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Sample records for metals ii positron

  1. Positron studies of defected metals, metallic surfaces

    SciTech Connect

    Bansil, A.

    1991-01-01

    Specific problems proposed under this project included the treatment of electronic structure and momentum density in various disordered and defected systems. Since 1987, when the new high-temperature superconductors were discovered, the project focused extensively on questions concerning the electronic structure and Fermiology of high-[Tc] superconductors, in particular, (i) momentum density and positron experiments, (ii) angle-resolved photoemission intensities, (iii) effects of disorder and substitutions in the high-[Tc]'s.

  2. Defects in metals. [Positron annihilation spectroscopy

    SciTech Connect

    Siegel, R.W.

    1982-06-01

    The application of positron annihilation spectroscopy (PAS) to the study of defects in metals has led to increased knowledge on lattice-defect properties during the past decade in two areas: the determination of atomic defect properties, particularly those of monovacancies, and the monitoring and characterization of vacancy-like microstructure development during post-irradiation and post-quench annealing. The study of defects in metals by PAS is reviewed within the context of the other available techniques for defect studies. The strengths and weaknesses of PAS as a method for the characterization of defect microstructures are considered. The additional possibilities for using the positron as a localized probe of the atomic and electronic structures of atomic defects are discussed, based upon theoretical calculations of the annihilation characteristics of defect-trapped positrons and experimental observations. Finally, the present status and future potential of PAS as a tool for the study of defects in metals is considered. 71 references, 9 figures.

  3. Positron-annihilation spectroscopy of defects in metals: an assessment

    SciTech Connect

    Siegel, R.W.

    1982-06-01

    Positron annihilation spectroscopy (PAS) has made significant contributions to our knowledge regarding lattice defects in metals in two areas: (i) the determination of atomic defect properties, particularly those of monovacancies, and (ii) the monitoring and characterization of vacancy-like microstructure development during post-irradiation of post-quench annealing. The application of PAS to the study of defects in metals is selectively reviewed and critically assessed within the context of other available techniques for such investigations. Possibilities for using the positron as a localized probe of the structure of atomic defects are discussed. Finally, the present status and future potential of PAS as a tool for the study of defects in metals are considered relative to other available techniques. 92 references, 20 figures.

  4. Positron collisions with alkali-metal atoms

    NASA Technical Reports Server (NTRS)

    Gien, T. T.

    1990-01-01

    The total cross sections for positron and electron collisions with potassium, sodium, lithium and rubidium are calculated, employing the modified Glauber approximation. The Modified Glauber cross sections for positron collision with potassium and sodium at low intermediate energies are found to agree reasonably well with existing experimental data.

  5. Monoenergetic positron beam at the reactor based positron source at FRM-II

    NASA Astrophysics Data System (ADS)

    Hugenschmidt, C.; Kögel, G.; Repper, R.; Schreckenbach, K.; Sperr, P.; Straßer, B.; Triftshäuser, W.

    2002-05-01

    The principle of the in-pile positron source at the Munich research reactor FRM-II is based on absorption of high energy prompt γ-rays from thermal neutron capture in 113Cd. For this purpose, a cadmium cap is placed inside the tip of the inclined beam tube SR-11 in the moderator tank of the reactor, where an undisturbed thermal neutron flux up to 2×10 14n cm-2 s-1 is expected. Inside the cadmium cap a structure of platinum foils is placed for converting high energy γ-radiation into positron-electron pairs. Due to the negative positron work function, moderation in annealed platinum leads to emission of monoenergetic positrons. Therefore, platinum will also be used as moderator, since its moderation property seems to yield long-term stability under reactor conditions and it is much easier to handle than tungsten. Model calculations were performed with SIMION-7.0w to optimise geometry and potential of Pt-foils and electrical lenses. It could be shown that the potentials between the Pt-foils must be chosen in the range of 1-10 V to extract moderated positrons. After successive acceleration to 5 keV by four electrical lenses the beam is magnetically guided in a solenoid field of 7.5 mT resulting in a beam diameter of about 25 mm. An intensity of about 10 10 slow positrons per second is expected in the primary positron beam. Outside of the reactor shield a W(1 0 0) single crystal remoderation stage will lead to an improvement of the positron beam brilliance before the positrons are guided to the experimental facilities.

  6. Liquid Metal Target for NLC Positron Source

    SciTech Connect

    Sheppard, John C.

    2002-08-19

    Possibility of creating the liquid lead target with parameters, optimum for the NLC positron source, is investigated. Target has a form of titanium vessel, filled with liquid lead, pumped through. The energy deposition in target is characterized by 35 kW average power and up to 250 J/g specific energy at optimum beam sigma 0.6 mm. The use of pumped through liquid lead as target material solves both the problems of power evacuation and target survival. The window for beam exit is made of both temperature and pressure resistive material--the diamond-like ceramic BN.

  7. Computational Study of Positron-Monovacancy Interaction in d-Block Metals

    NASA Astrophysics Data System (ADS)

    Ishibashi, Shoji

    2015-08-01

    The positron-monovacancy interaction in d-block metals (except for Mn, Tc, and Hg) has been studied by the two-component density-functional-theory formalism [E. Boroński and R. M. Nieminen, http://dx.doi.org/10.1103/PhysRevB.34.3820, Phys. Rev. B 34, 3820 (1986)]. On the unrelaxed structure, the positron lifetime calculated with the presence of a positron is generally longer than that obtained neglecting the positron effect. When the atomic positions are relaxed, the difference is widened, especially for the group V metals. The inward relaxation of the atoms surrounding the monovacancy is suppressed when the positron effect is taken into account. The difference in the positron lifetime can be also related to the bulk modulus and the cohesive energy.

  8. Positron studies of defected metals, metallic surfaces. Final report, July 1, 1985--December 1, 1991

    SciTech Connect

    Bansil, A.

    1991-12-31

    Specific problems proposed under this project included the treatment of electronic structure and momentum density in various disordered and defected systems. Since 1987, when the new high-temperature superconductors were discovered, the project focused extensively on questions concerning the electronic structure and Fermiology of high-{Tc} superconductors, in particular, (i) momentum density and positron experiments, (ii) angle-resolved photoemission intensities, (iii) effects of disorder and substitutions in the high-{Tc}`s.

  9. Probing of Unembedded Metallic Quantum Dots with Positrons

    SciTech Connect

    Fischer, C G; Denison, A B; Weber, M H; Wilcoxon, J P; Woessner, S; Lynn, K G

    2003-08-01

    We employed the two detector coincident Doppler Broadening Technique (coPAS) to investigate Ag, Au and Ag/Au alloy quantum dots of varying sizes which were deposited in thin layers on glass slides. The Ag quantum dots range from 2 to 3 nm in diameter, while the Ag/Au alloy quantum dots exhibit Ag cores of 2 nm and 3 nm and Au shells of varying thickness. We investigate the possibility of positron confinement in the Ag core due to positron affinity differences between Ag and Au. We describe the results and their significance to resolving the issue of whether positrons annihilate within the quantum dot itself or whether surface and positron escape effects play an important role.

  10. Ultra Fine-Grained Metals Prepared by Severe Plastic Deformation: A Positron Annihilation Study

    NASA Astrophysics Data System (ADS)

    Čížek, J.; Procházka, I.; Kužel, R.; Matĕj, Z.; Cherkaska, V.; Cieslar, M.; Smola, B.; Stulíková, I.; Brauer, G.; Anwand, W.; Islamgaliev, R. K.; Kulyasova, O.

    2005-05-01

    Recent investigations of ultra fine-grained metals (Cu, Fe, Ni) performed within a Prague-Rossendorf-Ufa collaboration will be reviewed. The specimens were prepared by severe plastic deformation: the high-pressure torsion and equal channel angular pressing. Positron annihilation spectroscopy was used as the main method including (i) the conventional lifetime and the Doppler broadening measurements with 22Na and (ii) the slow-positron implantation spectroscopy with the Doppler broadening measurement. Other methods were also involved: transmission electron microscopy, X-ray diffraction, and microhardness. First, the mean grain size was determined and defects were identified in the as-deformed materials. Defects concentration and spatial distribution were studied in detail. Dislocations situated in distorted regions along grain boundaries, and a few-vacancy clusters distributed homogeneously inside dislocations-free grains, were observed in the ultra fine-grained Cu, Fe, and Ni. Subsequently, the thermal evolution of the ultra fine-grained structures during isochronal annealing was studied.

  11. Annihilation characteristics of positrons in free-standing thin metal and polymer films

    NASA Astrophysics Data System (ADS)

    Uedono, A.; Ito, K.; Nakamori, H.; Ata, S.; Ougizawa, T.; Ito, K.; Kobayashi, Y.; Cao, X.; Kurihara, T.; Oshima, N.; Ohdaira, T.; Suzuki, R.; Akahane, T.; Doyama, M.; Matsuya, K.; Jinno, S.; Fujinami, M.

    2008-03-01

    Annihilation characteristics of positrons and positronium (Ps) in thin metal and polymer films were studied. Monoenergetic positrons were implanted into free-standing thin W and Au films and the annihilation γ-rays of positron-electron pairs were measured as a function of the incident energy of positrons. At the front-side surfaces of the films, an emission of Ps into vacuum and a resultant self-annihilation of ortho-Ps (o-Ps) were observed. At the backside surfaces, the Ps emission was found to be enhanced by an increase in the numbers of epithermal positrons and/or secondary electrons introduced by the impact of energetic positrons. For thin polymer films (polyester and polystyrene), the emission rate of o-Ps from the backside surfaces was higher than that from the metal films, which was attributed to the out-diffusion of o-Ps formed in the films. Those results suggested that the emission rate of Ps into vacuum was sensitive to the Ps formation process in the bulk and at the surface.

  12. Positron binding to alkali-metal hydrides: The role of molecular vibrations

    SciTech Connect

    Gianturco, Franco A.; Franz, Jan; Buenker, Robert J.; Liebermann, Heinz-Peter; Pichl, Lukas; Rost, Jan-Michael; Tachikawa, Masanori; Kimura, Mineo

    2006-02-15

    The bound vibrational levels for J=0 have been computed for the series of alkali-metal hydride molecules from LiH to RbH, including NaH and KH. For all four molecules the corresponding potential-energy curves have been obtained for each isolated species and for its positron-bound complex (e{sup +}XH). It is found that the calculated positron affinity values strongly depend on the molecular vibrational state for which they are obtained and invariably increase as the molecular vibrational energy content increases. The consequences of our findings on the likelihood of possibly detecting such weakly bound species are briefly discussed.

  13. Annihilation momentum density of positrons trapped at vacancy-type defects in metals and alloys

    SciTech Connect

    Bansil, A.; Prasad, R.; Benedek, R.

    1988-01-01

    Positron annihilation, especially the angular correlation of annihilation radiation, is a powerful tool for investigating the electronic spectra of ordered as well as defected materials. The tendency of positrons to trap at vacancy-type defects should enable this technique to study the local environment of such defects. However, we need to develop a theoretical basis for calculating the two-photon annihilation momentum density rho/sub 2gamma/(p-vector). We have recently formulated and implemented a theory of rho/sub 2gamma/(p-vector) from vacancy-type defects in metals and alloys. This article gives an outline of our approach together with a few of our results. Section 2 summarizes the basic equations for evaluating rho/sub 2gamma/(p-vector). Our Green's function-based approach is nonperturbative and employs a realistic (one-particle) muffin-tin Hamiltonian for treating electrons and positrons. Section 3 presents and discusses rho/sub 2gamma/(p-vector) results for a mono-vacancy in Cu. We have neglected the effects of electron-positron correlations and of lattice distortion around the vacancy. Section 4 comments briefly on the question of treating defects such as divacancies and metal-impurity complexes in metals and alloys. Finally, in Section 5, we remark on the form of rho/sub 2gamma/(p-vector) for a mono-vacancy in jellium. 2 figs.

  14. Free volumes in bulk nanocrystalline metals studied by the complementary techniques of positron annihilation and dilatometry.

    PubMed

    Würschum, Roland; Oberdorfer, Bernd; Steyskal, Eva-Maria; Sprengel, Wolfgang; Puff, Werner; Pikart, Philip; Hugenschmidt, Christoph; Pippan, Reinhard

    2012-07-15

    Free-volume type defects, such as vacancies, vacancy-agglomerates, dislocations, and grain boundaries represent a key parameter in the properties of ultrafine-grained and nanocrystalline materials. Such free-volume type defects are introduced in high excess concentration during the processes of structural refinement by severe plastic deformation. The direct method of time-differential dilatometry is applied in the present work to determine the total amount and the kinetics of free volume by measuring the irreversible length change upon annealing of bulk nanocrystalline metals (Fe, Cu, Ni) prepared by high-pressure torsion (HPT). In the case of HPT-deformed Ni and Cu, distinct substages of the length change upon linear heating occur due to the loss of grain boundaries in the wake of crystallite growth. The data on dilatometric length change can be directly related to the fast annealing of free-volume type defects studied by in situ Doppler broadening measurements performed at the high-intensity positron beam of the FRM II (Garching, Munich, Germany).

  15. Spectroscopic, Elemental and Thermal Analysis, and Positron Annihilation Studies on Ca(II), Sr(II), Ba(II), Pb(II), and Fe(III) Penicillin G Potassium Complexes

    NASA Astrophysics Data System (ADS)

    Refat, M. S.; Sharshara, T.

    2015-11-01

    The [Pb(Pin)2] · 3H2O, [M(Pin)(H2O)2(Cl)] · nH2O (M = SrII, CaII or BaII; n = 0-1), and [Fe(Pin)2(Cl)(H2O)] · H2O penicillin G potassium (Pin) complexes were synthesized and characterized using elemental analyses, molar conductivity, thermal analysis and electronic spectroscopy techniques. The positron annihilation lifetime (PAL) and Doppler broadening (DB) techniques have been employed to probe the defects and structural changes of Pin ligand and its complexes. The PAL and DB line-shape parameters were discussed in terms of the structure, molecular weight, ligand-metal molar ratio, and other properties of the Pin complexes.

  16. Online beam energy measurement of Beijing electron positron collider II linear accelerator

    NASA Astrophysics Data System (ADS)

    Wang, S.; Iqbal, M.; Liu, R.; Chi, Y.

    2016-02-01

    This paper describes online beam energy measurement of Beijing Electron Positron Collider upgraded version II linear accelerator (linac) adequately. It presents the calculation formula, gives the error analysis in detail, discusses the realization in practice, and makes some verification. The method mentioned here measures the beam energy by acquiring the horizontal beam position with three beam position monitors (BPMs), which eliminates the effect of orbit fluctuation, and is much better than the one using the single BPM. The error analysis indicates that this online measurement has further potential usage such as a part of beam energy feedback system. The reliability of this method is also discussed and demonstrated in this paper.

  17. Track structure simulation for positron emitters of physical interest. Part II: The case of the radiometals

    NASA Astrophysics Data System (ADS)

    Le Loirec, C.; Champion, C.

    2007-11-01

    The development of radiochemical services in hospitals, due to the wide use of Positron Emission Tomography (PET) in nuclear medicine, has led to the synthesis of new radiotracers among them radiometals which present a large panel of advantages in terms of half-life times and emission spectra. The most encouraging are the copper isotopes 62Cu and 64Cu as well as 60Cu and 61Cu and the technetium isotope 94mTc used for diagnosis and pharmacokinetic studies. The manganese isotopes 52mMn, 52Mn and 51Mn also present some interesting characteristics, especially 52mMn produced during the decay of 52Fe. Finally, the less known isotopes 89Zr, 45Ti, and 86Y can also be used as surrogates of some therapeutic agents, whereas 38K, 55Co and 66Ga may be used as PET imaging tracers. In this work, we propose an intercomparison of these PET radiometal isotopes. To do that, we have used the home-made Monte Carlo simulation previously described in Champion and Le Loirec [Phys. Med. Biol. 51 (2006) 1707] to simulate the complete decay of β + tracers in biological matter. Under these conditions, we access to a complete description of the positronic irradiation during PET exams using metallic isotopes. The results obtained are also compared with existing theoretical and experimental data and good agreement is generally observed.

  18. Performance study of whole-body, multislice positron computed tomograph: POSITOLOGICA-II

    SciTech Connect

    Takami, K.; Murayama, H.; Nohara, N.; Okajima, K.; Tanaka, E.; Tomitani, T.; Veda, K.; Yamamoto, M.

    1983-02-01

    A 3-detector ring, 5-slice whole-body positron CT has been developed and is being tested. The PCT, POSITOLOGICA-II, has a total of 480 BGO's (160/ring), and employs continuous rotation scan (0.5rps). By using a 15mm wide BGO, a 9.2mm FWHM spatial resolution for reconstructed image is obtained at the center of FOV. Measured phantom diameter dependence of the true count rate shows good agreement with theoretically anticipated characteristics, including maximum sensitivity at around 30cm dia. Sensitivities for 20cm dia. phantom are 28 and 38 kcps/..mu..Ci/ml for in-plane and cross-plane, respectively, including scattered coincidences. Relative system detection efficiency measured with a line source at FOV center is 96% at 15ns time window (90% at 12ns), basing on 100% efficiency in 2024ns.

  19. Ab initio quantum Monte Carlo study of the binding of a positron to alkali-metal hydrides.

    PubMed

    Kita, Yukiumi; Maezono, Ryo; Tachikawa, Masanori; Towler, Mike D; Needs, Richard J

    2011-08-07

    Quantum Monte Carlo methods are used to investigate the binding of a positron to the alkali-metal hydrides, XH (X = Na and K). We obtain positron affinities for the NaH and KH molecules of 1.422(10) eV and 2.051(39) eV, respectively. These are considerably larger than the previous results of 1.035 eV and 1.273 eV obtained from multireference single- and double-excitation configuration interaction calculations. Together with our previous results for [LiH;e(+)] [Y. Kita et al., J. Chem. Phys. 131, 134310 (2009)], our study confirms the strong correlation between the positron affinity and dipole moment of alkali-metal hydrides.

  20. Current-induced spin polarization on metal surfaces probed by spin-polarized positron beam.

    PubMed

    Zhang, H J; Yamamoto, S; Fukaya, Y; Maekawa, M; Li, H; Kawasuso, A; Seki, T; Saitoh, E; Takanashi, K

    2014-04-29

    Current-induced spin polarization (CISP) on the outermost surfaces of Au, Cu, Pt, Pd, Ta, and W nanoscaled films were studied using a spin-polarized positron beam. The Au and Cu surfaces showed no significant CISP. In contrast, the Pt, Pd, Ta, and W films exhibited large CISP (3~15% per input charge current of 10(5) A/cm(2)) and the CISP of Ta and W were opposite to those of Pt and Pd. The sign of the CISP obeys the same rule in spin Hall effect suggesting that the spin-orbit coupling is mainly responsible for the CISP. The magnitude of the CISP is explained by the Rashba-Edelstein mechanism rather than the diffusive spin Hall effect. This settles a controversy, that which of these two mechanisms dominates the large CISP on metal surfaces.

  1. [Count rate characteristics and count loss correction of Positologica II: a whole body positron emission tomograph].

    PubMed

    Endo, M; Nohara, N; Iinuma, T A; Shinoto, H; Tanaka, E; Yoshida, K; Himi, T; Kagaya, A; Ogushi, A; Inoue, S

    1987-05-01

    This paper describes evaluation and correction of count rate characteristics of POSITOLOGICA II, a multi-slice whole body positron emission tomography system. The present study was performed using three phantoms; a 5 cm inner diameter, water-filled lucite cylinder, a 20 cm inner diameter, water-filled lucite cylinder and a chest phantom. After injection of high activity (about 1.85 GBq (50 mCi] of 13N ammonia into each phantom, rates of true coincidence, random coincidence and single photon detections were measured during decay of the isotope through more than two orders of magnitude of activity. At very high levels of activity, count rate characteristics of the system were saturated and limited to 660 kcps of total coincidence rate, which was the sum of rates in on-time and off-time windows, by the FIFO (first-in first-out) output frequency. Below those levels of activity the relationship between count loss and true coincidence rate was not unique but depended on the phantom configurations, suggesting that count loss correction using the above relationship was inadequate for quantitative study. However, the relationship between count loss and single rate was almost independent of the phantom configurations. Thus in conclusion count loss could be corrected using single rate for POSITOLOGICA II. A practical method of count loss correction was also proposed.

  2. The electron-cloud instability in the arcs of the PEP-II positron ring

    SciTech Connect

    Furman, Miguel A.; Lambertson, Glen R.

    1998-03-01

    We have applied our simulation code ''POSINST'' to evaluate, in linear approximation, the contribution to the growth rate of the electron-cloud instability (ECI) from the pumping sections and the dipole bending magnets in the arcs of the PEP-II positron ring. A key ingredient in our model is a detailed description of the secondary emission process off the TiN-coated chambers. Another important element is the analytic computation of the electric field produced by the beam, including the effects from surface charges. Space-charge forces of the electron cloud upon itself are also included, although these forces are negligible under nominal conditions. Bunch-length effects are optionally included by slicing the bunch into several kicks. We conclude that the growth rate is dominated by the pumping sections and scales linearly with the photoelectric yield Y'. For Y' = 1, our present estimate is in the range {approx} 1000-1300 s{sup -1}, depending upon the value of the photon reflectivity R. This is in the range controllable by the transverse feedback system. The contributions to the growth rate from other magnets and from other sections of the ring remain to be evaluated.

  3. The beam energy feedback system for Beijing electron positron collider II linac.

    PubMed

    Wang, S; Iqbal, M; Chi, Y; Liu, R; Huang, X

    2017-03-01

    A beam-energy feedback system has been developed for the injection linac to meet the beam quality needed for the Beijing electron positron collider II storage ring. This paper describes the implementation and commissioning of this system in detail. The system consists of an energy measurement unit, application software, and an actuator unit. A non-intersecting beam energy monitor was developed to allow real-time online energy adjustment. The beam energy adjustment is achieved by adjusting the output microwave phase of the RF power source station. The phase control mechanism has also been modified, and a new control method taking the return difference of the phase shifter into account is used to improve the system's performance. This system achieves the design aim and can adjust the beam center energy with a rate of 2 Hz. With the energy feedback system, the stability of the injection rate is better; the fluctuation range is reduced from 20 mA/min to 10 mA/min, while the stability of the beam center energy is maintained within ±0.1%.

  4. Evaluation of copper-labeled Cu(II) bis(thiosemicarbazone) complexes as blood flow tracers for positron emission tomography

    SciTech Connect

    Bott, A.J.

    1990-01-01

    Positron emmision tomography (PET) is an imaging technique not widely available for clinical diagnosis due to the costs of producing positron-emitting radiolabels. The development of radiotracers labeled with generator-produced positron emitters would facilitate the use of PET by eliminating the need for an in-house cyclotron. Copper-62 is a generator-produced positron emitter potentially useful for labeling PET radiopharmaceuticals. Copper-62 labeled Cu(II) pyruvaldehyde bis(N[sup 4]-methylthiosemicarbazone), Cu(PTSM), is a proposed PET perfusion tracer of the brain, heart, and kidneys. After IV injection in animals, copper-labeled Cu(PTSM) affords high initial uptake followed by prolonged retention of radiocopper in these organs. This retention is thought to be a result of reductive decomposition of the copper-labeled copper(II) complex by intracellular glutathione, GSH. To validate copper-62 labeled Cu(PTSM) as a myocardial and renal perfusion tracer, the regional radiocopper level afforded by intravenous copper-67 labeled Cu(PTSM) was compared to the absolute blood flow measured with labeled microspheres in normal dog kidneys and surgically infarcted myocardia. In the heart and randomly sectioned kidneys, an excellent correlation resulted. In kidneys dissected to separate anatomical regions, radiocopper levels increased montonically with increasing blood flows for individual dogs, but a linear correlation was observed when data from 12 animals was combined. Should the distribution of Cu(PTSM) vary with naturally occuring GSH fluctuations, the clinical utility of this radiotracer would be limited. Therefore, to validate further copper-62 labeled Cu(PTSM), the biodistribution of copper-67 labeled (PTSM) was determined in GSH-depleted rats. Relatively large GSH reductions in the experimental animals caused only slight changes in the distribution of Cu(PTSM). Another 23 copper-67 labeled compounds were tested.

  5. Analysis of electron-positron momentum spectra of metallic alloys as supported by first-principles calculations

    NASA Astrophysics Data System (ADS)

    Folegati, P.; Makkonen, I.; Ferragut, R.; Puska, M. J.

