spectroscopic and biological studies of new mononuclear metal complexes of a bidentate NN and NO hydrazone-oxime ligand derived from egonol

NASA Astrophysics Data System (ADS)

Babahan, Ilknur; Emirdağ-Öztürk, Safiye; Poyrazoğlu-Çoban, Esin

2015-04-01

A novel ligand, vicinal dioxime ligand (egonol-hydrazone glyoxime) (LH2) was synthesized and characterized using 1H NMR, 13C NMR, MS, AAS, infrared spectroscopy, and magnetic susceptibility measurements. Mononuclear nickel (II), copper (II) and cobalt (II) complexes with a metal:ligand ratio of 1:2 for LH2 were also synthesized. Zn(II) forms complex [Zn(LH)Cl2] with a metal to ligand ratio of 1:1. IR spectrum shows that the ligand act in a bidentate manner and coordinates N4 donor groups of the ligands to NiII, CuII, CoII and ZnII ions. The detection of H-bonding (Osbnd H⋯O) in the [M(LH)2] metal complexes by IR spectra supported the square-planar MN4 coordination of Ni(II), Cu(II) and Co(II) complexes. The antimicrobial activities of compounds LH2 and their Ni(II), Cu(II), Co(II) and Zn(II) complexes were evaluated using the disc diffusion method against 16 bacteria and 5 yeasts. The minimal inhibitory concentrations (MICs) against all the bacteria and yeasts were also determined. Among the attempted test compounds, it is showed that all the compounds (L, LH2, [Ni(LH)2], [Cu(LH)2], [Co(LH)2(H2O)2], [Zn(LH)Cl2]) were effective against used test microorganisms.

Syntheses, spectroscopic and thermal analyses of cyanide bridged heteronuclear polymeric complexes: [M(L)2Ni(CN)4]n (Ldbnd N-methylethylenediamine or N-ethylethylenediamine; Mdbnd Ni(II), Cu(II), Zn(II) or Cd(II))

NASA Astrophysics Data System (ADS)

Karaağaç, Dursun; Kürkçüoğlu, Güneş Süheyla

2016-02-01

Polymeric tetracyanonickelate(II) complexes of the type [M(L)2Ni(CN)4]n (Ldbnd N-methylethylenediamine (men) or N-ethylethylenediamine (neen); Mdbnd Ni(II), Cu(II), Zn(II) or Cd(II)) have been prepared and characterized by FT-IR, Raman spectroscopy, thermal and elemental analysis techniques. Additionally, FT-IR and Raman spectral analyses of men and neen have experimentally and theoretically investigated in the range of 4000-250 cm-1. The corresponding vibration assignments of men and neen are performed by using B3LYP density functional theory (DFT) method together with 6-31 G(d) basis set. The spectral features of the complexes suggest that the coordination environment of the M(II) ions are surrounded by the two symmetry related men and neen ligands and the two symmetry related N atom of cyanide groups, whereas the Ni(II) atoms are coordinated with a square-planar to four C atoms of the cyanide groups. Polymeric structures of the complexes consist of one dimensional alternative chains of [M(L)2]2+ and [Ni(CN)4]2- moieties. The thermal decompositions in the temperature range 30-700 °C of the complexes were investigated in the static air atmosphere.

Cu(II), Co(II) and Ni(II) complexes of new Schiff base ligand: Synthesis, thermal and spectroscopic characterizations

NASA Astrophysics Data System (ADS)

Refat, Moamen S.; El-Sayed, Mohamed Y.; Adam, Abdel Majid A.

2013-04-01

Cu(II), Co(II), and Ni(II) complexes were synthesized from 2-[(5-o-chlorophenylazo-2-hydroxybenzylidin)amino]-phenol Schiff base (H2L). Metal ions coordinate in a tetradentate or hexadentate features with these O2N donor ligand, which are characterized by elemental analyses, magnetic moments, infrared, Raman laser, electronic, and 1H NMR spectral studies. The elemental analysis suggests the stoichiometry to be 1:1 (metal:ligand). Reactions with Cu(II), Co(II) and Ni(II), resulted [Cu(H2L)(H2O)2(Cl)]Cl, [Co(H2L)(H2O)3]Cl2ṡ3H2O and [Ni(H2L)(H2O)2]Cl2ṡ6H2O. The thermal decomposition behavior of H2L complexes has been investigated by thermogravimetric analysis (TG/DTG) at a heating rate of 10 °C min-1 under nitrogen atmosphere. The brightness side in this study is to take advantage for the preparation and characterizations of single phases of CuO, CoO and NiO nanoparticles using H2L complexes as precursors via a solid-state decomposition procedure. The crystalline structures of products using X-ray diffractometer (XRD), morphology of particles by scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX) were investigated.

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

NASA Astrophysics Data System (ADS)

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

2013-01-01

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

Adsorption of Pb(II), Cu(II), Cd(II), Zn(II), Ni(II), Fe(II), and As(V) on bacterially produced metal sulfides.

PubMed

Jong, Tony; Parry, David L

2004-07-01

The adsorption of Pb(II), Cu(II), Cd(II), Zn(II), Ni(II), Fe(II) and As(V) onto bacterially produced metal sulfide (BPMS) material was investigated using a batch equilibrium method. It was found that the sulfide material had adsorptive properties comparable with those of other adsorbents with respect to the specific uptake of a range of metals and, the levels to which dissolved metal concentrations in solution can be reduced. The percentage of adsorption increased with increasing pH and adsorbent dose, but decreased with increasing initial dissolved metal concentration. The pH of the solution was the most important parameter controlling adsorption of Cd(II), Cu(II), Fe(II), Ni(II), Pb(II), Zn(II), and As(V) by BPMS. The adsorption data were successfully modeled using the Langmuir adsorption isotherm. Desorption experiments showed that the reversibility of adsorption was low, suggesting high-affinity adsorption governed by chemisorption. The mechanism of adsorption for the divalent metals was thought to be the formation of strong, inner-sphere complexes involving surface hydroxyl groups. However, the mechanism for the adsorption of As(V) by BPMS appears to be distinct from that of surface hydroxyl exchange. These results have important implications to the management of metal sulfide sludge produced by bacterial sulfate reduction.

PubMed

Defagó, Victor

2017-10-10

Introducción: La incorporación de la Clínica y la Imagenología permiten una mejor comprensión de la Anatomía. El objetivo de este trabajo es desarrollar un prototipo rápido en material sintético que replique detalles anatómicos para ser utilizado en la docencia y el entrenamiento quirúrgico en Pediatría.Material y Método: Presentación de caso: Paciente de un año de edad con síndrome de dificultad respiratoria. En el examen endoscópico se halló una compresión traqueal distal. La angiotomografía confirmó la presencia de una malformación vascular. Con la finalidad de analizar una conducta adecuada, se solicitó la confección de un prototipo rápido a escala 1:1 que simulara una condición idéntica a la topografía torácica del paciente, utilizando imágenes virtuales 3D almacenadas en formato DICOM.Técnica de generación de prototipo rápido: Se obtuvo una malla digital tridimensional y se generó el código "g" que se utilizó para controlar el hardware de producción. Se efectuó simulación digital y producción en material plástico (ABS) con técnica de deposición y fusión (MDF). Se validó el prototipo comparándolo con las mediciones testigos del modelo virtual en 3 D.Resultados y Discusión: El modelo replicó exactamente los defectos hallados en la tomografía y endoscopía, confirmando la presencia de la malformación vascular y su repercusión sobre el aparato respiratorio. El prototipo rápido muestra las estructuras internas y externas del cuerpo humano con máxima precisión permitiendo una visión topográfica de situaciones "normales o patológicas" que facilitaría la docencia y el entrenamiento del equipo quirúrgico para proponer un plan de tratamiento adecuado. Hay numerosas áreas de la medicina que se beneficiarían con este modelo que podría ser construído con diversos tipos de materiales de diferente flexibilidad y consistencia. Conclusiones: El prototipo rápido le da estado físico a las imágenes virtuales 3D, permitiendo la docencia y entrenamiento del equipo quirúrgico.

Toward Advanced Nursing Practice along with People-Centered Care Partnership Model for Sustainable Universal Health Coverage and Universal Access to Health.

PubMed

Kamei, Tomoko; Takahashi, Keiko; Omori, Junko; Arimori, Naoko; Hishinuma, Michiko; Asahara, Kiyomi; Shimpuku, Yoko; Ohashi, Kumiko; Tashiro, Junko

2017-01-30

this study developed a people-centered care (PCC) partnership model for the aging society to address the challenges of social changes affecting people's health and the new role of advanced practice nurses to sustain universal health coverage. a people-centered care partnership model was developed on the basis of qualitative meta-synthesis of the literature and assessment of 14 related projects. The ongoing projects resulted in individual and social transformation by improving community health literacy and behaviors using people-centered care and enhancing partnership between healthcare providers and community members through advanced practice nurses. people-centered care starts when community members and healthcare providers foreground health and social issues among community members and families. This model tackles these issues, creating new values concerning health and forming a social system that improves quality of life and social support to sustain universal health care through the process of building partnership with communities. a PCC partnership model addresses the challenges of social changes affecting general health and the new role of advanced practice nurses in sustaining UHC. o estudo desenvolveu um modelo de parceria de cuidados centrados nas pessoas (CCP) para uma sociedade que está envelhecendo, com o fim de enfrentar os desafios das mudanças sociais que afetam a saúde das pessoas e o novo papel da prática avançada de enfermagem para sustentar a cobertura universal de saúde. um modelo de parceria de cuidados centrados nas pessoas foi desenvolvido com base na meta-síntese qualitativa da literatura e a avaliação de 14 projetos relacionados. Os projetos em curso resultaram na transformação individual e social, melhorando a alfabetização de saúde da comunidade e comportamentos que usam o cuidado centrado nas pessoas e aumentando a parceria entre os profissionais de saúde e membros da comunidade por meio da prática avançada de enfermagem. o cuidado centrado nas pessoas começa quando os membros da comunidade e os profissionais de saúde colocam em primeiro plano as questões sociais entre os membros da comunidade e das famílias. Esse modelo aborda essas questões, a criação de novos valores relativos à saúde e forma um sistema social que melhora a qualidade de vida e dá apoio social para sustentar o sistema de saúde universal por meio da construção de parcerias com as comunidades. um modelo de parceria CCP aborda os desafios das mudanças sociais que afetam a saúde geral e o novo papel das enfermeiras de prática avançada em sustentar a UHC. este estudio desarrolló un modelo de alianza para el cuidado centrado en las personas (CCP) para una sociedad envejecida, que haga frente a los retos de los cambios sociales que afectan a la salud de las personas y el nuevo papel de las enfermeras de práctica avanzada para apoyar la cobertura universal de salud. un modelo de alianza para el cuidado centrado en las personas fue desarrollado sobre la base de la meta-síntesis cualitativa de la literatura y la evaluación de 14 proyectos relacionados. Los proyectos en curso dieron lugar a la transformación individual y social mejorando la "alfabetización sanitaria" de la comunidad y los comportamientos, utilizando los cuidados centrados en las personas y aumentando la colaboración entre los profesionales sanitarios y miembros de la comunidad a través de las enfermeras de práctica avanzada. el cuidado centrado en las personas comienza cuando los miembros de la comunidad y los profesionales sanitarios ponen en primer plano a la salud y las cuestiones sociales entre los miembros de la comunidad y las familias. Este modelo aborda estas cuestiones, creando nuevos valores relativos a la salud y formando un sistema social que mejora la calidad de vida y el apoyo social para hacer sostenible la atención sanitaria universal a través del proceso de construcción de alianzas con las comunidades. un modelo de alianza para CCP responde a los desafíos de los cambios sociales que afectan a la salud en general y al nuevo papel de las enfermeras de práctica avanzada en el sostenimiento de la Cobertura Universal en Salud (CUS).

Sequential determination of nickel and cadmium in tobacco, molasses and refill solutions for e-cigarettes samples by molecular fluorescence.

PubMed

Talio, María Carolina; Alesso, Magdalena; Acosta, Mariano; Wills, Verónica S; Fernández, Liliana P

2017-11-01

In this work, a new procedure was developed for separation and preconcentration of nickel(II) and cadmium(II) in several and varied tobacco samples. Tobacco samples were selected considering the main products consumed by segments of the population, in particular the age (youth) and lifestyle of the consumer. To guarantee representative samples, a randomized strategy of sampling was used. In the first step, a chemofiltration on nylon membrane is carried out employing eosin (Eo) and carbon nanotubes dispersed in sodium dodecylsulfate (SDS) solution (phosphate buffer pH 7). In this condition, Ni(II) was selectively retained on the solid support. After that, the filtrate liquid with Cd(II) was re-conditioned with acetic acid /acetate buffer solution (pH 5) and followed by detection. A spectrofluorimetric determination of both metals was carried out, on the solid support and the filtered aqueous solution, for Ni(II) and Cd(II), respectively. The solid surface fluorescence (SSF) determination was performed at λ em = 545nm (λ ex = 515nm) for Ni(II)-Eo complex and the fluorescence of Cd(II)-Eo was quantified in aqueous solution using λ em = 565nm (λ ex = 540nm). The calibration graphs resulted linear in a range of 0.058-29.35μgL -1 for Ni(II) and 0.124-56.20μgL -1 for Cd(II), with detection limits of 0.019 and 0.041μgL -1 (S/N = 3). The developed methodology shows good sensitivity and adequate selectivity, and it was successfully applied to the determination of trace amounts of nickel and cadmium present in tobacco samples (refill solutions for e-cigarettes, snuff used in narguille (molasses) and traditional tobacco) with satisfactory results. The new methodology was validated by ICP-MS with adequate agreement. The proposed methodology represents a novel fluorescence application to Ni(II) and Cd(II) quantification with sensitivity and accuracy similar to atomic spectroscopies, introducing for the first time the quenching effect on SSF. Copyright © 2017 Elsevier B.V. All rights reserved.

Syntheses, structures, and properties of trinuclear complexes [M(bpca)(2)(M'(hfac)(2))(2)], constructed with the complexed bridging ligand [M(bpca)(2)] [M, M' = Ni(II), Mn(II); Cu(II), Mn(II); Fe(II), Mn(II); Ni(II), Fe(II); and Fe(II), Fe(II); Hbpca = Bis(2-pyridylcarbonyl)amine, Hhfac = Hexafluoroacetylacetone].

PubMed

Kamiyama, Asako; Noguchi, Tomoko; Kajiwara, Takashi; Ito, Tasuku

2002-02-11

Five trinuclear complexes [M(bpca)(2)(M'(hfac)(2))(2)] (where MM'(2) = NiMn(2), CuMn(2), FeMn(2), NiFe(2), and FeFe(2); Hbpca = bis(2-pyridylcarbonyl)amine; and Hhfac = hexafluoroacetylacetone) were synthesized almost quantitatively by the reaction of [M(bpca)(2)] and [M'(hfac)(2)] in 1:2 molar ratio, and their structures and magnetic properties were investigated. Three complexes, with M' = Mn, crystallize in the same space group, Pna2(1), whereas two complexes, with M' = Fe, crystallize in P4(1), and complexes within each set are isostructural to one another. In all complexes, [M(bpca)(2)] acts as a bis-bidentate bridging ligand to form a linear trinuclear complex in which three metal ions are arranged in the manner M'-M-M'. The central metal ion is in a strong ligand field created by the N(6) donor set, and hence the Fe(II) in the [Fe(bpca)(2)] moiety is in a low-spin state. The terminal metal ions (M') are surrounded by O(6) donor sets with a moderate ligand field, which leads to the high-spin configuration of Fe(II). Three metal ions in all complexes are almost collinear, and metal-metal distances are ca. 5.5 A. The magnetic behavior of NiMn(2) and NiFe(2) shows a weak ferromagnetic interaction between the central Ni(II) ion and the terminal Mn(II) or Fe(II) ions. In these complexes, sigma-spin orbitals of the central Ni(II) ion and those of terminal metal ions have different symmetry about a 2-fold rotation axis through the Ni-N(amide)-M'(terminal) atoms, and this results in orthogonality between the neighboring sigma-spin orbitals and thus ferromagnetic interactions.

Efficient flow injection and sequential injection methods for spectrophotometric determination of oxybenzone in sunscreens based on reaction with Ni(II).

PubMed

Chisvert, A; Salvador, A; Pascual-Martí, M C; March, J G

2001-04-01

Spectrophotometric determination of a widely used UV-filter, such as oxybenzone, is proposed. The method is based on the complexation reaction between oxybenzone and Ni(II) in ammoniacal medium. The stoichiometry of the reaction, established by the Job method, was 1:1. Reaction conditions were studied and the experimental parameters were optimized, for both flow injection (FI) and sequential injection (SI) determinations, with comparative purposes. Sunscreen formulations containing oxybenzone were analyzed by the proposed methods and results compared with those obtained by HPLC. Data show that both FI and SI procedures provide accurate and precise results. The ruggedness, sensitivity and LOD are adequate to the analysis requirements. The sample frequency obtained by FI is three-fold higher than that of SI analysis. SI is less reagent-consuming than FI.

Complexation of nitrogen and sulphur donor Schiff's base ligand to Cr(III) and Ni(II) metal ions: Synthesis, spectroscopic and antipathogenic studies

NASA Astrophysics Data System (ADS)

Sharma, Amit Kumar; Chandra, Sulekh

2011-01-01

2,6-Diacetyl pyridine based ligand was synthesized by the reaction of 2,6-diacetyl pyridine with thiocarbohydrazide in presence of acetic acid. The coordination compounds with Cr(III) and Ni(II) metal ions having [Cr(L)X]X 2 and [Ni(L)X]X compositions (where L = ligand and X = NO 3-, Cl - and CH 3COO -) were synthesized and characterized by physicochemical and spectral studies. The studies like elemental analyses, molar conductance measurements, magnetic susceptibility measurements, IR, UV-Vis, NMR, mass and EPR reveal that the complexes are octahedral. The compounds were examined against the pathogenic fungal and bacterial strains like Alternaria brassicae, Aspergillus niger, Fusarium oxysporum, Xanthomonas compestris and Pseudomonas aeruginosa. A. niger causes the diseases Apergillosis and Otomycosis in humans.

Synthesis, characterization and antibacterial activity of new sulfonyl hydrazone derivatives and their nickel(II) complexes

NASA Astrophysics Data System (ADS)

Özmen, Ümmühan Özdemir; Olgun, Gülçin

2008-08-01

Prophane sulfonic acid hydrazide (psh: CH 3CH 2CH 2SO 2NHNH 2) derivatives as salicylaldehydeprophanesulfonylhydrazone (salpsh), 5-methylsalicylaldehydeprophanesulfonylhydrazone (5-msalpsh), 2-hydroxyacetophenoneprophanesulfonylhydrazone (afpsh), 5-methyl-2-hydroxyacetophenoneprophanesulfonylhydrazone (5-mafpsh) and their Ni(II) complexes have been synthesized. The structure of these compounds has been investigated by using elemental analysis, FTIR, 1H NMR, LC/MS, UV-vis spectrophotometric method, magnetic susceptibility and conductivity measurements. The complexes were found to have general compositions [NiL2]. Square-planer structures are proposed for the Ni(II) complexes on the basis of magnetic evidence, electronic spectra and TGA data. Bacterial activities of sulfonyl hydrazone compounds were studied against gram-positive bacteria: Staphylococcus aureus, Bacillus subtilis, Bacillus magaterium and gram-negative bacteria: Salmonella enteritidis, Escherichia coli by using minimum inhibitory concentrations (MICs) method.

Synthesis, structural characterization and DFT calculation on a square-planar Ni(II) complex of a compartmental Schiff base ligand

NASA Astrophysics Data System (ADS)

Biswas, Surajit; Dolai, Malay; Dutta, Arpan; Ali, Mahammad

2016-12-01

Reaction of a symmetric compartmental Schiff-base ligand, (H2L) with nickel(II) perchlorate hexahydrate in 1:1 M ratio in methanol gives rise to a mononuclear nickel(II) compound, NiL (1). The compound has been characterized by C, H, N microanalyses and UV-Vis spectra. The single crystal X-ray diffraction studies reveal a square planar geometry around the Ni(II) center. The compound crystallizes in monoclinic system with space group C2/c with a = 21.6425(6), b = 9.9481(3), c = 13.1958(4) Å, β = 107.728(2)°, V = 2706.16(14) Å3 and Z = 4. Ground state DFT optimization and TDDFT calculations on the ligand and complex were performed to get their UV-Vis spectral pattern.

Design, synthesis and characterization of macrocyclic ligand based transition metal complexes of Ni(II), Cu(II) and Co(II) with their antimicrobial and antioxidant evaluation

NASA Astrophysics Data System (ADS)

Gull, Parveez; Malik, Manzoor Ahmad; Dar, Ovas Ahmad; Hashmi, Athar Adil

2017-04-01

Three new complexes Ni(II), Cu(II) and Co(II) were synthesized of macrocyclic ligand derived from 1, 4-dicarbonyl-phenyl-dihydrazide and O-phthalaldehyde in the ratio of 2:2. The synthesized compounds were characterized by elemental analyses, molar conductance, magnetic susceptibility measurements, FTIR, UV-Vis., Mass and 1H NMR spectral studies. The electronic spectra of the metal complexes indicate a six coordinate octahedral geometry of the central metal ion. These metal complexes and the ligand were evaluated for antimicrobial activity against bacteria (E. coli, B. subtilis, S. aureus) and fungi (A. niger, A. flavus, C. albicans) and compared against standard drugs chloramphenicol and nystatin respectively. In addition, the antioxidant activity of the compounds was also investigated through scavenging effect on DPPH radicals.

Synthesis, spectral and theoretical studies of Ni(II), Pd(II) and Pt(II) complexes of 5-mercapto-1,2,4-triazole-3-imine-2‧-hydroxynaphyhaline

NASA Astrophysics Data System (ADS)

Gaber, Mohamed; El-Ghamry, Hoda; Atlam, Faten; Fathalla, Shaimaa

2015-02-01

Ni(II), Pd(II) and Pt(II) complexes of 5-mercapto-1,2,4-triazole-3-imine-2‧-hydroxynaphthaline have been isolated and characterized by elemental analysis, IR, 1H NMR, EI-mass, UV-vis, molar conductance, magnetic moment measurements and thermogravimetric analysis. The molar conductance values indicated that the complexes are non-electrolytes. The magnetic moment values of the complexes displayed diamagnetic behavior for Pd(II) and Pt(II) complexes and tetrahedral geometrical structure for Ni(II) complex. From the bioinorganic applications point of view, the interaction of the ligand and its metal complexes with CT-DNA was investigated using absorption and viscosity titration techniques. The Schiff-base ligand and its metal complexes have also been screened for their antimicrobial and antitumor activities. Also, theoretical investigation of molecular and electronic structures of the studied ligand and its metal complexes has been carried out. Molecular orbital calculations were performed using DFT (density functional theory) at B3LYP level with standard 6-31G(d,p) and LANL2DZ basis sets to access reliable results to the experimental values. The calculations were performed to obtain the optimized molecular geometry, charge density distribution, extent of distortion from regular geometry, the highest occupied molecular orbital (HOMO), the lowest unoccupied molecular orbital (LUMO), Mulliken atomic charges, reactivity index (ΔE), dipole moment (D), global hardness (η), softness (σ), electrophilicity index (ω), chemical potential and Mulliken electronegativity (χ).

Development of a reduced-graphene-oxide based superparamagnetic nanocomposite for the removal of nickel (II) from an aqueous medium via a fluorescence sensor platform.

PubMed

Nandi, Debabrata; Saha, Indranil; Ray, Suprakas Sinha; Maity, Arjun

2015-09-15

Reduced-graphene-oxide based superparamagnetic nanocomposite (GC) was fabricated and applied for the remediation of Ni(II) from an aqueous medium. The as-prepared GC was extensively characterized by Raman, TEM, AFM, SEM-EDX, SQUID, and BET analyses. Quantitative immobilization of Ni(II) in an aqueous solution by the fluorescent sensor platform of GC was explored at varying pH, doses, contact times, and temperatures. The pseudo-second-order kinetics equation governed the overall sorption process at optimized pH of 5 (±0.2). The superior monolayer sorption capacity was 228mgg(-1) at 300K. Negative ΔG(0) indicated the spontaneous sorption nature, whereas the positive ΔH(0) resulted from an increase in entropy (positive ΔS(0)) at the solid-liquid interface during the endothermic reaction. The lower enthalpy agreed with the relatively high regeneration (approximately 91%) of the GC by 0.1M HCl, because of the formation of stable tetrahedral complex. The physisorption was well corroborated by calculated sorption energy (EDR ∼7kJmol(-1)) and the nature of the Stern-Volmer plot of the fluorescence-quenching data with reaction time. The GC played a pivotal role as a static fluorescent sensor platform (fluorophore) for Ni(II) adsorption. Magnetic property also indicated that GC could be easily separated from fluids by exploiting its superparamagnetic property. Copyright © 2015 Elsevier Inc. All rights reserved.

Synthesis, characterization and biological activity of Cu(II), Ni(II) and Zn(II) complexes of biopolymeric Schiff bases of salicylaldehydes and chitosan.

PubMed

de Araújo, Eliene Leandro; Barbosa, Hellen Franciane Gonçalves; Dockal, Edward Ralph; Cavalheiro, Éder Tadeu Gomes

2017-02-01

Schiff bases have been prepared from biopolymer chitosan and salicylaldehyde, 5-methoxysalicylaldehyde, and 5-nitrosalicylaldehyde. Ligands were synthesized in a 1:1.5mol ratio, and their Cu(II), Ni(II) and Zn(II) complexes in a 1:1mol ratio (ligand:metal). Ligands were characterized by 1 H NMR and FTIR, resulting in degrees of substitution from 43.7 to 78.7%. Complexes were characterized using FTIR, electronic spectra, XPRD. The compounds were confirmed by the presence of an imine bond stretching in the 1630-1640cm -1 and νMetal-N and νMetal-O at <600cm -1 . Electronic spectra revealed that both Cu(II) and Ni(II) complexes present a square plane geometry. The crystallinity values were investigated by X-ray powder diffraction. Thermal behavior of all compounds was evaluated by TGA/DTG and DTA curves with mass losses related to dehydration and decomposition, with characteristic events for ligand and complexes. Schiff base complexes presented lower thermal stability and crystallinity than the starting chitosan. Residues were the metallic oxides as confirmed by XPRD, whose amounts were used in the calculation of the percentage of complexed metal ions. Surface morphologies were analyzed with SEM-EDAX. Preliminary cytotoxicity tests were performed using MTT assay with HeLa cells. Despite the differences in solubility, the free bases presented relatively low toxicity. Copyright © 2016 Elsevier B.V. All rights reserved.

Design, spectral characterization, thermal, DFT studies and anticancer cell line activities of Co(II), Ni(II) and Cu(II) complexes of Schiff bases derived from 4-amino-5-(pyridin-4-yl)-4H-1,2,4-triazole-3-thiol.

PubMed

Tyagi, Prateek; Chandra, Sulekh; Saraswat, B S; Yadav, Deepak

2015-06-15

A series of two biologically active Schiff base ligands L(1), L(2) have been synthesized in equimolar reaction of 4-amino-5-(pyridin-4-yl)-4H-1,2,4-triazole-3-thiol with thiophene-2-carbaldehyde and furan-2-carbaldehyde. The synthesized Schiff bases were used for complexation with different metal ions like Co(II), Ni(II) and Cu(II) by using a molar ratio of ligand: metal as 1:1 and 2:1. The characterization of Schiff bases and metal complexes was done by (1)H NMR, UV-Vis, TGA, IR, mass spectrometry and molar conductivity studies. The in DFT studies the geometries of Schiff bases and metal complexes were fully optimized with respect to the energy using the 6-31+g(d,p) basis set. On the basis of the spectral studies an octahedral geometry has been assigned for Co(II), Ni(II) and Cu(II) complexes. The effect of these complexes on proliferation of human breast cancer cell line (MCF-7) and human hepatocellular liver carcinoma cell line (Hep-G2) were studied and compared with those of free ligand. The anticancer cell line results reveal that all metal complexes show moderate to significant % cytotoxicity on cell line HepG2 and MCF-7. Copyright © 2015 Elsevier B.V. All rights reserved.

Fructose-1,6-bisphosphate aldolase (class II) is the primary site of nickel toxicity in Escherichia coli.

PubMed

Macomber, Lee; Elsey, Scott P; Hausinger, Robert P

2011-12-01

Nickel is toxic to all forms of life, but the mechanisms of cell damage are unknown. Indeed, environmentally relevant nickel levels (8 µM) inhibit wild-type Escherichia coli growth on glucose minimal medium. The same concentration of nickel also inhibits growth on fructose, but not succinate, lactate or glycerol; these results suggest that fructose-1,6-bisphosphate aldolase (FbaA) is a target of nickel toxicity. Cells stressed by 8 µM Ni(II) for 20 min lost 75% of their FbaA activity, demonstrating that FbaA is inactivated during nickel stress. Furthermore, overexpression of fbaA restored growth of an rcnA mutant in glucose minimal medium supplemented with 4 µM Ni(II), thus confirming that FbaA is a primary target of nickel toxicity. This class II aldolase has an active site zinc and a non-catalytic zinc nearby. Purified FbaA lost 80 % of its activity within 2 min when challenged with 8 µM Ni(II). Nickel-challenged FbaA lost 0.8 zinc and gained 0.8 nickel per inactivated monomer. FbaA mutants (D144A and E174A) affecting the non-catalytic zinc were resistant to nickel inhibition. These results define the primary site of nickel toxicity in E. coli as the class II aldolase FbaA through binding to the non-catalytic zinc site. © 2011 Blackwell Publishing Ltd.

Synthesis, structural elucidation, biological, antioxidant and nuclease activities of some 5-Fluorouracil-amino acid mixed ligand complexes

NASA Astrophysics Data System (ADS)

Shobana, Sutha; Subramaniam, Perumal; Mitu, Liviu; Dharmaraja, Jeyaprakash; Arvind Narayan, Sundaram

2015-01-01

Some biologically active mixed ligand complexes (1-9) have been synthesized from 5-Fluorouracil (5-FU; A) and amino acids (B) such as glycine (gly), L-alanine (ala) and L-valine (val) with Ni(II), Cu(II) and Zn(II) ions. The synthesized mixed ligand complexes (1-9) were characterized by various physico-chemical, spectral, thermal and morphological studies. 5-Fluorouracil and its mixed ligand complexes have been tested for their in vitro biological activities against some pathogenic bacterial and fungal species by the agar well diffusion method. The in vitro antioxidant activities of 5-Fluorouracil and its complexes have also been investigated by using the DPPH assay method. The results demonstrate that Cu(II) mixed ligand complexes (4-6) exhibit potent biological as well as antioxidant activities compared to 5-Fluorouracil and Ni(II) (1-3) and Zn(II) (7-9) mixed ligand complexes. Further, the cleaving activities of CT DNA under aerobic conditions show moderate activity with the synthesized Cu(II) and Ni(II) mixed ligand complexes (1-6) while no activity is seen with Zn(II) complexes (7-9). Binding studies of CT DNA with these complexes show a decrease in intensity of the charge transfer band to the extent of 5-15% along with a minor red shift. The free energy change values (Δ‡G) calculated from intrinsic binding constants indicate that the interaction between mixed ligand complex and DNA is spontaneous.

Synthesis, X-ray structure and cytotoxic effect of nickel(II) complexes with pyrazole ligands.

PubMed

Sobiesiak, Marta; Lorenz, Ingo-Peter; Mayer, Peter; Woźniczka, Magdalena; Kufelnicki, Aleksander; Krajewska, Urszula; Rozalski, Marek; Budzisz, Elzbieta

2011-12-01

Here we present the synthesis of the new Ni(II) complexes with chelating ligands 1-benzothiazol-2-yl-3,5-dimethyl-1H-pyrazole (a), 5-(2-hydroxyphenyl)-3-methyl-1-(2-pyridylo)-1H-pyrazole-4-carboxylic acid methyl ester (b) and 1-benzothiazol-2-yl-5-(2-hydroxyphenyl)-3-methyl-1H-pyrazole-4-carboxylic acid methyl ester (c). These ligands a-c create solid complexes with Ni(II). The crystal and molecular structures of two complexes were determined by X-ray diffraction method. Thermal stability of two complexes with ligand c by TG/DTG and DSC methods were also shown. Cytotoxic activity of all the complexes against three tumour cell lines and to normal endothelial cells (HUVEC) was also estimated. Complexes with ligand c exhibited relatively high cytotoxic activity towards HL-60 and NALM-6 leukaemia cells and WM-115 melanoma cells. Cytotoxic effectiveness of one of these complexes against melanoma WM-115 cells was two times higher than that of cisplatin. The protonation constant log K=9.63 of ligand b corresponding to the phenol 2-hydroxy group has been determined in 10% (v/v) DMSO/water solution (25°C). The coordination modes (formation of two monomeric species: NiL and NiL(2)) in the complexes with Ni(II) are discussed for b on the basis of the potentiometric and UV/Vis data. Copyright © 2011 Elsevier Masson SAS. All rights reserved.

Genetic and physiological responses of Bacillus subtilis to metal ion stress.

PubMed

Moore, Charles M; Gaballa, Ahmed; Hui, Monica; Ye, Rick W; Helmann, John D

2005-07-01

Metal ion homeostasis is regulated principally by metalloregulatory proteins that control metal ion uptake, storage and efflux genes. We have used transcriptional profiling to survey Bacillus subtilis for genes that are rapidly induced by exposure to high levels of metal ions including Ag(I), Cd(II), Cu(II), Ni(II) and Zn(II) and the metalloid As(V). Many of the genes affected by metal stress were controlled by known metalloregulatory proteins (Fur, MntR, PerR, ArsR and CueR). Additional metal-induced genes are regulated by two newly defined metal-sensing ArsR/SmtB family repressors: CzrA and AseR. CzrA represses the CadA efflux ATPase and the cation diffusion facilitator CzcD and this repression is alleviated by Zn(II), Cd(II), Co(II), Ni(II) and Cu. CadA is the major determinant for Cd(II) resistance, while CzcD protects the cell against elevated levels of Zn(II), Cu, Co(II) and Ni(II). AseR negatively regulates itself and AseA, an As(III) efflux pump which contributes to arsenite resistance in cells lacking a functional ars operon. Our results extend the range of identified effectors for the As(III)-sensor ArsR to include Cd(II) and Ag(I) and for the Cu-sensor CueR to include Ag(I) and, weakly, Cd(II) and Zn(II). In addition to systems dedicated to metal homeostasis, specific metal stresses also strongly induced pathways related to cysteine, histidine and arginine metabolism.

78 FR 30399 - United States v. Anheuser-Busch InBev SA/NV, Grupo Modelo S.A.B de C.V.; Proposed Final Judgment...

Federal Register 2010, 2011, 2012, 2013, 2014

2013-05-22

..., Mexico. Modelo is the third-largest brewer of beer sold in the United States. Modelo's Corona Extra brand... include Corona Light, Modelo Especial, Negra Modelo, Victoria, and Pacifico. 19. ABI currently holds a 35... such as Dogfish Head, Flying Dog, and also imported beers, the best selling of which is Modelo's Corona...

Electrochemical hydrogenation of a homogeneous nickel complex to form a surface adsorbed hydrogen-evolving species

DOE PAGES

Martin, Daniel J.; McCarthy, Brian D.; Donley, Carrie L.; ...

2014-12-04

Here, a Ni(ii) complex with nitrogen and sulfur donor ligands degrades electrochemically in the presence of acid in acetonitrile to form an electrode adsorbed film that catalytically evolves hydrogen.

Coordination Polymer: Synthesis, Spectral Characterization and Thermal Behaviour of Starch-Urea Based Biodegradable Polymer and Its Polymer Metal Complexes

PubMed Central

Malik, Ashraf; Parveen, Shadma; Ahamad, Tansir; Alshehri, Saad M.; Singh, Prabal Kumar; Nishat, Nahid

2010-01-01

A starch-urea-based biodegradable coordination polymer modified by transition metal Mn(II), Co(II), Ni(II), Cu(II), and Zn(II) was prepared by polycondensation of starch and urea. All the synthesized polymeric compounds were characterized by Fourier transform-infrared spectroscopy (FT-IR), 1H-NMR spectroscopy, 13C-NMR spectroscopy, UV-visible spectra, magnetic moment measurements, differential scanning calorimeter (DSC), and thermogravimetric analysis (TGA). The results of electronic spectra and magnetic moment measurements indicate that Mn(II), Co(II), and Ni(II) complexes show octahedral geometry, while Cu(II) and Zn(II) complexes show square planar and tetrahedral geometry, respectively. The thermogravimetric analysis revealed that all the polymeric metal complexes are more thermally stable than the parental ligand. In addition, biodegradable studies of all the polymeric compounds were also carried out through ASTM standards of biodegradable polymers by CO2 evolution method. PMID:20414461

Structure and spectroscopic investigations of a bi-dentate N‧-[(4-ethylphenyl)methylidene]-4-hydroxybenzohydrazide and its Co(II), Ni(II), Cu(II) and Cd(II) complexes: Insights relevant to biological properties

NASA Astrophysics Data System (ADS)

Gopal Reddy, N. B.; Krishna, P. Murali; Shantha Kumar, S. S.; Patil, Yogesh P.; Nethaji, Munirathinam

2017-06-01

The present paper describes the synthesis of novel ligand, N‧-[(4-ethylphenyl)methylidene]-4-hydroxy benzohydrazide (HL) and its Co(II), Ni(II), Cu(II) and Cd(II) complexes. The ligand (HL) crystallizes in orthorhombic lattice in P212121 space group with a = 7.9941 (7) Å, b = 11.6154 (10) Å, c = 15.2278 (13) Å, α = β = γ = 90°. Spectroscopic data gives the strong evidence that ligand is coordinated through azomethine nitrogen and enolic oxygen with metal ion. The DNA binding studies revealed that the complexes bind to CT-DNA via intercalation/electrostatic interaction. All the targeted compounds showed more pronounced DNA cleavage activity in the presence of H2O2 and also inhibit the growth of in vitro antibacterial activity against Gram-positive and Gram-negative bacteria.

Gold nanoparticle capture within protein crystal scaffolds.

PubMed

Kowalski, Ann E; Huber, Thaddaus R; Ni, Thomas W; Hartje, Luke F; Appel, Karina L; Yost, Jarad W; Ackerson, Christopher J; Snow, Christopher D

2016-07-07

DNA assemblies have been used to organize inorganic nanoparticles into 3D arrays, with emergent properties arising as a result of nanoparticle spacing and geometry. We report here the use of engineered protein crystals as an alternative approach to biologically mediated assembly of inorganic nanoparticles. The protein crystal's 13 nm diameter pores result in an 80% solvent content and display hexahistidine sequences on their interior. The hexahistidine sequence captures Au25(glutathione)∼17 (nitrilotriacetic acid)∼1 nanoclusters throughout a chemically crosslinked crystal via the coordination of Ni(ii) to both the cluster and the protein. Nanoparticle loading was validated by confocal microscopy and elemental analysis. The nanoparticles may be released from the crystal by exposure to EDTA, which chelates the Ni(ii) and breaks the specific protein/nanoparticle interaction. The integrity of the protein crystals after crosslinking and nanoparticle capture was confirmed by single crystal X-ray crystallography.

Influence of thermal history on the electrochemical properties of Li[Ni0.5Mn1.5]O4

NASA Astrophysics Data System (ADS)

Liu, Guoqiang; Park, Kyu-Sung; Song, Jie; Goodenough, John B.

2013-12-01

The oxygen-stoichiometric spinel Li[Ni0.5Mn1.5]O4 is an insulator with ordered Ni(II) and Mn(IV). Although it delivers 4.7 V versus Li, the ordered phase gives poor performance as the cathode of a Li-ion battery. Here we demonstrate control of the degree of cation order by adjusting the oxygen stoichiometry with thermal history of the synthesis rather than by doping 2M(III) for Ni(II) + Mn(IV) (M = Cr, Mn, Fe, Co, Al, Ga). We report retention of capacity near 100 mAh g-1 at room temperature at 10C/10C charge/discharge rate with little capacity fade; at 55 °C, a capacity fade occurs as a result of reaction with the electrolyte, but it is reduced to a level comparable to that obtained by doping.

Complexation of nitrogen and sulphur donor Schiff's base ligand to Cr(III) and Ni(II) metal ions: synthesis, spectroscopic and antipathogenic studies.

PubMed

Sharma, Amit Kumar; Chandra, Sulekh

2011-01-01

2,6-diacetyl pyridine based ligand was synthesized by the reaction of 2,6-diacetyl pyridine with thiocarbohydrazide in presence of acetic acid. The coordination compounds with Cr(III) and Ni(II) metal ions having [Cr(L)X]X2 and [Ni(L)X]X compositions (where L=ligand and X=NO3-, Cl- and CH3COO-) were synthesized and characterized by physicochemical and spectral studies. The studies like elemental analyses, molar conductance measurements, magnetic susceptibility measurements, IR, UV-Vis, NMR, mass and EPR reveal that the complexes are octahedral. The compounds were examined against the pathogenic fungal and bacterial strains like Alternaria brassicae, Aspergillus niger, Fusarium oxysporum, Xanthomonas compestris and Pseudomonas aeruginosa. A. niger causes the diseases Apergillosis and Otomycosis in humans. Copyright © 2010. Published by Elsevier B.V.

Direct Observation of Very Large Zero-Field Splitting in a Tetrahedral Ni(II)Se4 Coordination Complex.

PubMed

Jiang, Shang-Da; Maganas, Dimitrios; Levesanos, Nikolaos; Ferentinos, Eleftherios; Haas, Sabrina; Thirunavukkuarasu, Komalavalli; Krzystek, J; Dressel, Martin; Bogani, Lapo; Neese, Frank; Kyritsis, Panayotis

2015-10-14

The high-spin (S = 1) tetrahedral Ni(II) complex [Ni{(i)Pr2P(Se)NP(Se)(i)Pr2}2] was investigated by magnetometry, spectroscopic, and quantum chemical methods. Angle-resolved magnetometry studies revealed the orientation of the magnetization principal axes. The very large zero-field splitting (zfs), D = 45.40(2) cm(-1), E = 1.91(2) cm(-1), of the complex was accurately determined by far-infrared magnetic spectroscopy, directly observing transitions between the spin sublevels of the triplet ground state. These are the largest zfs values ever determined--directly--for a high-spin Ni(II) complex. Ab initio calculations further probed the electronic structure of the system, elucidating the factors controlling the sign and magnitude of D. The latter is dominated by spin-orbit coupling contributions of the Ni ions, whereas the corresponding effects of the Se atoms are remarkably smaller.

Asymmetric synthesis of α-amino acids via homologation of Ni(II) complexes of glycine Schiff bases. Part 3: Michael addition reactions and miscellaneous transformations.

PubMed

Aceña, José Luis; Sorochinsky, Alexander E; Soloshonok, Vadim

2014-09-01

The major goal of this review is a critical discussion of the literature data on asymmetric synthesis of α-amino acids via Michael addition reactions involving Ni(II)-complexes of amino acids. The material covered is divided into two conceptually different groups dealing with applications of: (a) Ni(II)-complexes of glycine as C-nucleophiles and (b) Ni(II)-complexes of dehydroalanine as Michael acceptors. The first group is significantly larger and consequently subdivided into four chapters based on the source of stereocontrolling element. Thus, a chiral auxiliary can be used as a part of nucleophilic glycine Ni(II) complex, Michael acceptor or both, leading to the conditions of matching vs. mismatching stereochemical preferences. The particular focus of the review is made on the practical aspects of the methodology under discussion and mechanistic considerations.

Synthesis, characterization and antimicrobial activity of some nickel, cadmium and mercury complexes of 5-methyl pyrazole-3yl-N-(2‧-methylthiophenyl) methyleneimine, (MPzOATA) ligand

NASA Astrophysics Data System (ADS)

Mandal, Susmita; Mondal, Monojit; Biswas, Jayanta Kumar; Cordes, David B.; Slawin, Alexandra M. Z.; Butcher, Ray J.; Saha, Manan; Chandra Saha, Nitis

2018-01-01

Herein, we report the syntheses and structures of Ni(II) complexes, [Ni(MPzOATA)2] (Cl) (PF6) (I), [Ni(MPzOATA)2](ClO4)2.CH3CN (II) & [Ni(MPzOATA)2](BF4)2.H2O (III); Cd(II) complex, [Cd(MPzOATA)Cl2]2 (IV) and a Hg(II) complex, [Hg(MPzOATA)Cl2] (V), of a pyrazole based 'NNS' donor ligand, 5-methylpyrazole-3yl-N-(2‧-methylthiophenyl)methyleneimine, (MPzOATA). The complexes are characterized by elemental analyses, electronic, IR, 1H- NMR (only for IV &V) spectral parameters, conductivity and fluorescence measurements. X-ray crystallographic data of the complexes reveal that the Ni(II) complexes have NiN4S2 octahedral coordination, one of them is a mixed-anion complex having Cl- and PF6- as counter anions; the Cd(II) complex is a chloro bridged binuclear complex with octahedral coordination environment around each metal centre, while the Hg(II) complex is a square pyramidal one. Among the reported complex species, the Ni(II) complexes are non-fluorescent, while the Cd(II) and Hg(II) complexes can be used as potential photoactive materials as indicated from their characteristic emission properties. The reported complexes are screened for their antimicrobial activities against some Gram positive and Gram negative microbial strains, and they are found to be potential antimicrobial agents in broad spectrum against both Gram positive and Gram negative bacteria.

Simultaneous decomplexation in blended Cu(II)/Ni(II)-EDTA systems by electro-Fenton process using iron sacrificing electrodes.

PubMed

Zhao, Zilong; Dong, Wenyi; Wang, Hongjie; Chen, Guanhan; Tang, Junyi; Wu, Yang

2018-05-15

This research explored the application of electro-Fenton (E-Fenton) technique for the simultaneous decomplexation in blended Cu(II)/Ni(II)-EDTA systems by using iron sacrificing electrodes. Standard discharge (0.3 mg L -1 for Cu and 0.1 mg L -1 for Ni in China) could be achieved after 30 min reaction under the optimum conditions (i.e. initial solution pH of 2.0, H 2 O 2 dosage of 6 mL L -1  h -1 , current density of 20 mA/cm 2 , inter-electrode distance of 2 cm, and sulfate electrolyte concentration of 2000 mg L -1 ). The distinct differences in apparent kinetic rate constants (k app ) and intermediate removal efficiencies corresponding to mere and blended systems indicated the mutual promotion effect toward the decomplexation between Cu(II) and Ni(II). Massive accumulation of Fe(Ⅲ) favored the further removal of Cu(II) and Ni(II) by metal ion substitution. Species distribution results demonstrated that the decomplexation of metal-EDTA in E-Fenton process was mainly contributed to the combination of various reactions, including Fenton reaction together with the anodic oxidation, electro-coagulation (E-coagulation) and electrodeposition. Unlike hypophosphite and citrate, the presence of chlorine ion displayed favorable effects on the removal efficiencies of Cu(II) and Ni(II) at low dosage, but facilitated the ammonia nitrogen (NH 4 + -N) removal only at high dosage. Copyright © 2018 Elsevier B.V. All rights reserved.

Batch and dynamic sorption of Ni(II) ions by activated carbon based on a native lignocellulosic precursor.

PubMed

Nabarlatz, Debora; de Celis, Jorge; Bonelli, Pablo; Cukierman, Ana Lea

2012-04-30

Vinal-derived Activated Carbon (VAC) developed by phosphoric acid activation of sawdust from Prosopis ruscifolia native wood was tested for the adsorption of Ni(II) ions from dilute solutions in both batch and dynamic modes, comparing it with a Commercial Activated Carbon (CAC). Batch experiments were performed to determine adsorption kinetics and equilibrium isotherms for both carbons. It was possible to remove near 6.55 mg Ni g(-1) VAC and 7.65 mg Ni g(-1) CAC after 5 h and 10 h contact time, respectively. A pseudo second order equation fitted well with the kinetics of the process, and Langmuir adsorption model was used to adjust the experimental results concerning the adsorption isotherm. The parameters obtained indicate a stronger interaction between sorbent and sorbate for VAC (K = 26.56 L mmol(-1)) than for CAC (K = 19.54 L mmol(-1)). Continuous experiments were performed in a fixed-bed column packed with the investigated carbons, evaluating the influence of operational parameters such as flow rate, bed height and feed concentration on the breakthrough curves obtained. The breakthrough occurred more slowly for low concentrations of the metal ion in the feed, low flow rates and high bed height. The breakthrough curves were properly represented by Hall's model for both carbon types. Regeneration of the vinal activated carbon in column was tested, obtaining the same breakthrough curve in a new cycle of use. Finally, vinal-derived activated carbon can effectively be used to treat wastewater having until 30 ppm Ni(II). Copyright © 2011 Elsevier Ltd. All rights reserved.

Co(II), Ni(II), Cu(II) and Zn(II) complexes of tridentate ONO donor Schiff base ligand: Synthesis, characterization, thermal, non-isothermal kinetics and DFT calculations

NASA Astrophysics Data System (ADS)

Kusmariya, Brajendra S.; Mishra, A. P.

2017-02-01

We report here four mononuclear Co(II), Ni(II), Cu(II) and Zn(II) coordination compounds of general formula [M(L)2] {L = dcp; M = CoII, CuII & ZnII} and [M(L)(H2O)]·H2O {L = dcp; M = NiII} derived from tridentate 2,4-dichloro-6-{[(3-chloro-2-hydroxy-5-nitrophenyl)imino]methyl}phenol (dcp) ligand. These compounds were synthesized and characterized by elemental analysis, FT-IR, uv-vis, 1H NMR, molar conductance, magnetic moment, thermal, PXRD and SEM-EDX. The Powder X-ray Diffraction patterns and SEM analyses showed the crystalline nature of synthesized compounds. The peak broadening was explained in terms of crystallite size and the lattice strain using Scherrer and Williamson-Hall method. Thermogravimetric analysis was performed to determine the thermal stability of synthesized compounds under nitrogen atmosphere up to 820 K at 10 Kmin-1 heating rate. The kinetic and thermodynamic parameters of thermal decomposition were calculated using Coats-Redfern (C-R), Piloyan-Novikova (P-N) and Horowitz-Metzger (H-M) methods assuming first order degradation. The calculated optical band gap values of complexes were found to be in semiconducting range. To support the experimental findings, and derive some fruitful information viz. frequency calculations, HOMO-LUMO, energy gap (ΔE), molecular electrostatic potential (MEP), spin density, absorption spectra etc.; theoretical calculations by means of DFT and TD-DFT at B3LYP level were incorporated.

Synthesis, spectral and theoretical studies of Ni(II), Pd(II) and Pt(II) complexes of 5-mercapto-1,2,4-triazole-3-imine-2'-hydroxynaphthaline.

PubMed

Gaber, Mohamed; El-Ghamry, Hoda; Atlam, Faten; Fathalla, Shaimaa

2015-02-25

Ni(II), Pd(II) and Pt(II) complexes of 5-mercapto-1,2,4-triazole-3-imine-2'-hydroxynaphthaline have been isolated and characterized by elemental analysis, IR, (1)H NMR, EI-mass, UV-vis, molar conductance, magnetic moment measurements and thermogravimetric analysis. The molar conductance values indicated that the complexes are non-electrolytes. The magnetic moment values of the complexes displayed diamagnetic behavior for Pd(II) and Pt(II) complexes and tetrahedral geometrical structure for Ni(II) complex. From the bioinorganic applications point of view, the interaction of the ligand and its metal complexes with CT-DNA was investigated using absorption and viscosity titration techniques. The Schiff-base ligand and its metal complexes have also been screened for their antimicrobial and antitumor activities. Also, theoretical investigation of molecular and electronic structures of the studied ligand and its metal complexes has been carried out. Molecular orbital calculations were performed using DFT (density functional theory) at B3LYP level with standard 6-31G(d,p) and LANL2DZ basis sets to access reliable results to the experimental values. The calculations were performed to obtain the optimized molecular geometry, charge density distribution, extent of distortion from regular geometry, the highest occupied molecular orbital (HOMO), the lowest unoccupied molecular orbital (LUMO), Mulliken atomic charges, reactivity index (ΔE), dipole moment (D), global hardness (η), softness (σ), electrophilicity index (ω), chemical potential and Mulliken electronegativity (χ). Copyright © 2014 Elsevier B.V. All rights reserved.

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

PubMed

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

2004-11-01

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

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

NASA Astrophysics Data System (ADS)

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

2004-11-01

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

Synthesis, crystal structures and properties of new homoleptic Ni(II)/Pd(II) β-oxodithioester chelates

NASA Astrophysics Data System (ADS)

Yadav, Chote L.; Manar, Krishna K.; Yadav, Manoj K.; Tiwari, Neeraj; Singh, Rakesh K.; Drew, Michael G. B.; Singh, Nanhai

2018-05-01

Six new cis-chelate complexes, [M(L)2] (L = methyl-3-hydroxy-3-(furyl)-2-propenedithioate L1, M = Ni(II) 1, Pd(II) 4; methyl-3-hydroxy-3-(thiophenyl)-2-propenedithioate L2, M = Ni(II) 2, Pd(II) 5 and methyl-3-hydroxy-3-(phenyl)-2-propenedithioate L3, M = Ni(II) 3, Pd(II) 6 have been prepared and characterized by elemental analyses, spectroscopy (IR, UV-Vis., 1H and 13C{1H} NMR). The structures of 2-6 have been revealed by X-ray crystallography. In all the crystal structures, the metal has four-coordinate slightly distorted square planar geometry with a cis-configuration of the ligands. Anti-leishmanial properties of the complexes have been studied; 2, 3 and 6 showed potential anti-promastigote and anti-amastigote activities with IC50 values of 1.70 ± 0.50, 1.62 ± 0.19, 9.20 ± 2.16 μg/mL and IC50 2.50 ± 0.10, 2.05 ± 0.40, 12.84 ± 3.46 μg/mL respectively. Cytotoxicity assays on these complexes showed toxicity on the promastigotes but less toxicity against RAW 264.7 cell lines at different concentrations. Palladium complexes 4, 5 and 6 show luminescent characteristics in CH2Cl2 solution at room temperature. Complexes 1-6 are weakly conducting (σrt = 10-4-10-6 S cm-1, Ea = 0.19-1.13 eV) but show semiconducting behavior in the solid phase.

Exhaustive oxidation of a nickel dithiolate complex: some mechanistic insights en route to sulfate formation.

PubMed

Hosler, Erik R; Herbst, Robert W; Maroney, Michael J; Chohan, Balwant S

2012-01-21

A study of the step-wise oxidation of a Ni(II) diaminodithiolate complex through the formation of sulfate, the ultimate sulfur oxygenate, is reported. Controlled oxygenations or peroxidations of a neutral, planar, tetracoordinate, low-spin Ni(II) complex of a N(2)S(2)-donor ligand, (N,N'-dimethyl-N-N'-bis(2-mecaptoethyl)-1,3-propanediaminato) nickel(ii) (1), led to a series of sulfur oxygenates that have been isolated and characterized by ESI-MS and single-crystal X-ray diffraction. A monosulfenate complex (2) was detected by ESI-MS as a product of oxidation with one equivalent of H(2)O(2). However, this complex proved too unstable to isolate. Reaction of the dithiolate (1) with two equivalents of H(2)O(2) or one O(2) molecule leads to the formation of a monosulfinate complex (3), which was isolated and fully characterized by crystallography. The oxidation product of the monosulfinate (3) produced with either O(2) or H(2)O(2) is an interesting dimeric complex containing both sulfonate and thiolate ligands (4), this complex was fully characterized by crystallography, details of which were reported earlier by us. A disulfonate complex (7) is produced by reaction of 1 in the presence of O(2) or by reaction with exactly six equivalents of H(2)O(2). This complex was isolated and also fully characterized by crystallography. Possible intermediates in the conversion of the monosulfinate complex (3) to the disulfonate complex (7) include complexes with mixed sulfonate/sulfenate (5) or sulfonate/sulfinate (6) ligands. Complex 5, a four-oxygen adduct of 1, was not detected, but the sulfonate/sulfinate complex (6) was isolated and characterized. The oxidation chemistry of 1 is very different from that reported for other planar cis-N(2)S(2) Ni(ii) complexes including N,N'-dimethyl-N-N'-bis(2-mecaptoethyl)-1,3-ethylenediaminato) nickel(II), (8), and N,N'-bis(mercaptoethyl)-1,5-diazacyclooctane nickel(II). To address the structural aspects of the reactivity differences, the crystal structure of 8 was also determined. A comparison of the structures of planar Ni(II) complexes containing cis-dithiolate ligands, strongly suggests that the differences in reactivity are determined in part by the degree of flexibility that is allowed by the NN' chelate ring.

Synthesis of MFe3S4 clusters containing a planar M(II) site (M = Ni, Pd, Pt), a structural element in the C-cluster of carbon monoxide dehydrogenase.

PubMed

Panda, Rashmishree; Berlinguette, Curtis P; Zhang, Yugen; Holm, Richard H

2005-08-10

Synthesis of an analogue of the C-cluster of C. hydrogenoformans carbon monoxide dehydrogenase requires formation of a planar Ni(II) site and attachment of an exo iron atom in the core unit NiFe(4)S(5). The first objective has been achieved by two reactions: (i) displacement of Ph(3)P or Bu(t)()NC at tetrahedral Ni(II) sites of cubane-type [NiFe(3)S(4)](+) clusters with chelating diphosphines, and (ii) metal atom incorporation into a cuboidal [Fe(3)S(4)](0) cluster with a M(0) reactant in the presence of bis(1,2-dimethylphosphino)ethane (dmpe). The isolated product clusters [(dmpe)MFe(3)S(4)(LS(3))](2-) (M = Ni(II) (9), Pd(II) (12), Pt(II) (13); LS(3) = 1,3,5-tris((4,6-dimethyl-3-mercaptophenyl)thio)-2,4,6-tris(p-tolylthio)benzene(3-)) contain the cores [MFe(3)(mu(2)-S)(mu(3)-S)(3)](+) having planar M(II)P(2)S(2) sites and variable nonbonding M...S distances of 2.6-3.4 A. Reaction (i) involves a tetrahedral --> planar Ni(II) structural change between isomeric cubane and cubanoid [NiFe(3)S(4)](+) cores. Based on the magnetic properties of 12 and earlier considerations, the S = (5)/(2) ground state of the cubanoid cluster arises from the [Fe(3)S(4)](-) fragment, whereas the S = (3)/(2) ground state of the cubane cluster is a consequence of antiferromagnetic coupling between the spins of Ni(2+) (S = 1) and [Fe(3)S(4)](-). Other substitution reactions of [NiFe(3)S(4)](+) clusters and 1:3 site-differentiated [Fe(4)S(4)](2+) clusters are described, as are the structures of 12, 13, [(Me(3)P)NiFe(3)S(4)(LS(3))](2-), and [Fe(4)S(4)(LS(3))L'](2-) (L' = Me(2)NC(2)H(4)S(-), Ph(2)P(O)C(2)H(4)S(-)). This work significantly expands our initial report of cluster 9 (Panda et al. J. Am. Chem. Soc. 2004, 126, 6448-6459) and further demonstrates that a planar M(II) site can be stabilized within a cubanoid [NiFe(3)S(4)](+) core.

Plasma-assisted MBE growth kinetics and characterization studies of wide bandgap III-V epitaxial materials

NASA Astrophysics Data System (ADS)

O'Steen, Mark Lee

2000-10-01

Scope and method of study. The purpose of this research was to understand the physics of RF plasma-assisted molecular beam epitaxial growth of GaN epitaxial films and InGaN/GaN superlattice structures grown on Al2O3 (0001) substrates. The techniques used to characterize the RF-MBE grown samples include in situ reflection high energy electron diffraction (RHEED) and optical pyrometry, and ex situ spatially-resolved high resolution X-ray diffraction, spatially-resolved reflectance spectroscopy, atomic force microscopy, and low-temperature photoluminescence (PL) spectroscopy. Findings and conclusions. RF plasma-assisted molecular beam epitaxy (RF-MBE) has been used to grow GaN epitaxial films and InGaN/GaN superlattice structures. The most important growth parameters in the growth of GaN epitaxial films were identified as the substrate temperature, incident N*/Ga flux ratio, and GaN growth rate. The effect of these growth parameters on GaN growth and quality of GaN epitaxial films is discussed. Additionally, an interpretation of the effects of growth conditions on the underlying microscopic growth processes occurring is presented. All of the observed GaN growth results may be understood in terms of these microscopic growth processes. InGaN/GaN superlattice samples are grown to identify and quantitatively access the InGaN growth phenomenology. It is inferred that InN requires a higher N*/III flux ratio than does GaN for stoichiometric growth. At substrate temperatures below 590°C, the In composition of the superlattice samples is nominally constant. However, in the narrow temperature range 590--670°C, the In composition decreases by more than an order-or-magnitude at the lowest N*/III flux ratio of this study. Additionally, the incident N*/III flux ratio is found to strongly influence the In composition as well. Nearly an order-of-magnitude increase in In composition is observed despite only a 20% increase in the N*/III flux ratio at the highest temperature of this study. RHEED and PL measurements support the assessment of the In reduction mechanism as thermally-activated surface-segregation and surface-desorption of In. Implications of these results for device growth are discussed.

Evolução química de galáxias HII anãs

NASA Astrophysics Data System (ADS)

Ferraresi, M., Jr.; Cuisinier, F.; Telles, E.

2003-08-01

Galáxias HII anãs são galáxias de baixa massa, com alto conteúdo de gás, e se encontram em uma fase intensa de formação estelar. A taxa de formação estelar está tão alta nestas galáxias que não pode ter se mantido durante sua vida inteira. O tempo máximo de duração do episódio atual de formação estelar deve ser no máximo de algumas dezenas de milhões de anos, bem inferior à idade destas galáxias. Isto leva naturalmente a idéia de que já aconteceram surtos anteriores. Abundâncias químicas oferecem uma ferramenta poderosa para investigar a história evolutiva destas galáxias, porque aumentam de geração em geração estelar. O hidrogênio, o oxigênio, o nitrogênio produzem algumas das linhas mais importantes em um gás foto-ionizado, permitindo a determinação das abundâncias destes elementos facilmente. A dispersão das abundâncias em oxigênio e nitrogênio é significativa, sendo maior que os erros observacionais. O oxigênio é produzido em estrelas massivas, que explodem quase instâneamente, enquanto o nitrogênio é produzido em estrelas de massa intermediária, que só o liberam depois de um atraso de @ 500 mihões de anos. Construímos um modelo de evolução química semi-analítico, utilizando rendimentos empíricos baseados nas abundâncias observadas destes dois elementos. Conseguimos através deste modelo rudimentar explicar nas galáxias de mais baixas metalicidades as abundâncias de oxigênio e de nitrogênio, assim como a dispersão dos dados observacionais devida a formação estelar descontínua, e isto com um número baixo de surtos (1 ou 2, no máximo 3).

A self-assembled supramolecular optical sensor for NiII, CdII, and CrIII.

PubMed

Resendiz, Marino J E; Noveron, Juan C; Disteldorf, Hendrick; Fischer, Sonja; Stang, Peter J

2004-03-04

A new chromogenic supramolecular sensor for transition metals is reported. It is based on a newly designed phenanthroline-containing molecule that self-assembles via an organometallic "clip" into a supramolecular optical sensor for metals. [reaction: see text

High capacity nickel battery material doped with alkali metal cations

DOEpatents

Jackovitz, John F.; Pantier, Earl A.

1982-05-18

A high capacity battery material is made, consisting essentially of hydrated Ni(II) hydroxide, and about 5 wt. % to about 40 wt. % of Ni(IV) hydrated oxide interlayer doped with alkali metal cations selected from potassium, sodium and lithium cations.

Alkali slurry ozonation to produce a high capacity nickel battery material

DOEpatents

Jackovitz, John F.; Pantier, Earl A.

1984-11-06

A high capacity battery material is made, consisting essentially of hydrated Ni(II) hydroxide, and about 5 wt. % to about 40 wt. % of Ni(IV) hydrated oxide interlayer doped with alkali metal cations selected from potassium, sodium and lithium cations.

Diseno de una Actividad de Aprendizaje Basada en la Argumentacion Dialogica en un curso Virtual de Biotecnologia y su Incidencia en el Desarrollo de Competencias Cientificas

NASA Astrophysics Data System (ADS)

Ortiz Benavides, Fedra Lorena

El proposito de la investigacion fue evaluar la efectividad de una actividad de aprendizaje basado en la argumentacion dialogica en linea y su incidencia en el desarrollo de competencias cientificas. Se fundamenta en la teoria del aprendizaje socio cultural de Vigotsky (1984), los principios del diseno instruccional de la cognicion situada por Hung y Der-Thang (2001) y como estrategia se aplico la argumentacion dialogica utilizando el Modelo Argumentativo de Toulmin MAT (1984). El diseno experimental comparo dos grupos de estudiantes A y B en el curso virtual de Biotecnologia. El grupo A (experimental) desarrollo la discusion a partir de la estrategia disenada para este estudio y el grupo B (control) realizo la discusion desde las actividades tradicionales. El desarrollo de la competencia argumentativa se valoro con el instrumento de evaluacion para argumentacion dialogica en linea propuesta por Clark y Sampson (2008). La evaluacion de las competencias cientificas se realizo a partir de una postprueba. Los datos fueron analizados con pruebas estadisticas no parametricas. Los resultados de la investigacion, indicaron diferencias significativas en el nivel de la competencia argumental en el grupo experimental en comparacion al grupo control. Igualmente se demostro que existe una relacion positiva entre el nivel de desarrollo de la competencia argumentativa y el nivel de desarrollo de las competencias cientificas.

Comparative studies of mononuclear Ni(II) and UO2(II) complexes having bifunctional coordinated groups: Synthesis, thermal analysis, X-ray diffraction, surface morphology studies and biological evaluation

NASA Astrophysics Data System (ADS)

Fahem, Abeer A.