    2007-02-01

    Electron-positron momentum distributions measured by the coincidence Doppler broadening method can be used in the chemical analysis of the annihilation environment, typically a vacancy-impurity complex in a solid. In the present work, we study possibilities for a quantitative analysis, i.e., for distinguishing the average numbers of different atomic species around the defect. First-principles electronic structure calculations self-consistently determining electron and positron densities and ion positions are performed for vacancy-solute complexes in Al-Cu , Al-Mg-Cu , and Al-Mg-Cu-Ag alloys. The ensuing simulated coincidence Doppler broadening spectra are compared with measured ones for defect identification. A linear fitting procedure, which uses the spectra for positrons trapped at vacancies in pure constituent metals as components, has previously been employed to find the relative percentages of different atomic species around the vacancy [A. Somoza Phys. Rev. B 65, 094107 (2002)]. We test the reliability of the procedure by the help of first-principles results for vacancy-solute complexes and vacancies in constituent metals.

  6. Study of PRIMAVERA steel samples by positron annihilation spectroscopy technique II - Lifetime measurements

    NASA Astrophysics Data System (ADS)

    Krsjak, V.; Grafutin, V.; Ilyukhina, O.; Burcl, R.; Ballesteros, A.; Hähner, P.

    2012-02-01

    In the present article, a positron annihilation lifetime technique was used for the study of VVER-440/230 weld materials, manufactured in the frame of the international PRIMAVERA project on microstructural investigation of the irradiated WWER-440 reactor pressure vessel steel. The present results complement our previous report of positron angular correlation experiments and provide in-depth characterization of vacancy type defects behavior under irradiation and thermal treatment. The results give new insight into the previously published atom probe tomography and angular correlation of annihilation radiation studies. The measurements do not show any association of phosphorus or its segregation to the open volume defects investigated by positron annihilation spectroscopy. The embrittlement effects related to the phosphorus seem to be effectively annealed-out during 475 °C thermal treatment and the post annealing microstructure and mechanical properties of the material are consequently affected mostly by agglomerations of vacancy clusters coarsened during thermal treatment.

  7. To the problem of positron states in metal-insulator nanosandwiches

    NASA Astrophysics Data System (ADS)

    Babich, A. V.; Vakula, P. V.; Pogosov, V. V.

    2015-01-01

    The potential profiles, wave functions, energies of surface subbands, and lifetimes of positrons in aluminum nanofilms bordering insulators (solid inert gases and SiO2) have been calculated self-consistently in the previously proposed models. The size effects and the influence of the effective masses of electrons and positrons on the energy and annihilation characteristics in systems with double potential wells formed by image potentials have been investigated. The possibility of localizing a positronium atom in nanosandwiches has been discussed.

  8. Large-dimension configuration-interaction calculations of positron binding to the group-II atoms

    SciTech Connect

    Bromley, M. W. J.; Mitroy, J.

    2006-03-15

    The configuration-interaction (CI) method is applied to the calculation of the structures of a number of positron binding systems, including e{sup +}Be, e{sup +}Mg, e{sup +}Ca, and e{sup +}Sr. These calculations were carried out in orbital spaces containing about 200 electron and 200 positron orbitals up to l=12. Despite the very large dimensions, the binding energy and annihilation rate converge slowly with l, and the final values do contain an appreciable correction obtained by extrapolating the calculation to the l{yields}{infinity} limit. The binding energies were 0.00317 hartree for e{sup +}Be, 0.0170 hartree for e{sup +}Mg, 0.0189 hartree for e{sup +}Ca, and 0.0131 hartree for e{sup +}Sr.

  9. CHARACTERIZATION OF PLASTICALLY-INDUCED STRUCTURAL CHANGES IN A Zr-BASED BULK METALLIC GLASS USING POSITRON ANNIHILATION SPECTROCOPY

    SciTech Connect

    Flores, K M; Kanungo, B P; Glade, S C; Asoka-Kumar, P

    2005-09-16

    Flow in metallic glasses is associated with stress-induced cooperative rearrangements of small groups of atoms involving the surrounding free volume. Understanding the details of these rearrangements therefore requires knowledge of the amount and distribution of the free volume and how that distribution evolves with deformation. The present study employs positron annihilation spectroscopy to investigate the free volume change in Zr{sub 58.5}Cu{sub 15.6}Ni{sub 12.8}Al{sub 10.3}Nb{sub 2.8} bulk metallic glass after inhomogeneous plastic deformation by cold rolling and structural relaxation by annealing. Results indicate that the size distribution of open volume sites is at least bimodal. The size and concentration of the larger group, identified as flow defects, changes with processing. Following initial plastic deformation the size of the flow defects increases, consistent with the free volume theory for flow. Following more extensive deformation, however, the size distribution of the positron traps shifts, with much larger open volume sites forming at the expense of the flow defects. This suggests that a critical strain is required for flow defects to coalesce and form more stable nanovoids, which have been observed elsewhere by high resolution TEM. Although these results suggest the presence of three distinct open volume size groups, further analysis indicates that all groups have the same line shape parameter. This is in contrast to the distinctly different interactions observed in crystalline materials with multiple defect types. This similarity may be due to the disordered structure of the glass and positron affinity to particular atoms surrounding open-volume regions.

  10. Plant rhamnogalacturonan II complexation of heavy metal cations

    DOEpatents

    O'Neill, Malcolm A.; Pellerin, Patrice J. M.; Warrenfeltz, Dennis; Vidal, Stephane; Darvill, Alan G.; Albersheim, Peter

    1999-01-01

    The present invention provides rhamnogalacturonan-II (RG-II) and relates to its ability to complex specific multivalent heavy metal cations. In the presence of boric acid, RG-II monomers form dimers that are cross-linked by a borate ester. The yield of such borate ester cross-linked dimers of RG-II is enhanced in the presence of specific heavy metal cations. The present invention further relates to the utility of RG-II in assays for the detection of specific heavy metal contamination; as a reagent useful in the removal of specific heavy metal cations contaminating foods and liquids, for example, fish, wines, etc.; as a pharmaceutical composition useful as an antidote in specific heavy metal cation poisoning; as a treatment for the detoxification of specific heavy metal cations from blood and/or tissues; and in a method of remediation of waters and soils contaminated with specific heavy metal cations.

  11. Plant rhamnogalacturonan II complexation of heavy metal cations

    DOEpatents

    O`Neill, M.A.; Pellerin, P.J.M.; Warrenfeltz, D.; Vidal, S.; Darvill, A.G.; Albersheim, P.

    1999-03-02

    The present invention provides rhamnogalacturonan-II (RG-II) and relates to its ability to complex specific multivalent heavy metal cations. In the presence of boric acid, RG-II monomers form dimers that are cross-linked by a borate ester. The yield of such borate ester cross-linked dimers of RG-II is enhanced in the presence of specific heavy metal cations. The present invention further relates to the utility of RG-II in assays for the detection of specific heavy metal contamination; as a reagent useful in the removal of specific heavy metal cations contaminating foods and liquids, for example, fish, wines, etc.; as a pharmaceutical composition useful as an antidote in specific heavy metal cation poisoning; as a treatment for the detoxification of specific heavy metal cations from blood and/or tissues; and in a method of remediation of waters and soils contaminated with specific heavy metal cations. 15 figs.

  12. In Vivo Targeting and Positron Emission Tomography Imaging of Tumor with Intrinsically Radioactive Metal-Organic Frameworks Nanomaterials.

    PubMed

    Chen, Daiqin; Yang, Dongzhi; Dougherty, Casey A; Lu, Weifei; Wu, Hongwei; He, Xianran; Cai, Ting; Van Dort, Marcian E; Ross, Brian D; Hong, Hao

    2017-04-25

    Nanoscale metal-organic frameworks (nMOF) materials represent an attractive tool for various biomedical applications. Due to the chemical versatility, enormous porosity, and tunable degradability of nMOFs, they have been adopted as carriers for delivery of imaging and/or therapeutic cargos. However, the relatively low stability of most nMOFs has limited practical in vivo applications. Here we report the production and characterization of an intrinsically radioactive UiO-66 nMOF ((89)Zr-UiO-66) with incorporation of positron-emitting isotope zirconium-89 ((89)Zr). (89)Zr-UiO-66 was further functionalized with pyrene-derived polyethylene glycol (Py-PGA-PEG) and conjugated with a peptide ligand (F3) to nucleolin for targeting of triple-negative breast tumors. Doxorubicin (DOX) was loaded onto UiO-66 with a relatively high loading capacity (1 mg DOX/mg UiO-66) and served as both a therapeutic cargo and a fluorescence visualizer in this study. Functionalized (89)Zr-UiO-66 demonstrated strong radiochemical and material stability in different biological media. Based on the findings from cellular targeting and in vivo positron emission tomography (PET) imaging, we can conclude that (89)Zr-UiO-66/Py-PGA-PEG-F3 can serve as an image-guidable, tumor-selective cargo delivery nanoplatform. In addition, toxicity evaluation confirmed that properly PEGylated UiO-66 did not impose acute or chronic toxicity to the test subjects. With selective targeting of nucleolin on both tumor vasculature and tumor cells, this intrinsically radioactive nMOF can find broad application in cancer theranostics.

  13. Positron microscopy

    SciTech Connect

    Hulett, L.D. Jr.; Xu, J.

    1995-02-01

    The negative work function property that some materials have for positrons make possible the development of positron reemission microscopy (PRM). Because of the low energies with which the positrons are emitted, some unique applications, such as the imaging of defects, can be made. The history of the concept of PRM, and its present state of development will be reviewed. The potential of positron microprobe techniques will be discussed also.

  14. Exploiting the Metal-Chelating Properties of the Drug Cargo for In Vivo Positron Emission Tomography Imaging of Liposomal Nanomedicines

    PubMed Central

    2016-01-01

    The clinical value of current and future nanomedicines can be improved by introducing patient selection strategies based on noninvasive sensitive whole-body imaging techniques such as positron emission tomography (PET). Thus, a broad method to radiolabel and track preformed nanomedicines such as liposomal drugs with PET radionuclides will have a wide impact in nanomedicine. Here, we introduce a simple and efficient PET radiolabeling method that exploits the metal-chelating properties of certain drugs (e.g., bisphosphonates such as alendronate and anthracyclines such as doxorubicin) and widely used ionophores to achieve excellent radiolabeling yields, purities, and stabilities with 89Zr, 52Mn, and 64Cu, and without the requirement of modification of the nanomedicine components. In a model of metastatic breast cancer, we demonstrate that this technique allows quantification of the biodistribution of a radiolabeled stealth liposomal nanomedicine containing alendronate that shows high uptake in primary tumors and metastatic organs. The versatility, efficiency, simplicity, and GMP compatibility of this method may enable submicrodosing imaging studies of liposomal nanomedicines containing chelating drugs in humans and may have clinical impact by facilitating the introduction of image-guided therapeutic strategies in current and future nanomedicine clinical studies. PMID:27781436

  15. A search for supersymmetric electrons with the Mark II detector at PEP (Positron Electron Project)

    SciTech Connect

    LeClaire, B.W.

    1987-10-01

    An experimental search for selectrons, the supersymmetric partner of the electron, has been performed at the PEP storage ring at SLAC using the Mark II detector. The experimental search done was based upon hypothetical reaction in e/sup +/e/sup -/ interactions at PEP center of mass energies of 29 GeV. In this reaction the selectrons, e-tilde, are assumed produced by the interaction of one of initial state electrons with a photon radiated from the other initial state electron. This latter electron is assumed to continue down the beam pipe undetected. The photon and electron then produce a selectron and a photino, ..gamma..-tilde, in the supersymmetric analog of Compton scattering. The photino is assumed to be the lightest supersymmetric particle, and as such, does not interact in the detector, thereby escaping detection very much like a neutrino. The selectron is assumed to immediately decay into an electron and photino. This electron is produced with large p perpendicular with respect to the beam pipe, since it must balance the transverse momentum carried off by the photinos. Thus, the experimental signature of the process is a single electron in the detector with a large unbalanced tranverse momentum. No events of this type were observed in the original search of 123 pb/sup -1/ of data, resulting in a cross section limit of less than 2.4 x 10/sup -2/ pb (at the 95% CL) within the detector acceptance. This cross section upper limit applies to any process which produces anomalous single electron events with missing transverse momentum. When interpreted as a supersymmetry search it results in a lower selectron mass limit of 22.2 GeV/c/sup 2/ for the case of massless photinos. Limits for non-zero mass photinos have been calculated. 87 refs., 67 figs., 17 tabs.

  16. Type II supernovae as probes of environment metallicity: observations of host H II regions

    NASA Astrophysics Data System (ADS)

    Anderson, J. P.; Gutiérrez, C. P.; Dessart, L.; Hamuy, M.; Galbany, L.; Morrell, N. I.; Stritzinger, M. D.; Phillips, M. M.; Folatelli, G.; Boffin, H. M. J.; de Jaeger, T.; Kuncarayakti, H.; Prieto, J. L.

    2016-05-01

    Context. Spectral modelling of type II supernova atmospheres indicates a clear dependence of metal line strengths on progenitor metallicity. This dependence motivates further work to evaluate the accuracy with which these supernovae can be used as environment metallicity indicators. Aims: To assess this accuracy we present a sample of type II supernova host H ii-region spectroscopy, from which environment oxygen abundances have been derived. These environment abundances are compared to the observed strength of metal lines in supernova spectra. Methods: Combining our sample with measurements from the literature, we present oxygen abundances of 119 host H ii regions by extracting emission line fluxes and using abundance diagnostics. These abundances are then compared to equivalent widths of Fe ii 5018 Å at various time and colour epochs. Results: Our distribution of inferred type II supernova host H ii-region abundances has a range of ~0.6 dex. We confirm the dearth of type II supernovae exploding at metallicities lower than those found (on average) in the Large Magellanic Cloud. The equivalent width of Fe ii 5018 Å at 50 days post-explosion shows a statistically significant correlation with host H ii-region oxygen abundance. The strength of this correlation increases if one excludes abundance measurements derived far from supernova explosion sites. The correlation significance also increases if we only analyse a "gold" IIP sample, and if a colour epoch is used in place of time. In addition, no evidence is found of a correlation between progenitor metallicity and supernova light-curve or spectral properties - except for that stated above with respect to Fe ii 5018 Å equivalent widths - suggesting progenitor metallicity is not a driving factor in producing the diversity that is observed in our sample. Conclusions: This study provides observational evidence of the usefulness of type II supernovae as metallicity indicators. We finish with a discussion of the

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

    PubMed

    Vasák, M; Kägi, J H

    1981-11-01

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

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

    PubMed Central

    Vasák, M; Kägi, J H

    1981-01-01

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

  19. Nondestructive examination using neutron activated positron annihilation

    DOEpatents

    Akers, Douglas W.; Denison, Arthur B.

    2001-01-01

    A method is provided for performing nondestructive examination of a metal specimen using neutron activated positron annihilation wherein the positron emitter source is formed within the metal specimen. The method permits in situ nondestructive examination and has the advantage of being capable of performing bulk analysis to determine embrittlement, fatigue and dislocation within a metal specimen.

  20. Metallic fuels: The EBR-II legacy and recent advances

    SciTech Connect

    Douglas L. Porter; Steven L. Hayes; J. Rory Kennedy

    2012-09-01

    Experimental Breeder Reactor – II (EBR-II) metallic fuel was qualified for high burnup to approximately 10 atomic per cent. Subsequently, the electrometallurgical treatment of this fuel was demonstrated. Advanced metallic fuels are now investigated for increased performance, including ultra-high burnup and actinide burning. Advances include additives to mitigate the fuel/cladding chemical interaction and uranium alloys that combine Mo, Ti and Zr to improve alloy performance. The impacts of the advances—on fabrication, waste streams, electrorefining, etc.—are found to be minimal and beneficial. Owing to extensive research literature and computational methods, only a modest effort is required to complete their development.

  1. TEMPERATURE STRUCTURE AND METALLICITY IN H II REGIONS

    SciTech Connect

    Rodriguez, Monica; GarcIa-Rojas, Jorge E-mail: jogarcia@iac.e

    2010-01-10

    The metallicities implied by collisionally excited lines (CELs) of heavy elements in H II regions are systematically lower than those implied by recombination lines (RLs) by factors of approx2, introducing uncertainties of the same order in the metallicities inferred for the interstellar medium of any star-forming galaxy. Most explanations of this discrepancy are based on the different sensitivities of CELs and RLs to electron temperature, and invoke either some extra heating mechanism producing temperature fluctuations in the ionized region or the addition of cold gas in metal-rich inclusions or ionized by cosmic rays or X-rays. These explanations will change the temperature structure of the ionized gas from the one predicted by simple photoionization models, and depending on which one is correct, will imply different metallicities for the emitting gas. We select nine H II regions with observed spectra of high quality and show that simple models with metallicities close to the ones implied by oxygen CELs reproduce easily their temperature structure, measured with T{sub e}([N II])/T{sub e}([O III]), and their oxygen CELs emission. We discuss the strong constraints that this agreement places on the possible explanations of the discrepancy and suggest that the simplest explanation, namely errors in the line recombination coefficients by factors approx2, might be the correct one. In such case, CELs will provide the best estimates of metallicity.

  2. Positron follow-up in liquid water: II. Spatial and energetic study for the most important radioisotopes used in PET.

    PubMed

    Champion, C; Le Loirec, C

    2007-11-21

    With the increasing development of positron emission tomography (PET), beta(+)-emitters are more and more regularly used in nuclear medicine. Therefore, today it is of prime importance to have a reliable description of their behavior in living matter in order to quantify the full spectra of the molecular damages potentially radio-induced and then to access a cellular dosimetry. In this work, we present a detailed inter-comparison of the main isotopes commonly used in PET: (18)F, (11)C, (13)N, (15)O, (68)Ga and (82)Rb. We have used an event-by-event Monte Carlo code recently developed for positron tracking in water (Champion and Le Loirec 2006 Phys. Med. Biol. 51 1707-23) which consists in simulating step-by-step, interaction after interaction, the history of each ionizing particle created during the irradiation of the biological matter. This simulation has been finally adapted for describing the decays of medically important positron emitters. Quantitative information about positron penetrations, Positronium formation, annihilation event distributions, energy deposit patterns and dose profiles is then accessible and compared to published measurements and/or calculations.

  3. Transition metal-ligand bonding. II

    NASA Technical Reports Server (NTRS)

    Bauschlicher, C. W., Jr.

    1986-01-01

    The nature of the bonding of CO, H2O, and NH3 to transition metal atoms is analyzed using the constrained-space-orbital-variation (CSOV) technique. The cooperative effects for Ni(CO)2 are found to be different than those for Ni(H2O)2. The bonding between neutral systems and the positive ions is found to be quite different; NiCO(+) has little pi bonding, while NiCO has strong pi bonding. The positive ion of NiH2O is far more strongly bound than the neutral, while for NiCO the positive ion and neutral are bound by about the same energy.

  4. Surface sealing using self-assembled monolayers and its effect on metal diffusion in porous low-k dielectrics studied using monoenergetic positron beams

    NASA Astrophysics Data System (ADS)

    Uedono, Akira; Armini, Silvia; Zhang, Yu; Kakizaki, Takeaki; Krause-Rehberg, Reinhard; Anwand, Wolfgang; Wagner, Andreas

    2016-04-01

    Surface sealing effects on the diffusion of metal atoms in porous organosilicate glass (OSG) films were studied by monoenergetic positron beams. For a Cu(5 nm)/MnN(3 nm)/OSG(130 nm) sample fabricated with pore stuffing, C4F8 plasma etch, unstuffing, and a self-assembled monolayer (SAM) sealing process, it was found that pores with cubic pore side lengths of 1.1 and 3.1 nm coexisted in the OSG film. For the sample without the SAM sealing process, metal (Cu and Mn) atoms diffused from the top Cu/MnN layer into the OSG film and were trapped by the pores. As a result, almost all pore interiors were covered with those metals. For the sample damaged by an Ar/C4F8 plasma etch treatment before the SAM sealing process, SAMs diffused into the OSG film, and they were preferentially trapped by larger pores. The cubic pore side length in these pores containing self-assembled molecules was estimated to be 0.7 nm. Through this work, we have demonstrated that monoenergetic positron beams are a powerful tool for characterizing capped porous films and the trapping of atoms and molecules by pores.

  5. High-dose boron and silver ion implantation into PMMA probed by slow positrons: Effects of carbonization and formation of metal nanoparticles

    NASA Astrophysics Data System (ADS)

    Kavetskyy, T.; Iida, K.; Nagashima, Y.; Kuczumow, A.; Šauša, O.; Nuzhdin, V.; Valeev, V.; Stepanov, A. L.

    2017-01-01

    The Doppler broadening slow positron beam spectroscopy (SPBS) data for the previously observed effect of carbonization in high-dose (>1016 ion/cm2) 40 keV boron-ion-implanted polymethylmethacrylate (B:PMMA) and another one obtained for the effect of formation of metal nanoparticles in high-dose 30 keV silver-ion-implanted polymer (Ag:PMMA) are compared. Following to the Doppler broadening SPBS results, a difference in the high-dose ion-irradiation-induced processes in B:PMMA and Ag:PMMA is detected.

  6. Biosorption of Cu(II), Zn(II), Ni(II) and Pb(II) ions by cross-linked metal-imprinted chitosans with epichlorohydrin.

    PubMed

    Chen, Chia-Yun; Yang, Cheng-Yu; Chen, Arh-Hwang

    2011-03-01

    Cross-linked metal-imprinted chitosan microparticles were prepared from chitosan, using four metals (Cu(II), Zn(II), Ni(II), and Pb(II)) as templates, and epichlorohydrin as the cross-linker. The microparticles were characterized by Fourier transform infrared spectroscopy, solid state (13)C nuclear magnetic resonance spectroscopy, and energy-dispersive X-ray spectroscopy. They were used for comparative biosorption of Cu(II), Zn(II), Ni(II) and Pb(II) ions in an aqueous solution. The results showed that the sorption capacities of Cu(II), Zn(II), Ni(II), and Pb(II) on the templated microparticles increased from 25 to 74%, 13 to 46%, 41 to 57%, and 12 to 43%, respectively, as compared to the microparticles without metal ion templates. The dynamic study showed that the sorption process followed the second-order kinetic equation. Three sorption models, Langmuir, Freundlich, and Dubinin-Radushkevich, were applied to the equilibrium isotherm data. The result showed that the Langmuir isotherm equation best fitted for monolayer sorption processes. Furthermore, the microparticles can be regenerated and reused for the metal removal.

  7. Mixed metal copper(II)-nickel(II) and copper(II)-zinc(II) complexes of multihistidine peptide fragments of human prion protein.

    PubMed

    Jószai, Viktória; Turi, Ildikó; Kállay, Csilla; Pappalardo, Giuseppe; Di Natale, Giuseppe; Rizzarelli, Enrico; Sóvágó, Imre

    2012-07-01

    Mixed metal copper(II)-nickel(II) and copper(II)-zinc(II) complexes of four peptide fragments of human prion protein have been studied by potentiometric, UV-vis and circular dichroism spectroscopic techniques. One peptide contained three histidyl residues: HuPrP(84-114) with H85 inside and H96, H111 outside the octarepeat domain. The other three peptides contained two histidyl residues; H96 and H111 for HuPrP(91-115) and HuPrP(84-114)H85A while HuPrP(84-114)H96A contained the histidyl residues at positions 85 and 111. It was found that both histidines of the latter peptides can simultaneously bind copper(II) and nickel(II) ions and dinuclear mixed metal complexes can exist in slightly alkaline solution. One molecule of the peptide with three histidyl residues can bind two copper(II) and one nickel(II) ions. H85 and H111 were identified as the major copper(II) and H96 as the preferred nickel(II) binding sites in mixed metal species. The studies on the zinc(II)-PrP peptide binary systems revealed that zinc(II) ions can coordinate to the 31-mer PrP peptide fragments in the form of macrochelates with two or three coordinated imidazol-nitrogens but the low stability of these complexes cannot prevent the hydrolysis of the metal ion in slightly alkaline solution. These data provide further support for the outstanding affinity of copper(II) ions towards the peptide fragments of prion protein but the binding of nickel(II) can significantly modify the distribution of copper(II) among the available metal binding sites.

  8. Positron implantation in solids

    SciTech Connect

    Ghosh, V.J.; Lynn, K.G.; Welch, D.O.