2012-03-01

Two Schiff base ligands derived from condensation of phthalaldehyde and o-phenylenediamine in 1:2 (L1) and 2:1 (L2) having bifunctional coordinated groups (NH2 and CHO groups, respectively) and their metal complexes with Ni(II) and UO2(II) have been synthesized and characterized by elemental analysis, molar conductance, magnetic susceptibilities and spectral data (IR, 1H NMR, mass and solid reflectance) as well as thermal, XRPD and SEM analysis. The formula [Ni(L1)Cl2]·2.5H2O, [UO2(L1)(NO3)2]·2H2O, [Ni(L2)Cl2]·1.5H2O and [UO2(L2)(NO3)2] have been suggested for the complexes. The vibrational spectral data show that the ligands behave as neutral ligands and coordinated to the metal ions in a tetradentate manner. The Ni(II) complexes are six coordinate with octahedral geometry and the ligand field parameters: Dq, B, β and LFSE were calculated while, UO2(II) complexes are eight coordinate with dodecahedral geometry and the force constant, FUsbnd O and bond length, RUsbnd O were calculated. The thermal decomposition of complexes ended with metal chloride/nitrate as a final product and the highest thermal stability is displayed by [UO2(L2)(NO3)2] complex. The X-ray powder diffraction data revealed the formation of nano sized crystalline complexes. The SEM analysis provides the morphology of the synthesized compounds and SEM image of [UO2(L2)(NO3)2] complex exhibits nano rod structure. The growth-inhibiting potential of the ligands and their complexes has been assessed against a variety of bacterial and fungal strains.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Taha, Mohd F., E-mail: faisalt@petronas.com.my; Shaharun, Maizatul S.; Shuib, Anis Suhaila, E-mail: anisuha@petronas.com.my

An attempt was made to investigate the potential of rice husk-based activated carbon as an alternative low-cost adsorbent for the removal of Ni(II), Zn(II) and Pb(II) ions from single aqueous solution. Rice husk-based activated carbon was prepared via treatment of rice husk with NaOH followed by the carbonization process at 400°C for 2 hours. Three samples, i.e. raw rice husk, rice husk treated with NaOH and rice husk-based activated carbon, were analyzed for their morphological characteristics using field-emission scanning electron microscope/energy dispersive X-ray (FESEM/EDX). These samples were also analyzed for their carbon, hydrogen, nitrogen, oxygen and silica contents using CHNmore » elemental analyzer and FESEM/EDX. The porous properties of rice husk-based activated carbon were determined by Brunauer-Emmett-Teller (BET) surface area analyzer, and its surface area and pore volume were 255 m{sup 2}/g and 0.17 cm{sup 2}/g, respectively. The adsorption studies for the removal of Ni(II), Zn(II) and Pb(II) ions from single metal aqueous solution were carried out at a fixed initial concentration of metal ion (150 ppm) with variation amount of adsorbent (rice husk-based activated carbon) as a function of varied contact time at room temperature. The concentration of each metal ion was analyzed using atomic absorption spectrophotometer (AAS). The results obtained from adsorption studies indicate the potential of rice husk as an economically promising precursor for the preparation of activated carbon for removal of Ni(II), Zn(II) and Pb(II) ions from single aqueous solution. Isotherm and kinetic model analyses suggested that the experimental data of adsorption studies fitted well with Langmuir, Freundlich and second-order kinetic models.« less

Study of the heavy metal phytoextraction capacity of two forage species growing in an hydroponic environment.

PubMed

Bonfranceschi, Barros A; Flocco, C G; Donati, E R

2009-06-15

Sorghum and alfalfa are two important forage crops. We studied their capacity for accumulating heavy metals in hydroponic experiments. Cadmium, nickel (as divalent cations) and chromium (trivalent and hexavalent) were added individually to the nutrient solution in a range of concentrations from 1 to 80 mg/l. Cr(III) was complexed with EDTA to increase its bioavailability. In alfalfa the increases in the concentration of Cr(III) and Cr(VI) favoured translocation of the metals to the upper parts of the plants, while with Ni(II) the level of translocated metal remained almost unchanged. In sorghum, both Cr(VI) and Ni(II) produced similar results to those in alfalfa, but increases in the concentrations of Cd(II) and Cr(III) in the solution lead to a higher accumulation of the metal at the root level. The concentrations referred to the dry biomass of alfalfa were 500 mg/kg (aerial parts) and 1500 mg/kg (roots) of Cr(III), simultaneously enhancing plant growth. Sorghum captured 500 and 1100 mg/kg (in aerial parts) and 300 and 2000 mg/kg (in roots) for Ni(II) and Cd(II) respectively, without significant damage to its biomass. The results show that alfalfa and sorghum can not only grow in the presence of high heavy metal concentration but also capture and translocate them to the aerial parts; because of these results special attention should be given to these crop plants for their possible use in phytoremediation of large contaminated areas but especially to avoid the possible introduction of the metals accumulated in aerial parts into the food chain when those plants grow in contaminated areas.

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

NASA Astrophysics Data System (ADS)

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

2014-04-01

Extensive temperature-dependent phonon studies and low-temperature magnetic measurements of CoCr2-xFexO4 (for x=0.5, 1 and 2) and Co0.9Ni0.1Cr2O4 polycrystalline powders are presented. The main aim of these studies was to obtain information on phonon and structural properties of these compounds as well as strength of spin-phonon coupling in the magnetically ordered phases. IR and Raman spectra show that doping of CoCr2O4 with Fe(III) ions leads to broadening of bands and appearance of new bands due to the formation of inverted spinel structure. In contrast to this behavior, doping with 10 mol% of Ni(II) ions leads to weak increase of band width only. Magnetization measured as a function of temperature and external magnetic field showed that magnetic properties of Co0.9Ni0.1Cr2O4 sample are similar to those reported for pure CoCr2O4, i.e., partial substitution of Ni(II) for Co(II) leads to slight shift of the ferrimagnetic phase transition at TC and spiral spin order transition at TS towards lower values. The change of crystallization preference induced by incorporation of increasing concentration of Fe(III) ions in the spinel lattice causes significant increase of TC and decrease of TS. The latter transition disappears completely for higher concentrations of Fe(III). The performed temperature-dependent IR studies revealed interesting anomalous behavior of phonons below TC for CoCr1.5Fe0.5O4 and Co0.9Ni0.1Cr2O4, which was attributed to spin-phonon coupling.

{μ-2-[(3-Amino-2,2-dimethyl-prop-yl)imino-meth-yl]-6-meth-oxy-phenolato-1:2κ(5)O(1),O(6):N,N',O(1)}{2-[(3-amino-2,2-dimethyl-prop-yl)imino-meth-yl]-6-meth-oxy-phenolato-1κ(3)N,N',O(1)}-μ-azido-1:2κ(2)N:N-azido-2κN-methanol-2κO-dinickel(II).

PubMed

Ghaemi, Akbar; Rayati, Saeed; Fayyazi, Kazem; Ng, Seik Weng; Tiekink, Edward R T

2012-08-01

Two distinct coordination geometries are found in the binuclear title complex, [Ni(2)(C(13)H(19)N(2)O(2))(2)(N(3))(2)(CH(3)OH)], as one Schiff base ligand is penta-dentate, coordinating via the anti-cipated oxide O, imine N and amine N atoms (as for the second, tridentate, ligand) but the oxide O is bridging and coordination also occurs through the meth-oxy O atom. The Ni(II) atoms are linked by a μ(2)-oxide atom and one end of a μ(2)-azide ligand, forming an Ni(2)ON core. The coordination geometry for the Ni(II) atom coordinated by the tridentate ligand is completed by the meth-oxy O atom derived from the penta-dentate ligand, with the resulting N(3)O(3) donor set defining a fac octa-hedron. The second Ni(II) atom has its cis-octa-hedral N(4)O(2) coordination geometry completed by the imine N and amine N atoms of the penta-dentate Schiff base ligand, a terminally coordinated azide N and a methanol O atom. The arrangement is stabilized by an intra-molecular hydrogen bond between the methanol H and the oxide O atom. Linear supra-molecular chains along the a axis are formed in the crystal packing whereby two amine H atoms from different amine atoms hydrogen bond to the terminal N atom of the monodentate azide ligand.

Spectroscopic and computational studies of a trans-mu-1,2-disulfido-bridged dinickel species, [{(tmc)Ni}(2)(S(2))](OTf)(2): comparison of end-on disulfido and peroxo bonding in (Ni(II))(2) and (Cu(II))(2) species.

PubMed

Van Heuvelen, Katherine M; Kieber-Emmons, Matthew T; Riordan, Charles G; Brunold, Thomas C

2010-04-05

A powerful means of enhancing our understanding of the structures and functions of enzymes that contain nickel-sulfur bonds, such as Ni superoxide dismutase, acetyl-coenzyme A synthase/carbon monoxide dehydrogenase, [NiFe] hydrogenase, and methyl-CoM reductase, involves the investigation of model compounds with similar structural and/or electronic properties. In this study, we have characterized a trans-mu-1,2-disulfido-bridged dinickel(II) species, [{(tmc)Ni}(2)(S(2))](2+) (1, tmc = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane) by using electronic absorption, magnetic circular dichroism (MCD), and resonance Raman (rR) spectroscopic techniques, as well as density functional theory (DFT) and time-dependent DFT computational methods. Our computational results, validated on the basis of the experimental MCD data and previously reported (1)H NMR spectra, reveal that 1 is best described as containing two antiferromagnetically coupled high-spin Ni(II) centers. A normal coordinate analysis of the rR vibrational data was performed to quantify the core bond strengths, yielding force constants of k(Ni-S) = 2.69 mdyn/A and k(S-S) = 2.40 mdyn/A. These values provide a useful basis for a comparison of metal-S/O bonding in 1 and related Ni(2)(O(2)), Cu(2)(O(2)), and Cu(2)(S(2)) dimers. In both the disulfido and the peroxo species, the lower effective nuclear charge of Ni(II) as compared to Cu(II) results in a decreased covalency, and thus relatively weaker metal-S/O bonding interactions in the Ni(2) dimers than in the Cu(2) complexes.

Michael Addition Reactions between Chiral Equivalents of a Nucleophilic Glycine and (S)- or (R)-3-[(E)-Enoyl]-4-phenyl-1,3-oxazolidin-2-ones as a General Method for Efficient Preparation of β-Substituted Pyroglutamic Acids. Case of Topographically Controlled Stereoselectivity

PubMed Central

Soloshonok*, Vadim A.; Cai, Chaozhong; Yamada, Takeshi; Ueki, Hisanori; Ohfune, Yasufumi; Hruby, Victor J.

2006-01-01

This paper describes a systematic study of addition reactions between the chiral Ni(II) complex of the Schiff base of glycine with (S)-o-[N-(N-benzylprolyl)amino]benzophenone and (S)- or (R)-3-[(E)-enoyl]-4-phenyl-1,3-oxazolidin-2-ones as a general and synthetically efficient approach to β-substituted pyroglutamic acids and relevant compounds. These reactions were shown to occur at room temperature in the presence of nonchelating organic bases and, most notably, with very high (>98% diastereomeric excess (de)) stereoselectivity at both newly formed stereogenic centers. The stereochemical outcome of the reactions was found to be overwhelmingly controlled by the stereochemical preferences of the Michael acceptors, and the chirality of the glycine complex influenced only the reaction rate. Thus, in the reactions of both the (S)-configured Ni(II) complex and the Michael acceptors, the reaction rates were exceptionally high, allowing preparation of the corresponding products with virtually quantitative (>98%) chemical and stereochemical yields. In contrast, reactions of the (S)-configured Ni(II) complex and (R)-configured Michael acceptors proceeded at noticeably lower rates, but the addition products were obtained in high diastereo-and enantiomeric purity. To rationalize the remarkably high and robust stereoselectivity observed in these reactions, we consider an enzyme–substrate-like mode of interaction involing a topographical match or mismatch of two geometric figures. Excellent chemical and stereochemical yields, combined with the simplicity and operational convenience of the experimental procedures, render the present method of immediate use for preparing various β-substituted pyroglutamic acids and related compounds. PMID:16248672

Michael addition reactions between chiral equivalents of a nucleophilic glycine and (S)- or (R)-3-[(E)-enoyl]-4-phenyl-1,3-oxazolidin-2-ones as a general method for efficient preparation of beta-substituted pyroglutamic acids. Case of topographically controlled stereoselectivity.

PubMed

Soloshonok, Vadim A; Cai, Chaozhong; Yamada, Takeshi; Ueki, Hisanori; Ohfune, Yasufumi; Hruby, Victor J

2005-11-02

This paper describes a systematic study of addition reactions between the chiral Ni(II) complex of the Schiff base of glycine with (S)-o-[N-(N-benzylprolyl)amino]benzophenone and (S)- or (R)-3-[(E)-enoyl]-4-phenyl-1,3-oxazolidin-2-ones as a general and synthetically efficient approach to beta-substituted pyroglutamic acids and relevant compounds. These reactions were shown to occur at room temperature in the presence of nonchelating organic bases and, most notably, with very high (>98% diastereomeric excess (de)) stereoselectivity at both newly formed stereogenic centers. The stereochemical outcome of the reactions was found to be overwhelmingly controlled by the stereochemical preferences of the Michael acceptors, and the chirality of the glycine complex influenced only the reaction rate. Thus, in the reactions of both the (S)-configured Ni(II) complex and the Michael acceptors, the reaction rates were exceptionally high, allowing preparation of the corresponding products with virtually quantitative (>98%) chemical and stereochemical yields. In contrast, reactions of the (S)-configured Ni(II) complex and (R)-configured Michael acceptors proceeded at noticeably lower rates, but the addition products were obtained in high diastereo- and enantiomeric purity. To rationalize the remarkably high and robust stereoselectivity observed in these reactions, we consider an enzyme-substrate-like mode of interaction involving a topographical match or mismatch of two geometric figures. Excellent chemical and stereochemical yields, combined with the simplicity and operational convenience of the experimental procedures, render the present method of immediate use for preparing various beta-substituted pyroglutamic acids and related compounds.

D-Amino acid oxidase bio-functionalized platforms: Toward an enhanced enzymatic bio-activity

NASA Astrophysics Data System (ADS)

Herrera, Elisa; Valdez Taubas, Javier; Giacomelli, Carla E.

2015-11-01

The purpose of this work is to study the adsorption process and surface bio-activity of His-tagged D-amino acid oxidase (DAAO) from Rhodotorula gracilis (His6-RgDAAO) as the first step for the development of an electrochemical bio-functionalized platform. With such a purpose this work comprises: (a) the His6-RgDAAO bio-activity in solution determined by amperometry, (b) the adsorption mechanism of His6-RgDAAO on bare gold and carboxylated modified substrates in the absence (substrate/COO-) and presence of Ni(II) (substrate/COO- + Ni(II)) determined by reflectometry, and (c) the bio-activity of the His6-RgDAAO bio-functionalized platforms determined by amperometry. Comparing the adsorption behavior and bio-activity of His6-RgDAAO on these different solid substrates allows understanding the contribution of the diverse interactions responsible for the platform performance. His6-RgDAAO enzymatic performance in solution is highly improved when compared to the previously used pig kidney (pk) DAAO. His6-RgDAAO exhibits an amperometrically detectable bio-activity at concentrations as low as those expected on a bio-functional platform; hence, it is a viable bio-recognition element of D-amino acids to be coupled to electrochemical platforms. Moreover, His6-RgDAAO bio-functionalized platforms exhibit a higher surface activity than pkDAAO physically adsorbed on gold. The platform built on Ni(II) modified substrates present enhanced bio-activity because the surface complexes histidine-Ni(II) provide with site-oriented, native-like enzymes. The adsorption mechanism responsible of the excellent performance of the bio-functionalized platform takes place in two steps involving electrostatic and bio-affinity interactions whose prevalence depends on the degree of surface coverage.

Metal selectivity of the E. coli nickel metallochaperone, SlyD

PubMed Central

Kaluarachchi, Harini; Siebel, Judith F.; Kaluarachchi-Duffy, Supipi; Krecisz, Sandra; Sutherland, Duncan E. K.; Stillman, Martin J.; Zamble, Deborah B.

2012-01-01

SlyD is a Ni(II)-binding protein that contributes to nickel homeostasis in Escherichia coli. The C-terminal domain of SlyD contains a rich variety of metal-binding amino acids, suggesting broader metal-binding capabilities, and previous work demonstrated that the protein can coordinate several types of first row transition metals. However, the binding of SlyD to metals other than Ni(II) has not been previously characterized. To further our understanding of the in vitro metal-binding activity of SlyD and how it correlates with the in vivo function of this protein, the interactions between SlyD and the series of biologically relevant transition metals Mn(II), Fe(II), Co(II), Cu(I) and Zn(II) were examined by using a combination of optical spectroscopy and mass spectrometry. SlyD binding to Mn(II) or to Fe(II) ions was not detected but the protein coordinates multiple ions of Co(II), Zn(II) and Cu(I) with appreciable affinities (KD ≤ nM), highlighting the promiscuous nature of this protein. The order of affinities of SlyD for the metals examined is Mn(II), Fe(II) < Co(II) < Ni(II) ~ Zn(II) ≪ Cu(I). Although the purified protein is unable to overcome the large thermodynamic preference for Cu(I) and exclude Zn(II) chelation in the presence of Ni(II), in vivo studies reveal a Ni(II)-specific function for the protein. Furthermore, these latter experiments support a specific role for SlyD as a [NiFe]-hydrogenase enzyme maturation factor. The implications of the divergence between the metal selectivity of SlyD in vitro and the specific activity in vivo are discussed. PMID:22047179

Synthesis and spectroscopic studies on the new Schiff base derived from the 1:2 condensation of 2,6-diformyl-4-methylphenol with 5-aminouracil (BDF5AU) and its transition metal complexes. Influence on biologically active peptides-regulating aminopeptidases.

PubMed

Hueso-Ureña, Francisco; Illán-Cabeza, Nuria A; Moreno-Carretero, Miguel N; Martínez-Martos, José M; Ramírez-Expósito, María J

2003-04-01

The synthesis, spectroscopic (IR, 1H and 13C NMR, UV-Vis-NIR, EPR), magnetic measurements and biological studies of a number of complexes of Co(II), Ni(II), Cu(II), Zn(II), Cd(II), Au(III) and Hg(II) of the Schiff base derived from the 1:2 condensation of 2,6-diformyl-4-methylphenol and 5-aminouracil, ((5-[[(3-[[(2,4-dioxopyrimidin-5(1H,3H)-yl)imino]methyl]-2-hydroxy-5-methylphenyl)methylene]amino]pyrimidine-2,4(1H,3H)-dione, hereafter denoted as BDF5AU) are reported. In all cases, the complexes appear to be monomeric. The deprotonated ligand in the phenolic oxygen atom shows a tridentate coordination mode through the two azomethine nitrogen atoms and the phenolic oxygen atom. The coordination of the neutral ligand takes place through the phenolic oxygen atom and one azomethine nitrogen atom and the carbonylic oxygen atom in fourth position of one uracil ring. The biological properties of some perchlorate complexes on the activity of some neutral, acid, basic and omega aminopeptidases (AP) are assayed, demonstrating a general inhibitory effect. Neutral and basic AP are mainly inhibited by Cu(II), Ni(II) and Cd(II) complexes, although tyrosyl-AP is activated by Zn(II) complex. Glutamyl-AP but not aspartyl-AP is inhibited by all the complexes assayed excepting Zn(II) complex. Finally, omega AP is inhibited by Ni(II) and Cd(II) complexes. Copyright 2003 Elsevier Science Inc.

Synthesis, characterization, and biological activity of some novel Schiff bases and their Co(II) and Ni(II) complexes: A new route for Co3O4 and NiO nanoparticles for photocatalytic degradation of methylene blue dye

NASA Astrophysics Data System (ADS)

Nassar, Mostafa Y.; Aly, Hisham M.; Abdelrahman, Ehab A.; Moustafa, Moustafa E.

2017-09-01

Six novel Co(II) and Ni(II)-triazole Schiff base complexes have been successfully synthesized by refluxing the prepared triazole Schiff bases with CoCl2·6H2O or NiCl2·6H2O. The Schiff base ligands were prepared through condensation of 3-R-4-amino-5-hydrazino-1,2,4-triazole with dibenzoylmethane [Rdbnd H, CH3, and CH2CH3; namely, L1, L2, and L3, respectively]. The prepared Co(II) and Ni(II) complexes have been identified using elemental analysis, FT-IR, UV-Vis, magnetic moment, conductivity, and thermal analysis. On the basis of the conductance results, it was concluded that all the prepared complexes are nonelectrolytes. Interestingly, the prepared Co(II) and Ni(II) complexes were employed as precursors for producing of Co3O4 and NiO nanoparticles, respectively. The produced nanostructures have been identified by XRD, HR-TEM, FT-IR and UV-Vis spectra. The produced nanoparticles revealed good photocatalytic activity for the degradation of methylene blue dye under UV illumination in presence of hydrogen peroxide. The percent of degradation was estimated to be 55.71% in 420.0 min and 90.43% in 360.0 min for Co3O4 and NiO, respectively. Moreover, the synthesized complexes, nano-sized Co3O4, and NiO products have been examined, employing modified Bauer- Kirby method, for antifungal (Candida albicans and Aspergillus flavus) and antibacterial (Staphylococcus aureus and Escherichia coli) activities.

Removal of copper and iron by polyurethane foam column in FIA system for the determination of nickel in pierced ring.

PubMed

Vongboot, Monnapat; Suesoonthon, Monrudee

2015-01-01

Polyurethane foam (PUF) mini-column was used to eliminate copper and iron for the determination of nickel in pierced rings. The PUF mini-column was connected to FIA system for on-line sorption of copper and iron in complexes form of CuSCN(+) and FeSCN(2+). For this season, the acid solution containing a mixture of Ni(II), Fe(III), Cu(II) and SCN(-) ions was firstly flew into the PUF column. Then, the percolated solution which Fe(III) and Cu(II) ions is separated from analysis was injected into FIA system to react with 4-(2-pyridylazo) resorcinol (PAR) reagent in basic condition which this method is called pH gradient technique. The Ni-PAR complexes obtained were measured theirs absorbance at 500 nm by UV visible spectrophotometer. In this study, it was found that Cu(II) and Fe(III) were completely to form complexes with 400 mmol/L KSCN and entirely to eliminate in acidic condition at pH 3.0. In the optimum condition of these experiments, the method provided the linear relationship between absorbance and the concentration of Ni(II) in the range from 5.00 to 30.00 mg/L. Linear equation is y=0.0134x+0.0033 (R(2)=0.9948). Precision, assessed in the term of the relative standard deviation, RSD, and accuracy for multiple determinations obtained in values of 0.77-1.73% and 97.4%, respectively. The level of an average amount of Ni(II) in six piercing rings was evaluated to be 14.78 mg/g. Copyright © 2014 Elsevier B.V. All rights reserved.

Supramolecular complexes of Co(II), Ni(II) and Zn(II) p-hydroxybenzoates with caffeine: Synthesis, spectral characterization and crystal structure

NASA Astrophysics Data System (ADS)

Taşdemir, Erdal; Özbek, Füreya Elif; Sertçelik, Mustafa; Hökelek, Tuncer; Çelik, Raziye Çatak; Necefoğlu, Hacali

2016-09-01

Three novel complexes Co(II), Ni(II) and Zn(II) containing p-hydroxybenzoates and caffeine ligands were synthesized and characterized by elemental analysis, FT-IR and UV-vis Spectroscopy, molar conductivity and single crystal X-ray diffraction methods. The thermal properties of the synthesized complexes were investigated by TGA/DTA. The general formula of the complexes is [M(HOC6H4COO)2(H2O)4]·2(C8H10N4O2)·8H2O (where: M: Co, Ni and Zn). The IR studies showed that carboxylate groups of p-hydroxybenzoate ligands have monodentate coordination mode. The M2+ ions are octahedrally coordinated by two p-hydroxybenzoate ligands, four water molecules leading to an overall MO6 coordination environment. The medium-strength hydrogen bondings involving the uncoordinated caffeine ligands and water molecules, coordinated and uncoordinated water molecules and p-hydroxybenzoate ligands lead to three-dimensional supramolecular networks in the crystal structures.

Free metal ion depletion by "Good's" buffers. III. N-(2-acetamido)iminodiacetic acid, 2:1 complexes with zinc(II), cobalt(II), nickel(II), and copper(II); amide deprotonation by Zn(II), Co(II), and Cu(II).

PubMed

Lance, E A; Rhodes, C W; Nakon, R

1983-09-01

Potentiometric, visible, infrared, electron spin, and nuclear magnetic resonance studies of the complexation of N-(2-acetamido)iminodiacetic acid (H2ADA) by Ca(II), Mg(II), Mn(II), Zn(II), Co(II), Ni(II), and Cu(II) are reported. Ca(II) and Mg(II) were found not to form 2:1 ADA2- to M(II) complexes, while Mn(II), Cu(II), Ni(II), Zn(II), and Co(II) did form 2:1 metal chelates at or below physiological pH values. Co(II) and Zn(II), but not Cu(II), were found to induce stepwise deprotonation of the amide groups to form [M(H-1ADA)4-(2)]. Formation (affinity) constants for the various metal complexes are reported, and the probable structures of the various metal chelates in solution are discussed on the basis of various spectral data.

Rapid Adsorption of Heavy Metals by Fe3O4/Talc Nanocomposite and Optimization Study Using Response Surface Methodology

PubMed Central

Kalantari, Katayoon; Ahmad, Mansor B.; Masoumi, Hamid Reza Fard; Shameli, Kamyar; Basri, Mahiran; Khandanlou, Roshanak

2014-01-01

Fe3O4/talc nanocomposite was used for removal of Cu(II), Ni(II), and Pb(II) ions from aqueous solutions. Experiments were designed by response surface methodology (RSM) and a quadratic model was used to predict the variables. The adsorption parameters such as adsorbent dosage, removal time, and initial ion concentration were used as the independent variables and their effects on heavy metal ion removal were investigated. Analysis of variance was incorporated to judge the adequacy of the models. Optimal conditions with initial heavy metal ion concentration of 100, 92 and 270 mg/L, 120 s of removal time and 0.12 g of adsorbent amount resulted in 72.15%, 50.23%, and 91.35% removal efficiency for Cu(II), Ni(II), and Pb(II), respectively. The predictions of the model were in good agreement with experimental results and the Fe3O4/talc nanocomposite was successfully used to remove heavy metals from aqueous solutions. PMID:25050784

trans-Bis(thio­cyanato-κN)tetra­kis­(3,4,5-trimethyl-1H-pyrazole-κN 2)nickel(II)–3,4,5-trimethyl-1H-pyrazole (1/1)

PubMed Central

Hossaini Sadr, Moayad; Engle, James T.; Ziegler, Christopher J.; Soltani, Behzad; Mousavi, Zahra

2011-01-01

In the title compound, [Ni(NCS)2(C6H10N2)4]·C6H10N2, the asymmetric unit comprises a NiII complex and a co-crystallised mol­ecule of 3,4,5-trimethyl-1H-pyrazole (PzMe3). The NiII atom is coordinated by four PzMe3 mol­ecules and two thio­cyanate anions to define a trans N4S2 distorted octa­hedral geometry. A number of intra­molecular N—H⋯N, N—H⋯S and C—H⋯N inter­actions contribute to the stability of the complex. The crystal structure is stabilized by inter­molecular N—H⋯S inter­actions, which link neighbouring mol­ecules into chains along the a axis. PMID:22219831

Bis[1-meth­oxy-2,2,2-tris­(pyrazol-1-yl-κN 2)ethane]­nickel(II) bis­(tri­fluoro­methane­sulfonate) methanol disolvate

PubMed Central

Lyubartseva, Ganna; Parkin, Sean; Mallik, Uma Prasad

2013-01-01

In the title salt, [Ni(C12H14N6O)2](CF3SO3)2·2CH3OH, the NiII ion is coordinated by six N atoms from two tridentate 1-meth­oxy-2,2,2-tris­(pyrazol-1-yl)ethane ligands in a distorted octa­hedral geometry. The NiII ion is situated on an inversion centre. The Ni—N distances range from 2.0589 (19) to 2.0757 (19) Å, intra-ligand N—Ni—N angles range from 84.50 (8) to 85.15 (8)°, and adjacent inter-ligand N—Ni—N angles range between 94.85 (8) and 95.50 (8)°. In the crystal, O—H⋯O hydrogen bonds between methanol solvent mol­ecules and tri­fluoro­methane­sulfonate anions are observed. PMID:24098170

A one-dimensional nickel(II) coordination polymer containing 2,6-dipicolinate and dipyrido[3,2-a:2',3'-c]phenazine.

PubMed

Ma, Yi; Zhang, Li-Tian; Wang, Xiao-Fang; He, Yong-Ke; Han, Zheng-Bo

2007-12-01

A new coordination polymer, catena-poly[[(dipyrido[3,2-a:2',3'-c]phenazine-kappa(2)N,N')nickel(II)]-mu-2,6-dipicolinato-kappa(4)O(2),N,O(6):O(2')], [Ni(C7H3NO4)(C18H10N4)]n, exhibits a one-dimensional structure in which 2,6-dipicolinate acts as a bridging ligand interconnecting adjacent nickel(II) centers to form a chain structure. The asymmetric unit contains one Ni(II) center, one dipyrido[3,2-a:2',3'-c]phenazine ligand and one 2,6-dipicolinate ligand. Each Ni(II) center is six-coordinated and surrounded by three N atoms and three O atoms from one dipyrido[3,2-a:2',3'-c]phenazine ligand and two different 2,6-dipicolinate ligands, leading to a distorted octahedral geometry. Adjacent chains are linked by pi-pi stacking interactions and weak interactions to form a three-dimensional supramolecular network.

Synthesis, characterization, antibacterial activities and carbonic anhydrase enzyme inhibitor effects of new arylsulfonylhydrazone and their Ni(II), Co(II) complexes

NASA Astrophysics Data System (ADS)

Özdemir, Ümmühan Özmen; Arslan, Fatma; Hamurcu, Fatma

2010-01-01

Ethane sulfonic acide hydrazide ( esh: CH 3CH 2SO 2NHNH 2) derivatives as 5-methylsalicyl-aldehydeethanesulfonylhydrazone ( 5msalesh), 5-methyl-2-hydroxyacetophenoneethane sulfonylhydrazone ( 5mafesh) and their Ni(II), Co(II) complexes have been synthesized for the first time. The structure of these compounds has been investigated by elemental analysis, FT-IR, 1H NMR, 13C NMR, LC/MS, UV-vis spectrophotometric method, magnetic susceptibility, thermal studies and conductivity measurements. The antibacterial activities of synthesized compounds were studied against Gram positive bacteria; Staphylococcus aureus, Bacillus subtilis, Bacillus magaterium and Gram negative bacteria; Salmonella enteritidis, Escherichia coli by using the microdilution broth method. The biological activity screening showed that ligands have more activity than complexes against the tested bacteria. The inhibition activities of these compounds on carbonic anhydrase II (CA II) have been investigated by comparing IC 50 and Ki values and it has been found that 5msalesh and its complexes have more enzyme inhibition efficiency than other compounds.

Synthesis, spectroscopic characterization and biological activities of N4O2 Schiff base ligand and its metal complexes of Co(II), Ni(II), Cu(II) and Zn(II)

NASA Astrophysics Data System (ADS)

Al-Resayes, Saud I.; Shakir, Mohammad; Abbasi, Ambreen; Amin, Kr. Mohammad Yusuf; Lateef, Abdul

The Schiff base ligand, bis(indoline-2-one)triethylenetetramine (L) obtained from condensation of triethylenetetramine and isatin was used to synthesize the complexes of type, [ML]Cl2 [M = Co(II), Ni(II), Cu(II) and Zn(II)]. L was characterized on the basis of the results of elemental analysis, FT-IR, 1H and 13C NMR, mass spectroscopic studies. The stoichiometry, bonding and stereochemistries of complexes were ascertained on the basis of results of elemental analysis, magnetic susceptibility values, molar conductance and various spectroscopic studies. EPR, UV-vis and magnetic moments revealed an octahedral geometry for complexes. L and its Cu(II) and Zn(II) complexes were screened for their antibacterial activity. Analgesic activity of Cu(II) and Zn(II) complexes was also tested in rats by tail flick method. Both complexes were found to possess good antibacterial and moderate analgesic activity.

Removal of Heavy Metals by Adsorption onto Activated Carbon Derived from Pine Cones of Pinus roxburghii.

PubMed

Saif, Muhammad Jawwad; Zia, Khalid Mahmood; Fazal-ur-Rehman; Usman, Muhammad; Hussain, Abdullah Ijaz; Chatha, Shahzad Ali Shahid

2015-04-01

Activated carbon derived from cones of Pinus roxburghii (Himalayan Pine) was used as an adsorbent for the removal of copper, nickel and chromium ions from waste water. Surface analysis was carried out to determine the specific surface area and pore size distribution of the pine cone derived activated carbon. Optimal parameters, effect of adsorbent quantity, pH, equilibrium time, agitation speed and temperature were studied. Equilibrium data were evaluated by Langmuir and Freundlich isotherm models. Langmuir isotherm afforded the best fit to the equilibrium data with a maximum adsorption capacity of 14.2, 31.4 and 29.6 mg/g for Cu(II), Ni(II) and Cr(VI) respectively. Maximum adsorption of Cu(II), Ni(II) was observed in the pH range 4.0 to 4.5, whereas the best adsorption of Cr(VI) was observed at pH 2.5. It was found that 180 minutes was sufficient to gain adsorption equilibrium. The adsorption process follows a pseudo-second-order kinetic model.

Rapid adsorption of heavy metals by Fe3O4/talc nanocomposite and optimization study using response surface methodology.

PubMed

Kalantari, Katayoon; Ahmad, Mansor B; Masoumi, Hamid Reza Fard; Shameli, Kamyar; Basri, Mahiran; Khandanlou, Roshanak

2014-07-21

Fe3O4/talc nanocomposite was used for removal of Cu(II), Ni(II), and Pb(II) ions from aqueous solutions. Experiments were designed by response surface methodology (RSM) and a quadratic model was used to predict the variables. The adsorption parameters such as adsorbent dosage, removal time, and initial ion concentration were used as the independent variables and their effects on heavy metal ion removal were investigated. Analysis of variance was incorporated to judge the adequacy of the models. Optimal conditions with initial heavy metal ion concentration of 100, 92 and 270 mg/L, 120 s of removal time and 0.12 g of adsorbent amount resulted in 72.15%, 50.23%, and 91.35% removal efficiency for Cu(II), Ni(II), and Pb(II), respectively. The predictions of the model were in good agreement with experimental results and the Fe3O4/talc nanocomposite was successfully used to remove heavy metals from aqueous solutions.

A Crystal Field Approach to Orbitally Degenerate SMMs: Beyond the Spin-Only Hamiltonian

NASA Astrophysics Data System (ADS)

Bhaskaran, Lakshmi; Marriott, Katie; Murrie, Mark; Hill, Stephen

Single-Molecule Magnets (SMMs) with large magnetization reversal barriers are promising candidates for high-density information storage. Recently, a large uniaxial magnetic anisotropy was observed for a mononuclear trigonal bipyramidal (TBP) [NiIICl3(Me-abco)2] SMM. High-field EPR studies analyzed on the basis of a spin-only Hamiltonian give ¦D¦>400 cm-1, which is close to the spin-orbit coupling parameter λ = 668 cm-1 for NiII, suggesting an orbitally degenerate ground state. The spin-only description is ineffective in this limit, necessitating the development of a model that includes the orbital moment. Here we describe a phenomenological approach that takes into account a full description of crystal field, electron-electron repulsion and spin-orbit coupling effects on the ground state of a NiII ion in a TBP coordination geometry. The model is in good agreement with the high-field EPR experiments, validating its use for spectroscopic studies of orbitally degenerate molecular nanomagnets. This work was supported by the NSF (DMR-1309463).

Structural characterization and antimicrobial activities of transition metal complexes of a hydrazone ligand

NASA Astrophysics Data System (ADS)

Bakale, Raghavendra P.; Naik, Ganesh N.; Machakanur, Shrinath S.; Mangannavar, Chandrashekhar V.; Muchchandi, Iranna S.; Gudasi, Kalagouda B.

2018-02-01

A hydrazone ligand has been synthesized by the condensation of 2-nitrobenzaldehyde and hydralazine, and its Co(II), Ni(II), Cu(II) and Zn(II) complexes have been reported. Structural characterization of the ligand and its metal complexes has been performed by various spectroscopic [IR, NMR, UV-Vis, Mass], thermal and other physicochemical methods. The structure of the ligand and its Ni(II) complex has been characterized by single crystal X-ray diffraction studies. All the synthesized compounds have been screened for in vitro antimicrobial activity. The antibacterial activity is tested against Gram-positive strains Enterococcus faecalis, Streptococcus mutans and Staphylococcus aureus and Gram-negative strains Escherichia coli, Pseudomonas aeruginosa and Klebsiella pneumoniae using ciprofloxacin as the reference standard. Antifungal activity is tested against Candida albicans, Aspergillus fumigatus and Aspergillus niger using ketoconazole as the reference standard. The minimum inhibitory concentration (MIC) was determined for test compounds as well as for reference standard. Ligand, Cu(II) and Zn(II) complexes have shown excellent activity against Candida albicans.

Octa-akis(4-amino-pyridine)-1κN,2κN-aqua-2κO-μ-carbonato-1:2κO,O':O''-dinickel(II) dichloride penta-hydrate.

PubMed

Fun, Hoong-Kun; Sinthiya, A; Jebas, Samuel Robinson; Ravindran Durai Nayagam, B; Alfred Cecil Raj, S

2008-10-18

In the title compound, [Ni(2)(CO(3))(C(5)H(6)N(2))(8)(H(2)O)]Cl(2)·5H(2)O, one of the the Ni(II) ions is six-coordinated in a distorted octa-hedral geometry, with the equatorial plane defined by four pyridine N atoms from four amino-pyridine ligands, the axial positions being occupied by one water O and a carbonate O atom. The other Ni(II) ion is also six-coordinated, by four other pyridine N atoms from four other amino-pyridine ligands and two carbonate O atoms to complete a distorted octa-hedral geometry. In the crystal structure, mol-ecules are linked into an infinite three-dimensional network by O-H⋯O, N-H⋯Cl, N-H⋯O, O-H⋯N, C-H⋯O, C-H⋯N and C/N-H⋯π inter-actions involving the pyridine rings.

Association between poor clinical prognosis and sleep duration among breast cancer patients.

PubMed

Mansano-Schlosser, Thalyta Cristina; Ceolim, Maria Filomena

2017-06-05

to investigate the association between clinical progression and the quality and duration of sleep in women with breast cancer. longitudinal study, with 114 participants, conducted in a hospital in Brazil. The instruments used were: questionnaire for sociodemographic and clinical characterization, Pittsburgh Sleep Quality Index; Beck Depression Inventory and Herth Hope Scale. Data were analyzed through descriptive statistics and survival analyses (outcome: poor clinical progression), using the Kaplan-Meier curve, Log-rank test and Cox proportional model. a higher probability of poor clinical progression was verified in women with sleep durations of less than six hours or nine hours and over (p=.0173). the results suggest the importance of further studies that seek to verify whether the quantitative management of sleep disorders would have an impact on the progression of breast cancer. Women should be encouraged to report sleep problems to nurses. mensurar a associação entre evolução clínica e qualidade e duração do sono em mulheres com câncer de mama. estudo longitudinal, com 114 participantes, realizado em um hospital do Brasil. Os instrumentos utilizados foram: questionário para caracterização sociodemográfica e clínica, Índice de Qualidade do Sono de Pittsburgh; Inventário de Depressão de Beck e Escala de Esperança de Herth. Os dados foram analisados via análises descritivas e de sobrevivência (resultado: evolução clínica desfavorável), utilizando-se a curva de Kaplan-Meier, o teste log-rank e o modelo proporcional de Cox. verificou-se maior probabilidade de evolução clínica desfavorável em mulheres com duração de sono inferior a seis ou mais de nove horas (p = 0,0173). os resultados sugerem a importância de mais estudos que buscam verificar se a gestão quantitativa dos distúrbios do sono teria um impacto sobre a evolução do câncer de mama. As mulheres devem ser encorajadas a relatar isso espontaneamente aos enfermeiros. medir la asociación entre progresión clínica y calidad y duración del sueño en mujeres con cáncer de mama. estudio longitudinal, con 114 participantes, realizado en un hospital de Brasil. Los instrumentos utilizados fueron: cuestionario para caracterización sociodemográfica y clínica; índice de calidad del sueño de Pittsburgh; Inventario de Depresión de Beck; y Escala de esperanza de Herth. Los datos se analizaron a través de análisis descriptivo y de supervivencia (resultado: evolución clínica desfavorable), utilizando la curva de Kaplan-Meier, la prueba log-rank y el modelo proporcional de Cox. se comprobó una mayor probabilidad de progresión clínica desfavorable en mujeres con duración de sueño inferior a seis horas o más de nueve horas (p = 0,0173). los resultados sugieren la importancia de realizar más estudios que busquen verificar si la gestión cuantitativa de los trastornos del sueño tendría un impacto en la progresión del cáncer de mama. Las mujeres deben ser alentadas a informar esto espontáneamente a las enfermeras.

Excited-state absorption in tetrapyridyl porphyrins: comparing real-time and quadratic-response time-dependent density functional theory

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bowman, David N.; Asher, Jason C.; Fischer, Sean A.

2017-01-01

Threemeso-substituted tetrapyridyl porphyrins (free base, Ni(ii), and Cu(ii)) were investigated for their optical limiting (OL) capabilities using real-time (RT-), linear-response (LR-), and quadratic-response (QR-) time-dependent density functional theory (TDDFT) methods.

O2-dependent Aliphatic Carbon-carbon Bond Cleavage Reactivity in a Ni(II) Enolate Complex Having a Hydrogen Bond Donor Microenvironment; Comparison with a Hydrophobic Analog

PubMed Central

Grubel, Katarzyna; Fuller, Amy L.; Chambers, Bonnie M.; Arif, Atta M.; Berreau, Lisa M.

2010-01-01

A mononuclear Ni(II) complex having an acireductone type ligand, and supported by the bnpapa (N,N-bis((6-neopentylamino-2-pyridyl)methyl-N-((2-pyridyl)methyl)amine ligand, [(bnpapa)Ni(PhC(O)C(OH)C(O)Ph)]ClO4 (14), has been prepared and characterized by elemental analysis, 1H NMR, FTIR, and UV-vis. To gain insight into the 1H NMR features of 14, the air stable analog complexes [(bnpapa)Ni(CH3C(O)CHC(O)CH3)]ClO4 (16) and [(bnpapa)Ni(ONHC(O)CH3)]ClO4 (17) were prepared and characterized by X-ray crystallography, 1H NMR, FTIR, UV-vis, mass spectrometry, and solution conductivity measurements. Compounds 16 and 17 are 1:1 electrolyte species in CH3CN. 1H and 2H NMR studies of 14, 16, and 17 and deuterated analogs revealed that the complexes having six-membered chelate rings for the exogenous ligand (14 and 16) do not have a plane of symmetry within the solvated cation and thus exhibit more complicated 1H NMR spectra. Compound 17, as well as other simple Ni(II) complexes of the bnpapa ligand (e.g. [(bnpapa)Ni(ClO4)(CH3CN)]ClO4 (18) and [(bnpapaNi)2(μ-Cl)2](ClO4)2 (19)), exhibit 1H NMR spectra consistent with the presence of a plane of symmetry within the cation. Treatment of [(bnpapa)Ni(PhC(O)C(OH)C(O)Ph)]ClO4 (14) with O2 results in aliphatic carbon-carbon bond cleavage within the acireductone-type ligand and the formation of [(bnpapa)Ni(O2CPh)]ClO4 (9), benzoic acid, benzil, and CO. Use of 18O2 in the reaction gives high levels of incorporation (>80%) of one labeled oxygen atom into 9 and benzoic acid. The product mixture and level of 18O incorporation in this reaction is different than that exhibited by the analog supported the hydrophobic 6-Ph2TPA ligand, [(6-Ph2TPA)Ni(PhC(O)C(OH)C(O)Ph)]ClO4 (2). We propose that this difference is due to variations in the reactivity of bnpapa- and 6-Ph2TPA-ligated Ni(II) complexes with triketone and/or peroxide species produced in the reaction pathway. PMID:20039645

Study of the Local Horizon. (Spanish Title: Estudio del Horizonte Local.) Estudo do Horizonte Local

NASA Astrophysics Data System (ADS)

Ros, Rosa M.

2009-12-01

The study of the horizon is fundamental to easy the first observations of the students at any education center. A simple model, to be developed in each center, allows to easy the study and comprehension of the rudiments of astronomy. The constructed model is presented in turn as a simple equatorial clock, other models (horizontal and vertical) may be constructed starting from it. El estudio del horizonte es fundamental para poder facilitar las primeras observaciones de los alumnos en un centro educativo. Un simple modelo, que debe realizarse para cada centro, nos permite facilitar el estudio y la comprensión de los primeros rudimentos astronómicos. El modelo construido se presenta a su vez como un sencillo modelo de reloj ecuatorial y a partir de él se pueden construir otros modelos (horizontal y vertical). O estudo do horizonte é fundamental para facilitar as primeiras observações dos alunos num centro educativo. Um modelo simples, que deve ser feito para cada centro, permite facilitar o estudo e a compreensão dos primeiros rudimentos astronômicos. O modelo construído apresenta-se, por sua vez, como um modelo simples de relógio equatorial e a partir dele pode-se construir outros modelos (horizontal e vertical)

Chemical Remediation of Nickel(II) Waste: A Laboratory Experiment for General Chemistry Students

ERIC Educational Resources Information Center

Corcoran, K. Blake; Rood, Brian E.; Trogden, Bridget G.

2011-01-01

This project involved developing a method to remediate large quantities of aqueous waste from a general chemistry laboratory experiment. Aqueous Ni(II) waste from a general chemistry laboratory experiment was converted into solid nickel hydroxide hydrate with a substantial decrease in waste volume. The remediation method was developed for a…

β-Octakis(methylthio)porphycenes: synthesis, characterisation and third order nonlinear optical studies.

PubMed

Rana, Anup; Lee, Sangsu; Kim, Dongho; Panda, Pradeepta K

2015-05-04

A novel electron deficient β-octakis(methylthio)porphycene, along with its Zn(ii) and Ni(ii) derivatives, was synthesized for the first time. The macrocyclic structure exhibits core ruffling with a largely red shifted absorption band (∼750 nm) and also a large enhancement in the third order nonlinear optical response.

Activated biochar: Preparation, characterization and electroanalytical application in an alternative strategy of nickel determination.

PubMed

Kalinke, Cristiane; Oliveira, Paulo Roberto; Oliveira, Geovane Arruda; Mangrich, Antonio Sálvio; Marcolino-Junior, Luiz H; Bergamini, Márcio F

2017-08-29

This work reports for the first time the use of chemically activated biochar as electrode modifier for nickel determination. The biochar activation was performed by refluxing with HNO 3 , which promoted a higher nickel preconcentration compared to unmodified and modified biochar precursor electrodes. Morphological and structural characterization revealed the increase of surface acid groups, surface area and porosity of biochar after activation. Nickel determination was investigated adopting an alternative voltammetric methodology based on monitoring the Ni(II)/Ni(III) redox couple. In the proposed method, it was not necessary to use a complexing agent and the biochar itself was responsible for the analyte preconcentration. A linear response for Ni(II) concentration range from 1.0 to 30 μmol L -1 and a limit of detection of 0.25 μmol L -1 were obtained. The method was successfully applied for Ni(II) determination in spiked samples of bioethanol fuel and discharge water, with recoveries values between 103 and 109%. Copyright © 2017 Elsevier B.V. All rights reserved.

Electrocatalytic Hydrogen Production by a Nickel(II) Complex with a Phosphinopyridyl Ligand.

PubMed

Tatematsu, Ryo; Inomata, Tomohiko; Ozawa, Tomohiro; Masuda, Hideki

2016-04-18

A novel nickel(II) complex [Ni(L)2 Cl]Cl with a bidentate phosphinopyridyl ligand 6-((diphenylphosphino)methyl)pyridin-2-amine (L) was synthesized as a metal-complex catalyst for hydrogen production from protons. The ligand can stabilize a low Ni oxidation state and has an amine base as a proton transfer site. The X-ray structure analysis revealed a distorted square-pyramidal Ni(II)  complex with two bidentate L ligands in a trans arrangement in the equatorial plane and a chloride anion at the apex. Electrochemical measurements with the Ni(II) complex in MeCN indicate a higher rate of hydrogen production under weak acid conditions using acetic acid as the proton source. The catalytic current increases with the stepwise addition of protons, and the turnover frequency is 8400 s(-1) in 0.1 m [NBu4 ][ClO4 ]/MeCN in the presence of acetic acid (290 equiv) at an overpotential of circa 590 mV. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis, characterization, antimicrobial activity and DFT studies of 2-(pyrimidin-2-ylamino)naphthalene-1,4-dione and its Mn(II), Co(II), Ni(II) and Zn(II) complexes

NASA Astrophysics Data System (ADS)

Chioma, Festus; Ekennia, Anthony C.; Ibeji, Collins U.; Okafor, Sunday N.; Onwudiwe, Damian C.; Osowole, Aderoju A.; Ujam, Oguejiofo T.

2018-07-01

A pyrimidine-based ligand, 2-(pyrimidin-2-ylamino)naphthalene-1,4-dione (L), has been synthesized by the reaction of 2-aminopyrimidine with 2-hydroxy-1,4-napthoquinone. Reaction of the ligand with Ni(II), Co(II), Mn(II) and Zn(II) acetate gave the corresponding metal complexes which were characterized by spectroscopic techniques, (infrared, electronic), elemental analysis, room-temperature magnetometry, conductance measurements and thermogravimetry-differential scanning calorimetry (TG-DSC) analyses. The room-temperature magnetic data and electronic spectral measurements of the complexes gave evidence of 4-coordinate square planar/tetrahedral geometry. The thermal analyses values obtained indicated the monohydrate complexes. The antimicrobial screening of the compounds showed mild to very good results. The Mn(II) complex showed the best result within in the range of 11.5-29 mm. The electronic, structural and spectroscopic properties of the complexes were further discussed using density functional theory. Molecular docking studies showed significant binding affinity with the drug targets and the metal complexes have potentials to be used as drugs.

Cytogenetic toxicity effects of inorganic nickel and organic Ni(II) complexes on Brassica oleracea L. root meristem.

PubMed

Molas, J

2001-01-01

Experiments were carried out on the effect of nickel as an inorganic compound (NiSO4.7H2O) and organic Ni(II) complexes (i.e. Ni(II)-Glu and Ni(II)-EDTA) in concentrations of 20, 40 and 85 ?M dm-3 on meristematic cells of root tips of Brassica oleracea L. cv. Sława from Enkhouizen. All three tested chemical forms of nickel had a mitodepressive effect and inhibited root elongation. With respect to the degree of root elongation inhibition and mitodepressive effect, the tested forms of nickel can be put in the following order: Ni(II)-Glu NiSO4.7H2O Ni(II)-EDTA. In all three tested forms, nickel caused disturbances in mitotic divisions, resulting in anaphase bridges and binuclear cells, whose nuclei were joined by a bridge of condensed chromatin or separated. Inorganic nickel and Ni(II)-Glu in higher concentrations damaged nuclei (the amount of condensed chromatin increased), nucleoli (their structure became more condensed and vacuolisation was observed), endoplasmic reticulum (fragmentation, swelling of cisternae) and mitochondria (structure condensation).

Application of novel Ni(II) complex and ZrO2 nanoparticle as mediators for electrocatalytic determination of N-acetylcysteine in drug samples.

PubMed

Karimi-Maleh, Hassan; Salehi, Mehdi; Faghani, Fatemeh

2017-10-01

The electrooxidation of N-acetylcysteine (N-AC) was studied by a novel Ni(II) complex modified ZrO 2 nanoparticle carbon paste electrode [Ni(II)/ZrO 2 /NPs/CPE] using voltammetric methods. The results showed that Ni(II)/ZrO 2 /NPs/CPE had high electrocatalytic activity for the electrooxidation of N-AC in aqueous buffer solution (pH = 7.0). The electrocatalytic oxidation peak currents increase linearly with N-AC concentrations over the concentration ranges of 0.05-600μM using square wave voltammetric methods. The detection limit for N-AC was equal to 0.009μM. The catalytic reaction rate constant, k h , was calculated (7.01 × 10 2  M -1  s -1 ) using the chronoamperometry method. Finally, Ni(II)/ZrO 2 /NPs/CPE was also examined as an ultrasensitive electrochemical sensor for the determination of N-AC in real samples such as tablet and urine. Copyright © 2017. Published by Elsevier B.V.

Synthesis, characterization and molecular modeling of some transition metal complexes of Schiff base derived from 5-aminouracil and 2-benzoyl pyridine

NASA Astrophysics Data System (ADS)

Abdel-Monem, Yasser K.; Abouel-Enein, Saeyda A.; El-Seady, Safa M.

2018-01-01

Multidentate Schiff base (H2L) ligand results from condensation of 5-aminouracil and 2-benzoyl pyridine and its metal chloride (Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Pd(II), Fe(III), Cr(III), Ru(III), Zr(IV) and Hf(IV)) complexes were prepared. The structural features of the ligand and its metal complexes were confirmed by elemental analyses, spectroscopic methods (IR, UV-Vis, 1H NMR, mass), magnetic moment measurements and thermal studies. The data refer to the ligand coordinates with metal ions in a neutral form and shows different modes of chelation toward the metal atom. All complexes have octahedral skeleton structure, tetrahedrally Mn(II), Ni(II), trigonalbipyramidal Co(II) and square planner Pd(II). Thermal decomposition of complexes as well as the interaction of different types of solvent of crystallization are assigned by thermogravimetric analysis. Molecular modeling of prepared complexes were investigated to study the expected anticancer activities of the prepared complexes. All metal complexes have no interaction except the complexes of Pd(II), Fe(III) and Mn(II).

Postsynthetic Improvement of the Physical Properties in a Metal-Organic Framework through a Single Crystal to Single Crystal Transmetallation.

PubMed

Grancha, Thais; Ferrando-Soria, Jesús; Zhou, Hong-Cai; Gascon, Jorge; Seoane, Beatriz; Pasán, Jorge; Fabelo, Oscar; Julve, Miguel; Pardo, Emilio

2015-05-26

A single crystal to single crystal transmetallation process takes place in the three-dimensional (3D) metal-organic framework (MOF) of formula Mg(II) 2 {Mg(II) 4 [Cu(II) 2 (Me3 mpba)2 ]3 }⋅45 H2 O (1; Me3 mpba(4-) =N,N'-2,4,6-trimethyl-1,3-phenylenebis(oxamate)). After complete replacement of the Mg(II) ions within the coordination network and those hosted in the channels by either Co(II) or Ni(II) ions, 1 is transmetallated to yield two novel MOFs of formulae Co2 (II) {Co(II) 4 [Cu(II) 2 (Me3 mpba)2 ]3 }⋅56 H2 O (2) and Ni2 (II) {Ni(II) 4 [Cu(II) 2 (Me3 mpba)2 ]3 }⋅ 54 H2 O (3). This unique postsynthetic metal substitution affords materials with higher structural stability leading to enhanced gas sorption and magnetic properties. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Antimicrobial, spectral, magnetic and thermal studies of Cu(II), Ni(II), Co(II), UO(2)(VI) and Fe(III) complexes of the Schiff base derived from oxalylhydrazide.

PubMed

Melha, Khlood Abou

2008-04-01

The Schiff base ligand, oxalyl [( 2 - hydroxybenzylidene) hydrazone] [corrected].H(2)L, and its Cu(II), Ni(II), Co(II), UO(2)(VI) and Fe(III) complexes were prepared and tested as antibacterial agents. The Schiff base acts as a dibasic tetra- or hexadentate ligand with metal cations in molar ratio 1:1 or 2:1 (M:L) to yield either mono- or binuclear complexes, respectively. The ligand and its metal complexes were characterized by elemental analyses, IR, (1)H NMR, Mass, and UV-Visible spectra and the magnetic moments and electrical conductance of the complexes were also determined. For binuclear complexes, the magnetic moments are quite low compared to the calculated value for two metal ions complexes and this shows antiferromagnetic interactions between the two adjacent metal ions. The ligand and its metal complexes were tested against a Gram + ve bacteria (Staphylococcus aureus), a Gram -ve bacteria (Escherichia coli), and a fungi (Candida albicans). The tested compounds exhibited high antibacterial activities.

Octa­akis(4-amino­pyridine)-1κ4 N 1,2κ4 N 1-aqua-2κO-μ-carbonato-1:2κ3 O,O′:O′′-dinickel(II) dichloride penta­hydrate

PubMed Central

Fun, Hoong-Kun; Sinthiya, A; Jebas, Samuel Robinson; Ravindran Durai Nayagam, B.; Alfred Cecil Raj, S.

2008-01-01

In the title compound, [Ni2(CO3)(C5H6N2)8(H2O)]Cl2·5H2O, one of the the NiII ions is six-coordinated in a distorted octa­hedral geometry, with the equatorial plane defined by four pyridine N atoms from four amino­pyridine ligands, the axial positions being occupied by one water O and a carbonate O atom. The other NiII ion is also six-coordinated, by four other pyridine N atoms from four other amino­pyridine ligands and two carbonate O atoms to complete a distorted octa­hedral geometry. In the crystal structure, mol­ecules are linked into an infinite three-dimensional network by O—H⋯O, N—H⋯Cl, N—H⋯O, O—H⋯N, C—H⋯O, C—H⋯N and C/N—H⋯π inter­actions involving the pyridine rings. PMID:21580879

Model determination in a case of heterogeneity of variance using sampling techniques.

PubMed

Varona, L; Moreno, C; Garcia-Cortes, L A; Altarriba, J

1997-01-12

A sampling determination procedure has been described in a case of heterogeneity of variance. The procedure makes use of the predictive distributions of each data given the rest of the data and the structure of the assumed model. The computation of these predictive distributions is carried out using a Gibbs Sampling procedure. The final criterion to compare between models is the Mean Square Error between the expectation of predictive distributions and real data. The procedure has been applied to a data set of weight at 210 days in the Spanish Pirenaica beef cattle breed. Three proposed models have been compared: (a) Single Trait Animal Model; (b) Heterogeneous Variance Animal Model; and (c) Multiple Trait Animal Model. After applying the procedure, the most adjusted model was the Heterogeneous Variance Animal Model. This result is probably due to a compromise between the complexity of the model and the amount of available information. The estimated heritabilities under the preferred model have been 0.489 ± 0.076 for males and 0.331 ± 0.082 for females. RESUMEN: Contraste de modelos en un caso de heterogeneidad de varianzas usando métodos de muestreo Se ha descrito un método de contraste de modelos mediante técnicas de muestreo en un caso de heterogeneidad de varianza entre sexos. El procedimiento utiliza las distribucviones predictivas de cada dato, dado el resto de datos y la estructura del modelo. El criterio para coparar modelos es el error cuadrático medio entre la esperanza de las distribuciones predictivas y los datos reales. El procedimiento se ha aplicado en datos de peso a los 210 días en la raza bovina Pirenaica. Se han propuesto tres posibles modelos: (a) Modelo Animal Unicaracter; (b) Modelo Animal con Varianzas Heterogéneas; (c) Modelo Animal Multicaracter. El modelo mejor ajustado fue el Modelo Animal con Varianzas Heterogéneas. Este resultado es probablemente debido a un compromiso entre la complejidad del modelo y la cantidad de datos disponibles. Las heredabilidades estimadas bajo el modelo preferido han sido 0,489 ± 0,076 en los machos y 0,331 ± 0,082 en las hembras. 1997 Blackwell Verlag GmbH.

PubMed

Abrutzky, Rosana; Torres, Fernando Adrián; Ossorio, María Fabiana; Ferrero, Fernando

2018-04-11

Objetivo: evaluar el impacto de los contaminantes atmosféricos y el clima en el número de consultas al departamento de emergencias de un hospital pediátrico en Buenos Aires, Argentina. Material y métodos: estudio ecológico utilizando análisis de series temporales con modelos aditivos generalizados (GAM) para el período 2012-2014, analizando cantidad diaria de consultas en función de tres contaminantes del aire: monóxido de carbono (CO), dióxido de nitrógeno (NO2) y material particulado de diámetro menor a 10 micrones (PM10), temperatura diaria, humedad relativa, dirección y velocidad del viento y lluvia, controlando por día de la semana y tendencia de largo plazo. Resultados: las consultas en invierno (286 diarias) fueron significativamente mayores que en las demás estaciones (p<0.0001). La variación en el nivel de contaminación del aire no mostró correlación significativa y consistente con las consultas. La temperatura, humedad relativa, lluvia y viento no resultaron significativas en ninguno de los rezagos analizados. Conclusiones: en esta población y considerando las consultas de emergencia, la contaminación del aire no afecta significativamente el resultado en salud, pero sí lo hacen las epidemias estacionales. Estudios sobre otras variables de salud son necesarios para establecer el impacto de la contaminación del aire sobre la salud infantil en Buenos Aires.

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

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

Synthesis, characterization, DFT calculations and molecular docking studies of metal (II) complexes

NASA Astrophysics Data System (ADS)

Ekennia, Anthony C.; Osowole, Aderoju A.; Olasunkanmi, Lukman O.; Onwudiwe, Damian C.; Olubiyi, Olujide O.; Ebenso, Eno E.

2017-12-01

Two novel ligands, 2-methyl-6-[(5-methyl benzothiazol-2-ylimino)-methyl]-2-methoxycyclohexa-1,5-dienol (HL1) and 2-methyl-6-[(5-floro-benzothiazol-2-ylimino)-methyl]-2-methoxycyclohexa-1,5-dienol (HL2) were synthesized from the condensation reaction of 2-hydroxy-3-methoxybenzaldehyde with 2-amino-6-methylbenzothiazole and 2-amino-6-florobenzothiazole respectively. Mononuclear Cu(II), Ni(II) and Co(II) complexes of the ligands were synthesized and characterized using elemental analysis, magnetic susceptibility, thermogravimetric, conductance, infrared and UV-visible spectroscopic measurements. The 1H NMR, 13C NMR, Dept-90 NMR spectroscopy of the ligands was also recorded to establish the formation of the Schiff bases. The analytical data of the complexes showed that the metal to ligand ratio was 1:1 for Cu(II), Ni(II) and Co(II) complexes of HL1 and Cu(II) complexes of HL2, while Ni(II) and Co(II) complexes of HL2 was 1:2. The infrared spectral data showed that the chelation behaviour of the ligands towards transition metal ions was through phenolic oxygen and azomethine nitrogen atoms. Molar conductivity revealed the non-electrolytic nature of all chelates in DMSO solution. The geometry of the complexes was deduced from thermal, magnetic susceptibility and UV-visible spectroscopic results and was further confirmed with DFT calculations. The compounds were subjected to in-vitro antibacterial screening using agar well diffusion method on some clinically isolated Gram positive and Gram negative bacteria strains. The compounds showed varied antibacterial activities. Molecular docking studies were carried out to study the molecular interaction between the compounds and different enzymes of the bacterial strains. The antioxidant potentials of the compounds were studied using ferrous ion chelating assay and 2, 2-diphenyl-1-picrylhydrazyl (DPPH) radical scavenging assay. However, the complexes had better antioxidant potentials compared to the ligands.

Pupil constriction evoked in vitro by stimulation of the oculomotor nerve in the turtle (Trachemys scripta elegans).

PubMed

Dearworth, James R; Brenner, J E; Blaum, J F; Littlefield, T E; Fink, D A; Romano, J M; Jones, M S

2009-01-01

The pond turtle (Trachemys scripta elegans) exhibits a notably sluggish pupillary light reflex (PLR), with pupil constriction developing over several minutes following light onset. In the present study, we examined the dynamics of the efferent branch of the reflex in vitro using preparations consisting of either the isolated head or the enucleated eye. Stimulation of the oculomotor nerve (nIII) using 100-Hz current trains resulted in a maximal pupil constriction of 17.4% compared to 27.1% observed in the intact animal in response to light. When current amplitude was systematically increased from 1 to 400 microA, mean response latency decreased from 64 to 45 ms, but this change was not statistically significant. Hill equations fitted to these responses indicated a current threshold of 3.8 microA. Stimulation using single pulses evoked a smaller constriction (3.8%) with response latencies and threshold similar to that obtained using train stimulation. The response evoked by postganglionic stimulation of the ciliary nerve using 100-Hz trains was largely indistinguishable from that of train stimulation of nIII. However, application of single-pulse stimulation postganglionically resulted in smaller pupil constriction at all current levels relative to that of nIII stimulation, suggesting that there is amplification of efferent drive at the ganglion. Time constants for constrictions ranged from 88 to 154 ms with relaxations occurring more slowly at 174-361 ms. These values for timing from in vitro are much faster than the time constant 1.66 min obtained for the light response in the intact animal. The rapid dynamics of pupil constriction observed here suggest that the slow PLR of the turtle observed in vivo is not due to limitations of the efferent pathway. Rather, the sluggish response probably results from photoreceptive mechanisms or central processing.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yao, Shuang; Yi, Fei-Yan; Li, Guanghua

Two coordination polymers [Co{sub 2}(TA)(4,4′-bipy){sub 2}(H{sub 2}O){sub 2}]·H{sub 2}O (1) and [Ni{sub 2}(TA)(4,4′-bipy){sub 2}(H{sub 2}O){sub 4}]·3H{sub 2}O (2) were prepared by hydrothermal reactions of MCl{sub 2}·6H{sub 2}O (M = Co, Ni) with a V-shaped ligand TDPA (3,3′,4,4′-thiodiphthalic anhydride) and a I-shaped N-donor co-ligand (4,4′-bipy). They were characterized by elemental analyses, thermogravinetric analyses, and magnetic behavior. As is expected, TDPA hydrolyzes into the corresponding tetra-carboxylate acid H{sub 4}TA (3,3′,4,4′-thiodiphthalic acid) during the reactions. Co{sub 2} dimer and Ni mononuclear center are connected into two-dimensional (2D) layers by H{sub 4}TA and 4,4′-bipy bridge in 1 and 2, respectively. The most amazing featuremore » is that 1 and 2 exhibit interesting spin-canting metamagnetism and weak ferromagnetic behavior, respectively, with the critical Néel temperature of T{sub N} =4 K for 1 and T{sub N} =13 K for 2, based on variable temperature magnetic susceptibility measurements. In low mono- or dinuclear metal system, such magnetic behaviors have rare been observed. Furthermore, complex 1 will be a potential metamagnet material. - Graphical abstract: Two Co(II) and Ni(II) coordination polymers were synthesized by hydrothermal reactions from a V-shape ligand (3,3′,4,4′-thiodiphthalic anhydride) and a I-shape ligand (4,4′-bipy), which were characterized by single crystal X-ray diffraction, elemental analyses, thermogravinetric analyses, and magnetic behavior, and exhibit interesting spin-canting metamagnetism and weak ferromagnetic behavior, respectively. - Highlights: • Two Co(II) and Ni(II) coordination polymers were successfully synthesized. • Co(II) coordination polymer shows an interesting spin-canting metamagnetism. • Ni(II) coordination polymer exhibits a weak ferromagnetic behavior.« less

Mononuclear Ni(II) complexes of Schiff base ligands formed from unsymmetrical tripodal amines of differing arm lengths: Spectral, X-ray crystal structural, antimicrobial and DNA cleavage activity

NASA Astrophysics Data System (ADS)

Keypour, Hassan; Shayesteh, Maryam; Rezaeivala, Majid; Dhers, Sébastien; Küp, Fatma Öztürk; Güllü, Mithat; Ng, Seikweng

2017-11-01

The synthesis of two unsymmetrical N-capped tripodal amines, 2-((4-aminobutyl)(pyridin-2-ylmethyl)amino)ethanol (3) and 3-((2-aminoethyl)(pyridin-2-ylmethyl)amino)propan-1-ol (4) is reported. They feature a longer, 3-hydroxypropyl or butylamino arm than that in the analogues previously employed. All four tripodal amines, 1-4, are equipped with a 2-methylpyridyl-arm, and either an ethylamino-arm (1 and 4), propylamino-arm (2) or butylamino-arm (3). The amines, 3 and 4, have been employed in one pot condensation reactions with salicylaldehyde and its derivatives in the presence of Ni(II) metal ion. A series of new mononuclear complexes, [NiIILaldi](ClO4) or [NiIILaldi(solvent)](ClO4) with different geometry, of Schiff base ligands were generated. X-ray crystal structure determinations of [NiIILOMe3(H2O)](ClO4)·2H2O and [NiIILOMe4](ClO4) revealed them to be mononuclear. The Ni(II) ion in [NiIILOMe4](ClO4) complex is in a distorted square-planar environment whilst this ion is in distorted octahedral environment in [NiIILOMe3(H2O)](ClO4)·2H2O complex despite the longer arm length of L3. While, in related systems in our previous work, they had led to dimeric complexes. These results clearly showed that the variation of the arm lengths of the ligands and metal ions has a remarkable impact on the formation and structure of the complexes. The cleavage of DNA by all synthesised complexes was examined using gel electrophoresis experiments. Also, the antibacterial effects of components were determined against the three Gram-positive bacteria, and against the three Gram-negative bacteria and against the three yeast Candida albicans ATCC 10231, Candida krusei ATCC 1424 and Candida tropicalis ATCC 13803.

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

PubMed

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

2017-12-01

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

Characterization of a novel chelating resin of enhanced hydrophilicity and its analytical utility for preconcentration of trace metal ions.

PubMed

Islam, Aminul; Laskar, Mohammad Asaduddin; Ahmad, Akil

2010-06-15

A stable extractor of metal ions was synthesized through azo linking of p-hydroxybenzoic acid with Amberlite XAD-4 and was characterized by elemental analyses, infrared spectral and thermal studies. Its water regain value and hydrogen ion capacity were found to be 15.80 and 7.52mmolg(-1), respectively. Both batch and column methods were employed to study the sorption behavior for the metal ions which were subsequently determined by flame atomic absorption spectrophotometry. The optimum pH range for Co(II), Ni(II), Cu(II), Zn(II), and Pb(II) ions were 10.0, 8.0-9.0, 7.0, 7.0-8.0 and 7.0-8.0, respectively. The half-loading time, t(1/2), are 6.0, 8.0, 8.0, 8.0 and 4.0min, respectively. Comparison of breakthrough and overall capacities of the metals ascertains the high degree of column utilization (>75%). The breakthrough capacities for Co(II), Ni(II), Cu(II), Zn(II), and Pb(II) ions were found to be 0.46, 0.43, 0.42, 0.09 and 0.06mmolg(-1) with the corresponding preconcentration factor of 460, 460, 460, 360 and 260, respectively. The limit of preconcentration was in the range of 4.3-7.6microgL(-1). The detection limit for Co(II), Ni(II), Cu(II), Zn(II) and Pb(II) were found to be 0.47, 0.45, 0.50, 0.80, and 1.37microgL(-1), respectively. The Student's t (t-test) values for the analysis of standard reference materials were found to be less than the critical Student's t values at 95% confidence level. The AXAD-4-HBA has been successfully applied for the analysis of natural water, multivitamin formulation, infant milk substitute, hydrogenated oil and fish.

Ferrate(VI)-prompted removal of metals in aqueous media: mechanistic delineation of enhanced efficiency via metal entrenchment in magnetic oxides.

PubMed

Prucek, Robert; Tuček, Jiří; Kolařík, Jan; Hušková, Ivana; Filip, Jan; Varma, Rajender S; Sharma, Virender K; Zbořil, Radek

2015-02-17

The removal efficiency of heavy metal ions (cadmium(II), Cd(II); cobalt(II), Co(II); nickel(II), Ni(II); copper(II), Cu(II)) by potassium ferrate(VI) (K2FeO4, Fe(VI)) was studied as a function of added amount of Fe(VI) (or Fe) and varying pH. At pH = 6.6, the effective removal of Co(II), Ni(II), and Cu(II) from water was observed at a low Fe-to-heavy metal ion ratio (Fe/M(II) = 2:1) while a removal efficiency of 70% was seen for Cd(II) ions at a high Fe/Cd(II) weight ratio of 15:1. The role of ionic radius and metal valence state was explored by conducting similar removal experiments using Al(III) ions. The unique combination of X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), in-field Mössbauer spectroscopy, and magnetization measurements enabled the delineation of several distinct mechanisms for the Fe(VI)-prompted removal of metal ions. Under a Fe/M weight ratio of 5:1, Co(II), Ni(II), and Cu(II) were removed by the formation of MFe2O4 spinel phase and partially through their structural incorporation into octahedral positions of γ-Fe2O3 (maghemite) nanoparticles. In comparison, smaller sized Al(III) ions got incorporated easily into the tetrahedral positions of γ-Fe2O3 nanoparticles. In contrast, Cd(II) ions either did not form the spinel ferrite structure or were not incorporated into the lattic of iron(III) oxide phase due to the distinct electronic structure and ionic radius. Environmentally friendly removal of heavy metal ions at a much smaller dosage of Fe than those of commonly applied iron-containing coagulants and the formation of ferrimagnetic species preventing metal ions leaching back into the environment and allowing their magnetic separation are highlighted.

Assessment of electrokinetic removal of heavy metals from soils by sequential extraction analysis.

PubMed

Reddy, K R; Xu, C Y; Chinthamreddy, S

2001-06-29

Electrokinetic remediation of metal-contaminated soils is strongly affected by soil-type and chemical species of contaminants. This paper investigates the speciation and extent of migration of heavy metals in soils during electrokinetic remediation. Laboratory electrokinetic experiments were conducted using two diverse soils, kaolin and glacial till, contaminated with chromium as either Cr(III) or Cr(VI). Initial total chromium concentrations were maintained at 1000mg/kg. In addition, Ni(II) and Cd(II) were used in concentrations of 500 and 250mg/kg, respectively. The contaminated soils were subjected to a voltage gradient of 1 VDC/cm for over 200h. The extent of migration of contaminants after the electric potential application was determined. Sequential extractions were performed on the contaminated soils before and after electrokinetic treatment to provide an understanding of the distribution of the contaminants in the soils. The initial speciation of contaminants was found to depend on the soil composition as well as the type and amounts of different contaminants present. When the initial form of chromium was Cr(III), exchangeable and soluble fractions of Cr, Ni, and Cd ranged from 10 to 65% in kaolin; however, these fractions ranged from 0 to 4% in glacial till. When the initial form of chromium was Cr(VI), the exchangeable and soluble fractions of Cr, Ni and Cd ranged from 66 to 80% in kaolin. In glacial till, however, the exchangeable and soluble fraction for Cr was 38% and Ni and Cd fractions were 2 and 10%, respectively. The remainder of the contaminants existed as the complex and precipitate fractions. During electrokinetic remediation, Cr(VI) migrated towards the anode, whereas Cr(III), Ni(II) and Cd(II) migrated towards the cathode. The speciation of contaminants after electrokinetic treatment showed that significant change in exchangeable and soluble fractions occurred. In kaolin, exchangeable and soluble Cr(III), Ni(II), and Cd(II) decreased near the anode and increased near the cathode, whereas exchangeable and soluble Cr(VI) decreased near the cathode and increased near the anode. In glacial till, exchangeable and soluble Cr(III), Ni(II), and Cd(II) were low even before electrokinetic treatment and no significant changes were observed after the electrokinetic treatment. However, significant exchangeable and soluble Cr(VI) that was present in glacial till prior to electrokinetic treatment decreased to non-detectable levels near the cathode and increased significantly near the anode. In both kaolin and glacial till, low migration rates occurred as a result of contaminants existing as immobile complexes and precipitates. The overall contaminant removal efficiency was very low (less than 20%) in all tests.

Dinuclear complexes containing linear M-F-M [M = Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II)] bridges: trends in structures, antiferromagnetic superexchange interactions, and spectroscopic properties.

PubMed

Reger, Daniel L; Pascui, Andrea E; Smith, Mark D; Jezierska, Julia; Ozarowski, Andrew

2012-11-05

The reaction of M(BF(4))(2)·xH(2)O, where M is Fe(II), Co(II), Ni(II), Cu(II), Zn(II), and Cd(II), with the new ditopic ligand m-bis[bis(3,5-dimethyl-1-pyrazolyl)methyl]benzene (L(m)*) leads to the formation of monofluoride-bridged dinuclear metallacycles of the formula [M(2)(μ-F)(μ-L(m)*)(2)](BF(4))(3). The analogous manganese(II) species, [Mn(2)(μ-F)(μ-L(m)*)(2)](ClO(4))(3), was isolated starting with Mn(ClO(4))(2)·6H(2)O using NaBF(4) as the source of the bridging fluoride. In all of these complexes, the geometry around the metal centers is trigonal bipyramidal, and the fluoride bridges are linear. The (1)H, (13)C, and (19)F NMR spectra of the zinc(II) and cadmium(II) compounds and the (113)Cd NMR of the cadmium(II) compound indicate that the metallacycles retain their structure in acetonitrile and acetone solution. The compounds with M = Mn(II), Fe(II), Co(II), Ni(II), and Cu(II) are antiferromagnetically coupled, although the magnitude of the coupling increases dramatically with the metal as one moves to the right across the periodic table: Mn(II) (-6.7 cm(-1)) < Fe(II) (-16.3 cm(-1)) < Co(II) (-24.1 cm(-1)) < Ni(II) (-39.0 cm(-1)) ≪ Cu(II) (-322 cm(-1)). High-field EPR spectra of the copper(II) complexes were interpreted using the coupled-spin Hamiltonian with g(x) = 2.150, g(y) = 2.329, g(z) = 2.010, D = 0.173 cm(-1), and E = 0.089 cm(-1). Interpretation of the EPR spectra of the iron(II) and manganese(II) complexes required the spin Hamiltonian using the noncoupled spin operators of two metal ions. The values g(x) = 2.26, g(y) = 2.29, g(z) = 1.99, J = -16.0 cm(-1), D(1) = -9.89 cm(-1), and D(12) = -0.065 cm(-1) were obtained for the iron(II) complex and g(x) = g(y) = g(z) = 2.00, D(1) = -0.3254 cm(-1), E(1) = -0.0153, J = -6.7 cm(-1), and D(12) = 0.0302 cm(-1) were found for the manganese(II) complex. Density functional theory (DFT) calculations of the exchange integrals and the zero-field splitting on manganese(II) and iron(II) ions were performed using the hybrid B3LYP functional in association with the TZVPP basis set, resulting in reasonable agreement with experiment.

Rational design of azide-bridged bimetallic complexes. Crystal structure and magnetic properties of Fe(III)MFe(III) (M = Ni(II) and Cu(II)) trinuclear species.

PubMed

Colacio, Enrique; Costes, Jean-Pierre; Domínguez-Vera, José M; Maimoun, Ikram Ben; Suárez-Varela, José

2005-01-28

The first examples of azide-bridged bimetallic trinuclear complexes ([M(cyclam)][FeL(N3)(mu1,5-N3)]2) (H2L = 4,5-dichloro-1,2-bis(pyridine-2-carboxamido) benzene) have been structurally and magnetically characterized.

Whole-genome sequence of Cupriavidus sp. strain BIS7, a heavy-metal-resistant bacterium.

PubMed

Hong, Kar Wai; Thinagaran, Dinaiz al; Gan, Han Ming; Yin, Wai-Fong; Chan, Kok-Gan

2012-11-01

Cupriavidus sp. strain BIS7 is a Malaysian tropical soil bacterium that exhibits broad heavy-metal resistance [Co(II), Zn(II), Ni(II), Se(IV), Cu(II), chromate, Co(III), Fe(II), and Fe(III)]. It is particularly resistant to Fe(II), Fe(III), and Zn(II). Here we present the assembly and annotation of its genome.

Two new Ni(II) supramolecular complexes based on ethyl isonicotinate and ethyl nicotinate for removal of acid blue 92 dye

NASA Astrophysics Data System (ADS)

Etaiw, Safaa El-din H.; Marie, Hassan

2018-03-01

Two new luminescent supramolecular complexes (SC); [Ni(EIN)4(NCS)2] SC1 and [Ni2(EN)8(NCS)4] SC2, (EIN = ethyl isonicotinate, EN = ethyl nicotinate), have been synthesized by self-assembly method and structurally characterized by X-ray single crystal, FT-IR and UV-Vis spectra, PXRD, elemental and thermogravimetric analyses. Both SC1 and SC2 are monoclinic crystals however, they have different asymmetric units. Ni(II) atoms in both SC are isostructural and have similar hexa-coordinate environment. The structures of SC1 and SC2 consist of parallel polymeric 1D-chains, extended in two and three dimensional supramolecular frameworks by intermolecular hydrogen bonding interactions. SC1 and SC2 are luminescent materials which can be used in applications as molecular sensing systems. SC1 and SC2 were used as heterogeneous catalysts for degradation of acid blue 92 (AB-92) under sun light irradiation. The fluorescence measurements of terephthalic acid technique as a probe molecule were used to determine the •OH radicals. Also the radicals trapping experiments using isopropanol alcohol (IPA) as radical scavenger were discussed. In addition a mechanism of degradation was proposed and discussed.

Genetic characterization, nickel tolerance, biosorption, kinetics, and uptake mechanism of a bacterium isolated from electroplating industrial effluent.

PubMed

Nagarajan, N; Gunasekaran, P; Rajendran, P

2015-04-01

Electroplating industries in Madurai city produce approximately 49,000 L of wastewater and 1200 L of sludge every day revealing 687-5569 ppm of nickel (Ni) with other contaminants. Seventeen Ni-tolerant bacterial strains were isolated from nutrient-enriched effluents. Among them one hyper Ni accumulating strain was scored and identified as Bacillus cereus VP17 on the basis of morphology, biochemical tests, 16S rDNA gene sequencing, and phylogenetic analysis. Equilibrium data of Ni(II) ions using the bacterium as sorbent at isothermal conditions (37 °C) and pH 6 were best adjusted by Langmuir (R(2) = 0.6268) and Freundlich models (R(2) = 0.9505). Experimental validation reveals Ni sorption takes place on a heterogeneous surface of the biosorbent, and predicted metal sorption capacity is 434 ppm. The pseudo-second-order kinetic model fitted the biosorption kinetic data better than the pseudo-first-order kinetic model (R(2) = 0.9963 and 0.3625). Scanning electron microscopy, energy dispersive X-ray, and Fourier transform infrared spectroscopy studies of the bacterial strain with and without Ni(II) ion reveals the biosorption mechanism. The results conclude possibilities of using B. cereus VP17 for Ni bioremediation.

DNA Binding, Cleavage and Antibacterial Activity of Mononuclear Cu(II), Ni(II) and Co(II) Complexes Derived from Novel Benzothiazole Schiff Bases.

PubMed

Vamsikrishna, Narendrula; Kumar, Marri Pradeep; Tejaswi, Somapangu; Rambabu, Aveli; Shivaraj

2016-07-01

A series of novel bivalent metal complexes M(L1)2 and M(L2)2 where M = Cu(II), Ni(II), Co(II) and L1 = 2-((benzo [d] thiazol-6-ylimino)methyl)-4-bromophenol [BTEMBP], L2 = 1-((benzo [d] thiazol-6-ylimino)methyl) naphthalen-2-ol [BTEMNAPP] were synthesized. All the compounds have been characterized by elemental analysis, SEM, Mass, (1)H NMR, (13)C NMR, UV-Vis, IR, ESR, spectral data and magnetic susceptibility measurements. Based on the analytical and spectral data four-coordinated square planar geometry is assigned to all the complexes. DNA binding properties of these complexes have been investigated by electronic absorption spectroscopy, fluorescence and viscosity measurements. It is observed that these binary complexes strongly bind to calf thymus DNA by an intercalation mode. DNA cleavage efficacy of these complexes was tested in presence of H2O2 and UV light by gel electrophoresis and found that all the complexes showed better nuclease activity. Finally the compounds were screened for antibacterial activity against few pathogens and found that the complexes have potent biocidal activity than their free ligands.

Synthesis, characterization and biological activity of complexes of 2-hydroxy-3,5-dimethylacetophenoneoxime (HDMAOX) with copper(II), cobalt(II), nickel(II) and palladium(II)

NASA Astrophysics Data System (ADS)

Singh, Bibhesh K.; Jetley, Umesh K.; Sharma, Rakesh K.; Garg, Bhagwan S.

2007-09-01

A new series of complexes of 2-hydroxy-3,5-dimethyl acetophenone oxime (HDMAOX) with Cu(II), Co(II), Ni(II) and Pd(II) have been prepared and characterized by different physical techniques. Infrared spectra of the complexes indicate deprotonation and coordination of the phenolic OH. It also confirms that nitrogen atom of the oximino group contributes to the complexation. Electronic spectra and magnetic susceptibility measurements reveal square planar geometry for Cu(II), Ni(II) and Pd(II) complexes and tetrahedral geometry for Co(II) complex. The elemental analyses and mass spectral data have justified the ML 2 composition of complexes. Kinetic and thermodynamic parameters were computed from the thermal decomposition data using Coats and Redfern method. The geometry of the metal complexes has been optimized with the help of molecular modeling. The free ligand (HDMAOX) and its metal complexes have been tested in vitro against Alternarie alternate, Aspergillus flavus, Aspergillus nidulans and Aspergillus niger fungi and Streptococcus, Staph, Staphylococcus and Escherchia coli bacteria in order to assess their antimicrobial potential. The results indicate that the ligand and its metal complexes possess antimicrobial properties.

Spectroscopic studies on 2-[2-(4-methylquinolin-2-yl)hydrazono]-1,2-diphenylethanone molecule and its metal complexes

NASA Astrophysics Data System (ADS)

Seleem, H. S.; El-Inany, G. A.; Mousa, M.; Hanafy, F. I.

2009-11-01

The electronic absorption spectra of a hydrazone: 2-[2-(4-methylquinolin-2-yl)hydrazono]-1,2-diphenylethanone (BHQ) derived from 2-hydrazino-4-methylquinoline and 1,2-diphenylethan-1,2-dione (benzil) have been studied in various solvents of different polarities. The dependence of the band shift Δ ύ on the solvent parameters viz.D, Z, ET, DN, AN, α, β and π* was discussed. Also, the effect of pH on the free hydrazone and its Co(II), Ni(II) and Cu(II) complexes was studied spectrophotometrically in 75% (v/v) dioxane-water in order to determine the dissociation and stability constants. The stoichiometry of the formed complexes was determined by three different methods: Job's, mole ratio and slope ratio which indicate the formation of 1:2, M:L complexes for Co(II) and Cu(II) and 1:1, Ni(II):L. Beer's law is valid in the range 0.32-7.04 μg/mL depending on the type of the metal ion. The use of BHQ as an indicator via a spectrophotometric titration of Cu(II) and Ni(II) with EDTA was efficient.

Synthesis, characterization and biological activity of complexes of 2-hydroxy-3,5-dimethylacetophenoneoxime (HDMAOX) with copper(II), cobalt(II), nickel(II) and palladium(II).

PubMed

Singh, Bibhesh K; Jetley, Umesh K; Sharma, Rakesh K; Garg, Bhagwan S

2007-09-01

A new series of complexes of 2-hydroxy-3,5-dimethyl acetophenone oxime (HDMAOX) with Cu(II), Co(II), Ni(II) and Pd(II) have been prepared and characterized by different physical techniques. Infrared spectra of the complexes indicate deprotonation and coordination of the phenolic OH. It also confirms that nitrogen atom of the oximino group contributes to the complexation. Electronic spectra and magnetic susceptibility measurements reveal square planar geometry for Cu(II), Ni(II) and Pd(II) complexes and tetrahedral geometry for Co(II) complex. The elemental analyses and mass spectral data have justified the ML(2) composition of complexes. Kinetic and thermodynamic parameters were computed from the thermal decomposition data using Coats and Redfern method. The geometry of the metal complexes has been optimized with the help of molecular modeling. The free ligand (HDMAOX) and its metal complexes have been tested in vitro against Alternarie alternate, Aspergillus flavus, Aspergillus nidulans and Aspergillus niger fungi and Streptococcus, Staph, Staphylococcus and Escherchia coli bacteria in order to assess their antimicrobial potential. The results indicate that the ligand and its metal complexes possess antimicrobial properties.

Concerted ligand exchange and the roles of counter anions in the reversible structural switching of crystalline peptide metallo-macrocycles.

PubMed

Miyake, Ryosuke; Shionoya, Mitsuhiko

2014-06-02

To understand reversible structural switching in crystalline materials, we studied the mechanism of reversible crystal-to-crystal transformation of a tetranuclear Ni(II) macrocycle consisting of artificial β-dipeptides. On the basis of detailed structural analyses and thermodynamic measurements made in a comparison of pseudo-isostructural crystals (NO3 and BF4 salts), we herein discuss how ligand-exchange reactions take place in the crystal due to changes in water content and temperature. Observations of the structural transformation of NO3 salt indicated that a pseudo crystalline phase transformation takes place through concerted ligand-exchange reactions at the four Ni(II) centers of the macrocycle with hydrogen bond switching. A mechanism for this ligand exchange was supported by IR spectroscopy. Thermodynamic measurements suggested that the favorable compensation relationship of the enthalpy changes due to water uptake and structural changes are keys to the reversible structural transformation. On the basis of a comparison with the pseudo-isostructural crystals, it is apparent that the crystal packing structure and the types of counter anions are important factors for facilitating reversible ligand exchange with single crystallinity.

Tridentate N2S ligand from 2,2′-dithiodibenzaldehyde and N,N-dimethylethylenediamine: Synthesis, structure, and characterization of a Ni(II) complex with relevance to Ni Superoxide Dismutase

PubMed Central

Zimmerman, Joshua R.; Smucker, Bradley W.; Dain, Ryan P.; VanStipdonk, Michael J.

2011-01-01

Nickel Superoxide Dismutase (NiSOD) and the A-cluster of Carbon Monoxide Dehydrogenase/Acetyl Coenzyme A Synthase (CODH/ACS) both feature active sites with Ni coordinated by thiolate and amide donors. It is likely that the particular set of donors is important in tuning the redox potential of the Ni center(s). We report herein an expansion of our efforts involving the use of 2,2′-dithiodibenzaldehyde (DTDB) as a synthon for metal-thiolate complexes to reactions with Ni complexes of N,N-dimethylethylenediamine (dmen). In the presence of coordinating counterions, these reactions result in monomeric square-planar complexes of the tridentate N2S donor ligand derived from the Schiff-base condensation of dmen and DTDB. In the absence of a coordinating counterion, we have isolated a Ni(II) complex with an asymmetric N2S2 donor set involving one amine and one imine N donor in addition to two thiolate donors. This latter complex is discussed with respect to its relevance to the active site of NiSOD. PMID:21666847

Análise da aplicação e dos resultados do modelo OPM3® para a área da saúde

PubMed Central

Augusto dos Santos, Luis; de Fátima Marin, Heimar

2015-01-01

Esta pesquisa procurou analisar se um modelo de questionário criado por uma comunidade internacional de gerenciamento de projetos e se é aplicavél a organizações voltadas a área de saúde. O modelo OPM3® (Organizational Project Management Maturity Model) foi criado para que organizações de qualquer área ou porte pudessem identificar a presença, ou ausência, de boas práticas de gerenciamento. O objetivo da aplicação desse modelo é avaliar sempre a organização e não o entrevistado. No presente artigo, são apresentados os resultados da aplicação desse modelo em uma organização que possuía produtos e serviços de tecnologia da informação aplicados à área de saúde. Este estudo verificou que o modelo é aplicável de forma rápida e que a organização analisada possuía um número expressivo de boas práticas. PMID:26924862

Etnografía acelerada para transformar normas sociales sobre género y sexualidad en hombres puertorriqueños heterosexuales1,2

PubMed Central

Ortiz-Torres, Blanca; Rivera-Ortiz, Rafael J.; Mendoza, Sigrid

2014-01-01

Resumen La construcción de roles de género dominantes contribuyen al riesgo de contraer VIH, y por tal razón se ha urgido a que se integren las normas sociales relativas al género en las intervenciones preventivas del VIH. Este estudio pretende adaptar y desarrollar una intervención que facilite la transformación de normas sociales del género y de prácticas sexuales en hombres puertorriqueños. La intervención propone transformar normas sociales relacionadas al género y sexualidad en barras comunitarias utilizando el modelo de líderes de opinión. Luego de ser elegidos/as, los/as líderes de opinión diseminan mensajes integrando la importancia de relaciones equitativas entre parejas para la prevención del VIH. La primera fase de esta intervención es discutida en este artículo, la cual incluye un proceso de etnografía acelerada para identificar los escenarios comunitarios en los que podemos desarrollar esta intervención y permitirnos entender la cultura de las barras comunitarias. A partir de las observaciones etnográficas, pudimos: desarrollar un protocolo de seguridad para realizar las observaciones, desarrollar un perfil de la cultura de las barras, elegir las barras a participar en las dos condiciones del estudio y adaptar los instrumentos de la intervención para que respondieran a la particularidad de los/as participantes. PMID:25530828

INTERVENCIÓN EDUCATIVA EFECTIVA EN VIH PARA MUJERES

PubMed Central

Miner, Sarah; Poupin, Lauren; Bernales, Margarita; Ferrer, Lilian; Cianelli, Rosina

2016-01-01

RESUMEN En Chile se estima que aproximadamente 38 mil personas viven con el Virus de Inmunodeficiencia Humana [VIH]. En el año 2001, 1.092 mujeres chilenas vivían con VIH, actualmente se cree que hay más de 7.600 mujeres con el virus. Frente a estas cifras surge la necesidad de crear estrategias de prevención dirigidas a mujeres chilenas. Objetivo analizar los estudios ya realizados en la prevención de VIH para determinar qué aspectos se deben incluir en programas exitosos de prevención de VIH en mujeres. Diseño y Método se realizó una revisión de la literatura utilizando la base de datos Proquest, CINAHL, Pubmed y Scielo. Los límites comprendieron: textos completos, de los últimos 10 años, de acceso gratuito y escrito en español o inglés. Se seleccionaron 15 artículos para la revisión. Resultados todos los artículos comprenden la evaluación del efecto de una intervención sobre conocimiento y conductas relacionadas con VIH/SIDA. Catorce muestran resultados significativos en cambios positivos de conducta o conocimientos relacionados con la prevención de VIH. Conclusiones los programas de prevención de VIH en mujeres pueden ser efectivos para lograr cambios de conducta y de conocimiento. Las intervenciones exitosas son aquellas basadas en teorías o modelos de prevención y en cambios de conductas, todas adaptadas a la cultura de la población estudiada. PMID:27667897

Whole-Genome Sequence of Cupriavidus sp. Strain BIS7, a Heavy-Metal-Resistant Bacterium

PubMed Central

Hong, Kar Wai; Thinagaran, Dinaiz a/l; Gan, Han Ming; Yin, Wai-Fong

2012-01-01

Cupriavidus sp. strain BIS7 is a Malaysian tropical soil bacterium that exhibits broad heavy-metal resistance [Co(II), Zn(II), Ni(II), Se(IV), Cu(II), chromate, Co(III), Fe(II), and Fe(III)]. It is particularly resistant to Fe(II), Fe(III), and Zn(II). Here we present the assembly and annotation of its genome. PMID:23115161

The n-propyl 3-azido-2,3-dideoxy-β-D-arabino-hexopyranoside: Syntheses, crystal structure, physical properties and stability constants of their complexes with Cu(II), Ni(II) and VO(II)

NASA Astrophysics Data System (ADS)

Barabaś, Anna; Madura, Izabela D.; Marek, Paulina H.; Dąbrowska, Aleksandra M.

2017-11-01

The structure, conformation and configuration of the n-propyl 3-azido-2,3-dideoxy-β-D-arabino-hexopyranoside (BAra-nPr) were determined by 1H NMR, 13C NMR, and IR spectroscopy, as well as by optical rotation. The crystal structure was confirmed by single-crystal X-ray diffraction studies at room temperature. The compound crystallizes in P21 space group symmetry of the monoclinic system. The molecule has a 4C1 chair conformation with azide group in the equatorial position both in a solution as well as in the crystal. The spatial arrangement of azide group is compared to other previously determined azidosugars. The hydrogen bonds between the hydroxyl group of sugar molecules lead to a ribbon structure observed also for the ethyl homolog. The packing of ribbons is dependent on the alkyl substituent length and with the elongation changes from pseudohexagonal to lamellar. Acidity constants for the n-propyl 3-azido-2,3-dideoxy-β-D-arabino-hexopyranoside (BAra-nPr) in an aqueous solution were evaluated by the spectrophotometric and potentiometric titrations methods. Title compound exhibit blue absorption with the maximum wavelengths in the range of 266 nm and 306 nm. Based on these measurements we showed equilibria existing in a particular solution and a distribution of species which have formed during the titration. We also investigated interactions between Cu(II), Ni(II) and VO(II) and title compound (as ligand L) during complexometric titration. On these bases we identified that in [CuII-BAra-nPr]2+ the ratio of the ligand L to metal ion M(II) was 3:1, while in [NiII-BAra-nPr]2+ and [VOII-BAra-nPr]2+ complexes 2:1 ratios were found. The cumulative stability constants (as log β) occurring in an aqueous solution for the complexes of BAra-nPr with Cu(II), Ni(II) and VO(IV) were 14.57; 11.71 and 4.20, respectively.

Synthesis, spectral and quantum chemical studies and use of (E)-3-[(3,5-bis(trifluoromethyl)phenylimino)methyl]benzene-1,2-diol and its Ni(II) and Cu(II) complexes as an anion sensor, DNA binding, DNA cleavage, anti-microbial, anti-mutagenic and anti-cancer agent

NASA Astrophysics Data System (ADS)

Ünver, Hüseyin; Boyacıoğlu, Bahadır; Zeyrek, Celal Tuğrul; Yıldız, Mustafa; Demir, Neslihan; Yıldırım, Nuray; Karaosmanoğlu, Oğuzhan; Sivas, Hülya; Elmalı, Ayhan

2016-12-01

We report the synthesis of a novel Schiff base (E)-3-[(3,5-bis(trifluoromethyl) phenylimino)methyl] benzene-1,2-diol from the reaction of 2,3-dihydroxybenzaldehyde with 3,5-bis(trifluoromethyl)aniline, and its Ni(II) and Cu(II) complexes. The molecular structure of the Schiff base was experimentally determined using X-ray single-crystal data and was compared to the structure predicted by theoretical calculations using density functional theory (DFT), Hartree-Fock (HF) and Möller-Plesset second-order perturbation (MP2). In addition, nonlinear optical (NLO) effects of the compound was predicted using DFT. The antimicrobial activities of the compounds were investigated for their minimum inhibitory concentration. UV-Vis spectroscopy studies of the interactions between the compounds and calf thymus DNA (CT-DNA) showed that the compounds interacts with CT-DNA via intercalative binding. A DNA cleavage study showed that the Cu(II) complex cleaved DNA without any external agents. The compounds inhibited the base pair mutation in the absence of S9 with high inhibition rate. In addition, in vitro cytotoxicity of the Ni(II) complex towards HepG2 cell line was assayed by the MTT method. Also, the colorimetric response of the Schiff base in DMSO to the addition of equivalent amount of anions (F-, Br-, I-, CN-, SCN-, ClO4-, HSO4-, AcO-, H2PO4-, N3- and OH-) was investigated. In this regard, while the addition of F-, CN-, AcO- and OH- anions into the solution containing Schiff base resulted in a significant color change, the addition of Br-, I-, SCN-, ClO4-, HSO4-, H2PO4- and N3- anions resulted in no color change. The most discernable color change in the Schiff base was caused by CN-, which demonstrated that the ligand can be used to selectively detect CN-.

Dual shell-like magnetic clusters containing Ni(II) and Ln(III) (Ln = La, Pr, and Nd) ions.

PubMed

Kong, Xiang-Jian; Ren, Yan-Ping; Long, La-Sheng; Zheng, Zhiping; Nichol, Gary; Huang, Rong-Bin; Zheng, Lan-Sun

2008-04-07

Dual shell-like nanoscopic magnetic clusters featuring a polynuclear nickel(II) framework encapsulating that of lanthanide ions (Ln = La, Pr, and Nd) were synthesized using Ni(NO3)(2).6H2O, Ln(NO3)(3).6H2O, and iminodiacetic acid (IDA) under hydrothermal conditions. Structurally established by crystallographic studies, these clusters are [La20Ni30(IDA)30(CO3)6(NO3)6(OH)30(H2O)12](CO3)(6).72H2O (1), [Ln20Ni21(C4H5NO4)21(OH)24(C2H2O3)6(C2O4)3(NO3)9(H2O)12](NO3)9.nH2O [C2H2O3 is the alkoxide form of glycolate; Ln = Pr (2), n = 42; Nd (3), n = 50], and {[La4Ni5Na(IDA)5(CO3)(NO3)4(OH)5(H2O)5][CO3].10H2O} infinity (4). Carbonate, oxalate, and glycolate are products of hydrothermal decomposition of IDA. Compositions of these compounds were confirmed by satisfactory elemental analyses. It has been found that the cluster structure is dependent on the identity of the lanthanide ion as well as the starting Ln/Ni/IDA ratio. The cationic cluster of 1 features a core of the Keplerate type with an outer icosidodecahedron of Ni(II) ions encaging a dodecahedral kernel of La(III). Clusters 2 and 3, distinctly different from 1, are isostructural, possessing a core of an outer shell of 21 Ni(II) ions encapsulating an inner shell of 20 Ln(III) ions. Complex 4 is a three-dimensional assembly of cluster building blocks connected by units of Na(NO3)/La(NO3)3; the structure of the building block resembles closely that of 1, with a hydrated La(III) ion internalized in the decanuclear cage being an extra feature. Magnetic studies indicated ferromagnetic interactions in 1, while overall antiferromagnetic interactions were revealed for 2 and 3. The polymeric, three-dimensional cluster network 4 displayed interesting ferrimagnetic interactions.

Synthesis, characterization and solid state electrical properties of 1-D coordination polymer of the type [Cu{sub x}Ni{sub 1-x}(dadb){center_dot}yH{sub 2}O]{sub n}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Prasad, R.L., E-mail: rlpjc@yahoo.co.in; Kushwaha, A.; Shrivastava, O.N.

2012-12-15

New heterobimetallic complexes [Cu{sub x}Ni{sub 1-x}(dadb){center_dot}yH{sub 2}O]{sub n} {l_brace}where dadb=2,5-Diamino-3,6-dichloro-1,4-benzoquinone (1); x=1 (2), 0.5 (4), 0.25 (5), 0.125 (6), 0.0625 (7) and 0 (3); y=2; n=degree of polymerization{r_brace} were synthesized and characterized. Heterobimetallic complexes show normal magnetic moments, whereas, monometallic complexes exhibit magnetic moments less than the value due to spin only. Thermo-gravimetric analysis shows that degradation of the ligand dadb moiety is being controlled by the electronic environment of the Cu(II) ions in preference over Ni(II) in heterobimetallic complexes. Existence of the mixed valency/non-integral oxidation states of copper and nickel metal ions in the complex 4 has been attributedmore » from magnetic moment and ESR spectral results. Solid state dc electrical conductivity of all the complexes was investigated. Monometallic complexes were found to be semiconductors, whereas heterobimetallic coordination polymer 4 was found to exhibit metallic behaviour. Existence of mixed valency/ non-integral oxidation state of metal ions seems to be responsible for the metallic behaviour. - Graphical abstract: Contrast to the semiconductor monometallic complexes 2 and 3, the heterobimetallic complex 4 exhibits metallic behaviour attributed to the mixed valency/non-integral oxidation state of the metal ions concluded from magnetic and ESR spectral studies. Highlights: Black-Right-Pointing-Pointer 1-D coordination compounds of the type Cu{sub x}Ni{sub 1-x}(dadb){center_dot}yH{sub 2}O were synthesized and characterized. Black-Right-Pointing-Pointer Thermal degradation of the complexes provides an indication of long range electronic communication between metal to ligand. Black-Right-Pointing-Pointer On inclusion of Ni(II) into 1-D coordination polymer of Cu(II). (a) Cu(II) and Ni(II) ions exhibit non-integral oxidation state. (b) resulting heterobimetallic complex 4 exhibits metallic behaviour at all temperature range of the present study whereas monometallic complexes are semiconductor.« less

Factors associated with young adults' knowledge regarding family history of Stroke.

PubMed

Lima, Maria Jose Melo Ramos; Moreira, Thereza Maria Magalhães; Florêncio, Raquel Sampaio; Braga, Predro

2016-11-21

to analyze the factors associated with young adults' knowledge regarding family history of stroke. an analytical transversal study, with 579 young adults from state schools, with collection of sociodemographic, clinical and risk factor-related variables, analyzed using logistic regression (backward elimination). a statistical association was detected between age, civil status, and classification of arterial blood pressure and abdominal circumference with knowledge of family history of stroke. In the final logistic regression model, a statistical association was observed between knowledge regarding family history of stroke and the civil status of having a partner (ORa=1.61[1.07-2.42]; p=0.023), abdominal circumference (ORa=0.98[0.96-0.99]; p=0.012) and normal arterial blood pressure (ORa=2.56[1.19-5.52]; p=0.016). an association was observed between socioeconomic factors and risk factors for stroke and knowledge of family history of stroke, suggesting the need for health education or even educational programs on this topic for the clientele in question. analisar os fatores associados ao conhecimento dos adultos jovens sobre histórico familiar de Acidente Vascular Cerebral (AVC). estudo transversal analítico, com 579 adultos jovens de escolas públicas, com coleta de variáveis sociodemográficas, clínicas e de fatores de risco em formulário, analisados utilizando-se regressão logística (backward elimination). detectou-se associação estatística de idade, situação conjugal, classificação da pressão arterial e circunferência abdominal com conhecimento do histórico familiar de AVC. No modelo final de regressão logística, observou-se associação estatística do conhecimento sobre histórico familiar de AVC com situação conjugal com companheiro (ORa=1,61[1,07-2,42]; p=0,023), circunferência abdominal (ORa=0,98[0,96-0,99]; p=0,012) e pressão arterial normal (ORa=2,56[1,19-5,52]; p=0,016). foi constatada associação de fatores socioeconômicos e de risco para AVC com o conhecimento do histórico familiar de AVC, sugerindo a necessidade de educação em saúde ou mesmo de programas educacionais sobre o tema junto à clientela em estudo. analizar los factores asociados al conocimiento de los adultos jóvenes sobre el histórico familiar de Accidente Vascular Cerebral (AVC). estudio transversal analítico en 579 adultos jóvenes de escuelas públicas, con recolección de variables sociodemográficas, clínicas y de factores de riesgo en formulario, los datos fueron analizados utilizando la regresión logística (backward elimination). se detectó asociación estadística de edad, situación conyugal, clasificación de la presión arterial y circunferencia abdominal con el conocimiento del histórico familiar de AVC. En el modelo final de regresión logística, se observó una asociación estadística del conocimiento sobre el histórico familiar de AVC con: situación conyugal con compañero (ORa=1,61[1,07-2,42] p=0,023); circunferencia abdominal (ORa=0,98[0,96-0,99] p=0,012); y presión arterial normal (ORa=2,56[1,19-5,52] p=0,016). fue constatada asociación de factores socioeconómicos y de riesgo para AVC con el conocimiento del histórico familiar de AVC; se sugiere la necesidad de realizar acciones de educación en salud o inclusive de preparar programas educacionales sobre el tema para la población estudiada.

Distribution of stable isotopes in arid storms . II. A double-component model of kinematic wave flow and transport

NASA Astrophysics Data System (ADS)

Yakirevich, Alexander; Dody, Avraham; Adar, Eilon M.; Borisov, Viacheslav; Geyh, Mebus

A new mathematical method based on a double-component model of kinematic wave flow and approach assesses the dynamic isotopic distribution in arid rain storms and runoff. This model describes the transport and δ18O evolution of rainfall to overland flow and runoff in an arid rocky watershed with uniformly distributed shallow depression storage. The problem was solved numerically. The model was calibrated using a set of temporal discharge and δ18O distribution data for rainfall and runoff collected on a small rocky watershed at the Sede Boker Experimental Site, Israel. Simulation of a reliable result with respect to observation was obtained after parameter adjustment by trial and error. Sensitivity analysis and model application were performed. The model is sensitive to changes in parameters characterizing the depression storage zones. The model reflects the effect of the isotopic memory in the water within the depression storage between sequential rain spells. The use of the double-component model of kinematic wave flow and transport provides an appropriate qualitative and quantitative fitting between computed and observed δ18O distribution in runoff. RésuméUne nouvelle méthode mathématique basée sur un modèle à double composante d'écoulement et de transport par une onde cinématique a été développée pour évaluer la distribution dynamique en isotopes dans les précipitations et dans l'écoulement en région aride. Ce modèle décrit le transport et les variations des δ18O de la pluie vers le ruissellement et l'écoulement de surface dans un bassin aride rocheux où le stockage se fait dans des dépressions peu profondes uniformément réparties. Le problème a été résolu numériquement. Le modèle a été calibré au moyen d'une chronique de débits et d'une distribution des δ18O dans la pluie et dans l'écoulement de surface sur un petit bassin versant rocheux du site expérimental de Sede Boker (Israël). La simulation d'un résultat crédible par rapport aux observations a été obtenu après un ajustement des paramètres par une méthode d'essais et d'erreurs. L'analyse de sensibilité et l'application du modèle ont ensuite été réalisés. Le modèle est plutôt sensible aux changements des paramètres caractérisant les zones de stockage dans les dépressions. Le modèle rend compte de l'effet de mémoire isotopique dans l'eau dans le stockage des dépressions entre les événements séquentiels de pluie. L'utilisation d'un modèle à double composante d'écoulement et de transport par onde cinématique permet un ajustement qualitatif et quantitatif adapté entre les distributions des δ18O calculées et observées dans l'écoulement de surface. Resumen Un nuevo método matemático basado en un modelo de doble componente de onda cinemática de flujo y transporte permite caracterizar la distribución isotópica dinámica de las tormentas en zonas áridas y la escorrentía. Este modelo describe el transporte y la evolución del δ18O en la lluvia, flujo superficial y escorrentía en una cuenca rocosa de clima árido con detención superficial distribuida uniformemente. El modelo se calibró numéricamente utilizando un conjunto de datos de descarga temporal y de distribución de δ18O para lluvia y escorrentía recogida en una pequeña cuenca rocosa en el Centro de Experimentación de Sede Boker, Israel. Se obtuvo un buen ajuste a los datos tras un ajuste de parámetros mediante prueba y error. Se realizó un análisis de sensibilidad que indicó que el modelo resulta ser bastante sensible a cambios en los parámetros que caracterizan las zonas de baja detención superficial. El modelo también refleja el efecto de la memoria isotópica en el agua de estas zonas de detención entre los distintos periodos de lluvias. El uso de un modelo de doble componente de onda cinemática de flujo y transporte proporciona un buen ajuste cualitativo y cuantitativo entre los datos medidos y calculados de δ18O en la escorrentía.

Hydrochemical tracers in the middle Rio Grande Basin, USA: 2. Calibration of a groundwater-flow model

NASA Astrophysics Data System (ADS)

Sanford, Ward E.; Plummer, L. Niel; McAda, Douglas P.; Bexfield, Laura M.; Anderholm, Scott K.

The calibration of a groundwater model with the aid of hydrochemical data has demonstrated that low recharge rates in the Middle Rio Grande Basin may be responsible for a groundwater trough in the center of the basin and for a substantial amount of Rio Grande water in the regional flow system. Earlier models of the basin had difficulty reproducing these features without any hydrochemical data to constrain the rates and distribution of recharge. The objective of this study was to use the large quantity of available hydrochemical data to help calibrate the model parameters, including the recharge rates. The model was constructed using the US Geological Survey's software MODFLOW, MODPATH, and UCODE, and calibrated using 14C activities and the positions of certain flow zones defined by the hydrochemical data. Parameter estimation was performed using a combination of nonlinear regression techniques and a manual search for the minimum difference between field and simulated observations. The calibrated recharge values were substantially smaller than those used in previous models. Results from a 30,000-year transient simulation suggest that recharge was at a maximum about 20,000 years ago and at a minimum about 10,000 years ago. Le calibrage d'un modèle hydrogéologique avec l'aide de données hydrochimiques a démontré que la recharge relativement faible dans le Grand Bassin du Middle Rio est vraisemblablement responsable d'une dépression des eaux souterraines dans le centre du bassin et de la présence d'une quantité substantielle d'eau du Rio Grande dans l'aquifère du Groupe de Santa Fe. Les modèles antérieurs avaient des difficultés à reproduire ses conclusions sans l'aide de données hydrochimiques pour contraindre les taux et la distribution de la recharge. L'objectif de cette étude était d'utiliser une grande quantité de données hydrochimiques permettant de calibrer les paramètres du modèle, et notamment les taux de recharge. Le modèle a été construit avec les logiciels MODFLOW, MODPATH et UCODE, et calibré en utilisant les concentrations en 14C et la position de certaines zones définies par les données hydrochimiques. L'estimation de certains paramètres a été réalisée en utilisant une combinaison de techniques de régression non linéaire et une méthode de recherche exhaustive (Brute Force Search) de l'erreur minimum entre les résultats des observations et les simulations. Les valeurs de la recharge calibrée sont substantiellement plus basses que celles estimées dans les modèles antérieurs. Les résultats d'une simulation en régime transitoire sur 30.000 ans suggèrent que la recharge au maximum de la dernière glaciation (last glacial maximum, LGM) était 10 fois supérieure au taux actuel, mais que la recharge qui a suivit la LGM était plus bas que la recharge actuelle. La calibración de un modelo de aguas subterráneas con el apoyo de datos hidroquímicos ha demostrado que la recarga relativamente baja en la cuenca media del Río Grande es probablemente responsable de una depresión de aguas subterráneas en el centro de la cuenca y de la presencia de una cantidad considerable de agua del Río Grande en el acuífero del Grupo Santa Fe. Los modelos propuestos con anterioridad para la cuenca tenían dificultades para reproducir estas características ya que no tenían datos hidroquímicos que permitieran delimitar los ritmos y distribución de recarga. El objetivo del presente estudio consistió en utilizar una gran cantidad de datos hidroquímicos disponibles para ayudar a calibrar los parámetros del modelo, incluyendo los ritmos de recarga. El modelo se construyó utilizando los modelos MODFLOW, MODPATH, y UCODE del USGS, mientras que la calibración se realizó en base a concentraciones de 14C y a la posición de ciertas zonas definidas con los datos hidroquímicos. La estimación de parámetros se realizó en base a una combinación de técnicas de regresiones no lineares y a una búsqueda a viva fuerza del error mínimo entre los datos observados y los simulados. Los valores de recarga calibrados fueron significativamente más bajos que los estimados en los modelos anteriores. Los resultados de una simulación transitoria de 30,000 años sugieren que la recarga durante la última glacial máxima (LGM) fue diez veces el ritmo moderno, pero que la recarga que ocurrió inmediatamente después de la LGM fue más baja que el ritmo moderno.

Ondas de choque em jatos de quasares e objetos BL Lacertae

NASA Astrophysics Data System (ADS)

Melo, F. E.; Botti, L. C. L.

2003-08-01

Este trabalho é parte de um projeto que vem sendo realizado há dois anos no CRAAM, cujos objetivos principais são analisar e aplicar um modelo generalizado de ondas de choque em jatos relativísticos de plasma, presentes em quasares e objetos BL Lacertae, para explicar a variabilidade observada nestes objetos. O método consiste em uma decomposição de curvas de luz em séries de explosões similares, em várias freqüências, baseando-se em uma evolução espectro-temporal média das explosões. A partir da evolução média, um ajuste de cada explosão é feito com base em equações empíricas, modificando-se apenas parâmetros específicos de cada explosão. Inicialmente o modelo foi aplicado ajustando-se as curvas de luz a explosões delineadas por uma evolução do choque em três estágios, segundo a predominância do processo de emissão: síncrotron, Compton e adiabático. Entretanto, nesta nova fase de projeto, visando uma parametrização mais concisa, uma otimização do algoritmo de ajuste e uma convergência mais rápida, a formulação para cada evento foi assumida com uma evolução em apenas dois estágios: subida e descida. Isto possibilitou uma ótima delineação das curvas de luz das fontes OV236, OJ287, 3C273 e BL Lac, entre 1980 e 2000, nas freqüências 4.8, 8.0, 14.5 e 22 GHz, utilizando-se dados do Observatório da Universidade de Michigan, do Observatório do Itapetinga (Atibaia SP) e do Observatório Metsähovi. Como conclusões importantes, verificou-se que: os parâmetros ajustados descrevem o comportamento do jato; os valores do índice que descreve a expansão do jato sugerem que o mesmo se expande de uma forma não-cônica; o campo magnético é turbulento atrás da frente de choque; e as peculiaridades das explosões são devidas à influência de grandezas tais como o coeficiente da distribuição espectral de energia dos elétrons, a intensidade de campo magnético e o fator de feixe Doppler, no início do choque.

Synthesis, characterization, and reactivity of pentamethylcyclopentadienyl complexes of divalent cobalt and nickel

DOE Office of Scientific and Technical Information (OSTI.GOV)

Smith, Michael Edward

1993-10-01

The thesis is divided into the following 4 chapters: synthesis, characterization, and reactivity of trinuclear pentamethylcyclopentadienyl cobalt and nickel clusters with triply-bridging methylidyne groups; chemical and physical properties of pentamethylcyclopentadienyl acetylacetonate complexes of Co(II) and Ni(II); synthesis, characterization, and reactivity of pentamethylcyclopentadienyl halide complexes of Co and Ni; and crystallographic studies of distortions in metallocenes with C 5-symmetrical cyclopentadienyl rings.

Synthesis, spectroscopic characterization, electrochemical behaviour, reactivity and antibacterial activity of some transition metal complexes with 2-(N-salicylideneamino)-3-carboxyethyl-4,5-dimethylthiophene.

PubMed

Daniel, Varughese P; Murukan, B; Kumari, B Sindhu; Mohanan, K

2008-07-01

Mn(II), Fe(II), Co(II), Ni(II), Cu(II) and Zn(II) complexes with a potentially tridentate Schiff base, formed by condensation of 2-amino-3-carboxyethyl-4,5-dimethylthiophene with salicylaldehyde were synthesized and characterized on the basis of elemental analyses, molar conductance values, magnetic susceptibility measurements, UV-vis, IR, EPR and NMR spectral data, wherever possible and applicable. Spectral studies reveal that the free ligand exists in a bifunctionally hydrogen bonded manner and coordinates to the metal ion in a tridentate fashion through the deprotonated phenolate oxygen, azomethine nitrogen and ester carbonyl group. On the basis of electronic spectral data and magnetic susceptibility measurements, suitable geometry has been proposed for each complex. The EPR spectral data of the Cu(II) complex showed that the metal-ligand bonds have considerable covalent character. The Ni(II) complex has undergone facile transesterification reaction when refluxed in methanol for a lengthy period. X-ray diffraction studies of Cu(II) complex showed that the complex has an orthorhombic crystal lattice. In view of the biological activity of thiophene derivatives, the ligand and the complexes were subjected to antibacterial screening. It has been observed that the antibacterial activity of the ligand increased on chelation with metal ion.

Synthesis of non-toxic As and Cr nanoparticles through redox activity of highly flexible layered coordination polymer of Ni(II).

PubMed

Agarwal, Rashmi A

2018-03-09

A simple method for the sequestration of As(III) and Cr(VI) from water has been demonstrated by utilizing a highly flexible porous coordination polymer (PCP) of Ni(II) in its as synthesized form or without solvent removal. This PCP reduces the high toxicity of As(III) and Cr(VI) ions into non-toxic As(0) and Cr/Cr 2 O 3 /CrO 2 (zero, tri and tetravalent) nanoparticles (NPs) within its pores, and this is characterized by powder x-ray diffraction, x-ray photoelectron spectroscopy and high-resolution transmission electron microscopy analysis. The high functionality of this polymer is due to the presence of monodentate carboxylate groups of a benzenetricarboxylate linker, which provide anchoring sites to the metal ions of the metal precursors. Due to the highly oxidising nature of these toxic ions, a redox reaction takes place between the framework metal ions and toxic metal ions, which is explained by an electron paramagnetic resonance study. This is the first report to synthesize non-toxic, as well as useful, NPs of As and Cr from their highly toxic ions within the cavities of a PCP for remediation of the toxic waste stream and contaminated waste water.

Modeling the active site of [NiFe] hydrogenases and the [NiFeu] subsite of the C-cluster of carbon monoxide dehydrogenases: low-spin iron(II) versus high-spin iron(II).

PubMed

Weber, Katharina; Erdem, Özlen F; Bill, Eckhard; Weyhermüller, Thomas; Lubitz, Wolfgang

2014-06-16

A series of four [S2Ni(μ-S)2FeCp*Cl] compounds with different tetradentate thiolate/thioether ligands bound to the Ni(II) ion is reported (Cp* = C5Me5). The {S2Ni(μ-S)2Fe} core of these compounds resembles structural features of the active site of [NiFe] hydrogenases. Detailed analyses of the electronic structures of these compounds by Mössbauer and electron paramagnetic resonance spectroscopy, magnetic measurements, and density functional theory calculations reveal the oxidation states Ni(II) low spin and Fe(II) high spin for the metal ions. The same electronic configurations have been suggested for the Cred1 state of the C-cluster [NiFeu] subsite in carbon monoxide dehydrogenases (CODH). The Ni-Fe distance of ∼3 Å excludes a metal-metal bond between nickel and iron, which is in agreement with the computational results. Electrochemical experiments show that iron is the redox active site in these complexes, performing a reversible one-electron oxidation. The four complexes are discussed with regard to their similarities and differences both to the [NiFe] hydrogenases and the C-cluster of Ni-containing CODH.

Structural, theoretical and corrosion inhibition studies on some transition metal complexes derived from heterocyclic system

NASA Astrophysics Data System (ADS)

Gupta, Shraddha Rani; Mourya, Punita; Singh, M. M.; Singh, Vinod P.

2017-06-01

A Schiff base, (E)-N‧-((1H-indol-3-yl)methylene)-2-aminobenzohydrazide (Iabh) and its Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) complexes have been synthesized. These compounds have been characterized by different physico-chemical and spectroscopic tools (UV-Vis, IR, NMR and ESI-Mass). The molecular structure of Iabh is determined by single crystal X-ray diffraction technique. The ligand Iabh displays E-configuration about the >Cdbnd N- bond. The structure of ligand is stabilized by intra-molecular H-bonding. In all the metal complexes the ligand coordinates through azomethine-N and carbonyl-O resulting a distorted octahedral geometry for Mn(II), Co(II) and Cu(II) complexes in which chloride ions occupy axial positions. Ni(II) and Zn(II) complexes, however, form 4-coordinate distorted square planer and tetrahedral geometry around metal ion, respectively. The structures of the complexes have been satisfactorily modeled by calculations based on density functional theory (DFT) and time dependent-DFT (TD-DFT). The corrosion inhibition study of the compounds have been performed against mild steel in 0.5 M H2SO4 solution at 298 K by using weight loss, potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). They show appreciable corrosion inhibition property.

Determination of kinetic and equilibrium parameters of the batch adsorption of Mn(II), Co(II), Ni(II) and Cu(II) from aqueous solution by black carrot (Daucus carota L.) residues.

PubMed

Güzel, Fuat; Yakut, Hakan; Topal, Giray

2008-05-30

In this study, the effect of temperature on the adsorption of Mn(II), Ni(II), Co(II) and Cu(II) from aqueous solution by modified carrot residues (MCR) was investigated. The equilibrium contact times of adsorption process for each heavy metals-MCR systems were determined. Kinetic data obtained for each heavy metal by MCR at different temperatures were applied to the Lagergren equation, and adsorption rate constants (kads) at these temperatures were determined. These rate constants related to the adsorption of heavy metal by MCR were applied to the Arrhenius equation, and activation energies (Ea) were determined. In addition, the isotherms for adsorption of each heavy metal by MCR at different temperatures were also determined. These isothermal data were applied to linear forms of isotherm equations that they fit the Langmuir adsorption isotherm, and the Langmuir constants (qm and b) were calculated. b constants determined at different temperatures were applied to thermodynamic equations, and thermodynamic parameters such as enthalpy (Delta H), free energy (Delta G), and entropy (Delta S) were calculated and these values show that adsorption of heavy metal on MCR was an endothermic process and process of adsorption was favoured at high temperatures.

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

PubMed

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

2016-08-20

The present study describes the ecofriendly method for the preparation of chitosan film loaded with silver nanoparticles (CS-AgNPs) and application of this film as efficient sorbent for separation and enrichment of Al(III), Cd(II), Cu(II), Co(II), Fe(III), Ni(II), Pb(II) and Zn(II). The stable CS-AgNPs colloid was prepared by dispersing the AgNPs sol in chitosan solution at appropriate ratio and further used to obtain a cast film with very good stability under storage and good mechanical strength for easy handling in aqueous medium. The incorporation of AgNPs in the structure of CS film and interaction between the polymer matrix and nanoparticles were confirmed by UV-vis and FTIR spectroscopy. The homogeneously embedded AgNPs (average diameter 29nm, TEM analysis) were clearly observed throughout the film by SEM. The CS-AgNPs nanocomposite film shows high sorption activity toward trace metals under optimized chemical conditions. The results suggest that the CS-AgNPs nanocomposite film can be feasibly used as a novel sorbent material for solid-phase extraction of metal pollutants from surface waters. Copyright © 2016 Elsevier Ltd. All rights reserved.

Oxoaporphine Metal Complexes (CoII, NiII, ZnII) with High Antitumor Activity by Inducing Mitochondria-Mediated Apoptosis and S-phase Arrest in HepG2

PubMed Central

Qin, Jiao-Lan; Shen, Wen-Ying; Chen, Zhen-Feng; Zhao, Li-Fang; Qin, Qi-Pin; Yu, Yan-Cheng; Liang, Hong

2017-01-01

Three new oxoaporphine Co(II), Ni(II) and Zn(II) complexes 1–3 have been synthesized and fully characterized. 1–3 have similar mononuclear structures with the metal and ligand ratio of 1:2. 1–3 exhibited higher cytotoxicity than the OD ligand and cisplatin against HepG2, T-24, BEL-7404, MGC80–3 and SK-OV-3/DDP cells, with IC50 value of 0.23−4.31 μM. Interestingly, 0.5 μM 1–3 significantly caused HepG2 arrest at S-phase, which was associated with the up-regulation of p53, p21, p27, Chk1 and Chk2 proteins, and decrease in cyclin A, CDK2, Cdc25A, PCNA proteins. In addition, 1–3 induced HepG2 apoptosis via a caspase-dependent mitochondrion pathway as evidenced by p53 activation, ROS production, Bax up-regulation and Bcl-2 down-regulation, mitochondrial dysfunction, cytochrome c release, caspase activation and PARP cleavage. Furthermore, 3 inhibited tumor growth in HepG2 xenograft model, and displayed more safety profile in vivo than cisplatin. PMID:28436418

Effect of pyoverdine supply on cadmium and nickel complexation and phytoavailability in hydroponics.

PubMed

Ferret, C; Cornu, J Y; Elhabiri, M; Sterckeman, T; Braud, A; Jezequel, K; Lollier, M; Lebeau, T; Schalk, I J; Geoffroy, V A

2015-02-01

Siderophores are chelators with a high selectivity for Fe(III) and a good affinity for divalent metals, including Cd(II) and Ni(II). Inoculation with siderophore-producing bacteria (SPB) has thus been proposed as an alternative to chelator supply in phytoremediation. Accurate assessments of the potential of this association require a dissection of the interaction of siderophores with metals at the soil-root interface. This study focuses on pyoverdine (Pvd), the main siderophore produced by Pseudomonas aeruginosa. We first assessed the ability of Pvd to coordinate Ni(II). The stability constant of Pvd-Ni(II) (log K (L'Ni) = 10.9) was found to be higher than that of Pvd-Cd(II) (log K (L'Cd) = 8.2). We then investigated the effect of a direct supply of Pvd on the mobilization, speciation, and phytoavailability of Cd and Ni in hydroponics. When supplied at a concentration of 50 μM, Pvd selectively promoted Ni mobilization from smectite. It decreased plant Ni and Cd contents and the free ionic fractions of these two metals, consistent with the free ion activity model. Pvd had a more pronounced effect for Ni than for Cd, as predicted from its coordination properties. Inoculation with P. aeruginosa had a similar effect on Ni phytoavailability to the direct supply of Pvd.

Mononuclear nickel (II) and copper (II) coordination complexes supported by bispicen ligand derivatives: Experimental and computational studies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Singh, Nirupama; Niklas, Jens; Poluektov, Oleg

2017-01-01

The synthesis, characterization and density functional theory calculations of mononuclear Ni and Cu complexes supported by the N,N’-Dimethyl-N,N’-bis-(pyridine-2-ylmethyl)-1,2-diaminoethane ligand and its derivatives are reported. The complexes were characterized by X-ray crystallography as well as by UV-visible absorption spectroscopy and EPR spectroscopy. The solid state structure of these coordination complexes revealed that the geometry of the complex depended on the identity of the metal center. Solution phase characterization data are in accord with the solid phase structure, indicating minimal structural changes in solution. Optical spectroscopy revealed that all of the complexes exhibit color owing to d-d transition bands in the visiblemore » region. Magnetic parameters obtained from EPR spectroscopy with other structural data suggest that the Ni(II) complexes are in pseudo-octahedral geometry and Cu(II) complexes are in a distorted square pyramidal geometry. In order to understand in detail how ligand sterics and electronics affect complex topology detailed computational studies were performed. The series of complexes reported in this article will add significant value in the field of coordination chemistry as Ni(II) and Cu(II) complexes supported by tetradentate pyridyl based ligands are rather scarce.« less

Simultaneous removal of heavy-metal ions in wastewater samples using nano-alumina modified with 2,4-dinitrophenylhydrazine.

PubMed

Afkhami, Abbas; Saber-Tehrani, Mohammad; Bagheri, Hasan

2010-09-15

2,4-Dinitrophenylhydrazine (DNPH) immobilized on sodium dodecyl sulfate coated nano-alumina was developed for the removal of metal cations Pb(II), Cd(II), Cr(III), Co(II), Ni(II) and Mn(II) from water samples. The research results displayed that adsorbent has the highest adsorption capacity for Pb(II), Cr(III) and Cd(II) in ions mixture system. Optimal experimental conditions including pH, adsorbent dosage and contact time have been established. Langmuir and Freundlich isotherm models were applied to analyze the experimental data. The best interpretation for the experimental data was given by the Freundlich adsorption isotherm equation for Mn(II), Pb(II), Cr(III) and Cd(II) ions and by Langmuir isotherm equation for Ni(II) and Co(II) ions. Desorption experiments by elution of the adsorbent with a mixture of nitric acid and methanol show that the modified alumina nanoparticles could be reused without significant losses of its initial properties even after three adsorption-desorption cycles. Thus, modified nano-alumina with DNPH is favorable and useful for the removal of these metal ions, and the high adsorption capacity makes it a good promising candidate material for Pb(II),Cr(III) and Cd(II) removal. Copyright 2010 Elsevier B.V. All rights reserved.

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

PubMed

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

2012-11-01

Transition metal complexes of various acetylacetone based ligands of the type ML [where M=Cu(II), Ni(II), Co(II); L=3-(aryl)-pentane-2,4-dione] have been synthesized. The structural features have been derived from their elemental analysis, magnetic susceptibility, molar conductance, IR, UV-Vis, (1)H NMR, Mass and ESR spectral studies. Conductivity measurements reveal that all the complexes are non-electrolytic in nature. Spectroscopic and other analytical data of the complexes suggest octahedral geometry for other metal(II) complexes. The redox behavior of the copper(II) complexes have been studied by cyclic voltammetry. The free ligands and their metal complexes have been screened for their in vitro biological activities against the bacteria Pseudomonas aeruginosa, Escherichia coli and Staphylococcus aureus as well as the fungus Candida albicans by well diffusion method. The zone of inhibition value indicates that the most of the metal(II) complexes are found to possess increased activities compared to those of the free ligands. All synthesized compounds may serve as potential photoactive materials as indicated from their characteristic fluorescence properties. The second harmonic generation (SHG) efficiency of the ligands (L1-L3) was found to be considerable effect than that of urea and KDP (potassium dihydrogen phosphate). Copyright © 2012 Elsevier B.V. All rights reserved.

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

NASA Astrophysics Data System (ADS)

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

2012-11-01

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

Flexible porous coordination polymer of Ni(II) for developing nanoparticles through acid formation and redox activity of the framework

NASA Astrophysics Data System (ADS)

Agarwal, Rashmi A.

2017-10-01

Immobilization of the nanoparticles (NPs) in a two dimensional porous coordination polymer (PCP) is currently an emerging field for a number of applications. But still it is a great challenge to fabricate any specified metal NPs in a single network. Herein the synthesis of Au, Pd, Mn, Fe, Cu, Zn, Mg, Li, Fe/Cu, Zn/Mg etc, NPs in a highly flexible PCP of Ni(II); {[Ni3(TBIB)2(BTC)2(H2O)6]·5C2H5OH·9H2O}n [TBIB = 1,3,5-tri(1H-benzo[d]imidazol-1-yl)benzene, H3BTC = 1,3,5-benzenetricarboxylic acid] have been reported. This universal host is able to grow mixed metal NPs from mixed metal precursors. Monodentate carboxylate groups of BTC linker act as anchoring sites for the metal ions of the metal precursors. This is the main driving force to grow NPs within the cavities along with the high flexibility of this polymer at room temperature. Mechanism involves acid formation followed by redox reaction to synthesize metal NPs explained by EPR and FTIR. Paramagnetic properties have been shown by as-synthesized Fe NPs integrated framework at room temperature under applied magnetic field up to 17,500 Oe.

Synthesis, spectroscopic characterization, antimicrobial and antitumor studies of mono-, bi- and tri-nuclear metal complexes of a new Schiff base ligand derived from o-acetoacetylphenol

NASA Astrophysics Data System (ADS)

Adly, Omima M. I.; Shebl, Magdy; El-Shafiy, Hoda F.; Khalil, Saied M. E.; Taha, A.; Mahdi, Mohammed A. N.

2017-12-01

New mono-, bi- and trinuclear metal complexes of Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and UO2(VI) with a new Schiff base ligand H3L; ((E)-2-hydroxy-N‧-(4-(2-hydroxyphenyl)-4-oxobutan-2-ylidene)) benzohydrazide (H3L) have been synthesized. The ligand and its metal complexes were characterized by elemental analyses, IR, 1H NMR, electronic, ESR and mass spectra, conductivity and magnetic susceptibility measurements as well as thermal analyses. The metal complexes exhibited octahedral and tetrahedral geometrical arrangements. Kinetic parameters (Ea, A, ΔH, ΔS and ΔG) of the thermal decomposition stages have been evaluated using Coats-Redfern equations. Structural parameters of the synthesized compounds were calculated on the basis of DFT level implemented in the Gaussian 09 program and Hyperchem 7.52 and correlated with the experimental data. The antimicrobial activity of the present compounds was screened against Gram-positive bacteria (Staphylococcus aureus and Bacillus subtilis), Gram-negative bacteria (Salmonella typhimurium and Escherichia coli), yeast (Candida albicans) and fungus (Aspergillus fumigatus). The antitumor activity of the ligand and its Ni(II) and Cu(II) complexes was investigated against HepG2 cell line.

Changes in spectrochemical and catalytic properties of biopolymer anchored Cu(II) and Ni(II) catalysts by electron beam irradiation.