    1993-12-31

    The Monte Carlo technique for modeling positron prior to annihilation and electron implantation in semi-infinite metals is described. Particle implantation is modelled as a multistep process, a series of collisions with the atoms of the host material. In elastic collisions with neutral atoms there is no transfer of energy. The particle loses energy by several different channels, excitation of the electron gas, ionization of the ion cores, or, at low energies, by phonon excitation. These competing scattering mechanisms have been incorporated into the Monte Carlo framework and several different models are being used. Brief descriptions of these Monte Carlo schemes, as well as an analytic model for positron implantation are included. Results of the Monte Carlo simulations are presented and compared with expermental data. Problems associated with modeling positron implantation are discuss and the need for more expermental data on energy-loss in different materials is stressed. Positron implantation in multilayers of different metals is briefly described and extensions of this work to include a study of multilayers and heterostructures is suggested.

  9. Preparation and Characterization of Bi-metallic and Tri-metallic Metal Organic Frameworks Based on Trimesic Acid and Co(II), Ni(II), and Cu(II) Ions

    NASA Astrophysics Data System (ADS)

    Sahiner, Nurettin; Demirci, Sahin; Yildiz, Mustafa

    2017-02-01

    Trimesic acid-M1(II):M2(II) (M1,2(II)=M(II)=Co(II), Ni(II) and Cu(II)) bi-metallic or tri-metallic organic frameworks (MOFs) were synthesized by the reaction of trimesic acid (H3BTC) ligand with the corresponding MCl2nH2O aqueous solutions. Here, bi- and tri-metallic MOF preparations were demonstrated by using H3BTC as an organic linker, with dual metal ion mixtures at different mole ratios such as Co(II):Ni(II), Ni(II):Cu(II), and Cu(II):Co(II) as metal ion sources in the synthesis of bi-metallic MOFs, and the triple metal ion mixture of Co(II):Ni(II):Cu(II) as the metal ion source in the synthesis of tri-metallic MOFs. The bi- or tri-metallic MOFs were characterized via the Brunauer-Emmett-Teller method, thermogravimetric analyzer (TGA), and magnetic susceptibility measurements with the Gouy method, FT-IR spectroscopy, and electronic spectral studies. The results revealed that the H3BTC MOFs have octahedral and distorted octahedral arrangement around the metal ions, and the d-d transition was not observed in the complex. It was further found that all the prepared MOFs contain water molecules confirmed by Fourier transform infrared (FT-IR) and TGA analyses. The FT-IR spectra of the MOF complexes were characterized by the appearance of a broad band in the region of 3454-3300 cm-1 due to the ν(-OH) of the coordinated water; therefore, the location of the two water molecules was assumed to be inside the complex structure. Remarkably, the synthesized bi-metallic MOFs had unique and distinct colors depending on the amounts of metal ions used in the feed, implying that these bi-metallic MOFs with tunable M1(II) and M2(II) ratios offer great potential in the design of color-coded materials for use as sensors.

  10. Heat Deposition in Positron Sources for ILC

    SciTech Connect

    Bharadwaj, V.; Pitthan, R.; Sheppard, J.; Vincke, H.; Wang, J.W.; /SLAC

    2006-03-15

    In the International Linear Collider (ILC) positron source, multi-GeV electrons or multi-MeV photons impinge on a metal target to produce the needed positrons in the resulting electromagnetic showers. The incoming beam power is hundreds of kilowatts. Various computer programs -- such as FLUKA or MARS -- can calculate how the incoming beam showers in the target and can track the particle showers through the positron source system. Most of the incoming energy ends up as heat in the various positron source elements. This paper presents results from such calculations and their impact on the design of a positron source for the ILC.

  11. Annealing behaviors of vacancy-type defects near interfaces between metal contacts and GaN probed using a monoenergetic positron beam

    SciTech Connect

    Uedono, Akira Yoshihara, Nakaaki; Fujishima, Tatsuya; Piedra, Daniel; Palacios, Tomás; Ishibashi, Shoji; Sumiya, Masatomo; Laboutin, Oleg; Johnson, Wayne

    2014-08-04

    Vacancy-type defects near interfaces between metal contacts and GaN grown on Si substrates by metal organic chemical vapor deposition have been studied using a monoenergetic positron beam. Measurements of Doppler broadening spectra of the annihilation radiation for Ti-deposited GaN showed that optically active vacancy-type defects were introduced below the Ti/GaN interface after annealing at 800 °C. Charge transition of those defects due to electron capture was observed and was found to correlate with a yellow band in the photoluminescence spectrum. The major defect species was identified as vacancy clusters such as three to five Ga-vacancies coupled with multiple nitrogen-vacancies. The annealing behaviors of vacancy-type defects in Ti-, Ni-, and Pt-deposited GaN were also examined.

  12. Positron Physics

    NASA Technical Reports Server (NTRS)

    Drachman, Richard J.

    2003-01-01

    I will give a review of the history of low-energy positron physics, experimental and theoretical, concentrating on the type of work pioneered by John Humberston and the positronics group at University College. This subject became a legitimate subfield of atomic physics under the enthusiastic direction of the late Sir Harrie Massey, and it attracted a diverse following throughout the world. At first purely theoretical, the subject has now expanded to include high brightness beams of low-energy positrons, positronium beams, and, lately, experiments involving anti-hydrogen atoms. The theory requires a certain type of persistence in its practitioners, as well as an eagerness to try new mathematical and numerical techniques. I will conclude with a short summary of some of the most interesting recent advances.

  13. Positron Physics

    NASA Technical Reports Server (NTRS)

    Drachman, Richard J.

    2003-01-01

    I will give a review of the history of low-energy positron physics, experimental and theoretical, concentrating on the type of work pioneered by John Humberston and the positronics group at University College. This subject became a legitimate subfield of atomic physics under the enthusiastic direction of the late Sir Harrie Massey, and it attracted a diverse following throughout the world. At first purely theoretical, the subject has now expanded to include high brightness beams of low-energy positrons, positronium beams, and, lately, experiments involving anti-hydrogen atoms. The theory requires a certain type of persistence in its practitioners, as well as an eagerness to try new mathematical and numerical techniques. I will conclude with a short summary of some of the most interesting recent advances.

  14. Incorporation of Time-of-Flight Information Reduces Metal Artifacts in Simultaneous Positron Emission Tomography/Magnetic Resonance Imaging: A Simulation Study.

    PubMed

    Davison, Helen; ter Voert, Edwin E G W; de Galiza Barbosa, Felipe; Veit-Haibach, Patrick; Delso, Gaspar

    2015-07-01

    This study aimed to describe and evaluate the influence of time-of-flight (TOF) information on metal artifact reduction in positron emission tomography (PET) image quality in clinical simultaneous PET/magnetic resonance (MR) scanning. A total of 7 patients with various malignant tumors were included and underwent a PET/MR examination after standard PET/computed tomography. Baseline TOF and non-TOF PET images were reconstructed. Next, the TOF and non-TOF PET reconstructions were repeated after the introduction of artificial signal voids in the attenuation map to simulate metal artifacts of various sizes in a range of locations. Three different sizes of signal voids were inserted in the attenuation maps for each location of interest: over the maxilla, humeral head, chest, sternum, thoracic and lumbar spine, as well as the femoral head to replicate clinically relevant metal artifacts. The reconstructed images with the artifacts were then compared with the baseline reconstructed images. The mean percentage error in a region of interest surrounding the simulated artifact was used to compare between TOF and non-TOF images. Further comparison between TOF and non-TOF images was performed using histogram analysis. In all cases, the mean percentage error in a region of interest surrounding the simulated artifact was reduced when TOF information was included in the reconstruction. The inclusion of TOF also changes the distribution of smaller errors away from the origin of the artifact. In some anatomical regions, an increase in the number of small errors was noted with TOF, although the differences with non-TOF were minimal. Positron emission tomographic imaging benefits from the integration of TOF information in simultaneous PET/MR. The inclusion of TOF information in simultaneous PET/MR imaging reduces errors related to metal artifacts at the site of the artifact.

  15. Bulk Materials Analysis Using High-Energy Positron Beams

    SciTech Connect

    Glade, S C; Asoka-Kumar, P; Nieh, T G; Sterne, P A; Wirth, B D; Dauskardt, R H; Flores, K M; Suh, D; Odette, G R

    2002-11-11

    This article reviews some recent materials analysis results using high-energy positron beams at Lawrence Livermore National Laboratory. We are combining positron lifetime and orbital electron momentum spectroscopic methods to provide electron number densities and electron momentum distributions around positron annihilation sites. Topics covered include: correlation of positron annihilation characteristics with structural and mechanical properties of bulk metallic glasses, compositional studies of embrittling features in nuclear reactor pressure vessel steel, pore characterization in Zeolites, and positron annihilation characteristics in alkali halides.

  16. Macrocyclic receptor showing extremely high Sr(II)/Ca(II) and Pb(II)/Ca(II) selectivities with potential application in chelation treatment of metal intoxication.

    PubMed

    Ferreirós-Martínez, Raquel; Esteban-Gómez, David; Tóth, Éva; de Blas, Andrés; Platas-Iglesias, Carlos; Rodríguez-Blas, Teresa

    2011-04-18

    Herein we report a detailed investigation of the complexation properties of the macrocyclic decadentate receptor N,N'-Bis[(6-carboxy-2-pyridil)methyl]-4,13-diaza-18-crown-6 (H(2)bp18c6) toward different divalent metal ions [Zn(II), Cd(II), Pb(II), Sr(II), and Ca(II)] in aqueous solution. We have found that this ligand is especially suited for the complexation of large metal ions such as Sr(II) and Pb(II), which results in very high Pb(II)/Ca(II) and Pb(II)/Zn(II) selectivities (in fact, higher than those found for ligands widely used for the treatment of lead poisoning such as ethylenediaminetetraacetic acid (edta)), as well as in the highest Sr(II)/Ca(II) selectivity reported so far. These results have been rationalized on the basis of the structure of the complexes. X-ray crystal diffraction, (1)H and (13)C NMR spectroscopy, as well as theoretical calculations at the density functional theory (B3LYP) level have been performed. Our results indicate that for large metal ions such as Pb(II) and Sr(II) the most stable conformation is Δ(δλδ)(δλδ), while for Ca(II) our calculations predict the Δ(λδλ)(λδλ) form being the most stable one. The selectivity that bp18c6(2-) shows for Sr(II) over Ca(II) can be attributed to a better fit between the large Sr(II) ions and the relatively large crown fragment of the ligand. The X-ray crystal structure of the Pb(II) complex shows that the Δ(δλδ)(δλδ) conformation observed in solution is also maintained in the solid state. The Pb(II) ion is endocyclically coordinated, being directly bound to the 10 donor atoms of the ligand. The bond distances to the donor atoms of the pendant arms (2.55-2.60 Å) are substantially shorter than those between the metal ion and the donor atoms of the crown moiety (2.92-3.04 Å). This is a typical situation observed for the so-called hemidirected compounds, in which the Pb(II) lone pair is stereochemically active. The X-ray structures of the Zn(II) and Cd(II) complexes show that

  17. Propagation and Generation of Electromagnetic Waves at Proton Gyrofrequencies in a Relativistic Electron-Positron Plasma. II. Excitation of Electromagnetic Waves

    NASA Astrophysics Data System (ADS)

    Zheleznyakov, V. V.; Bespalov, P. A.

    2016-04-01

    In part I of this work [1], we study the dispersion characteristics of low-frequency waves in a relativistic electron-positron plasma. In part II, we examine the electromagnetic wave instability in this plasma caused by an admixture of nonrelativistic protons with energy comparable with the energy of relativistic low-mass particles. The instability occurs in the frequency band between the fundamental harmonic of proton gyrofrequency and the fundamental harmonic of relativistic electron gyrofrequency. The results can be used for the interpretation of known observations of the pulsar emissions obtained with a high time and frequency resolution. The considered instability can probably be the initial stage of the microwave radio emission nanoshots typical of the pulsar in the Crab Nebula.

  18. Unexpected Ni(II) and Cu(II) polynuclear assemblies--a balance between ligand and metal ion coordination preferences.

    PubMed

    Shuvaev, Kontantin V; Tandon, Santokh S; Dawe, Louise N; Thompson, Laurence K

    2010-07-14

    Polytopic ligand design involves matching the coordination pocket composition with the metal ion coordination 'algorithm', but despite targeting [4 x 4] grids as the final outcome, metal ion preferences and ligand control can lead to widely varying complexes in the self-assembly process with Ni(II) and Cu(II).

  19. H II Region Metallicity Distribution in the Milky Way Disk

    NASA Astrophysics Data System (ADS)

    Balser, Dana S.; Rood, Robert T.; Bania, T. M.; Anderson, L. D.

    2011-09-01

    The distribution of metals in the Galaxy provides important information about galaxy formation and evolution. H II regions are the most luminous objects in the Milky Way at mid-infrared to radio wavelengths and can be seen across the entire Galactic disk. We used the National Radio Astronomy Observatory (NRAO) Green Bank Telescope to measure radio recombination line and continuum emission in 81 Galactic H II regions. We calculated LTE electron temperatures using these data. In thermal equilibrium metal abundances are expected to set the nebular electron temperature with high abundances producing low temperatures. Our H II region distribution covers a large range of Galactocentric radius (5-22 kpc) and samples the Galactic azimuth range 330°-60°. Using our highest quality data (72 objects) we derived an O/H Galactocentric radial gradient of -0.0383 ± 0.0074 dex kpc-1. Combining these data with a similar survey made with the NRAO 140 Foot telescope we get a radial gradient of -0.0446 ± 0.0049 dex kpc-1 for this larger sample of 133 nebulae. The data are well fit by a linear model and no discontinuities are detected. Dividing our sample into three Galactic azimuth regions produced significantly different radial gradients that range from -0.03 to -0.07 dex kpc-1. These inhomogeneities suggest that metals are not well mixed at a given radius. We stress the importance of homogeneous samples to reduce the confusion of comparing data sets with different systematics. Galactic chemical evolution models typically derive chemical evolution along only the radial dimension with time. Future models should consider azimuthal evolution as well.

  20. Positron trapping at grain boundaries

    SciTech Connect

    Dupasquier, A. ); Romero, R.; Somoza, A. )

    1993-10-01

    The standard positron trapping model has often been applied, as a simple approximation, to the interpretation of positron lifetime spectra in situations of diffusion-controlled trapping. This paper shows that this approximation is not sufficiently accurate, and presents a model based on the correct solution of the diffusion equation, in the version appropriate for studying positron trapping at grain boundaries. The model is used for the analysis of new experimental data on positron lifetime spectra in a fine-grained Al-Ca-Zn alloy. Previous results on similar systems are also discussed and reinterpreted. The analysis yields effective diffusion coefficients not far from the values known for the base metals of the alloys.

  1. Heterometallic rare earth/group II metal chalcogenolate clusters

    SciTech Connect

    Berardini, M.; Emge, T.; Brennan, J.G. )

    1994-07-27

    Heterometallic Group II/rare earth (RE) thiolates, selenolates, and tellurolates have a broad range of potential applications in the rapidly developing field of RE-doped semiconductor technology . Given the tendency of RE chalcogenolates to form polymetallic species with bridging chalcogenolate ligands, we reasoned that RE complexes of the heavier chalcogenolates could be stabilized by bridging the chalcogenide to a softer Group II metal to form heterometallic compounds. In this paper, we show that such stabilization is significant, and we describe the isolation and structural characterization of the first two examples of a broad class of heterometallic chalcogenolate complexes having the general formula MM[prime](EPh)[sub x](L)[sub y] [M = Zn, Cd, Hg; M[prime] = divalent (x = 4) or trivalent (x = 5) rare earth; E = S, Se, Te; L = THF, pyridine]. 9 refs., 1 fig.

  2. EBR-II metallic driver fuel - a live option

    SciTech Connect

    Seidel, B.R.; Walters, L.C.

    1981-10-01

    The exceptional performance of metallic driver fuel has been demonstrated by the irradiation of a large number of Experimental Breeder Reactor II (EBR-II) driver-fuel elements of uranium-5 wt percent fissium clad in austenitic stainless steel. High burnup with high reliability has been achieved by a close coupling of element design and materials selection. The irradiation performance has been improved by decreasing the fuel smear density, increasing the plenum volume, increasing the cladding thickness, and selecting a higher-strength, lower-swelling cladding alloy which exhibits less fuel-cladding chemical interaction. Quantification of reliability has allowed full utilization of the element lifetime. Lifetimes much greater than 10 at. percent could be achieved by a design change of the restrainer, which currently limits life. Use of U-Pu-Zr fuel alloy with current cladding material would provide higher-temperature capability. Metallic fuel systems with their inherently superior breeding and irradiation performance are a capable and attractive next-generation power systems. 19 refs.

  3. The chemical evolution of globular clusters - II. Metals and fluorine

    NASA Astrophysics Data System (ADS)

    Sánchez-Blázquez, P.; Marcolini, A.; Gibson, B. K.; Karakas, A. I.; Pilkington, K.; Calura, F.

    2012-01-01

    In the first paper of this series, we proposed a new framework in which to model the chemical evolution of globular clusters. This model is predicated upon the assumption that clusters form within an interstellar medium enriched locally by the ejecta of a single Type Ia supernova and varying numbers of asymptotic giant branch stars, superimposed on an ambient medium pre-enriched by low-metallicity Type II supernovae. Paper I was concerned with the application of this model to the observed abundances of several reactive elements and so-called non-metals for three classical intermediate-metallicity clusters, with the hallmark of the work being the successful recovery of many of their well-known elemental and isotopic abundance anomalies. Here, we expand upon our initial analysis by (i) applying the model to a much broader range of metallicities (from the factor of 3 explored in Paper I, to now a factor of ˜50; i.e. essentially, the full range of Galactic globular cluster abundances; and (ii) incorporating a broader suite of chemical species, including a number of iron-peak isotopes, heavier α-elements and fluorine. While allowing for an appropriate fine-tuning of the model input parameters, most empirical globular cluster abundance trends are reproduced; our model would suggest the need for a higher production of calcium, silicon and copper in low-metallicity (or so-called 'prompt') Type Ia supernovae than predicted in current stellar models in order to reproduce the observed trends in NGC 6752, and a factor of 2 reduction in carbon production from asymptotic giant branch stars to explain the observed trends between carbon and nitrogen. Observations of heavy-element isotopes produced primarily by Type Ia supernovae, including those of titanium, iron and nickel, could support/refute unequivocally our proposed framework, although currently the feasibility of the proposed observations is well beyond current instrumental capabilities. Hydrodynamical simulations would

  4. Metallicity from Type II supernovae from the (i)PTF

    SciTech Connect

    Taddia, F.; Moquist, P.; Sollerman, J.; Rubin, A.; Leloudas, G.; Gal-Yam, A.; Arcavi, I.; Cao, Y.; Filippenko, A. V.; Graham, M. L.; Mazzali, P. A.; Nugent, P. E.; Pan, Y. -C.; Silverman, J. M.; Xu, D.; Yaron, O.

    2016-03-01

    Type IIP supernovae (SNe IIP) have recently been proposed as metallicity (Z) probes. The spectral models of Dessart et al. (2014, MNRAS, 440, 1856) showed that the pseudo-equivalent width of Fe ii λ5018 (pEW5018) during the plateau phase depends on the primordial Z, but there was a paucity of SNe IIP exhibiting pEW5018 that were compatible with Z < 0.4 Z. This lack might be due to some physical property of the SN II population or to the fact that those SNe have been discovered in luminous, metal-rich targeted galaxies. In this paper, we use SN II observations from the untargeted (intermediate) Palomar Transient Factory [(i)PTF] survey, aiming to investigate the pEW5018 distribution of this SN population and, in particular, to look for the presence of SNe II at lower Z. We perform pEW5018 measurements on the spectra of a sample of 39 (i)PTF SNe II, selected to have well-constrained explosion epochs and light-curve properties. Based on the comparison with the pEW5018 spectral models, we subgrouped our SNe into four Z bins from Z ≈ 0.1 Z up to Z ≈ 2 Z. We also independently investigated the Z of the hosts by using their absolute magnitudes and colors and, in a few cases, using strong-line diagnostics from spectra. We searched for possible correlations between SN observables, such as their peak magnitudes and the Z inferred from pEW5018. We found 11 events with pEW5018 that were small enough to indicate Z ≈ 0.1 Z. The trend of pEW5018 with Z matches the Z estimates obtained from the host-galaxy photometry, although the significance of the correlation is weak. Finally, we also found that SNe with brighter peak magnitudes have smaller pEW5018 and occur at lower Z.

  5. Metallicity from Type II supernovae from the (i)PTF

    DOE PAGES

    Taddia, F.; Moquist, P.; Sollerman, J.; ...

    2016-03-01

    Type IIP supernovae (SNe IIP) have recently been proposed as metallicity (Z) probes. The spectral models of Dessart et al. (2014, MNRAS, 440, 1856) showed that the pseudo-equivalent width of Fe ii λ5018 (pEW5018) during the plateau phase depends on the primordial Z, but there was a paucity of SNe IIP exhibiting pEW5018 that were compatible with Z < 0.4 Z⊙. This lack might be due to some physical property of the SN II population or to the fact that those SNe have been discovered in luminous, metal-rich targeted galaxies. In this paper, we use SN II observations from themore » untargeted (intermediate) Palomar Transient Factory [(i)PTF] survey, aiming to investigate the pEW5018 distribution of this SN population and, in particular, to look for the presence of SNe II at lower Z. We perform pEW5018 measurements on the spectra of a sample of 39 (i)PTF SNe II, selected to have well-constrained explosion epochs and light-curve properties. Based on the comparison with the pEW5018 spectral models, we subgrouped our SNe into four Z bins from Z ≈ 0.1 Z⊙ up to Z ≈ 2 Z⊙. We also independently investigated the Z of the hosts by using their absolute magnitudes and colors and, in a few cases, using strong-line diagnostics from spectra. We searched for possible correlations between SN observables, such as their peak magnitudes and the Z inferred from pEW5018. We found 11 events with pEW5018 that were small enough to indicate Z ≈ 0.1 Z⊙. The trend of pEW5018 with Z matches the Z estimates obtained from the host-galaxy photometry, although the significance of the correlation is weak. Finally, we also found that SNe with brighter peak magnitudes have smaller pEW5018 and occur at lower Z.« less

  6. Metal Zn(II), Cu(II), Ni (II) complexes of ursodeoxycholic acid as putative anticancer agents

    PubMed Central

    Dyakova, Lora; Culita, Daniela-Cristina; Marinescu, Gabriela; Alexandrov, Marin; Kalfin, Reni; Patron, Luminita; Alexandrova, Radostina

    2014-01-01

    The aim of the study was to evaluate the influence of metal [Zn(II), Cu(II), Ni(II)] complexes with ursodeoxycholic acid (UDCA) on the viability and proliferation of tumour and non-tumour cells. Cell lines established from retrovirus-transformed chicken hepatoma (LSCC-SF-Mc29) and rat sarcoma (LSR-SF-SR) as well as from human cancers of the breast (MCF-7), uterine cervix (HeLa), lung (A549) and liver (HepG2) were used as model systems. Non-tumour human embryo (Lep-3) cells were also included in some of the experiments. The investigations were carried out by the thiazolyl blue tetrazolium bromide (MTT) test, neutral red uptake cytotoxicity assay, crystal violet staining, double staining with acridine orange and propidium iodide and the colony-forming method. The results obtained revealed that: (1) UDCA and its metal complexes in the tested concentrations decreased (to a varying degree) the viability and proliferation of the treated cells in a time- and concentration-dependent manner; (2) chicken hepatoma (LSCC-SF-Mc29) cells were most sensitive to the cytotoxic and antiproliferative action of the compounds tested, followed by rat sarcoma (LSR-SF-SR) cells; (3) Cu‒UDCA and Ni‒UDCA were more effective against animal LSCC-SF-Mc29 and LSR-SF-SR cells, while Zn‒UDCA significantly decreased the viability and proliferation of human tumour cell lines; (4) applied independently, UDCA expressed lower cytotoxic/cytostatic activity as compared to metal complexes; and (5) the sensitivity of the non-tumour embryonic Lep-3 cells to the effects of UDCA and its metal complexes was comparable or even higher than those of the human tumour cells. PMID:26019542

  7. Immobilization of heavy metal ions (CuII, CdII, NiII, and PbII) by broiler litter-derived biochars in water and soil.

    PubMed

    Uchimiya, Minori; Lima, Isabel M; Thomas Klasson, K; Chang, SeChin; Wartelle, Lynda H; Rodgers, James E

    2010-05-12

    Chars, a form of environmental black carbon resulting from incomplete burning of biomass, can immobilize organic contaminants by both surface adsorption and partitioning mechanisms. The predominance of each sorption mechanism depends upon the proportion of organic to carbonized fractions comprising the sorbent. Information is currently lacking in the effectiveness of char amendment for heavy metal immobilization in contaminated (e.g., urban and arms range) soils where several metal contaminants coexist. The present study employed sorbents of a common biomass origin (broiler litter manure) that underwent various degrees of carbonization (chars formed by pyrolysis at 350 and 700 degrees C and steam-activated analogues) for heavy metal (Cd(II), Cu(II), Ni(II), and Pb(II)) immobilization in water and soil. ATR-FTIR, (1)H NMR, and Boehm titration results suggested that higher pyrolysis temperature and activation lead to the disappearance (e.g., aliphatic -CH(2) and -CH(3)) and the formation (e.g., C-O) of certain surface functional groups, portions of which are leachable. Both in water and in soil, pH increase by the addition of basic char enhanced the immobilization of heavy metals. Heavy metal immobilization resulted in nonstoichiometric release of protons, that is, several orders of magnitude greater total metal concentration immobilized than protons released. The results suggest that with higher carbonized fractions and loading of chars, heavy metal immobilization by cation exchange becomes increasingly outweighed by other controlling factors such as the coordination by pi electrons (C=C) of carbon and precipitation.