PubMed

Antony, R; Suja Pon Mini, P S; Theodore David Manickam, S; Sanjeev, Ganesh; Mitu, Liviu; Balakumar, S

2015-01-01

Chitosan (a biopolymer) anchored Cu(II) and Ni(II) Schiff base complexes, [M(OIAC)Cl2] (M: Cu/Ni and OIAC: ([2-oxo-1H-indol-3-ylidene]amino)chitosan) were electron beam irradiated by different doses (100 Gy, 1 kGy and 10 kGy). The electron beam has shown potential impact on biopolymer's support, in detail chain linking and chain scissoring, as evidenced by viscosity studies, FT-IR and X-ray diffraction spectroscopic techniques. Due to these structural changes, thermal properties of the complexes were found to be changed. The surface of these heterogeneous complexes was also effectually altered by electron beam. As a consequence, pores and holes were created as probed by SEM technique. The catalytic activity of both non-irradiated and irradiated complexes was investigated in the aerobic oxidation of cyclohexane using hydrogen peroxide oxidant. The catalytic ability of the complexes was enhanced significantly after irradiation as the result of surface changes. The reusability of the complexes was also greatly affected because of the structural variations in polymeric support. In terms of both better catalytic activity along with the reusability, 1 kGy is suggested as the best dose to attain adequate increase in catalytic activity and good reusability. Copyright © 2015 Elsevier B.V. All rights reserved.

Synthesis of non-toxic As and Cr nanoparticles through redox activity of highly flexible layered coordination polymer of Ni(II)

NASA Astrophysics Data System (ADS)

Agarwal, Rashmi A.

2018-03-01

A simple method for the sequestration of As(III) and Cr(VI) from water has been demonstrated by utilizing a highly flexible porous coordination polymer (PCP) of Ni(II) in its as synthesized form or without solvent removal. This PCP reduces the high toxicity of As(III) and Cr(VI) ions into non-toxic As(0) and Cr/Cr2O3/CrO2 (zero, tri and tetravalent) nanoparticles (NPs) within its pores, and this is characterized by powder x-ray diffraction, x-ray photoelectron spectroscopy and high-resolution transmission electron microscopy analysis. The high functionality of this polymer is due to the presence of monodentate carboxylate groups of a benzenetricarboxylate linker, which provide anchoring sites to the metal ions of the metal precursors. Due to the highly oxidising nature of these toxic ions, a redox reaction takes place between the framework metal ions and toxic metal ions, which is explained by an electron paramagnetic resonance study. This is the first report to synthesize non-toxic, as well as useful, NPs of As and Cr from their highly toxic ions within the cavities of a PCP for remediation of the toxic waste stream and contaminated waste water.

N-((5-chloropyridin-2-yl)carbamothioyl)furan-2-carboxamide and its Co(II), Ni(II) and Cu(II) complexes: Synthesis, characterization, DFT computations, thermal decomposition, antioxidant and antitumor activity

NASA Astrophysics Data System (ADS)

Yeşilkaynak, Tuncay; Özpınar, Celal; Emen, Fatih Mehmet; Ateş, Burhan; Kaya, Kerem

2017-02-01

N-((5-chloropyridin-2-yl)carbamothioyl)furan-2-carboxamide (HL: C11H8ClN3O2S) and its Co(II), Ni(II) and Cu(II) complexes have been synthesized and characterized by elemental analysis, FT-IR,1H NMR and HR-MS methods. The HL was characterized by single crystal X-ray diffraction technique. It crystallizes in the monoclinic system. The HL has the space group P 1 21/c 1, Z = 4, and its unit cell parameters are a = 4.5437(5) Å, b = 22.4550(3) Å, c = 11.8947(14) Å. The ligand coordinates the metal ions as bidentate and thus essentially yields neutral complexes of the [ML2] type. ML2 complex structures were optimized using B97D/TZVP level. Molecular orbitals of both HL ligand were calculated at the same level. Thermal decomposition of the complexes has been investigated by thermogravimetry. The complexes were screened for their anticancer and antioxidant activities. Antioxidant activity of the complexes was determined by using the DPPH and ABTS assays. The anticancer activity of the complexes was studied by using MTT assay in MCF-7 breast cancer cells.

Syntheses, spectroscopic characterization, thermal study, molecular modeling, and biological evaluation of novel Schiff's base benzil bis(5-amino-1,3,4-thiadiazole-2-thiol) with Ni(II), and Cu(II) metal complexes

NASA Astrophysics Data System (ADS)

Chandra, Sulekh; Gautam, Seema; Rajor, Hament Kumar; Bhatia, Rohit

2015-02-01

Novel Schiff's base ligand, benzil bis(5-amino-1,3,4-thiadiazole-2-thiol) was synthesized by the condensation of benzil and 5-amino-1,3,4-thiadiazole-2-thiol in 1:2 ratio. The structure of ligand was determined on the basis of elemental analyses, IR, 1H NMR, mass, and molecular modeling studies. Synthesized ligand behaved as tetradentate and coordinated to metal ion through sulfur atoms of thiol ring and nitrogen atoms of imine group. Ni(II), and Cu(II) complexes were synthesized with this nitrogen-sulfur donor (N2S2) ligand. Metal complexes were characterized by elemental analyses, molar conductance, magnetic susceptibility measurements, IR, electronic spectra, EPR, thermal, and molecular modeling studies. All the complexes showed molar conductance corresponding to non-electrolytic nature, expect [Ni(L)](NO3)2 complex, which was 1:2 electrolyte in nature. [Cu(L)(SO4)] complex may possessed square pyramidal geometry, [Ni(L)](NO3)2 complex tetrahedral and rest of the complexes six coordinated octahedral/tetragonal geometry. Newly synthesized ligand and its metal complexes were examined against the opportunistic pathogens. Results suggested that metal complexes were more biological sensitive than free ligand.

p-halo N4-phenyl substituted thiosemicarbazones: Crystal structure, supramolecular architecture, characterization and bio-assay of their Co(III) and Ni(II) complexes

NASA Astrophysics Data System (ADS)

Kotian, Avinash; Kumara, Karthik; Kamat, Vinayak; Naik, Krishna; Kokare, Dhoolesh G.; Nevrekar, Anupama; Lokanath, Neratur Krishnappagowda; Revankar, Vidyanand K.

2018-03-01

In the present work, three potential metal ion chelating ligands, p-halo N4-phenyl substituted thiosemicarbazones are synthesized and characterized. The molecular structure of all (E)-4-(4-halophenyl)-1-(3-hydroxyiminobutan-2-ylidene) thiosemicarbazones (halo = F/Cl/Br) are determined by single crystal X-ray diffraction method. All the molecules have crystallized in monoclinic crystal system with P21/n space group. The ligands show Csbnd H⋯S and Nsbnd H⋯S intermolecular interactions, which are responsible to form the supramolecular self-assemblies through R22(8), R22(12) and R22(14) ring motifs. Hirshfeld surface analysis is carried out to explore the intermolecular interactions. A series of Co(III) and Ni(II) mononuclear transition metal complexes derived from these ligands have been synthesized and characterized by various spectro-analytical methods. The metal to ligand stoichiometry has been found to be 1:2 in all the complexes. The synthesized compounds have been investigated for their in vitro antimicrobial potencies. The compounds are found to be more active than the standard used, in the case of E. coli and A. niger. Additionally, they are also screened for their in vitro antitubercular activity.

Mononuclear thiocyanate containing nickel(II) and binuclear azido bridged nickel(II) complexes of N4-coordinate pyrazole based ligand: Syntheses, structures and magnetic properties

NASA Astrophysics Data System (ADS)

Solanki, Ankita; Monfort, Montserrat; Kumar, Sujit Baran

2013-10-01

Two mononuclear nickel(II) complexes [NiL1(NCS)2] (1) and [NiL2(NCS)2] (2) and two azido bridged binuclear nickel(II) complexes [Ni(()2()2] (3) and [Ni(()2()2] (4), where L1, L2, L1‧ and L2‧ are N,N-diethyl-N‧,N‧-bis((3,5-dimethyl-1H-pyrazol-1-yl)methyl)ethane-1,2-diamine (L1), N,N-bis((1H-pyrazol-1-yl)methyl)-N‧,N‧-diethylethane-1,2-diamine (L2), N,N-diethyl-N‧-((3,5-dimethyl-1H-pyrazol-1-yl)methyl)ethane-1,2-diamine (L1‧) and N-((1H-pyrazol-1-yl)methyl)-N‧,N‧-diethylethane-1,2-diamine (L2‧) have been synthesized and characterized by microanalyses and physico-chemical methods. Single crystal X-ray diffraction analyses revealed that complexes 1 and 2 are mononuclear NCS- containing Ni(II) complex with octahedral geometry and complexes 3 and 4 are end-on (μ-1,1) azido bridged binuclear Ni(II) complexes with distorted octahedral geometry. Variable temperature magnetic studies of the complexes 3 and 4 display ferromagnetic interaction with J values 19 and 32 cm-1, respectively.

Synthesis, spectroscopic, thermal and DFT calculations of 2-(3-amino-2-hydrazono-4-oxothiazolidin-5-yl) acetic acid binuclear metal complexes

NASA Astrophysics Data System (ADS)

Hassan, Walid M. I.; Badawy, M. A.; Mohamed, Gehad G.; Moustafa, H.; Elramly, Salwa

2013-07-01

The binuclear complexes of 2-(3-amino-2-hydrazono-4-oxothiazolidin-5-yl) acetic acid ligand (HL) with Fe(III), Co(II), Ni(II), Cu(II) and Zn(II) ions were prepared and their stoichiometry was determined by elemental analysis. The stereochemistry of the studied series of metal complexes was established by analyzing their infrared, 1H NMR spectra and the magnetic moment measurements. According to the elemental analysis data, the complexes were found to have the formulae [Fe2L(H2O)8]Cl5 and [M2L(H2O)8]Cl3 (M = Co(II), Ni(II), Cu(II) and Zn(II)). The present analyses demonstrate that all metal ions coordinated to the ligand via O(9), O(11), N(16) and N(18) atoms. Thermal decomposition studies of the ligand-metal complexes have been performed to verify the status of water molecules present in these metal complexes and their general decomposition pattern. Density Functional Theory (DFT) calculations at the B3LYP/6-31G* level of theory have been carried out to investigate the equilibrium geometry of the ligand and complexes. Moreover, charge density distribution, extent of distortion from regular geometry, dipole moment and orientation have been performed and discussed.

Syntheses, crystal structures and Hirshfeld surface analysis of a coordination polymer of Cu(II) chlorido and a tris-octahedral complex of Ni(II) containing isonicotinoylhydrazone blockers

NASA Astrophysics Data System (ADS)

Mahmoudi, Ghodrat; Chowdhury, Habibar; Ghosh, Barindra K.; Lofland, Samuel E.; Maniukiewicz, Waldemar

2018-05-01

One-pot reactions of pre-assigned molar ratios of appropriate metal (II) salts and HL1 (2-acetylpyridine nicotinoylhydrazone) or HL2 (2-acetylpyridine isonicotinoylhydrazone) in MeOH solutions at room temperature afford 1D coordination polymeric chain [Cu(μ-L1) (Cl)]n (1) and a mononuclear complex [Ni(L2)2] (2). The compounds (1) and (2) were characterized using elemental analyses, spectral and other physicochemical methods. Single crystal X-ray diffraction measurements for (1) and (2) have been made to define the molecular aggregates and crystalline architectures. In (1), each copper (II) center adopts a distorted square pyramidal geometry with a CuN3OCl chromophore linked through μ-L1 to form the 1D polymeric chain. While in (2) each Ni(II) cation is six-coordinate with octahedral structure having NiN4O2 chromophore containing two L2 units each functioning as a classical tridentate (N,N,O) chelator. Different weak non-covalent interactions promote dimensionalities in the compounds. A Hirshfeld surface analysis was employed to gain additional insight into interactions responsible for packing of (1) and (2). Magnetic susceptibility measurement of (1) in the 4-300 K range reveals simple paramagnetism.

Construyendo modelos confiables de estrellas rías

NASA Astrophysics Data System (ADS)

Mauas, P. J.; Falchi, A.

Se estudian las aproximaciones que se realizan usualmente al calcular modelos de estrellas frías (redistribución completa para la lí nea Lyman-α, despreciar el ``line-blanketing", suponer los metales en LTE), y cómo influyen en los distintos observables. Asimismo, se evalúa cuál es la información que cada observable nos da sobre la atmósfera de la estrella, y cuáles son las incertidumbres de cada modelo.

Structural Investigation of Dinuclear Clusters Incorporated in Polyoxotungstates

NASA Astrophysics Data System (ADS)

Nagy, C.; Rusu, D.; Somesan, C.; Filip, S.; Rusu, M.; David, L.

2011-10-01

The new K10[M2Bi2W20O70]ṡH2O (M = Mn(II), Co(II), Ni(II), Cu(II)) sandwich-type complex have been investigated by spectroscopic (FT-IR, UV-VIS, ESR) methods. The main goal was to obtain information about the metal ions coordination to the trilacunary regions of Keggin polioxoanion ligands, the local symmetry around the metal ions and the presence of possible metal-metal couplings.

USSR Report, Chemistry

DTIC Science & Technology

1985-03-14

USSR Academy of Sciences lAbstract] A study is made of the mechanism of attachment of Ni(II) by covalent bonding to a polyethylene-graft- polyacrylic ...and 12.5 percent of its plastics and synthetic resins.. The republic’s share in national production of potassium fertilizers, which is 53.6 percent...our republic, the return from 1 kg of active ingredient in nitrogen-phosphorus- potassium fertilizer averages 6 kg of grain, which is the reason why

Albumin Redhill, a human albumin variant.

PubMed

Brand, S; Hutchinson, D W; Donaldson, D

1984-01-31

Albumin Redhill, a variant human albumin with the same C-terminal amino acid as albumin A but with arginine at the N-terminus has been isolated by chromatofocusing from the sera of an English family. Albumin Redhill appears to contain two sites of mutation in its protein chain and is probably a proalbumin. The ability of albumin Redhill to bind Ni(II) or Cu(II) ions is considerably less than that of albumin A.

Estudio de distintos modelos de protuberancias solares

NASA Astrophysics Data System (ADS)

Cirigliano, D.; Rovira, M.; Mauas, P.

En este trabajo presentamos perfiles de líneas del CaII, MgII y HeI calculados para distintos modelos de protuberancias, y los comparamos con observaciones obtenidas por los satélites OSO 8 y SOHO. Para obtener las poblaciones de los distintos niveles de los átomos, utilizamos un código numérico que combina las ecuaciones de transporte de radiación y equilibrio estadístico en un único sistema de ecuaciones no lineal. Los modelos básicos que consideramos para las protuberancias consisten en placas homogéneas y unidimensionales apoyadas sobre la superficie del Sol. Dichas placas se hallan estratificadas en hebras y los modelos difieren entre sí en la temperatura y ancho de la placa, en la presión a la cual se halla el plasma y en el número de hebras. A partir de estos modelos se investiga cada uno de estos parámetros libres y como influyen en la atmósfera de las protuberancias solares y en el perfil de línea de cada especie estudiada, con el objetivo de determinar las condiciones en las que se halla el material atmosférico de estas protuberancias.

Chelation, spectroscopic characterization, biological activity and crystal structure of 2,3-butanedione isonicotinylhydrazone: Determination of Zr4+ after flotation separation

NASA Astrophysics Data System (ADS)

Al-Fulaij, O. A.; Jeragh, B.; El-Sayed, A. E. M.; El-Defrawy, M. M.; El-Asmy, A. A.

2015-02-01

New metal complexes of Co(II), Ni(II) Cu(II), Zn(II), Cd(II), Pd(II) and Hg(II) with 2,3-butanedione isonicotinylhydrazone [BINH] have been prepared and investigated. Single crystal for BINH is grown and solved as orthorhombic with P 21 21 2 space group. The formula of the ligand was assigned based on the elemental analysis, mass spectra and conductivity measurements. The complexes assigned the formulae [M(BINH-H)Cl]ṡnH2O (Mdbnd Co(II), Ni(II), Cu(II), Zn(II); n = 0 or 1); [Hg(BINH-H)(H2O)2Cl]; [Cd(BINH)Cl2]ṡ2H2O and [Pd(BINH)Cl2]ṡH2O. All complexes are nonelectrolytes. BINH acts as a tridentate ligand in [M(BINH-H)Cl]ṡnH2O and [Hg(BINH-H)(H2O)2Cl] coordinating through Cdbnd Oketonic, Csbnd Oamedic and Cdbnd Nhy and as a neutral bidentate through Cdbnd Oketonic and Cdbnd Nhy in [Cd(BINH)Cl2]ṡ2H2O and [Pd(BINH)Cl2]ṡH2O; the pyridine nitrogen has no rule in coordination. The data are supported by NMR (1H and 13C) spectra. The magnetic moments and electronic spectra provide a tetrahedral structure for the Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) complexes; square-planar for the Pd(II) complex and octahedral for the Hg(II) complex. The TGA of the complexes depicted the outer and inner water molecules as well as the final residue. The cobalt and cadmium complexes ended with the metal while the Cu(II), Zn(II) and Pd(II) complexes ended with complex species. [Hg(BINH-H)(H2O)2Cl] has no residue. The ligand is inactive against all tested organisms except for Bacillus thuringiensis. The Hg(II) complex is found more active than the other complexes. The flotation technique is found applicable for the separation of micro amount (10 ppm) of Zr4+ using 10 ppm of BINH and 1 × 10-5 mol L-1 of oleic acid at pH 6 with efficiency of 98% with no interferences.

Synthesis, crystallographic and spectral studies of homochiral cobalt(II) and nickel(II) complexes of a new terpyridylaminoacid ligand

NASA Astrophysics Data System (ADS)

Wang, Xing; Gao, Chang-Qing; Gao, Zhi-Yang; Wu, Ben-Lai; Niu, Yun-Yin

2018-04-01

Based on a chiral terpyridylaminoacid ligand, a series of homochiral Co(II) and Ni(II) complexes, namely, [Co(H2L)(HL)]·Cl·(PF6)2·2H2O (1), [Ni(H2L)(HL)]·Cl·(PF6)2 (2), [Co2(L)2(CH3OH)(H2O)]·(PF6)2·CH3OH (3), [Ni2(L)2(CH3OH)2]·(PF6)2·2CH3OH (4), [Co2(L)2(N3)2]·3H2O (5), and [Ni2(L)2(SCN)2]·4H2O (6) have been successfully synthesized and characterized by elemental analysis, TGA, spectroscopic methods (IR, CD and electronic absorption spectra) and single-crystal X-ray diffraction structural analysis (HL = (S)-2-((4-([2,2':6‧,2″-terpyridin]-4‧-yl)benzyl)amino)-4-methylpentanoic acid). In the acidic reaction conditions, one protonated (H2L)+ and one zwitterionic HL only used their terpyridyl groups to chelate one metal ion Co(II) or Ni(II), forming chiral mononuclear cationic complexes 1 or 2. But in the basic and hydro(solvo)thermal reaction conditions, deprotonated ligands (L)‒ acting as bridges used their terpyridyl and amino acid groups to link with two Co(II) or Ni(II) ions, fabricating chiral dinuclear metallocyclic complexes 3-6. Those chiral mononuclear and dinuclear complexes whose chirality originates in the homochiral ligand HL further self-assemble into higher-dimensional homochiral supramolecular frameworks through intermolecular hydrogen-bonding and π···π interactions. Notably, the coordination mode, hydrogen-bonding site, and existence form of HL ligand can be controlled by the protonation of its amino group, and the architectural diversity of those supramolecular frameworks is adjusted by pH and counter anions. Very interestingly, the 3D porous supramolecular frameworks built up from the huge chiral mononuclear cationic complexes 1 and 2 have novel helical layers only formed through every right-handed helical chain intertwining with two adjacent same helical chains, and the 2D supramolecular helicate 5 consists of two types of left-handed helical chains.

Modelo analítico del efecto de PRS sobre satélites GPS

NASA Astrophysics Data System (ADS)

Meza, A.; Brunini, C.; Usandivaras, J. C.

El sistema GPS (Global Position System) es, hoy en día, la herramienta de navegación y posicionamiento más potente y lo será sin duda en la próxima década. Gran parte de su valiosa utilidad se debe a la alta precisión que permite lograr y ésta, a su vez, depende, entre otras causas, de la precisión con que se conocen las órbitas de los satélites. La presión de radiación solar (PRS) fija el límite de la precisión con que pueden calcularse en la actualidad las efemérides satelitarias. El objetivo de este trabajo es proponer una mejor resolución de este fenómeno. El modelo analítico aquí presentado, se basa en el análisis del comportamiento de los residuos de un ajuste por mínimos cuadrados en el que se utiliza el modelo de PRS propuesto por Beutler. El mismo consiste en un modelo determinista del fenómeno con dos parámetros libres. Los resultados obtenidos ponen de manifiesto que, aún después de aplicar dichos parámetros, prevalecen en los residuos efectos semidiurnos en las componentes radial,tangencial y normal. Estos resultados obtenidos se comparan con los de un trabajo desarrollado por el Instituto de Berne (Beutler et al., 1994), en el que se utilizaron como pseudo-observaciones las órbitas precisas del IGS (CODE). El intervalo de integración escogido por este centro fueron las semanas 680 y 681. En resumen se tienen arcos de 14 días para todos los satélites, donde las efemérides precisas de los mismos para los 14 días fueron utilizados como pseudo-observaciones. El modelo de fuerza que empleó dicho centro fue básicamente el tradicional en lo que respecta al modelo de las fuerzas gravitacionales, y para la PRS utilizo el modelo standard de Beutler. Los parámetros de este modelo junto con las 6 condiciones iniciales (posición y velocidad) fueron ajustados por el método general de mínimos cuadrados. Los residuos en la componente radial, tangencial y normal, para los satélites con un buen comportamiento, presentan una componente semidiurna. El modelo analítico planteado en este trabajo, predice el comportamiento de los residuos que se observan en las publicaciones más recientes. Esto abre el camino para plantear una estimación distinta de las incógnitas del problema, basado en el método de colocación por mínimos cuadrados. Ello requiere modelar estadísticamente la señal debida a las componentes de la PRS que no son tomadas en cuenta en el modelo determinista.

Espectro de radiación derivado de un modelo de colapso protoestelar

NASA Astrophysics Data System (ADS)

Coca, S.; Rohrmann, R.

El exceso de emisión infrarroja en objetos protoestelares es atribuido usualmente a un disco de material en torno al cuerpo central. A pesar del avance alcanzado en la elaboración de modelos, aún existen dificultades para explicar la ley de temperatura del disco necesaria para reproducir las luminosidades y perfiles de energía observados. Nuestra propuesta consiste en determinar la distribución espectral de la radiación derivada de un particular modelo de colapso protoestelar, y estudiar la evolución del espectro desde estadíos tempranos de la contracción gravitatoria. Este plan es orientado a evaluar las propiedades del modelo (distribuciones de masa y temperatura del material circunestelar) por comparación con datos observacionales, a fin de inferir de ello los posibles ajustes requeridos en la teoría actualmente empleada.

Ferrate(VI)-Prompted Removal of Metals in Aqueous Media: Mechanistic Delineation of Enhanced Efficiency via Metal Entrenchment in Magnetic Oxides

EPA Science Inventory

The removal efficiency of heavy metal ions (cadmium(II) – Cd(II), cobalt(II) – Co(II), nickel(II) – Ni(II), and copper(II) – Cu(II)) by potassium ferrate(VI) (K2FeO4, Fe(VI)), was studied as a function of added amount of Fe(VI) (or Fe) and varying pH. At pH = 6.6, the effective r...

trans-Bis(azido-kappaN)bis(pyridine-2-carboxamide-kappa2N1,O2)nickel(II).

PubMed

Daković, Marijana; Popović, Zora

2007-11-01

In the title compound, [Ni(N(3))(2)(C(6)H(6)N(2)O)(2)], the Ni(II) atom lies on an inversion centre. The distorted octahedral nickel(II) coordination environment contains two planar trans-related N,O-chelating picolinamide ligands in one plane and two monodentate azide ligands perpendicular to this plane. Molecules are linked into a three-dimensional framework by N-H...N hydrogen bonds.

Impregnated multiwalled carbon nanotubes as efficient sorbent for the solid phase extraction of trace amounts of heavy metal ions in food and water samples.

PubMed

Gouda, Ayman A; Al Ghannam, Sheikha M

2016-07-01

A new, sensitive and simple solid phase extraction (SPE), separation and preconcentration method of some heavy metal ions, Cd(II), Cu(II), Ni(II), Pb(II) and Zn(II) at trace levels using multiwalled carbon nanotubes (MWCNTs) impregnated with 2-(2-benzothiazolylazo)orcinol (BTAO) from food and water samples were investigated. The effect of analytical parameters was examined. The metals retained on the nanotubes at pH 7.0 were eluted by 5.0mL HNO3 (2.0molL(-1)). The influence of matrix ions on the proposed method was evaluated. The preconcentration factor was calculated and found to be 100. The detection limits (LODs) for Cd(II), Cu(II), Ni(II), Pb(II) and Zn(II) were found at 0.70, 1.2, 0.80, 2.6 and 2.2μgL(-1), respectively. The relative standard deviation (RSD) and the recoveries of the standard addition method were lower than 5.0% and 95-102%, respectively. The new procedure was successfully applied to the determination of trace amounts of the studied metal ions in various food and water samples and validated using certified reference materials SRM 1570A (spinach leaves) with satisfactory and compatible results. Copyright © 2016 Elsevier Ltd. All rights reserved.

Crystal structure, DNA binding, cleavage, antioxidant and antibacterial studies of Cu(II), Ni(II) and Co(III) complexes with 2-((furan-2-yl)methylimino)methyl)-6-ethoxyphenol Schiff base

NASA Astrophysics Data System (ADS)

Venkateswarlu, Kadtala; Kumar, Marri Pradeep; Rambabu, Aveli; Vamsikrishna, Narendrula; Daravath, Sreenu; Rangan, Krishnan; Shivaraj

2018-05-01

Three novel binary metal complexes; 1 [Cu(L)2], 2 [Ni(L)2] and 3 [Co(L)3] where, L (2-(((furan-2-yl) methylimino)methyl)-6-ethoxyphenol, C14H15NO3), were synthesized and characterized by various spectral techniques. Based on spectral studies square planar geometry is assigned for Cu(II) and Ni(II) complexes, whereas Co(III) owned octahedral geometry. Ligand, [Cu(L)2] and [Ni(L)2] are crystallized and found to be monoclinic crystal systems. CT-DNA absorption binding studies revealed that the complexes show good binding propensity (Kb = 5.02 × 103 M-1, 2.77 × 103 M-1, 1.63 × 104 M-1 for 1, 2 and 3 respectively). The role of these complexes in the oxidative and photolytic cleavage of supercoiled pBR322 DNA was studied and found that the complexes cleave the pBR322 DNA effectively. The catalytic ability of 1, 2 and 3 follows the order: 3 > 1 >2. Antioxidant studies of the new complexes revealed that they exhibit significant antioxidant activity against DPPH radical. The Schiff base and its metal complexes have been screened for antibacterial studies by Minimum Inhibitory Concentration method. It is observed that all metal complexes showed more activity than free ligand.

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

NASA Astrophysics Data System (ADS)

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).

A Novel Micellar Electrokinetic Chromatographic Method for Separation of Metal-DDTC Complexes

PubMed Central

Mallah, Arfana; Memon, Saima Q.; Solangi, Amber R.; Memon, Najma; Abbassi, Kulsoom; Khuhawar, Muhammad Yar

2012-01-01

Micellar electrokinetic chromatography (MEKC) was examined for the separation and determination of Mo(VI), Cr(VI), Ni(II), Pd(II), and Co(III) as diethyl dithiocarbamate (DDTC) chelates. The separation was achieved from fused silica capillary (52 cm × 75 μm id) with effective length 40 cm, background electrolyte (BGE) borate buffer pH 9.1 (25 mM), CTAB 30% (100 mM), and 1% butanol in methanol (70 : 30 : 5 v/v/v) with applied voltage of −10 kV using reverse polarity. The photodiode array detection was achieved at 225 nm. The linear calibration for each of the element was obtained within 0.16–10 μg/mL with a limit of detection (LOD) 0.005–0.0167 μg/mL. The separation and determination was repeatable with relative standard deviation (RSD) within 2.4–3.3% (n = 4) in terms of migration time and peak height/peak area. The method was applied for the determination of Mo(VI) from potatoes and almond, Ni(II) from hydrogenated vegetable oil, and Co(III) from pharmaceutical preparations with RSD within 3.9%. The results obtained were checked by standard addition and rechecked by atomic absorption spectrometry. PMID:22649320

Removal of Cr6 + and Ni2+ from aqueous solution using bagasse and fly ash.

PubMed

Rao, M; Parwate, A V; Bhole, A G

2002-01-01

Raw bagasse and fly ash, the waste generated in sugar mills and boilers respectively have been used as low-cost potential adsorbents. Raw bagasse was pretreated with 0.1N NaOH followed by 0.1N CH3COOH before its application. These low-cost adsorbents were used for the removal of chromium and nickel from an aqueous solution. The kinetics of adsorption and extent of adsorption at equilibrium are dependent on the physical and chemical characteristics of the adsorbent, adsorbate and experimental system. The effect of hydrogen ion concentration, contact time, sorbent dose, initial concentrations of adsorbate and adsorbent and particle size on the uptake of chromium and nickel were studied in batch experiments. The Sorption data has been correlated with Langmuir, Freundlich and Bhattacharya and Venkobachar adsorption models. The efficiencies of adsorbent materials for the removal of Cr(VI) and Ni(II) were found to be between 56.2 and 96.2% and 83.6 and 100%, respectively. These results were obtained at the optimized conditions of pH, contact time, sorbent dose, sorbate concentration of 100 mg/l and with the variation of adsorbent particles size between 0.075 and 4.75 mm. The order of selectivity is powdered activated carbon > bagasse > fly ash for Cr(VI) removal and powdered activated carbon > fly ash > bagasse for Ni(II) removal.

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

NASA Astrophysics Data System (ADS)

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.

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

NASA Astrophysics Data System (ADS)

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

2017-09-01

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

Bright metal coatings from sustainable electrolytes: the effect of molecular additives on electrodeposition of nickel from a deep eutectic solvent.

PubMed

Abbott, Andrew P; Ballantyne, Andrew; Harris, Robert C; Juma, Jamil A; Ryder, Karl S

2017-01-25

Organic and inorganic additives are often added to nickel electroplating solutions to improve surface finish, reduce roughness and promote uniform surface morphology of the coatings. Such additives are usually small molecules and often referred to as brighteners or levellers. However, there have been limited investigations into the effect of such additives on electrodeposition from ionic liquids (ILs) and deep eutectic solvents (DESs). Here we study the effect of four additives on electrolytic nickel plating from an ethyleneglycol based DES; these are nicotinic acid (NA), methylnicotinate (MN), 5,5-dimethylhydantoin (DMH) and boric acid (BA). The additives show limited influence on the bulk Ni(ii) speciation but have significant influence on the electrochemical behaviour of Ni deposition. Small concentrations (ca. 15 mM) of NA and MN show inhibition of Ni(ii) reduction whereas high concentrations of DMH and BA are required for a modest difference in behaviour from the additive free system. NA and MN also show that they significantly alter the nucleation and growth mechanism when compared to the additive free system and those with DMH and BA. Each of the additive systems had the effect of producing brighter and flatter bulk electrodeposits with increased coating hardness but XRD shows that NA and MN direct crystal growth to the [111] orientation whereas DMH and BA direct crystal growth to the [220] orientation.

Gas-phase noncovalent functionalization of carbon nanotubes with a Ni(II) tetraaza[14]annulene complex

NASA Astrophysics Data System (ADS)

Basiuk, Vladimir A.; Henao-Holguín, Laura Verónica; Álvarez-Zauco, Edgar; Bassiouk, María; Basiuk, Elena V.

2013-04-01

The noncovalent functionalization of carbon nanotubes (CNTs) with aromatic polyazamacrocyclic compounds, based on π-π-interactions, keeps the intrinsic electronic structure of CNTs totally intact and allows for combining unique properties of the two interacting components. In addition to porphyrins and phthalocyanines, there are other, simpler compounds exhibiting similar properties, potentially useful for photovoltaic, catalytic and electrochemical applications: for example, tetraaza[14]annulenes. Many of them are highly thermally stable, which makes it possible to employ physical vapor deposition for the preparation of macrocycle-nanotube hybrids. One of such compounds is Ni(II) complex of 5,7,12,14-tetramethyldibenzo-1,4,8,11-tetraazacyclotetradeca-3,5,7,10,12,14-hexaene (also called Ni(II)-tetramethyldibenzotetraaza[14]annulene, or NiTMTAA for simplicity). In the present work, we attempted the noncovalent functionalization of both single-walled and multi-walled CNTs with NiTMTAA in the gas phase at two selected temperatures of 220 and 270 °C, which does not require the use of organic solvents and therefore can be considered as ecologically friendly. The nanohybrids obtained were characterized by means of scanning and transmission electron microscopy, energy dispersive X-ray, Fourier-transform infrared and Raman spectroscopy, as well as thermogravimetric analysis. An additional insight into the structure of adsorption complexes of NiTMTAA on CNTs was provided from density functional theory and molecular mechanics calculations.

Syntheses, spectroscopic characterization, thermal study, molecular modeling, and biological evaluation of novel Schiff's base benzil bis(5-amino-1,3,4-thiadiazole-2-thiol) with Ni(II), and Cu(II) metal complexes.

PubMed

Chandra, Sulekh; Gautam, Seema; Rajor, Hament Kumar; Bhatia, Rohit

2015-02-25

Novel Schiff's base ligand, benzil bis(5-amino-1,3,4-thiadiazole-2-thiol) was synthesized by the condensation of benzil and 5-amino-1,3,4-thiadiazole-2-thiol in 1:2 ratio. The structure of ligand was determined on the basis of elemental analyses, IR, (1)H NMR, mass, and molecular modeling studies. Synthesized ligand behaved as tetradentate and coordinated to metal ion through sulfur atoms of thiol ring and nitrogen atoms of imine group. Ni(II), and Cu(II) complexes were synthesized with this nitrogen-sulfur donor (N2S2) ligand. Metal complexes were characterized by elemental analyses, molar conductance, magnetic susceptibility measurements, IR, electronic spectra, EPR, thermal, and molecular modeling studies. All the complexes showed molar conductance corresponding to non-electrolytic nature, expect [Ni(L)](NO3)2 complex, which was 1:2 electrolyte in nature. [Cu(L)(SO4)] complex may possessed square pyramidal geometry, [Ni(L)](NO3)2 complex tetrahedral and rest of the complexes six coordinated octahedral/tetragonal geometry. Newly synthesized ligand and its metal complexes were examined against the opportunistic pathogens. Results suggested that metal complexes were more biological sensitive than free ligand. Copyright © 2014 Elsevier B.V. All rights reserved.

Importance of reduced sulfur for the equilibrium chemistry and kinetics of Fe(II), Co(II) and Ni(II) supplemented to semi-continuous stirred tank biogas reactors fed with stillage.

PubMed

Shakeri Yekta, Sepehr; Lindmark, Amanda; Skyllberg, Ulf; Danielsson, Asa; Svensson, Bo H

2014-03-30

The objective of the present study was to assess major chemical reactions and chemical forms contributing to solubility and speciation of Fe(II), Co(II), and Ni(II) during anaerobic digestion of sulfur (S)-rich stillage in semi-continuous stirred tank biogas reactors (SCSTR). These metals are essential supplements for efficient and stable performance of stillage-fed SCSTR. In particular, the influence of reduced inorganic and organic S species on kinetics and thermodynamics of the metals and their partitioning between aqueous and solid phases were investigated. Solid phase S speciation was determined by use of S K-edge X-ray absorption near-edge spectroscopy. Results demonstrated that the solubility and speciation of supplemented Fe were controlled by precipitation of FeS(s) and formation of the aqueous complexes of Fe-sulfide and Fe-thiol. The relatively high solubility of Co (∼ 20% of total Co content) was attributed to the formation of compounds other than Co-sulfide and Co-thiol, presumably of microbial origin. Nickel had lower solubility than Co and its speciation was regulated by interactions with FeS(s) (e.g. co-precipitation, adsorption, and ion substitution) in addition to precipitation/dissolution of discrete NiS(s) phase and formation of aqueous Ni-sulfide complexes. Copyright © 2014 Elsevier B.V. All rights reserved.

Nickel(II) complexes of tripodal 4N ligands as catalysts for alkane oxidation using m-CPBA as oxidant: ligand stereoelectronic effects on catalysis.

PubMed

Balamurugan, Mani; Mayilmurugan, Ramasamy; Suresh, Eringathodi; Palaniandavar, Mallayan

2011-10-07

Several mononuclear Ni(II) complexes of the type [Ni(L)(CH(3)CN)(2)](BPh(4))(2) 1-7, where L is a tetradentate tripodal 4N ligand such as N,N-dimethyl-N',N'-bis(pyrid-2-ylmethyl)ethane-1,2-diamine (L1), N,N-diethyl-N',N'-bis(pyrid-2-ylmethyl)ethane-1,2-diamine (L2), N,N-dimethyl-N'-(1-methyl-1H-imidazol-2-ylmethyl)-N'-(pyrid-2-ylmethyl)ethane-1,2-diamine (L3), N,N-dimethyl-N',N'-bis(1-methyl-1H-imidazol-2-ylmethyl)ethane-1,2-diamine (L4), N,N-dimethyl-N',N'-bis(quinolin-2-ylmethyl)ethane-1,2-diamine (L5), tris(benzimidazol-2-ylmethyl)amine (L6) and tris(pyrid-2-ylmethyl)amine (L7), have been isolated and characterized using CHN analysis, UV-Visible spectroscopy and mass spectrometry. The single-crystal X-ray structures of the complexes [Ni(L1)(CH(3)CN)(H(2)O)](ClO(4))(2) 1a, [Ni(L2)(CH(3)CN)(2)](BPh(4))(2) 2, [Ni(L3)(CH(3)CN)(2)](BPh(4))(2) 3 and [Ni(L4)(CH(3)CN)(2)](BPh(4))(2) 4 have been determined. All these complexes possess a distorted octahedral coordination geometry in which Ni(II) is coordinated to four nitrogen atoms of the tetradentate ligands and two CH(3)CN (2, 3, 4) or one H(2)O and one CH(3)CN (1a) are located in cis positions. The Ni-N(py) bond distances (2.054(2)-2.078(3) Å) in 1a, 2 and 3 are shorter than the Ni-N(amine) bonds (2.127(2)-2.196(3) Å) because of sp(2) and sp(3) hybridizations of the pyridyl and tertiary amine nitrogens respectively. In 3 the Ni-N(im) bond (2.040(5) Å) is shorter than the Ni-N(py) bond (2.074(4) Å) due to the stronger coordination of imidazole compared with the pyridine donor. In dichloromethane/acetonitrile solvent mixture, all the Ni(ii) complexes possess an octahedral coordination geometry, as revealed by the characteristic ligand field bands in the visible region. They efficiently catalyze the hydroxylation of alkanes when m-CPBA is used as oxidant with turnover number (TON) in the range of 340-620 and good alcohol selectivity for cyclohexane (A/K, 5-9). By replacing one of the pyridyl donors in TPA by a weakly coordinating -NMe(2) or -NEt(2) donor nitrogen atom the catalytic activity decreases slightly with no change in the selectivity. In contrast, upon replacing the pyridyl nitrogen donor by the strongly σ-bonding imidazolyl or sterically demanding quinolyl/benzimidazolyl nitrogen donor, both the catalytic activity and selectivity decrease, possibly due to destabilization of the intermediate [(4N)(CH(3)CN)Ni-O˙](+) radical species. Adamantane is selectively (3°/2°, 12-17) oxidized to 1-adamantanol, 2-adamantanol and 2-adamantanone while cumene is selectively oxidized to 2-phenyl-2-propanol. In contrast to cyclohexane oxidation, the incorporation of sterically hindering quinolyl/benzimidazolyl donors around Ni(ii) leads to a high 3°/2° bond selectivity for adamantane oxidation. A linear correlation between the metal-ligand covalency parameter (β) and the turnover number has been observed.

Discos de acreción circumplanares: Modelo de Co-acreción

NASA Astrophysics Data System (ADS)

Parisi, M. G.; de Elía, G.

Los discos de acreción circumplanetarios precursores de los satélites regulares de los planetas gigantes, se pueden formar por cuatro mecanismos (Pollack y otros, 1991, In Uranus, Bergtralh, Miner y Mattews, Eds., p. 469, Univ. de Arizona Press, Tucson). En este trabajo estudiamos uno de tales mecanismos: el Modelo de Co-acreción. En dicho modelo, el disco circumplanetario se forma a partir de las colisiones mutuas entre planetesimales dentro de la esfera de Hill del planeta durante el proceso de formación planetaria. Realizamos un modelo semi-analítico para calcular la masa del disco y compararla con la masa requerida para formar los satélites regulares de los planetas gigantes. Hemos obtenido una cota superior para la masa del disco que resulta inferior a la masa de los satélites más grandes de los planetas gigantes. En principio, estos resultados permitirían descartar el modelo de co-acreción como uno de los procesos que podrían dar lugar a la formación de los satélites regulares. Estos resultados permiten obtener restricciones en el escenario de formación planetaria y en los mecanismos de formación de sistemas de satélites.

The conceptualization model problem—surprise

NASA Astrophysics Data System (ADS)

Bredehoeft, John

2005-03-01

The foundation of model analysis is the conceptual model. Surprise is defined as new data that renders the prevailing conceptual model invalid; as defined here it represents a paradigm shift. Limited empirical data indicate that surprises occur in 20-30% of model analyses. These data suggest that groundwater analysts have difficulty selecting the appropriate conceptual model. There is no ready remedy to the conceptual model problem other than (1) to collect as much data as is feasible, using all applicable methods—a complementary data collection methodology can lead to new information that changes the prevailing conceptual model, and (2) for the analyst to remain open to the fact that the conceptual model can change dramatically as more information is collected. In the final analysis, the hydrogeologist makes a subjective decision on the appropriate conceptual model. The conceptualization problem does not render models unusable. The problem introduces an uncertainty that often is not widely recognized. Conceptual model uncertainty is exacerbated in making long-term predictions of system performance. C'est le modèle conceptuel qui se trouve à base d'une analyse sur un modèle. On considère comme une surprise lorsque le modèle est invalidé par des données nouvelles; dans les termes définis ici la surprise est équivalente à un change de paradigme. Des données empiriques limitées indiquent que les surprises apparaissent dans 20 à 30% des analyses effectuées sur les modèles. Ces données suggèrent que l'analyse des eaux souterraines présente des difficultés lorsqu'il s'agit de choisir le modèle conceptuel approprié. Il n'existe pas un autre remède au problème du modèle conceptuel que: (1) rassembler autant des données que possible en utilisant toutes les méthodes applicables—la méthode des données complémentaires peut conduire aux nouvelles informations qui vont changer le modèle conceptuel, et (2) l'analyste doit rester ouvert au fait que le modèle conceptuel peut bien changer lorsque des nouvelles informations apparaissent. Dans l'analyse finale le hydrogéologue prend une décision subjective sur le modèle conceptuel approprié. Le problème du le modèle conceptuel ne doit pas rendre le modèle inutilisable. Ce problème introduit une incertitude qui n'est pas toujours reconnue. Les incertitudes du modèle conceptuel deviennent plus importantes dans les cases de prévisions à long terme dans l'analyse de performance. La base para hacer un análisis de un modelo es el modelo conceptual. Se define aquí la sorpresa como los datos nuevos que convierten en incoherente al modelo conceptual previamente aceptado; tal como se define aquí esto representa un cambio de paradigma. Los datos empíricos limitados indican que estas sorpresas suceden entre un 20 a un 30% de los análisis de modelos. Esto sugiere que los analistas de modelos de agua subterránea tienen dificultades al seleccionar el modelo conceptual apropiado. No hayotra solución disponible a este problema del modelo conceptual diferente de: (1) Recolectar tanta información como sea posible, mediante la utilización de todos los métodos aplicables, lo cual puede resultar en que esta nueva información ayude a cambiar el modelo conceptual vigente, y (2) Que el analista de modelos se mantenga siempre abierto al hecho de que un modelo conceptual puede cambiar de manera total, en la medida en que se colecte mas información. En el análisis final el hidrogeólogo toma una decisión subjetiva en cuanto al modelo conceptual apropiado. El problema de la conceptualización no produce modelos inútiles. El problema presenta una incertidumbre, la cual a menudo no es tenida en cuentade manera adecuada. Esta incertidumbre en los modelos conceptuales se aumenta, cuando se hacen predicciones a largo plazo del comportamiento de un sistema dado.

Evolução química em galáxias compactas azuis (BCGs)

NASA Astrophysics Data System (ADS)

Lanfranchi, G. A.; Matteucci, F.

2003-08-01

Neste trabalho, a formação estelar e evolução quí mica em galáxias Compactas Azuis (Blue Compact Galaxies - BCGs) foram estudadas através da comparação de previsões de modelos de evolução quí mica a várias razões de abundância quí mica observadas nestas galáxias. Modelos detalhados com recentes dados de nucleossí ntese e que levam em consideração o papel desempenahdo por supernovas de ambos os tipos (II e Ia) na evolução galáctica foram desenvolvidos para as BCGs permitindo seguir a evolução de vários elementos quí micos (H, D, He, C, N, O, Mg, Si, S, Ca, e Fe). O modelo é caracterizado pelas prescrições adotadas para a formação estelar, a qual ocorre em vários surtos de atividade separados por longos perí odos quiescentes. Após ajustar os melhores modelos aos dados observacionais, as previsões destes modelos foram comparadas também a razões de abundância observadas em sistemas Damped Lyman alpha (DLAs) e a origem do N (primária ou secundária) foi discutida. Alguns dos resultados obtidos são: i) as razões de abundância observadas nas BCGs são reproduzidas por modelos com 2 a 7 surtos de formação estelar com eficiência entre n = 0.2-0.9 Gano-1; ii) os baixos valores de N/O observados nestas galáxias são um resultado natural de uma formação estelar em surtos; iii) os modelos para BCGs podem reproduzir os dados dos DLAs, iv) uma quantidade "baixa" de N primário produzido em estrelas de alta massa pode ser uma explicação para os baixos valores de [N/a] observados em DLAs.

En la búsqueda de características en eyecciones coronales de masa que discriminen entre dos paradigmas físicos en modelos de ECMs

NASA Astrophysics Data System (ADS)

Paissan, G.; Stenborg, G.; Rovira, M.

Se conocen tres diferentes fenómenos de gran escala que ocurren en la atmósfera solar, denominados eyecciones coronales de masa (ECMs), protuberancias eruptivas y grandes fulguraciones de dos bandas. Estos fenómenos están estrechamente relacionados y podrían ser distintas manifestaciones de un único proceso físico. Las ECMs son definidas como eyecciones de gran escala de masa y flujo magnético desde la baja corona al espacio interplanetario. Desde su descubrimiento en los '70, muchos modelos han sido propuestos para explicar su origen y evolución. La explicación física de las ECMs es un tema de debate intenso. No obstante, los modelos pueden sintetizarse en dos grandes grupos: 1) los modelos de inyección de flujo y 2) los modelos de almacenamiento y liberación. En este trabajo, se presentan los estudios realizados con una serie de eventos observados con el coronógrafo MICA (Mirror Coronograph for Argentina), el telescopio en H-alfa HASTA (H-alpha Solar Telescope for Argentina) y los coronógrafos C2 y C3 de la sonda SOHO (Solar and Heliospheric Observatory). Los eventos que pudieron ser identificados como ECMs son contrastados dentro del esquema de los dos paradigmas teóricos propuestos.

Spectral Characterization and 3D Molecular Modeling Studies of Metal Complexes Involving the O, N-Donor Environment of Quinazoline-4(3H)-one Schiff Base and Their Biological Studies

PubMed Central

Siddappa, Kuruba; Mane, Sunilkumar B.

2014-01-01

A simple condensation of 3-amino-2-methylquinazoline-4-one with 2-hydroxy-1-naphthaldehyde produced new tridentate ONO donor Schiff base ligand with efficient yield. The structural characterization of ligand and its Cu(II), Ni(II), Co(II), Mn(II), Zn(II), and Cd(II) complexes were achieved by the aid of elemental analysis, spectral characterization such as (UV-visible, IR, NMR, mass, and ESR), and magnetic data. The analytical and spectroscopic studies suggest the octahedral geometries of Cu(II), Co(II), Ni(II) and Mn(II) complexes and tetrahedral geometry of Zn(II) and Cd(II) complexes with the tridentate ONO Schiff base ligand. Furthermore, the conclusions drawn from these studies afford further support to the mode of bonding discussed on the basis of their 3D molecular modeling studies by considering different bond lengths, bond angles, and bond distance. The ligand and its metal complexes evaluated for their antimicrobial activity against Staphylococcus aureus (MTCC number 7443), Bacillus subtilis (MTCC number 9878), Escherichia coli (MTCC number 1698), Aspergillus niger (MTCC number 281), and Aspergillus flavus (MTCC number 277). The MIC of these compounds was found to be most active at 10 μg/mL concentration in inhibiting the growth of the tested organisms. The DNA cleavage activity of all the complexes was studied by gel electrophoresis method. PMID:24678278

Synthesis, characterization of 1,2,4-triazole Schiff base derived 3d-metal complexes: Induces cytotoxicity in HepG2, MCF-7 cell line, BSA binding fluorescence and DFT study

NASA Astrophysics Data System (ADS)

Tyagi, Prateek; Tyagi, Monika; Agrawal, Swati; Chandra, Sulekh; Ojha, Himanshu; Pathak, Mallika

2017-01-01

Two novel Schiff base ligands H2L1 and H2L2 have been synthesized by condensation reaction of amine derivative of 1,2,4-triazole moiety with 2-hydroxy-4-methoxybenzaldehyde. Co(II), Ni(II), Cu(II) and Zn(II) of the synthesized Schiff bases were prepared by using a molar ratio of ligand:metal as 1:1. The structure of the Schiff bases and synthesized metal complexes were established by 1H NMR, UV-Vis, IR, Mass spectrometry and molar conductivity. The thermal stability of the complexes was study by TGA. Fluorescence quenching mechanism of metal complexes 1-4 show that Zn(II) and Cu(II) complex binds more strongly to BSA. In DFT studies the geometries of Schiff bases and metal complexes were fully optimized with respect to the energy using the 6-31 + g(d,p) basis set. The spectral data shows that the ligands behaves as binegative tridentate. On the basis of the spectral studies, TGA and DFT data an octahedral geometry has been assigned for Co(II), Ni(II), square planar for Cu(II) and tetrahedral for Zn(II) complexes. The anticancer activity were screened against human breast cancer cell line (MCF-7) and human hepatocellular liver carcinoma cell line (Hep-G2). Result indicates that metal complexes shows increase cytotoxicity in proliferation to cell lines as compared to free ligand.

Sequence of ligand binding and structure change in the diphtheria toxin repressor upon activation by divalent transition metals.

PubMed

Rangachari, Vijayaraghavan; Marin, Vedrana; Bienkiewicz, Ewa A; Semavina, Maria; Guerrero, Luis; Love, John F; Murphy, John R; Logan, Timothy M

2005-04-19

The diphtheria toxin repressor (DtxR) is an Fe(II)-activated transcriptional regulator of iron homeostatic and virulence genes in Corynebacterium diphtheriae. DtxR is a two-domain protein that contains two structurally and functionally distinct metal binding sites. Here, we investigate the molecular steps associated with activation by Ni(II)Cl(2) and Cd(II)Cl(2). Equilibrium binding energetics for Ni(II) were obtained from isothermal titration calorimetry, indicating apparent metal dissociation constants of 0.2 and 1.7 microM for two independent sites. The binding isotherms for Ni(II) and Cd(II) exhibited a characteristic exothermic-endothermic pattern that was used to infer the metal binding sequence by comparing the wild-type isotherm with those of several binding site mutants. These data were complemented by measuring the distance between specific backbone amide nitrogens and the first equivalent of metal through heteronuclear NMR relaxation measurements. Previous studies indicated that metal binding affects a disordered to ordered transition in the metal binding domain. The coupling between metal binding and structure change was investigated using near-UV circular dichroism spectroscopy. Together, the data show that the first equivalent of metal is bound by the primary metal binding site. This binding orients the DNA binding helices and begins to fold the N-terminal domain. Subsequent binding at the ancillary site completes the folding of this domain and formation of the dimer interface. This model is used to explain the behavior of several mutants.

Nickel(II) and copper(II) complexes of N,N-dialkyl-N‧-3-chlorobenzoylthiourea: Synthesis, characterization, crystal structures, Hirshfeld surfaces and antimicrobial activity

NASA Astrophysics Data System (ADS)

Binzet, Gun; Gumus, Ilkay; Dogen, Aylin; Flörke, Ulrich; Kulcu, Nevzat; Arslan, Hakan

2018-06-01

We synthesized four new N,N-dialkyl-N‧-3-chlorobenzoylthiourea ligands (Alkyl: Dimethyl, diethyl, di-n-propyl and di-n-butyl) and their metal complexes with copper and nickel atoms. The structure of all synthesized compounds was fully characterized by physicochemical, spectroscopic and single crystal X-ray diffraction analysis techniques. The physical, spectral and analytical data of the newly synthesized metal complexes have shown the formation of 1:2 (metal:ligand) ratio. The benzoylthiourea ligands coordinate with metal atoms through oxygen and sulphur atoms. The metal atoms are in slightly distorted square-planar coordination geometry in Ni(II) or Cu(II) complex. Two oxygen and two sulphur atoms are mutually cis to each other in Ni(II) or Cu(II) complex. The intermolecular contacts in the compounds, which are HL1 and HL3, were examined by Hirshfeld surfaces and fingerprint plots using the data obtained from X-ray single crystal diffraction measurement. Besides these, their antimicrobial activities against Gram-positive bacteria (Bacillus subtilis, Staphylococcus aureus, Streptococcus pyogenes and Enterococcus faecalis) and Gram-negative bacteria (Escherichia coli and Pseudomonas aeruginosa) and anti-yeast activity (Candida glabrata, Candida parapsilosis and Candida albicans) were investigated. This exhibited some promising results towards testing organism. Among all the compounds, Ni(L1)2 complex showed high activity against Bacillus subtilis with MIC values at 7.81 μg/mL.

Controls on Fe(II)-Activated Trace Element Release from Goethite and Hematite

DOE Office of Scientific and Technical Information (OSTI.GOV)

Frierdich, Andrew J.; Catalano, Jeffrey G.

2012-03-26

Electron transfer and atom exchange (ETAE) between aqueous Fe(II) and Fe(III) oxides induces surface growth and dissolution that affects trace element fate and transport. We have recently demonstrated Ni(II) cycling through goethite and hematite (adsorbed Ni incorporates into the mineral structure and preincorporated Ni releases to solution) during Fe(II)-Fe(III) ETAE. However, the chemical parameters affecting net trace element release remain unknown. Here, we examine the chemical controls on Ni(II) and Zn(II) release from Ni- and Zn-substituted goethite and hematite during reaction with Fe(II). Release follows a rate law consistent with surface reaction limited mineral dissolution and suggests that release occursmore » near sites of Fe(III) reductive dissolution during Fe(II)-Fe(III) ETAE. Metal substituent type affects reactivity; Zn release is more pronounced from hematite than goethite, whereas the opposite trend occurs for Ni. Buildup of Ni or Zn in solution inhibits further release but this resumes upon fluid exchange, suggesting that sustained release is possible under flow conditions. Mineral and aqueous Fe(II) concentrations as well as pH strongly affect sorbed Fe(II) concentrations, which directly control the reaction rates and final metal concentrations. Our results demonstrate that structurally incorporated trace elements are mobilized from iron oxides into fluids without abiotic or microbial net iron reduction. Such release may affect micronutrient availability, contaminant transport, and the distribution of redox-inactive trace elements in natural and engineered systems.« less

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

NASA Astrophysics Data System (ADS)

Fantola Lazzarini, Anna L.; Lazzarini, Ennio

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

Controlling the Chiral Inversion Reaction of the Metallopeptide Ni-Asparagine-Cysteine-Cysteine with Dioxygen

PubMed Central

Glass, Amanda M.; Krause, Mary E.; Laurence, Jennifer S.; Jackson, Timothy A.

2014-01-01

Synthetically generated metallopeptides have the potential to serve a variety of roles in biotechnology applications, but the use of such systems is often hampered by the inability to control secondary reactions. We have previously reported that the NiII complex of the tripeptide LLL-asparagine-cysteine-cysteine, LLL-NiII-NCC, undergoes metal-facilitated chiral inversion to DLD-NiII-NCC, which increases the observed superoxide scavenging activity. However, the mechanism for this process remained unexplored. Electronic absorption and circular dichroism studies of the chiral inversion reaction of NiII-NCC reveal a unique dependence on dioxygen. Specifically, in the absence of dioxygen, the chiral inversion is not observed, even at elevated pH, whereas the addition of O2 initiates this reactivity and concomitantly generates superoxide. Scavenging experiments using acetaldehyde are indicative of the formation of carbanion intermediates, demonstrating that inversion takes place by deprotonation of the alpha carbons of Asn1 and Cys3. Together, these data are consistent with the chiral inversion being dependent on the formation of a NiIII-NCC intermediate from NiII-NCC and O2. The data further suggest that the anionic thiolate and amide ligands in NiII-NCC inhibit Cα–H deprotonation for the NiII oxidation state, leading to a stable complex in the absence of O2. Together, these results offer insights into the factors controlling reactivity in synthetic metallopeptides. PMID:22928993

Adsorption and co-adsorption of graphene oxide and Ni(II) on iron oxides: A spectroscopic and microscopic investigation.

PubMed

Sheng, Guodong; Huang, Chengcai; Chen, Guohe; Sheng, Jiang; Ren, Xuemei; Hu, Baowei; Ma, Jingyuan; Wang, Xiangke; Huang, Yuying; Alsaedi, Ahmed; Hayat, Tasawar

2018-02-01

Graphene oxide (GO) may strongly interact with toxic metal ions and mineral particles upon release into the soil environment. We evaluated the mutual effects between GO and Ni (Ni(II)) with regard to their adsorption and co-adsorption on two minerals (goethite and hematite) in aqueous phase. Results indicated that GO and Ni could mutually facilitate the adsorption of each other on both goethite and hematite over a wide pH range. Addition of Ni promoted GO co-adsorption mainly due to the increased positive charge of minerals and cation-π interactions, while the presence of GO enhanced Ni co-adsorption predominantly due to neutralization of positive charge and strong interaction with oxygen-containing functional groups on adsorbed GO. Increasing adsorption of GO and Ni on minerals as they coexist may thus reduce their mobility in soil. Extended X-ray absorption fine structure (EXAFS) spectroscopy data revealed that GO altered the microstructure of Ni on minerals, i.e., Ni formed edge-sharing surface species (at R Ni-Fe ∼3.2 Å) without GO, while a GO-bridging ternary surface complexes (at R Ni-C ∼2.49 Å and R Ni-Fe ∼4.23 Å) was formed with GO. These findings improved the understanding of potential fate and toxicity of GO as well as the partitioning processes of Ni ions in aquatic and soil environments. Copyright © 2017 Elsevier Ltd. All rights reserved.

Analytical performance of a versatile laboratory microscopic X-ray fluorescence system for metal uptake studies on argillaceous rocks

NASA Astrophysics Data System (ADS)

Gergely, Felicián; Osán, János; Szabó, B. Katalin; Török, Szabina

2016-02-01

Laboratory-scale microscopic X-ray fluorescence (micro-XRF) plays an increasingly important role in various fields where multielemental investigations of samples are indispensable. In case of geological samples, the reasonable detection limits (LOD) and spatial resolutions are necessary to identify the trace element content in microcrystalline level. The present study focuses on the analytical performance of a versatile laboratory-scale micro-XRF system with various options of X-ray sources and detectors to find the optimal experimental configuration in terms of sensitivities and LOD for selected elements in loaded petrographic thin sections. The method was tested for sorption studies involving thin sections prepared from cores of Boda Claystone Formation, which is a potential site for a high-level radioactive waste repository. Loaded ions in the sorption measurements were Cs(I) and Ni(II) chemically representing fission and corrosion products. Based on the collected elemental maps, the correlation between the elements representative of main rock components and the selected loaded ion was studied. For the elements of interest, Cs(I) and Ni(II) low-power iMOXS source with polycapillary and silicon drift detector was found to be the best configuration to reach the optimal LOD values. Laboratory micro-XRF was excellent to identify the responsible key minerals for the uptake of Cs(I). In case of nickel, careful corrections were needed because of the relatively high Ca content of the rock samples. The results were compared to synchrotron radiation micro-XRF.

Interaction of a Ni(II) tetraazaannulene complex with elongated fullerenes as simple models for carbon nanotubes.

PubMed

Henao-Holguín, Laura Verónica; Basiuk, Vladimir A

2015-06-01

Nickel(II) complex of 5,14-dihydro-6,8,15,17-tetramethyldibenzo[b,i][1,4,8,11] tetraazacyclotetradecine (NiTMTAA), which can be employed for noncovalent functionalization of carbon nanotubes (CNTs), represents a more complex and interesting case in terms of structure of the resulting nanohybrids, as compared to the related materials functionalized with porphyrins and phthalocyanines. Due to its saddle shape, the NiTMTAA molecule adsorbed can adopt different, energetically non-equivalent orientations with respect to CNT, depending on whether CH3 or C6H4 groups contact the latter. The main goal of the present work was to provide information on the interactions of NiTMTAA with simple single-walled CNT (SWNT) models accessible for dispersion-corrected DFT calculations. For reasons of comparison, we employed three such functionals: M06-2X and LC-BLYP as implemented in Gaussian 09 package, and PBE-G as implemented in Materials Studio 6.0. In order to roughly estimate the effect of nanotube chirality on the interaction strenght, we considered two short closed-end SWNT models (also referred to as 'elongated fullerenes'), one armchair and one zigzag, derived from C60 and C80 hemispheres. In addition, we calculated similar complexes with C60, as well as I h and D 5h isomers of C80. The results were analyzed in terms of optimized geometries, formation energies, HOMO-LUMO gap energies, and intermolecular separations. Graphical Abstract Interaction of Ni(II) tetraazaannulene complex with elongated fullerenes.

Nickel-quinolones interaction. Part 4. Structure and biological evaluation of nickel(II)-enrofloxacin complexes compared to zinc(II) analogues.

PubMed

Skyrianou, Kalliopi C; Psycharis, Vassilis; Raptopoulou, Catherine P; Kessissoglou, Dimitris P; Psomas, George

2011-01-01

The nickel(II) complexes with the second-generation quinolone antibacterial agent enrofloxacin in the presence or absence of the nitrogen-donor heterocyclic ligands 1,10-phenanthroline, 2,2'-bipyridine or pyridine have been synthesized and characterized. Enrofloxacin acts as bidentate ligand coordinated to Ni(II) ion through the ketone oxygen and a carboxylato oxygen. The crystal structure of (1,10-phenanthroline)bis(enrofloxacinato)nickel(II) has been determined by X-ray crystallography. UV study of the interaction of the complexes with calf-thymus DNA (CT DNA) has shown that they bind to CT DNA and bis(pyridine)bis(enrofloxacinato)nickel(II) exhibits the highest binding constant to CT DNA. The cyclic voltammograms of the complexes have shown that in the presence of CT DNA the complexes can bind to CT DNA by the intercalative binding mode which has also been verified by DNA solution viscosity measurements. Competitive study with ethidium bromide (EB) has shown that the complexes can displace the DNA-bound EB indicating that they bind to DNA in strong competition with EB. The complexes exhibit good binding propensity to human or bovine serum albumin protein having relatively high binding constant values. The biological properties of the complexes have been evaluated in comparison to the corresponding Zn(II) enrofloxacinato complexes as well as Ni(II) complexes with the first-generation quinolone oxolinic acid. Copyright © 2010 Elsevier Inc. All rights reserved.

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

NASA Astrophysics Data System (ADS)

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.

Critical thinking: concept analysis from the perspective of Rodger's evolutionary method of concept analysis.

PubMed

Carbogim, Fábio da Costa; Oliveira, Larissa Bertacchini de; Püschel, Vilanice Alves de Araújo

2016-09-01

to analyze the concept of critical thinking (CT) in Rodger's evolutionary perspective. documentary research undertaken in the Cinahl, Lilacs, Bdenf and Dedalus databases, using the keywords of 'critical thinking' and 'Nursing', without limitation based on year of publication. The data were analyzed in accordance with the stages of Rodger's conceptual model. The following were included: books and articles in full, published in Portuguese, English or Spanish, which addressed CT in the teaching and practice of Nursing; articles which did not address aspects related to the concept of CT were excluded. the sample was made up of 42 works. As a substitute term, emphasis is placed on 'analytical thinking', and, as a related factor, decision-making. In order, the most frequent preceding and consequent attributes were: ability to analyze, training of the student nurse, and clinical decision-making. As the implications of CT, emphasis is placed on achieving effective results in care for the patient, family and community. CT is a cognitive skill which involves analysis, logical reasoning and clinical judgment, geared towards the resolution of problems, and standing out in the training and practice of the nurse with a view to accurate clinical decision-making and the achieving of effective results. analisar o conceito de pensamento crítico (PC), na perspectiva evolucionista de Rodgers. pesquisa documental realizada nas bases de dados Cinahl, Lilacs, Bdenf e Dedalus, utilizando-se as palavras-chave pensamento crítico e Enfermagem, sem delimitação de ano de publicação. Os dados foram analisados conforme etapas do modelo conceitual de Rodgers. Incluíram-se livros e artigos na íntegra, publicados em português, inglês ou espanhol que abordavam o PC no ensino e prática de Enfermagem, excluindo-se estudos que não abordassem aspectos relacionados ao conceito do PC. a amostra foi constituída por 42 trabalhos. Como termo substituto, destacou-se pensamento analítico e, como fator relacionado, tomada de decisão. Pela ordem, os atributos, antecedentes e consequentes mais frequentes, foram: capacidade de análise, formação do estudante de enfermagem e tomada de decisão clínica. Como implicação do PC, destaca-se o alcance de resultados efetivos na assistência ao paciente, família e comunidade. o PC é uma habilidade cognitiva que envolve análise, raciocínio lógico e julgamento clínico, orientado para resolução de problemas e destacando-se na formação e prática do enfermeiro com vistas à tomada de decisão clínica acurada e alcance de resultados efetivos. analizar el concepto de Pensamiento Crítico (PC), en la perspectiva evolucionista de Rodgers. investigación documental realizada en las bases de datos Cinahl, Lilacs, Bdenf y Dedalus, utilizando las palabras clave pensamiento crítico y Enfermería, sin delimitación de año de publicación. Los datos fueron analizados conforme etapas del modelo conceptual de Rodgers. Se incluyeron libros y artículos completos, publicados en portugués, inglés o español, que abordaban el PC en la enseñanza y práctica de Enfermería, excluyendo estudios que no abordasen aspectos relacionados al concepto del PC. la muestra estuvo constituida por 42 trabajos. Como término sustituto, se destacó el pensamiento analítico y, como factor relacionado la toma de decisiones. Por orden, los atributos, antecedentes y consecuentes más frecuentes, fueron: capacidad de análisis, formación del estudiante de enfermería y toma de decisiones clínicas. Como implicación del PC, se destaca el alcance de resultados efectivos en la asistencia al paciente, familia y comunidad. el PC es una habilidad cognitiva que envuelve análisis, raciocinio lógico y juzgamiento clínico, es orientado para la resolución de problemas y se destaca en la formación y práctica del enfermero, objetivando la toma de decisiones clínicas precisas y la obtención de resultados efectivos.

El rol de Ia colaboracion y el Modelo de Aprendizaje Basado en Proyectos (ABPr) mediante el lente de la Teoria de Actividad (CHAT): un estudio de caso con estudiantes de 9no grado

NASA Astrophysics Data System (ADS)

Delgado, Isabel C.

Los modelos de eensenanza y aprendizaje constructivistas conceptualizan el aprendizaje como un proceso activo. El modelo de Aprendizaje Basado en Proyectos (ABPr) se distingue por una serie de componentes, entre los cuales se destaca el aspecto colaborativo y cooperativo como un reto al momento de su implantacion. Son pocas las investigaciones que se concentran en este aspecto del modelo. En este estudio, se analizaron las diversas interacciones que surgen durante la implantacion de una unidad curricular sobre el tema de Geologia de Puerto Rico, la cual se diseno con el modelo ABPr cuyo enfoque es orientacion a proyectos. Particularmente, se examinaron las interacciones sociales que surgen entre los pares y entre pares y docente durante el proceso de planificacion y desarrollo de los productos finales, al igual que las interacciones entre los estudiantes y el material didactico en estas etapas del modelo. La investigacion es de tipo cualitativo e incorpora como diseno el estudio de caso. Las diversas interacciones constituyen la unidad de analisis. En el estudio participaron 19 estudiantes de 9no grado, a quienes se organizaron en 5 grupos colaborativos por temas de interes (Pangea, Placas tectonicas, Volcanes, Tsunamis y Terremotos). Las tecnicas que se utilizaron para recopilar los datos fueron: observaciones participativas, grupos focales y analisis de documentos (cuadernos reflexivos y respuestas de los estudiantes a la pregunta central del proyecto). Para el analisis de los datos se aplico la teoria de actividad (CHAT) que concentra la unidad de analisis en la actividad humana en un contexto particular. Los resultados del estudio senalan que las interacciones entre pares, entre pares y docente, asi como entre estudiantes y material didactico son fundamentales en el proceso de aprendizaje. Una mayor interaccion entre pares durante las etapas de planificar y desarrollar los productos finales de la unidad, promueve una mejor comprension de los conceptos de la unidad, segun evidencia los productos finales del ABPr. La interaccion con el docente es muy importante para mediar los conflictos y desacuerdos que surgen como parte de las interacciones entre pares. Por lo tanto, el uso de diversas estrategias de andamiaje por parte del docente durante las reuniones de los grupos colaborativos es esencial para el exito del modelo ABPr.

Bis(2,3,5,6-tetra-2-pyridyl­pyrazine-κ3 N 2,N 1,N 6)nickel(II) dithio­cyanate dihydrate

PubMed Central

De la Pinta, Noelia; Fidalgo, M. Luz; Ezpeleta, José M.; Cortés, Roberto; Madariaga, Gotzon

2011-01-01

In the title compound, [Ni(C24H16N6)2](NCS)2·2H2O, the central NiII ion is octahedrally coordinated by six N atoms of two tridentate 2,3,5,6-tetra-2-pyridyl­pyrazine ligands (tppz). Two thio­cyanate anions act as counter-ions and two water mol­ecules act as solvation agents. O—H⋯N hydrogen bonds are observed in the crystral structure. PMID:21522540

Diazido­bis(5,5′-dimethyl-2,2′-bipyridyl-κ2 N,N′)nickel(II) monohydrate

PubMed Central

Phatchimkun, Jaturong; Kongsaeree, Palangpon; Suchaichit, Nattawut; Chaichit, Narongsak

2009-01-01

In the crystal structure of the title compound, [Ni(N3)2(C12H12N2)2]·H2O, the NiII atom is situated on a twofold axis and adopts a distorted octa­hedral geometry with the two 5,5′-dimethyl-2,2′-bipyridyl (dmbpy) and the two azide ligands in a cis arrangement. The water solvent mol­ecule is disordered over two positions in a 1:1 ratio. PMID:21577389

Tris(5,6-dimethyl-1H-benzimidazole-κN(3))(pyridine-2,6-dicarboxyl-ato-κ(3)O(2),N,O(6))nickel(II).

PubMed

Li, Yue-Hua; Li, Feng-Feng; Liu, Xin-Hua; Zhao, Ling-Yan

2012-06-01

The title mononuclear complex, [Ni(C(7)H(3)NO(4))(C(9)H(10)N(2))(3)], shows a central Ni(II) atom which is coordinated by two carboxyl-ate O atoms and the N atom from a pyridine-2,6-dicarboxyl-ate ligand and by three N atoms from different 5,6-dimethyl-1H--benzimidazole ligands in a distorted octa-hedral geometry. The crystal structure shows intermolecular N-H⋯O hydrogen bonds.

A nickel catalyst for the addition of organoboronate esters to ketones and aldehydes.

PubMed

Bouffard, Jean; Itami, Kenichiro

2009-10-01

A Ni(cod)(2)/IPr catalyst promotes the intermolecular 1,2-addition of arylboronate esters to unactivated aldehydes and ketones. Diaryl, alkyl aryl, and dialkyl ketones show good reactivity under mild reaction conditions (< or = 80 degrees C, nonpolar solvents, no strong base or acid additives). A dramatic ligand effect favors either carbonyl addition (IPr) or C-OR cross-coupling (PCy(3)) with aryl ether substrates. A Ni(0)/Ni(II) catalytic cycle initiated by the oxidative cyclization of the carbonyl substrate is proposed.

Modelo B/Dual Language Programmes in the Basque Country and the USA

ERIC Educational Resources Information Center

Torres-Guzman, Maria E.; Etxeberria, Feli

2005-01-01

In this paper, we undertake a cross-national comparison of early partial immersion programmes, known as dual language or Modelo B programmes, in the USA and the Basque Country in Spain, respectively. We attempt to make sense of their growth, the expanded social uses of the minority languages, and address seemingly contradictory pedagogical…

Service-Learning in Physical Education Teacher Training. Physical Education in the Modelo Prison, Barcelona

ERIC Educational Resources Information Center

Lleixà, Teresa; Ríos, Merche

2015-01-01

In the Psychiatric Unit of the Modelo Prison, Barcelona, a physical education programme is carried out annually with the participation of University of Barcelona (UB) students. In this context, we carried out a study based on service-learning parameters. The aim of the study was twofold: to determine the impact on inmates of the physical education…

Synthesis and structure of 1,3-dimethyl-5-(p-sulfonamide-phenylazo)-6-aminouracil and its Ni(II) complex: Topological insights and investigation for noncovalent interactions

NASA Astrophysics Data System (ADS)

Debnath, Diptanu; Roy, Subhadip; Purkayastha, Atanu; Bauzá, Antonio; Choudhury, Rupasree; Ganguly, Rakesh; Frontera, Antonio; Misra, Tarun Kumar

2017-08-01

The azo-derivative, 1,3-dimethyl-5-(p-sulfonamide-phenylazo)-6-aminouracil (HL) containing 6-aminouracil (a biomolecule) and sulfonamide functionality (commonly found in sulfa-drugs), and its Ni(II) complex, NiIIL2 were synthesized. Single-crystal X-ray diffraction studies show that the ligand (HL) consists of an E conformation about the azo-linkage with a nearly planar geometry and the complex possesses distorted square planar geometry. The H-bonded underlying networks of HL and NiIIL2 were topologically classified revealing distinct topological types, namely tts and hxl, respectively. Moreover, topology of molecular packings in HL and NiIIL2 has also been discussed. Density functional theory (DFT) calculations, at the M06-2X/def2TZVP level of theory, are employed to characterize a great variety of non-covalent interactions that explicitly show the importance of antiparallel stacking interactions established by π--π+ interactions and H-bonds in the self-assembled dimmers in HL and lp-π/C-H⋯π interactions in NiIIL2. The results of NMR and UV-vis spectroscopies evidence that the ligand exists in hydrazone-imine-keto (B) tautomeric form in solution. The ligand absorption bands consist of the overlapping bands of π→π* and n→π* transitions. The complex experiences electronic transitions that consist of basically ILCT in character with some sort of participation of the atomic d-orbitals of the nickel. The pKa value of the ligand is found to be 4.09.

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

NASA Astrophysics Data System (ADS)

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

2014-10-01

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

Synthesis, characterization and properties of some divalent metal(II) complexes: Their electrochemical, catalytic, thermal and antimicrobial activity studies

NASA Astrophysics Data System (ADS)

Tümer, Mehmet; Ekinci, Duygu; Tümer, Ferhan; Bulut, Akif

2007-07-01

In this study, we synthesized the amine compound 2-(2-aminoethyliminomethyl)phenol (H 3A) as the starting material, and then we prepared the polydentate Schiff base ligands from the reactions of the amine compound (H 3A) with phtaldialdehyde (H 2L), 4-methyl-2,6-di-formlyphenol (H 3L 1) and 4- t-butyl-2,6-di-formylphenol (H 3L 2) in the ethanol solution. Moreover, the complexes Cd(II), Cu(II), Co(II), Ni(II), Zn(II) and Sn(II) of the ligands H 2L, H 3L 1 and H 3L 2 have been prepared. All compounds have been characterized by the analytical and spectroscopic methods. In addition, the magnetic susceptibility and molar conductance measurements have been made. The catalytic properties of the mono- and binuclear Co(II) and Cu(II) complexes have been studied on the 3,5-di- tert-butylcatechol (3,5-DTBC) and ascorbic acid (aa) as a substrate. The oxidative C-C coupling properties of the Co(II) and Cu(II) complexes have been investigated on the sterically hindered 2,6-di- tert-butylphenol (dtbp). The antimicrobial activity properties of the ligands and their mono- and binuclear complexes have been studied against the bacteria and fungi. The results have been compared to the antibacterial and fungi drugs. The TGA curves show that the decomposition takes place in three steps for all complexes. Electrochemical properties of the complexes Cu(II) and Ni(II) have been investigated for the first time in acetonitrile by cyclic voltammetry.

DNA incision evaluation, binding investigation and biocidal screening of Cu(II), Ni(II) and Co(II) complexes with isoxazole Schiff bases.

PubMed

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

2017-10-01

Two new series of binary metal complexes [M(L 1 ) 2 ] and [M(L 2 ) 2 ] where, M=Cu(II), Ni(II) & Co(II) and L 1 =4-((3,4-dimethylisoxazol-5-ylimino)methyl)benzene-1,3-diol; L 2 =2-((3,4-dimethylisoxazol-5-ylimino)methyl)-5-methoxyphenol were synthesized and characterized by elemental analysis, 1 H NMR, 13 C NMR, FT-IR, ESI mass, UV-Visible, magnetic moment, ESR, SEM and powder XRD studies. Based on these results, a square planar geometry is assigned for all the metal complexes where the Schiff base acts as uninegatively charged bidentate chelating agent via the hydroxyl oxygen and azomethine nitrogen atoms. DNA binding studies of all the complexes with calf thymus DNA have been comprehensively investigated using electronic absorption spectroscopy, fluorescence quenching and viscosity studies. The oxidative and photo cleavage affinity of metal complexes towards supercoiled pBR322 DNA has been ascertained by agarose gel electrophoresis assay. From the results, it is observed that all the metal complexes bind effectively to CT-DNA via an intercalative mode of binding and also cleave pBR322 DNA in a promising manner. Further the Cu(II) complexes have shown better binding and cleavage properties towards DNA. The antimicrobial activities of the Schiff bases and their metal complexes were studied on bacterial and fungal strains and the results denoted that the complexes are more potent than their Schiff base ligands. Copyright © 2017 Elsevier B.V. All rights reserved.

Synthesis, characterization and biological approach of metal chelates of some first row transition metal ions with halogenated bidentate coumarin Schiff bases containing N and O donor atoms.

PubMed

Prabhakara, Chetan T; Patil, Sangamesh A; Toragalmath, Shivakumar S; Kinnal, Shivashankar M; Badami, Prema S

2016-04-01

The impregnation of halogen atoms in a molecule is an emerging trend in pharmaceutical chemistry. The presence of halogens (Cl, Br, I and F) increases the lipophilic nature of molecule and improves the penetration of lipid membrane. The presence of electronegative halogen atoms increases the bio- activity of core moiety. In the present study, Co(II), Ni(II) and Cu(II) complexes are synthesised using Schiff bases (HL(I) and HL(II)), derived from 8-formyl-7-hydroxy-4-methylcoumarin/3-chloro-8-formyl-7-hydroxy-4-methylcoumarin with 2,4-difluoroaniline/o-toluidine respectively. The synthesized compounds were characterized by spectral (IR, NMR, UV-visible, Mass, ESI-MS, ESR), thermal, fluorescence and molar conductivity studies. All the synthesized metal complexes are completely soluble in DMF and DMSO. The non-electrolytic nature of the metal complexes was confirmed by molar conductance studies. Elemental analysis study suggest [ML2(H2O)2] stoichiometry, here M=Co(II), Ni(II) and Cu(II), L=deprotonated ligand. The obtained IR data supports the binding of metal ion to Schiff base. Thermal study suggests the presence of coordinated water molecules. Electronic spectral results reveal six coordinated geometry for the synthesized metal complexes. The Schiff bases and their metal complexes were evaluated for antibacterial (Pseudomonas aureginosa and Proteus mirabilis), antifungal (Aspergillus niger and Rhizopus oryzae), anthelmintic (Pheretima posthuma) and DNA cleavage (Calf Thymus DNA) activities. Copyright © 2016 Elsevier B.V. All rights reserved.

Synthesis of Optode Thin Layer using Sol Gel Hybrid of Trietoxysiloxane monomer and 3-(Trimethoxysilyl) Propilamine with Ionophore 4-(2-Pyridilazo)-1,3-Benzenadiol (PAR)

NASA Astrophysics Data System (ADS)

Wahyuningsih, S.; Rahmawati, F.; Kamal, S.; Slamet, S.; Yunianto, M.; Rahmawati, P.; Aini, F. N.

2018-03-01

Optode (Optical sensors) is one of the modern chemical sensors in the field of analytical chemistry that has utilized of inorganic polymers. The optode based on MLCT (Metal to Ligand Charge Transfer) (or MMLL’CT, Mixing Metal-Ligand to Ligand Charge Transfer) or LMCT (Ligand to Metal Charge Transfer) phenomenons have beed generated from oktyltrietxysilane, aminopropyltrimethoxysilane and 4-(2-pyrydilazo) resorcinol (abbreviated as OTES-APTS-PAR) for Cu(II), Cr(III), Ni(II), Fe(III), Cd(II), and Zn(II) ions target. The syntheses of thin layer optode were performed by sol gel method followed by evaporation in glass substrat. The formation of 4-(2-pyrydilazo) resorcinol complexes with ions target have gained strong absorption spectras in visible region because of charge transfer phenomenons. The optical sensor of OTES-APTS-PAR was analysed thermal properties using Differential Thermal Analysis (DTA). DTA thermogram showed a glass transition peaks at a temperature of 315.5 °C. Fourier transform Infrared (FTIR) spectras have showed that the optode materials consisted NH aryl groups indicated IR absorption at 1577.7 cm-1 and also –CH aromatic at 1469.0 cm-1. Synthesized optode materials have strong broad visible absorption with the maximum wavelengths (λmax) = 405 nm and 508.5 nm, respectively. This material have excellent optical responds to several metal ions such as Cu(II), Cr(III), Ni(II), Fe(III), Cd(II), and Zn(II) that was showed from huge Δλmax and the increase of Ktotal

Synthesis, characterization and analytical applications of Ni(II)-ion imprinted polymer

NASA Astrophysics Data System (ADS)

Singh, D. K.; Mishra, Shraddha

2010-10-01

Ion recognition-based separation techniques have received much attention because of their high selectivity for target ions. In this study, we have prepared a novel ion imprinted polymer (IIP) to remove nickel ions with high selectivity. The imprinted polymer was prepared by copolymerization of 2-hydroxy ethyl methacrylate (HEMA) with nickel vinylbenzoate complex in the presence of ethylene glycol dimethacrylate (EGDMA) as a crosslinker. The polymerization was carried out in bulk with free radical initiation using 2-methoxy ethanol as a solvent and porogen. The adsorbed nickel was completely eluted with 15 mL of 1 M HCl. Control polymer was also prepared by similar experimental conditions without using imprint ion. The above synthesized polymers were characterized by surface area measurements, FT-IR, microanalysis and SEM analysis. The adsorption capacity of IIP and CP was found to be 1.51 and 0.65 mmol g -1, respectively. The optimal pH for quantitative enrichment was 6.5. Nature of eluent, eluent concentration and eluent volume were also studied. The relative selectivity factor ( αr) values of Ni(II)/Zn(II), Ni(II)/Cu(II) and Ni(II)/Co(II) were 78.6, 111.1 and 91.6, respectively. Five replicate determinations of 30 μg L -1 of Ni(II) gave a mean absorbance of 0.067 with a relative standard deviation of 1.06%. The lowest concentration determined by GTA-AAS below which the recovery becomes non-quantitative is 6 μg L -1. IIP was tested for removal of Ni(II) from sea water sample.

Synthesis, spectroscopic and DNA binding ability of CoII, NiII, CuII and ZnII complexes of Schiff base ligand (E)-1-(((1H-benzo[d]imidazol-2-yl)methylimino)methyl)naphthalen-2-ol. X-ray crystal structure determination of cobalt (II) complex.

PubMed

Yarkandi, Naeema H; El-Ghamry, Hoda A; Gaber, Mohamed

2017-06-01

A novel Schiff base ligand, (E)-1-(((1H-benzo[d]imidazol-2-yl)methylimino)methyl)naphthalen-2-ol (HL), has been designed and synthesized in addition to its metal chelates [Co(L) 2 ]·l2H 2 O, [Ni(L)Cl·(H 2 O) 2 ].5H 2 O, [Cu(L)Cl] and [Zn(L)(CH 3 COO)]. The structures of the isolated compounds have been confirmed and identified by means of different spectral and physicochemical techniques including CHN analysis, 1 H & 13 C NMR, mass spectral analysis, molar conductivity measurement, UV-Vis, infrared, magnetic moment in addition to TGA technique. The infrared spectral results ascertained that the ligand acts as monobasic tridentate binding to the metal centers via deprotonated hydroxyl oxygen, azomethine and imidazole nitrogen atoms. The UV-Vis, magnetic susceptibility and molar conductivity data implied octahedral geometry for Co(II) & Ni(II) complexes, tetrahedral for Zn(II) complex and square planar for Cu(II) complex. X-ray structural analysis of Co(II) complex 1 has been reported and discussed. Moreover, the type of interaction between the ligand & its complexes towards salmon sperm DNA (SS-DNA) has been examined by the measurement of absorption spectra and viscosity which confirmed that the ligand and its complexes interact with DNA via intercalation interaction as concluded from the values of binding constants (K b ). Copyright © 2017 Elsevier B.V. All rights reserved.

Spectral, thermal, kinetic, molecular modeling and eukaryotic DNA degradation studies for a new series of albendazole (HABZ) complexes

NASA Astrophysics Data System (ADS)

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.

Synthesis, characterization, nucleic acid interactions and photoluminescent properties of methaniminium hydrazone Schiff base and its Mn(II), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) complexes

NASA Astrophysics Data System (ADS)

Sennappan, M.; Murali Krishna, P.; Hosamani, Amar A.; Hari Krishna, R.

2018-07-01

An environmental benign and efficient reaction was carried out via amine exchange and condensation reaction in water and methanol mixture (3:1) and absence of catalyst between 1-[3-(2-hydroxy benzylidene)amine)phenyl]ethanone and benzhydrazide yields methaniminium hydrazone Schiff base in high yield. The prepared ligand was structurally characterized by using single crystal XRD, elemental analysis and spectroscopy (UV-Vis, FT-IR, LC-MS and NMR) techniques. The crystal data indicates the ligand crystallizes in orthorhombic system with Pna21 space group. Further, the ligand was used in synthesis of mononuclear Mn(II), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) complexes and were characterized by elemental analysis, magnetic moment and spectroscopy (UV-Vis, FT-IR and ESR) studies. The spectral data showed that ligand is coordinated to the metal ion through azomethine nitrogen and methaniminium nitrogen. The DNA binding absorption titrations reveals that, ligand, L and its metal complexes, 1-6 are avid binders to CT- DNA. The apparent binding constant values of compounds are in the order of 106 M-1. The nuclease activity of ligand, L and its metal complexes, 1-6 were investigated by gel electrophoresis method using pUC18 DNA. The photoluminescent properties of the methaniminium hydrazone ligand, L and its various metal complexes, 1-6 were investigated. The emission spectra of both ligand (L) and metal complexes (1-6) exhibits emission in the range of blue to red.

Synthesis and characterization of Cu(II), Co(II) and Ni(II) complexes of a number of sulfadrug azodyes and their application for wastewater treatment

NASA Astrophysics Data System (ADS)

El-Baradie, K.; El-Sharkawy, R.; El-Ghamry, H.; Sakai, K.

2014-03-01

The azodye ligand (HL1) was synthesized from the coupling of sulfaguanidine diazonium salt with 2,4-dihydroxy-benzaldehyde while the two ligands, HL2 and HL3, were prepared by the coupling of sulfadiazine diazonium salt with salicylaldehyde (HL2) and 2,4-dihydroxy-benzaldehyde (HL3). The prepared ligands were characterized by elemental analysis, IR, 1H NMR and mass spectra. Cu(II), Co(II) and Ni(II) complexes of the prepared ligands have been synthesized and characterized by various spectroscopic techniques like IR, UV-Visible as well as magnetic and thermal (TG and DTA) measurements. It was found that all the ligands behave as a monobasic bidentate which coordinated to the metal center through the azo nitrogen and α-hydroxy oxygen atoms in the case of HL1 and HL3. HL2 coordinated to the metal center through sulfonamide oxygen and pyrimidine nitrogen. The applications of the prepared complexes in the oxidative degradation of indigo carmine dye exhibited good catalytic activity in the presence of H2O2 as an oxidant. The reactions followed first-order kinetics and the rate constants were determined. The degradation reaction involved the catalytic action of the azo-dye complexes toward H2O2 decomposition, which can lead to the generation of HOrad radicals as a highly efficient oxidant attacking the target dye. The detailed kinetic studies and the mechanism of these catalytic reactions are under consideration in our group.

Líneas metálicas en protuberancias solares

NASA Astrophysics Data System (ADS)

Stenborg, G.; Rovira, M. G.; Mauas, P.

Para determinar cual de los modelos existentes de protuberancias solares explica mejor las observaciones, es necesario, no solo ajustar los perfiles de las líneas de hidrógeno, sino también utilizar perfiles de distintos metales. En este trabajo, utilizamos un código desarrollado especialmente para calcular el equilibrio estadístico de cualquier especie atómica, aplicándolo al cálculo de los perfiles de las líneas del Ca II, el Mg II y el He, para determinar cómo se comportan ante variaciones en los parámetros de los modelos de protuberancia (ancho, presión y temperatura centrales y número de hebras), y comparamos con las observaciones existentes para determinar que modelo las ajusta mejor.

Experiências internacionais da aplicação de sistemas de apoio à decisão clínica em gastroenterologia

PubMed Central

Tenório, Josceli Maria; Hummel, Anderson Diniz; Sdepanian, Vera Lucia; Pisa, Ivan Torres; de Fátima Marin, Heimar

2015-01-01

Objetivo Descrever as experiências recentes com a aplicação de sistemas de apoio à decisão clínica em gastroenterologia, de forma a estabelecer o nível de desenvolvimento, testes e vantagens conferidas à prática médica com a introdução desses softwares. Métodos Foi realizada busca nas bases de dados PubMed, LILACS e ISI Web of Knowledge, utilizando termos relacionados à sistemas de apoio à decisão e à gastroenterogia, incluindo artigos originais publicados no período entre 2005 e 2010. Foram recuperadas 104 publicações, na busca inicial e, após a aplicação dos critérios de inclusão e exclusão, foram eleitos nove estudos para leitura do texto completo. Resultados Os sistemas de apoio à decisão clínica apresentam grande multiplicidade de problemas clínicos e investigação de doenças. Em 89% dos casos, são descritos modelos experimentais para o desenvolvimento de sistemas de apoio à decisão clínica. A descrição dos resultados obtidos por técnicas de inteligência artificial em 78% das publicações. Em dois dos estudos foram realizadas comparações com o médico e em apenas uma publicação um estudo controlado foi descrito, mostrando evidências de melhorias na prática médica. Conclusão Os estudos mostram potenciais benefícios dos sistemas de apoio à decisão clínica à prática médica, porém, estudos controlados em ambiente real devem ser realizados para comprovar esta perspectiva. PMID:26491625

Factors associated with the incidence of pressure ulcer during hospital stay.

PubMed

Matozinhos, Fernanda Penido; Velasquez-Melendez, Gustavo; Tiensoli, Sabrina Daros; Moreira, Alexandra Dias; Gomes, Flávia Sampaio Latini

2017-05-25

Estimating the incidence rate of pressure ulcers and verifying factors associated with this occurrence in a cohort of hospitalized patients. This is a cohort study in which the considered outcome was the time until pressure ulcer occurrence. Estimated effect of the variables on the cumulative incidence ratio of the outcome was performed using the Cox proportional hazards model. Variable selection occurred via the Logrank hypothesis test. The sample consisted of 442 adults, with 25 incidents of pressure ulcers. Patients with high scores on the Braden scale presented a higher risk of pressure ulcer incidence when compared to those classified into the low score category. These results reinforce the importance of using the Braden Scale to assist in identifying patients more likely to develop pressure ulcers. Estimar a taxa de incidência de úlcera por pressão e verificar fatores associados a essa ocorrência em uma coorte de pacientes hospitalizados. Trata-se de estudo de coorte no qual o desfecho foi a ocorrência da úlcera por pressão. A estimativa do efeito das variáveis para a proporção de incidência acumulada do desfecho foi realizada utilizando o modelo de riscos proporcionais de Cox. A seleção das variáveis ocorreu por meio do teste de hipóteses Logrank. A amostra foi composta de 442 adultos, com 25 casos incidentes de úlcera por pressão. Pacientes com altos escores na escala de Braden apresentaram maior risco de incidência de úlcera por pressão quando comparados com aqueles classificados na categoria de baixo escore. Os resultados reforçam a importância do uso da Escala de Braden para auxiliar na identificação dos pacientes com maior probabilidade de desenvolver úlcera por pressão.

Is there any link between accreditation programs and the models of organizational excellence?

PubMed

Berssaneti, Fernando Tobal; Saut, Ana Maria; Barakat, Májida Farid; Calarge, Felipe Araujo

2016-01-01

To evaluate whether accredited health organizations perform better management practices than non-accredited ones. The study was developed in two stages: a literature review, and a study of multiple cases in 12 healthcare organizations in the state of São Paulo, Brazil. It surveyed articles comparing hospital accreditation with the EFQM (European Foundation for Quality Management) model of excellence in management. According to the pertinent literature, the accreditation model and the EFQM model are convergent and supplementary in some aspects. With 99% confidence, one can say that there is evidence that accredited organizations scored better in the evaluation based on the EFQM model in comparison to non-accredited organizations. This result was also confirmed in the comparison of results between the categories Facilitators and Results in the EFQM model. There is convergence between the accreditation model and the EFQM excellence model, suggesting that accreditation helps the healthcare sector to implement the best management practices already used by other business sectors. Avaliar se as organizações de saúde acreditadas possuem melhores práticas de gestão do que as não acreditadas. A pesquisa foi dividida em duas etapas: revisão da literatura e estudo de casos múltiplos com 12 organizações de saúde, localizadas no estado de São Paulo ‒ Brasil. Foram pesquisados artigos que comparavam a acreditação hospitalar com o modelo de excelência em gestão da EFQM (European Foundation for Quality Management), sendo que a literatura pertinente considera que o modelo de acreditação e o modelo da EFQM são convergentes e, ao mesmo tempo, complementares em determinados aspectos. Com 99% de confiança, pode-se afirmar que há evidência de que as organizações com acreditação obtiveram uma pontuação maior na avaliação baseada no modelo EFQM comparativamente às organizações não acreditadas. Este resultado também se confirmou na comparação dos resultados das categorias Facilitadores e Resultados do modelo EFQM. Há uma convergência entre o modelo de acreditação e o modelo de excelência da EFQM, sugerindo que a acreditação contribui para o setor de saúde implementar as melhores práticas de gestão já difundidas em outros setores de negócio.

Concepciones Alternativas de "Fotosintesis" en estudiantes Universitarios del curso basico de Biologia y posibles correcciones con el Modelo Educativo MODEF

NASA Astrophysics Data System (ADS)

De Jesus Roman, Sandra

Concepciones Alternativas de Fotosíntesis en estudiantes Universitariosdel curso básico de Biología y posibles correcciones con el Modelo Educativo MODEF El modelo educativo para la enseñanza de Fotosíntesis (MODEF) se implantó para trabajar el problema de las concepciones alternativas (CA) en un curso de Biología General. Se evaluaron los resultados en cuanto al logro del aprendizaje significativo. La pregunta central de la investigación fue: ¿Cómo aporta el modelo educativo en la didáctica y comprensión del tema de fotosíntesis? Se efectuó una investigación acción con una fase cuantitativa y una cualitativa. Para la fase cuantitativa se elaboró una prueba para determinar las concepciones alternativas, se validó y se sometió a los estudiantes que participaron en el estudio antes y después de ofrecer la unidad de metabolismo celular. Los participantes eran estudiantes de primer año de la Universidad de Puerto Rico en Bayamón (UPRB). Se llevó a cabo un análisis de consistencia interna de la prueba mediante el método Alfa de Cronbach. Se analizaron las contestaciones a cada pregunta mediante la prueba de Ji cuadrado de contingencia, se efectuó la prueba de t y el coeficiente r de Pearson. La fase cualitativa incluyó la observación participativa de la investigadora- profesora, las reflexiones de los estudiantes y la información de las entrevistas semi-estructuradas que se realizaron a tres estudiantes del curso. El análisis se llevó a cabo mediante el Modelo de Wolcott. Se trabajaron diez CA de las cuales siete fueron corregidas mediante el Modelo MODEF. Las actividades más importantes para el proceso de aprendizaje incluyeron el trabajo de investigación o búsqueda de información para hacer una presentación digital, la elaboración de tablas, los mapas de conceptos, el uso de visuales o videos y las analogías para explicar conceptos o procesos. En conclusión: se recomienda el uso del Modelo MODEF para la discusión del tema de Fotosíntesis a base de los resultados cuantitativos y cualitativos de esta investigación. El Comité Institucional para la Protección de los Seres Humanos en la Investigación (CIPSHI) autorizó el estudio.

NOAA Weather Radio

Science.gov Websites

unidades portátiles portátiles que atiende clima radiofónicas, a los modelos de escritorio y consola que específica o modelo del receptor. Las listas siguientes, que contienen algunos de los muchos NOAA Weather , dependiendo del número de características incluidas. Multi-multi-Band/función de receptores: los receptores

Hospitalization in older adults: association with multimorbidity, primary health care and private health plan.

PubMed

Nunes, Bruno Pereira; Soares, Mariangela Uhlmann; Wachs, Louriele Soares; Volz, Pâmela Moraes; Saes, Mirelle de Oliveira; Duro, Suele Manjourany Silva; Thumé, Elaine; Facchini, Luiz Augusto

2017-05-04

Evaluate the association of multimorbidity, primary health care model and possession of a private health plan with hospitalization. A population-based cross-sectional study with 1,593 elderly individuals (60 years old or older) living in the urban area of the city of Bagé, State of Rio Grande do Sul, Brazil. The outcome was hospitalization in the year preceding the interview. The multimorbidity was evaluated through two cut-off points (≥ 2 and ≥ 3). The primary health care model was defined by residence in areas covered by traditional care or by Family Health Strategy. The older adults mentioned the possession of a private health plan. We performed a gross and adjusted analysis by Poisson regression using a hierarchical model. The adjustment included demographic, socioeconomic, functional capacity disability and health services variables. The occurrence of overall and non-surgical hospitalization was 17.7% (95%CI 15.8-19.6) and 10.6% (95%CI 9.1-12.1), respectively. Older adults with multimorbidity were admitted to hospitals more often when to older adults without multimorbidity, regardless of the exhibition' form of operation. Having a private health plan increased the hospitalization by 1.71 (95%CI 1.09-2.69) times among residents in the areas of the Family Health Strategy when compared to elderly residents in traditional areas without a private health plan. The multimorbidity increased the occurrence of hospitalizations, especially non-surgical ones. Hospitalization was more frequent in older adults with private health plan and those living in Family Health Strategy areas, regardless of the presence of multiple diseases. Avaliar a associação da multimorbidade, modelo de atenção básica e posse de plano de saúde com hospitalização. Estudo transversal de base populacional com 1.593 idosos (60 anos ou mais) residentes na zona urbana do município de Bagé, Rio Grande do Sul. O desfecho foi a hospitalização no ano anterior à entrevista. A multimorbidade foi avaliada por meio de dois pontos de corte (≥ 2 e ≥ 3). O modelo de atenção básica foi definido pela residência em áreas cobertas pela atenção tradicional ou da Estratégia Saúde da Família. A posse de plano de saúde foi referida pelos idosos. Realizou-se análise bruta e ajustada por regressão de Poisson utilizando modelo hierarquizado. O ajuste incluiu variáveis demográficas, socioeconômicas, capacidades funcionais e de serviços de saúde. A ocorrência de hospitalização geral e não cirúrgica foi de 17,7% (IC95% 15,8-19,6) e 10,6% (IC95% 9,1-12,1), respectivamente. Idosos com multimorbidade hospitalizaram mais em comparação com os idosos sem multimorbidade, independentemente da forma de operacionalização da exposição. O plano de saúde aumentou em 1,71 (IC95% 1,09-2,69) vezes a internação hospitalar entre residentes nas áreas da Estratégia Saúde da Família em comparação aos idosos residentes nas áreas tradicionais sem plano de saúde. A multimorbidade aumentou a ocorrência de hospitalizações, principalmente aquelas não cirúrgicas. Idosos com plano de saúde e residentes em áreas de Estratégia Saúde da Família internaram mais, independentemente da presença de múltiplas doenças.

General and mild Ni(0)-catalyzed α-arylation of ketones using aryl chlorides.

PubMed

Fernández-Salas, José A; Marelli, Enrico; Cordes, David B; Slawin, Alexandra M Z; Nolan, Steven P

2015-03-02

A general methodology for the α-arylation of ketones using a nickel catalyst has been developed. The new well-defined [Ni(IPr*)(cin)Cl] (1 c) pre-catalyst showed great efficiency for this transformation, allowing the coupling of a wide range of ketones, including acetophenone derivatives, with various functionalised aryl chlorides. This cinnamyl-based Ni-N-heterocyclic carbene (NHC) complex has demonstrated a different behaviour to previously reported NHC-Ni catalysts. Preliminary mechanistic studies suggest a Ni(0)/Ni(II) catalytic cycle to be at play. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A new surfactant-introduction strategy for separating the pure single-phase of metal-organic frameworks.

PubMed

Zhao, Jun; Wang, Yenan; Dong, Wenwen; Wu, Yapan; Li, Dongsheng; Liu, Bin; Zhang, Qichun

2015-06-11

By introducing different surfactants into a reaction system, two previous mixed-phase Ni(II)-MOFs constructed from an undeveloped pyridyl-tetracarboxylate and Ni(II) salts were successfully isolated to obtain two pure products. Compound 1 exhibits a 3D H-bonded network with (3,8)-connected {4.5(2)}2{4(2).5(6).6(14).7(2).8(4)} topology, while 2 features a 3D 2-fold interpenetrating framework with a self-penetrating (3,4,4)-connected {6(2).10(3).12}{6(3)}2{6(4).8.10}2 topological net.

Tris(5,6-dimethyl-1H-benzimidazole-κN 3)(pyridine-2,6-dicarboxyl­ato-κ3 O 2,N,O 6)nickel(II)

PubMed Central

Li, Yue-Hua; Li, Feng-Feng; Liu, Xin-Hua; Zhao, Ling-Yan

2012-01-01

The title mononuclear complex, [Ni(C7H3NO4)(C9H10N2)3], shows a central NiII atom which is coordinated by two carboxyl­ate O atoms and the N atom from a pyridine-2,6-dicarboxyl­ate ligand and by three N atoms from different 5,6-dimethyl-1H-­benzimidazole ligands in a distorted octa­hedral geometry. The crystal structure shows intermolecular N—H⋯O hydrogen bonds. PMID:22719301

Physicochemical properties of sorbents based on silica gel modified by 1-phenylazo-2-naphtholic complexes of transition metals

NASA Astrophysics Data System (ADS)

Makarycheva, A. I.; Slizhov, Yu. G.

2017-09-01

Gas chromatography sorbents based on Silokhrom C80 and modified by 1-phenylazo-2-naphtholic complexes of 3 d metals (Co(II), Ni(II), Cu(II)) are obtained. Their structural, chromatographic, and sorption characteristics are investigated. It is found that modifying them with 1-phenylazo-2-naphthols of transition metals has a considerable effect on the chromatographic polarity and selectivity of sorption materials. The prospects for the practical application of the obtained sorbents are demonstrated by experiments on the gas chromatographic separation of mixtures of different classes of organic compounds.

A novel tridentate coordination mode for the carbonatonickel system exhibited in an unusual hexanuclear nickel(II) mu3-carbonato-bridged complex.

PubMed

Anderson, James C; Blake, Alexander J; Moreno, Rafael Bou; Raynel, Guillaume; van Slageren, Joris

2009-11-14

The fixation of CO(2) at ambient temperature has been achieved by the reaction of Ni(cod)(2) and TMEDA in CO(2) saturated THF that yields a novel hexanuclear nickel(II) mu(3)-carbonato bridged complex [Ni(6)(mu(3)-CO(3))(4)(TMEDA)(6)(H(2)O)(12)](OH)(4) in 59% yield. The complex was characterised by MS analysis and the structure corroborated by single-crystal X-ray crystallography. The complex exhibits a rare carbonato binding mode for Ni(II) complexes and moderately strong antiferromagnetic interactions.

Descripción de la zona de alta difusión en un modelo bidimensional para hojas de corriente

NASA Astrophysics Data System (ADS)

Montero, M. F.; Paola, C. A.; Platzeck, A. M.

Los modelos bidimensionales para describir hojas de corriente de alta simetría no suministran una descripción detallada de las regiones donde la difusión es considerablemente importante. Tal es el caso de los modelos desarrollados en la década del '60 por Sweet, Parker, Petschek y Sonnerup. En esta comunicación presentamos una solución de las ecuaciones MHD en el entorno del origen, construyendo series bidimensionales para todas las magnitudes físicas involucradas. Valiéndonos de la alta simetría y de las características del problema, logramos reducir el número de coeficientes a calcular. Utilizamos un programa autoconsistente para extender el cálculo a regiones vecinas con difusión moderada o despreciable.

Determinación de temperatura efectiva y gravedad superficial de estrellas B y A de secuencia principal

NASA Astrophysics Data System (ADS)

Nieva, M. F.; Pintado, O. I.; Adelman, S.; Rayle, K. E.; Sanders, S. E., Jr.

Las temperaturas efectivas (Teff) y gravedades superficiales (log g) de un grupo de estrellas de tipo B y A de Secuencia Principal se determinaron en varias etapas. En una primera aproximación se usaron los índices fotométricos de Strömgren para realizar el cálculo con el programa de Napiwotski et al.(1993). Luego se hizo un ajuste comparando datos espectrofotométricos con flujos obtenidos con el modelo ATLAS9 en la región visible. Y a continuación se hizo un mejor ajuste comparando los perfiles de la línea Hγ con espectros sintéticos calculados con SYNTHE. Además, se analizó el efecto de usar el modelo de Canuto y Mazzitelli (1991), donde se considera The Mixing Length Theory, en modelos de atmósferas de estrellas.

Uptake of Nickel by Synthetic Mackinawite | Science Inventory ...

EPA Pesticide Factsheets

The uptake of aqueous Ni(II) by synthetic mackinawite (FeS) was examined in anaerobic batch experiments at near-neutral pH (5.2 to 8.4). Initial molar ratios of Ni(II) to FeS ranged from 0.008 to 0.83 and maximum Ni concentrations in mackinawite, expressed as the cation mol fraction, were as high as XNi = 0.56 (Fe1-xNixS; 0  x  1). Greater than 99% Ni removal from solution occurred when Ni loading remained below 0.13 ± 0.03 (1σ) mol Ni per mol FeS due to sorption of Ni at the mackinawite surface. Characterization of experimental solids using X-ray diffraction and Raman spectroscopy showed patterns characteristic of nanocrystalline mackinawite; no evidence of nickel monosulfide (α-NiS or millerite), polydymite (Ni3S4), or godlevskite [(Ni,Fe)9S8] formation was indicated regardless of the amount of Ni loading. Slight expansion of the c-axis correlated with increasing Ni content in synthetic mackinawite, from c = 5.07 ± 0.01 Å at XNi = 0.02 to c = 5.10 ± 0.01 Å at XNi = 0.38. Ni K-edge extended X-ray absorption fine structure (EXAFS) spectra of synthetic Ni-bearing mackinawite are similar in phase and amplitude to the Fe K-edge EXAFS spectrum of Ni-free mackinawite, indicating that the molecular environment of Ni2+ in Ni-bearing mackinawite is similar to that of Fe2+ in Ni-free mackinawite. EXAFS data fitting of Ni-bearing mackinawite with XNi = 0.42 indicated a coordination number of 4.04 ± 0.30 and an average Ni-S bond distance of 2.28 Å, in good a

Ternary metal complexes of guaifenesin drug: Synthesis, spectroscopic characterization and in vitro anticancer activity of the metal complexes.

PubMed

Mahmoud, W H; Mahmoud, N F; Mohamed, G G; El-Sonbati, A Z; El-Bindary, A A

2015-01-01

The coordination behavior of a series of transition metal ions named Cr(III), Fe(III), Mn(II), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) with a mono negative tridentate guaifenesin ligand (GFS) (OOO donation sites) and 1,10-phenanthroline (Phen) is reported. The metal complexes are characterized based on elemental analyses, IR, (1)H NMR, solid reflectance, magnetic moment, molar conductance, UV-vis spectral studies, mass spectroscopy, ESR, XRD and thermal analysis (TG and DTG). The ternary metal complexes were found to have the formulae of [M(GFS)(Phen)Cl]Cl·nH2O (M=Cr(III) (n=1) and Fe(III) (n=0)), [M(GFS)(Phen)Cl]·nH2O (M=Mn(II) (n=0), Zn(II) (n=0) and Cu(II) (n=3)) and [M(GFS)(Phen)(H2O)]Cl·nH2O (M=Co(II) (n=0), Ni(II) (n=0) and Cd(II) (n=4)). All the chelates are found to have octahedral geometrical structures. The ligand and its ternary chelates are subjected to thermal analyses (TG and DTG). The GFS ligand, in comparison to its ternary metal complexes also was screened for their antibacterial activity on gram positive bacteria (Bacillus subtilis and Staphylococcus aureus), gram negative bacteria (Escherichia coli and Neisseria gonorrhoeae) and for in vitro antifungal activity against (Candida albicans). The activity data show that the metal complexes have antibacterial and antifungal activity more than the parent GFS ligand. The complexes were also screened for its in vitro anticancer activity against the Breast cell line (MFC7) and the results obtained show that they exhibit a considerable anticancer activity. Copyright © 2015 Elsevier B.V. All rights reserved.

Novel Cu(I)-selective chelators based on a bis(phosphorothioyl)amide scaffold.

PubMed

Amir, Aviran; Ezra, Alon; Shimon, Linda J W; Fischer, Bilha

2014-08-04

Bis(dialkyl/aryl-phosphorothioyl)amide (BPA) derivatives are versatile ligands known by their high metal-ion affinity and selectivity. Here, we synthesized related chelators based on bis(1,3,2-dithia/dioxaphospholane-2-sulfide)amide (BTPA/BOPA) scaffolds targeting the chelation of soft metal ions. Crystal structures of BTPA compounds 6 (N(-)R3NH(+)) and 8 (NEt) revealed a gauche geometry, while BOPA compound 7 (N(-)R3NH(+)) exhibited an anti-geometry. Solid-state (31)P magic-angle spinning NMR spectra of BTPA 6-Hg(II) and 6-Zn(II) complexes imply a square planar or tetrahedral geometry of the former and a distorted tetrahedral geometry of the latter, while both BTPA 6-Ni(II) and BOPA 7-Ni(II) complexes possibly form a polymeric structure. In Cu(I)-H2O2 system (Fenton reaction conditions) BTPA compounds 6, 8, and 10 (NCH2Ph) were identified as most potent antioxidants (IC50 32, 56, and 29 μM, respectively), whereas BOPA analogues 7, 9 (NEt), and 11 (NCH2Ph) were found to be poor antioxidants. In Fe(II)-H2O2 system, IC50 values for both BTPA and BOPA compounds exceeded 500 μM indicating high selectivity to Cu(I) versus the borderline Fe(II)-ion. Neither BTPA nor BOPA derivatives showed radical scavenging properties in H2O2 photolysis, implying that inhibition of the Cu(I)-induced Fenton reaction by both BTPA and BOPA analogues occurred predominantly through Cu(I)-chelation. In addition, NMR-monitored Cu(I)- and Zn(II)-titration of BTPA compounds 8 and 10 showed their high selectivity to a soft metal ion, Cu(I), as compared to a borderline metal ion, Zn(II). In summary, lipophilic BTPA analogues are promising highly selective Cu(I) ion chelators.

Pharmacologically significant complexes of Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) of novel Schiff base ligand, (E)-N-(furan-2-yl methylene) quinolin-8-amine: Synthesis, spectral, XRD, SEM, antimicrobial, antioxidant and in vitro cytotoxic studies

NASA Astrophysics Data System (ADS)

Shakir, M.; Hanif, Summaiya; Sherwani, Mohd. Asif; Mohammad, Owais; Al-Resayes, Saud I.

2015-07-01

A novel series of metal complexes of the types, [ML2(H2O)2]Cl2 and [ML2]Cl2 [M = Mn(II), 1; Co(II), 2; Ni(II), 3; Cu(II), 4; and Zn(II), 5] were synthesized by the interaction of ligand, L (E)-N-(furan-2-yl methylene) quinolin-8-amine, derived from the condensation of 2-furaldehyde and 8-aminoquinoline. The synthesized ligand and its metal complexes were characterized on the basis of results obtained from elemental analysis, ESI-MS, XRD, SEM, TGA/DTA, FT-IR, UV-Vis, magnetic moment and 1H and 13C NMR spectroscopic studies. EPR parameters were recorded in case of complex 4. The comparative in-vitro antimicrobial activities against various pathogens with reference to known antibiotics and antioxidant activity against standard control at variable concentrations revealed that the metal complexes show enhanced antimicrobial and free radical scavenging activities in general as compared to free ligand. However, the complexes 1 and 5 have shown best antioxidant activity among all the metal complexes. Furthermore, comparative in-vitro antiproliferative activity on ligand and its metal chelates performed on MDA-MB-231 (breast carcinoma), KCL22 (blood lymphoid carcinoma), HeLa (cervical carcinoma) cell lines and normal cells (PBMC) revealed that metal chelates show moderate to good activity as compared to ligand where as complex 1 seems to be the most promising one possessing a broad spectrum of activity against all the selected cancer cell lines with IC50 < 2.10 μM.

Symmetrical and unsymmetrical pincer complexes with group 10 metals: synthesis via aryl C-H activation and some catalytic applications.

PubMed

Niu, Jun-Long; Hao, Xin-Qi; Gong, Jun-Fang; Song, Mao-Ping

2011-05-21

Aryl-based pincer metal complexes with anionic terdentate ligands have been widely applied in organic synthesis, organometallic catalysis and other related areas. Synthetically, the most simple and convenient method for the construction of these complexes is the direct metal-induced C(aryl)-H bond activation, which can be fulfilled by choosing the appropriate functional donor groups in the two side arms of the aryl-based pincer preligands. In this perspective, we wish to summarize some results achieved by our group in this context. Successful examples include symmetrical chiral bis(imidazoline) NCN pincer complexes with Ni(II), Pd(II) and Pt(II), bis(phosphinite) and bis(phosphoramidite) PCP pincer Pd(II) complexes, unsymmetrical (pyrazolyl)phosphinite, (amino)phosphinite and (imino)phosphinite PCN pincer Pd(II) complexes, chiral (imidazolinyl)phosphinite and (imidazolinyl)phosphoramidite PCN pincer complexes with Ni(II) and Pd(II) as well as unsymmetrical (oxazolinyl)amine and (oxazolinyl)pyrazole NCN' pincer Pd(II) complexes. Among them, the P-donor containing complexes are efficiently synthesized by the "one-pot phosphorylation/metalation" method. The obtained symmetrical and unsymmetrical pincer complexes have been used as catalysts in Suzuki-Miyaura reaction (Pd), asymmetric Friedel-Crafts alkylation of indole with trans-β-nitrostyrene (Pt) as well as in asymmetric allylation of aldehyde and sulfonimine (Pd). In the Suzuki couplings conducted at 40-50 °C, some unsymmetrical Pd complexes exhibit much higher activity than the related symmetrical ones which can be attributed to their faster release of active Pd(0) species resulting from the hemilabile coordination of the ligands. Literature results on the synthesis of some related pincer complexes as well as their activities in the above catalytic reactions are also presented.

Scanning tunneling microscopy, orbital-mediated tunneling spectroscopy, and ultraviolet photoelectron spectroscopy of metal(II) tetraphenylporphyrins deposited from vapor.

PubMed

Scudiero, L; Barlow, D E; Mazur, U; Hipps, K W

2001-05-02

Thin films of vapor-deposited Ni(II) and Co(II) complexes of tetraphenylporphyrin (NiTPP and CoTPP) were studied supported on gold and embedded in Al-Al(2)O(3)-MTPP-Pb tunnel diodes, where M = Ni or Co. Thin films deposited onto polycrystalline gold were analyzed by ultraviolet photoelectron spectroscopy (UPS) using He I radiation. Scanning tunneling microscopy (STM) and orbital-mediated tunneling spectroscopy (STM-OMTS) were performed on submonolayer films of CoTPP and NiTPP supported on Au(111). Inelastic electron tunneling spectroscopy (IETS) and OMTS were measured in conventional tunnel diode structures. The highest occupied pi molecular orbital of the porphyrin ring was seen in both STM-OMTS and UPS at about 6.4 eV below the vacuum level. The lowest unoccupied pi molecular orbital of the porphyrin ring was observed by STM-OMTS and by IETS-OMTS to be located near 3.4 eV below the vacuum level. The OMTS spectra of CoTPP had a band near 5.2 eV (below the vacuum level) that was attributed to transient oxidation of the central Co(II) ion. That is, it is due to electron OMT via the half-filled d(z)(2) orbital present in Co(II) of CoTPP. The NiTPP OMTS spectra show no such band, consistent with the known difficulty of oxidation of the Ni(II) ion. The STM-based OMTS allowed these two porphyrin complexes to be easily distinguished. The present work is the first report of the observation of STM-OMTS, tunnel junction OMTS, and UPS of the same compounds. Scanning tunneling microscope-based orbital-mediated tunneling provides more information than UPS or tunnel junction-based OMTS and does so with molecular-scale resolution.

A preconcentration method for indirect determination of acrylamide from chips, crackers and cereal-based baby foods using flame atomic absorption spectrometry.

PubMed

Altunay, Nail; Gürkan, Ramazan; Orhan, Ulaş

2016-12-01

Acrylamide is a toxic species for human health, and is a Maillard reaction product which forms spontaneously in heat treatment process of foods. Therefore, a simple, fast and cost-effective method was developed for the indirect determination of acrylamide in processed foods particularly consumed by children. The method is based on ion-pairing of acrylamide with fluorescein (F 2- ) in presence of Ni(II) ions at pH 9.0, and then extraction of the formed ternary complex into micellar phase of poly(ethyleneglycol-mono-p-nonylphenylether) (PONPE 7.5) before analysis by flame atomic absorption spectrometry (FAAS). The ultrasonic-assisted cloud point extraction (UA-CPE) has been used for the preconcentration of acrylamide in the samples prior to its FAAS detection. The matrix matched calibration curve is linear in range of 0.3-150µgkg -1 under optimal reagent conditions (1.75mL of 0.1molL -1 ammonia buffer at pH 9.0, 2.2mgL -1 Ni(II), 4.0×10 -4 molL -1 F 2- , 0.4% (w/v) NH 4 Cl and 0.7% (v/v) PONPE 7.5) with sensitivity enhancement of 160-fold. The proposed method has been validated by assessment of the following parameters; the limits of detection (LOD) and quantification (LOQ) (0.08µgkg -1 and 0.28µgkg -1 , respectively) with a relative standard deviation (RSD%) lower than 6.3%, and extractive recovery higher than 95% for acrylamide spiked at levels of 5 and 25µgkg -1 . The method was successfully applied to the indirect determination of acrylamide in the processed foods and two CRMs with satisfactory results. Copyright © 2016 Elsevier B.V. All rights reserved.

Comparison of cumulative dissipated energy delivered by active-fluidic pressure control phacoemulsification system versus gravity-fluidics.

PubMed

Gonzalez-Salinas, Roberto; Garza-Leon, Manuel; Saenz-de-Viteri, Manuel; Solis-S, Juan C; Gulias-Cañizo, Rosario; Quiroz-Mercado, Hugo

2017-08-22

To compare the cumulative dissipated energy (CDE), aspiration time and estimated aspiration fluid utilized during phacoemulsification cataract surgery using two phacoemulsification systems . A total of 164 consecutive eyes of 164 patients undergoing cataract surgery, 82 in the active-fluidics group and 82 in the gravity-fluidics group were enrolled in this study. Cataracts graded NII to NIII using LOCS II were included. Each subject was randomly assigned to one of the two platforms with a specific configuration: the active-fluidics Centurion ® phacoemulsification system or the gravity-fluidics Infiniti ® Vision System. CDE, aspiration time (AT) and the mean estimated aspiration fluid (EAF) were registered and compared. A mean age of 68.3 ± 9.8 years was found (range 57-92 years), and no significant difference was evident between both groups. A positive correlation between the CDE values obtained by both platforms was verified (r = 0.271, R 2  = 0.073, P = 0.013). Similarly, a significant correlation was evidenced for the EAF (r = 0.334, R 2  = 0.112, P = 0.046) and AT values (r = 0.156, R 2  = 0.024, P = 0.161). A statistically significantly lower CDE count, aspiration time and estimated fluid were obtained using the active-fluidics configuration when compared to the gravity-fluidics configuration by 19.29, 12.10 and 9.29%, respectively (P = 0.001, P < 0.0001 and P = 0.001). The active-fluidics Centurion ® phacoemulsification system achieved higher surgical efficiency than the gravity-fluidics Infiniti ® IP system for NII and NIII cataracts.

Magnetic quantum tunneling: key insights from multi-dimensional high-field EPR.

PubMed

Lawrence, J; Yang, E-C; Hendrickson, D N; Hill, S

2009-08-21

Multi-dimensional high-field/frequency electron paramagnetic resonance (HFEPR) spectroscopy is performed on single-crystals of the high-symmetry spin S = 4 tetranuclear single-molecule magnet (SMM) [Ni(hmp)(dmb)Cl](4), where hmp(-) is the anion of 2-hydroxymethylpyridine and dmb is 3,3-dimethyl-1-butanol. Measurements performed as a function of the applied magnetic field strength and its orientation within the hard-plane reveal the four-fold behavior associated with the fourth order transverse zero-field splitting (ZFS) interaction, (1/2)B(S + S), within the framework of a rigid spin approximation (with S = 4). This ZFS interaction mixes the m(s) = +/-4 ground states in second order of perturbation, generating a sizeable (12 MHz) tunnel splitting, which explains the fast magnetic quantum tunneling in this SMM. Meanwhile, multi-frequency measurements performed with the field parallel to the easy-axis reveal HFEPR transitions associated with excited spin multiplets (S < 4). Analysis of the temperature dependence of the intensities of these transitions enables determination of the isotropic Heisenberg exchange constant, J = -6.0 cm(-1), which couples the four spin s = 1 Ni(II) ions within the cluster, as well as a characterization of the ZFS within excited states. The combined experimental studies support recent work indicating that the fourth order anisotropy associated with the S = 4 state originates from second order ZFS interactions associated with the individual Ni(II) centers, but only as a result of higher-order processes that occur via S-mixing between the ground state and higher-lying (S < 4) spin multiplets. We argue that this S-mixing plays an important role in the low-temperature quantum dynamics associated with many other well known SMMs.

Spectral studies, thermal investigation and biological activity of some metal complexes derived from (E)-N‧-(1-(4-aminophenyl)ethylidene)morpholine-4-carbothiohydrazide

NASA Astrophysics Data System (ADS)

El-Samanody, El-Sayed A.; Polis, Magdy W.; Emara, Esam M.

2017-09-01

A new series of biologically active Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) complexes derived from the novel thiosemicarbazone ligand; (E)-N‧-(1-(4-aminophenyl)ethylidene)morpholine-4-carbothiohydrazide (HL) were synthesized. The mode of bonding of the ligand and the geometrical structures of its metal complexes were achieved by different analytical and spectral methods. The ligand coordinated with metal ions in a neutral bidentate fashion through the thione sulfur and azomethine nitrogen atoms. All metal complexes adopted octahedral geometry, except Cu(II) complexes (3, 6, 7) which have a square planar structure. The general thermal decomposition pathways of the ligand along with its metal complexes were explained. The thermal stability of the complexes is controlled by the number of outer and inner sphere water molecules, ionic radii and the steric hindrance. The activation thermodynamic parameters; (activation energy (E*), enthalpy of activation (ΔH*), entropy of activation (ΔS*) and Gibbs free energy (ΔG*)) along with order of reaction (n) were estimated from DTG curves. The ESR spectra of Cu(II) complexes indicated that (dx2-y2)1 is the ground state with covalence character of metal-ligand bonds. The molluscicidal and biochemical effects of the ligand and its Ni(II); Cu(II) complexes (2; 3, 5, 7) along with their combinations with metaldehyde were screened in vitro on the mucous gland of Eobania vermiculata. The tested compounds exhibited a significant toxicity against the tested animals and have almost the same toxic effect of metaldehyde which increases the mucous secretion of the snails and leads to death.

Neutral Ni(II), Pd(II) and Pt(II) ONS-pincer complexes of 5-acetylbarbituric-4N-dimethylthiosemicarbazone: synthesis, characterization and properties.

PubMed

Castiñeiras, Alfonso; Fernández-Hermida, Nuria; García-Santos, Isabel; Gómez-Rodríguez, Lourdes

2012-11-21

Octahedral 1:1 Ni(II) and square-planar 1:1 Pd(II) and Pt(II) complexes of formulae [Ni(HAcb4DM)(AcO)(H2O)2]·H2O (1), [Pd(HAcb4DM)Cl]·5H2O (2) and [Pt(HAcb4DM)Cl]·3H2O (3), where H2Acb4DM = 5-acetylbarbituric-4N-dimethylthiosemicarbazone (H2 denoting its two dissociable protons, one enolic and one thiolic), have been synthesized and characterized by elemental analysis and by 1H and 13C NMR, UV-vis, and IR spectroscopy. Crystallisation of compounds 1–3 from DMSO afforded complexes of formulae [Ni(HAcb4DM)2]·2H2O (1a), [Pd(Acb4DM)(DMSO)]·DMSO (2a) and [Pt(Acb4DM)(DMSO)]·DMSO (3a), the molecular and crystal structures of which were determined by X-ray diffractometry. The thiosemicarbazone in 1a coordinates to the metal ions in an ONS-tridentate manner in the O-enolate/S-thione form, but in complexes 2a and 3a the thiosemicarbazone binds Pd(II) or Pt(II) as an ONS-pincer ligand in the O-enolate/S-thiolate form. The 195Pt NMR spectrum of 3 shows a signal at −2950 ppm along with two new signals at −3348 and −2731 ppm, indicating the presence of solvolysis products. The catalytic activity of complex 2a has been explored in aryl–aryl Suzuki cross-coupling reactions. H2Acb4DM and complexes 2 and 3 were screened for in vitro cytotoxicity against a human tumour cell line (HeLa-229), with the clinically employed drug cisplatin as a reference.

Synthesis, spectroscopic characterization, electrochemistry and biological evaluation of some metal (II) complexes with ONO donor ligand containing benzo[b]thiophene and coumarin moieties

NASA Astrophysics Data System (ADS)

Mahendra Raj, K.; Mruthyunjayaswamy, B. H. M.

2014-09-01

Schiff base ligand 3-chloro-N‧-((7-hydroxy-4-methyl-2-oxo-2H-chromen-8-yl)methylene)benzo[b]thiophene-2-carbohydrazide and its Cu(II), Co(II), Ni(II) and Zn(II) complexes were synthesized, characterized by elemental analysis and various physico-chemical techniques like, IR, 1H NMR, ESI-mass, UV-Visible, thermogravimetry - differential thermal analysis, magnetic measurements and molar conductance. Spectral analysis indicates octahedral geometry for all the complexes. Cu(II) complex have 1:1 stoichiometry of the type [M(L)(Cl)(H2O)2], whereas Co(II), Ni(II) and Zn(II) complexes have 1:2 stoichiometric ratio of the type [M(L)2]. The bonding sites are the oxygen atom of amide carbonyl, nitrogen of azomethine function and phenolic oxygen of the Schiff base ligand via deprotonation. The thermogravimetry - differential thermal analysis studies gave evidence for the presence of coordinated water molecules in the composition of Cu(II) complex which was further supported by IR measurements. All the complexes were investigated for their electrochemical activity, but only the Cu(II) complex showed the redox property. In order to evaluate the effect of antimicrobial potency of metal ions upon chelation, ligand and its metal complexes along with their respective metal chlorides were screened for their antibacterial and antifungal activities by minimum inhibitory concentration (MIC) method. The results showed that the metal complexes were found to be more active than free ligand. Ligand and its complexes were screened for free radical scavenging activity by DPPH method and DNA cleavage activity using Calf-thymus DNA (Cat. No-105850).

Synthesis, spectroscopic characterization, electrochemistry and biological evaluation of some binuclear transition metal complexes of bicompartmental ONO donor ligands containing benzo[b]thiophene moiety

NASA Astrophysics Data System (ADS)

Mahendra Raj, K.; Vivekanand, B.; Nagesh, G. Y.; Mruthyunjayaswamy, B. H. M.

2014-02-01

A series of new binucleating Cu(II), Co(II), Ni(II) and Zn(II) complexes of bicompartmental ligands with ONO donor were synthesized. The ligands were obtained by the condensation of 3-chloro-6-substituted benzo[b]thiophene-2-carbohydrazides and 4,6-diacetylresorcinol. The synthesized ligands and their complexes were characterized by elemental analysis and various spectroscopic techniques. Elemental analysis, IR, 1H NMR, ESI-mass, UV-Visible, TG-DTA, magnetic measurements, molar conductance and powder-XRD data has been used to elucidate their structures. The bonding sites are the oxygen atom of amide carbonyl, azomethine nitrogen and phenolic oxygen for ligands 1 and 2. The binuclear nature of the complexes was confirmed by ESR spectral data. TG-DTA studies for some complexes showed the presence of coordinated water molecules and the final product is the metal oxide. All the complexes were investigated for their electrochemical activity, only the Cu(II) complexes showed the redox property. Cu(II) complexes were square planar, whereas Co(II), Ni(II) and Zn(II) complexes were octahedral. Powder-XRD pattern have been studied in order to test the degree of crystallinity of the complexes and unit cell calculations were made. In order to evaluate the effect of antimicrobial activity of metal ions upon chelation, both the ligands and their metal complexes were screened for their antibacterial and antifungal activities by minimum inhibitory concentration (MIC) method. The results showed that the metal complexes were found to be more active than free ligands. The DNA cleaving capacities of all the complexes were analyzed by agarose gel electrophoresis method against supercoiled plasmid DNA. Among the compounds tested for antioxidant capacity, ligand 1 displayed excellent activity than its metal complexes.

Spectroscopic characteristic (FT-IR, 1H, 13C NMR and UV-Vis) and theoretical calculations (MEP, DOS, HOMO-LUMO, PES, NBO analysis and keto-enol tautomerism) of new tetradentate N,N‧-bis(4-hydroxysalicylidene)-1,4-phenylenediamine ligand as chelating agent for the synthesis of dinuclear Co(II), Ni(II), Cu(II) and Zn(II) complexes

NASA Astrophysics Data System (ADS)

Rajaei, Iman; Mirsattari, Seyed Nezamoddin

2018-07-01

The synthesis and characterization of a novel symmetrical Schiff base ligand N,Nʹ-bis(4-hydroxysalicylidene)-1,4-phenylenediamine (BHSP) was presented in this study and characterized by FT-IR, NMR (1H and 13C) and UV-Vis spectroscopy experimentally and theoretically. Also a series of binuclear Co(II), Ni(II), Cu(II) and Zn(II) complexes of BHSP ligand have been synthesized by conventional sequential route in 1:1 equivalent of L:M ratio and characterized by routine physicochemical characterizations. The molecular geometry and vibrational frequencies of the BHSP in the ground state were calculated by using density functional theory (DFT) B3LYP method invoking 6-31G(d,p) and 6-31++G(d,p) basis sets. To study different conformations of the molecule, potential energy surface (PES) scan investigations were performed. The energetic behavior of the ligand compound (BHSP) in solvent media has been examined using B3LYP method with the 6-31G(d,p) and 6-31++G(d,p) basis sets by applying the polarized continuum model (PCM). In addition, DFT calculations of the BHSP ligand, molecular electrostatic potential (MEP), contour map, natural bond orbital (NBO) analysis, frontier molecular orbitals (FMO) analysis, NMR analysis and TD-DFT calculations were conducted. The calculated properties are in agreement with the available experimental data and closely related molecule BSP. The calculated results show that the optimized geometry can well reproduce the crystal structural parameters.

Improvement of oxygen-containing functional groups on olive stones activated carbon by ozone and nitric acid for heavy metals removal from aqueous phase.

PubMed

Bohli, Thouraya; Ouederni, Abdelmottaleb

2016-08-01

Recently, modification of surface structure of activated carbons in order to improve their adsorption performance toward especial pollutants has gained great interest. Oxygen-containing functional groups have been devoted as the main responsible for heavy metal binding on the activated carbon surface; their introduction or enhancement needs specific modification and impregnation methods. In the present work, olive stones activated carbon (COSAC) undergoes surface modifications in gaseous phase using ozone (O3) and in liquid phase using nitric acid (HNO3). The activated carbon samples were characterized using N2 adsorption-desorption isotherm, SEM, pHpzc, FTIR, and Boehm titration. The activated carbon parent (COSAC) has a high surface area of 1194 m(2)/g and shows a predominantly microporous structure. Oxidation treatments with nitric acid and ozone show a decrease in both specific surface area and micropore volumes, whereas these acidic treatments have led to a fixation of high amount of surface oxygen functional groups, thus making the carbon surface more hydrophilic. Activated carbon samples were used as an adsorbent matrix for the removal of Co(II), Ni(II), and Cu(II) heavy metal ions from aqueous solutions. Adsorption isotherms were obtained at 30 °C, and the data are well fitted to the Redlich-Peterson and Langmuir equation. Results show that oxidized COSACs, especially COSAC(HNO3), are capable to remove more Co(II), Cu(II), and Ni(II) from aqueous solution. Nitric acid-oxidized olive stones activated carbon was tested in its ability to remove metal ions from binary systems and results show an important maximum adsorbed amount as compared to single systems.