  8. Adsorptive removal of Cu(II) and Ni(II) from single-metal, binary-metal, and industrial wastewater systems by surfactant-modified alumina.

    PubMed

    Khobragade, Moni U; Pal, Anjali

    2015-01-01

    Batch adsorption was carried out to investigate the possibility of utilizing surfactant-modified alumina (SMA) as an adsorbent for the removal of Cu(II) and Ni(II) from single-metal and binary-metal solutions. Scanning electron microscopic (SEM) images of SMA before and after metal removal from single-metal matrix, showed no significant changes, whereas energy dispersive X-ray (EDX) studies confirmed the incorporation of Cu(II) (∼ 0.74 atomic%) and Ni(II) (∼ 0.64 atomic%) on the adsorbent surface. The removal of Cu(II) and Ni(II), using SMA depends on contact time, adsorbent dose and medium pH. The sorption kinetics followed pseudo-second-order model for Cu(II). However, for Ni(II), either pseudo-first-order or pseudo-second-order model is applicable. The batch experimental data were fitted to Langmuir and Freundlich isotherm, and based on the correlation coefficient value (R(2)), the adsorption could be described more precisely by the Freundlich isotherm. The maximum adsorption capacity from Langmuir isotherm of Cu(II) was 9.34 mg g(-1) and for Ni(II) 6.87 mg g(-1). In a synthetic binary mixture of Cu(II) and Ni(II), having a concentration of 10 mg L(-1) each, removal of Cu(II) was better. The treatment method was further applied to real wastewater from an electroplating industry. The batch experiment results showed that SMA was effective in the simultaneous removal of Cu(II) and Ni(II) to a significant extent, with additional improvement of water quality of the industrial effluent considered.

  9. DNA interaction studies of tridentate bridged Ru(II)-Pt(II) mixed-metal supramolecules.

    PubMed

    Prussin, Aaron J; Zhao, Shengliang; Jain, Avijita; Winkel, Brenda S J; Brewer, Karen J

    2009-03-01

    Reported herein are studies of the concentration and temperature dependent interactions with DNA of the stereochemically defined mixed-metal supramolecular complexes, [(tpy)Ru(tppz)PtCl](PF(6))(3) and [ClPt(tppz)Ru(tppz)PtCl](PF(6))(4) (tpy=2,2':6',2''-terpyridine and tppz=2,3,5,6-tetrakis(2-pyridyl)pyrazine). These metal complexes couple a ruthenium based light absorber (LA) to the bioactive platinum sites (BAS) using a tridentate bridging ligand (BL). The complexes exhibit intense Ru-->tppz(pi*) metal to ligand charge transfer (MLCT) transitions in the visible region and adopt a square planar geometry around the Pt(II) center. The effect of incubating these metal complexes with DNA on the subsequent migration of DNA through an agarose gel was found to be more dramatic than that observed for the well known anticancer drug, cis-[Pt(NH(3))(2)Cl(2)] (cisplatin). This effect was enhanced with increased incubation temperature. Unwinding of supercoiled plasmid DNA was found to be more pronounced for the trimetallic complex, [ClPt(tppz)Ru(tppz)PtCl](PF(6))(4), than for the bimetallic complex, [(tpy)Ru(tppz)PtCl](PF(6))(3).

  10. Noninvasive positron emission tomography imaging of cell death using a novel small-molecule probe, (18)F labeled bis(zinc(II)-dipicolylamine) complex.

    PubMed

    Wang, Hongliang; Tang, Xiaolan; Tang, Ganghua; Huang, Tingting; Liang, Xiang; Hu, Kongzhen; Deng, Huaifu; Yi, Chang; Shi, Xinchong; Wu, Kening

    2013-08-01

    The synthetic bis(zinc(II)-dipicolylamine) (DPAZn2) coordination complexes are known to have a high specific and selective affinity to target the exposed phosphatidylserine (PS) on the surface of dead and dying cells. An (18)F-labeled DPAZn2 complex (4-(18)F-Fluoro-benzoyl-bis(zinc(II)-dipicolylamine), (18)F-FB-DPAZn2) as positron emission tomography (PET) tracer was developed and evaluated for in vivo imaging of tumor treated with a chemical agent. The in vitro cell stain studies revealed that fluorescent DPAZn2 complexes (Dansyl-DPAZn2) stained the same cells (apoptotic and necrotic cells) as fluorescein isothiocyanate (FITC) labeled Annexin V (FITC-Annexin V). The radiosynthesis of (18)F-FB-DPAZn2 was achieved through the amidation the precursor bis(2,2'-dipicolylamine) derivative (DPA2) with the prosthetic group N-succinimidyl-4-[(18)F]-fluorobenzoate ((18)F-SFB) and chelation with zinc nitrate. In the biodistribution study, the fast clearance of (18)F-FB-DPAZn2 from blood and kidney was observed and high uptake in liver and intestine within 90 min postinjection was also found. For the PET imaging, significantly higher tumor uptake of (18)F-FB-DPAZn2 was observed in the adriamycin (ADM)-treated Hepa1-6 hepatocellular carcinoma-bearing mice than that in the untreated tumor-model mice, while a slightly decreased tumor uptake of (18)F-FDG was found in the ADM-treated tumor-bearing mice. The results indicate that (18)F-FB-DPAZn2 has the similar capability of apoptosis detection as FITC-Annexin V and seems to be a potential PET tracer for noninvasive evaluation and monitoring of anti-tumor chemotherapy. The high uptake of (18)F-FB-DPAZn2 in the abdomen needs to optimize the structure for improving its pharmacokinetics characteristics in the future work.

  11. Impact of 18F-fluoro-2-deoxyglucose positron emission tomography on treatment strategy and radiotherapy planning for stage I-II Hodgkin disease: a prospective multicenter study.

    PubMed

    Pommier, Pascal; Dussart, Sophie; Girinsky, Théodore; Chabaud, Sylvie; Lagrange, Jean Leon; Nguyen, Tan Dat; Beckendorff, Véronique; D'Hombres, Anne; Artignan, Xavier; Bondiau, Pierre Yves; Carrie, Christian; Giammarile, Francesco

    2011-03-01

    To quantify the impact of preradiotherapy 18F-fluoro-2-deoxyglucose positron-emission tomography (FDG-PET) on treatment strategy and radiotherapy planning for patients with Stage I/II Hodgkin disease included in a large prospective multicenter study. Conventional computed tomography and FDG-PET were performed just before the planned radiotherapy. The radiotherapy plan was first elaborated under blinded conditions for FDG-PET data. Then, the medical staff was asked to confirm or not confirm the treatment strategy and, if appropriate, to modify the radiotherapy plan based on additional information from FDG-PET. Between January 2004 and January 2006, 137 patients were included (124 were available for analysis) in 11 centers (108 adults, 16 children). All but 1 patient had received chemotherapy before inclusion. Prechemotherapy work-up included FDG-PET for 61 patients, and data were available for elaboration of the first radiotherapy plan. Based on preradiotherapy FDG-PET data, the radiotherapy was cancelled in 6 patients (4.8%), and treatment plan modifications occurred in 16 patients (12.9%): total dose (11 patients), CTV volume (5 patients), number of beam incidences (6 patients), and number of CTV (6 patients). The concordance between the treatment strategies with or without preradiotherapy FDG-PET was 82.3%. Concordance results were not significantly different when prechemotherapy PET-CT information was available. Preradiotherapy FDG-PET for treatment planning in Hodgkin lymphoma may lead to significant modification of the treatment strategy and the radiotherapy planning in patients with Stage I or II Hodgkin disease, even in those who have undergone FDG-PET as part of the prechemotherapy work-up. Copyright © 2011 Elsevier Inc. All rights reserved.

  12. Impact of 18F-Fluoro-2-Deoxyglucose Positron Emission Tomography on Treatment Strategy and Radiotherapy Planning for Stage I-II Hodgkin Disease: A Prospective Multicenter Study

    SciTech Connect

    Pommier, Pascal; Dussart, Sophie; Girinsky, Theodore; Chabaud, Sylvie; Lagrange, Jean Leon; Nguyen, Tan Dat; Beckendorff, Veronique; D'Hombres, Anne; Artignan, Xavier; Bondiau, Pierre Yves; Carrie, Christian; Giammarile, Francesco

    2011-03-01

    Purpose: To quantify the impact of preradiotherapy 18F-fluoro-2-deoxyglucose positron-emission tomography (FDG-PET) on treatment strategy and radiotherapy planning for patients with Stage I/II Hodgkin disease included in a large prospective multicenter study. Patients and Methods: Conventional computed tomography and FDG-PET were performed just before the planned radiotherapy. The radiotherapy plan was first elaborated under blinded conditions for FDG-PET data. Then, the medical staff was asked to confirm or not confirm the treatment strategy and, if appropriate, to modify the radiotherapy plan based on additional information from FDG-PET. Results: Between January 2004 and January 2006, 137 patients were included (124 were available for analysis) in 11 centers (108 adults, 16 children). All but 1 patient had received chemotherapy before inclusion. Prechemotherapy work-up included FDG-PET for 61 patients, and data were available for elaboration of the first radiotherapy plan. Based on preradiotherapy FDG-PET data, the radiotherapy was cancelled in 6 patients (4.8%), and treatment plan modifications occurred in 16 patients (12.9%): total dose (11 patients), CTV volume (5 patients), number of beam incidences (6 patients), and number of CTV (6 patients). The concordance between the treatment strategies with or without preradiotherapy FDG-PET was 82.3%. Concordance results were not significantly different when prechemotherapy PET-CT information was available. Conclusion: Preradiotherapy FDG-PET for treatment planning in Hodgkin lymphoma may lead to significant modification of the treatment strategy and the radiotherapy planning in patients with Stage I or II Hodgkin disease, even in those who have undergone FDG-PET as part of the prechemotherapy work-up.

  13. Mixed metal hydroxycarboxylic acid complexes. Spectrophotometric study of complexes of U(VI) with In(III), Cu(II), Zn(II) and Cd(II)

    SciTech Connect

    Manzurola, E.; Apelblat, A.; Markovits, G.; Levy, O. )

    1988-01-01

    The formation of mixed metal complexes between uranium (VI), as the central metal ion, and aluminum (III), indium (III), copper (II), zinc (II) and cadmium (II), as the additional metal ions, with a hydroxycarboxylic acid chosen between citric, tartaric or malic, has been studied using spectrophotometric methods. The effect of pH has been examined, and the results show that at pH = 4 stable complexes are formed for most of the systems. At this pH the method of mole ratio and Job's method of continuous variations, were employed to determine the stoichiometry of the mixed metal complexes. Al(III), In(III) and Cu(II) showed a high tendency to form mixed metal complexes with U(VI), while the formation of complexes is uncertain for Cd(II) and Zn(II). The ratio of the ligand to the total metal ion has been found to be 2:1 and metal:metal ratios of 1:1 and 1:2 have been observed.

  14. Positron spectroscopy for materials characterization

    SciTech Connect

    Schultz, P.J.; Snead, C.L. Jr.

    1988-01-01

    One of the more active areas of research on materials involves the observation and characterization of defects. The discovery of positron localization in vacancy-type defects in solids in the 1960's initiated a vast number of experimental and theoretical investigations which continue to this day. Traditional positron annihilation spectroscopic techniques, including lifetime studies, angular correlation, and Doppler broadening of annihilation radiation, are still being applied to new problems in the bulk properties of simple metals and their alloys. In addition new techniques based on tunable sources of monoenergetic positron beams have, in the last 5 years, expanded the horizons to studies of surfaces, thin films, and interfaces. In the present paper we briefly review these experimental techniques, illustrating with some of the important accomplishments of the field. 40 refs., 19 figs.

  15. Early Positron Emission Tomography Response-Adapted Treatment in Stage I and II Hodgkin Lymphoma: Final Results of the Randomized EORTC/LYSA/FIL H10 Trial.

    PubMed

    André, Marc P E; Girinsky, Théodore; Federico, Massimo; Reman, Oumédaly; Fortpied, Catherine; Gotti, Manuel; Casasnovas, Olivier; Brice, Pauline; van der Maazen, Richard; Re, Alessandro; Edeline, Véronique; Fermé, Christophe; van Imhoff, Gustaaf; Merli, Francesco; Bouabdallah, Réda; Sebban, Catherine; Specht, Lena; Stamatoullas, Aspasia; Delarue, Richard; Fiaccadori, Valeria; Bellei, Monica; Raveloarivahy, Tiana; Versari, Annibale; Hutchings, Martin; Meignan, Michel; Raemaekers, John

    2017-03-14

    Purpose Patients who receive combined modality treatment for stage I and II Hodgkin lymphoma (HL) have an excellent outcome. Early response evaluation with positron emission tomography (PET) scan may improve selection of patients who need reduced or more intensive treatments. Methods We performed a randomized trial to evaluate treatment adaptation on the basis of early PET (ePET) after two cycles of doxorubicin, bleomycin, vinblastine, and dacarbazine (ABVD) in previously untreated-according to European Organisation for Research and Treatment of Cancer criteria favorable (F) and unfavorable (U)-stage I and II HL. The standard arm consisted of ABVD followed by involved-node radiotherapy (INRT), regardless of ePET result. In the experimental arm, ePET-negative patients received ABVD only (noninferiority design), whereas ePET-positive patients switched to two cycles of bleomycin, etoposide, doxorubicin, cyclophosphamide, vincristine, procarbazine, and prednisone (BEACOPPesc) and INRT (superiority design). Primary end point was progression-free survival (PFS). Results Of 1,950 randomly assigned patients, 1,925 received an ePET-361 patients (18.8%) were positive. In ePET-positive patients, 5-year PFS improved from 77.4% for standard ABVD + INRT to 90.6% for intensification to BEACOPPesc + INRT (hazard ratio [HR], 0.42; 95% CI, 0.23 to 0.74; P = .002). In ePET-negative patients, 5-year PFS rates in the F group were 99.0% versus 87.1% (HR, 15.8; 95% CI, 3.8 to 66.1) in favor of ABVD + INRT; the U group, 92.1% versus 89.6% (HR, 1.45; 95% CI, 0.8 to 2.5) in favor of ABVD + INRT. For both F and U groups, noninferiority of ABVD only compared with combined modality treatment could not be demonstrated. Conclusion In stage I and II HL, PET response after two cycles of ABVD allows for early treatment adaptation. When ePET is positive after two cycles of ABVD, switching to BEACOPPesc + INRT significantly improved 5-year PFS. In ePET-negative patients, noninferiority of ABVD only

  16. Design Issues for the ILC Positron Source

    SciTech Connect

    Bharadwaj, V.; Batygin, Yu.K.; Pitthan, R.; Schultz, D.C.; Sheppard, J.; Vincke, H.; Wang, J.W.; Gronberg, J.; Stein, W.; /LLNL, Livermore

    2006-02-15

    A positron source for the International Linear Collider (ILC) can be designed using either a multi-GeV electron beam or a multi-MeV photon beam impinging on a metal target. The major design issues are: choice of drive beam and its generation, choice of target material, the target station, positron capture section, target vault and beam transport to the ILC positron damping ring complex. This paper lists the ILC positron source requirements and their implications for the design of the positron source. A conceptual design for the ILC is expected to be finished in the next two years. With emphasis on this timescale, source design issues and possible solutions are discussed.

  17. Modeling of Copper(II), Cadmium(II), and Lead(II) Adsorption on Red Mud from Metal-EDTA Mixture Solutions.

    PubMed

    Güçlü; Apak

    2000-08-15

    The adsorption of toxic heavy metal cations, i.e., Cu(II), Cd(II), and Pb(II), from metal-EDTA mixture solutions on a composite adsorbent having a heterogeneous surface, i.e., bauxite waste red mud, has been investigated and modeled with the aid of a modified surface complexation approach in respect to pH and complexant dependency of heavy metal adsorption. EDTA was selected as the modeling ligand in view of its wide usage as an anthropogenic chelating agent and abundance in natural waters. The adsorption experiments were conducted for metal salts (nitrates), metal-EDTA complexes alone, or in mixtures containing (metal+metal-EDTA). The adsorption equilibrium constants for the metal ions and metal-EDTA complexes were calculated. For all studied cases, the solid adsorbent phase concentrations of the adsorbed metal and metal-EDTA complexes were found by using the derived model equations with excellent compatibility of experimental and theoretically generated adsorption isotherms. The model was useful for metal and metal-EDTA mixture solutions either at their natural pH of equilibration with the sorbent, or after pH elevation with NaOH titration up to a certain pH. Thus adsorption of every single species (M(2+) or MY(2-)) or of possible mixtures (M(2+)+MY(2-)) at natural pH or after NaOH titration could be calculated by the use of simple quadratic model equations, once the initial concentrations of the corresponding species, i.e., [M(2+)](0) or [MY(2-)](0), were known. The compatibility of theoretical and experimental data pairs of adsorbed species concentrations was verified by means of nonlinear regression analysis. The findings of this study can be further developed so as to serve environmental risk assessment concerning the expansion of a heavy metal contaminant plume with groundwater move ment in soil consisting of hydrated-oxide type minerals. Copyright 2000 Academic Press.

  18. Thermal positron interactions with alkali covered tungsten

    NASA Astrophysics Data System (ADS)

    Yamashita, Takashi; Iida, Shimpei; Terabe, Hiroki; Nagashima, Yasuyuki

    2016-11-01

    The branching ratios of positron reemission, positronium emission, positronium negative ion emission and capture to the surface state for thermalized positrons at polycrystalline tungsten surfaces coated with Na, K and Cs have been measured. The data shows that the ratios depend on the coverage of the alkali-metal coating. The fraction of the emitted positronium increases with the coverage of the coating up to 90%.

  19. Phase II safety and clinical comparison with single-photon emission computed tomography myocardial perfusion imaging for detection of coronary artery disease: flurpiridaz F 18 positron emission tomography.

    PubMed

    Berman, Daniel S; Maddahi, Jamshid; Tamarappoo, B K; Czernin, Johannes; Taillefer, Raymond; Udelson, James E; Gibson, C Michael; Devine, Marybeth; Lazewatsky, Joel; Bhat, Gajanan; Washburn, Dana

    2013-01-29

    This was a phase II trial to assess flurpiridaz F 18 for safety and compare its diagnostic performance for positron emission tomography (PET) myocardial perfusion imaging (MPI) with Tc-99m single-photon emission computed tomography (SPECT) MPI with regard to image quality, interpretative certainty, defect magnitude, and detection of coronary artery disease (CAD) (≥50% stenosis) on invasive coronary angiography (ICA). In pre-clinical and phase I studies, flurpiridaz F 18 has shown characteristics of an essentially ideal MPI tracer. One hundred forty-three patients from 21 centers underwent rest-stress PET and Tc-99m SPECT MPI. Eighty-six patients underwent ICA, and 39 had low-likelihood of CAD. Images were scored by 3 independent, blinded readers. A higher percentage of images were rated as excellent/good on PET versus SPECT on stress (99.2% vs. 88.5%, p < 0.01) and rest (96.9% vs. 66.4, p < 0.01) images. Diagnostic certainty of interpretation (percentage of cases with definitely abnormal/normal interpretation) was higher for PET versus SPECT (90.8% vs. 70.9%, p < 0.01). In 86 patients who underwent ICA, sensitivity of PET was higher than SPECT (78.8% vs. 61.5%, respectively, p = 0.02). Specificity was not significantly different (PET: 76.5% vs. SPECT: 73.5%). Receiver-operating characteristic curve area was 0.82 ± 0.05 for PET and 0.70 ± 0.06 for SPECT (p = 0.04). Normalcy rate was 89.7% with PET and 97.4% with SPECT (p = NS). In patients with CAD on ICA, the magnitude of reversible defects was greater with PET than SPECT (p = 0.008). Extensive safety assessment revealed that flurpiridaz F 18 was safe in this cohort. In this phase 2 trial, PET MPI with flurpiridaz F 18 was safe and superior to SPECT MPI for image quality, interpretative certainty, and overall CAD diagnosis. Copyright © 2013 American College of Cardiology Foundation. Published by Elsevier Inc. All rights reserved.

  20. Structure and mode of action of cyclic lipopeptide pseudofactin II with divalent metal ions.

    PubMed

    Janek, Tomasz; Rodrigues, Lígia R; Gudiña, Eduardo J; Czyżnikowska, Żaneta

    2016-10-01

    The interaction of natural lipopeptide pseudofactin II with a series of doubly charged metal cations was examined by matrix-assisted laser-desorption ionization-time of flight (MALDI-TOF) mass spectrometry and molecular modelling. The molecular modelling for metal-pseudofactin II provides information on the metal-peptide binding sites. Overall, Mg(2+), Ca(2+) and Zn(2+) favor the association with oxygen atoms spanning the peptide backbone, whereas Cu(2+) is coordinated by three nitrogens. Circular dichroism (CD) results confirmed that Zn(2+) and Cu(2+) can disrupt the secondary structure of pseudofactin II at high concentrations, while Ca(2+) and Mg(2+) did not essentially affect the structure of the lipopeptide. Interestingly, our results showed that the addition of Zn(2+) and Cu(2+) helped smaller micelles to form larger micellar aggregates. Since pseudofactin II binds metals, we tested whether this phenomena was somehow related to its antimicrobial activity against Staphylococcus epidermidis and Proteus mirabilis. We found that the antimicrobial effect of pseudofactin II was increased by supplementation of culture media with all tested divalent metal ions. Finally, by using Gram-positive and Gram-negative bacteria we showed that the higher antimicrobial activity of metal complexes of pseudofactin II is attributed to the disruption of the cytoplasmic membrane. Copyright © 2016 Elsevier B.V. All rights reserved.

  1. Five coordinate M(II)-diphenolate [M = Zn(II), Ni(II), and Cu(II)] Schiff base complexes exhibiting metal- and ligand-based redox chemistry.

    PubMed

    Franks, Mark; Gadzhieva, Anastasia; Ghandhi, Laura; Murrell, David; Blake, Alexander J; Davies, E Stephen; Lewis, William; Moro, Fabrizio; McMaster, Jonathan; Schröder, Martin

    2013-01-18

    Five-coordinate Zn(II), Ni(II), and Cu(II) complexes containing pentadentate N(3)O(2) Schiff base ligands [1A](2-) and [1B](2-) have been synthesized and characterized. X-ray crystallographic studies reveal five coordinate structures in which each metal ion is bound by two imine N-donors, two phenolate O-donors, and a single amine N-donor. Electron paramagnetic resonance (EPR) spectroscopic studies suggest that the N(3)O(2) coordination spheres of [Cu(1A)] and [Cu(1B)] are retained in CH(2)Cl(2) solution and solid-state superconducting quantum interference device (SQUID) magnetometric studies confirm that [Ni(1A)] and [Ni(1B)] adopt high spin (S = 1) configurations. Each complex exhibits two reversible oxidation processes between +0.05 and +0.64 V vs [Fc](+)/[Fc]. The products of one- and two-electron oxidations have been studied by UV/vis spectroelectrochemistry and by EPR spectroscopy which confirm that each oxidation process for the Zn(II) and Cu(II) complexes is ligand-based with sequential formation of mono- and bis-phenoxyl radical species. In contrast, the one-electron oxidation of the Ni(II) complexes generates Ni(III) products. This assignment is supported by spectroelectrochemical and EPR spectroscopic studies, density functional theory (DFT) calculations, and the single crystal X-ray structure of [Ni(1A)][BF(4)] which contains Ni in a five-coordinate distorted trigonal bipyramidal geometry.

  2. Sculpture, Metallic Formations II, Art Education: 6683.12b.

    ERIC Educational Resources Information Center

    Dubocq, Edward R.

    An exploratory course in the creation of shapes using a variety of metals and techniques is described in this guide for quinmester elective course for grades 7-12. Students cut, form, weld, rivet, cast and finish such metals as steel, copper, aluminum, brass, pewter, and bronze. They develop a working knowledge of the various tools and processes,…

  3. General Metal Trades. Book II. Units of Instruction. Teacher's Guide.

    ERIC Educational Resources Information Center

    Hohhertz, Durwin

    This teacher's guide was developed to aid in presenting units on general metal trades to students in Texas. The units are intended to provide students with basic knowledge and skills for each area of instruction in the general metal trades, and with the basic entry-level skills they will need to have in order to enter industry as trained workers.…

  4. General Metal Trades. Book II. Units of Instruction. Teacher's Guide.

    ERIC Educational Resources Information Center

    Hohhertz, Durwin

    This teacher's guide was developed to aid in presenting units on general metal trades to students in Texas. The units are intended to provide students with basic knowledge and skills for each area of instruction in the general metal trades, and with the basic entry-level skills they will need to have in order to enter industry as trained workers.…

  5. 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.

  6. Multiple metal ions drive DNA association by PvuII endonuclease.

    PubMed

    Conlan, Lori H; Dupureur, Cynthia M

    2002-12-17

    Restriction enzymes serve as important model systems for understanding the role of metal ions in phosphodiester hydrolysis. To this end, a number of laboratories have reported dramatic differences between the metal ion-dependent and metal ion-independent DNA binding behaviors of these systems. In an effort to illuminate the underlying mechanistic details which give rise to these differences, we have quantitatively dissected these equilibrium behaviors into component association and dissociation rates for the representative PvuII endonuclease and use these data to assess the stoichiometry of metal ion involvement in the binding process. The dependence of PvuII cognate DNA on Ca(II) concentration binding appears to be cooperative, exhibiting half-saturation at 0.6 mM metal ion and yielding an n(H) of 3.5 +/- 0.2 per enzyme homodimer. Using both nitrocellulose filter binding and fluorescence assays, we observe that the cognate DNA dissociation rate (k(-)(1) or k(off)) is very slow (10(-)(3) s(-)(1)) and exhibits a shallow dependence on metal ion concentration. DNA trap cleavage experiments with Mg(II) confirm the general irreversibility of DNA binding relative to cleavage, even at low metal ion concentrations. More dramatically, the association rate (k(1) or k(on)) also appears to be cooperative, increasing more than 100-fold between 0.2 and 10 mM Ca(II), with an optimum value of 2.7 x 10(7) M(-)(1) s (-)(1). Hill analysis of the metal ion dependence of k(on) indicates an n(H) of 3.6 +/- 0.2 per enzyme dimer. This value is consistent with the involvement in DNA association of two metal ions per subunit active site, a result which lends new strength to arguments for two-metal ion mechanisms in restriction enzymes.

  7. Detecting positron-atom bound states through resonant annihilation.

    PubMed

    Dzuba, V A; Flambaum, V V; Gribakin, G F

    2010-11-12

    A method is proposed for detecting positron-atom bound states by observing enhanced positron annihilation due to electronic Feshbach resonances at electron-volt energies. The method is applicable to a range of open-shell transition-metal atoms which are likely to bind the positron: Fe, Co, Ni, Tc, Ru, Rh, Sn, Sb, Ta, W, Os, Ir, and Pt. Estimates of their binding energies are provided.

  8. Beryllium metal II. a review of the available toxicity data.

    PubMed

    Strupp, Christian

    2011-01-01

    Beryllium metal was classified in Europe collectively with beryllium compounds, e.g. soluble salts. Toxicological equivalence was assumed despite greatly differing physicochemical properties. Following introduction of the Registration, Evaluation, Authorization and Restriction of Chemicals (REACH) regulation, beryllium metal was classified as individual substance and more investigational efforts to appropriately characterize beryllium metal as a specific substance apart from soluble beryllium compounds was required. A literature search on toxicity of beryllium metal was conducted, and the resulting literature compiled together with the results of a recently performed study package into a comprehensive data set. Testing performed under Organisation for Economic Co-Operation and Development guidelines and Good Laboratory Practice concluded that beryllium metal was neither a skin irritant, an eye irritant, a skin sensitizer nor evoked any clinical signs of acute oral toxicity; discrepancies between the current legal classification of beryllium metal in the European Union (EU) and the experimental results were identified. Furthermore, genotoxicity and carcinogenicity were discussed in the context of the literature data and the new experimental data. It was concluded that beryllium metal is unlikely to be a classical nonthreshold mutagen. Effects on DNA repair and morphological cell transformation were observed but need further investigation to evaluate their relevance in vivo. Animal carcinogenicity studies deliver evidence of carcinogenicity in the rat; however, lung overload may be a species-specific confounding factor in the existing studies, and studies in other species do not give convincing evidence of carcinogenicity. Epidemiology has been intensively discussed over the last years and has the problem that the studies base on the same US beryllium production population and do not distinguish between metal and soluble compounds. It is noted that the correlation

  9. Beryllium Metal II. A Review of the Available Toxicity Data

    PubMed Central

    Strupp, Christian

    2011-01-01

    Beryllium metal was classified in Europe collectively with beryllium compounds, e.g. soluble salts. Toxicological equivalence was assumed despite greatly differing physicochemical properties. Following introduction of the Registration, Evaluation, Authorization and Restriction of Chemicals (REACH) regulation, beryllium metal was classified as individual substance and more investigational efforts to appropriately characterize beryllium metal as a specific substance apart from soluble beryllium compounds was required. A literature search on toxicity of beryllium metal was conducted, and the resulting literature compiled together with the results of a recently performed study package into a comprehensive data set. Testing performed under Organisation for Economic Co-Operation and Development guidelines and Good Laboratory Practice concluded that beryllium metal was neither a skin irritant, an eye irritant, a skin sensitizer nor evoked any clinical signs of acute oral toxicity; discrepancies between the current legal classification of beryllium metal in the European Union (EU) and the experimental results were identified. Furthermore, genotoxicity and carcinogenicity were discussed in the context of the literature data and the new experimental data. It was concluded that beryllium metal is unlikely to be a classical nonthreshold mutagen. Effects on DNA repair and morphological cell transformation were observed but need further investigation to evaluate their relevance in vivo. Animal carcinogenicity studies deliver evidence of carcinogenicity in the rat; however, lung overload may be a species-specific confounding factor in the existing studies, and studies in other species do not give convincing evidence of carcinogenicity. Epidemiology has been intensively discussed over the last years and has the problem that the studies base on the same US beryllium production population and do not distinguish between metal and soluble compounds. It is noted that the correlation

  10. Recent status of A Positron-Electron Experiment (APEX)

    NASA Astrophysics Data System (ADS)

    Saitoh, H.; Pedersen, T. S.; Hergenhahn, U.; Stenson, E. V.; Paschkowski, N.; Hugenschmidt, C.

    2014-04-01

    A project is underway to generate an electron-positron plasma by using the NEPOMUC positron source at the FRM-II facility combined with a multicell-type Penning trap (PAX) and a superconducting dipole magnetic field trap (APEX). In the APEX project, proof-of principle experiments are proposed for the development of efficient injection methods of positrons by using a small dipole magnetic field trap with a permanent magnet. Plans for the APEX project and its recent status are reported.

  11. Effect of biofilm coatings at metal-oxide/water interfaces II: Competitive sorption between Pb(II) and Zn(II) at Shewanella oneidensis/metal-oxide/water interfaces

    NASA Astrophysics Data System (ADS)

    Wang, Yingge; Gélabert, Alexandre; Michel, F. Marc; Choi, Yongseong; Eng, Peter J.; Spormann, Alfred M.; Brown, Gordon E.

    2016-09-01

    Competitive sorption of Pb(II) and Zn(II) on Shewanella oneidensis MR-1 biofilm-coated single-crystal α-Al2O3 (1 -1 0 2) and α-Fe2O3 (0 0 0 1) surfaces was investigated using long-period X-ray standing wave-florescence yield (LP-XSW-FY) spectroscopy. In situ partitioning of aqueous Pb(II) and Zn(II) between the biofilms and underlying metal-oxide substrates was probed following exposure of these complex interfaces to equi-molar Pb and Zn solutions (0.01 M NaNO3 as background electrolyte, pH = 6.0, and 3-h equilibration time). At higher Pb and Zn concentrations (⩾10-5 M), more than 99% of these ions partitioned into the biofilms at S. oneidensis/α-Al2O3 (1 -1 0 2)/water interfaces, which is consistent with the partitioning behavior of both Pb(II) or Zn(II) in single-metal-ion experiments. Thus, no apparent competitive effects were found in this system at these relatively high metal-ion concentrations. However, at lower equi-molar concentrations (⩽10-6 M), Pb(II) and Zn(II) partitioning in the same system changed significantly compared to the single-metal-ion systems. The presence of Zn(II) decreased Pb(II) partitioning onto α-Al2O3 (1 -1 0 2) substantially (∼52% to ∼13% at 10-7 M, and ∼23% to ∼5% at 10-6 M), whereas the presence of Pb(II) caused more Zn(II) to partition onto α-Al2O3 (1 -1 0 2) surfaces (∼15% to ∼28% at 10-7 M, and ∼1% to ∼7% at 10-6 M). The higher observed partitioning of Zn(II) (∼28%) at the α-Al2O3 (1 -1 0 2) surfaces compared to Pb(II) (∼13%) in the mixed-metal-ion systems at the lowest concentration (10-7 M) suggests that Zn(II) is slightly favored over Pb(II) for sorption sites on α-Al2O3 (1 -1 0 2) surfaces under our experimental conditions. Competitive sorption of Pb(II) and Zn(II) at S. oneidensis/α-Fe2O3 (0 0 0 1)/water interfaces at equi-molar metal-ion concentrations of ⩽10-6 M showed that the presence of Pb(II) ions decreased Zn(II) partitioning onto α-Fe2O3 (0 0 0 1) significantly (∼45% to <1% at 10

  12. First platinum moderated positron beam based on neutron capture

    NASA Astrophysics Data System (ADS)

    Hugenschmidt, C.; Kögel, G.; Repper, R.; Schreckenbach, K.; Sperr, P.; Triftshäuser, W.

    2002-12-01

    A positron beam based on absorption of high energy prompt γ-rays from thermal neutron capture in 113Cd was installed at a neutron guide of the high flux reactor at the ILL in Grenoble. Measurements were performed for various source geometries, dependent on converter mass, moderator surface and extraction voltages. The results lead to an optimised design of the in-pile positron source which will be implemented at the Munich research reactor FRM-II. The positron source consists of platinum foils acting as γ-e +e --converter and positron moderator. Due to the negative positron work function moderation in heated platinum leads to emission of monoenergetic positrons. The positron work function of polycrystalline platinum was determined to 1.95(5) eV. After acceleration to several keV by four electrical lenses the beam was magnetically guided in a solenoid field of 7.5 mT leading to a NaI-detector in order to detect the 511 keV γ-radiation of the annihilating positrons. The positron beam with a diameter of less than 20 mm yielded an intensity of 3.1×10 4 moderated positrons per second. The total moderation efficiency of the positron source was about ɛ=1.06(16)×10 -4. Within the first 20 h of operation a degradation of the moderation efficiency of 30% was observed. An annealing procedure at 873 K in air recovers the platinum moderator.

  13. 40 CFR Appendix I to Part 266 - Tier I and Tier II Feed Rate and Emissions Screening Limits for Metals

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 26 2010-07-01 2010-07-01 false Tier I and Tier II Feed Rate and...—Tier I and Tier II Feed Rate and Emissions Screening Limits for Metals Table I-A—Tier I and Tier II Feed Rate and Emissions Screening Limits for Noncarcinogenic Metals for Facilities in Noncomplex...

  14. Removal of Ni(II), Zn(II) and Pb(II) ions from single metal aqueous solution using rice husk-based activated carbon

    SciTech Connect

    Taha, Mohd F. Shaharun, Maizatul S.; Shuib, Anis Suhaila Borhan, Azry

    2014-10-24

    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 CHN 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.

  15. Removal of Ni(II), Zn(II) and Pb(II) ions from single metal aqueous solution using rice husk-based activated carbon

    NASA Astrophysics Data System (ADS)

    Taha, Mohd F.; Shuib, Anis Suhaila; Shaharun, Maizatul S.; Borhan, Azry

    2014-10-01

    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 CHN 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 m2/g and 0.17 cm2/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.

  16. Chromium(II) Metal-Organic Polyhedra as Highly Porous Materials.

    PubMed

    Park, Jinhee; Perry, Zachary; Chen, Ying-Pin; Bae, Jaeyeon; Zhou, Hong-Cai

    2017-08-23

    Herein we report for the first time the synthesis of Cr(II)-based metal-organic polyhedra (MOPs) and the characterization of their porosities. Unlike the isostructural Cu(II)- or Mo(II)-based MOPs, Cr(II)-based MOPs show unusually high gas uptakes and surface areas. The combination of comparatively robust dichromium paddlewheel units (Cr2 units), cage symmetries, and packing motifs enable these materials to achieve Brunauer-Emmett-Teller surface areas of up to 1000 m(2)/g. Reducing the aggregation of the Cr(II)-based MOPs upon activation makes their pores more accessible than their Cu(II) or Mo(II) counterparts. Further comparisons of surface areas on a molar (m(2)/mol cage) rather than gravimetric (m(2)/g) basis is proposed as a rational method of comparing members of a family of related molecular materials.

  17. Creation of a putative third metal binding site in type II dihydroorotases significantly enhances enzyme activity.

    PubMed

    Huang, Yen-Hua; Huang, Cheng-Yang

    2015-01-01

    Dihydroorotase (DHOase) is the third enzyme in the de novo biosynthesis pathway of pyrimidine nucleotides. DHOase is divided into two types (I and II). Type II DHOase generally contains a binuclear metal center in its active site. Recently, the crystal structure of DHOase domain in human CAD protein (huDHOase) has revealed three metal ions in the protein's active site. However, whether type II DHOase can have the critical third metal ion, as observed in huDHOase, remains unknown. In the present study, the putative third metal binding site in type II enzymes, such as the prokaryotic Salmonella enterica serovar Typhimurium LT2 DHOase (StDHOase) and the eukaryotic Saccharomyces cerevisiae DHOase (ScDHOase), was created and identified. StDHOase T198E and ScDHOase T208E mutants had higher activities compared with their wild-type enzymes. The need for a higher DHOase stability and activity may drive creation of the third metal ion binding site in huDHOase, which can be achieved by mutating a highly conserved position T in type II dihydroorotases to E, similar to that in huDHOase.

  18. Effect of biofilm coatings at metal-oxide/water interfaces II: Competitive sorption between Pb(II) and Zn(II) at Shewanella oneidensis/metal-oxide/water interfaces

    DOE PAGES

    Wang, Yingge; Gelabert, Alexandre; Michel, F. Marc; ...

    2016-05-07

    Competitive sorption of Pb(II) and Zn(II) on Shewanella oneidensis MR-1 biofilm-coated single-crystal α-Al2O3 (1 –1 0 2) and α-Fe2O3 (0 0 0 1) surfaces was investigated using long-period X-ray standing wave-florescence yield (LP-XSW-FY) spectroscopy. In situ partitioning of aqueous Pb(II) and Zn(II) between the biofilms and underlying metal-oxide substrates was probed following exposure of these complex interfaces to equi-molar Pb and Zn solutions (0.01 M NaNO3 as background electrolyte, pH = 6.0, and 3-h equilibration time). At higher Pb and Zn concentrations (≥10–5 M), more than 99% of these ions partitioned into the biofilms at S. oneidensis/α-Al2O3 (1 –1 0more » 2)/water interfaces, which is consistent with the partitioning behavior of both Pb(II) or Zn(II) in single-metal-ion experiments. Furthermore, no apparent competitive effects were found in this system at these relatively high metal-ion concentrations. However, at lower equi-molar concentrations (≤10–6 M), Pb(II) and Zn(II) partitioning in the same system changed significantly compared to the single-metal-ion systems. The presence of Zn(II) decreased Pb(II) partitioning onto α-Al2O3 (1 –1 0 2) substantially (~52% to ~13% at 10–7 M, and ~23% to ~5% at 10–6 M), whereas the presence of Pb(II) caused more Zn(II) to partition onto α-Al2O3 (1 –1 0 2) surfaces (~15% to ~28% at 10–7 M, and ~1% to ~7% at 10–6 M) .The higher observed partitioning of Zn(II) (~28%) at the α-Al2O3 (1 –1 0 2) surfaces compared to Pb(II) (~13%) in the mixed-metal-ion systems at the lowest concentration (10–7 M) suggests that Zn(II) is slightly favored over Pb(II) for sorption sites on α-Al2O3 (1 –1 0 2) surfaces under our experimental conditions.« less

  19. Electron capture from solids by positrons

    SciTech Connect

    Howell, R.

    1987-08-01

    The capture of electrons in solids is modified from that in gasses by several factors. The most important is the collective interaction of the electrons which results in a density of electron states in the solid in wide bands. Also the high density of electrons in many solids gives a high frequency of interaction as compared to gasses, and quickly destroys any electron-positron states in the metal matrix. Consequently, most positrons implanted in a metal will rapidly thermalize, and unless they reach the surface will annihilate with an electron in an uncorrelated state. Positronium formation from positrons scattered at a metal surface is analogous to ion neutralization however, most of the positronium comes from positrons passing through the surface from the bulk. The dominant motivation for studying positronium formation has been the hope that the distribution of the electrons at the surface would be obtained through the annihilation properties of positrons trapped at the surface or through analysis of the energy and angular distributions of the positronium emitted into the vacuum. These distributions have been measured and are included in this paper. 17 refs.

  20. Positron-rubidium scattering

    NASA Technical Reports Server (NTRS)

    Mceachran, R. P.; Horbatsch, M.; Stauffer, A. D.

    1990-01-01

    A 5-state close-coupling calculation (5s-5p-4d-6s-6p) was carried out for positron-Rb scattering in the energy range 3.7 to 28.0 eV. In contrast to the results of similar close-coupling calculations for positron-Na and positron-K scattering the (effective) total integrated cross section has an energy dependence which is contrary to recent experimental measurements.

  1. Use of Divalent Metal Ions in the DNA Cleavage Reaction of Human Type II Topoisomerases†

    PubMed Central

    Deweese, Joseph E.; Burch, Amber M.; Burgin, Alex B.; Osheroff, Neil

    2009-01-01

    All type II topoisomerases require divalent metal ions in order to cleave and ligate DNA. In order to further elucidate the mechanistic basis for these critical enzyme-mediated events, the role of the metal ion in the DNA cleavage reaction of human topoisomerase IIβ was characterized and compared to that of topoisomerase IIα. The present study utilized divalent metal ions with varying thiophilicities in conjunction with DNA cleavage substrates that substituted a sulfur atom for the 3′-bridging oxygen or the non-bridging oxygens of the scissile phosphate. Based on time courses of DNA cleavage, cation titrations, and metal ion mixing experiments, we propose the following model for the use of divalent metal ions by human type II topoisomerases. First, both enzymes employ a two-metal-ion mechanism to support DNA cleavage. Second, an interaction between one divalent metal ion and the 3′-bridging atom of the scissile phosphate greatly enhances enzyme-mediated DNA cleavage, most likely by stabilizing the leaving 3′-oxygen. Third, there is an important interaction between a divalent second metal ion and a non-bridging atom of the scissile phosphate that stimulates DNA cleavage mediated by topoisomerase IIβ. If this interaction exists in topoisomerase IIα, its effects on DNA cleavage are equivocal. This last aspect of the model highlights a difference in metal ion utilization during DNA cleavage mediated by human topoisomerase IIα and IIβ. PMID:19222228

  2. Metal ion catalysis during group II intron self-splicing: parallels with the spliceosome

    PubMed Central

    Sontheimer, Erik J.; Gordon, Peter M.; Piccirilli, Joseph A.

    1999-01-01

    The identical reaction pathway executed by the spliceosome and self-splicing group II intron ribozymes has prompted the idea that both may be derived from a common molecular ancestor. The minimal sequence and structural similarities between group II introns and the spliceosomal small nuclear RNAs, however, have left this proposal in question. Mechanistic comparisons between group II self-splicing introns and the spliceosome are therefore important in determining whether these two splicing machineries may be related. Here we show that 3′-sulfur substitution at the 5′ splice site of a group II intron causes a metal specificity switch during the first step of splicing. In contrast, 3′-sulfur substitution has no significant effect on the metal specificity of the second step of cis-splicing. Isolation of the second step uncovers a metal specificity switch that is masked during the cis-splicing reaction. These results demonstrate that group II intron ribozymes are metalloenzymes that use a catalytic metal ion for leaving group stabilization during both steps of self-splicing. Furthermore, because 3′-sulfur substitution of a spliceosomal intron has precisely the same effects as were observed during cis-splicing of the group II intron, these results provide striking parallels between the catalytic mechanisms employed by these two systems. PMID:10398685

  3. Design, spectral characterization and biological studies of transition metal(II) complexes with triazole Schiff bases

    NASA Astrophysics Data System (ADS)

    Hanif, Muhammad; Chohan, Zahid H.

    2013-03-01

    A new series of three biologically active triazole derived Schiff base ligands L1-L3 have been synthesized in equimolar reaction of 3-amino-1H-1,2,4-triazole with pyrrol-2-carboxaldehyde, 4-bromo-thiophene-2-carboxaldehyde, and 5-iodo-2-hydroxy benzaldehyde. The prepared Schiff bases were used for further complex formation reaction with different metal elements like Co(II), Ni(II), Cu(II) and Zn(II) as chlorides by using a molar ratio of ligand:metal as 2:1. The structure and bonding nature of all the compounds were identified by their physical, spectral and analytical data. All the metal(II) complexes possessed an octahedral geometry except the Cu(II) complexes which showed a distorted octahedral geometry. All the synthesized compounds, were studied for their in vitro antibacterial, and antifungal activities, against four Gram-negative (Escherichia coli, Shigella sonnei, Pseudomonas aeruginosa and Salmonella typhi) and two Gram-positive (Bacillus subtilis and Staphylococcus aureus) bacterial strains and against six fungal strains (Trichophyton longifusus, Candida albicans, Aspergillus flavus, Microsporum canis, Fusarium solani and Candida glabrata) by using agar-well diffusion method. It has been shown that all the synthesized compounds showed moderate to significant antibacterial activity against one or more bacterial strains. In vitro Brine Shrimp bioassay was also carried out to investigate the cytotoxic properties of these compounds. The data also revealed that the metal complexes showed better activity than the ligands due to chelation/coordination.

  4. Design, spectral characterization and biological studies of transition metal(II) complexes with triazole Schiff bases.

    PubMed

    Hanif, Muhammad; Chohan, Zahid H

    2013-03-01

    A new series of three biologically active triazole derived Schiff base ligands L(1)-L(3) have been synthesized in equimolar reaction of 3-amino-1H-1,2,4-triazole with pyrrol-2-carboxaldehyde, 4-bromo-thiophene-2-carboxaldehyde, and 5-iodo-2-hydroxy benzaldehyde. The prepared Schiff bases were used for further complex formation reaction with different metal elements like Co(II), Ni(II), Cu(II) and Zn(II) as chlorides by using a molar ratio of ligand:metal as 2:1. The structure and bonding nature of all the compounds were identified by their physical, spectral and analytical data. All the metal(II) complexes possessed an octahedral geometry except the Cu(II) complexes which showed a distorted octahedral geometry. All the synthesized compounds, were studied for their in vitro antibacterial, and antifungal activities, against four Gram-negative (Escherichia coli, Shigella sonnei, Pseudomonas aeruginosa and Salmonella typhi) and two Gram-positive (Bacillus subtilis and Staphylococcus aureus) bacterial strains and against six fungal strains (Trichophyton longifusus, Candida albicans, Aspergillus flavus, Microsporum canis, Fusarium solani and Candida glabrata) by using agar-well diffusion method. It has been shown that all the synthesized compounds showed moderate to significant antibacterial activity against one or more bacterial strains. In vitro Brine Shrimp bioassay was also carried out to investigate the cytotoxic properties of these compounds. The data also revealed that the metal complexes showed better activity than the ligands due to chelation/coordination.

  5. Stellar kinematics and metallicities in the ultra-faint dwarf galaxy Reticulum II

    SciTech Connect

    Simon, J. D.