Interaction with biomacromolecules and antiproliferative activities of Mn(II), Ni(II), Zn(II) complexes of demethylcantharate and 2,2'-bipyridine

NASA Astrophysics Data System (ADS)

Zhang, Fan; Lin, Qiu-Yue; Hu, Wan-Li; Song, Wen-Ji; Shen, Shu-Ting; Gui, Pan

2013-06-01

Three new transition metal complexes [Mn2(DCA)2(bipy)2]·5H2O (1), [M2(DCA)2(bipy)2(H2O)]·10H2O(M = Ni(II)(2);Zn(II)(3)), (DCA = demethylcantharate, 7-oxabicyclo[2,2,1]heptane-2,3-dicarboxylate, C8H8O5) were synthesized and characterized by elemental analysis, molar conductance, infrared spectra and X-ray diffraction techniques. Each metal ion was six-coordinated in complexes. Complex 1 has a Mn2O2 center. Complexes 2 and 3 have asymmetric binuclear structure. Great amount of intermolecular hydrogen-bonding and π-π* stacking interactions were formed in these complex structures. The DNA-binding properties of complexes were investigated by electronic absorption spectra and viscosity measurements. The DNA binding constants Kb/(L mol-1) were 1.71 × 104 (1), 2.62 × 104 (2) and 1.59 × 104 (3) at 298 K. The complexes could quench the intrinsic fluorescence of bovine serum albumin (BSA) strongly through static quenching. The protein binding constants Ka/(L mol-1) were 7.27 × 104 (1), 4.55 × 104 (2) and 7.87 × 104 L mol-1 (3) and binding site was one. The complexes bind more tightly with DNA and BSA than with ligands. Complexes 1 and 3 had stronger inhibition ratios than Na2(DCA) against human hepatoma cells (SMMC-7721) lines and human gastric cancer cells (MGC80-3) lines in vitro. Complex 3 showed the strongest antiproliferative activity against SMMC-7721 (IC50 = 29.46 ± 2.12 μmol L-1) and MGC80-3 (IC50 = 27.02 ± 2.38 μmol L-1), which shows potential in anti-cancer drug development.

Preparation, spectral, X-ray powder diffraction and computational studies and genotoxic properties of new azo-azomethine metal chelates

NASA Astrophysics Data System (ADS)

Bitmez, Şirin; Sayin, Koray; Avar, Bariş; Köse, Muhammet; Kayraldız, Ahmet; Kurtoğlu, Mükerrem

2014-11-01

A new tridentate azo-azomethine ligand, N‧-[{2-hydroxy-5-[(4-nitrophenyl)diazenyl]phenyl}methylidene]benzohydrazidemonohydrate, (sbH·H2O) (1), is prepared by condensation of benzohydrazide and 2-hydroxy-5-[(4-nitrophenyl)diazenyl]benzaldehyde (a) with treatment of a solution of diazonium salt of p-nitroaniline and 2-hydroxybenzaldehyde in EtOH. The five coordination compounds, [Co(sb)2]·4H2O (2), [Ni(sb)2]·H2O (3), [Cu(sb)2]·4H2O (4), [Zn(sb)2]·H2O (5) and [Cd(sb)2]·H2O (6) are prepared by reacting the Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) ions with the ligand. The structures of the compounds are elucidated from the elemental analyses data and spectroscopic studies. It is found the ligand acts as a tridentate bending through phenolic and carbonyl oxygens and nitrogen atom of the Cdbnd Nsbnd group similar to the most of salicylaldimines. Comparison of the infrared spectra of the ligand and its metal complexes confirm that azo-Schiff base behaves as a monobasic tridentate ligand towards the central metal ion with an ONO donor sequence. Upon complexation with the ligand, the Cd(II), and Zn(II) ions form monoclinic structures, while Co(II), Cu(II) and Ni(II) ions form orthorhombic structures. Quantum chemical calculations are performed on tautomers and its metal chelates by using DFT/B3LYP method. Most stable tautomer is determined as tautomer (1a). The geometrical parameters of its metal chelates are obtained as theoretically. The NLO properties of tautomer (1a) and its metal complexes are investigated. Finally, the ligand and its metal complexes are assessed for their genotoxicity.

PdNi- and Pd-coated electrodes prepared by electrodeposition from ionic liquid for nonenzymatic electrochemical determination of ethanol and glucose in alkaline media.

PubMed

Huang, Hsin-Yi; Chen, Po-Yu

2010-12-15

Nonenzymatic electrochemical determination of ethanol and glucose was respectively achieved using PdNi- and Pd-coated electrodes prepared by electrodeposition from the novel metal-free ionic liquid (IL); N-butyl-N-methylpyrrolidinium dicyanamide (BMP-DCA). BMP-DCA provided an excellent environment and wide cathodic limit for electrodeposition of metals and alloys because many metal chlorides could dissolve in this IL where the reduction potentials of Pd(II) and Ni(II) indeed overlapped, leading to the convenience of potentiostatic codeposition. In aqueous solutions, the reduction potentials of Pd(II) and Ni(II) are considerably separated. The bimetallic PdNi coatings with atomic ratios of ∼ 80/20 showed the highest current for ethanol oxidation reaction (EOR). Ethanol was detected by either cyclic voltammetry (CV) or hydrodynamic amperometry (HA). Using CV, the dependence of EOR peak current on concentration was linear from 4.92 to 962 μM with a detection limit of 2.26 μM (σ=3), and a linearity was observed from 4.92 to 988 μM using HA (detection limit 0.83 μM (σ=3)). The Pd-coated electrodes prepared by electrodeposition from BMP-DCA showed electrocatalytic activity to glucose oxidation and CV, HA, and square-wave voltammetry (SWV) were employed to determine glucose. SWV showed the best sensitivity and linearity was observed from 2.86 μM to 107 μM, and from 2.99 mM to 10.88 mM with detection limits of 0.78 μM and 25.9 μM (σ=3), respectively. For glucose detection, the interference produced from ascorbic acid, uric acid, and acetaminophen was significantly suppressed, compared with a regular Pt disk electrode. Copyright © 2010 Elsevier B.V. All rights reserved.

Melhoramentos no código Wilson-Devinney para binárias eclipsantes

NASA Astrophysics Data System (ADS)

Vieira, L. A.; Vaz, L. P. R.

2003-08-01

A análise de curvas de luz e velocidades radiais de sistemas binários eclipsantes pode ser feita por meio de vários modelos. Um desses é o Modelo Wilson-Devinney (WD). Ao longo dos anos, esse modelo sofreu várias alterações em seus códigos principais, com a finalidade de torná-lo mais consistente tanto fíisica como numericamente. O Modelo WD tem sido melhorado de várias maneiras em seus dois códigos: um para a predição das curvas de luz teórica e de velocidade radiais e outra para as soluções destas curvas. Teoricamente, na física do modelo, nós introduzimos a possibilidade de levar em conta os efeitos do movimento apsidal. Numericamente, nós introduzimos a possibilidade de usar o Método SIMPLEX no procedimento da solução, como uma alternativa para o já implementado Método de Mínimos Quadrados (Least Squares Method). Estas modificações, juntamente com outras já introduzidas pelo nosso grupo anteriormente, tornam o código mais eficiente na solução das curvas de luz e de velocidade radiais de binárias eclipsantes. Como o modelo tem sido usado para analisar sistemas com componentes pré-sequência principal (TY CrA, Casey et al. 1998, Vaz et al. 1998), SM 790, Stassun et al. 2003), este melhoramento beneficiará estes casos também. Apresentamos os resultados obtidos com a modificação do código WD por meio do uso de dados da estrela GL Carinae, comprovando, (1) que os parâmetros orbitais calculados por nós são coerentes com os obtidos anteriormente na literatura (Giménez & Clausen, 1986) e com os obtidos por Faria (1987), e (2) que a implementação do Método SIMPLEX torna o código mais lento mas completamente consistente internamente e evita os problemas gerados pelo uso do Método de Mínimos Quadrados, tais como imprecisão no cálculo das derivadas parciais e convergência para mínimos locais.

Are probiotics effective to prevent traveler’s diarrhea?

PubMed

Pinos, Yazmín; Castro-Gutiérrez, Victoria; Rada, Gabriel

2016-12-23

La diarrea aguda es la enfermedad más común que afecta a los viajeros, principalmente aquellos que se dirigen a regiones de alto riesgo. El uso de probióticos podría prevenir su aparición, sin embargo, los datos que apoyan su uso no son consistentes y no se recomiendan en las guías clínicas actuales. Utilizando la base de datos Epistemonikos, la cual es mantenida mediante búsquedas en múltiples bases de datos, identificamos cuatro revisiones sistemáticas que en conjunto incluyen siete estudios aleatorizados pertinentes a esta pregunta. Realizamos un metanálisis y tablas de resumen de los resultados utilizando el método GRADE. Concluimos que los probióticos podrían prevenir la diarrea del viajero, pero la certeza de la evidencia es baja.

Synthesis and characterization of Ni(II) complex with 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradeca-7,14-dienium bromide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yusoff, Latifah M.; Yusoff, Siti Fairus M.; Ismail, Wafiuddin

Nickel(II) complex have been synthesized by treating a 14-membered ring tetraaza macrocyclic compound, 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradeca-7,14-dienium, bromide (Me{sub 6}N{sub 4}H{sub 4})Br{sub 2} with nickel acetate in metanol. The complex was characterized using elemental analysis, Fourier Transform Infrared (FTIR), Ultraviolet-Visible (UV-Vis), and single crystal diffraction (X-ray). The nickel atom coordinates through four nitrogen atoms in the ligand. Square planar geometry has been proposed for this complex.

A novel coumarin Schiff-base as a Ni(II) ion colorimetric sensor

NASA Astrophysics Data System (ADS)

Wang, Lingyun; Ye, Decheng; Cao, Derong

2012-05-01

A novel coumarin Schiff base compound (L) prepared from 7-diethylaminocoumarin-3-aldehyde and 3-amino-7-hydroxycoumarin was synthesized and evaluated as a chemoselective Ni2+ sensor. Addition of Ni2+ to CH3CN solution of L resulted in a rapid color change from yellow to red together with a large red shift from 465 to 516 nm. Moreover, other common alkali-, alkaline earth-, transition- and rare earth metal ions induced no or minimal spectral changes. Experimental results indicated that L could be used as a potential Ni2+ colorimetric and naked-eye chemosensor in CH3CN solution.

Mesoporous Silica Nanoparticles as an Adsorbent for Preconcentration and Determination of Trace Amount of Nickel in Environmental Samples by Atom Trap Flame Atomic Absorption Spectrometry

NASA Astrophysics Data System (ADS)

Shirkhanloo, H.; Falahnejad, M.; Zavvar Mousavi, H.

2016-01-01

A rapid enrichment method based on solid-phase extraction (SPE) has been established for preconcentration and separation of trace Ni(II) ions in water samples prior to their determination by atom trap flame atomic absorption spectrometry. A column filled with bulky NH2-UVM7 was used as the novel adsorbent. Under optimal conditions, the linear range, limit of detection (LOD), and preconcentration factor (PF) were 3-92 μg/L, 0.8 μg/L, and 100, respectively. The validity of the method was checked by the standard reference material.

Synthesis, characterization, crystal structure and DNA-binding studies of transition metal hydrazone complexes

NASA Astrophysics Data System (ADS)

Kanchanadevi, S.; Parveen, S.; Mahalingam, V.

2018-04-01

Three new complexes containing salicylaldazine (HL) ligand were synthesised by reacting suitable precursor complex [MCl2(PPh3)2] with the ligand (where M = Cu(II) or Ni(II) or Co(II)). The new complexes were characterised by various spectral studies such as IR, UV-Vis,1H NMR,EPR,fluorescence and elemental analyses. The binding modes of the complexes with HS-DNA have been studied by UV-Vis absorption titration. Binding of the complexes with bovine serum albumin (BSA) protein has been investigated using UV-visible, fluorescence and synchronous fluorescence spectroscopic methods. Redox behaviour of the complexes has been investigated by cyclic voltammetry.

Advanced asymmetric synthesis of (1R,2S)-1-amino-2-vinylcyclopropanecarboxylic acid by alkylation/cyclization of newly designed axially chiral Ni(II) complex of glycine Schiff base.

PubMed

Kawashima, Aki; Shu, Shuangjie; Takeda, Ryosuke; Kawamura, Akie; Sato, Tatsunori; Moriwaki, Hiroki; Wang, Jiang; Izawa, Kunisuke; Aceña, José Luis; Soloshonok, Vadim A; Liu, Hong

2016-04-01

Asymmetric synthesis of (1R,2S)-1-amino-2-vinylcyclopropanecarboxylic acid (vinyl-ACCA) is in extremely high demand due to the pharmaceutical importance of this tailor-made, sterically constrained α-amino acid. Here we report the development of an advanced procedure for preparation of the target amino acid via two-step SN2 and SN2' alkylation of novel axially chiral nucleophilic glycine equivalent. Excellent yields and diastereoselectivity coupled with reliable and easy scalability render this method of immediate use for practical synthesis of (1R,2S)-vinyl-ACCA.

Studies on Some Biologically Cobalt(II), Copper(II) and Zinc(II) Complexes With ONO, NNO and SNO Donor Pyrazinoylhydrazine-Derived Ligands

PubMed Central

Praveen, Marapaka; Sherazi, Syed K. A.

1998-01-01

Biologically active complexes of Co(II), Ni(II), Cu(II) and Zn(II) with novel ONO, NNO and SNO donor pyrazinoylhydrazine-derived compounds have been prepared and characterized on the basis of analytical data and various physicochemical studies. Distorted octahedral structures for all the complexes have been proposed. The synthesized ligands and their complexes have been screened for their antibacterial activity against bacterial species Escherichia coli, Pseudomonas aeruginosa, Staphylococcus aureus and Klebsiella pneumonae. The activity data show the metal complexes to be more active than the parent free ligands against one or more bacterial species. PMID:18475857

Estudo de não gaussianidade nas anisotropias da RCF medidas Wmap

NASA Astrophysics Data System (ADS)

Andrade, A. P. A.; Wuensche, C. A.; Ribeiro, A. L. B.

2003-08-01

A investigação do campo de flutuações da Radiação Cósmica de Fundo (RCF) pode oferecer um importante teste para os modelos cosmológicos que descrevem a origem e a evolução das flutuações primordiais. De um lado, apresenta-se o modelo inflacionário que prevê um espectro de flutuações adiabáticas distribuídas segundo uma gaussiana e, de outro, os modelos de defeitos topológicos (dentre outros) que descrevem um mecanismo para a geração de flutuações de isocurvatura que obedecem a uma distribuição não gaussiana. Este trabalho tem como objetivo caracterizar traços do modelo não gaussiano de campo misto (entre flutuações adiabáticas e de isocurvatura) nos mapas do Wilkinson Microwave Anisotropy Probe (WMAP). Simulações das anisotropias da RCF no contexto de mistura indicam traços marcantes na distribuição das flutuações de temperatura, mesmo quando consideradas pequenas contribuições do campo de isocurvatura (da ordem de 0.001). O efeito da mistura entre os campos resulta na transferência de potência de flutuações em escalas angulares intermediárias para flutuações em pequenas escalas angulares. Este efeito pode ser caracterizado pela relação entre as amplitudes dos primeiros picos acústicos no espectro de potência da RCF. Neste trabalho, investigamos a contribuição do campo de isocurvatura, no contexto de mistura, sobre as observações recentes da RCF realizadas pelo WMAP. As previsões do modelo de campo misto, uma vez confrontadas com as observações em pequenas escalas angulares, podem ajudar a revelar a natureza das flutuações primordiais.

Readiness to tackle chronicity in Spanish health care organisations: a two-year experience with the Instrumento de Evaluación de Modelos de Atención ante la Cronicidad/Assessment of Readiness for Chronicity in Health Care Organisations instrument

PubMed Central

Mira, José Joaquín; Fernández-Cano, Paloma; Contel, Joan Carlos; Guilabert-Mora, Mercedes; Solas-Gaspar, Olga

2015-01-01

Introduction: The Instrumento de Evaluación de Modelos de Atención ante la Cronicidad/Assessment of Readiness for Chronicity in Health Care Organisations instrument was developed to implement the conceptual framework of the Chronic Care Model in the Spanish national health system. It has been used to assess readiness to tackle chronicity in health care organisations. In this study, we use self-assessments at macro-, meso- and micro-management levels to (a) describe the two-year experience with the Instrumento de Evaluación de Modelos de Atención ante la Cronicidad/Assessment of Readiness for Chronicity in Health Care Organisations tool in Spain and (b) assess the validity and reliability of this instrument. Methods: The results from 55 organisational self-assessments were included and described. In addition to that, the internal consistency, reliability and construct validity of Instrumento de Evaluación de Modelos de Atención ante la Cronicidad/Assessment of Readiness for Chronicity in Health Care Organisations were examined using Cronbach's alpha, the Spearman–Brown coefficient and factorial analysis. Results: The obtained scores reflect opportunities for improvement in all dimensions of the instrument. Cronbach's alpha ranged between 0.90 and 0.95 and the Spearman–Brown coefficient ranged between 0.77 and 0.94. All 27 components converged in a second-order factorial solution that explained 53.8% of the total variance, with factorial saturations for the components of between 0.57 and 0.94. Conclusions: Instrumento de Evaluación de Modelos de Atención ante la Cronicidad/Assessment of Readiness for Chronicity in Health Care Organisations is an instrument that allows health care organisations to perform self-assessments regarding their readiness to tackle chronicity and to identify areas for improvement in chronic care. PMID:27118958

Readiness to tackle chronicity in Spanish health care organisations: a two-year experience with the Instrumento de Evaluación de Modelos de Atención ante la Cronicidad/Assessment of Readiness for Chronicity in Health Care Organisations instrument.

PubMed

Mira, José Joaquín; Nuño-Solinís, Roberto; Fernández-Cano, Paloma; Contel, Joan Carlos; Guilabert-Mora, Mercedes; Solas-Gaspar, Olga

2015-01-01

The Instrumento de Evaluación de Modelos de Atención ante la Cronicidad/Assessment of Readiness for Chronicity in Health Care Organisations instrument was developed to implement the conceptual framework of the Chronic Care Model in the Spanish national health system. It has been used to assess readiness to tackle chronicity in health care organisations. In this study, we use self-assessments at macro-, meso- and micro-management levels to (a) describe the two-year experience with the Instrumento de Evaluación de Modelos de Atención ante la Cronicidad/Assessment of Readiness for Chronicity in Health Care Organisations tool in Spain and (b) assess the validity and reliability of this instrument. The results from 55 organisational self-assessments were included and described. In addition to that, the internal consistency, reliability and construct validity of Instrumento de Evaluación de Modelos de Atención ante la Cronicidad/Assessment of Readiness for Chronicity in Health Care Organisations were examined using Cronbach's alpha, the Spearman-Brown coefficient and factorial analysis. The obtained scores reflect opportunities for improvement in all dimensions of the instrument. Cronbach's alpha ranged between 0.90 and 0.95 and the Spearman-Brown coefficient ranged between 0.77 and 0.94. All 27 components converged in a second-order factorial solution that explained 53.8% of the total variance, with factorial saturations for the components of between 0.57 and 0.94. Instrumento de Evaluación de Modelos de Atención ante la Cronicidad/Assessment of Readiness for Chronicity in Health Care Organisations is an instrument that allows health care organisations to perform self-assessments regarding their readiness to tackle chronicity and to identify areas for improvement in chronic care.

Epinephrine in cardiac arrest: systematic review and meta-analysis.

PubMed

Morales-Cané, Ignacio; Valverde-León, María Del Rocío; Rodríguez-Borrego, María Aurora

2016-12-08

evaluate the effectiveness of epinephrine used during cardiac arrest and its effect on the survival rates and neurological condition. systematic review of scientific literature with meta-analysis, using a random effects model. The following databases were used to research clinical trials and observational studies: Medline, Embase and Cochrane, from 2005 to 2015. when the Return of Spontaneous Circulation (ROSC) with administration of epinephrine was compared with ROSC without administration, increased rates were found with administration (OR 2.02. 95% CI 1.49 to 2.75; I2 = 95%). Meta-analysis showed an increase in survival to discharge or 30 days after administration of epinephrine (OR 1.23; 95% IC 1.05-1.44; I2=83%). Stratification by shockable and non-shockable rhythms showed an increase in survival for non-shockable rhythm (OR 1.52; 95% IC 1.29-1.78; I2=42%). When compared with delayed administration, the administration of epinephrine within 10 minutes showed an increased survival rate (OR 2.03; 95% IC 1.77-2.32; I2=0%). administration of epinephrine appears to increase the rate of ROSC, but when compared with other therapies, no positive effect was found on survival rates of patients with favorable neurological status. avaliar a efetividade da adrenalina na parada cardíaca e seu efeito na sobrevivência e no estado neurológico. revisão sistemática da literatura científica com meta-análise utilizando um modelo de efeitos aleatórios. Revisão em Medline, Embase e Cochrane, desde 2005 até 2015 de ensaios clínicos e estudos observacionais. observou-se aumento nas taxas de retorno de circulação espontânea com a administração de adrenalina (OR 2,02; 95% IC 1,49-2,75; I2=95%) comparadas com a não administração de adrenalina. A meta-análise mostrou um aumento da sobrevivência na alta ou depois de 30 dias da administração de adrenalina (OR 1,23; 95% IC 1,05-1,44; I2=83%). Quando estratificados por ritmos desfibrilháveis e não desfibrilháveis apareceu um aumento da sobrevivência nos ritmos não desfibrilháveis (OR 1,52; 95% IC 1,29-1,78; I2=42%). Também observou-se um incremento de sobrevivência na alta ou depois de 30 dias, quando administrada a adrenalina antes de 10 minutos, isto comparado com administração tardia (OR 2,03; 95% IC 1,77-2,32; I2=0%). a administração de adrenalina parece incrementar a taxa de retorno da circulação espontânea, mas não se tem encontrado um efeito positivo nas taxas de sobrevivência nem nas taxas de pacientes com estado neurológico favorável, em comparação com outras terapias. evaluar la efectividad de la adrenalina en el paro cardíaco y su efecto en la supervivencia y en el estado neurológico. revisión sistemática de la literatura científica con metaanálisis utilizando un modelo de efectos aleatorios. Revisión en Medline, Embase y Cochrane, desde 2005 hasta 2015, de ensayos clínicos y estudios observacionales. se observó aumento en las tasas de retorno de circulación espontánea cuando administrada adrenalina (OR 2,02; 95% IC 1,49-2,75; I2=95%) comparada con la no administración de adrenalina. El metaanálisis mostró un aumento de la supervivencia al alta hospitalaria o a los 30 días cuando administrada adrenalina (OR 1,23; 95% IC 1,05-1,44; I2=83%). La estratificación por ritmos desfibrilables y no desfibrilables mostró un aumento de la supervivencia en ritmos no desfibrilables (OR 1,52; 95% IC 1,29-1,78; I2=42%). También, se observó un incremento en la supervivencia al alta hospitalaria o a los 30 días en la administración de adrenalina antes de 10 minutos comparada con la administración tardía (OR 2,03; 95% IC 1,77-2,32; I2=0%). la administración de adrenalina parece incrementar la tasa de retorno de circulación espontánea, pero no se ha encontrado un efecto positivo en tasas de supervivencia ni en tasas de pacientes con estado neurológico favorable, en comparación con otras terapias.

Insight into the structure and mechanism of nickel-containing superoxide dismutase derived from peptide-based mimics.

PubMed

Shearer, Jason

2014-08-19

Nickel superoxide dismutase (NiSOD) is a nickel-containing metalloenzyme that catalyzes the disproportionation of superoxide through a ping-pong mechanism that relies on accessing reduced Ni(II) and oxidized Ni(III) oxidation states. NiSOD is the most recently discovered SOD. Unlike the other known SODs (MnSOD, FeSOD, and (CuZn)SOD), which utilize "typical" biological nitrogen and oxygen donors, NiSOD utilizes a rather unexpected ligand set. In the reduced Ni(II) oxidation state, NiSOD utilizes nitrogen ligands derived from the N-terminal amine and an amidate along with two cysteinates sulfur donors. These are unusual biological ligands, especially for an SOD: amine and amidate donors are underrepresented as biological ligands, whereas cysteinates are highly susceptible to oxidative damage. An axial histidine imidazole binds to nickel upon oxidation to Ni(III). This bond is long (2.3-2.6 Å) owing to a tight hydrogen-bonding network. All of the ligating residues to Ni(II) and Ni(III) are found within the first 6 residues from the NiSOD N-terminus. Thus, small nickel-containing metallopeptides derived from the first 6-12 residues of the NiSOD sequence can reproduce many of the properties of NiSOD itself. Using these nickel-containing metallopeptide-based NiSOD mimics, we have shown that the minimal sequence needed for nickel binding and reproduction of the structural, spectroscopic, and functional properties of NiSOD is H2N-HCXXPC. Insight into how NiSOD avoids oxidative damage has also been gained. Using small NiN2S2 complexes and metallopeptide-based mimics, it was shown that the unusual nitrogen donor atoms protect the cysteinates from oxidative damage (both one-electron oxidation and oxygen atom insertion reactions) by fine-tuning the electronic structure of the nickel center. Changing the nitrogen donor set to a bis-amidate or bis-amine nitrogen donor led to catalytically nonviable species owing to nickel-cysteinate bond oxidative damage. Only the amine/amidate nitrogen donor atoms within the NiSOD ligand set produce a catalytically viable species. These metallopeptide-based mimics have also hinted at the detailed mechanism of SOD catalysis by NiSOD. One such aspect is that the axial imidazole likely remains ligated to the Ni center under rapid catalytic conditions (i.e., high superoxide loads). This reduces the degree of structural rearrangement about the nickel center, leading to higher catalytic rates. Metallopeptide-based mimics have also shown that, although an axial ligand to Ni(III) is required for catalysis, the rates are highest when this is a weak interaction, suggesting a reason for the long axial His-Ni(III) bond found in NiSOD. These mimics have also suggested a surprising mechanistic insight: O2(-) reduction via a "H(•)" tunneling event from a R-S(H(+))-Ni(II) moiety to O2(-) is possible. The importance of this mechanism in NiSOD has not been verified.

Distribución espacial de órbitas con diferentes grados de caoticidad en modelos autoconsistentes de satélites galácticos

NASA Astrophysics Data System (ADS)

Muzzio, J. C.; Mosquera, M.

En trabajos anteriores (Carpintero et al., Cel. Mech. Dynam. Astron. 85, 247, 2003), mostramos que las órbitas caóticas son muy importantes en los satélites galácticos. Sin embargo, los únicos modelos autoconsistentes de los que se disponía para ellos eran los de Heggie-Ramamani, cuya función de distribución depende sólo de la energía por lo que no mostraban diferencias entre las distribuciones de sus órbitas regulares y caóticas. Ahora, mediante una aproximación cuadrupolar, hemos logrado construir modelos autoconsistentes de satélites galácticos con distribuciones de velocidades anisotrópicas (lo que indica que sus funciones de distribución no dependen sólo de la energía) y hemos logrado revelar las diferencias entre las estructuras espaciales de las órbitas de distinta caoticidad.

Uso Del Condón en Adolescentes Nahuas, un Modelo Explicativo.

PubMed

Tirado, María de Los Ángeles Meneses; Benavides-Torres, Raquel A; Navarro, Sergio Meneses; de la Colina, Juan Antonio Doncel; Rodríguez, Dora Julia Onofre; Hernández, Francisco Javier Baéz

2018-03-01

En México, la población indígena supera los siete millones de habitantes, en Puebla el grupo más representativo es el Náhuatl. Sin embargo, las condiciones de vida, salud, educación y transporte son precarias para esta población. En los adolescentes, las responsabilidades como el matrimonio, la familia y los compromisos ante la comunidad, favorecen conductas de riesgo sexual que dificultan su desarrollo económico, social y reproductivo. El objetivo fue proponer un modelo explicativo del uso del condón en adolescentes nahuas. Método. Bajo el marco de la teoría social cognitiva, el concepto de valores culturales de Leininger y el proceso de la sustracción teórica, se desarrolló este artículo. Se muestran las relaciones del modelo con las proposiciones y los factores que influyen en el uso del condón para este grupo específico. Finalmente, el modelo explica las variables de interés, los niveles de abstracción y las relaciones entre sí en el contexto náhuatl. El siguiente paso será implementar los indicadores empíricos para conocer el grado de influencia de los factores personales y ambientales hacia el uso del condón en adolescentes nahuas. Resultados que aportarán información para el desarrollo del conocimiento en enfermería y la reducción de riesgo sexual de esta población.

Biaxial seismic behaviour of reinforced concrete columns =

NASA Astrophysics Data System (ADS)

Rodrigues, Hugo Filipe Pinheiro

A analise dos efeitos dos sismos mostra que a investigacao em engenharia sismica deve dar especial atencao a avaliacao da vulnerabilidade das construcoes existentes, frequentemente desprovidas de adequada resistencia sismica tal como acontece em edificios de betao armado (BA) de muitas cidades em paises do sul da Europa, entre os quais Portugal. Sendo os pilares elementos estruturais fundamentais na resistencia sismica dos edificios, deve ser dada especial atencao a sua resposta sob acoes ciclicas. Acresce que o sismo e um tipo de acao cujos efeitos nos edificios exige a consideracao de duas componentes horizontais, o que tem exigencias mais severas nos pilares comparativamente a acao unidirecional. Assim, esta tese centra-se na avaliacao da resposta estrutural de pilares de betao armado sujeitos a acoes ciclicas horizontais biaxiais, em tres linhas principais. Em primeiro lugar desenvolveu-se uma campanha de ensaios para o estudo do comportamento ciclico uniaxial e biaxial de pilares de betao armado com esforco axial constante. Para tal foram construidas quatro series de pilares retangulares de betao armado (24 no total) com diferentes caracteristicas geometricas e quantidades de armadura longitudinal, tendo os pilares sido ensaiados para diferentes historias de carga. Os resultados experimentais obtidos sao analisados e discutidos dando particular atencao a evolucao do dano, a degradacao de rigidez e resistencia com o aumento das exigencias de deformacao, a energia dissipada, ao amortecimento viscoso equivalente; por fim e proposto um indice de dano para pilares solicitados biaxialmente. De seguida foram aplicadas diferentes estrategias de modelacao nao-linear para a representacao do comportamento biaxial dos pilares ensaiados, considerando nao-linearidade distribuida ao longo dos elementos ou concentrada nas extremidades dos mesmos. Os resultados obtidos com as varias estrategias de modelacao demonstraram representar adequadamente a resposta em termos das curvas envolventes forca-deslocamento, mas foram encontradas algumas dificuldades na representacao da degradacao de resistencia e na evolucao da energia dissipada. Por fim, e proposto um modelo global para a representacao do comportamento nao-linear em flexao de elementos de betao armado sujeitos a acoes biaxiais ciclicas. Este modelo tem por base um modelo uniaxial conhecido, combinado com uma funcao de interacao desenvolvida com base no modelo de Bouc- Wen. Esta funcao de interacao foi calibrada com recurso a tecnicas de otimizacao e usando resultados de uma serie de analises numericas com um modelo refinado. E ainda demonstrada a capacidade do modelo simplificado em reproduzir os resultados experimentais de ensaios biaxiais de pilares.

The Model of Optimization of Micro Energy; HOMER: El Modelo de Optimizacin de Micro energa (in Spanish)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Not Available

2004-05-01

HOMER, the model of optimization of micro energy, helps to disear systems out of the network and interconnected to the network. You can use HOMER to carry out the analysis to explore an extensive rank of questions of diseo. HOMER, el modelo de optimizacin de micro energa, le ayuda a disear sistemas fuera de la red e interconectados a la red. Usted puede usar HOMER para llevar a cabo el anlisis para explorar un amplio rango de preguntas de diseo.

Bis(diethylenetriamine-kappa3N)nickel(II) 5-amino-1,3,4-thiadiazole-2-sulfonamidate chloride monohydrate.

PubMed

Liu-Gonzalez, M; Sanz-Ruiz, F; Chufán, E E; Pedregosa, J C; Borras-Tortonda, J

2001-10-01

In the X-ray crystal structure of the title complex, [Ni(C(4)H(13)N(3))(2)](C(2)H(3)N(4)O(2)S(2))Cl.H(2)O, the coordination polyhedron is composed of non-centrosymmetric [Ni(diethylenetriamine)(2)](2+) cations in which the triamine ligands coordinate to the metal centre as tridentate ligands in a facial position. The Ni(II) ions are linked to six N atoms in an octahedral arrangement, slightly compressed in one extreme. The sulfonamide behaves as a counter-ion instead of as a ligand. Important information about the deprotonated sulfonamide group conformation has been obtained.

The Synthesis and Characterization of a Group of Transition Metal Octabutoxynaphthalocyanines and the Absorption and Emission Properties of the Co, Rh, Ir, Ni, Pd and Pt Members of This Group

PubMed Central

Kim, Junhwan; Soldatova, Alexandra V.; Rodgers, Michael A. J.; Kenney, Malcolm E.

2013-01-01

The synthesis and photophysical properties of new metallo-octabutoxynaphthalocyanines with Rh(III), Ir(III), and Pt(II) are reported. Various metals were inserted into the metal-free octabutoxynaphthalocyanine and the resultant metal complexes were fully characterized by NMR, UV-vis spectroscopy, and mass spectrometry. The absorption and emission properties of these new complexes were also examined and compared to those of Co(II), Ni(II), and Pd(II) octabutoxynaphthalocyanines. The results provide useful information to understand the effect of these transition metals on the properties of this macrocyclic ring. PMID:23745014

Electronic structure of transition metal-cysteine complexes from X-ray absorption spectroscopy.

PubMed

Leung, Bonnie O; Jalilehvand, Farideh; Szilagyi, Robert K

2008-04-17

The electronic structures of HgII, NiII, CrIII, and MoV complexes with cysteine were investigated by sulfur K-edge X-ray absorption near-edge structure (XANES) spectroscopy and density functional theory. The covalency in the metal-sulfur bond was determined by analyzing the intensities of the electric-dipole allowed pre-edge features appearing in the XANES spectra below the ionization threshold. Because of the well-defined structures of the selected cysteine complexes, the current work provides a reference set for further sulfur K-edge XAS studies of bioinorganic active sites with transition metal-sulfur bonds from cysteine residues as well as more complex coordination compounds with thiolate ligands.

Synthesis, crystal structures, molecular docking and urease inhibition studies of Ni(II) and Cu(II) Schiff base complexes

NASA Astrophysics Data System (ADS)

Sangeeta, S.; Ahmad, K.; Noorussabah, N.; Bharti, S.; Mishra, M. K.; Sharma, S. R.; Choudhary, M.

2018-03-01

[Ni(L)2] 1 and [Cu(L)2] 2 [HL = 2-((E)-(2-methoxyphenylimino)methyl)-4,6-dichlorophenol] Schiff base complexes have been successfully synthesized and were characterized by FT-IR, UV-Vis, fluorescence spectroscopy and thermogravimetric analysis. The crystal structures of the two complexes were determined through X-ray crystallography. Its inhibitory activity against Helicobacter pylori urease was evaluated in vitro and showed strong inhibitory activity against H. pylori urease compared with acetohydroxamic acid (IC50 = 42.12 μmolL-1), which is a positive reference. A docking analysis using the AutoDock 4.0 program could explain the inhibitory activity of the complex against urease.

Layered transition metal carboxylates: efficient reusable heterogeneous catalyst for epoxidation of olefins.

PubMed

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.

Synthesis, spectroscopic characterization and antimicrobial studies of Co(II), Ni(II), Cu(II) and Zn(II) complexes with Schiff bases derived from 5-bromo-salicylaldehyde

NASA Astrophysics Data System (ADS)

Kursunlu, Ahmed Nuri; Guler, Ersin; Sevgi, Fatih; Ozkalp, Birol

2013-09-01

In this study, the new Schiff base ligands derived from condensation of amine and 5-bromo-salicylaldehyde were characterized. All compounds, the Schiff bases and the metal complexes, were characterized by elemental analyzes, FT-IR, 1H NMR, 13C NMR and magnetic susceptibility measurements. The synthesized ligands, along with their metal (II) complexes, were screened for their in vitro antibacterial activity against four Gram-negative (Escherichia coli, Klebsiella pneumoniae, Pseudomonas aeruginosa and Salmonella enteritidis) and four Gram-positive (Streptococcus pyogones, Bacillus cereus, Staphylococcus aureus and Methicillin-resistant S. aureus) bacterial strains by using disc diffusion and broth microdilution techniques.

Assessment of Ni accumulation capability by fungi for a possible approach to remove metals from soils and waters.

PubMed

Cecchi, Grazia; Roccotiello, Enrica; Di Piazza, Simone; Riggi, Alex; Mariotti, Mauro Giorgio; Zotti, Mirca

2017-03-04

Abandoned industrial sites and mines may constitute possible hazards for surrounding environment due to the presence of toxic compounds that may contaminate soils and waters. The possibility to remove metal contaminants, specifically nickel (Ni), by means of fungi was presented exploiting a set of fungal strains isolated from a Ligurian dismissed mine. The achieved results demonstrate the high Ni(II) tolerance, up to 500 mg Ni l -1 , and removal capability of a Trichoderma harzianum strain. This latter hyperaccumulates up to 11,000 mg Ni kg -1 , suggesting its possible use in a bioremediation protocol able to provide a sustainable reclamation of broad contaminated areas.

Studies on magnetocaloric and magnetic coupling effects =

NASA Astrophysics Data System (ADS)

Amaral, Joao Cunha de Sequeira

O presente trabalho apresenta novas metodologias desenvolvidas para a analise das propriedades magneticas e magnetocaloricas de materiais, sustentadas em consideracoes teoricas a partir de modelos, nomeadamente a teoria de transicoes de fase de Landau, o modelo de campo medio molecular e a teoria de fenomeno critico. Sao propostos novos metodos de escala, permitindo a interpretacao de dados de magnetizacao de materiais numa perspectiva de campo medio molecular ou teoria de fenomeno critico. E apresentado um metodo de estimar a magnetizacao espontanea de um material ferromagnetico a partir de relacoes entropia/magnetizacao estabelecidas pelo modelo de campo medio molecular. A termodinamica das transicoes de fase magneticas de primeira ordem e estudada usando a teoria de Landau e de campo medio molecular (modelo de Bean-Rodbell), avaliando os efeitos de fenomenos fora de equilibrio e de condicoes de mistura de fase em estimativas do efeito magnetocalorico a partir de medidas magneticas. Efeitos de desordem, interpretados como uma distribuicao na interaccao magnetica entre ioes, estabelecem os efeitos de distribuicoes quimicas/estruturais nas propriedades magneticas e magnetocaloricas de materiais com transicoes de fase de segunda e de primeira ordem. O uso das metodologias apresentadas na interpretacao das propriedades magneticas de variados materiais ferromagneticos permitiu obter: 1) uma analise quantitativa da variacao de spin por iao Gadolinio devido a transicao estrutural do composto Gd5Si2Ge2, 2) a descricao da configuracao de cluster magnetico de ioes Mn na fase ferromagnetica em manganites da familia La-Sr e La-Ca, 3) a determinacao dos expoentes criticos β e δ do Niquel por metodos de escala, 4) a descricao do efeito da pressao nas propriedades magneticas e magnetocaloricas do composto LaFe11.5Si1.5 atraves do modelo de Bean-Rodbell, 5) uma estimativa da desordem em manganites ferromagneticas com transicoes de segunda e primeira ordem, 6) uma descricao de campo medio das propriedades magneticas da liga Fe23Cu77, 7) o estudo de efeitos de separacao de fase na familia de compostos La0.70-xErxSr0.30MnO3 e 8) a determinacao realista da variacao de entropia magnetica na familia de compostos de efeito magnetocalorico colossal Mn1-x-yFexCryAs.

Novas determinações dos parâmetros atmosféricos das estrelas anãs brancas DA

NASA Astrophysics Data System (ADS)

Giovannini, O.; Costa, A. F. M.; Kepler, S. O.

2003-08-01

Nós temos selecionado uma amostra de estrelas anãs brancas DA (atmosfera de hidrogênio) a partir dos índices de Strömgren cujos valores estão próximos a região de instabilidade das estrelas anãs brancas DA variáveis, as chamadas estrelas DAV ou ZZ Ceti. O objetivo é determinar os parâmetros fundamentais (temperatura efetiva, Teff, aceleração da gravidade, log g, e massa) destas estrelas para verificar quais os parâmetros estelares estão envolvidos com o mecanismo de pulsação das estrelas DAV. Nós obtemos, até agora, mais de 120 espectros óticos de estrelas DA. Entre as estrelas selecionadas há 20 estrelas variáveis (DAV). Assim, podemos verificar se existem ou não estrelas não variáveis dentro da faixa de instabilidade das estrelas ZZ Ceti. Neste trabalho nós apresentamos a determinação dos parâmetros atmosféricos (temperatura efetiva, Teff, e aceleração da gravidade, log g) das estrelas anãs brancas DA usando os novos modelos de atmosfera ML2/a = 0.6. Estes modelos têm sido utilizados recentemente por fornecerem uma excelente consistência interna na determinação das temperaturas nas regiões do ultra-violeta e ótico. Os parâmetros atmosféricos são determinados espectroscopicamente através da comparação do fluxo de energia das linhas de Balmer (Hb à H9) entre os espectros observados e sintéticos (gerados pelos modelos de atmosfera). As temperaturas obtidas com os novos modelos são, em geral, menores (~ 1000 K menos) que as temperaturas determinadas anteriormente, com modelos ML1. Os valores de log g não mudaram significativamente (menos de 10%). A faixa de instabilidade das DAVs está entre 11000 e 13000 K, consistente com dados de outros autores.

Significado de psicólogas/os de atención primaria de salud sobre la intervención psicosocial de grupo en el tratamiento de la depresión en Chile.

PubMed

Andrade, Gonzalo; Espinoza, Adriana

2017-11-01

En Chile, el tratamiento de la depresión en salud pública promueve la realización de Intervenciones Psicosociales en Grupo (IPG) para todos los casos diagnosticados, no obstante, se observa una baja implementación de estas prestaciones. El presente artículo describe y caracteriza, desde el punto de vista de la disciplina psicológica, el significado de psicólogas/os que trabajan en consultorios de atención primaria de salud (APS) sobre las IPG en el tratamiento de la depresión. Se entrevistaron a ocho psicólogas/os de los distintos Servicios de Salud de la Región Metropolitana de Santiago. Este estudio se basó en las premisas de la Teoría Fundamentada, utilizando sus estrategias de análisis. La categoría "los grupos no nos resultan" expone las principales barreras que impiden la realización de estas intervenciones. La carga laboral centrada en atenciones individuales, el escaso presupuesto destinado a su implementación, y la falta de instalaciones adecuadas para realizar las IPG emergen como barreras institucionales. Asi mismo, la "poca fe" en la efectividad del trabajo en grupo, la figura de las/os psicólogas/os como únicas/os profesionales capacitadas/os para trabajar con las emociones, la idea de que la baja adherencia al tratamiento no depende de su ejercicio laboral, y el hecho de que la implementación de las IPG dependa del interés individual de algunas/os profesionales, emergen como las principales resistencias profesionales a su realización. Se discuten los alcances de estas barreras, y se proponen soluciones que favorezcan el cambio cultural necesario para que las/los profesionales e instituciones de salud puedan alinearse en plenitud con el modelo comunitario de salud propuesto por el Plan Nacional de Salud Mental y Psiquiatría (PNSMP).

Desarrollo de un instrumento para medir percepciones sobre el contexto de construccion del conocimiento cientifico de estudiantes universitarios de nuevo ingreso

NASA Astrophysics Data System (ADS)

Garcia-Ramirez, Jaime Antonio

En esta investigacion, se desarrollo un instrumento que permite medir percepciones relacionadas al contexto de constriccion del conocimiento cientifico. Se examinaron instrumentos existentes y se encontro que el VOSTS (Views on science, technology, and society), instrumento desarrollado empiricamente en Canada por Aikenhead, Ryan y Fleming, podia traducirse y validarse en el contexto cultural puertorriqueno. El instrumento es extenso, consta de 113 reactivos, cada uno con una premisa basica relacionada a la tematica ciencia, tecnologia y sociedad y un numero de alternativas relacionadas a la premisa que oscila entre siete y trece. Se delimito su utilizacion a los quince reactivos identificados por los autores como relacionados a la construccion social del conocimiento cientifico. Metodologicamente, se procedio a utilizar el modelo de adaptacion intercultural, que permite que el instrumento desarrollado satisfaga las dimensiones de equivalencia semantica, de contenido, tecnica, de criterio y conceptual, atemperado asi al instrumento original. Se cumplio con este proposito mediante la traduccion de la version original en ingles al espanol y viceversa. Se utilizaron comites para examinar la traduccion y la retro-traduccion del instrumento. Se realizo una prueba piloto con estudiantes universitarios de nuevo ingreso, utilizando el instrumento traducido para asegurar su intelegibilidad. La confiabilidad del instrumento se determino mediante la intervencion de un panel de expertos quienes clasificaron las distintas posiciones dentro de cada reactivo en: realista, con merito e ingenua; se transformaron estas opciones en valores numericos lo que permitio establecer una escala Likert para cada una. Se suministro el instrumento a una muestra de estudiantes universitarios de nuevo ingreso con caracteristicas similares a las de la poblacion puertorriquena en cuanto a ejecucion en las pruebas de aptitud verbal y matematica del College Board. Los resultados de sus contestaciones fueron transformados numericamente para poder obtener el coeficiente de correlacion de Spearman-Brown para el instrumento (0.661, p < 0.01). El analisis de las contestaciones de los estudiantes refleja percepciones diversas y, en algunos casos, contradictorias con respecto al contexto de construccion del conocimiento cientifico.

Investigaccion-accion en la sala de clases sobre las creencias de la cultura de la ciencia de un grupo de estudiantes universitarios y su relacion reciproca con el aprendizaje de las ciencias biologicas

NASA Astrophysics Data System (ADS)

Cordova-Santiago, Lizzette Astrid

La investigacion---accion que se llevo a cabo en la sala de clases tenia como punto de partida las creencias de la cultura de la ciencia de un grupo de estudiantes universitarios para luego examinar sus implicaciones en el proceso de aprendizaje de las Ciencias Biologicas. ¿Que se supone que hagan las creencias en relacion con el aprendizaje? ¿En que consiste incorporar este aspecto a la practica educativa universitaria? Utilizando el modelo de Kemmis y McTaggart (1987) la investigacion-accion se planteo como un proceso dinamico en cuatro momentos en espiral constituidos por la planificacion, la accion, la observacion y la reflexion. Cada una de las fases tuvo una intencion retrospectiva y prospectiva formando una espiral de autorreflexion del conocimiento y la accion. Se llevaron a cabo audio grabaciones en clases y analisis de documentos. Ademas, la profesora-investigadora hizo un portafolio para reflexionar sobre las creencias de la cultura de la ciencia que tienen los estudiantes y las creencias del aprendizaje que tiene la profesora y sobre como la comprension de estos elementos ayudo a mejorar su practica educativa a traves del tiempo. Los resultados obtenidos apuntan a que las creencias de la cultura de la ciencia que tiene el grupo de estudiantes son diversas. Ellos si creen que la ciencia tiene una cultura la cual describieron como: complicada y desconocida que evoluciona constantemente, que es un conjunto de metodos, que es altamente tecnologica, que resuelve problemas de salud, ayuda a interpretar la realidad del mundo que los rodea y su origen y que existen unas intersecciones entre la ciencia y el poder. Sobre las creencias del proceso de aprendizaje de la profesora-investigadora, estas senalan que el modelaje de actores, la vision de la academia que tiene ella asi como la participacion y negociacion entre todos los involucrados en el proceso educativo, son factores que inciden en el proceso de aprendizaje.

The Diterpene Sclareol Vascular Effect in Normotensive and Hypertensive Rats.

PubMed

Campos, Debora Ribeiro; Celotto, Andrea Carla; Albuquerque, Agnes Afrodite S; Ferreira, Luciana Garros; Monteiro, Ariadne Santana E Neves; Coelho, Eduardo Barbosa; Evora, Paulo Roberto Barbosa

2017-06-29

The diterpene Sclareol has antimicrobial action, cytotoxic and cytostatic effects and anti-tumor activities. However, researches on the cardiovascular system are scarce. This study was designed to investigate the mechanisms involved in the Sclareol cardiovascular effect in normotensive and hypertensive rats. The arterial hypertension was promoted using 2-kidneys 1-clip model in rats. The effect of sclareol on blood pressure was performed by using three dose (10, 20 and 40 mg/kg). Cumulative dose-response curves for Sclareol were determined for endothelium-intact and endothelium-denuded aortic rings in presence or absence of L-NAME and ODQ. The NOx levels were measure in the plasma sample. The Sclareol administration in vivo caused a significant reduction in blood pressure in both groups. In vitro the sclareol promoted relaxation in aorta, with endothelium, pre-contracted to Phe. The inhibitors of the nitric oxide synthase and soluble guanylate cyclase were as efficient as the removal of endothelium, in inhibiting the Sclareol-induced relaxation. Otherwise, it was no change of NOx. Also, for unknown reasons, the Sclareol is not selective for hypertensive animals. The diterpene Sclareol showed in vivo hypotensive and in-vitro vasodilator effects; The chemiluminescence plasmatic NO analysis showed no significant difference between groups and The Sclareol exhibit better effect on normotensive than hypertensive animals to reduce blood pressure. It is concluded that the diterpenes metabolites would be a promising source prototype for the development of new agents in the cardiovascular therapy. O diterpeno Esclareol tem ação antimicrobiana, efeitos citotóxicos e citostáticos e atividades antitumorais. No entanto, pesquisas sobre o sistema cardiovascular são escassas. Este estudo foi desenvolvido para investigar os mecanismos envolvidos no efeito cardiovascular de Esclareol em ratos normotensos e hipertensos. A hipertensão arterial foi promovida utilizando modelo de 2 clones de 1-clipe em ratos. O efeito do esclareol sobre a pressão arterial foi realizado utilizando três doses (10, 20 e 40 mg/kg). As curvas dose-resposta cumulativas para Esclareol foram determinadas para anéis aórticos endotélio-intactos e desprovidos de endotélio na presença ou ausência de L-NAME e ODQ. Os níveis de NOx foram medidos na amostra de plasma. A administração de Esclareol in vivo causou uma redução significativa na pressão sanguínea em ambos os grupos. In vitro o esclareol promoveu relaxamento na aorta, com endotélio, pré-contraído a Phe. Os inibidores da óxido nítrico sintase e da guanilato ciclase solúvel foram tão eficientes quanto a remoção do endotélio, na inibição do relaxamento induzido por Esclareol. Por outra parte, não houve mudança de NOx. Além disso, por razões desconhecidas, o Sclareol não é seletivo para animais hipertensos. O diterpeno Esclareol apresentou efeitos hipotensores in vivo e vasodilatadores in vitro; A análise de NO plasmático por quimioluminescência não mostrou diferença significativa entre os grupos e O Esclareol exibe melhor efeito sobre os animais normotensos do que hipertensos para reduzir a pressão arterial. Conclui-se que os metabólitos de diterpenos seriam um protótipo de fonte promissora para o desenvolvimento de novos agentes na terapia cardiovascular.

Structure and mechanism of Cu- and Ni-substituted analogs of metallo-β-lactamase L1

PubMed Central

Hu, Zhenxin; Spadafora, Lauren J.; Hajdin, Christine E.; Bennett, Brian; Crowder, Michael W.

2009-01-01

In an effort to further probe metal binding to metallo-β-lactamase L1 (mβl L1), Cu- (Cu-L1) and Ni-substituted (Ni-L1) L1 were prepared and characterized by kinetic and spectroscopic studies. Cu-L1 bound 1.7 equivalents of Cu and small amounts of Zn(II) and Fe. The EPR spectrum of Cu-L1 exhibited two overlapping, axial signals, indicative of type 2 sites with distinct affinities for Cu(II). Both signals indicated multiple nitrogen ligands. Despite the expected proximity of the Cu(II) ions, however, only indirect evidence was found for spin-spin coupling. Cu-L1 exhibited higher kcat (96 s−1) and Km (224 μM) values, as compared to the values of dinuclear Zn(II)-containing L1, when nitrocefin was used as substrate. The Ni-L1 bound 1 equivalent of Ni and 0.3 equivalents of Zn(II). Ni-L1 was EPR-silent, suggesting that the oxidation state of nickel was +2; this suggestion was confirmed by 1H NMR spectra, which showed relatively sharp proton resonances. Stopped-flow kinetic studies showed that ZnNi-L1 stabilized significant amounts of the nitrocefin-derived intermediate and that the decay of intermediate is rate-limiting. 1H NMR spectra demonstrate that Ni(II) binds in the Zn2 site and that the ring-opened product coordinates Ni(II). Both Cu-L1 and ZnNi-L1 hydrolyze cephalosporins and carbapenems, but not penicillins, suggesting that the Zn2 site modulates substrate preference in mβ1 L1. These studies demonstrate that the Zn2 site in L1 is very flexible and can accommodate a number of different transition metal ions; this flexibility could possibly offer an organism that produces L1 an evolutionary advantage when challenged with β-lactam containing antibiotics. PMID:19228020

Synthesis, structures, and properties of crystalline salts with radical anions of metal-containing and metal-free phthalocyanines.

PubMed

Konarev, Dmitri V; Kuzmin, Alexey V; Faraonov, Maxim A; Ishikawa, Manabu; Khasanov, Salavat S; Nakano, Yoshiaki; Otsuka, Akihiro; Yamochi, Hideki; Saito, Gunzi; Lyubovskaya, Rimma N

2015-01-12

Radical anion salts of metal-containing and metal-free phthalocyanines [MPc(3-)](·-), where M = Cu(II), Ni(II), H2, Sn(II), Pb(II), Ti(IV)O, and V(IV)O (1-10) with tetraalkylammonium cations have been obtained as single crystals by phthalocyanine reduction with sodium fluorenone ketyl. Their formation is accompanied by the Pc ligand reduction and affects the molecular structure of metal phthalocyanine radical anions as well as their optical and magnetic properties. Radical anions are characterized by the alternation of short and long C-Nimine bonds in the Pc ligand owing to the disruption of its aromaticity. Salts 1-10 show new bands at 833-1041 nm in the NIR range, whereas the Q- and Soret bands are blue-shifted by 0.13-0.25 eV (38-92 nm) and 0.04-0.07 eV (4-13 nm), respectively. Radical anions with Ni(II), Sn(II), Pb(II), and Ti(IV)O have S = 1/2 spin state, whereas [Cu(II)Pc(3-)](·-) and [V(IV)OPc(3-)](·-) containing paramagnetic Cu(II) and V(IV)O have two S = 1/2 spins per radical anion. Central metal atoms strongly affect EPR spectra of phthalocyanine radical anions. Instead of narrow EPR signals characteristic of metal-free phthalocyanine radical anions [H2Pc(3-)](·-) (linewidth of 0.08-0.24 mT), broad EPR signals are manifested (linewidth of 2-70 mT) with g-factors and linewidths that are strongly temperature-dependent. Salt 11 containing the [Na(I)Pc(2-)](-) anions as well as previously studied [Fe(I)Pc(2-)](-) and [Co(I)Pc(2-)](-) anions that are formed without reduction of the Pc ligand do not show changes in molecular structure or optical and magnetic properties characteristic of [MPc(3-)](·-) in 1-10. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis, spectral and thermal studies of some transition metal mixed ligand complexes: Modeling of equilibrium composition and biological activity

NASA Astrophysics Data System (ADS)

Neelakantan, M. A.; Sundaram, M.; Nair, M. Sivasankaran

2011-09-01

Several mixed ligand Ni(II), Cu(II) and Zn(II) complexes of 2-amino-3-hydroxypyridine (AHP) and imidazoles viz., imidazole (him), benzimidazole (bim), histamine (hist) and L-histidine (his) have been synthesized and characterized by elemental and spectral (vibrational, electronic, 1H NMR and EPR) data as well as by magnetic moment values. On the basis of elemental analysis and molar conductance values, all the complexes can be formulated as [MAB]Cl except histidine complexes as MAB. Thermogravimetric studies reveal the presence of coordinated water molecules in most of the complexes. From the magnetic measurements and electronic spectral data, octahedral structure was proposed for Ni(II) and Cu(II)-AHP-his, tetrahedral for Cu(II)-AHP-him/bim/hist, but square planar for the Cu(II)-AHP complex. The g∥/ A∥ calculated supports tetrahedral environment around the Cu(II) in Cu(II)-AHP-him/bim/hist and distorted octahedral for Cu(II)-AHP-his complexes. The morphology of the reported metal complexes was investigated by scanning electron micrographs (SEM). The potentiometric study has been performed in aqueous solution at 37 °C and I = 0.15 mol dm -3 NaClO 4. MABH, MAB and MAB 2 species has been identified in the present systems. Proton dissociation constants of AHP and stability constants of metal complexes were determined using MINIQUAD-75. The most probable structure of the mixed ligand species is discussed based upon their stability constants. The in vitro biological activity of the complexes was tested against the Gram positive and Gram negative bacteria, fungus and yeast. The oxidative DNA cleavage studies of the complexes were performed using gel electrophoresis method. Cu(II) complexes have been found to promote DNA cleavage in presence of biological reductant such as ascorbate and oxidant like hydrogen peroxide.

Nickel binding and [NiFe]-hydrogenase maturation by the metallochaperone SlyD with a single metal-binding site in Escherichia coli.

PubMed

Kaluarachchi, Harini; Altenstein, Matthias; Sugumar, Sonia R; Balbach, Jochen; Zamble, Deborah B; Haupt, Caroline

2012-03-16

SlyD (sensitive to lysis D) is a nickel metallochaperone involved in the maturation of [NiFe]-hydrogenases in Escherichia coli (E. coli) and specifically contributes to the nickel delivery step during enzyme biosynthesis. This protein contains a C-terminal metal-binding domain that is rich in potential metal-binding residues that enable SlyD to bind multiple nickel ions with high affinity. The SlyD homolog from Thermus thermophilus does not contain the extended cysteine- and histidine-rich C-terminal tail of the E. coli protein, yet it binds a single Ni(II) ion tightly. To investigate whether a single metal-binding motif can functionally replace the full-length domain, we generated a truncation of E. coli SlyD, SlyD155. Ni(II) binding to SlyD155 was investigated by using isothermal titration calorimetry, NMR and electrospray ionization mass spectrometry measurements. This in vitro characterization revealed that SlyD155 contains a single metal-binding motif with high affinity for nickel. Structural characterization by X-ray absorption spectroscopy and NMR indicated that nickel was coordinated in an octahedral geometry with at least two histidines as ligands. Heterodimerization between SlyD and another hydrogenase accessory protein, HypB, is essential for optimal hydrogenase maturation and was confirmed for SlyD155 via cross-linking experiments and NMR titrations, as were conserved chaperone and peptidyl-prolyl isomerase activities. Although these properties of SlyD are preserved in the truncated version, it does not modulate nickel binding to HypB in vitro or contribute to the maturation of [NiFe]-hydrogenases in vivo, unlike the full-length protein. This study highlights the importance of the unusual metal-binding domain of E. coli SlyD in hydrogenase biogenesis. Copyright © 2012 Elsevier Ltd. All rights reserved.

Citrate, in collaboration with a guanidinium ion, as a generator of cubane-like complexes with a range of metal cations: synthesis, structures, and magnetic properties of [C(NH2)3]8[(M(II))4(cit)4].8H2O (M = Mg, Mn, Fe, Co, Ni, and Zn; cit = Citrate).

PubMed

Hudson, Timothy A; Berry, Kevin J; Moubaraki, Boujemaa; Murray, Keith S; Robson, Richard

2006-05-01

Aqueous reaction mixtures containing citric acid, guanidinium carbonate, and a range of metal cations (Mg2+, Mn2+, Fe2+, Co2+, Ni2+, and Zn2+) at room temperature give crystalline products of composition [C(NH2)3]8[(M(II))4(cit)4].8H2O (cit = citrate). In all cases, the crystals are suitable for single-crystal X-ray diffraction studies, which reveal that the compounds are isostructural (space group P4(2)/n; a approximately 16.2 A, and c approximately 11.5 A). As was intended, cubane-like [M4(cit)4]8- complex anions are present. The individual citrate units are chiral, but each cubane unit contains two of one hand and two of the other, related around an S4 axis. The cubane units are involved in no less than 40 H-bonding interactions with guanidinium cations and lattice water molecules. Detailed susceptibility and magnetization studies show that the intracluster magnetic coupling within the Mn(II), Fe(II), Co(II), and Ni(II) cubanes is very weak in all cases with J values of -0.82, -0.43, and -0.09 cm(-1) for the Mn, Fe, and Co species, respectively. A two-J model gave the best agreement with the susceptibility and high-field magnetization data for the Ni(II) case, over the whole temperature range studied, and the sign of the parameters, J12 = -0.3 cm(-1) and J13 = +2.97 cm(-1), correlated with the two Ni-(mu3-O)-Ni angles observed in the cluster structure. All members of the 3d-block [M4(cit)4]8- family have spin ground states, ST, of zero, with the higher ST levels just a few reciprocal centimeters away in energy.

Equilibrium of particle nitrite with gas phase HONO: Tropospheric measurements in the high Arctic during polar sunrise

NASA Astrophysics Data System (ADS)

Li, Shao-Meng

1994-12-01

Gas phase HONO(g) and nitrite in particles of <5-μm size were measured in the troposphere during the Polar Sunrise Experiment at Alert, Northwest Territories, Canada, during January 19 to April 20, 1992, using denuder-filter pack sampling and IC-UV detection. The measurements indicated that HONO(g) existed at concentrations of up to 70 ppt before polar sunrise but gradually decreased to 5-10 ppt after sunrise. The calculated OH formation rate from HONO(g) photolysis was greater than from the photolysis of both O3 and CH2O by more than one order of magnitude during the sunlit period and led to moderately high levels of OH, e.g., 3×105 molecules cm-3 OH at noontime on April 5. Particle nitrite measurements showed a gradual increase in concentrations with increasing solar insolation, but the concentrations were generally less than 10 ppt. The pH and the sulfate molar concentrations of the particles and the water vapor mixing ratio indicate that the particles were highly acidic being approximately 70% (W/W) H2SO4 solution. In such highly concentrated H2SO4 solution, most particle nitrite should exist as hydrated nitrosonium ion H2ONO+. Taking this into consideration, the particle nitrite was in an approximate equilibrium with the measured HONO(g). This equilibrium, with HONO(g) rapidly photolyzed, was a good indication that the particles were effective sources of HONO(g) and implied rapid production of particle N(+III) during this period. Two possible pathways leading to the formation of particle N(+III) species are suggested, i.e., reduction of HNO3(aq) by SO2(g) and reduction of NO3-; (aq) by Br- (aq). However, N2O5 reaction with NaBr cannot be ruled out as the alternative HONO(g) formation mechanism which bypasses the equilibrium.

Molecular landscape of the interaction between the urease accessory proteins UreE and UreG.

PubMed

Merloni, Anna; Dobrovolska, Olena; Zambelli, Barbara; Agostini, Federico; Bazzani, Micaela; Musiani, Francesco; Ciurli, Stefano

2014-09-01

Urease, the most efficient enzyme so far discovered, depends on the presence of nickel ions in the catalytic site for its activity. The transformation of inactive apo-urease into active holo-urease requires the insertion of two Ni(II) ions in the substrate binding site, a process that involves the interaction of four accessory proteins named UreD, UreF, UreG and UreE. This study, carried out using calorimetric and NMR-based structural analysis, is focused on the interaction between UreE and UreG from Sporosarcina pasteurii, a highly ureolytic bacterium. Isothermal calorimetric protein-protein titrations revealed the occurrence of a binding event between SpUreE and SpUreG, entailing two independent steps with positive cooperativity (Kd1=42±9μM; Kd2=1.7±0.3μM). This was interpreted as indicating the formation of the (UreE)2(UreG)2 hetero-oligomer upon binding of two UreG monomers onto the pre-formed UreE dimer. The molecular details of this interaction were elucidated using high-resolution NMR spectroscopy. The occurrence of SpUreE chemical shift perturbations upon addition of SpUreG was investigated and analyzed to establish the protein-protein interaction site. The latter appears to involve the Ni(II) binding site as well as mobile portions on the C-terminal and the N-terminal domains. Docking calculations based on the information obtained from NMR provided a structural basis for the protein-protein contact site. The high sequence and structural similarity within these protein classes suggests a generality of the interaction mode among homologous proteins. The implications of these results on the molecular details of the urease activation process are considered and analyzed. Copyright © 2014 Elsevier B.V. All rights reserved.

Fine-Tuning the Activity of Metal–Organic Framework Supported Cobalt Catalysts for the Oxidative Dehydrogenation of Propane

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Zhanyong; Peters, Aaron W.; Platero-Prats, Ana E.

Few-atom cobalt-oxide clusters, when dispersed on a Zr-based metal–organic framework (MOF) NU-1000, have previously been shown to be active for the oxidative dehydrogenation (ODH) of propane at low temperatures (< 230 °C), affording a selective and stable propene production catalyst. In our current work, a series of promoter ions with varying Lewis acidity, including Ni(II), Zn(II), Al(III), Ti(IV) and Mo(VI), are anchored as metal-oxide,hydroxide clusters to NU-1000 via SIM (solvothermal deposition within MOFs–specifically the nodes) followed by incorporation of Co(II) ions via vapor-phase AIM (atomic layer deposition (ALD) in MOFs). This process yields a series of NU-1000-supported bimetallic-oxo,hydroxo,aqua clusters. Usingmore » difference envelope density (DED) analyses, the spatial locations of the promoter ions and catalytic cobalt ions are determined. For all samples the SIM-anchored promoter ions are sited between pairs of Zr 6 nodes along the MOF c-axis (channel-aligned axis) whereas the location of the AIM-anchored cobalt ions varies depending on the identity of promoter metal ion. With Ni(II)-, Al(III)-, or Ti(IV)-containing clusters as promoters, the oxy-cobalt species are sited atop the promoter sites; with Mo(VI) they grow exclusively on the MOF nodes sites (hexa-Zr(IV)- oxo,hydroxo,aqua units); with Zn(II) they grow on both the node and promoter. The NU-1000- supported bimetallic-oxide clusters are active for propane ODH after thermal activation under O 2 to open a cobalt coordination site and to oxidize Co(II) to Co(III), as evidenced by operando Xray absorption spectroscopy at the Co K-edge. The cobalt component is exclusively responsible for the observed catalysis. In accord with the decreasing Lewis acidity of the promoter ion, catalytic activity increases in the order: Mo(VI)« less

Fine-Tuning the Activity of Metal–Organic Framework Supported Cobalt Catalysts for the Oxidative Dehydrogenation of Propane

DOE PAGES

Li, Zhanyong; Peters, Aaron W.; Platero-Prats, Ana E.; ...