    2015-07-23

    With this study, we present Magellan/M2FS, Very Large Telescope/GIRAFFE, and Gemini South/GMOS spectroscopy of the newly discovered Milky Way satellite Reticulum II. Based on the spectra of 25 Ret II member stars selected from Dark Energy Survey imaging, we measure a mean heliocentric velocity of $62.8\\pm 0.5\\;\\mathrm{km}\\;{\\rm{s}}^{-1}$ and a velocity dispersion of $3.3\\pm 0.7\\;\\mathrm{km}\\;{\\rm{s}}^{-1}$. The mass-to-light ratio of Ret II within its half-light radius is $470\\pm 210\\ {M}_{\\odot }/{L}_{\\odot }$, demonstrating that it is a strongly dark matter-dominated system. Despite its spatial proximity to the Magellanic Clouds, the radial velocity of Ret II differs from that of the LMC and SMC by 199 and 83 $\\mathrm{km}\\ {{\\rm{s}}}^{-1}$, respectively, suggesting that it is not gravitationally bound to the Magellanic system. The likely member stars of Ret II span 1.3 dex in metallicity, with a dispersion of 0.28 ± 0.09 dex, and we identify several extremely metal-poor stars with ${\\rm{[Fe/H]}}\\lt -3$. In combination with its luminosity, size, and ellipticity, these results confirm that Ret II is an ultra-faint dwarf galaxy. With a mean metallicity of ${\\rm{[Fe/H]}}=-2.65\\pm 0.07$, Ret II matches Segue 1 as the most metal-poor galaxy known. Although Ret II is the third-closest dwarf galaxy to the Milky Way, the line-of-sight integral of the dark matter density squared is ${\\mathrm{log}}_{10}(J)=18.8\\pm 0.6\\;\\;\\mathrm{GeV}{\\;}^{2}\\;{\\mathrm{cm}}^{-5}\\;$ within 0fdg2, indicating that the predicted gamma-ray flux from dark matter annihilation in Ret II is lower than that of several other dwarf galaxies.

  6. Stellar Kinematics and Metallicities in the Ultra-faint Dwarf Galaxy Reticulum II

    NASA Astrophysics Data System (ADS)

    Simon, J. D.; Drlica-Wagner, A.; Li, T. S.; Nord, B.; Geha, M.; Bechtol, K.; Balbinot, E.; Buckley-Geer, E.; Lin, H.; Marshall, J.; Santiago, B.; Strigari, L.; Wang, M.; Wechsler, R. H.; Yanny, B.; Abbott, T.; Bauer, A. H.; Bernstein, G. M.; Bertin, E.; Brooks, D.; Burke, D. L.; Capozzi, D.; Carnero Rosell, A.; Carrasco Kind, M.; D'Andrea, C. B.; da Costa, L. N.; DePoy, D. L.; Desai, S.; Diehl, H. T.; Dodelson, S.; Cunha, C. E.; Estrada, J.; Evrard, A. E.; Fausti Neto, A.; Fernandez, E.; Finley, D. A.; Flaugher, B.; Frieman, J.; Gaztanaga, E.; Gerdes, D.; Gruen, D.; Gruendl, R. A.; Honscheid, K.; James, D.; Kent, S.; Kuehn, K.; Kuropatkin, N.; Lahav, O.; Maia, M. A. G.; March, M.; Martini, P.; Miller, C. J.; Miquel, R.; Ogando, R.; Romer, A. K.; Roodman, A.; Rykoff, E. S.; Sako, M.; Sanchez, E.; Schubnell, M.; Sevilla, I.; Smith, R. C.; Soares-Santos, M.; Sobreira, F.; Suchyta, E.; Swanson, M. E. C.; Tarle, G.; Thaler, J.; Tucker, D.; Vikram, V.; Walker, A. R.; Wester, W.; DES Collaboration

    2015-07-01

    We present Magellan/M2FS, Very Large Telescope/GIRAFFE, and Gemini South/GMOS spectroscopy of the newly discovered Milky Way satellite Reticulum II. Based on the spectra of 25 Ret II member stars selected from Dark Energy Survey imaging, we measure a mean heliocentric velocity of 62.8+/- 0.5 {km} {{{s}}}-1 and a velocity dispersion of 3.3+/- 0.7 {km} {{{s}}}-1. The mass-to-light ratio of Ret II within its half-light radius is 470+/- 210 {M}⊙ /{L}⊙ , demonstrating that it is a strongly dark matter-dominated system. Despite its spatial proximity to the Magellanic Clouds, the radial velocity of Ret II differs from that of the LMC and SMC by 199 and 83 {km} {{{s}}}-1, respectively, suggesting that it is not gravitationally bound to the Magellanic system. The likely member stars of Ret II span 1.3 dex in metallicity, with a dispersion of 0.28 ± 0.09 dex, and we identify several extremely metal-poor stars with {{[Fe/H]}}\\lt -3. In combination with its luminosity, size, and ellipticity, these results confirm that Ret II is an ultra-faint dwarf galaxy. With a mean metallicity of {{[Fe/H]}}=-2.65+/- 0.07, Ret II matches Segue 1 as the most metal-poor galaxy known. Although Ret II is the third-closest dwarf galaxy to the Milky Way, the line-of-sight integral of the dark matter density squared is {{log}}10(J)=18.8+/- 0.6 {GeV}{ }2 {{cm}}-5 within 0.°2, indicating that the predicted gamma-ray flux from dark matter annihilation in Ret II is lower than that of several other dwarf galaxies. Based on data obtained from the ESO Science Archive Facility under request number 157689.

  7. The metallomics approach: use of Fe(II) and Cu(II) footprinting to examine metal binding sites on serum albumins.

    PubMed

    Duff, Michael R; Kumar, Challa V

    2009-11-01

    Metal binding to serum albumins is examined by oxidative protein-cleavage chemistry, and relative affinities of multiple metal ions to particular sites on these proteins were identified using a fast and reliable chemical footprinting approach. Fe(ii) and Cu(ii), for example, mediate protein cleavage at their respective binding sites on serum albumins, in the presence of hydrogen peroxide and ascorbate. This metal-mediated protein-cleavge reaction is used to evaluate the binding of metal ions, Na(+), Mg(2+), Ca(2+), Al(3+), Cr(3+), Mn(2+), Co(2+), Ni(2+), Zn(2+), Cd(2+), Hg(2+), Pb(2+), and Ce(3+) to albumins, and the relative affinities (selectivities) of the metal ions are rapidly evaluated by examining the extent of inhibition of protein cleavage. Four distinct systems Fe(II)/BSA, Cu(II)/BSA, Fe(II)/HSA and Cu(II)/HSA are examined using the above strategy. This metallomics approach is novel, even though the cleavage of serum albumins by Fe(II)/Cu(II) has been reported previously by this laboratory and many others. The protein cleavage products were analyzed by SDS PAGE, and the intensities of the product bands quantified to evaluate the extent of inhibition of the cleavage and thereby evaluate the relative binding affinities of specific metal ions to particular sites on albumins. The data show that Co(II) and Cr(III) showed the highest degree of inhibition, across the table, followed by Mn(II) and Ce(III). Alakali metal ions and alkaline earth metal ions showed very poor affinity for these metal sites on albumins. Thus, metal binding profiles for particular sites on proteins can be obtained quickly and accurately, using the metallomics approach.

  8. Metal-Based Antibacterial and Antifungal Agents: Synthesis, Characterization, and In Vitro Biological Evaluation of Co(II), Cu(II), Ni(II), and Zn(II) Complexes With Amino Acid-Derived Compounds

    PubMed Central

    Chohan, Zahid H.; Arif, M.; Akhtar, Muhammad A.; Supuran, Claudiu T.

    2006-01-01

    A series of antibacterial and antifungal amino acid-derived compounds and their cobalt(II), copper(II), nickel(II), and zinc(II) metal complexes have been synthesized and characterized by their elemental analyses, molar conductances, magnetic moments, and IR, and electronic spectral measurements. Ligands (L1)−(L5) were derived by condensation of β-diketones with glycine, phenylalanine, valine, and histidine and act as bidentate towards metal ions (cobalt, copper, nickel, and zinc) via the azomethine-N and deprotonated-O of the respective amino acid. The stoichiometric reaction between the metal(II) ion and synthesized ligands in molar ratio of M : L (1 : 1) resulted in the formation of the metal complexes of type [M(L)(H2O)4]Cl (where M = Co(II), Cu(II), and Zn(II)) and of M : L (1 : 2) of type [M(L)2(H2O)2] (where M = Co(II), Cu(II), Ni(II), and Zn(II)). The magnetic moment data suggested for the complexes to have an octahedral geometry around the central metal atom. The electronic spectral data also supported the same octahedral geometry of the complexes. Elemental analyses and NMR spectral data of the ligands and their metal(II) complexes agree with their proposed structures. The synthesized ligands, along with their metal(II) complexes, were screened for their in vitro antibacterial activity against four Gram-negative (Escherichia coli, Shigella flexeneri, Pseudomonas aeruginosa, and Salmonella typhi) and two Gram-positive (Bacillus subtilis and Staphylococcus aureus) bacterial strains and for in vitro antifungal activity against Trichophyton longifusus, Candida albicans, Aspergillus flavus, Microsporum canis, Fusarium solani, and Candida glaberata. The results of these studies show the metal(II) complexes to be more antibacterial/antifungal against one or more species as compared to the uncomplexed ligands. The brine shrimp bioassay was also carried out to study their in vitro cytotoxic properties. Five compounds, (3), (7), (10), (11), and (22), displayed

  9. Local stellar kinematics from RAVE data - II. Radial metallicity gradient

    NASA Astrophysics Data System (ADS)

    Coşkunoǧlu, B.; Ak, S.; Bilir, S.; Karaali, S.; Önal, Ö.; Yaz, E.; Gilmore, G.; Seabroke, G. M.

    2012-02-01

    We investigate radial metallicity gradients for a sample of dwarf stars from the RAdial Velocity Experiment (RAVE) Data Release 3 (DR3). We select a total of approximately 17 000 F-type and G-type dwarfs, using a selection of colour, log g and uncertainty in the derived space motion, and calculate for each star a probabilistic (kinematic) population assignment to a thick or thin disc using space motion and additionally another (dynamical) assignment using stellar vertical orbital eccentricity. We additionally subsample by colour, to provide samples biased toward young thin-disc and older thin-disc stars. We derive a metallicity gradient as a function of Galactocentric radial distance, i.e. d[M/H]/dRm=-0.051 ± 0.005 dex kpc-1, for the youngest sample, F-type stars with vertical orbital eccentricities ev≤ 0.04. Samples biased toward older thin-disc stars show systematically shallower abundance gradients.

  10. Transition Metal(II) Complexes with Cefotaxime-Derived Schiff Base: Synthesis, Characterization, and Antimicrobial Studies

    PubMed Central

    Amzoiu, Emilia; Spînu, Cezar Ionuţ

    2014-01-01

    New [ML2(H2O)2] complexes, where M = Co(II), Ni(II), Cu(II), and Zn(II) while L corresponds to the Schiff base ligand, were synthesized by condensation of cefotaxime with salicylaldehyde in situ in the presence of divalent metal salts in ethanolic medium. The complexes were characterized by elemental analyses, conductance, and magnetic measurements, as well as by IR and UV-Vis spectroscopy. The low values of the molar conductance indicate nonelectrolyte type of complexes. Based on spectral data and magnetic moments, an octahedral geometry may be proposed for Co(II), Ni(II), and Zn(II) complexes while a tetragonal geometry for Cu(II) complex. Molecular structure of the Schiff base ligand and its complexes were studied using programs dedicated to chemical modeling and quantomolecular calculation of chemical properties. All the synthesized complexes were tested for in vitro antibacterial activity against some pathogenic bacterial strains, namely Escherichia coli, Klebsiella pneumoniae, Pseudomonas aeruginosa, Bacillus subtilis, and Staphylococcus aureus. The MIC values shown by the complexes against these bacterial strains revealed that the metal complexes possess superior antibacterial activity than the Schiff base. PMID:24688454

  11. Positrons in surface physics

    NASA Astrophysics Data System (ADS)

    Hugenschmidt, Christoph

    2016-12-01

    Within the last decade powerful methods have been developed to study surfaces using bright low-energy positron beams. These novel analysis tools exploit the unique properties of positron interaction with surfaces, which comprise the absence of exchange interaction, repulsive crystal potential and positron trapping in delocalized surface states at low energies. By applying reflection high-energy positron diffraction (RHEPD) one can benefit from the phenomenon of total reflection below a critical angle that is not present in electron surface diffraction. Therefore, RHEPD allows the determination of the atom positions of (reconstructed) surfaces with outstanding accuracy. The main advantages of positron annihilation induced Auger-electron spectroscopy (PAES) are the missing secondary electron background in the energy region of Auger-transitions and its topmost layer sensitivity for elemental analysis. In order to enable the investigation of the electron polarization at surfaces low-energy spin-polarized positrons are used to probe the outermost electrons of the surface. Furthermore, in fundamental research the preparation of well defined surfaces tailored for the production of bound leptonic systems plays an outstanding role. In this report, it is envisaged to cover both the fundamental aspects of positron surface interaction and the present status of surface studies using modern positron beam techniques.

  12. INTEGRAL FIELD SPECTROSCOPY OF SUPERNOVA EXPLOSION SITES: CONSTRAINING THE MASS AND METALLICITY OF THE PROGENITORS. II. TYPE II-P AND II-L SUPERNOVAE

    SciTech Connect

    Kuncarayakti, Hanindyo; Maeda, Keiichi; Doi, Mamoru; Morokuma, Tomoki; Hashiba, Yasuhito; Aldering, Greg; Arimoto, Nobuo; Pereira, Rui

    2013-08-01

    Thirteen explosion sites of Type II-P and II-L supernovae (SNe) in nearby galaxies have been observed using integral field spectroscopy, enabling both spatial and spectral study of the explosion sites. We used the properties of the parent stellar population of the coeval SN progenitor star to derive its metallicity and initial mass. The spectrum of the parent stellar population yields estimates of metallicity via the strong-line method and age via a comparison with simple stellar population models. These metallicity and age parameters are adopted for the progenitor star. Age, or lifetime of the star, was used to derive the initial (zero-age main sequence) mass of the star using comparisons with stellar evolution models. With this technique, we were able to determine the metallicities and initial masses of the SN progenitors in our sample. Our results indicate that some Type II SN progenitors may have been stars with masses comparable to those of SN Ib/c progenitors.

  13. Two trinuclear transition metal(II)-Radical complexes with triple-triazole bridges

    NASA Astrophysics Data System (ADS)

    Li, Ting; Shi, Xiu-Juan; Chen, Peng-Yun; Tian, Li; Xu, Yuan-Yuan; Hua, Feng Zhen

    2017-08-01

    Two new transition complexes were obtained by using triazole nitronyl nitroxide radical as ligand. The complexes with formula [M3(4-Me-3-Nit-trz)6](ClO4)6 [M = Co(II) 1, Ni(II) 2; 4-Me-3-Nit-trz = 2-[3-(4-methyl-l,2,4-triazolyl)]-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide] were characterized structurally and magnetically. They were both linear trinuclear structures with neighboring metal ions triply bridged by triazole sbnd NNsbnd moieties and the molecules have a three-fold axis. All of the metal ions in 1 and 2 are in octahedral environment and adopt two kinds of coordination modes. The radical oxygen atoms participate in the 6-membered chelation at the terminal nickel(II) or cobalt(II) ions and the central nickel(II) or cobalt(II) ion is coordinated to six nitrogen atoms from six triazole group. The magnetic behaviors for 1 and 2 indicate that the metal ions and the direct coordinated radicals are strongly antiferromagnetically coupled. A theoretical model has been developed to interpret the magnetic data for complex 2.

  14. Positrons for linear colliders

    SciTech Connect

    Ecklund, S.

    1987-11-01

    The requirements of a positron source for a linear collider are briefly reviewed, followed by methods of positron production and production of photons by electromagnetic cascade showers. Cross sections for the electromagnetic cascade shower processes of positron-electron pair production and Compton scattering are compared. A program used for Monte Carlo analysis of electromagnetic cascades is briefly discussed, and positron distributions obtained from several runs of the program are discussed. Photons from synchrotron radiation and from channeling are also mentioned briefly, as well as positron collection, transverse focusing techniques, and longitudinal capture. Computer ray tracing is then briefly discussed, followed by space-charge effects and thermal heating and stress due to showers. (LEW)

  15. Oligomerization of glycine and alanine on metal(II) octacynaomolybdate(IV): role of double metal cyanides in prebiotic chemistry.

    PubMed

    Kumar, Anand; Kamaluddin

    2012-12-01

    Condensation reactions of amino acid (glycine and alanine) on the surface of metal(II) octacyanomolybdate(IV) (MOCMo) complexes are investigated using high-performance liquid chromatography (HPLC) and electron spray ionizations-mass spectroscopy (ESI-MS). The series of MOCMo have been synthesized and the effect of outer sphere metal ions present in the MOCMo on the oligomerization of glycine and alanine at different temperature and time found out. Formation of peptides was observed to start after 7 days at 60 °C. Maximum yield of peptides was found after 35 days at 90 °C. It has been found that zinc(II) octacyanomolybdate(IV) and cobalt(II) were the most effective metal cations present in outer sphere of the MOCMo for the production of high yield of oligomerized products. Surface area of MOCMo seems to play dominating parameter for the oligomerization of alanine and glycine. The results of the present study reveal the role of MOCMo in chemical evolution for the oligomerization of biomolecules.

  16. The application of positron emission tomography (PET/CT) in diagnosis of breast cancer. Part II. Diagnosis after treatment initiation, future perspectives

    PubMed Central

    Jodłowska, Elżbieta; Czarnywojtek, Agata; Rewers, Amanda; Jarząbek, Grażyna; Kędzia, Witold; Ruchała, Marek

    2016-01-01

    Similarly to the applications described in the first part of this publication, positron emission tomography with computed tomography (PET/CT) is also gaining importance in monitoring a tumour's response to therapy and diagnosing breast cancer recurrences. This is additionally caused by the fact that many new techniques (dual-time point imaging, positron emission tomography with magnetic resonance PET/MR, PET/CT mammography) and radiotracers (16α-18F-fluoro-17β-estradiol, 18F-fluorothymidine) are under investigation. The highest sensitivity and specificity when monitoring response to treatment is achieved when the PET/CT scan is made after one or two chemotherapy courses. Response to anti-hormonal treatment can also be monitored, also when new radiotracers, such as FES, are used. When monitoring breast cancer recurrences during follow-up, PET/CT has higher sensitivity than conventional imaging modalities, making it possible to monitor the whole body simultaneously. New techniques and radiotracers enhance the sensitivity and specificity of PET and this is why, despite relatively high costs, it might become more widespread in monitoring response to treatment and breast cancer recurrences. PMID:27647983

  17. Biochemical and structural characterization of Salmonella typhimurium glyoxalase II: new insights into metal ion selectivity.

    PubMed

    Campos-Bermudez, Valeria A; Leite, Ney Ribeiro; Krog, Renata; Costa-Filho, Antonio J; Soncini, Fernando C; Oliva, Glaucius; Vila, Alejandro J

    2007-10-02

    Glyoxalase II is a hydrolytic enzyme part of the glyoxalase system, responsible for detoxifying several cytotoxic compounds employing glutathione. Glyoxalase II belongs to the superfamily of metallo-beta-lactamases, with a conserved motif able to bind up to two metal ions in their active sites, generally zinc. Instead, several eukaryotic glyoxalases II have been characterized with different ratios of iron, zinc, and manganese ions. We have expressed a gene coding for a putative member of this enzyme superfamily from Salmonella typhimurium that we demonstrate, on the basis of its activity, to be a glyoxalase II, named GloB. Recombinant GloB expressed in Escherichia coli was purified with variable amounts of iron, zinc, and manganese. All forms display similar activities, as can be shown from protein expression in minimal medium supplemented with specific metal ions. The crystal structure of GloB solved at 1.4 A shows a protein fold and active site similar to those of its eukaryotic homologues. NMR and EPR experiments also reveal a conserved electronic structure at the metal site. GloB is therefore able to accommodate these different metal ions and to carry out the hydrolytic reaction with similar efficiencies in all cases. The metal promiscuity of this enzyme (in contrast to other members of the same superfamily) can be accounted for by the presence of a conserved Asp residue acting as a second-shell ligand that is expected to increase the hardness of the metal binding site, therefore favoring iron uptake in glyoxalases II.

  18. Metal-ion environment in solid Mn(II), Co(II) and Ni(II) hyaluronates.

    PubMed

    Tratar Pirc, Elizabeta; Arcon, Iztok; Kodre, Alojz; Bukovec, Peter

    2004-10-20

    Amorphous powders and films of some metal hyaluronate complexes of general composition (C14H20O11N)2 x xH2O (M = Mn2+, Ni2+ and Co2+) have been prepared at pH 5.5-6.0. The coordination geometry around the metal ions has been analyzed by EXAFS (extended X-ray absorption fine structure) and FTIR spectroscopy. Mn2+, Ni2+, and Co2+ ions are coordinated to carboxylate oxygen atoms and water molecules. The process of local geometry formation round the metal ions is sensitive to sample preparation.

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

    PubMed Central

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

    1975-01-01

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

  20. Metal-dependent inhibition of glyoxalase II: a possible mechanism to regulate the enzyme activity.

    PubMed

    Campos-Bermudez, Valeria A; Morán-Barrio, Jorgelina; Costa-Filho, Antonio J; Vila, Alejandro J

    2010-07-01

    Glyoxalase II (GLX2, EC 3.1.2.6., hydroxyacylglutathione hydrolase) is a metalloenzyme involved in crucial detoxification pathways. Different studies have failed in identifying the native metal ion of this enzyme, which is expressed with iron, zinc and/or manganese. Here we report that GloB, the GLX2 from Salmonella typhimurium, is differentially inhibited by glutathione (a reaction product) depending on the bound metal ion, and we provide a structural model for this inhibition mode. This metal-dependent inhibition was shown to occur in metal-enriched forms of the enzyme, complementing the spectroscopic data. Based on the high levels of free glutathione in the cell, we suggest that the expression of the different metal forms of GLX2 during Salmonella infection could be exploited as a mechanism to regulate the enzyme activity.

  1. Triangulum II: A Very Metal-poor and Dynamically Hot Stellar System

    NASA Astrophysics Data System (ADS)

    Martin, Nicolas F.; Ibata, Rodrigo A.; Collins, Michelle L. M.; Rich, R. Michael; Bell, Eric F.; Ferguson, Annette M. N.; Laevens, Benjamin P. M.; Rix, Hans-Walter; Chapman, Scott C.; Koch, Andreas

    2016-02-01

    We present a study of the recently discovered compact stellar system Triangulum II. From observations conducted with the DEIMOS spectrograph on Keck II, we obtained spectra for 13 member stars that follow the CMD features of this very faint stellar system and include two bright red giant branch stars. Tri II has a very negative radial velocity (< {v}{{r}}> =-{383.7}-3.3+3.0 {km} {{{s}}}-1) that translates to < {v}{{r},{gsr}}> ≃ -264 {km} {{{s}}}-1 and confirms it is a Milky Way satellite. We show that, despite the small data set, there is evidence that Tri II has complex internal kinematics. Its radial velocity dispersion increases from {4.4}-2.0+2.8 {km} {{{s}}}-1 in the central 2\\prime to {14.1}-4.2+5.8 {km} {{{s}}}-1 outwards. The velocity dispersion of the full sample is inferred to be {σ }{vr}={9.9}-2.2+3.2 {km} {{{s}}}-1. From the two bright RGB member stars we measure an average metallicity < {{[Fe/H]}}> =-2.6+/- 0.2, placing Tri II among the most metal-poor Milky Way dwarf galaxies. In addition, the spectra of the fainter member stars exhibit differences in their line widths that could be the indication of a metallicity dispersion in the system. All these properties paint a complex picture for Tri II, whose nature and current state are largely speculative. The inferred metallicity properties of the system however lead us to favor a scenario in which Tri II is a dwarf galaxy that is either disrupting or embedded in a stellar stream.

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

    NASA Astrophysics Data System (ADS)

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

    2009-05-01

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

  3. Synthesis and structural characterisation of iron(II) and copper(II) diphosphates containing flattened metal oxotetrahedra

    SciTech Connect

    Keates, Adam C.; Wang, Qianlong; Weller, Mark T.

    2014-02-15

    Single crystal and bulk polycrystalline forms of K{sub 2}MP{sub 2}O{sub 7} (M=Fe(II), Cu(II)) have been synthesised and their structures determined from single crystal X-ray diffraction data. Both compounds crystallize in the tetragonal system, space group P-42{sub 1}m. Their structures are formed from infinite sheets of linked oxopolyhedra of the stoichiometry [MP{sub 2}O{sub 7}]{sup 2−} with potassium cations situated between the layers. The MO{sub 4} tetrahedra share oxygen atoms with [P{sub 2}O{sub 7}]{sup 4−} diphosphate groups and the potassium ions have KO{sub 8} square prismatic geometry. In both compounds the M(II) centre has an unusual strongly flattened, tetrahedral coordination to oxygen, as a result of the Jahn–Teller (JT) effect for the high spin d{sup 6} Fe(II) and p-orbital mixing or a second order JT effect for d{sup 9} Cu(II) centres in four fold coordination. The uncommon transition metal ion environments found in these materials are reflected in their optical absorption spectra and magnetism data. - Graphical abstract: The structures of the tetragonal polymorphs of K{sub 2}MP{sub 2}O{sub 7}, M=Cu(II), Fe(II), consist of infinite sheets of stoichiometry [MP{sub 2}O{sub 7}]{sup 2−}, formed from linked pyrophosphate groups and MO{sub 4} tetrahedra, separated by potassium ions. In both compounds the unusual tetrahedral coordination of the M(II) centre is strongly flattened as a result of Jahn–Teller (JT) effects for high spin, d{sup 6} Fe(II) and p-orbital mixing and second-order JT effects for d{sup 9} Cu(II). Display Omitted - Highlights: • Tetrahedral copper and iron(II) coordinated by oxygen. • New layered phosphate structure. • Jahn–Teller and d{sup 10} distorted coordinations.

  4. Metallicity calibration and photometric parallax estimation: II. SDSS photometry

    NASA Astrophysics Data System (ADS)

    Tunçel Güçtekin, S.; Bilir, S.; Karaali, S.; Plevne, O.; Ak, S.; Ak, T.; Bostancı, Z. F.

    2017-01-01

    We used the updated [Fe/H] abundances of 168 F-G type dwarfs and calibrated them to a third order polynomial in terms of reduced ultraviolet excess, δ_{0.41} defined with ugr data in the SDSS. We estimated the Mg absolute magnitudes for the same stars via the re-reduced Hipparcos parallaxes and calibrated the absolute magnitude offsets, Δ Mg, relative to the intrinsic sequence of Hyades to a third order polynomial in terms of δ_{0.41}. The ranges of the calibrations are -2<[Fe/H]≤ 0.3 dex and 4< Mg≤ 6 mag. The mean of the residuals and the corresponding standard deviation for the metallicity calibration are 0 and 0.137 mag; while, for the absolute magnitude calibration they are 0 and 0.179 mag, respectively. We applied our procedures to 23,414 dwarf stars in the Galactic field with the Galactic coordinates 85° ≤ b≤ 90°, 0° ≤ l≤ 360° and size 78 deg2. We estimated absolute magnitude Mg dependent vertical metallicity gradients as a function of vertical distance Z. The gradients are deep in the range of 0< Z≤ 5 kpc, while they are very small positive numbers beyond Z=5 kpc. All dwarfs with 5< Mg≤ 6 mag are thin-disc stars and their distribution shows a mode at (g-r)0≈ 0.38 mag, while the absolute magnitudes 4< Mg ≤ 5 are dominated by thick disc and halo stars, i.e. the apparently bright ones (g0≤ 18 mag) are thick-disc stars with a mode at (g-r)0˜ 0.38 mag, while the halo population is significant in the faint stars (g0>18 mag).

  5. An Investigation Of The Metallicity Dependence Of The Sn Type Ii Mn Production

    NASA Astrophysics Data System (ADS)

    Kim, Yeunjin; Sobeck, J.; Frohlich, C.; Truran, J.

    2010-01-01

    Element abundance trends over the history of our Galaxy serve as important guides in establishing relative contributions from supernovae of Types Ia and II. In particular, spectroscopic studies have revealed a deficiency of manganese (Mn) relative to the abundances of neighboring iron-peak nuclei in metal-poor stars. However, more recent analyses of the observational data have found a constant Mn/Fe abundance ratio over a wide range of metallicity and hence, contradict these previous findings. In this project, we will study the nucleosynthetic yields of Type II supernovae as a function of metallicity by parameterizing the initial properties of the shock. We will compare our results with the two distinct manganese abundance trends identified above. Once we study the metallicity dependency of Type II yields as reflected in observations at lower metallicities, we will explore the constraints this imposes on Type Ia supernova contributions to Mn in different stellar and galactic populations. We acknowledge the financial support by the National Science Foundation for the Frontier Center Joint Institute for Nuclear Astrophysics (JINA). C.F. acknowledges an Enrico Fermi Fellowship.

  6. Physicochemical impact studies of gamma rays on "aspirin" analgesics drug and its metal complexes in solid form: Synthesis, spectroscopic and biological assessment of Ca(II), Mg(II), Sr(II) and Ba(II) aspirinate complexes

    NASA Astrophysics Data System (ADS)

    Refat, Moamen S.; Sharshar, T.; Elsabawy, Khaled M.; Heiba, Zein K.

    2013-09-01

    Metal aspirinate complexes, M2(Asp)4, where M is Mg(II), Ca(II), Sr(II) or Ba(II) are formed by refluxed of aspirin (Asp) with divalent non-transition metal ions of group (II) and characterized by elemental analysis and spectroscopic measurements (infrared, electronic, 1H NMR, Raman, X-ray powder diffraction and scanning electron microscopy). Elemental analysis of the chelates suggests the stoichiometry is 1:2 (metal:ligand). Infrared spectra of the complexes agree with the coordination to the central metal atom through three donation sites of two oxygen atoms of bridge bidentate carboxylate group and oxygen atom of sbnd Cdbnd O of acetyl group. Infrared spectra coupled with the results of elemental analyzes suggested a distorted octahedral structure for the M(II) aspirinate complexes. Gamma irradiation was tested as a method for stabilization of aspirin as well as their complexes. The effect of gamma irradiation, with dose of 80 Gy, on the properties of aspirinate complexes was studied. The aspirinate chelates have been screened for their in vitro antibacterial activity against four bacteria, gram-positive (Bacillus subtilis and Staphylococcus aureus) and gram-negative (Escherichia coli and Pseudomonas aeruginosa) and two strains of fungus (Aspergillus flavus and Candida albicans). The metal chelates were shown to possess more antibacterial activity than the free aspirin chelate.

  7. Coordinate regulation of mouse metallothionein I and II genes by heavy metals and glucocorticoids.

    PubMed Central

    Yagle, M K; Palmiter, R D

    1985-01-01

    Regulation of the endogenous mouse metallothionein I and II (MT-I and MT-II) genes by heavy metals and glucocorticoids was studied in cultured mouse cells. Both mRNAs were measured simultaneously by solution hybridization with [3H]MT-I cDNA and [32P]MT-II cDNA, and the absolute amount of each mRNA was calculated by using a single-stranded M13 standard that contained both mRNA sequences. Both genes responded identically to different concentrations of metals (zinc, cadmium, and copper) and dexamethasone. Furthermore, the time courses of induction of both mRNAs were the same. However, under all conditions there was 1.2- to 1.9-fold more MT-I mRNA than MT-II mRNA. We conclude that both genes are regulated identically by receptors for glucocorticoids and metals but that the rate of transcription from the MT-I gene is slightly higher than from the MT-II gene. PMID:3838360

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

    NASA Astrophysics Data System (ADS)

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

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

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

    PubMed

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

    2012-07-01

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

  10. The HK-II Survey: Kinematics of Metal-Poor Stars in the Galaxy

    NASA Astrophysics Data System (ADS)

    Rhee, J.; Beers, T. C.

    2003-12-01

    The digitized HK-II survey (Rhee 2000, Ph.D. thesis, MSU) was originated as a follow-on to the HK-I survey of Beers and colleagues (e.g., Beers et al. 1992, AJ, 103, 1987). HK-I was based on visually-selected candidate metal-poor stars from objective-prism plates. Unfortunately, in the absence of color information, this selection technique introduced a rather severe temperature-related bias. As a result, the HK-I candidates do not include large numbers of metal-deficient giants. In HK-II, candidate metal-poor stars are quantitatively selected from digitized objective-prism spectra with JHK color information from the recently completeted 2MASS catalog. This approach eliminates much of the temperature bias. We have begun to survey candidate very metal-poor ([Fe/H] ≤ -2.0) giants from HK-II, over the magnitude range 11.0 ≤ B ≤ 16.0, covering some ˜7000 deg2 of intermediate to high Galactic-latitudes. Ongoing medium-resolution ( ˜ 1-2Å ) spectroscopic follow-up using NOAO observing facilities has allowed us to obtain, to date, some 1000 spectra (400, 450, and 150 spectra for red giants, subgiants near the main-sequence turnoff, and FHB/A stars, respectively) for the HK-II metal-poor star candidates. In particular, the detection rate of bona fide very metal-poor giants is about 45 %, which is quite encouraging. Most of the "mistakes" are slightly more metal-rich giants, with -2.0 < [Fe/H] < -1.0. Metallicities and radial velocities are determined from our spectroscopy, and proper motions for most of the program stars are obtained from the recently released UCAC2 astrometric survey catalog. Here we present an analysis of the full space motions for numerous metal-poor stars from the HK-II survey. A comparision of the chemical and kinematic properties between high- and low-halo populations (that is, giants vs. sub-giants) will aid us in understanding the formation history of the Milky Way. J.R. acknowledges partial support for this work by NASA through the AAS

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

    PubMed

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

    2014-09-15

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

  12. The Methods and Study Progress about Estimating Metallicities of Galaxies(II): Luminosity-Metallicity Relation

    NASA Astrophysics Data System (ADS)

    Liang, Yan-Chun; Hammer, François; Deng, Li-Cai; Zhao Gang

    2007-03-01

    The luminosity-metallicity (L-Z) relation (stellar mass-metallicity, mass-Z, relation) is one of the fundamental parameters of galaxies, and can trace the assembly history of metals and stellar masses in the galaxies. The authors review the study progress about (L-Z) and mass-Z relations of galaxies, including the local, the intermediate-z (0.4 < z < 1) and the high-z (z > 2) galaxies. Since the observations extent to a wide cosmic time scale, this can help to understand the evolutionary process of the L-Z relations of galaxies, hence to understand the whole evolutionary scenario of galaxies. In Sect.2 the relations between B-band absolute magnitudes and metallicities (MB-Z) of nearby galaxies are introduced, including the irregular, the spiral galaxies, the UV-selected and nearby HII galaxies, the KISS sample, the 2dFGRS sample, and the SDSS galaxies. Some of the important formulas of such relations are presented. In Sect.3 the study about the relationship between near-infrared J, H, K band absolute magnitudes and metallicities of nearby galaxies are presented. The majority is the result of 400 KISS galaxies obtained from 2MASS. The MK-Z relations of a small sample of distant luminous infrared galaxies is also mentioned. In Sect.4 the relations between stellar mass and metallicities of nearby star-forming galaxies derived from the SDSS database are specially introduced. All these results show that the more luminous (massive) galaxies are more metal-rich generally. The luminosity correlates with metallicity over 10 magnitudes in luminosity and 2 dex in metallicity, with indication that the relationship may be environmental and morphology free. In Sect.5 the L-Z (mass-Z) relations of the intermediate-z and high-z galaxies are introduced. With the increasing ability of observations, more and more distant galaxies have been obtained their L-Z (mass-Z) relations, such as the intermediate-z (0.4 < z < 1) luminous infrared galaxies, the galaxies selected fromm GOODS

  13. Characterization of Irradiated Metal Waste from the Pyrometallurgical Treatment of Used EBR-II Fuel

    SciTech Connect

    B.R. Westphal; K.C. Marsden; W.M. McCartin; S.M. Frank; D.D. Keiser, Jr.; T.S. Yoo; D. Vaden; D.G. Cummings; K.J. Bateman; J. J. Giglio; T. P. O'Holleran; P. A. Hahn; M. N. Patterson

    2013-03-01

    As part of the pyrometallurgical treatment of used Experimental Breeder Reactor-II fuel, a metal waste stream is generated consisting primarily of cladding hulls laden with fission products noble to the electrorefining process. Consolidation by melting at high temperature [1873 K (1600 degrees C)] has been developed to sequester the noble metal fission products (Zr, Mo, Tc, Ru, Rh, Te, and Pd) which remain in the iron-based cladding hulls. Zirconium from the uranium fuel alloy (U-10Zr) is also deposited on the hulls and forms Fe-Zr intermetallics which incorporate the noble metals as well as residual actinides during processing. Hence, Zr has been chosen as the primary indicator for consistency of the metal waste. Recently, the first production-scale metal waste ingot was generated and sampled to monitor Zr content for Fe-Zr intermetallic phase formation and validation of processing conditions. Chemical assay of the metal waste ingot revealed a homogeneous distribution of the noble metal fission products as well as the primary fuel constituents U and Zr. Microstructural characterization of the ingot confirmed the immobilization of the noble metals in the Fe-Zr intermetallic phase.

  14. Characterization of Irradiated Metal Waste from the Pyrometallurgical Treatment of Used EBR-II Fuel

    NASA Astrophysics Data System (ADS)

    Westphal, Brian R.; Frank, S. M.; McCartin, W. M.; Cummings, D. G.; Giglio, J. J.; O'Holleran, T. P.; Hahn, P. A.; Yoo, T. S.; Marsden, K. C.; Bateman, K. J.; Patterson, M. N.

    2015-01-01

    As part of the pyrometallurgical treatment of used Experimental Breeder Reactor-II fuel, a metal waste stream is generated consisting primarily of cladding hulls laden with fission products noble to the electrorefining process. Consolidation by melting at high temperature [1873 K (1600 °C)] has been developed to sequester the noble metal fission products (Zr, Mo, Tc, Ru, Rh, Te, and Pd) which remain in the iron-based cladding hulls. Zirconium from the uranium fuel alloy (U-10Zr) is also deposited on the hulls and forms Fe-Zr intermetallics which incorporate the noble metals as well as residual actinides during processing. Hence, Zr has been chosen as the primary indicator for consistency of the metal waste. Recently, the first production-scale metal waste ingot was generated and sampled to monitor Zr content for Fe-Zr intermetallic phase formation and validation of processing conditions. Chemical assay of the metal waste ingot revealed a homogeneous distribution of the noble metal fission products as well as the primary fuel constituents U and Zr. Microstructural characterization of the ingot confirmed the immobilization of the noble metals in the Fe-Zr intermetallic phase.

  15. Reduction of aqueous transition metal species on the surfaces of Fe(II)-containing oxides

    USGS Publications Warehouse

    White, A.F.; Peterson, M.L.

    1996-01-01

    Experimental studies demonstrate that structural Fe(II) in magnetite and ilmenite heterogeneously reduce aqueous ferric, cupric, vanadate, and chromate ions at the oxide surfaces over a pH range of 1-7 at 25??C. For an aqueous transition metal m, such reactions are 3[Fe2+Fe3+2]O4(magnetite) + 2/nmz ??? 4[Fe3+2]O3(maghemite) + Fe2+ + 2/nmz-n and 3[Fe2+Ti]O3(ilmenite) + 2/nmz ??? Fe3+2Ti3O9(pseudorutile) + Fe2+ + 2/nmz-n, where z is the valance state and n is the charge transfer number. The half cell potential range for solid state oxidation [Fe(II)] ??? [Fe(III)] is -0.34 to -0.65 V, making structural Fe(II) a stronger reducing agent than aqueous Fe2+ (-0.77 V). Reduction rates for aqueous metal species are linear with time (up to 36 h), decrease with pH, and have rate constants between 0.1 and 3.3 ?? 10-10 mol m-2 s-1. Iron is released to solution both from the above reactions and from dissolution of the oxide surface. In the presence of chromate, Fe2+ is oxidized homogeneously in solution to Fe3+. X-ray photoelectron spectroscopy (XPS) denotes a Fe(III) oxide surface containing reduced Cr(III) and V(IV) species. Magnetite and ilmenite electrode potentials are insensitive to increases in divalent transition metals including Zn(II), Co(II), Mn(II), and Ni(II) and reduced V(IV) and Cr(III) but exhibit a log-linear concentration-potential response to Fe(III) and Cu(II). Complex positive electrode responses occur with increasing Cr(VI) and V(V) concentrations. Potential dynamic scans indicate that the high oxidation potential of dichromate is capable of suppressing the cathodic reductive dissolution of magnetite. Oxide electrode potentials are determined by the Fe(II)/Fe(III) composition of the oxide surface and respond to aqueous ion potentials which accelerate this oxidation process. Natural magnetite sands weathered under anoxic conditions are electrochemically reactive as demonstrated by rapid chromate reduction and the release of aqueous Fe(III) to experimental

  16. Sorption behavior of Pb(II) and Cd(II) on iron ore slime and characterization of metal ion loaded sorbent.

    PubMed

    Mohapatra, M; Rout, K; Mohapatra, B K; Anand, S

    2009-07-30

    The present investigation evaluates the sorption effectiveness of Pb(II) and Cd(II) ions on iron ore slime (IOS) obtained from Jindal Steel Ltd., Vijayanagaram, India. The sorption followed pseudo-second-order kinetics for both the cations. Pb(II) and Cd(II) sorption increased with the increase in pH from 2 to 4.5. The sorption data fitted well to Freundlich model as compared to Langmuir model. Synergistic effect of Pb(II) and Cd(II) on their sorption on IOS sample showed that Pb(II) sorption increases in presence of Cd(II) whereas Cd(II) sorption decreases. Presence of chloride or sulphate resulted in increased Pb(II) sorption but adversely affected Cd(II) sorption. The XRD patterns of Pb(II) adsorbed on IOS sample showed disappearance of some silica peaks and shifting of hematite peaks corresponding to 104 and 110 plane. For Cd(II) sorbed IOS sample, only peak shift for hematite of 104 and 110 plane was observed. Shifting of IR bands indicated that the Pb(II) sorption occurred through an inner sphere mechanism where as Cd(II) sorption occurred through outer sphere mechanism. EPMA studies showed that Pb(II) form a uniform thin layer and Cd(II) concentrate only on iron oxide phase. Regeneration and stability data on metal ion loaded IOS sample has been included.

  17. Hydride reactivity of Ni(II)-X-Ni(II) entities: mixed-valent hydrido complexes and reversible metal reduction.

    PubMed

    Gehring, Henrike; Metzinger, Ramona; Herwig, Christian; Intemann, Julia; Harder, Sjoerd; Limberg, Christian

    2013-01-28

    After the lithiation of PYR-H(2) (PYR(2-) =[{NC(Me)C(H)C(Me)NC(6)H(3)(iPr)(2)}(2)(C(5)H(3)N)](2-)), which is the precursor of an expanded β-diketiminato ligand system with two binding pockets, its reaction with [NiBr(2) (dme)] led to a dinuclear nickel(II)-bromide complex, [(PYR)Ni(μ-Br)NiBr] (1). The bridging bromide ligand could be selectively exchanged for a thiolate ligand to yield [(PYR)Ni(μ-SEt)NiBr] (3). In an attempt to introduce hydride ligands, both compounds were treated with KHBEt(3). This treatment afforded [(PYR)Ni(μ-H)Ni] (2), which is a mixed valent Ni(I)-μ-H-Ni(II) complex, and [(PYR-H)Ni(μ-SEt)Ni] (4), in which two tricoordinated Ni(I) moieties are strongly antiferromagnetically coupled. Compound 4 is the product of an initial salt metathesis, followed by an intramolecular redox process that separates the original hydride ligand into two electrons, which reduce the metal centres, and a proton, which is trapped by one of the binding pockets, thereby converting it into an olefin ligand on one of the Ni(I) centres. The addition of a mild acid to complex 4 leads to the elimination of H(2) and the formation of a Ni(II)Ni(II) compound, [(PYR)Ni(μ-SEt)NiOTf] (5), so that the original Ni(II) (μ-SEt)Ni(II) X core of compound 3 is restored. All of these compounds were fully characterized, including by X-ray diffraction, and their molecular structures, as well as their formation processes, are discussed.

  18. Correlation of Gas Permeability in a Metal-Organic Framework MIL-101(Cr)–Polysulfone Mixed-Matrix Membrane with Free Volume Measurements by Positron Annihilation Lifetime Spectroscopy (PALS)

    PubMed Central

    Jeazet, Harold B. Tanh; Koschine, Tönjes; Staudt, Claudia; Raetzke, Klaus; Janiak, Christoph

    2013-01-01

    Hydrothermally stable particles of the metal-organic framework MIL-101(Cr) were incorporated into a polysulfone (PSF) matrix to produce mixed-matrix or composite membranes with excellent dispersion of MIL-101 particles and good adhesion within the polymer matrix. Pure gas (O2, N2, CO2 and CH4) permeation tests showed a significant increase of gas permeabilities of the mixed-matrix membranes without any loss in selectivity. Positron annihilation lifetime spectroscopy (PALS) indicated that the increased gas permeability is due to the free volume in the PSF polymer and the added large free volume inside the MIL-101 particles. The trend of the gas transport properties of the composite membranes could be reproduced by a Maxwell model. PMID:24957061

  19. Correlation of Gas Permeability in a Metal-Organic Framework MIL-101(Cr)-Polysulfone Mixed-Matrix Membrane with Free Volume Measurements by Positron Annihilation Lifetime Spectroscopy (PALS).

    PubMed

    Jeazet, Harold B Tanh; Koschine, Tönjes; Staudt, Claudia; Raetzke, Klaus; Janiak, Christoph

    2013-10-25

    Hydrothermally stable particles of the metal-organic framework MIL-101(Cr) were incorporated into a polysulfone (PSF) matrix to produce mixed-matrix or composite membranes with excellent dispersion of MIL-101 particles and good adhesion within the polymer matrix. Pure gas (O2, N2, CO2 and CH4) permeation tests showed a significant increase of gas permeabilities of the mixed-matrix membranes without any loss in selectivity. Positron annihilation lifetime spectroscopy (PALS) indicated that the increased gas permeability is due to the free volume in the PSF polymer and the added large free volume inside the MIL-101 particles. The trend of the gas transport properties of the composite membranes could be reproduced by a Maxwell model.

  20. Controlled synthesis of ternary II-II'-VI nanoclusters and the effects of metal ion distribution on their spectral properties.

    PubMed

    Degroot, Marty W; Taylor, Nicholas J; Corrigan, John F

    2005-07-25

    The reaction of [(3,5-Me(2)-C(5)H(3)N)(2)Zn(ESiMe(3))(2)] (E = Se, Te) with cadmium(II) acetate in the presence of PhESiMe(3) and P(n)Pr(3) at low temperature leads to the formation of single crystals of the ternary nanoclusters [Zn(x)()Cd(10)(-)(x)()E(4)-(EPh)(12)(P(n)()Pr(3))(4)] [E = Se, x = 1.8 (2a), 2.6 (2b); Te, x = 1.8 (3a), 2.6 (3b)] in good yield. The clusters [Zn(3)Hg(7)Se(4)(SePh)(12)(P(n)()Pr(3))(4)] (4) and [Cd(3.7)Hg(6.3)Se(4)(SePh)(12)(P(n)()Pr(3))(4)] (5) can be accessed by similar reactions involving [(3,5-Me(2)-C(5)H(3)N)(2)Zn(SeSiMe(3))(2)] or [(N,N'-tmeda)Cd(SeSiMe(3))(2)] (1) and mercury(II) chloride. The metal silylchalcogenolate reagents are efficient delivery sources of {ME(2)} in cluster synthesis, and thus, the metal ion content of these clusters can be readily moderated by controlling the reaction stoichiometry. The reaction of cadmium acetate with [(3,5-Me(2)-C(5)H(3)N)(2)Zn(SSiMe(3))(2)], PhSSiMe(3), and P(n)()Pr(3) affords the larger nanocluster [Zn(2.3)Cd(14.7)S(4)(SPh)(26)(P(n)()Pr(3))(2)] (6). The incorporation of Zn(II) into {Cd(10)E} (E = Se, Te) and Zn(II) or Cd(II) into {Hg(10)Se} nanoclusters results in a significant blue shift in the energy of the first "excitonic" transition. Solid-state thermolysis of complexes 2 and 3 reveals that these clusters can be used as single-source precursors to bulk ternary Zn(x)Cd(1)(-)(x)E materials as well as larger intermediate clusters and that the metal ion ratio is retained during these reactions.

  1. Positron annihilation in solid and liquid Ni

    SciTech Connect

    Fluss, M.J.; Smedskjaer, L.C.; Chakraborty, B.; Chason, M.K.