2017-10-04

Few-atom cobalt-oxide clusters, when dispersed on a Zr-based metal–organic framework (MOF) NU-1000, have previously been shown to be active for the oxidative dehydrogenation (ODH) of propane at low temperatures (< 230 °C), affording a selective and stable propene production catalyst. In our current work, a series of promoter ions with varying Lewis acidity, including Ni(II), Zn(II), Al(III), Ti(IV) and Mo(VI), are anchored as metal-oxide,hydroxide clusters to NU-1000 via SIM (solvothermal deposition within MOFs–specifically the nodes) followed by incorporation of Co(II) ions via vapor-phase AIM (atomic layer deposition (ALD) in MOFs). This process yields a series of NU-1000-supported bimetallic-oxo,hydroxo,aqua clusters. Usingmore » difference envelope density (DED) analyses, the spatial locations of the promoter ions and catalytic cobalt ions are determined. For all samples the SIM-anchored promoter ions are sited between pairs of Zr 6 nodes along the MOF c-axis (channel-aligned axis) whereas the location of the AIM-anchored cobalt ions varies depending on the identity of promoter metal ion. With Ni(II)-, Al(III)-, or Ti(IV)-containing clusters as promoters, the oxy-cobalt species are sited atop the promoter sites; with Mo(VI) they grow exclusively on the MOF nodes sites (hexa-Zr(IV)- oxo,hydroxo,aqua units); with Zn(II) they grow on both the node and promoter. The NU-1000- supported bimetallic-oxide clusters are active for propane ODH after thermal activation under O 2 to open a cobalt coordination site and to oxidize Co(II) to Co(III), as evidenced by operando Xray absorption spectroscopy at the Co K-edge. The cobalt component is exclusively responsible for the observed catalysis. In accord with the decreasing Lewis acidity of the promoter ion, catalytic activity increases in the order: Mo(VI)« less

PN G068.1+11.0: A young pre-cataclysmic variable with an extremely hot primary

NASA Astrophysics Data System (ADS)

Mitrofanova, A. A.; Shimansky, V. V.; Borisov, N. V.; Spiridonova, O. I.; Gabdeev, M. M.

2016-02-01

An analysis of spectroscopic and photometric data for the young pre-cataclysmic variable (PCV) PN G068.1+11.0, which passed through its common-envelope stage relatively recently, is presented. The spectroscopic and photometric data were obtained with the 6-m telescope and Zeiss-1000 telescope of the Special Astrophysical Observatory. The light curves show sinusoidal brightness variations with the orbital-period time scale and brightness-variation amplitudes of Δ m = 1. m41, 1. m62, and 1. m57 in the B, V, and R bands, respectively. The system's spectrum exhibits weak HI (H β-H δ) andHeII λλ4541, 4686, 5411 Å absorption lines during the phases of minimum brightness, as well as HI, HeII, CIII, CIV, NIII, and OII emission lines whose intensity variations are synchronized with variations of the integrated brightness of the system. The emission-line formation in the spectra can be fully explained by the effects of fluorescence of the ultraviolet light from the primary at the surface of the cool star. All the characteristics of the optical light of PN G068.1+11.0 confirm that it is a young PCV containing sdO subdwarf. The radial velocities were measured from a blend of lines of moderately light elements, CIII+NIII λ4640 Å, which is formed at the surface of the secondary due to reflection effects. The ephemeris of the system has been improved through a joint analysis of the radial-velocity curves and light curves of pre-cataclysmic variable, using modelling of the reflection effects. The fundamental parameters of PN G068.1+11.0 have been determined using two evolutionary tracks for planetary-nebula nuclei of different masses (0.7 M ⊙and 0.78 M ⊙). The model spectra for the system and a comparison with the observations demonstrate the possibility of refining the components' effective temperatures if the quality of the spectra used is improved.

Flame atomic absorption spectrometric determination of heavy metals in aqueous solution and surface water preceded by co-precipitation procedure with copper(II) 8-hydroxyquinoline

NASA Astrophysics Data System (ADS)

Ipeaiyeda, Ayodele Rotimi; Ayoade, Abisayo Ruth

2017-12-01

Co-precipitation procedure has widely been employed for preconcentration and separation of metal ions from the matrices of environmental samples. This is simply due to its simplicity, low consumption of separating solvent and short duration for analysis. Various organic ligands have been used for this purpose. However, there is dearth of information on the application of 8-hydroxyquinoline (8-HQ) as ligand and Cu(II) as carrier element. The use of Cu(II) is desirable because there is no contamination and background adsorption interference. Therefore, the objective of this study was to use 8-HQ in the presence of Cu(II) for coprecipitation of Cd(II), Co(II), Cr(III), Ni(II) and Pb(II) from standard solutions and surface water prior to their determinations by flame atomic absorption spectrometry (FAAS). The effects of pH, sample volume, amount of 8-HQ and Cu(II) and interfering ions on the recoveries of metal ions from standard solutions were monitored using FAAS. The water samples were treated with 8-HQ under the optimum experimental conditions and metal concentrations were determined by FAAS. The metal concentrations in water samples not treated with 8-HQ were also determined. The optimum recovery values for metal ions were higher than 85.0%. The concentrations (mg/L) of Co(II), Ni(II), Cr(III), and Pb(II) in water samples treated with 8-HQ were 0.014 ± 0.002, 0.03 ± 0.01, 0.04 ± 0.02 and 0.05 ± 0.02, respectively. These concentrations and those obtained without coprecipitation technique were significantly different. Coprecipitation procedure using 8-HQ as ligand and Cu(II) as carrier element enhanced the preconcentration and separation of metal ions from the matrix of water sample.

Synthesis, Crystal Structures, Magnetic Properties, and Theoretical Investigation of a New Series of NiII-LnIII-WV Heterotrimetallics: Understanding the SMM Behavior of Mixed Polynuclear Complexes.

PubMed

Vieru, Veacheslav; Pasatoiu, Traian D; Ungur, Liviu; Suturina, Elizaveta; Madalan, Augustin M; Duhayon, Carine; Sutter, Jean-Pascal; Andruh, Marius; Chibotaru, Liviu F

2016-12-05

The polynuclear compounds containing anisotropic metal ions often exhibit efficient barriers for blocking of magnetization at fairly arbitrary geometries. However, at variance with mononuclear complexes, which usually become single-molecule magnets (SMM) under the sole requirement of a highly axial crystal field at the metal ion, the factors influencing the SMM behavior in polynuclear complexes, especially, with weakly axial magnetic ions, still remain largely unrevealed. As an attempt to clarify these conditions, we present here the synthesis, crystal structures, magnetic behavior, and ab initio calculations for a new series of Ni II -Ln III -W V trimetallics, [(CN) 7 W(CN)Ni(H 2 O)(valpn)Ln(H 2 O) 4 ]·H 2 O (Ln = Y 1, Eu 2, Gd 3, Tb 4, Dy 5, Lu 6). The surprising finding is the absence of the magnetic blockage even for compounds involving strongly anisotropic Dy III and Tb III metal ions. This is well explained by ab initio calculations showing relatively large transversal components of the g-tensor in the ground exchange Kramers doublets of 1 and 4 and large intrinsic tunneling gaps in the ground exchange doublets of 3 and 5. In order to get more insight into this behavior, another series of earlier reported compounds with the same trinuclear [W V Ni II Ln III ] core structure, [(CN) 7 W(CN)Ni(dmf)(valdmpn)Ln(dmf) 4 ]·H 2 O (Ln = Gd III 7, Tb III 8a, Dy III 9, Ho III 10), [(CN) 7 W(CN)Ni(H 2 O)(valdmpn)Tb(dmf) 2.5 (H 2 O) 1.5 ]·H 2 O·0.5dmf 8b, and [(CN) 7 W(CN)Ni(H 2 O)(valdmpn)Er(dmf) 3 (H 2 O) 1 ]·H 2 O·0.5dmf 11, has been also investigated theoretically. In this series, only 8b exhibits SMM behavior which is confirmed by the present ab initio calculations. An important feature for the entire series is the strong ferromagnetic coupling between Ni(II) and W(V), which is due to an almost perfect trigonal dodecahedron geometry of the octacyano wolframate fragment. The reason why only 8b is an SMM is explained by positive zero-field splitting on the nickel site, precluding magnetization blocking in complexes with fewer axial Ln ions. Further analysis has shown that, in the absence of ZFS on Ni ion, all compounds in the two series (except those containing Y and Gd) would be SMMs. The same situation arises for perfectly axial ZFS on Ni(II) with the main anisotropy axis parallel to the main magnetic axis of Ln(III) ions. In all other cases the ZFS on Ni(II) will worsen the SMM properties. The general conclusion is that the design of efficient SMMs on the basis of such complexes should involve isotropic or weekly anisotropic metal ions, such as Mn(II), Fe(III), etc., along with strongly axial lanthanides.

Órbitas caóticas en satelites galácticos

NASA Astrophysics Data System (ADS)

Carpintero, D. D.; Muzzio, J. C.; Vergne, M. M.; Wachlin, F. C.

En trabajos anteriores investigamos las órbitas de estrellas que forman los satelites galácticos utilizando análisis de frecuencias. Su uso estaba plenamente justificado por su velocidad y la gran información que brinda, amén de haber dado resultados muy concordantes con los exponentes de Liapunov. Sin embargo, más recientemente, encontramos algunos problemas en la utilización del análisis de frecuencias en sistemas de referencia rotantes (como se utilizan para los satélites), por lo que en este trabajo rehicimos nuestras investigaciones previas utilizando exclusivamente exponentes de Liapunov. Algunas conclusiones anteriores se han confirmado, en tanto que otras deben modificarse. Además, los nuevos resultados muestran que las escalas de tiempo de los procesos caóticos en los satélites galácticos son comparables a, o más cortas que, las escalas de tiempo de otros procesos dinámicos característicos de estos objetos.

Incorporando a variabilidade no processo de identificação do modelo de máximo global no Grade of Membership (GoM): considerações metodológicas

PubMed Central

Guedes, Gilvan Ramalho; Siviero, Pamila Cristina Lima; Caetano, André Junqueira; Machado, Carla Jorge; Brondízio, Eduardo

2012-01-01

A disponibilidade de bases de dados cada vez mais complexas e multidimensionais é um dos principais motivadores para o aumento do número de estudos que utilizam análises multivariadas baseadas em lógica de conjuntos nebulosos. Apesar da disseminação do método Grade of Membership nos trabalhos empíricos brasileiros da área de ciências sociais e saúde, questões relativas à identificabilidade e estabilidade dos parâmetros finais estimados pelo programa GoM 3.4 não foram suficientemente aprofundadas. Dada a relevância de se obterem parâmetros únicos e estáveis, Guedes et al. (2010) propuseram um procedimento empírico para localizar um modelo de máximo global (MG) com parâmetros estáveis. Entretanto, seu localizador de MG não incorpora qualquer medida de variabilidade. Neste artigo, tal limitação é contornada por meio da utilização de uma estatística de ponderação – Máximo Global Ponderado (MGP) – semelhante ao coeficiente de variação. Esse indicador busca não penalizar de forma desproporcional situações nas quais os desvios médios, apesar de diferentes de zero, são muito pequenos. Apresentam-se evidências de que o localizador MGP reduz a distância do modelo identificado à real estrutura latente dos dados em análise, quando comparados ao modelo identificado pelo localizador não ponderado, MG. PMID:23293402

A Novel Coordination Polymer Constructed by Hetero-Metal Ions and 2,3-Pyridine Dicarboxylic Acid: Synthesis and Structure of [NiNa2(PDC)2(μ-H2O)(H2O)2] n

NASA Astrophysics Data System (ADS)

Dou, Ming-Yu; Lu, Jing

2017-12-01

A novel coordination polymer containing hetero-metal ions, [NiNa2(PDC)2(μ-H2O)(H2O)2] n , where PDC is 2,3-pyridine dicarboxylate ion, has been synthesized. In the structure, the PDC ligand chelates and bridges two Ni(II) and two Na(I) centers. Two kinds of metal centers are connected by μ4-PDC and μ2-H2O to form 2D coordination layers. Hydrogen bonds between coordination water molecules and carboxylate oxygen atoms further link these 2D coordination layers to form 3D supramolecular network.

Synthesis, spectroscopic, biological activity and thermal characterization of ceftazidime with transition metals

NASA Astrophysics Data System (ADS)

Masoud, Mamdouh S.; Ali, Alaa E.; Elasala, Gehan S.; Kolkaila, Sherif A.

2018-03-01

Synthesis, physicochemical characterization and thermal analysis of ceftazidime complexes with transition metals (Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Hg(II)) were discussed. It's obtained that ceftazidime act as bidentate ligand. From magnetic measurement and spectral data, octahedral structures were proposed for all complexes except for cobalt, nickel and mercury had tetrahedral structural. Hyper chemistry program confirmed binding sites of ceftazidime. Ceftazidime complexes show higher activity than ceftazidime for some strains. From TG and DTA curves the thermal decomposition mechanisms of ceftazidime and their metal complexes were suggested. The thermal decomposition of the complexes ended with the formation of metal oxides as a final product except in case of Hg complex.

Structure of the Ni(II) complex of Escherichia coli peptide deformylase and suggestions on deformylase activities depending on different metal(II) centres.

PubMed

Yen, Ngo Thi Hai; Bogdanović, Xenia; Palm, Gottfried J; Kühl, Olaf; Hinrichs, Winfried

2010-02-01

Crystal structures of polypeptide deformylase (PDF) of Escherichia coli with nickel(II) replacing the native iron(II) have been solved with chloride and formate as metal ligands. The chloro complex is a model for the correct protonation state of the hydrolytic hydroxo ligand and the protonated status of the Glu133 side chain as part of the hydrolytic mechanism. The ambiguity that recently some PDFs have been identified with Zn(2+) ion as the active-site centre whereas others are only active with Fe(2+) (or Co(2+), Ni(2+) is discussed with respect to Lewis acid criteria of the metal ion and substrate activation by the CD loop.

Tentacle-type immobilized metal affinity cryogel for invertase purification from Saccharomyces cerevisiae.

PubMed

Çetin, Kemal; Perçin, Işık; Denizli, Fatma; Denizli, Adil

2017-11-01

The aim of this study is to investigate the usability of cryogel columns for the purification of invertase from Saccharomyces cerevisiae. Poly(2-hydroxyethyl methacrylate) monolithic columns were produced via cryogelation. Ester groups of the poly(2-hydroxyethyl methacrylate) structure were then converted to imine groups by the reaction with poly(ethylene imine) in the presence of NaHCO 3 . Transition metal ions, Cu(II), Co(II), and Ni(II), were chelated on the PEI-modified cryogel columns. Purification of invertase from natural source namely S. cerevisiae was also studied, and the purification fold values were obtained as 41.350, 44.714, and 30.302 for Cu(II)-chelated, Co(II)-chelated, and Ni(II)-chelated PHEMA/PEI columns, respectively.

Binaphthyl-containing Schiff base complexes with carboxyl groups for dye sensitized solar cell: An experimental and theoretical study

NASA Astrophysics Data System (ADS)

Tsaturyan, Arshak; Machida, Yosuke; Akitsu, Takashiro; Gozhikova, Inna; Shcherbakov, Igor

2018-06-01

We report on synthesis and characterization of binaphthyl containing Schiff base Ni(II), Cu(II), and Zn(II) complexes as promising photosensitizers for dye-sensitized solar cells (DSSC). Based on theoretical and experimental data, the possibility of their application in DSSC was confirmed. To our knowledge, we find dye performance of complex is steric and rigid structure widely spread to efficiency. The spatial and electronic structures of the complexes were studied by means of the quantum chemical modeling using DFT and TD-DFT approaches. The adsorption energies of the complexes on TiO2 cluster were calculated and appeared to be very close in value. The Zn(II) complex has the biggest value of molar extinction.

Uso de modelos mecânicos em curso informal de astronomia para deficientes visuais. Resgate de uma experiência

NASA Astrophysics Data System (ADS)

Tavares, E. T., Jr.; Klafke, J. C.

2003-08-01

O presente trabalho propõe-se a resgatar uma experiência que teve lugar no Planetário de São Paulo nos anos 60. Em 1962, o Sr. Acácio, então com 37 anos, deficiente visual desde os 27, passou a assistir às aulas ministradas pelo Prof. Aristóteles Orsini aos integrantes do corpo de servidores do Planetário. O Sr. Acácio era o único deficiente da turma e, embora possuísse conhecimentos básicos e relativamente avançados de matemática, enfrentava dificuldades na compreensão e acompanhamento da exposição, como também em estudos posteriores. Com o intuito de auxiliá-lo na superação desses problemas, o Prof. Orsini solicitou a construção de modelos mecânicos que, através do sentido do tato, permitissem o acompanhamento das aulas e a transposição do modelo para o "constructo" mental. Essa prática mostrou-se tão eficaz que facilitou sobejamente o aprendizado da matéria pelo sujeito. O Sr. Acácio passou a integrar o corpo de professores do Planetário/Escola Municipal de Astrofísica, tendo ficado responsável pelo curso de "Introdução à Astronomia" por vários anos. Além disso, a experiência foi tão bem sucedida que alguns dos modelos tiveram seus elementos constitutivos pintados diferencialmente para serem utilizados em cursos regulares do Planetário, tornando-se parte integrante do conjunto de recursos didáticos da instituição. É pensando nessa eficácia, tanto em seu objetivo original permitir o aprendizado de um deficiente visual quanto no subsidiário recurso didático sistemático da instituição que decidimos resgatar essa experiência. Estribados nela, acreditamos ser extremamente produtivo, em termos educacionais, o aperfeiçoamento dos modelos originais, agora resgatados e restaurados, e a criação de outros que pudessem ser utilizados no ensino dessa ciência a deficientes visuais.

Evolución de estrellas enanas blancas de Helio de masa baja e intermedia

NASA Astrophysics Data System (ADS)

Althaus, L. G.; Benvenuto, O. G.

Numerosas observaciones realizadas particularmente en los últimos dos años parecen confirmar que las enanas blancas (EB) de helio de masa baja e intermedia son el resultado de la evolución de sistemas binarios cercanos. Con el objeto de realizar una adecuada interpretación de estos objetos son necesarios modelos de EBs de helio lo más detallado posibles. En este estudio presentamos cálculos detallados de la evolución de EBs de helio con masas entre M=0.1Msolar y M=0.5Msolar a intervalos de 0.05Msolar . Para ello, hemos tenido en cuenta los efectos de temperatura finita mediante un código de evolución estelar lo más actualizado posible. En particular, el transporte de energía es descripto en el marco del nuevo modelo para la convección turbulenta desarrollado por Canuto - Mazzitelli. Además hemos considerado la nueva ecuación de estado para plasmas de helio de Saumon et al. y nuevas opacidades radiativas OPAL. Las pérdidas por neutrinos fueron asimismo tenidas en cuenta. Excepto para las EBs más masivas, nuestros modelos iniciales están ubicados en las cercanías de la correspondiente línea de Hayashi para configuraciones de helio. Nuestros resultados muestran que existe una región prohibida en el diagrama observacional HR donde ninguna EB de helio puede encontrarse. Dicha región es para log{(L/Lsolar )}>= -0.25 and log{Teff} >= 4.45. Hemos encontrado también que los tracks evolutivos en el diagrama HR en el dominio de alta luminosidad (pre - EB) son fuertemente afectados por la eficiencia convectiva y que las pérdidas por neutrinos son importantes en los modelos más masivos. Finalmente hemos analizado la estructura de la zona convectiva externa encontrando que la teoría de Canuto - Mazzitelli conduce a un perfil convectivo muy diferente del dado por cualquier versión de la popular teoría de la mixing length. Si bién este comportamiento es decisivo en el contexto de las inestabilides pulsacionales, los radios y gravedades superficiales de los modelos no son afectados al incluir la nueva teoría de convección.

Development and validation of the Hospitality Axiological Scale for Humanization of Nursing Care.

PubMed

Galán González-Serna, José María; Ferreras-Mencia, Soledad; Arribas-Marín, Juan Manuel

2017-08-03

to develop and validate a scale to evaluate nursing attitudes in relation to hospitality for the humanization of nursing care. Participants: the sample consisted of 499 nursing professionals and undergraduate students of the final two years of the Bachelor of Science in Nursing program. the instrument has been developed and validated to evaluate the ethical values related to hospitality using a methodological approach. Subsequently, a model was developed to measure the dimensions forming the construct hospitality. the Axiological Hospitality Scale showed a high internal consistency, with Cronbach's Alpha=0.901. The validation of the measuring instrument was performed using factorial, exploratory and confirmatory analysis techniques with high goodness of fit measures. the developed instrument showed an adequate validity and a high internal consistency. Based on the consistency of its psychometric properties, it is possible to affirm that the scale provides a reliable measurement of the hospitality. It was also possible to determine the dimensions or sources that embrace it: respect, responsibility, quality and transpersonal care. desenvolver e validar uma escala que permita avaliar a atitude dos enfermeiros em termos de hospitalidade, visando a humanização da enfermagem.Participantes: a amostra foi constituída por 499 profissionais e estudantes de enfermagem dos dois últimos anos do curso de graduação em Enfermagem. utilizando-seuma abordagem metodológica, foi desenvolvido e validado um instrumento para avaliar os valores éticos relacionados com a hospitalidade. Subsequentemente, foi formulado um modelo para mediras dimensões que constituem o construto hospitalidade. a Escala Axiológica de Hospitalidade mostrou uma consistência interna elevada, com Alfa de Cronbach=0,901. A validação do instrumento de medição foi realizada usando-se métodos de análise fatorial, exploratória e confirmatória, que apresentaram bons índices de qualidade de ajuste. o instrumento desenvolvido apresentou uma validade adequada e uma consistência interna elevada. Com base na consistência de suas propriedades psicométricas, é possível afirmar que a escala proporciona uma medida confiável da hospitalidade. Também foi possível determinar as dimensões ou fontes que a compõem: o respeito, a responsabilidade, a qualidade e o cuidado transpessoal. desarrollar y validar una escala que permita evaluar la actitud enfermera ante la hospitalidad para la humanización de enfermería. Participantes: la muestra la componen 499 profesionales de enfermería y estudiantes de los dos últimos niveles académicos de la titulación de Grado en Enfermería. mediante abordaje metodológico, se ha desarrollado y validado un instrumento para evaluar valores éticos relacionados con la hospitalidad. Posteriormente, se ha formulado un modelo de medida de las dimensiones que conforman el constructo hospitalidad. la Escala Axiológica de la Hospitalidad ha mostrado una alta consistencia interna, con un Alfa de Cronbach=0.901. La validación del instrumento de medida se realizó mediante las técnicas de análisis factorial, exploratorio y confirmatorio, que presentaron unos buenos índices de bondad de ajuste. el instrumento desarrollado ha presentado una adecuada validez y una alta consistencia interna. Sus adecuadas propiedades psicométricas permiten afirmar que la escala aporta una medición fiable de la hospitalidad. También ha permitido determinar las dimensiones o fuentes que la conforman: el respeto, la responsabilidad, la calidad y el cuidado transpersonal.

Ni xWO 2.72 nanorods as an efficient electrocatalyst for oxygen evolution reaction

DOE PAGES

Xi, Zheng; Mendoza-Garcia, Adriana; Zhu, Huiyuan; ...

2017-01-13

Ni xWO 2.72 nanorods (NRs) are synthesized by a one-pot reaction of Ni(acac) 2 and WCl 4. In the rod structure, Ni(II) intercalates in the defective perovskite-type WO 2.72 and is stabilized. The Ni xWO 2.72 NRs show the x-dependent electrocatalysis for the oxygen evolution reaction (OER) in 0.1M KOH with Ni 0.78WO 2.72 being the most efficient, even outperforming the commercial Ir-catalyst. Lastly, the synthesis is not limited to Ni xWO 2.72 but can be extended to M xWO 2.72 (M = Co, Fe) as well, providing a new class of oxide-based catalysts for efficient OER and other energymore » conversion reactions.« less

Access to Formally Ni(I) States in a Heterobimetallic NiZn System

PubMed Central

Uyeda, Christopher

2014-01-01

Heterobimetallic NiZn complexes featuring metal centers in distinct coordination environments have been synthesized using diimine-dioxime ligands as binucleating scaffolds. A tetramethylfuran-containing ligand derivative enables a stable one-electron-reduced S = 1/2 species to be accessed using Cp2Co as a chemical reductant. The resulting pseudo-square planar complex exhibits spectroscopic and crystallographic characteristics of a ligand-centered radical bound to a Ni(II) center. Upon coordination of a π-acidic ligand such as PPh3, however, a five-coordinate Ni(I) metalloradical is formed. The electronic structures of these reduced species provide insight into the subtle effects of ligand structure on the potential and reversibility of the NiII/I couple for complexes of redox-active tetraazamacrocycles. PMID:25614786

Observations of Cygnus X-2 with IUE: Ultraviolet results from a multiwavelength campaign

NASA Technical Reports Server (NTRS)

Vrtilek, S. D.; Raymond, J. C.; Garcia, M. R.; Verbunt, F.; Hasinger, Guenther; Kuerster, M.

1989-01-01

The observations of the low-mass x ray binary, Cyg X-2, taken with the International Ultraviolet Explorer (IUE) in a campaign conducted in June and October of 1988 are reported. A direct relationship between the strength of the UV continuum and line emission and the placement of the x ray spectrum in one of three branches of the so-called Z-shaped curve is found by comparison with simultaneous x ray observations. All three previously known x ray spectral states are detected; the UV continuum and line emission increase monotonically along the Z with the least emission in the horizontal branch, and the most in the flaring branch. Emission lines due to HeII, CIV, NIII, NIV, NV, SiIV, and MgII are observed.

The metamorphosis of heterometallic trinuclear antiferromagnetic complexes into nano-sized superparamagnetic spinels.

PubMed

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).

Copper(II)-rubeanic acid coprecipitation system for separation-preconcentration of trace metal ions in environmental samples for their flame atomic absorption spectrometric determinations.

PubMed

Soylak, Mustafa; Erdogan, Nilgun D

2006-09-21

A simple and facile preconcentration procedure based on the coprecipitation of trace heavy metal ions with copper(II)-rubeanic acid complex has been developed. The analytical parameters including pH, amounts of rubeanic acid, sample volume, etc. was investigated for the quantitative recoveries of Pb(II), Fe(III), Cd(II), Au(III), Pd(II) and Ni(II). No interferic effects were observed from the concomitant ions. The detection limits for analyte ions by 3 sigma were in the range of 0.14 microg/l for iron-3.4 microg/l for lead. The proposed coprecipitation method was successfully applied to water samples from Palas Lake-Kayseri, soil and sediment samples from Kayseri and Yozgat-Turkey.

FT-IR and FT-Raman spectra of cimetidine and its metallocomplexes

NASA Astrophysics Data System (ADS)

Barańska, M.; Proniewicz, L. M.

1999-11-01

We present vibrational spectra of three stable, well-reproducible, polymorphic forms of cimetidine ( cim), a drug which is a powerful histamine H 2-receptor antagonist used in the treatment of peptic ulcer and the Zollinger-Ellison syndrome. Assignments of Raman and IR bands are made using semiempirical methods: MNDO, AM1 and PM3. We also describe the synthesis of Me( cim) 2(ClO 4) 2, where Me=Cu(II), Cd(II), Co(II) and Ni(II), and present their vibrational data. We show that the obtained complexes are isostructural, however a metal ion that occupies a center of octahedral unit introduces some distortions that can be seen in the spectra. We also make tentative assignment of metal-ligand stretching modes observed in low frequency range.

Grafting transition metal-organophosphonate fragments onto heteropolyoxomolybdate: activity in photocatalysis.

PubMed

Sun, Xiaopeng; Liang, Zhijie; Ma, Pengtao; Ban, Ran; Jiang, Mingshuang; Zhang, Dongdi; Wang, Jingping; Niu, Jingyang

2015-10-28

A novel organophosphonate-functionalized heteropolyoxomolybdate incorporated nickel cluster, CsNa9[H2{Ni3O2(H2O)6}(PMo6O21)2{Ni(OOCCH2NHCH2PO3)2}3]·21H2O (1), has been synthesized, which represents the first member of the family of oxomolybdenum organophosphonate containing hexa-nuclear Ni(ii) in a polyanion framework. The polyanion comprises a unique ladder-type {Ni3O10(H2O)6} cluster and three {Ni(OOCCH2NHCH2PO3)2} bridgings, which are capped on either end by a {PMo6O28} group. Photocatalytic experiments indicate that 1 exhibits catalytic activity for the photodegradation of RhB solution. Furthermore, magnetic studies indicate that 1 displays antiferromagnetic interactions.

Solid-phase extraction of some heavy metal ions on a double-walled carbon nanotube disk and determination by flame atomic absorption spectrometry.

PubMed

Karatepe, Aslihan; Soylak, Mustafa; Elçi, Latif

2011-01-01

A new preconcentration method was developed for the determination of trace amounts of Cu(II), Fe(III), Pb(II), Ni(II), and Cd(II) on a double-walled carbon nanotube disk. 4-(2-Thiazolylazo) resorcinol was used as a complexing reagent. The effects of parameters, including pH of the solutions, amounts of complexing reagent, eluent type, sample volume, flow rates of solutions, and matrix ions were examined for quantitative recoveries of the studied analyte ions. The retained metal ions were eluted by 2 M HNO3. The LOD values for the analytes were in the range of 0.7-4.4 microg/mL. Natural water samples and standard reference materials were analyzed by the presented method.

Difusión de Arnold en un modelo simple

NASA Astrophysics Data System (ADS)

Cincotta, P. M.; Nuñez, J. A.; Miloni, O.

Investigadores como Merritt, Valluri, Pfenniger o Contopoulos (por citar los más relevantes) consideran seriamente la hipótesis que la difusión de Arnold juega un rol importante en la evolución dinámica de los sistemas estelares y planetarios. Sin embargo no existe ninguna evidencia. El mayor problema para investigar fenómenos como éste es que uno debe estudiar numéricamente sistemas multidimensionales (más de dos grados de libertad) y visualizar de alguna manera el espacio de fases (más de cuatro dimensiones). Más complicado aún es el caso de difusión de Arnold, donde deben considerarse tiempos de movimiento extremadamente largos y tratar con parámetros exponencialmente pequeños. El propósito de este trabajo es estudiar, en un modelo simple 3D, la existencia o no de difusión de Arnold mediante experimentos numéricos y estimaciones analíticas. Siguiendo los trabajos de Cincotta (2000) y Cincotta, Nuñez y Simo (2000), aquí se pretende ``visualizar" la difusión y, a la vez, determinar la escala de tiempo en la que ésta se podría manifestar. Este trabajo es el escalón inicial para luego abordar este problema en modelos.

Ajuste de parámetros libres en teorías de campos camaleones a partir de espectros de nubes moleculares galácticas y experimentos terrestres

NASA Astrophysics Data System (ADS)

Teppa Pannia, F. A.; Landau, S. J.

Resultados recientes, basados en el análisis de espectros moleculares de nubes galácticas a través del método del amoníaco, han arrojado nuevos límites sobre la variación del parámetro adimensional μ=m_e /m_p. Los resultados indican Δ μ/μ = (μ_{obs}-μ_{lab})/μ_{lab}= (2.2± 0.4_{est} ±0.3_{sist}) times 10 ^{-8}, en acuerdo con una variación no nula de dicha cantidad (Levshakov et al. 2010). En este trabajo, motivado por los datos astronómicos, estudiamos la solución lineal del modelo teórico fenomenológico de campo escalar camaleón, presentado por Mota y Shaw (2007), que predice variaciones en μ. Con el fin de cotejar estas predicciones con los resultados observacionales, utilizamos datos de experimentos terrestres que testean violaciones al Principio de Equivalencia para analizar el valor de los parámetros libres presentes en el modelo. El trabajo realizado muestra que la solución estudiada no se puede ajustar a los datos experimentales, sugiriendo que el modelo lineal debe ser descartado para explicar las observaciones astronómicas. FULL TEXT IN SPANISH

Estudio de la formación de galaxias espirales en un modelo de agregación jerárquica

NASA Astrophysics Data System (ADS)

Tissera, P.; Saiz, A.; Dominguez-Tenreiro, R.

El estudio de formación de galaxias espirales ha llevado al desarrollo de numerosos modelos teóricos (e.g. White & Rees 1978). En la actualidad, el modelo más aceptado predice la formación de una galaxia espiral a partir del colapso disipativo del gas en el pozo de potencial de un halo oscuro, conservando su momento angular específco (Fall & Efstathiou 1980). En los últimos años, ha sido posible realizar simulaciones numéricas hidrodinámicas, las cuales describen la evolución conjunta de la materia oscura y los bariones. Estos experimentos han señalado la dificultad de formar estructuras discoidales con propiedades consistentes con las observaciones, en modelos de agregación jerárquica. El problema principal se origina en la pérdida catastrófica de momento angular de la componente disipativa, durante el proceso de ensamblaje de los objetos, a través de la fusión de subestructura (Navarro & Steinmetz 1997). Estos experimentos no incluían procesos de formación estelar. En este trabajo, se expondrán resultados de simulaciones hidrodinámicas cosmológicas, incluyendo formación estelar (Tissera et al 1997), donde ha sido posible reproducir objetos discoidales con contrapartida observacional. El elemento fundamental ha sido la formación de bulbos estelares, los cuales han evitado la pérdida catastrófica de momento angular de los bariones. Se encontró que los discos exponenciales puramente gaseosos son altamente inestables y suceptibles de generar barras, responsables de la pérdida de momento angular y la caída violenta del gas hacia la región central. Estas inestabilidades son fácilmente inducidas durante interacciones y fusiones con objetos vecinos (Barnes & Hernquist 1996). Un bulbo estelar (o un objeto masivo y compacto) estabiliza el disco ante perturbaciones externas, asegurándole un potencial simétrico (Sellwood & Moore 1998, Van der Bosch 1998). En este caso, el gas en el disco no pierde completamente su momento angular intrínseco durante las fusiones, sino que, las sobrevive aportando una contribución distinta de cero, a partir de la cual el disco se regenera acretando en una segunda etapa, gas del halo de acuerdo al modelo tradicional de Fall & Efstathiou.

Condiciones Físicas en Nebulosas Gaseosas

NASA Astrophysics Data System (ADS)

Luridiana, V.

1999-03-01

El presente trabajo se ha enfocado a determinar y entender las condiciones físicas en una variedad de objetos nebulares, prestando particular atención al problema de la determinación de las abundancias químicas. Para este fin, hemos utilizado métodos analíticos en algunos casos, y modelos numéricos de fotoionización en otros. El objetivo general del trabajo es proveer de una visión amplia de las herramientas teórico-observacionales que se utilizan para la determinación de la estructura de temperatura y densidad de las regiones fotoionizadas, poniendo en evidencia posibles fuentes de errores sistemáticos y sus consecuencias para la determinación de las abundancias químicas, y proponiendo métodos para corregirlos. Los resultados principales de este trabajo est´n listados a continuación: a) Se discute el problema de la discrepancia entre T(C III) y T(O III) en las nebulosas planetarias, y se muestra como tal discrepancia implica probablemente la presencia de fluctuaciones de temperatura. Debido a que la temperatura de O++ es muy afectada por fluctuaciones de temperatura, se recomienda usar la temperatura de C++ para determinar la abundancia de carbono. b) Presentamos dos nuevos métodos para determinar la temperatura electrónica en nebulosas planetarias, basados en la medición de las intensidades de las líneas de He I. Las temperaturas que se obtienen a partir de estos métodos son menores que aquellas que se obtienen a partir de las líneas de [O III], implicando la presencia de fluctuaciones espaciales de temperatura. Despreciando las fluctuaciones de temperatura, se obtienen valores sesgados de las abundancias químicas. Determinamos las abundancias en las nebulosas planetarias de tipo I de algunos de los elementos más importantes, tomando en cuenta las fluctuaciones de temperatura. c) Presentamos modelos numéricos de las dos regiones H II extragalácticas gigantes NGC 2363 y NGC 5461. Con el modelaje numérico, pretendemos acotar las carácteristicas principales de las nubes ionizadas (distribución espacial del gas, estructura de ionización y de temperatura) y de los cúmulos ionizantes (función inicial de masa, historia de formación estelar, edad). En ambos casos, mostramos que con modelos numéricos calculados para el valor de metalicidad que se determina a partir de la temperatura de [O III], no es posible reproducir el espectro de emisión observado, y que para reproducir las restricciones más robustas es necesario subir la metalicidad de los modelos por un factor de 2. Esto constituye una fuerte indicación en favor de la presencia de fluctuaciones de temperatura. d) Para poder comparar los modelos numéricos con los datos observacionales. mostramos la importancia de corregir las predicciones de los modelos por el sesgo introducido por el tamaío finito de la rendija.

Is the Dark Side of the Moon Ever Illuminated by the Sun? (Breton Title: O Lado Escuro da Lua Nunca Apanha Sol?) El Lado Oscuro de la Luna Nunca Toma Sol?

NASA Astrophysics Data System (ADS)

Giovannini, Odilon; Pellenz, Daiana; Catelli, Francisco

2014-07-01

This work presents the elaboration of an answer to the question "Is the dark side of the moon ever illuminated by the sun?", in which issues related to the students' conceptions, how they arise, and the core elements that constitute a "good answer" are considered. These issues are initially elaborated from a literature review of the research in the field; then, and also based on this review, a didactic model that involves the relative motions of the Earth - Moon - Sun system is proposed. A description of the application of this model in a learning environment within middle school students is described. This work confirms the students' initial concepts described in the literature; on the other hand, the questions asked by students during the activity provide evidence that meaningful learning, at least to some degree, has occurred. Este trabalho apresenta a elaboração de uma resposta à pergunta "O lado escuro da Lua nunca apanha sol?" na qual são consideradas questões relacionadas às concepções iniciais dos alunos, de onde elas surgem e os elementos centrais que constituem uma "boa resposta". Essas questões são tratadas, inicialmente, a partir de uma revisão da literatura sobre pesquisas na área e, em seguida, também com base nessa revisão, um objeto modelo didático que envolve os movimentos relativos do sistema Terra - Lua - Sol é proposto. Uma descrição detalhada da aplicação deste modelo em um ambiente de aprendizagem com alunos do ensino fundamental é relatada. As concepções iniciais apresentadas na literatura se confirmam e os questionamentos feitos pelos estudantes por ocasião da aplicação do modelo fornecem indícios de que uma aprendizagem significativa, pelo menos em algum grau, ocorreu. El artículo se presenta el desarrollo de una respuesta a la pregunta "¿El lado oscuro de la luna nunca toma sol?", en la que se consideran algunas cuestiones vinculadas que se refieren a las concepciones iniciales de los estudiantes, dónde surgen y los elementos básicos que componen una "respuesta correcta". Estas cuestiones se tratan inicialmente a partir de una revisión bibliográfica de la investigación en el área; seguidamente, y también sobre la base de ésta revisión, se propone un modelo didáctico que ejemplifica los movimientos relativos del sistema Tierra - Luna - Sol. Se describe a continuación una aplicación de este modelo en un entorno de aprendizaje con alumnos del ciclo primario. Los conceptos iniciales presentados en la literatura se confirman y las cuestiones planteadas por los estudiantes durante la implementación del modelo proporcionan evidencia de que se ha producido un aprendizaje significativo, al menos en cierta medida.

Far-Infrared Spectroscopy of Planetary Nebulae with the KAO

NASA Technical Reports Server (NTRS)

Rubin, Robert H.; Colgan, S.; Haas, M. R.; Lord, S. D.; Simpson, Janet P.

1996-01-01

We present new far-infrared line observations of the planetary nebulae (PNs) NGC 7027, NGC 7009, and NGC 6210 obtained with the Kuiper Airborne Observatory (KAO). The bulk of our data are for NGC 7027 and NGC 7009, including [Ne(V)] 24 micrometers, [O(IV)] 26 micrometers, [O(III)] (52, 88) micrometers, and [N(III)] 57 micrometers. Our data for [O(III)] (52, 88) and [N(III)] 57 in NGC 7027 represent the first measurements of these lines in this source. The large [O(III)] 52/88-micrometer flux ratio implies an electron density (cubic cm) of log N(sub e)[O(III)] = 4.19, the largest Ne ever inferred from these lines. We derive N(++)/O(++) = 0.394 +/- 0.062 for NGC 7027 and 0.179 +/- 0.043 for NGC 6210. We are able to infer the O(+3)/O(++) ionic ratio from our data. As gauged by this ionic ratio, NGC 7027 is substantially higher ionization than is NGC 7009 - consistent with our observation that the former produces copious [Ne(V)] emission while the latter does not. These data help characterize the stellar ionizing radiation field. From our [O(IV)] and [O(III)] fluxes, we are able to show that O(++) is by far the dominant oxygen ion in NGC 7009. As a result, the O/H abundance inferred using these data tends to corroborate the value found from UV/optical, collisionally excited lines. We determined accurate rest wavelengths for the [Ne(V)] 2s(2)2p(2)P(sub 1) to 2s(2)2p(2)3P(sub 0) (lambda(sub rest) = 24.316 +/- 0.008 micrometers) and [O(IV)] 2s(2)2p(2)P(sup 0, sub 3/2) to 2s(2)2p(2)P(sup 0, sub 1/2) (lambda(sub rest) = 25.887 +/- 0.007 micrometers) transitions from observations of one or both of the bright PNs NGC 7027 and NGC 7009. Our [O(IV)] value, to the best of our knowledge, is the most accurate direct determination of this lambda(sub rest). These new KAO data will be beneficial for comparison with ISO observations of these PNs.

Synthesis, characterization and biological activity of some transition metals with Schiff base derived from 2-thiophene carboxaldehyde and aminobenzoic acid.

PubMed

Mohamed, Gehad G; Omar, M M; Hindy, Ahmed M M

2005-12-01

Metal complexes of Schiff base derived from 2-thiophene carboxaldehyde and 2-aminobenzoic acid (HL) are reported and characterized based on elemental analyses, IR, 1H NMR, solid reflectance, magnetic moment, molar conductance and thermal analysis (TGA). The ligand dissociation as well as the metal-ligand stability constants were calculated pH metrically at 25 degrees C and ionic strength mu=0.1 (1M NaCl). The complexes are found to have the formulae [M(HL)2](X)n.yH2O (where M=Fe(III) (X=Cl, n=3, y=3), Co(II) (X=Cl, n=2, y=1.5), Ni(II) (X=Cl, n=2, y=1) and UO2(II) (X=NO3, n=2, y=0)) and [M(L)2] (where M=Cu(II) (X=Cl) and Zn(II) (X=AcO)). The molar conductance data reveal that Fe(III) and Co(II), Ni(II) and UO2(II) chelates are ionic in nature and are of the type 3:1 and 2:1 electrolytes, respectively, while Cu(II) and Zn(II) complexes are non-electrolytes. IR spectra show that HL is coordinated to the metal ions in a terdentate manner with ONS donor sites of the carboxylate O, azomethine N and thiophene S. From the magnetic and solid reflectance spectra, it is found that the geometrical structure of these complexes are octahedral. The thermal behaviour of these chelates shows that the hydrated complexes losses water molecules of hydration in the first step followed immediately by decomposition of the anions and ligand molecules in the subsequent steps. The activation thermodynamic parameters, such as, E*, DeltaH*, DeltaS* and DeltaG* are calculated from the DrTG curves using Coats-Redfern method. The synthesized ligands, in comparison to their metal complexes also were screened for their antibacterial activity against bacterial species, Escherichia coli, Pseudomonas aeruginosa, Staphylococcus pyogones and Fungi (Candida). The activity data show that the metal complexes to be more potent/antibacterial than the parent Schiff base ligand against one or more bacterial species.

Synthesis, characterization and biological activity of some transition metals with Schiff base derived from 2-thiophene carboxaldehyde and aminobenzoic acid

NASA Astrophysics Data System (ADS)

Mohamed, Gehad G.; Omar, M. M.; Hindy, Ahmed M. M.

2005-12-01

Metal complexes of Schiff base derived from 2-thiophene carboxaldehyde and 2-aminobenzoic acid (HL) are reported and characterized based on elemental analyses, IR, 1H NMR, solid reflectance, magnetic moment, molar conductance and thermal analysis (TGA). The ligand dissociation as well as the metal-ligand stability constants were calculated pH metrically at 25 °C and ionic strength μ = 0.1 (1 M NaCl). The complexes are found to have the formulae [M(HL) 2](X) n· yH 2O (where M = Fe(III) (X = Cl, n = 3, y = 3), Co(II) (X = Cl, n = 2, y = 1.5), Ni(II) (X = Cl, n = 2, y = 1) and UO 2(II) (X = NO 3, n = 2, y = 0)) and [M(L) 2] (where M = Cu(II) (X = Cl) and Zn(II) (X = AcO)). The molar conductance data reveal that Fe(III) and Co(II), Ni(II) and UO 2(II) chelates are ionic in nature and are of the type 3:1 and 2:1 electrolytes, respectively, while Cu(II) and Zn(II) complexes are non-electrolytes. IR spectra show that HL is coordinated to the metal ions in a terdentate manner with ONS donor sites of the carboxylate O, azomethine N and thiophene S. From the magnetic and solid reflectance spectra, it is found that the geometrical structure of these complexes are octahedral. The thermal behaviour of these chelates shows that the hydrated complexes losses water molecules of hydration in the first step followed immediately by decomposition of the anions and ligand molecules in the subsequent steps. The activation thermodynamic parameters, such as, E*, Δ H*, Δ S* and Δ G* are calculated from the DrTG curves using Coats-Redfern method. The synthesized ligands, in comparison to their metal complexes also were screened for their antibacterial activity against bacterial species, Escherichia coli, Pseudomonas aeruginosa, Staphylococcus pyogones and Fungi (Candida). The activity data show that the metal complexes to be more potent/antibacterial than the parent Schiff base ligand against one or more bacterial species.

DESAFÍOS ÉTICOS DE LA INVESTIGACIÓN CON ANIMALES, MANIPULACIÓN GENÉTICA

PubMed Central

Yunta, Eduardo Rodríguez

2012-01-01

En la investigación con animales existen cuestionamientos éticos tanto en el uso como modelos de enfermedades humanas y requisito previo para ensayos en humanos como en la introducción de modificaciones genéticas. Algunos de estos cuestionamientos son: no representar exactamente la condición humana como modelos, realizar pruebas de toxicidad con grave daño para los animales, alterar su naturaleza mediante modificaciones genéticas, riesgos de la introducción de organismos genéticamente modificados. El uso de animales en investigación para beneficio humano, impone al ser humano la responsabilidad moral de respetarlo, no haciéndoles sufrir innecesariamente, al estar trabajando con seres vivientes y sentientes. PMID:23338641

The applicability of the concept of treatment adherence in the context of the Brazilian mental health system.

PubMed

Alvarez, Patricia Elizabeth Sanz de; Rosendo, Ernestina; Alchieri, João Carlos

2016-06-01

To present reflections on the type of research conducted on a treatment adherence among users of Public Mental Health System in Brazil and discuss the applicability of the concept of adherence to treatment in this context. Literature review in SciELO, LILACS, Cochrane Library and PubMed / MEDLINE using the Health Sciences Descriptors (DeCS) treatment, adhesion and "mental health" and the specific vocabulary of the Medical Subject Headings (MeSH) "patient compliance/psychologist" y "mental health". They were included for review the complete texts and theses published between 2007-2012 in Portuguese, English and Spanish. 127 articles were recovered, 32 specifically related to mental health. Eight were excluded for duplicates and after reading the remaining 24 articles were selected for this study 10 conducted in the field of Mental Health in Brazil. No investigations have been identified with focus on adherence to psychosocial treatment offered in public mental health. disregard of the mental health legislation and reinforce the asylum model of assistance. Presentar reflexiones sobre el tipo de investigaciones realizadas en Brasil sobre la adhesión al tratamiento de los usuarios del Sistema Público de Salud Mental y discutir la aplicabilidad del concepto de adhesión al tratamiento en dicho contexto. Revisión bibliográfica en las bases SciELO, LILACS, Biblioteca Cochrane y PubMed/MEDLINE utilizando los descriptores de Ciencias de la Salud (DeCS) adhesión, tratamiento y "salud mental" y el vocabulario específico de Medical Subject Headings (MeSH) "patient compliance/psychologist" y "mental health". Se incluyeron los textos completos y las tesis publicadas entre 2007-2012, en portugués, inglés y español. F1eron recuperados 127 artículos, 32 específicamente de la salud mental. Se excluyeron los 8 duplicados y de los 24 restantes fueron seleccionados para el presente trabajo los 10 realizados en Brasil. No se identificaron enfoques sobre la adhesión al tratamiento de perspectiva psicosocial ofrecido en la red pública de salud mental. Las investigaciones analizadas desconsideran el contexto y la complejidad del tratamiento ofrecido desconociendo la legislación en salud mental vigente y reforzando el modelo de atención asilar.

Design and synthesis of metal complexes of (2E)-2-[(2E)-3-phenylprop-2-en-1-ylidene]hydrazinecarbothioamide and their photocatalytic degradation of methylene blue.

PubMed

Krishna, P Murali; Reddy, N B Gopal; Kottam, Nagaraju; Yallur, B C; Katreddi, Hussain Reddy

2013-01-01

The photocatalytic degradation has been considered to be an efficient process for the degradation of organic pollutants, which are present in the effluents released by industries. The photocatalytic bleaching of cationic dye methylene blue was carried out spectrometrically on irradiation of UV light using Cu(II), Ni(II), and Co(II) complexes of (2E)-2-[(2E)-3-phenylprop-2-en-1-ylidene]hydrazinecarbothioamide (HL). The effects of pH and metal ion were studied on the efficiency of the reaction. Cu(II) complex shows better catalytic activity and the highest percentage degradation (~88.8%) of methylene blue was observed at pH 12. A tentative mechanism has also been proposed for the photocatalytic degradation of methylene blue.

"Periodic-table-style" paper device for monitoring heavy metals in water.

PubMed

Li, Miaosi; Cao, Rong; Nilghaz, Azadeh; Guan, Liyun; Zhang, Xiwang; Shen, Wei

2015-03-03

If a paper-based analytical device (μ-PAD) could be made by printing indicators for detection of heavy metals in chemical symbols of the metals in a style of the periodic table of elements, it could be possible for such μ-PAD to report the presence and the safety level of heavy metal ions in water simultaneously and by text message. This device would be able to provide easy solutions to field-based monitoring of heavy metals in industrial wastewater discharges and in irrigating and drinking water. Text-reporting could promptly inform even nonprofessional users of the water quality. This work presents a proof of concept study of this idea. Cu(II), Ni(II), and Cr(VI) were chosen to demonstrate the feasibility, specificity, and reliability of paper-based text-reporting devices for monitoring heavy metals in water.

The Origin of NIII λ990 and CIII λ977 Emission in NGC 1068

NASA Astrophysics Data System (ADS)

Ferguson, Jason W.; Ferland, Gary J.

1994-12-01

We discuss implications of HUT detections of C III λ977 and N III λ990 emission from the Narrow Lined Region (NLR) of the Seyfert 2 galaxy NGC 1068. In their discovery paper Kriss et al. (1992, ApJ, 394, L37) showed that unexpectedly great strength of these lines implies that the emitting gas must be shock heated if the lines are collisionally excited. Here we investigate other processes which excite these lines in photoionization equilibrium. Recombination, mainly dielectronic, and continuum fluorescence, are strong contributors to the line. The resulting intensities are sensitive to the velocity field of the emitting gas, and require that the turbulence be the same order of magnitude as the observed line width. We propose optical observations that will decide whether the gas is collisionally or radiatively heated.

A sigmoidal model for biosorption of heavy metal cations from aqueous media.

PubMed

Özen, Rümeysa; Sayar, Nihat Alpagu; Durmaz-Sam, Selcen; Sayar, Ahmet Alp

2015-07-01

A novel multi-input single output (MISO) black-box sigmoid model is developed to simulate the biosorption of heavy metal cations by the fission yeast from aqueous medium. Validation and verification of the model is done through statistical chi-squared hypothesis tests and the model is evaluated by uncertainty and sensitivity analyses. The simulated results are in agreement with the data of the studied system in which Schizosaccharomyces pombe biosorbs Ni(II) cations at various process conditions. Experimental data is obtained originally for this work using dead cells of an adapted variant of S. Pombe and represented by Freundlich isotherms. A process optimization scheme is proposed using the present model to build a novel application of a cost-merit objective function which would be useful to predict optimal operation conditions. Copyright © 2015. Published by Elsevier Inc.

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

NASA Astrophysics Data System (ADS)

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.

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

NASA Astrophysics Data System (ADS)

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

2016-05-01

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

Perda de massa em ventos empoeirados de estrelas supergigantes

NASA Astrophysics Data System (ADS)

Vidotto, A. A.; Jatenco-Pereira, V.

2003-08-01

Em praticamente todas as regiões do diagrama HR, as estrelas apresentam evidências observacionais de perda de massa. Na literatura, pode-se encontrar trabalhos que tratam tanto do diagnóstico da perda de massa como da construção de modelos que visam explicá-la. O amortecimento de ondas Alfvén tem sido utilizado como mecanismo de aceleração de ventos homogêneos. Entretanto, sabe-se que os envelopes de estrelas frias contêm grãos sólidos e moléculas. Com o intuito de estudar a interação entre as ondas Alfvén e a poeira e a sua conseqüência na aceleração do vento estelar, Falceta-Gonçalves & Jatenco-Pereira (2002) desenvolveram um modelo de perda de massa para estrelas supergigantes. Neste trabalho, apresentamos um estudo do modelo acima proposto para avaliar a dependência da taxa de perda de massa com alguns parâmetros iniciais como, por exemplo, a densidade r0, o campo magnético B0, o comprimento de amortecimento da onda L0, seu fluxo f0, entre outros. Sendo assim, aumentando f0 de 10% a partir de valores de referência, vimos que aumenta consideravelmente, enquanto que um aumento de mesmo valor em r0, B0 e L0 acarreta uma diminuição em .

Estudio ab initio del mecanismo de la reacción HSO + O3

NASA Astrophysics Data System (ADS)

Nebot Gil, I.

La reacción entre el radical HSO y el ozono ha sido ampliamente estudiada desde el punto de vista experimental debido a la importancia que tiene el radical HSO en la oxidación de los compuestos de azufre reductores y a que puede contribuir a la producción de H2SO4 [1-4]. Se realizaron diversos estudios teóricos sobre la cinética de la reacción entre el radical HSO y el ozono. La reacción del HSO con el ozono presenta tres canales diferentes : HSO + O3 &rightarrow &HSO2 + O2 &rightarrow &HS + 2 O2 &rightarrow &SO + OH + O2 La controversia existente entre los grupos experimentales sobre cuál de las tres vías es la predominante, se ha resuelto mediante un estudio teórico de todas ellas utilizando métodos ab initio. La estructura de todos los reactivos, productos, intermedios y estados de transición ha sido optimizada a nivel ab initio utilizando los métodos UMP2 /6-31G** y QCISD/6-31G**.

Operational tools and applications of EO satellite data to retrieve surface fluxes in semi-arid countries

NASA Astrophysics Data System (ADS)

Tanguy, Maliko

The objective of the thesis is to develop and evaluate useful tools and applications of Earth Observation (EO) satellite data to estimate surface fluxes in semi-arid countries. In a first part (Chapter 4), we assess the performance of a new parameterisation scheme of ground heat flux (G) to be used in remote sensing (RS) evapotranspiration (ET) estimation methods. The G-parameterisation optimized with AMMA flux data performs well and improves the sensible heat flux (H) and ET retrieved by means of the triangle method (Jiang & Islam, 2001). In a second part (Chapter 5), the triangle method is compared with ET estimated by means of a land surface model (JULES). An attempt is made to calibrate JULES using the triangle method through Monte Carlo simulations, but the two methods supply rather different results, indicating that further intercomparison tasks should be carried out to assess the performance of RS-based algorithms and land surface models in estimating the components of the land surface energy balance. Chapter 6 presents a set of operational examples for retrieving surface fluxes using RS data. The first example is the study of temporal evolution of ET-maps in Western Africa under monsoonal influence. In a second example, we apply the new scheme proposed in Chapter 4 to retrieve and analyse the long term evolution (2000-2009) of the surface energy balance components, G, H and ET at several sites of the Segura Basin (S-E Spain) using MODIS-Terra data (land surface temperature and NDVI). Temporal and spatial distribution of evapotranspiration reveals different controls on ET. (Chapter 6). In the last example, MODIS-Aqua Sea Surface Temperature (SST) is used to validate a mathematical model to retrieve surface fluxes in a Mediterranean coastal lagoon (Mar Menor, S-E Spain). El objetivo de esta tesis es de desarrollar y evaluar herramientas y aplicaciones de la teledetección para estimar flujos de superficie en zonas semiáridas. En una primera parte (Capítulo 4), se evalúa la fiabilidad de una nueva parametrización para estimar el flujo de calor en el suelo (G) con el fin de ser utilizado en métodos de estimación de la evapotranspiración (ET) usando datos de teledetección. La parametrización de G se optimiza usando datos de flujo de energía obtenido durante las campañas del proyecto AMMA, y muestra buenos resultados y una mejora de las estimaciones del flujo de calor sensible (H) y de ET cuando se utiliza conjuntamente con el método del triángulo (Jiang & Islam, 2001). En una segunda parte (Capítulo 5), el método del triángulo se compara con valores de ET estimado por un modelo de superficie terrestre (JULES). Se intenta calibrar JULES usando el método del triángulo mediante simulaciones de Monte Carlo, pero los dos métodos muestran resultados muy diferentes, indicando que se necesita tareas de comparación profundizadas para poder evaluar la eficacia de estos modelos (de superficie terrestre y basados en la teledetección) para estimar los flujos de energía a la superficie. El capítulo 6 presenta un conjunto de ejemplos de aplicaciones operacionales para estimar los flujos de superficie usando datos de teledetección. El primer ejemplo consiste en el estudio de la evolución temporal de mapas de ET en África occidental bajo la influencia del monzón africano. En el segundo ejemplo, se aplica la nueva parametrización de G descrita en el capítulo 4 para calcular y analizar la evolución a largo plazo (2000-2009) de los componentes del balance de energía a la superficie, G, H y ET, en diferentes puntos de la cuenca del río Segura (Sureste español) utilizando datos del sensor MODIS-Terra (temperatura superficial y NDVI). La distribución temporal y espacial de ET revela diferentes controles sobre ET. En el último ejemplo, datos de temperatura superficial del mar del sensor MODIS-Aqua se utilizaron para validar un modelo matemático para calcular los flujos superficiales de una laguna costera del Mediterráneo (Mar Menor en el Sureste español).

78 FR 58559 - United States

Federal Register 2010, 2011, 2012, 2013, 2014

2013-09-24

... license to ten Modelo Brand Beers, including Corona Extra, this country's bestselling imported beer and... failure of the government to discharge its duty, the Court, in making its public interest finding, should...

Sobre a largura da última superfície de espalhamento

NASA Astrophysics Data System (ADS)

Nobre, M. A. S.; Pires, N.; Lima, J. A. S.

2003-08-01

De acordo com o modelo do "Big-Bang", no universo primordial a matéria estava em equilíbrio térmico com a radiação. Com a expansão a temperatura da radiação cai. Quando a temperatura chega em torno dos 4.000K, os espalhamentos diminuem, começando a recombinação dos prótons e elétrons em Hidrogênio neutro (era conhecida como da recombinação). Ao final da recombinação, os fótons se propagam livremente sofrendo, em princípio, somente os efeitos do "redshift" cosmológico. Esses fótons nos alcançam hoje como a radiação cósmica de fundo (RCF), e parecem vir de uma superfície esférica ao nosso redor, tal que o raio dela é a distância que ele viajou desde seu último espalhamento na época da recombinação. Naturalmente, esse processo não ocorreu abruptamente, implicando na existência de uma largura no espaço dos "redshifts" que deve depender do modelo cosmológico específico e dos processos físicos considerados. Neste trabalho analisamos os efeitos de diferentes modelos - a saber, aqueles com decaimento do vácuo L(t), criação de matéria, quintessência e gás de Chaplygin - sobre a última superfície de espalhamento da RCF, em particular sua largura e a função visibilidade, que determina a probabilidade de um fóton ter tido seu último espalhamento num "redshift" z. No caso particular dos modelos com decaimento do vácuo, existe uma forte dependência da função visibilidade com L(t). Tais efeitos poderão ser testados através da análise dos resultados de experimentos mais precisos que estão atualmente em andamento, como por exemplo, o WMAP.

Structural and Dynamical Aspects of Electrodeposition

DTIC Science & Technology

1993-05-01

Lfquido Utilizando Ondas Estacionarias de Rayos X " Investigaci6n y Ciencia (Scientific American in Spanish) (invited and submitted) 10. Bommarito, G. M...investigations researchers have emphasized the underpotential deposition of metal mono and multilayers employing electrochemical, x -ray based and ultra high...of adsorbate employed. 2. The underpotential deposition of copper on an iodine covered platinum surface by x -ray based techniques with emphasis on: a

Los cambios en la velocidad de rotación terrestre y los fenómenos geomagnéticos

NASA Astrophysics Data System (ADS)

Gianibelli, J. C.

Uno de los aspectos importantes relativos a la geodinámica del interior terrestre es la correlación entre los eventos de cambio en la velocidad de rotación terrestre y los determinados en los elementos del campo geomagnético por ejemplo, la Declinación Magnética, o los coeficientes de los modelos matemáticos de representación global de dicho campo. En este trabajo se presentan los resultados de las características espectrales de los cambios observados en la longitud del día (ldd), y su relación con la estructura espectral de las coeficientes de los modelos matemáticos de campo denominados Campo Internacional Geomagnético de Referencia (CIGR). El intervalo estudiado comprende los últimos 100 años. Los resultados muestran una correlación en las bandas de 60 y 30 años, con posibles períodos mucho mayores que no son posibles determinar a partir de los modelos de CIRG. Se efectúa una simulación a partir de los resultados obtenidos por la aplicación del método de máxima entropía con longitudes del filtro predictor de error comprendida entre el 10% y el 95% de la longitud de la serie analizada. Se observan procesos sicrónicos y asincrónicos que, en muy largos intervalos de tiempos, podrían suponerse como caóticos.

Modelizacion, control e implementacion de un procesador energetico paralelo para aplicacion en sistemas multisalida

NASA Astrophysics Data System (ADS)

Ferreres Sabater, Agustin

Cualquier sistema electronico que incluya un procesado o tratamiento de la senal, y ademas, algun tipo de actuador mecanico generalmente necesita, como minimo, dos tensiones diferentes de alimentacion. Excluyendo los sistemas de alimentacion distribuida, la solucion tecnica mas utilizada para proporcionar dos o mas tensiones consiste en las fuentes de alimentacion multisalida. En una fuente de alimentacion multisalida los diferentes circuitos que conforman cada salida comparten un mismo transformador de potencia optimizando coste, masa, y volumen. Las ventajas obtenidas con este procedimiento tienen en su contra el efecto que sobre cada salida individual provocan las demas en su conjunto debido, principalmente, a los efectos de los elementos parasitos de los componentes. Un cambio de carga en una de las salidas produce un transitorio que es visto por todas las demas como un efecto de impedancia cruzada, y al final del transitorio, la tension de cada salida es diferente respecto a la que tenian antes del transitorio. Este ultimo resultado se conoce como regulacion cruzada. La disminucion de los efectos de la regulacion cruzada ha sido objeto de estudio durante los ultimos anos. El objetivo ha sido el desarrollo de distintas estrategias que permiten, desde disminuir los efectos de la regulacion cruzada hasta los niveles deseables, a eliminarla completamente. El resultado final suele suponer una penalizacion sobre el diseno del sistema directamente proporcional al grado de regulacion a conseguir en las distintas salidas. Entre las soluciones propuestas para eliminar la regulacion cruzada las tecnicas de post-regulacion se han consolidado como la opcion mas aceptada ya que, pueden aplicarse a cualquier convertidor y no suponen ninguna complejidad adicional a la hora de plantear el diseno. En esta Tesis Doctoral se abordara el estudio de la tecnica conocida como postregulacion mediante transformador controlado, que si bien se ha empleado en convertidores resonantes, su modelizacion, y aplicacion en convertidores PWM, esta aun por estudiar y valorar. El primer Capitulo consiste en una breve introduccion al problema de la regulacion cruzada y la impedancia cruzada para posteriormente describir las tecnicas de post-regulacion actualmente mas empleadas, con especial atencion al post-regulador con transformador controlado. El Capitulo segundo trata del estudio de las caracteristicas estaticas del postregulador con transformador controlado. Partiendo de los estudios disponibles sobre el postregulador se plantean mejoras en su modo de actuacion y se discuten tres alternativas diferentes para controlar el transformador. Las dos primeras consisten en emplear un convertidor auxiliar Boost en sus dos modos de funcionamiento, continuo y discontinuo. La tercera consiste en controlar el transformador con una tension PWM directamente, sin filtrado. Finalmente se comprueba experimentalmente, para el estado estacionario, el funcionamiento del post-regulador para cada uno de los tres metodos de control. El Capitulo tercero trata de la dinamica de la salida controlada con el post-regulador cuando este emplea un convertidor auxiliar tipo Boost. Mediante la tecnica de promediado de variables de estado se propone el modelo de pequena senal, tanto para el modo continuo como para el modo discontinuo de funcionamiento del convertidor auxiliar. Los resultados mas significativos de esta seccion son las expresiones analiticas de las impedancias cruzadas y de la impedancia de la salida post-regulada. Como complemento al modelo de pequena senal se plantea un modelo de gran senal implementado sobre el simulador Pspice. Con este nuevo modelo se reproducen los resultados obtenidos con el modelo de pequena senal y ademas es posible simular los transitorios en las tensiones de salida ante cambios de carga. La modelizacion del convertidor cuando el transformador se controla con una tension PWM sin filtrar es el objetivo del Capitulo 4. En las secciones siguientes del Capitulo se plantea el correspondiente modelo de gran senal aplicado a un nuevo prototipo experimental, de mayor tension de entrada y mayores corrientes de salida. El final del Capitulo contrasta los resultados experimentales con los teoricos confirmando la utilidad del modelo de gran senal como una herramienta basica de diseno. Finalmente, en el Capitulo 5, se presentan las conclusiones y la valoracion de los diferentes estudios plateados a lo largo de la Tesis Doctoral.

Elastoplasticidad anisotropa de metales en grandes deformaciones

NASA Astrophysics Data System (ADS)

Caminero Torija, Miguel Angel

El objetivo de este trabajo es el desarrollo de modelos y algoritmos numericos que simulen el comportamiento del material bajo estas condiciones en el contexto de programas de elementos finitos, dando como resultado predicciones mas precisas de los procesos de conformado y deformacion plastica en general. Para lograr este objetivo se han desarrollado diversas tareas destinadas a mejorar las predicciones en tres aspectos fundamentales. El primer aspecto consiste en la mejora de la descripcion del endurecimiento cinematico anisotropo en pequenas deformaciones, lo cual se ha realizado a traves de modelos y algoritmos implicitos de superficies multiples. Ha sido estudiada la consistencia de este tipo de modelos tanto si estan basados en una regla implicita similar a la de Mroz o en la regla de Prager. Ademas se han simulado los ensayos de Lamba y Sidebottom, obteniendo, en contra de la creencia general, muy buenas predicciones con la regla de Prager. Dichos modelos podrian ser extendidos de forma relativamente facil para considerar grandes deformaciones a traves de procedimientos en deformaciones logaritmicas, similares a los desarrollados en esta tesis y detallados a continuacion. El segundo aspecto consiste en la descripcion de la anisotropia elastoplastica inicial. Esto se ha conseguido mediante el desarrollo de modelos y algoritmos para plasticidad anisotropa en grandes deformaciones, bien ignorando la posible anisotropia elastica, bien considerandola simultaneamente con la anisotropia plastica. Para ello ha sido necesario desarrollar primero un nuevo algoritmo de elastoplasticidad anisotropa en pequenas deformaciones consistentemente linealizado y sin despreciar ningun termino, de tal forma que se conserve la convergencia cuadratica de los metodos de Newton. Este algoritmo en pequenas deformaciones ha servido para realizar la correccion plastica de dos algoritmos en grandes deformaciones. El primero de estos algoritmos es una variacion del clasico algoritmo de Eterovic y Bathe para incluir la posibilidad de plasticidad anisotropa con endurecimiento mixto. Este primer algoritmo esta restringido a casos de isotropia elastica. La isotropia elastica es una hipotesis bastante habitual en plasticidad anisotropa y tiene la ventaja de que permite el uso de formulaciones mixtas u/p. El segundo algoritmo, mas complejo y general, incluye la posibilidad de elasticidad anisotropa, plasticidad anisotropa y endurecimiento mixto. Este algoritmo supone una contribucion importante ya que esta basado en hipotesis comunmente aceptadas y utilizadas en elastoplasticidad isotropa: descomposicion multiplicativa del gradiente de deformaciones en parte elastica y parte plastica, descripcion hiperelastica sencilla en funcion de deformaciones logaritmicas e integracion exponencial que conserva el volumen. Ademas, la estructura final del algoritmo es modular y relativamente sencilla, consistiendo en un pre- y un postprocesador geometrico y una correccion plastica realizada en pequenas deformaciones. El algoritmo esta consistentemente linealizado para conservar la convergencia cuadratica asintotica de los metodos de Newton y la forma final que toma dicha linealizacion es similar al caso de isotropia elastoplastica implementado; consiste en el modulo tangente algoritmico de pequenas deformaciones sobre el que se aplica una transformacion para convertirlo en el de grandes deformaciones. Todos estos modelos han sido implementados en un codigo propio de elementos finitos denominado DULCINEA, el cual tiene formulaciones lagrangianas totales y actualizadas para grandes deformaciones. Una de las tareas necesarias para poder realizar las simulaciones, ha sido el estudio e implementacion de diferentes elementos que no sufran el bloqueo volumetrico severo que se observa en formulaciones estandar basadas en desplazamientos. Este bloqueo se debe a la condicion de quasi-incompresibilidad que imponen los modelos de plasticidad desviadores y consiste en una respuesta exageradamente rigida de la solucion obtenida por el metodo de los elementos finitos estandar. Entre los elementos implementados cabe destacar el basado en la formulacion mixta u/p, que contiene una interpolacion adicional de grados de libertad de presion. Estos grados de libertad adicionales habitualmente son internos al elemento en mecanica de solidos. En este trabajo se ha desarrollado e implementado en DULCINEA una familia de elementos tridimensionales mixtos en grandes deformaciones que incluye el caso particular BMIX 27/27/4, basado en la formulacion u/p, constituido por 27 nudos, con 27 puntos de integracion estandar y 4 grados de libertad de presiones, y que pasa la condicion Inf-Sup o de Babuska-Brezzi. Sin embargo, se ha observado que la formulacion u/p presenta ciertas limitaciones bajo las hipotesis conjuntas de anisotropia elastica y anisotropia plastica. (Abstract shortened by UMI.)

Trithiocyanurate complexes of iron, manganese and nickel and their anticholinesterase activity.

PubMed

Kopel, Pavel; Dolezal, Karel; Langer, Vratislav; Jun, Daniel; Adam, Vojtech; Kuca, Kamil; Kizek, Rene

2014-04-08

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-aminoethyl)amine 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.

Unusual reaction of [NiFe]-hydrogenases with cyanide.

PubMed

Hexter, Suzannah V; Chung, Min-Wen; Vincent, Kylie A; Armstrong, Fraser A

2014-07-23

Cyanide reacts rapidly with [NiFe]-hydrogenases (hydrogenase-1 and hydrogenase-2 from Escherichia coli) under mild oxidizing conditions, inhibiting the electrocatalytic oxidation of hydrogen as recorded by protein film electrochemistry. Electrochemical, EPR, and FTIR measurements show that the final enzyme product, formed within a second (even under 100% H2), is the resting state known as Ni-B, which contains a hydroxido-bridged species, Ni(III)-μ(OH)-Fe(II), at the active site. "Cyanide inhibition" is easily reversed because it is simply the reductive activation of Ni-B. This paper brings back into focus an observation originally made in the 1940s that cyanide inhibits microbial H2 oxidation and addresses the interesting mechanism by which cyanide promotes the formation of Ni-B. As a much stronger nucleophile than hydroxide, cyanide binds more rapidly and promotes oxidation of Ni(II) to Ni(III); however, it is quickly replaced by hydroxide which is a far superior bridging ligand.

Low-T magnetometry study of S = 1 Q2D [Ni(pyz) 2(H 2O) 2](BF 4) 2 (pyz = pyrazine)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Manson, J. L.; Villa, D. Y.; Blackmore, W. J. A.

2017-02-13

[Ni(pyz) 2(H 2O) 2](BF 4) 2 (pyz = N 2C 4H 4) was synthesized by a solvent-free technique and its structure solved by synchrotron X-ray powder diffraction.1 The compound contains S = 1 Ni(II) ions and has tetragonal symmetry. Two-D [Ni(pyz) 2(H 2O) 2] 2+ square lattices propagate in the ab-plane and stack along the c-axis (Fig. 1). Water ligands occupy axial sites and form H-bonds with interlayer BF 4 - ions. SQUID magnetometry shows a possible transition to long-range magnetic order near 3 K. We measured the magnetization of [Ni(pyz) 2(H 2O) 2](BF 4) 2 as a function ofmore » temperature to search for field-induced phase transitions and briefly report those findings here.« less

Aqua­{6,6′-dimeth­oxy-2,2′-[ethane-1,2-diylbis(nitrilo­methyl­idyne)]diphenolato}nickel(II)

PubMed Central

Guo, Zhenghua; Li, Lianzhi; Xu, Tao; Li, Jinghong; Wang, Daqi

2009-01-01

The title complex, [Ni(C18H18N2O4)(H2O)], lies on a mirror plane with the NiII ion coordinated by two N and two O atoms of a tetra­dentate Schiff base ligand and one water O atom in a distorted square-pyramidal enviroment. The –CH2–CH2– group of the ligand is disordered equally over two sites about the mirror plane. The dihedral angle between the mean planes of the two symmetry-related chelate rings is 37.16 (6)°. In the crystal structure, inter­molecular O—H⋯O hydrogen bonds link complex mol­ecules into one-dimensional chains along [100] and these chains are linked, in turn, by very weak inter­molecular C—H⋯O hydrogen bonds into a two-dimensional network. PMID:21577698

Synthesis, characterization, antimicrobial, DNA-cleavage and antioxidant activities of 3-((5-chloro-2-phenyl-1H-indol-3-ylimino)methyl)quinoline-2(1H)-thione and its metal complexes

NASA Astrophysics Data System (ADS)

Vivekanand, B.; Mahendra Raj, K.; Mruthyunjayaswamy, B. H. M.

2015-01-01

Schiff base 3-((5-chloro-2-phenyl-1H-indol-3-ylimino)methyl)quinoline-2(1H)-thione and its Cu(II), Co(II), Ni(II), Zn(II) and Fe(III), complexes have been synthesized and characterized by elemental analysis, UV-Visible, IR, 1H NMR, 13C NMR and mass spectra, molar conductance, magnetic susceptibility, ESR and TGA data. The ligand and its metal complexes have been screened for their antibacterial activity against Staphylococcus aureus and Pseudomonas aeruginosa, antifungal activity against Aspergillus niger and Aspergillus flavus in minimum inhibition concentration (MIC) by cup plate method respectively, antioxidant activity using 1,1-diphenyl-2-picryl hydrazyl (DPPH), which was compared with that of standard drugs vitamin-C and vitamin-E and DNA cleavage activity using calf-thymus DNA.

A novel coordination polymer of Ni(II) based on 1,3,5-benzenetricarboxylic acid synthesis, characterization, crystal structure, thermal study, and luminescent properties

NASA Astrophysics Data System (ADS)

Saheli, Sania; Rezvani, Alireza

2017-01-01

A new metal-organic framework (MOF) formulated as [Ni(H2btc)(OH)(H2O)2] (1) (H3btc = 1,3,5-benzenetricarboxylic acid) was synthesized using the hydrothermal technique. The complex 1 was characterized by elemental analysis, infrared spectroscopy, and powder X-ray diffraction in addition to single crystal X-ray diffraction. X-ray crystal structural analysis displayed that the compound belonged to the monoclinic space group P21/n with cell parameters a = 6.8658(14) Å, b = 18.849(4) Å, c = 8.5608(17) Å. In the title complex, ligand is linked to metal centers through two μ-oxo bridges and forming a 2D layer which is led to form an interesting geometry. The thermal stability and fluorescence property of 1 have also been investigated.

High yield synthesis of Ni-BTC metal-organic framework with ultrasonic irradiation: Role of polar aprotic DMF solvent.

PubMed

Israr, Farrukh; Chun, Daye; Kim, Yeongmin; Kim, Duk Kyung

2016-07-01

Nickel based porous solid was synthesized with 20 kHz ultrasonic irradiation. The reaction of Ni(II) nitrate hexahydrate with 1,3,5-benzene tricarboxylic acid in N,N-Dimethylformamide (DMF) as the sole solvent under ultrasonic radiation produced porous Ni-BTC MOF. Choice of correct solvent for the ultrasonic treatment was proven important. The effect of varying ultrasonic powers (40%, 60% and 80% of 750 W) along with different temperature conditions (50 °C, 60 °C, 70 °C and 80 °C) influenced the respective yield. A very high yield of 88% Ni-BTC MOF was obtained from 80% ultrasonic power at 60 °C. BET surface areas of the MOF crystals measured by N2 gas adsorption isotherms were in the range of 960-1000 m(2)/g. Copyright © 2015 Elsevier B.V. All rights reserved.

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

PubMed

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

2016-05-15

We synthesized 2-aminonicotinic acid (2-ANA) complexes with metals such as Co(II), Fe(III), Ni(II), Mn(II), Zn(II), Ag(I),Cr(III), Cd(II) and Cu(II) in aqueous media. The complexes were characterized and elucidated using FT-IR, UV-Vis, a fluorescence spectrophotometer and thermo gravimetric analysis (TGA). TGA data showed that the stoichiometry of complexes was 1:2 metal/ligand except for Ag(I) and Mn(II) where the ratio was 1:1. The metal complexes showed varied antibacterial, fungicidal and nematicidal activities. The silver and zinc complexes showed highest activity against Bacillus subtilis and Bacillus licheniformis respectively. Fusarium oxysporum was highly susceptible to nickel and copper complexes whereas Macrophomina phaseolina was completely inert to the complexes. The silver and cadmium complexes were effective against the root-knot nematode Meloidogyne javanica. Copyright © 2016 Elsevier B.V. All rights reserved.

Spectral and thermal study of the ternary complexes of nickel with sulfasalazine and some amino acids

NASA Astrophysics Data System (ADS)

Soliman, Ahmed A.

2006-12-01

The ternary complexes of Ni(II) with sulfasalazine (H 3SS) as a primary ligand and alanine (ala), aspartic acid (asp), histidene (hist), methionine (meth) and serine (ser) amino acids as secondary ligands have been synthesized. Characterization of the complexes was based on elemental analyses, IR, UV-vis, mass spectra, magnetic moment and thermal analysis (TG). The isolated complexes were found to have the general formula [M(HSS)(AA)]4H 2O (AA = ala, asp, hist, meth, or ser amino acid) where nickel is tetra-coordinated. The thermal stability of the complexes was studied and the weight losses for the decomposition of the complexes were calculated and correlated with the mass fragmentation pattern. In most cases, the amino acid moiety is removed along with the Schiff base moiety leaving NiO as a metallic residue. The metallic residue was confirmed by powder XRD measurements.

New metal phthalocyanines/metal simple hydroxide multilayers: experimental evidence of dipolar field-driven magnetic behavior.

PubMed

Bourzami, Riadh; Eyele-Mezui, Séraphin; Delahaye, Emilie; Drillon, Marc; Rabu, Pierre; Parizel, Nathalie; Choua, Sylvie; Turek, Philippe; Rogez, Guillaume

2014-01-21

A series of new hybrid multilayers has been synthesized by insertion-grafting of transition metal (Cu(II), Co(II), Ni(II), and Zn(II)) tetrasulfonato phthalocyanines between layers of Cu(II) and Co(II) simple hydroxides. The structural and spectroscopic investigations confirm the formation of new layered hybrid materials in which the phthalocyanines act as pillars between the inorganic layers. The magnetic investigations show that all copper hydroxide-based compounds behave similarly, presenting an overall antiferromagnetic behavior with no ordering down to 1.8 K. On the contrary, the cobalt hydroxide-based compounds present a ferrimagnetic ordering around 6 K, regardless of the nature of the metal phthalocyanine between the inorganic layers. The latter observation points to strictly dipolar interactions between the inorganic layers. The amplitude of the dipolar field has been evaluated from X-band and Q-band EPR spectroscopy investigation (Bdipolar ≈ 30 mT).

US Army Aeromedical Research Laboratory Annual Progress Report, FY 1981.

DTIC Science & Technology

1981-10-01

PROGRAM ELEMENT. PROJECT. TASK US Army Aeromedical Research Laboratory AREA 6 WORK UNIT NUMBERS PO Box 577 Fort Rucker, Alabama 36362 Listed on each DD...d J F I’ 0 l I I I I ;11 11 it Ili di fi li I t t o tim!L’ 151 niii tt 11 ,0 lo 1’ I I J rt 1,( K 1 soo m~r mOo I r I) o r t AIi t tO hi1t Lle I’I tu...I I, I ’ 11 t hit f:1iU :IJ . ] i ;)1T11C 1t 11i1 hs boo par kcW ind ulitac~u ho 1,1-i c " t I a It Cs rt I U I o v’! : a rd anId oxo c t cc ha at in

Synthesis, Characterization, Electrochemical Studies, and In Vitro Antibacterial Activity of Novel Thiosemicarbazone and Its Cu(II), Ni(II), and Co(II) Complexes

PubMed Central

Khan, Salman A.; Asiri, Abdullah M.; Al-Amry, Khalid; Malik, Maqsood Ahmad

2014-01-01

Metal complexes were prepared by the reaction of thiosemicarbazone with CuCl2, NiCl2, CoCl2, Cu(OAc)2, Ni(OAc)2, and Co(OAc)2. The thiosemicarbazone coordinates to metal through the thionic sulfur and the azomethine nitrogen. The thiosemicarbazone was obtained by the thiosemicarbazide with 3-acetyl-2,5-dimethylthiophene. The identities of these compounds were elucidated by IR, 1H, 13C-NMR, and GC-MS spectroscopic methods and elemental analyses. The antibacterial activity of these compounds was first tested in vitro by the disc diffusion assay against two Gram-positive and two Gram-negative bacteria, and then the minimum inhibitory concentration (MIC) was determined by using chloramphenicol as reference drug. The results showed that compound 1.1 is better inhibitor of both types of tested bacteria as compared to chloramphenicol. PMID:24523641

A Ni(iii) complex stabilized by silica nanoparticles as an efficient nanoheterogeneous catalyst for oxidative C-H fluoroalkylation.

PubMed

Khrizanforov, Mikhail N; Fedorenko, Svetlana V; Strekalova, Sofia O; Kholin, Kirill V; Mustafina, Asiya R; Zhilkin, Mikhail Ye; Khrizanforova, Vera V; Osin, Yuri N; Salnikov, Vadim V; Gryaznova, Tatyana V; Budnikova, Yulia H

2016-07-26

We have developed Ni(III)-doped silica nanoparticles ([(bpy)xNi(III)]@SiO2) as a recyclable, low-leaching, and efficient oxidative functionalization nanocatalyst for aromatic C-H bonds. The catalyst is obtained by doping the complex [(bpy)3Ni(II)] on silica nanoparticles along with its subsequent electrooxidation to [(bpy)xNi(III)] without an additional oxidant. The coupling reaction of arenes with perfluoroheptanoic acid occurs with 100% conversion of reactants in a single step at room temperature under nanoheterogeneous conditions. The catalyst content is only 1% with respect to the substrates under electrochemical regeneration conditions. The catalyst can be easily separated from the reaction mixture and reused a minimum of five times. The results emphasize immobilization on the silica support and the electrochemical regeneration of Ni(III) complexes as a facile route for developing an efficient nanocatalyst for oxidative functionalization.

Synthesis and characterization of ligational behavior of curcumin drug towards some transition metal ions: Chelation effect on their thermal stability and biological activity

NASA Astrophysics Data System (ADS)

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.

Synthesis, spectroscopic and thermal studies of transition metal complexes derived from benzil and diethylenetriamine

NASA Astrophysics Data System (ADS)

Khan, Sadaf; Nami, Shahab A. A.; Siddiqi, K. S.

2007-10-01

A macrocyclic ligand, bdta (where bdta = 3,6,9,12,15,18-hexaaza-1,2,10,11-tetraphenyl-2,9,11,18-tetraenecyclododecane) has been prepared by cyclocondensation of benzil with diethylenetriamine which efficiently encapsulates transition as well as pseudo-transition metal ions leading to the formation of M(bdta)Cl 2 type complexes [where M = Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Hg(II)]. The analytical, spectroscopic and magnetic moment data suggests an octahedral geometry for all the complexes. EPR spectra of Mn(II) and Cu(II) show considerable exchange interaction in the complex. They are non-conducting in DMSO. The TGA profile of the ligand and its complexes are identical and consists of two discreet stages. The voltammogram of Cu-complex exhibits a quasi-reversible one-electron transfer wave for Cu(II)/Cu(I) couple.

Synthesis, spectroscopic and thermal studies of transition metal complexes derived from benzil and diethylenetriamine.

PubMed

Khan, Sadaf; Nami, Shahab A A; Siddiqi, K S

2007-10-01

A macrocyclic ligand, bdta (where bdta=3,6,9,12,15,18-hexaaza-1,2,10,11-tetraphenyl-2,9,11,18-tetraenecyclododecane) has been prepared by cyclocondensation of benzil with diethylenetriamine which efficiently encapsulates transition as well as pseudo-transition metal ions leading to the formation of M(bdta)Cl2 type complexes [where M=Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Hg(II)]. The analytical, spectroscopic and magnetic moment data suggests an octahedral geometry for all the complexes. EPR spectra of Mn(II) and Cu(II) show considerable exchange interaction in the complex. They are non-conducting in DMSO. The TGA profile of the ligand and its complexes are identical and consists of two discreet stages. The voltammogram of Cu-complex exhibits a quasi-reversible one-electron transfer wave for Cu(II)/Cu(I) couple.

Synthesis, spectroscopic characterization, DNA interaction and antibacterial study of metal complexes of tetraazamacrocyclic Schiff base

NASA Astrophysics Data System (ADS)

Shakir, Mohammad; Khanam, Sadiqa; Firdaus, Farha; Latif, Abdul; Aatif, Mohammad; Al-Resayes, Saud I.

The template condensation reaction between benzil and 3,4-diaminotoulene resulted mononuclear 12-membered tetraimine macrocyclic complexes of the type, [MLCl2] [M = Co(II), Ni(II), Cu(II) and Zn(II)]. The synthesized complexes have been characterized on the basis of the results of elemental analysis, molar conductance, magnetic susceptibility measurements and spectroscopic studies viz. FT-IR, 1H and 13C NMR, FAB mass, UV-vis and EPR. An octahedral geometry has been envisaged for all these complexes, while a distorted octahedral geometry has been noticed for Cu(II) complex. Low conductivity data of all these complexes suggest their non-ionic nature. The interactive studies of these complexes with calf thymus DNA showed that the complexes are avid binders of calf thymus DNA. The in vitro antibacterial studies of these complexes screened against pathogenic bacteria proved them as growth inhibiting agents.

Bis(acesulfamato-kappaO4)diaquabis(3-methylpyridine-kappaN)nickel(II).

PubMed

Dege, Necmi; Içbudak, Hasan; Adiyaman, Elif

2007-01-01

In the crystal structure of the title compound [systematic name: diaquabis(6-methyl-2,2-dioxo-1,2,3-oxathiazin-4-olato-kappaO4)bis(3-methylpyridine-kappaN)nickel(II)], [Ni(C4H4NO4S)2(C6H7N)2(H2O)2], the Ni(II) centre resides on a centre of symmetry and has a distorted octahedral geometry. The basal plane is formed by two carbonyl O atoms of two monodentate trans-oriented acesulfamate ligands and two trans aqua ligands. The axial positions in the octahedron are occupied by two N atoms of two trans pyridine ligands. Molecules are stacked in columns running along the a axis. There are pi-pi stacking interactions between the molecules in each column, with a distance of 3.623 (2) A between the centroids of the pyridine rings. There are also O-H...O interactions between the columns.

Dinuclear metallacycles with single M-O(H)-M bridges [M = Fe(II), Co(II), Ni(II), Cu(II)]: effects of large bridging angles on structure and antiferromagnetic superexchange interactions.

PubMed

Reger, Daniel L; Pascui, Andrea E; Foley, Elizabeth A; Smith, Mark D; Jezierska, Julia; Ozarowski, Andrew

2014-02-17

The reactions of M(ClO4)2·xH2O and the ditopic ligands m-bis[bis(1-pyrazolyl)methyl]benzene (Lm) or m-bis[bis(3,5-dimethyl-1-pyrazolyl)methyl]benzene (Lm*) in the presence of triethylamine lead to the formation of monohydroxide-bridged, dinuclear metallacycles of the formula [M2(μ-OH)(μ-Lm)2](ClO4)3 (M = Fe(II), Co(II), Cu(II)) or [M2(μ-OH)(μ-Lm*)2](ClO4)3 (M = Co(II), Ni(II), Cu(II)). With the exception of the complexes where the ligand is Lm and the metal is copper(II), all of these complexes have distorted trigonal bipyramidal geometry around the metal centers and unusual linear (Lm*) or nearly linear (Lm) M-O-M angles. For the two solvates of [Cu2(μ-OH)(μ-Lm)2](ClO4)3, the Cu-O-Cu angles are significantly bent and the geometry about the metal is distorted square pyramidal. All of the copper(II) complexes have structural distortions expected for the pseudo-Jahn-Teller effect. The two cobalt(II) complexes show moderate antiferromagnetic coupling, -J = 48-56 cm(-1), whereas the copper(II) complexes show very strong antiferromagnetic coupling, -J = 555-808 cm(-1). The largest coupling is observed for [Cu2(μ-OH)(μ-Lm*)2](ClO4)3, the complex with a Cu-O-Cu angle of 180°, such that the exchange interaction is transmitted through the dz(2) and the oxygen s and px orbitals. The interaction decreases, but it is still significant, as the Cu-O-Cu angle decreases and the character of the metal orbital becomes increasingly d(x(2)-y(2)). These intermediate geometries and magnetic interactions lead to spin Hamiltonian parameters for the copper(II) complexes in the EPR spectra that have large E/D ratios and one g matrix component very close to 2. Density functional theory calculations were performed using the hybrid B3LYP functional in association with the TZVPP basis set, resulting in reasonable agreement with the experiments.

Square-antiprismatic eight-coordinate complexes of divalent first-row transition metal cations: a density functional theory exploration of the electronic-structural landscape.

PubMed

Conradie, Jeanet; Patra, Ashis K; Harrop, Todd C; Ghosh, Abhik

2015-02-16

Density functional theory (in the form of the PW91, BP86, OLYP, and B3LYP exchange-correlation functionals) has been used to map out the low-energy states of a series of eight-coordinate square-antiprismatic (D2d) first-row transition metal complexes, involving Mn(II), Fe(II), Co(II), Ni(II), and Cu(II), along with a pair of tetradentate N4 ligands. Of the five complexes, the Mn(II) and Fe(II) complexes have been synthesized and characterized structurally and spectroscopically, whereas the other three are as yet unknown. Each N4 ligand consists of a pair of terminal imidazole units linked by an o-phenylenediimine unit. The imidazole units are the strongest ligands in these complexes and dictate the spatial disposition of the metal three-dimensional orbitals. Thus, the dx(2)-y(2) orbital, whose lobes point directly at the coordinating imidazole nitrogens, has the highest orbital energy among the five d orbitals, whereas the dxy orbital has the lowest orbital energy. In general, the following orbital ordering (in order of increasing orbital energy) was found to be operative: dxy < dxz = dyz ≤ dz(2) < dx(2)-y(2). The square-antiprism geometry does not lead to large energy gaps between the d orbitals, which leads to an S = 2 ground state for the Fe(II) complex. Nevertheless, the dxy orbital has significantly lower energy relative to that of the dxz and dyz orbitals. Accordingly, the ground state of the Fe(II) complex corresponds unambiguously to a dxy(2)dxz(1)dyz(1)dz(2)(1)dx(2)-y(2)(1) electronic configuration. Unsurprisingly, the Mn(II) complex has an S = 5/2 ground state and no low-energy d-d excited states within 1.0 eV of the ground state. The Co(II) complex, on the other hand, has both a low-lying S = 1/2 state and multiple low-energy S = 3/2 states. Very long metal-nitrogen bonds are predicted for the Ni(II) and Cu(II) complexes; these bonds may be too fragile to survive in solution or in the solid state, and the complexes may therefore not be isolable. Overall, the different exchange-correlation functionals provided a qualitatively consistent and plausible picture of the low-energy d-d excited states of the complexes.

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

PubMed

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

2011-11-01

Nine new mononuclear Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Th(IV) and UO(2)(VI) complexes of lomefloxacin drug were synthesized. The structures of these complexes were elucidated by elemental analyses, IR, XRD, UV-vis, (1)H NMR as well as conductivity and magnetic susceptibility measurements and thermal analyses. The dissociation constants of lomefloxacin and stability constants of its binary complexes have been determined spectrophotometrically in aqueous solution at 25±1°C and at 0.1 M KNO(3) ionic strength. The discussion of the outcome data of the prepared complexes indicate that the lomefloxacin ligand behaves as a neutral bidentate ligand through OO coordination sites and coordinated to the metal ions via the carbonyl oxygen and protonated carboxylic oxygen with 1:1 (metal:ligand) stoichiometry for all complexes. The molar conductance measurements proved that the complexes are electrolytes. The powder XRD study reflects the crystalline nature for the investigated ligand and its complexes except Mn(II), Zn(II) and UO(2)(II). The geometrical structures of these complexes are found to be octahedral. The thermal behaviour of these chelates is studied where the hydrated complexes lose water molecules of hydration in the first steps followed by decomposition of the anions, coordinated water and ligand molecules in the subsequent steps. The activation thermodynamic parameters are calculated using Coats-Redfern and Horowitz-Metzger methods. A comparative study of the inhibition zones of the ligand and its metal complexes indicates that metal complexes exhibit higher antibacterial effect against one or more bacterial species than the free LFX ligand. The antifungal and anticancer activities were also tested. The antifungal effect of almost metal complexes is higher than the free ligand. LFX, [Co(LFX)(H(2)O)(4)]·Cl(2) and [Zn(LFX)(H(2)O)(4)]·Cl(2) were found to be very active with IC50 values 14, 11.2 and 43.1, respectively. While, other complexes had been found to be inactive at lower concentration than 100 μg/ml. Copyright © 2011 Elsevier B.V. All rights reserved.

Molecules based on M(v) (M=Mo, W) and Ni(II) ions: a new class of trigonal bipyramidal cluster and confirmation of SMM behavior for the pentadecanuclear molecule {NiII[NiII(tmphen)(MeOH)]6[Ni(H2O)3]2[micro-CN]30[WV(CN)3]6}.

PubMed

Hilfiger, Matthew G; Zhao, Hanhua; Prosvirin, Andrey; Wernsdorfer, Wolfgang; Dunbar, Kim R

2009-07-14

The preparation, single crystal X-ray crystallography, and magnetic properties are reported for four new clusters based on [M'V(CN)8]3- octacyanometallates (M'=Mo, W). Reactions of [M'V(CN)8]3- with mononuclear NiII ions in the presence of the tmphen blocking ligand (tmphen=3,4,7,8-tetramethyl-1,10-phenanthroline) in a 2:3:6 ratio, respectively, lead to the formation of the trigonal bipyramidal clusters [NiII(tmphen)2]3[M'V(CN)8]2. Analogous reactions with the same starting materials performed in a 2:3:2 ratio, respectively, produce pentadecanuclear clusters of the type {NiII[NiII(tmphen)(MeOH)]6[Ni(H2O)3]2[micro-CN]30[WV(CN)3]6}. The W2Ni3 (1) and Mo2Ni3(2) pentanuclear clusters and the W6Ni9 (3) and Mo6Ni9 (4) pentadecanuclear molecules are isostructural to each other and crystallize in the space groups P2(1)/c and R3 respectively. Magnetic measurements indicate that the ground states for the trigonal bipyamidal clusters are S=4 as a consequence of ferromagnetic coupling with JW-Ni=9.5 cm(-1), JMo-Ni=10 cm(-1). The pentadecanuclear clusters exhibit ferromagnetic coupling as well, which leads to S=12 ground states (JW-Ni=12 cm(-1), JMo-Ni=12.2 cm(-1)). Reduced magnetization studies on the W-Ni analogues support the conclusion that they exhibit a negative axial anisotropy term; the fits give D values of -0.24 cm(-1) for the W2Ni3 cluster and D=-0.04 cm(-1)for the W6Ni9 cluster. AC susceptibility measurements indicate the beginning of an out-of-phase signal for the W2Ni3 and the W6Ni9 compounds, but detailed low temperature studies on small crystals by the microSQUID technique indicate that only the pentadecanuclear cluster exhibits hysteresis in accord with SMM behavior. Neither Mo cluster reveals any evidence for slow paramagnetic relaxation at low temperatures.

Análise da medição do raio solar em ultravioleta

NASA Astrophysics Data System (ADS)

Saraiva, A. C. V.; Giménez de Castro, C. G.; Costa, J. E. R.; Selhorst, C. L.; Simões, P. J. A.

2003-08-01

A medição acurada do raio solar em qualquer banda do espectro eletromagnético é de relevância na formulação e calibração de modelos da estrutura e atmosfera solar. Esses modelos atribuem emissão do contínuo do Sol calmo em microondas à mesma região da linha Ha do Hell. Apresentamos a medição do raio solar em UV com imagens do EIT (Extreme Ultraviolet Image Telescope) entre 1996 e 2002, no comprimento de onda 30,9 nm (Ha do Hell), que se forma na região de transição/cromosfera solar. A técnica utilizada para o cálculo do raio UV foi baseada na transformada Wavelet B3spline. Fizemos um banco de dados com 1 imagem por dia durante o período citado. Obtivemos como resultado o raio médio da ordem de 975.61" e uma diminuição do mesmo para o período citado variando em média -0,45" /ano. Comparamos estes dados com os valores obtidos pelo ROI (Radio Observatório de Itapetinga) em 22/48 GHz e Nobeyama Radio Heliograph em 17 GHz mostrando que os raios médios são muito próximos o que indica que a região de formação nessas freqüências é a mesma conforme os modelos. Comparamos os resultados também com outros índices de atividade solar.

MOBRAL: Un Modelo para la Educacion de Adultos?

ERIC Educational Resources Information Center

Convergence, 1974

1974-01-01

Written in Spanish, the article explains that expanding an adult basic education program, the Brazilian Literacy Movement (MOBRAL), necessitates considering the social orientation of MOBRAL in the context of Brazil and of Latin America as a whole. (AG)

DISE Summary Report (1992)

DTIC Science & Technology

1994-03-01

Specification and Network Time Protocol(NTP) over the Implementation. RFC-o 119, Network OSI Remote Operations Service. RFC- Working Group, September...approximately ISIS implements a powerful model of 94% of the total computation time. distributed computation known as modelo Timing results are

Implementación de un modelo de capacitación multimedial para brindar orientación alimentaria a los beneficiarios de un programa de ayuda social en México.

PubMed

Amaya-Castellanos, Maritza Alejandra; Morales-Ruan, María Del Carmen; Uribe-Carvajal, Rebeca; Jiménez-Aguilar, Alejandra; Salazar-Coronel, Araceli Apolonia; Martínez-Tapia, Brenda; Shamah-Levy, Teresa

2018-03-01

Introducción: Se implementó un modelo de capacitación en orientación alimentaria para la población beneficiaria y el personal operativo del Programa de Abasto Rural (PAR) de Diconsa, el cual es una iniciativa social de ayuda alimentaria que abastece productos básicos y complementarios, además de brindar capacitación en localidades de alta marginación en México. Objetivo: Documentar la utilización de la Metodología de Capacitación Multimedial (MCM) en el desarrollo de un esquema de capacitación sobre orientación alimentaria y su implementación en la población beneficiaria del PAR, a través de la propia estructura operativa del PAR. Metodología: El modelo se fundamenta en la MCM, integrada por cuatro elementos didácticos e indivisibles que conforman el paquete pedagógico multimedial (PPM), compuesto a su vez por tres videos y rotafolios, material impreso, prácticas y las relaciones interpersonales. Los ejes temáticos fueron: alimentación correcta para una vida saludable, alimentación materno-infantil, elecciones saludables y gasto familiar. El modelo fue replicado en cascada en los tres niveles operativos del PAR (responsables de capacitación, supervisores operativos y beneficiarios del PAR), con un componente de multiplicación horizontal, e implementado como piloto en cuatro estados de México. Resultados: Se observó un cambio positivo sobre los conocimientos en alimentación correcta en todos los niveles de capacitación, principalmente en los beneficiarios del PAR. La evaluación del proceso mostró conocimientos previos de los responsables de capacitación en los temas, buen desempeño como facilitadores, y habilidades de presentación y manejo del grupo de los supervisores operativos. A partir de las evaluaciones y del acompañamiento en la prueba piloto, fueron modificados las actividades, las estrategias y los materiales educativos del PPM. Conclusiones: La capacitación multimedial y la educación nutricional promueven procesos de cambio y desarrollo comunitario, posibles a través de la toma de conciencia y la puesta en práctica de acciones que favorecen la salud.

Autofrecuencias de las ecuaciones de Helmholtz y Liouville para un modelo de tierra tipo Jeffreys simplificado.

NASA Astrophysics Data System (ADS)

Sevilla, M. J.; González-Camacho, A.

The authors obtain expressions for the free frequencies of polar motion for an ellipsoidal, rotating and perturbed earth model constituted by an elastic mantle with an homogeneous liquid core of additional simple motion.

Risk management in providing specialized care for people living with AIDS.

PubMed

Leadebal, Oriana Deyze Correia Paiva; Medeiros, Leidyanny Barbosa de; Morais, Kalline Silva de; Nascimento, João Agnaldo do; Monroe, Aline Aparecida; Nogueira, Jordana de Almeida

2016-01-01

Analyzing the provision of actions related to managing clinical risk in managing specialized care for people living with AIDS. A cross-sectional study carried out in a reference outpatient clinic in Paraíba, with a sample of 150 adults with AIDS. Data were collected through primary and secondary sources using a structured questionnaire, analyzed using descriptive statistics, multiple correspondence analysis and logistic regression model to determine the association between "providing care" and "clinical risk." Actions with satisfactory provision express a biological care focus; the dimensions that most contributed to a satisfactory assessment of care provision were "clinical and laboratory evaluations" and "prevention and self-care incentivization"; 45.3% of participants were categorized into high clinical risk, 34% into average clinical risk, and 20.7% into low clinical risk; a positive association between providing care and clinical risk was found. The need to use risk classification technologies to direct the planning of local care provision became evident considering its requirements, and thus qualifying the care provided in these areas. Analisar a oferta de ações relacionadas ao manejo de risco clínico na gestão do cuidado especializado a pessoas vivendo com aids. Estudo transversal realizado em ambulatório de referência na Paraíba, com amostra de 150 adultos com aids. Os dados foram coletados por meio de fontes primárias e secundárias utilizando-se de formulário estruturado, e analisados através de estatística descritiva, análise de correspondência múltipla e modelo de regressão logística para averiguar a associação entre "oferta" e "risco clínico". As ações de oferta satisfatória expressam foco biologicista do cuidado; as dimensões que mais contribuíram para o julgamento satisfatório da oferta foram "avaliação clínica e laboratorial" e "prevenção e estímulo ao autocuidado"; 45,3% dos participantes foram categorizados em risco clínico alto, 34% em risco clínico médio, e 20,7% em risco clínico baixo; e verificou-se associação positiva entre oferta e risco clínico. Ficou evidente a necessidade da utilização de tecnologias de classificação de risco para direcionar o planejamento da oferta local, considerando-se as necessidades, e assim qualificar o cuidado produzido nestes espaços.

Variaciones seculares de período en las RR Lyrae de ω~Centauri

NASA Astrophysics Data System (ADS)

Marraco, H. G.; Milesi, G. E.

Utilizando 689 observaciones de 35 estrellas RR Lyrae del cúmulo globular ω Centauri hemos obtenido nuevas determinaciones de sus períodos y sus correspondientes variaciones seculares. Las observaciones fueron obtenidas de la literatura con la excepción de un grupo 66 determinaciones que se presentan por vez primera aquí. Utilizando el parámetro testigo σ descripto en Marraco & Muzzio (Publ. Astron. Soc. Pacific 92, 700, 1980), hemos realizado un ajuste bidimensional en P y β (donde β es la variación secular del período). Con este fin la totalidad de las 689 observaciones fueron llevadas a un sistema fotométrico común. Para esto se realizó un cuidadoso análisis de los numerosos errores en la identificación de las estrellas de las series de comparación. Los resultados de los ajustes bidimensionales fueron analizados utilizando técnicas de procesamiento de imágenes. Con este fin el parámetro de ajuste σ fue representado como función de P y β. En las imágenes resultantes se buscaron los mínimos y al menor de ellos se lo aceptó como período instantáneo verdadero y su variación secular β. La determinación precisa de cada parámetro se realizó mediante ajuste de gaussianas y se determinaron sus errores. A modo de ejemplo la variable #8 fue analizada en una matriz de 501 × 501 elementos representando el parámetro σ para valores comprendidos entre 0,521034 < P < 0,521534 dias y -150×10-10 < β < +150×10-10 dias/dia. El mejor período instantáneo (correspondiente a la época DJ=2.426.908) y su variación secular son P = 0,5212859±0,0000001 días y β 14,012±,010×10-10 días/día respectivamente. Con estos valores el parámetro testigo resulta σ= 0,127 . Si no se tiene en cuenta la variación secular del período y se busca aquél de mejor ajuste para β = 0, se obtiene P = 0,5212960 días, pero entonces el parámetro de ajuste resulta tan alto como σ = 0,23 .

Comparação de modelos para o cálculo de perturbações orbitais devidas à maré terrestre

NASA Astrophysics Data System (ADS)

Vieira Pinto, J.; Vilhena de Moraes, R.

2003-08-01

Aplicações recentes de satélites artificiais com finalidades geodinâmicas requerem órbitas determinadas com bastante precisão. Em particular marés terrestres influenciam o potencial terrestre causando perturbações adicionais no movimento de satélites artificiais, as quais tem sido medidas por diversos processos. A atração exercida pela lua e pelo sol sobre a terra produz deslocamentos elásticos em seu interior e uma protuberância em sua superfície. O resultado é uma pequena variação na distribuição da massa na terra, consequentemente no geopotencial. As perturbações nos elementos orbitais de satélites artificiais terrestres devidas a maré terrestre podem ser estudadas a partir das equações de Lagrange, considerando-se um conveniente potencial. Por outro lado, como tem sido feito pelo IERS, as mudanças induzidas pela maré terrestre no geopotencial podem ser convenientemente modeladas como variações nos coeficientes Cnm e Snm do geopotencial. As duas teorias ainda não foram comparados para um mesmo satélite. Neste trabalho são apresentadas e comparadas as variações de longo período e seculares nas perturbações orbitais devidas à maré terrestre, calculadas por um modelo simples, o de Kozai, e pelo modelo do IERS. Resultados preliminares mostram, para os satélites SCD2 e CBERS1, e para a Lua em movimento elíptico e precessionando, as perturbações seculares no argumento do perigeu e na longitude do nodo ascendente.

MODELO PARA EVALUACION DE DERRAMES DE HIDROCARBUROS (HSSM) GUIA DEL USUARIO

EPA Science Inventory

The U.S. Environmental Protection Agency is charged by Congress with protecting the Nation's land, air, and water resources. Under a mandate of national environmental laws, the Agency strives to formulate and implement actions leading to a compatible balance between human acti...

Dinámica de planetas extrasolares resonantes

NASA Astrophysics Data System (ADS)

Beauge, C.

Actualmente se han detectado 117 planetas alrededor de estrellas de Secuencia Principal, incluyendo 12 sistemas planetarios, cada uno con dos o tres miembros. De estos últimos, ocho poseen planetas en órbitas próximas y sus perturbaciones gravitacionales se convierten en un factor fundamental para la estabilidad orbital del sistema. Todos se encuentran en configuraciones resonantes, desde la conmensurabilidad de movimientos 2/1 de Gliese 876, hasta la resonancia secular de Ups And. En esta presentación analizamos varios aspectos de la dinámica resonante de los planetas extrasolares, incluyendo la existencia de soluciones de equilibrio, construcción de modelos analógicos y métodos para la determinación de masas individuales. También discutimos por qué las resonancias son tan frecuentes en estos sistemas, comparado con nuestro propio Sistema Solar. Por último, intentamos relacionar estos modelos con la hipótesis de migración planetaria, buscando límites en su extensión y en los posibles mecanismos que le dieron origen.

Determination of nickel in water, food, and biological samples by electrothermal atomic absorption spectrometry after preconcentration on modified carbon nanotubes.

PubMed

Taher, Mohammad Ali; Mazaheri, Lida; Ashkenani, Hamid; Mohadesi, Alireza; Afzali, Daryoush

2014-01-01

A new and sensitive SPE method using modified carbon nanotubes for extraction and preconcentration, and electrothermal atomic absorption spectrometric determination of nickel (Ni) in real samples at ng/L levels was investigated. First, multiwalled carbon nanotubes were oxidized with concentrated HNO3, then modified with 2-(5-bormo-2-pyridylazo)-5-diethylaminophenol reagent. The adsorption was achieved quantitatively on a modified carbon nanotubes column in a pH range of 6.5 to 8.5; the adsorbed Ni(II) ions were then desorbed by passing 5.0 mL of 1 M HNO3. The effects of analytical parameters, including pH of the solution, eluent type and volume, sample volume, flow rate of the eluent, and matrix ions, were investigated for optimization of the presented procedure. The enrichment factor was 180, and the LOD for Ni was 4.9 ng/L. The method was applied to the determination of Ni in water, food, and biological samples, and reproducible results were obtained.

Arrested 1,2-hydrogen migration from silicon to nickel upon oxidation of a three-coordinate Ni(I) silyl complex.

PubMed

Iluc, Vlad M; Hillhouse, Gregory L

2010-09-01

Reaction of the dimeric Ni(I) chloride complex [(dtbpe)NiCl](2) (1) with dimesitylsilyl potassium affords the three-coordinate Ni(I) silyl complex (dtbpe)Ni(SiHMes(2)) (2). Alternatively, 2 can be prepared by an oxidative-addition reaction of Mes(2)Si(H)OTf (Tf = CF(3)SO(3)) with the nickel(0) complex [(dtbpe)Ni](2)(mu-C(6)H(6)) (3), with (dtbpe)Ni(OTf) (4) formed as an easily separable byproduct. The one-electron oxidation of 2 by ferrocenium affords diamagnetic [(dtbpe)Ni(mu-H)SiMes(2)][BAr(F)(4)] (5), a Ni(II) complex formed by partial 1,2-H migration from silicon to nickel and featuring an unusual 3-center, 2-electron bonding motif between Ni, Si, and the bridging H. Complex 5 was also obtained from Mes(2)SiH(2) activation by the neopentyl complex salt [(dtbpe)Ni(CH(2)CMe(3))][BAr(F)(4)] (6) with elimination of neopentane.

Zn(II), Ni(II), Cu(II) and Pb(II) complexes of tridentate asymmetrical Schiff base ligands: Synthesis, characterization, properties and biological activity

NASA Astrophysics Data System (ADS)

Şahin, Mustafa; Koçak, Nuriye; Erdenay, Damla; Arslan, Uğur

2013-02-01

New asymmetrical tridentate Schiff base ligands were synthesized using 1,2-phenylenediamine, 4-methyl-1,2-phenylenediamine, 2-hydroxy-1-napthaldehyde, 9-anthracenecarboxaldehyde. Schiff base ligands and their metal complexes were synthesised and characterized by using FT-IR, 1H NMR, 13C NMR, UV-Vis, XRD, ESR, elemental analysis and fluorescence studies. The antimicrobial activity of the ligands and their metal complexes were studied against Staphylococcus aureus ATCC 29213, S. aureus ATCC 25923, Streptococcus mutans RSHM 676, Enterococcus faecalis ATCC 29212, Escherichia coli ATCC 25922, Pseudomonas aeruginosa ATCC 27853. The determination of the antibacterial activity was done using the broth microdilution methods. In general, it has been determined that the studied compounds have MIC values similar to Gram-positive and Gram-negative bacteria. It has been found that Ni, Pb, Zn derivatives of HL1A and ZnL2A has lower MIC values than ampicillin for P. aeruginosa ATCC 27853 strain.

Metal-Metal Interactions in Heterobimetallic Complexes with Dinucleating Redox-Active Ligands.

PubMed

Broere, Daniël L J; Modder, Dieuwertje K; Blokker, Eva; Siegler, Maxime A; van der Vlugt, Jarl Ivar

2016-02-12

The tuning of metal-metal interactions in multinuclear assemblies is a challenge. Selective P coordination of a redox-active PNO ligand to Au(I) followed by homoleptic metalation of the NO pocket with Ni(II) affords a unique trinuclear Au-Ni-Au complex. This species features two antiferromagnetically coupled ligand-centered radicals and a double intramolecular d(8)-d(10) interaction, as supported by spectroscopic, single-crystal X-ray diffraction, and computational data. A corresponding cationic dinuclear Au-Ni analogue with a stronger d(8)-d(10) interaction is also reported. Although both heterobimetallic structures display rich electrochemistry, only the trinuclear Au-Ni-Au complex facilitates electrocatalytic C-X bond activation of alkyl halides in its doubly reduced state. Hence, the presence of a redox-active ligand framework, an available coordination site at gold, and the nature of the nickel-gold interaction appear to be essential for this reactivity. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Portable Multispectral Colorimeter for Metallic Ion Detection and Classification

PubMed Central

Jaimes, Ruth F. V. V.; Borysow, Walter; Gomes, Osmar F.; Salcedo, Walter J.

2017-01-01

This work deals with a portable device system applied to detect and classify different metallic ions as proposed and developed, aiming its application for hydrological monitoring systems such as rivers, lakes and groundwater. Considering the system features, a portable colorimetric system was developed by using a multispectral optoelectronic sensor. All the technology of quantification and classification of metallic ions using optoelectronic multispectral sensors was fully integrated in the embedded hardware FPGA ( Field Programmable Gate Array) technology and software based on virtual instrumentation (NI LabView®). The system draws on an indicative colorimeter by using the chromogen reagent of 1-(2-pyridylazo)-2-naphthol (PAN). The results obtained with the signal processing and pattern analysis using the method of the linear discriminant analysis, allows excellent results during detection and classification of Pb(II), Cd(II), Zn(II), Cu(II), Fe(III) and Ni(II) ions, with almost the same level of performance as for those obtained from the Ultravioled and visible (UV-VIS) spectrophotometers of high spectral resolution. PMID:28788082

Multiple heavy metal removal using an entomopathogenic fungi Beauveria bassiana.

PubMed

Gola, Deepak; Dey, Priyadarshini; Bhattacharya, Arghya; Mishra, Abhishek; Malik, Anushree; Namburath, Maneesh; Ahammad, Shaikh Ziauddin

2016-10-01

Towards the development of a potential remediation technology for multiple heavy metals [Zn(II), Cu(II), Cd(II), Cr(VI) and Ni(II)] from contaminated water, present study examined the growth kinetics and heavy metal removal ability of Beauveria bassiana in individual and multi metals. The specific growth rate of B. bassiana varied from 0.025h(-1) to 0.039h(-1) in presence of individual/multi heavy metals. FTIR analysis indicated the involvement of different surface functional groups in biosorption of different metals, while cellular changes in fungus was reflected by various microscopic (SEM, AFM and TEM) analysis. TEM studies proved removal of heavy metals via sorption and accumulation processes, whereas AFM studies revealed increase in cell surface roughness in fungal cells exposed to heavy metals. Present study delivers first report on the mechanism of bioremediation of heavy metals when present individually as well as multi metal mixture by entomopathogenic fungi. Copyright © 2016 Elsevier Ltd. All rights reserved.

Simultaneous spectrophotometric determination of four metals by two kinds of partial least squares methods

NASA Astrophysics Data System (ADS)

Gao, Ling; Ren, Shouxin

2005-10-01

Simultaneous determination of Ni(II), Cd(II), Cu(II) and Zn(II) was studied by two methods, kernel partial least squares (KPLS) and wavelet packet transform partial least squares (WPTPLS), with xylenol orange and cetyltrimethyl ammonium bromide as reagents in the medium pH = 9.22 borax-hydrochloric acid buffer solution. Two programs, PKPLS and PWPTPLS, were designed to perform the calculations. Data reduction was performed using kernel matrices and wavelet packet transform, respectively. In the KPLS method, the size of the kernel matrix is only dependent on the number of samples, thus the method was suitable for the data matrix with many wavelengths and fewer samples. Wavelet packet representations of signals provide a local time-frequency description, thus in the wavelet packet domain, the quality of the noise removal can be improved. In the WPTPLS by optimization, wavelet function and decomposition level were selected as Daubeches 12 and 5, respectively. Experimental results showed both methods to be successful even where there was severe overlap of spectra.

Synthesis, spectral, thermal and antimicrobial studies of transition metal complexes of 14-membered tetraaza[N4] macrocyclic ligand

NASA Astrophysics Data System (ADS)

Shankarwar, Sunil G.; Nagolkar, Bhagwat B.; Shelke, Vinod A.; Chondhekar, Trimbak K.

2015-06-01

A series of metal complexes of Mn(II), Co(II), Ni(II), Cu(II), have been synthesized with newly synthesized biologically active macrocyclic ligand. The ligand was synthesized by condensation of β-diketone 1-(4-chlorophenyl)-3-(2-hydroxyphenyl)propane-1,3-dione and o-phenylene diamine. All the complexes were characterized by elemental analysis, molar conductivity, magnetic susceptibility, thermal analysis, X-ray diffraction, IR, 1H-NMR, UV-Vis spectroscopy and mass spectroscopy. From the analytical data, stoichiometry of the complexes was found to be 1:2 (metal:ligand). Thermal behavior (TG/DTA) and kinetic parameters suggest more ordered activated state in complex formation. All the complexes are of high spin type and six coordinated. On the basis of IR, electronic spectral studies and magnetic behavior, an octahedral geometry has been assigned to these complexes. The antibacterial and antifungal activities of the ligand and its metal complexes, has been screened in vitro against Staphylococcus aureus, Escherichia coli and Aspergillus niger, Trichoderma respectively.

Metal based pharmacologically active complexes of Cu(II), Ni(II) and Zn(II): synthesis, spectral, XRD, antimicrobial screening, DNA interaction and cleavage investigation.

PubMed

Raman, Natarajan; Mahalakshmi, Rajkumar; Arun, T; Packianathan, S; Rajkumar, R

2014-09-05

The present contribution reports a thorough characterization of newly obtained metallointercalators incorporating Schiff bases, formed by the condensation of N-acetoacetyl-o-toluidine with 1-amino-4-nitrobenzene (L(1))/1-amino-4-chlorobenzene (L(2)) as main ligand and 1,10-phenanthroline as co-ligand respectively. The characterization of newly formed metallointercalators has been done by (1)H NMR, UV-Vis, IR, EPR spectroscopy and molar conductivity studies. X-ray powder diffraction illustrates that they are crystalline nature. Binding interaction of these complexes with calf thymus (CT-DNA) has been investigated by emission, absorption, viscosity, cyclic voltammetry and differential pulse voltammetry. DNA binding experiments results reveal that the synthesized complexes interact with DNA through intercalative mode. The in vitro antibacterial and antifungal assay indicate that these complexes are good antimicrobial agents against various pathogens. The DNA cleavage exhibits that they act as efficient cleaving agents. Copyright © 2014 Elsevier B.V. All rights reserved.

Role of pendant proton relays and proton-coupled electron transfer on the hydrogen evolution reaction by nickel hangman porphyrins

DOE PAGES

Bediako, D. Kwabena; Solis, Brian H.; Dogutan, Dilek K.; ...

2014-10-08

Here, the hangman motif provides mechanistic insights into the role of pendant proton relays in governing proton-coupled electron transfer (PCET) involved in the hydrogen evolution reaction (HER). We now show improved HER activity of Ni compared with Co hangman porphyrins. Cyclic voltammogram data and simulations, together with computational studies using density functional theory, implicate a shift in electrokinetic zone between Co and Ni hangman porphyrins due to a change in the PCET mechanism. Unlike the Co hangman porphyrin, the Ni hangman porphyrin does not require reduction to the formally metal(0) species before protonation by weak acids in acetonitrile. We concludemore » that protonation likely occurs at the Ni(I) state followed by reduction, in a stepwise proton transfer–electron transfer pathway. Spectroelectrochemical and computational studies reveal that upon reduction of the Ni(II) compound, the first electron is transferred to a metal-based orbital, whereas the second electron is transferred to a molecular orbital on the porphyrin ring.« less

Hydrometallurgical route to recover nickel, cobalt and cadmium from spent Ni-Cd batteries

NASA Astrophysics Data System (ADS)

Fernandes, Aline; Afonso, Julio Carlos; Bourdot Dutra, Achilles Junqueira

2012-12-01

In this work a hydrometallurgical route to recover nickel, cobalt and cadmium after leaching spent Ni-Cd batteries with hydrochloric acid was investigated. Co(II) and Cd(II) were both recovered by solvent extraction. Cd(II) was first extracted (99.7 wt.%) with pure tri-n-butylphosphate (TBP), in the original leachate acidity (5.1 mol L-1), in two stages at 25 °C with an aqueous/organic (A/O) phase ratio = 1 v/v. The Co(II) present in the raffinate (free acidity 4.1 mol L-1) was extracted with Alamine 336 or Alamine 304 (10 vol.% in kerosene) at 25 °C with an A/O ratio = 1 in two stages. 97.5 wt.% of Co(II) was extracted using Alamine 336 while only 90.4 wt.% was extracted in the case of Alamine 304. Ni(II) was isolated from the raffinate as oxalate after addition of ammonium oxalate at pH 2.

Portable Multispectral Colorimeter for Metallic Ion Detection and Classification.

PubMed

Braga, Mauro S; Jaimes, Ruth F V V; Borysow, Walter; Gomes, Osmar F; Salcedo, Walter J

2017-07-28

This work deals with a portable device system applied to detect and classify different metallic ions as proposed and developed, aiming its application for hydrological monitoring systems such as rivers, lakes and groundwater. Considering the system features, a portable colorimetric system was developed by using a multispectral optoelectronic sensor. All the technology of quantification and classification of metallic ions using optoelectronic multispectral sensors was fully integrated in the embedded hardware FPGA ( Field Programmable Gate Array) technology and software based on virtual instrumentation (NI LabView ® ). The system draws on an indicative colorimeter by using the chromogen reagent of 1-(2-pyridylazo)-2-naphthol (PAN). The results obtained with the signal processing and pattern analysis using the method of the linear discriminant analysis, allows excellent results during detection and classification of Pb(II), Cd(II), Zn(II), Cu(II), Fe(III) and Ni(II) ions, with almost the same level of performance as for those obtained from the Ultravioled and visible (UV-VIS) spectrophotometers of high spectral resolution.

Role of pendant proton relays and proton-coupled electron transfer on the hydrogen evolution reaction by nickel hangman porphyrins

PubMed Central

Bediako, D. Kwabena; Solis, Brian H.; Dogutan, Dilek K.; Roubelakis, Manolis M.; Maher, Andrew G.; Lee, Chang Hoon; Chambers, Matthew B.; Hammes-Schiffer, Sharon; Nocera, Daniel G.

2014-01-01

The hangman motif provides mechanistic insights into the role of pendant proton relays in governing proton-coupled electron transfer (PCET) involved in the hydrogen evolution reaction (HER). We now show improved HER activity of Ni compared with Co hangman porphyrins. Cyclic voltammogram data and simulations, together with computational studies using density functional theory, implicate a shift in electrokinetic zone between Co and Ni hangman porphyrins due to a change in the PCET mechanism. Unlike the Co hangman porphyrin, the Ni hangman porphyrin does not require reduction to the formally metal(0) species before protonation by weak acids in acetonitrile. We conclude that protonation likely occurs at the Ni(I) state followed by reduction, in a stepwise proton transfer–electron transfer pathway. Spectroelectrochemical and computational studies reveal that upon reduction of the Ni(II) compound, the first electron is transferred to a metal-based orbital, whereas the second electron is transferred to a molecular orbital on the porphyrin ring. PMID:25298534

Correlating Oxygen Evolution Catalysts Activity and Electronic Structure by a High-Throughput Investigation of Ni1-y-zFeyCrzOx

PubMed Central

Schwanke, Christoph; Stein, Helge Sören; Xi, Lifei; Sliozberg, Kirill; Schuhmann, Wolfgang; Ludwig, Alfred; Lange, Kathrin M.

2017-01-01

High-throughput characterization by soft X-ray absorption spectroscopy (XAS) and electrochemical characterization is used to establish a correlation between electronic structure and catalytic activity of oxygen evolution reaction (OER) catalysts. As a model system a quasi-ternary materials library of Ni1-y-zFeyCrzOx was synthesized by combinatorial reactive magnetron sputtering, characterized by XAS, and an automated scanning droplet cell. The presence of Cr was found to increase the OER activity in the investigated compositional range. The electronic structure of NiII and CrIII remains unchanged over the investigated composition spread. At the Fe L-edge a linear combination of two spectra was observed. These spectra were assigned to FeIII in Oh symmetry and FeIII in Td symmetry. The ratio of FeIII Oh to FeIII Td increases with the amount of Cr and a correlation between the presence of the FeIII Oh and a high OER activity is found. PMID:28287134

Correlating Oxygen Evolution Catalysts Activity and Electronic Structure by a High-Throughput Investigation of Ni1-y-zFeyCrzOx

NASA Astrophysics Data System (ADS)

Schwanke, Christoph; Stein, Helge Sören; Xi, Lifei; Sliozberg, Kirill; Schuhmann, Wolfgang; Ludwig, Alfred; Lange, Kathrin M.

2017-03-01

High-throughput characterization by soft X-ray absorption spectroscopy (XAS) and electrochemical characterization is used to establish a correlation between electronic structure and catalytic activity of oxygen evolution reaction (OER) catalysts. As a model system a quasi-ternary materials library of Ni1-y-zFeyCrzOx was synthesized by combinatorial reactive magnetron sputtering, characterized by XAS, and an automated scanning droplet cell. The presence of Cr was found to increase the OER activity in the investigated compositional range. The electronic structure of NiII and CrIII remains unchanged over the investigated composition spread. At the Fe L-edge a linear combination of two spectra was observed. These spectra were assigned to FeIII in Oh symmetry and FeIII in Td symmetry. The ratio of FeIII Oh to FeIII Td increases with the amount of Cr and a correlation between the presence of the FeIII Oh and a high OER activity is found.

Pentanuclear Cyanide-Bridged Complexes with High Spin Ground States S=6 and 9: Characterization and Magnetic Properties

NASA Astrophysics Data System (ADS)

Marvilliers, Arnaud; Hortholary, Cédric; Rogez, Guillaume; Audière, Jean-Paul; Rivière, Eric; Cano Boquera, Joan; Paulsen, Carley; Villar, Vincent; Mallah, Talal

2001-07-01

Two pentanuclear complexes are obtained from the reaction of hexacyanochromate(III) with one to two molar equivalents of [Ni(H2O)6]2+ and bidentate organic ligands that chelate the metal ion, leaving two coordination sites in cis positions. Even though the crystal structure was not solved, the full characterization supports the formation of pentanuclear discrete species. [Cr(CN)6]2[Ni(HIM2-py)2]3·7H2O, 1, has a ground spin state S=6 owing to the ferromagnetic interaction between CrIII (S=3/2) and NII (S=1). The presence of six organic radicals that couple ferromagnetically with NiII in [Cr(CN)6]2[Ni(IM2-py)2]3·7H2O, 2, leads to an S=9 ground state. A.c. susceptibility measurements below 2K indicate the occurrence of an antiferromagnetic order at 1.5 K in 2.

Improved assessment of accuracy and performance using a rotational paper-based device for multiplexed detection of heavy metals.

PubMed

Sun, Xiange; Li, Bowei; Qi, Anjin; Tian, Chongguo; Han, Jinglong; Shi, Yajun; Lin, Bingcheng; Chen, Lingxin

2018-02-01

In this work, a novel rotational microfluidic paper-based device was developed to improve the accuracy and performance of the multiplexed colorimetric detection by effectively avoiding the diffusion of colorimetric reagent on the detection zone. The integrated paper-based rotational valves were used to control the connection or disconnection between detection zones and fluid channels. Based on the manipulation of the rotational valves, this rotational paper-based device could prevent the random diffusion of colorimetric reagent and reduce the error of quantitative analysis considerably. The multiplexed colorimetric detection of heavy metals Ni(II), Cu(II) and Cr(VI) were implemented on the rotational device and the detection limits could be found to be 4.8, 1.6, and 0.18mg/L, respectively. The developed rotational device showed the great advantage in improving the detection accuracy and was expected to be a low-cost, portable analytical platform for the on-site detection. Copyright © 2017 Elsevier B.V. All rights reserved.

Preparation and Structural Studies on Hybrid Core-Shell Nanoparticles Consisting of Silica Core and Conjugated Block Copolymer Shell Prepared by Surface-Initiated Polymerization

NASA Astrophysics Data System (ADS)

Chatterjee, Sourav; Karam, Tony; Rosu, Cornelia; Li, Xin; Do, Changwoo; Youm, Sang Gil; Haber, Louis; Russo, Paul; Nesterov, Evgueni

Controlled Kumada catalyst-transfer polymerization occurring by chain-growth mechanism was developed for the synthesis of conjugated polymers and block copolymers from the surface of inorganic substrates such as silica nanoparticles. Although synthesis of conjugated polymers via Kumada polymerization became an established method for solution polymerization, carrying out the same reaction in heterogeneous conditions to form monodisperse polymer chains still remains a challenge. We developed and described a simple and efficient approach to the preparation of surface-immobilized layer of catalytic Ni(II) initiator, and demonstrated using it to prepare polymers and block copolymers on silica nanoparticle. The structure of the resulting hybrid nanostructures was thoroughly studied using small-angle neutron and X-ray scattering, thermal analysis, and optical spectroscopy. The photoexcitation energy transfer processes in the conjugated polymer shell were studied via steady-state and time resolved transient absorption spectroscopy. This study uncovered important details of the energy transfer, which will be discussed in this presentation.

Tuning the spin ground state in heterononanuclear nickel(II)-copper(II) cylinders with a triangular metallacyclophane core.

PubMed

Dul, Marie-Claire; Ferrando-Soria, Jesús; Pardo, Emilio; Lescouëzec, Rodrigue; Journaux, Yves; Ruiz-García, Rafael; Cano, Joan; Julve, Miguel; Lloret, Francesc; Fabelo, Oscar; Pasán, Jorge; Ruiz-Pérez, Catalina

2010-12-20

Two new heterometallic Ni(II)(n)Cu(II)((9-n)) complexes [n = 1 (2) and 2 (3)] have been synthesized following a multicomponent self-assembly process from a n:(3 - n):2:6 stoichiometric mixture of Ni(2+), Cu(2+), L(6-), and [CuL'](2+), where L and L' are the bridging and blocking ligands 1,3,5-benzenetris(oxamate) and N,N,N',N'',N''-pentamethyldiethylenetriamine, respectively. Complexes 2 and 3 possess a unique cyclindrical architecture formed by three oxamato-bridged trinuclear linear units connected through two 1,3,5-substituted benzenetris(amidate) bridges, giving a triangular metallacyclophane core. They behave as a ferromagnetically coupled trimer of two (2)/one (3) S = (1)/(2) Cu(II)(3) plus one (2)/two (3) S = 0 Ni(II)Cu(II)(2) linear units with overall S = 1 Ni(II)Cu(II)(8) (2) and S = (1)/(2) Ni(II)(2)Cu(II)(7) (3) ground states.

Functionalized Derivatives of Benzo-Crown Ethers. Part 4. Antifungal Macrocyclic Supramolecular Complexes of Transition Metal Ions Acting as Lanosterol-14-α-Demethylase Ihibitors

PubMed Central

Barboiu, Mihai; Scozzafava, Andrea; Guran, Cornelia; Diaconescu, Paula; Bojin, Mihaela; Iluc, Vlad; Cot, Louis

1999-01-01

Poly- and mononuclear metal complexes of 2,3,11,12-bis[4-(10-aminodecylcarbonyl)]benzo-18- crown-6 (L) and Cu(II); Ni(II); Co(II) and Cr(III) have been synthesized and characterized by standard physico-chemical procedures. In the newly prepared complexes the crown moiety oxygen atoms of the macrocyclic host did not generally interact with metal ions, whereas the two amino groups of the ligand always did. Several of the newly synthesized compounds act as effective antifungal agents against Aspergillus and Candida spp., some of them showing activities comparable to ketoconazole, with minimum inhibitory concentrations in the range of 0.3−0.5 μg/mL. The mechanism of antifungal action of these coordination compounds is probably connected to an inhibition of lanosterol-14-α-demethylase, a metallo-enzyme playing a key role in sterol biosynthesis in fungi, bacteria and eukariotes. PMID:18475888

Selective retention of basic compounds by metal aquo-ion affinity chromatography.

PubMed

Asakawa, Yoshiki; Yamamoto, Eiichi; Asakawa, Naoki

2014-10-01

A novel metal aquo-ion affinity chromatography has been developed for the analysis of basic compounds using heat-treated silica gel containing hydrated metal cations (metal aquo-ions) as the packing material. The packing materials of the metal aquo-ion affinity chromatography were prepared by the immobilization of a single metal component such as Fe(III), Al(III), Ag(I), and Ni(II) on silica gel followed by extensive heat treatment. The immobilized metals form aquo-ions to present cation-exchange ability for basic analytes and the cation-exchange ability for basic analytes depends on pKa of the immobilized metal species. In the present study, to evaluate the retention characteristics of metal aquo-ion affinity chromatography, the on-line solid-phase extraction of drugs was investigated. Obtained data clearly evidence the selective retention capability of metal aquo-ion affinity chromatography for basic analytes with sufficient capacity. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.