    1982-03-01

    New techniques have been developed for the study of metals via positron annihilation which provide for the in-situ melting of the samples and subsequent measurements via Doppler broadening of positron-annihilation radiation. Here we report these metods currently in use at our laboratory; ion implantation of /sup 58/Co and the use of Al/sub 2/O/sub 3/ crucibles for in-situ melting followed by the decomposition of the Doppler-broadened spectrum into a parabolic and a Gaussian component. Our earliest results obtained for pure Ni in the polycrystalline solid and in the liquid state are compared. An interesting similarity is reported for the distributions of the high-momentum (Gaussian) component for positrons annihilating in vacancies at high temperatures and those annihilating in liquid Ni.

  2. Resolvability of defect ensembles with positron annihilation studies

    SciTech Connect

    Fluss, M.J.; Howell, R.H.; Rosenberg, I.J.; Meyer, P.

    1984-11-12

    Recent advances in the use of positron annihilation to study defect ensembles in and on the surfaces of metals, are pointing the way towards studies where particular positron-electron annihilation modes may be identified and studied in the presence of one another. Although a great deal is understood about the annihilation of positrons in ostensibly defect-free metals, much less is understood when the positron annihilates in complex defect systems such as liquid metals, amorphous solids, or at or near the vacuum-solid interface. In this paper the results of three experiments, all of which demonstrate means by which we can resolve various poistron annihilation channels from one another, are discussed.

  3. Positron diffusion in Si

    SciTech Connect

    Nielsen, B.; Lynn, K.G.; Vehanen, A.; Schultz, P.J.

    1985-06-01

    Positron diffusion in Si(100) and Si(111) has been studied using a variable energy positron beam. The positron diffusion coefficient is found to be D/sub +/ = 2.7 +- 0.3 cm/sup 2//sec using a Makhov-type positron implantation profile, which is demonstrated to fit the data more reliably than the more commonly applied exponential profile. The diffusion related parameter, E/sub 0/, which results from the exponential profile, is found to be 4.2 +- 0.2 keV, significantly longer than previously reported values. A drastic reduction in E/sub 0/ is found after annealing the sample at 1300 K, showing that previously reported low values of E/sub 0/ are probably associated with the thermal history of the sample.

  4. The use of Apatite II™ to remove divalent metal ions zinc(II), lead(II), manganese(II) and iron(II) from water in passive treatment systems: column experiments.

    PubMed

    Oliva, Josep; De Pablo, Joan; Cortina, José-Luis; Cama, Jordi; Ayora, Carlos

    2010-12-15

    The conventional passive treatments for remediation of acid mine drainage using calcite are not totally efficient in the removal of certain heavy metal ions. Although pH increases to 6-7 and promotes the precipitation of trivalent and some divalent metals as hydroxides and carbonates, the remaining concentrations of some divalent metals ions do not fulfill the environmental regulations. In this study, Apatite II™, a biogenic hydroxyapatite, is used as an alternative reactive material to remove Zn(II), Pb(II), Mn(II) and Fe(II). Apatite II™ reacted with acid water releasing phosphate and increasing pH up to 6.5-7, inducing metals to precipitate mainly as metal-phosphates: zinc precipitated as hopeite, Zn(3)(PO(4))(2)·4H(2)O, lead as pyromorfite, Pb(5)(PO(4))(3)OH, manganese as metaswitzerite, Mn(3)(PO(4))(2)·4H(2)O and iron as vivianite, Fe(3)(PO(4))(2)·8H(2)O. Thus, metal concentrations from 30 to 75 mg L(-1) in the inflowing water were depleted to values below 0.10 mg L(-1). Apatite II™ dissolution is sufficiently fast to treat flows as high as 50 m/a. For reactive grain size of 0.5-3mm, the treatment system ends due to coating of the grains by precipitates, especially when iron and manganese are present in the solution. Copyright © 2010 Elsevier B.V. All rights reserved.

  5. Stellar kinematics and metallicities in the ultra-faint dwarf galaxy Reticulum II

    DOE PAGES

    Simon, J. D.

    2015-07-23

    With this study, we present Magellan/M2FS, Very Large Telescope/GIRAFFE, and Gemini South/GMOS spectroscopy of the newly discovered Milky Way satellite Reticulum II. Based on the spectra of 25 Ret II member stars selected from Dark Energy Survey imaging, we measure a mean heliocentric velocity ofmore » $$62.8\\pm 0.5\\;\\mathrm{km}\\;{\\rm{s}}^{-1}$$ and a velocity dispersion of $$3.3\\pm 0.7\\;\\mathrm{km}\\;{\\rm{s}}^{-1}$$. The mass-to-light ratio of Ret II within its half-light radius is $$470\\pm 210\\ {M}_{\\odot }/{L}_{\\odot }$$, demonstrating that it is a strongly dark matter-dominated system. Despite its spatial proximity to the Magellanic Clouds, the radial velocity of Ret II differs from that of the LMC and SMC by 199 and 83 $$\\mathrm{km}\\ {{\\rm{s}}}^{-1}$$, respectively, suggesting that it is not gravitationally bound to the Magellanic system. The likely member stars of Ret II span 1.3 dex in metallicity, with a dispersion of 0.28 ± 0.09 dex, and we identify several extremely metal-poor stars with $${\\rm{[Fe/H]}}\\lt -3$$. In combination with its luminosity, size, and ellipticity, these results confirm that Ret II is an ultra-faint dwarf galaxy. With a mean metallicity of $${\\rm{[Fe/H]}}=-2.65\\pm 0.07$$, Ret II matches Segue 1 as the most metal-poor galaxy known. Although Ret II is the third-closest dwarf galaxy to the Milky Way, the line-of-sight integral of the dark matter density squared is $${\\mathrm{log}}_{10}(J)=18.8\\pm 0.6\\;\\;\\mathrm{GeV}{\\;}^{2}\\;{\\mathrm{cm}}^{-5}\\;$$ within 0fdg2, indicating that the predicted gamma-ray flux from dark matter annihilation in Ret II is lower than that of several other dwarf galaxies.« less

  6. Detection of Toxic Heavy Metal, Co(II) Trace via Voltammetry with Semiconductor Microelectrodes

    PubMed Central

    Ly, Suw Young; Lee, Chang Hyun; Koo, Jae Mo

    2017-01-01

    The cobalt (Co(II)) ion is a main component of alloys and considered to be carcinogenic, especially due to the carcinogenic and toxicological effects in the aquatic environment. The toxic trace of the Co(II) detection was conducted using the infrared photodiode electrode (IPDE) using a working electrode, via the cyclic and square-wave anodic stripping voltammetry. The results indicated a sensitive oxidation peak current of Co(II) on the IPDE. Under the optimal conditions, the common-type glassy carbon, the metal platinum, the carbon paste, and the carbon fiber microelectrode were compared with the IPDE in the electrolyte using the standard Co(II). The IPDE was found to be far superior to the others. PMID:28503262

  7. Effect of biofilm coatings at metal-oxide/water interfaces II: Competitive sorption between Pb(II) and Zn(II) at Shewanella oneidensis/metal-oxide/water interfaces

    SciTech Connect

    Wang, Yingge; Gelabert, Alexandre; Michel, F. Marc; Choi, Yongseong; Eng, Peter J.; Spormann, Alfred M.; Brown, Jr., Gordon E.

    2016-05-07

    Competitive sorption of Pb(II) and Zn(II) on Shewanella oneidensis MR-1 biofilm-coated single-crystal α-Al2O3 (1 –1 0 2) and α-Fe2O3 (0 0 0 1) surfaces was investigated using long-period X-ray standing wave-florescence yield (LP-XSW-FY) spectroscopy. In situ partitioning of aqueous Pb(II) and Zn(II) between the biofilms and underlying metal-oxide substrates was probed following exposure of these complex interfaces to equi-molar Pb and Zn solutions (0.01 M NaNO3 as background electrolyte, pH = 6.0, and 3-h equilibration time). At higher Pb and Zn concentrations (≥10–5 M), more than 99% of these ions partitioned into the biofilms at S. oneidensis/α-Al2O3 (1 –1 0 2)/water interfaces, which is consistent with the partitioning behavior of both Pb(II) or Zn(II) in single-metal-ion experiments. Furthermore, no apparent competitive effects were found in this system at these relatively high metal-ion concentrations. However, at lower equi-molar concentrations (≤10–6 M), Pb(II) and Zn(II) partitioning in the same system changed significantly compared to the single-metal-ion systems. The presence of Zn(II) decreased Pb(II) partitioning onto α-Al2O3 (1 –1 0 2) substantially (~52% to ~13% at 10–7 M, and ~23% to ~5% at 10–6 M), whereas the presence of Pb(II) caused more Zn(II) to partition onto α-Al2O3 (1 –1 0 2) surfaces (~15% to ~28% at 10–7 M, and ~1% to ~7% at 10–6 M) .The higher observed partitioning of Zn(II) (~28%) at the α-Al2O3 (1 –1 0 2) surfaces compared to Pb(II) (~13%) in the mixed-metal-ion systems at the lowest concentration (10–7 M) suggests that Zn(II) is slightly favored over Pb(II) for sorption sites on α-Al2O3 (1 –1 0 2) surfaces under our experimental conditions.

  8. Effect of biofilm coatings at metal-oxide/water interfaces II: Competitive sorption between Pb(II) and Zn(II) at Shewanella oneidensis/metal-oxide/water interfaces

    SciTech Connect

    Wang, Yingge; Gelabert, Alexandre; Michel, F. Marc; Choi, Yongseong; Eng, Peter J.; Spormann, Alfred M.; Brown, Jr., Gordon E.

    2016-05-07

    Competitive sorption of Pb(II) and Zn(II) on Shewanella oneidensis MR-1 biofilm-coated single-crystal α-Al2O3 (1 –1 0 2) and α-Fe2O3 (0 0 0 1) surfaces was investigated using long-period X-ray standing wave-florescence yield (LP-XSW-FY) spectroscopy. In situ partitioning of aqueous Pb(II) and Zn(II) between the biofilms and underlying metal-oxide substrates was probed following exposure of these complex interfaces to equi-molar Pb and Zn solutions (0.01 M NaNO3 as background electrolyte, pH = 6.0, and 3-h equilibration time). At higher Pb and Zn concentrations (≥10–5 M), more than 99% of these ions partitioned into the biofilms at S. oneidensis/α-Al2O3 (1 –1 0 2)/water interfaces, which is consistent with the partitioning behavior of both Pb(II) or Zn(II) in single-metal-ion experiments. Furthermore, no apparent competitive effects were found in this system at these relatively high metal-ion concentrations. However, at lower equi-molar concentrations (≤10–6 M), Pb(II) and Zn(II) partitioning in the same system changed significantly compared to the single-metal-ion systems. The presence of Zn(II) decreased Pb(II) partitioning onto α-Al2O3 (1 –1 0 2) substantially (~52% to ~13% at 10–7 M, and ~23% to ~5% at 10–6 M), whereas the presence of Pb(II) caused more Zn(II) to partition onto α-Al2O3 (1 –1 0 2) surfaces (~15% to ~28% at 10–7 M, and ~1% to ~7% at 10–6 M) .The higher observed partitioning of Zn(II) (~28%) at the α-Al2O3 (1 –1 0 2) surfaces compared to Pb(II) (~13%) in the mixed-metal-ion systems at the lowest concentration (10–7 M) suggests that Zn(II) is slightly favored over Pb(II) for sorption sites on α-Al2O3 (1 –1 0 2) surfaces under our experimental conditions.

  9. Study of cerebral ischemic reversibility: Part II. Preliminary preoperative results of fluoromethane positron emission tomographic determination of perfusion reserve in patients with carotid TIA and stroke

    SciTech Connect

    Levine, R.L.; Sunderland, J.J.; Rowe, B.R.; Nickles, R.J.

    1986-01-01

    Symmetries and asymmetries in regional cerebral blood flow (rCBF) determinations are reported in eleven patients with symptomatic carotid artery occlusive disease. Flourine-18-fluoromethane rCBF values are obtained by means of a noninvasive positron emission tomographic (PET) technique during room air (RA) and following induced hypercapnia (CO/sub 2/). Areas of abnormal CO/sub 2/ reactivity predict both the hemodynamic significance of the vascular lesion in question and the areas most vulnerable for ischemic infarction. This data is intended to be preliminary in nature; future expansions of this data base will be made to include rCBF/CO/sub 2/ estimations, rCBF/glucose metabolism determinations, and rCBF/reserve evaluations over time and following brain-specific therapies. Once established, the potential viability and reversibility of these ischemic, uninfarcted or minimally infarcted areas can then be reestablished over time, thus providing a quantitative measure of the natural history of flow/metabolic coupling or uncoupling.

  10. Intense positron beam as a source for production of electron-positron plasma

    NASA Astrophysics Data System (ADS)

    Stoneking, M. R.; Horn-Stanja, J.; Stenson, E. V.; Pedersen, T. Sunn; Saitoh, H.; Hergenhahn, U.; Niemann, H.; Paschkowski, N.; Hugenschmidt, C.; Piochacz, C.

    2016-10-01

    We aim to produce magnetically confined, short Debye length electron-positron plasma and test predicted properties for such systems. A first challenge is obtaining large numbers of positrons; a table-top experiment (system size 5 cm) with a temperature less than 5 eV requires about 1010 positrons to have more than 10 Debye lengths in the system. The NEPOMUC facility at the FRM II research reactor in Germany is one of the world's most intense positron sources. We report on characterization (using a retarding field energy analyzer with magnetic field gradient) of the NEPOMUC beam as delivered to the open beam port at various beam energies and in both the re-moderated and primary beam configurations in order to design optimal trapping (and accumulation) schemes for production of electron-positron plasma. The intensity of the re-moderated (primary) beam is in the range 2 -3 x 107 /s (1 - 5 x 108 /s). The re-moderated beam is currently the most promising for direct injection and confinement experiments; it has a parallel energy spread of 15 - 35% and the transverse energy spread is 6 - 15% of the parallel energy. We report on the implications for injection and trapping in a dipole magnetic field as well as plans for beam development, in situ re-moderation, and accumulation. We also report results demonstrating a difference in phosphor luminescent response to low energy positrons versus electrons.

  11. New dinuclear copper(II) and zinc(II) complexes for the investigation of sugar-metal ion interactions.

    PubMed

    Bera, Manindranath; Patra, Ayan

    2011-10-18

    We have studied the binding interactions of biologically important carbohydrates (D-glucose, D-xylose and D-mannose) with the newly synthesized five-coordinate dinuclear copper(II) complex, [Cu(2)(hpnbpda)(μ-OAc)] (1) and zinc(II) complex, [Zn(2)(hpnbpda)(μ-OAc)] (2) [H(3)hpnbpda=N,N'-bis(2-pyridylmethyl)-2-hydroxy-1,3-propanediamine-N,N'-diacetic acid] in aqueous alkaline solution. The complexes 1 and 2 are fully characterized both in solid and solution using different analytical techniques. A geometrical optimization was made of the ligand H(3)hpnbpda and the complexes 1 and 2 by molecular mechanics (MM+) method in order to establish the stable conformations. All carbohydrates bind to the metal complexes in a 1:1 molar ratio. The binding events have been investigated by a combined approach of FTIR, UV-vis and (13)C NMR spectroscopic techniques. UV-vis spectra indicate a significant blue shift of the absorption maximum of complex 1 during carbohydrate coordination highlighting the sugar binding ability of complex 1. The apparent binding constants of the substrate-bound copper(II) complexes have been determined from the UV-vis titration experiments. The binding ability and mode of binding of these sugar substrates with complex 2 are indicated by their characteristic coordination induced shift (CIS) values in (13)C NMR spectra for carbon atoms C1, C2, and C3 of sugar substrates.

  12. Synthesis, characterization and biological evaluation of Rutin-zinc(II) flavonoid -metal complex.

    PubMed

    Ikeda, Norma Estefania Andrades; Novak, Estela Maria; Maria, Durvanei Augusto; Velosa, Adélia Segin; Pereira, Regina Mara Silva

    2015-09-05

    Synthesis of compounds analogous to natural products from secondary metabolites, such as flavonoids, is a promising source of novel drugs. Rutin (quercetin-3-O-rutinoside) is a natural flavone, which has, in its chemical structure, different sites for coordination with transition metals and the complexation with these metals enhances its biological properties. Rutin-zinc(II), a flavonoid-metal complex, was synthesized and characterized by UV-VIS, FT-IR, elemental analysis and (1)H NMR. The antioxidant and antitumor activities, as well as the cytotoxicity and in vivo toxicity of this complex were evaluated and compared with the free rutin. Rutin-zinc(II) has not shown any cytotoxicity against normal cells (fibroblasts and HUVECs) or toxicity in BALB/c mice, but has shown antioxidant activity in vitro and cytotoxicity against leukemia (KG1, K562 and Jurkat), multiple myeloma (RPMI8226) and melanoma (B16F10 and SK-Mel-28) cell lines in vitro. In Ehrlich ascites carcinoma model, Rutin-zinc(II) modulated the mitochondrial membrane potential and the expression of genes related to cell cycle progression, angiogenesis and apoptosis.

  13. Kinetics of metal exchange in Cd(II) octa(4-bromophenyl)porphyrinate with d-metal salts in organic solvents

    NASA Astrophysics Data System (ADS)

    Zvezdina, S. V.; Chizhova, N. V.; Mamardashvili, N. Zh.

    2017-03-01

    The reaction of metal exchange between Cd(II) octa(4-bromophenyl)porphyrinate with CuCl2 and ZnCl2 in DMFA and DMSO is studied by means of spectrophotometry. The kinetic parameters of the metal exchange reaction are calculated, a stoichiometric reaction mechanism is proposed. The effect the natures of the solvent, salt solvate, and the chemical modification of tetrapyrrole macrocycle have on the kinetic parameters of the metal exchange reaction are revealed.

  14. Type-II Dirac fermions in the PtSe2 class of transition metal dichalcogenides

    NASA Astrophysics Data System (ADS)

    Huang, Huaqing; Zhou, Shuyun; Duan, Wenhui

    2016-09-01

    Recently, a new "type-II" Weyl fermion, which exhibits exotic phenomena, such as an angle-dependent chiral anomaly, was discovered in a new phase of matter where electron and hole pockets contact at isolated Weyl points [Nature (London) 527, 495 (2015), 10.1038/nature15768]. This raises an interesting question about whether its counterpart, i.e., a type-II Dirac fermion, exists in real materials. Here, we predict the existence of symmetry-protected type-II Dirac fermions in a class of transition metal dichalcogenide materials. Our first-principles calculations on PtSe2 reveal its bulk type-II Dirac fermions which are characterized by strongly tilted Dirac cones, novel surface states, and exotic doping-driven Lifshitz transition. Our results show that the existence of type-II Dirac fermions in PtSe2-type materials is closely related to its structural P 3 ¯m 1 symmetry, which provides useful guidance for the experimental realization of type-II Dirac fermions and intriguing physical properties distinct from those of the standard Dirac fermions known before.

  15. Alkali and alkaline earth metallic (AAEM) species leaching and Cu(II) sorption by biochar.

    PubMed

    Li, Mi; Lou, Zhenjun; Wang, Yang; Liu, Qiang; Zhang, Yaping; Zhou, Jizhi; Qian, Guangren

    2015-01-01

    Alkali and alkaline earth metallic (AAEM) species water leaching and Cu(II) sorption by biochar prepared from two invasive plants, Spartina alterniflora (SA) and water hyacinth (WH), were explored in this work. Significant amounts of Na and K can be released (maximum leaching for Na 59.0 mg g(-1) and K 79.9 mg g(-1)) from SA and WH biochar when they are exposed to contact with water. Cu(II) removal by biochar is highly related with pyrolysis temperature and environmental pH with 600-700 °C and pH of 6 showing best performance (29.4 and 28.2 mg g(-1) for SA and WH biochar). Cu(II) sorption exerts negligible influence on Na/K/Mg leaching but clearly promotes the release of Ca. Biochars from these two plant species provide multiple benefits, including nutrient release (K), heavy metal immobilization as well as promoting the aggregation of soil particles (Ca) for soil amelioration. AAEM and Cu(II) equilibrium concentrations in sorption were analyzed by positive matrix factorization (PMF) to examine the factors underlying the leaching and sorption behavior of biochar. The identified factors can provide insightful understanding on experimental phenomena. Copyright © 2014 Elsevier Ltd. All rights reserved.

  16. Cytosolic Ni(II) sensor in cyanobacterium: nickel detection follows nickel affinity across four families of metal sensors.

    PubMed

    Foster, Andrew W; Patterson, Carl J; Pernil, Rafael; Hess, Corinna R; Robinson, Nigel J

    2012-04-06

    Efflux of surplus Ni(II) across the outer and inner membranes of Synechocystis PCC 6803 is mediated by the Nrs system under the control of a sensor of periplasmic Ni(II), NrsS. Here, we show that the product of ORF sll0176, which encodes a CsoR/RcnR-like protein now designated InrS (for internal nickel-responsive sensor), represses nrsD (NrsD is deduced to efflux Ni(II) across the inner membrane) from a cryptic promoter between the final two ORFs in the nrs operon. Transcripts initiated from the newly identified nrsD promoter accumulate in response to nickel or cobalt but not copper, and recombinant InrS forms specific, Ni(II)-inhibited complexes with the nrsD promoter region. Metal-dependent difference spectra of Ni(II)- and Cu(I)-InrS are similar to Cu(I)-sensing CsoR and dissimilar to Ni(II)/Co(II)-sensing RcnR, consistent with factors beyond the primary coordination sphere switching metal selectivity. Competition with chelators mag-fura-2, nitrilotriacetic acid, EDTA, and EGTA estimate K(D) Ni(II) for the tightest site of InrS as 2.05 (±1.5) × 10(-14) m, and weaker K(D) Ni(II) for the cells' metal sensors of other types: Zn(II) co-repressor Zur, Co(II) activator CoaR, and Zn(II) derepressor ZiaR. Ni(II) transfer to InrS occurs upon addition to Ni(II) forms of each other sensor. InrS binds Ni(II) sufficiently tightly to derepress Ni(II) export at concentrations below K(D) Ni(II) of the other sensors.

  17. Alternative positron-target design for electron-positron colliders

    SciTech Connect

    Donahue, R.J. ); Nelson, W.R. )

    1991-04-01

    Current electron-positron linear colliders are limited in luminosity by the number of positrons which can be generated from targets presently used. This paper examines the possibility of using an alternate wire-target geometry for the production of positrons via an electron-induced electromagnetic cascade shower. 39 refs., 38 figs., 5 tabs.

  18. Application of positron annihilation in materials science

    SciTech Connect

    Siegel, R.W.; Fluss, M.J.; Smedskjaer, L.C.

    1984-05-01

    Owing to the ability of the positron to annihilate from a variety of defect-trapped states, positron annihilation spectroscopy (PAS) has been applied increasingly to the characterization and study of defects in materials in recent years. In metals particularly, it has been demonstrated that PAS can yield defect-specific information which, by itself or in conjunction with more traditional experimental techniques, has already made a significant impact upon the determination of atomic-defect properties and the monitoring and characterization of vacancy-like microstructure development, as occurs during post-irradiation annealing. The applications of PAS are now actively expanding to the study of more complex defect-related phenomena in irradiated or deformed metals and alloys, phase transformations and structural disorder, surfaces and near-surface defect characterization. A number of these applications in materials science are reviewed and discussed with respect to profitable future directions.

  19. Aggregation of nanoscale iron oxyhydroxides and corresponding effects on metal uptake, retention, and speciation: II. Temperature and time

    NASA Astrophysics Data System (ADS)

    Stegemeier, J. P.; Reinsch, B. C.; Lentini, C. J.; Dale, J. G.; Kim, C. S.

    2015-01-01

    The aggregation and growth of nanosized particles can greatly impact their capacity to sorb and retain dissolved metals, thus affecting metal fate and transport in contaminated systems. Aqueous suspensions of synthesized nanoscale iron oxyhydroxides were exposed to dissolved Zn(II) or Cu(II) and aged at room temperature (∼20 °C), 50 °C, and 75 °C for timeframes ranging from 0 to 96 h before sorbed metal ions were desorbed by lowering the suspension pH. Atomic absorption spectroscopic analysis of supernatants both before and after the desorption step determined how temperature and time affect macroscopic metal uptake and retention capacities. Extended X-ray absorption fine structure (EXAFS) spectroscopy analysis described the local binding environment of the sorbed/retained metals on the solid phase. With increasing aging temperature and time, the initial ∼5-nm oblong nanoparticles formed dense aggregates, lost reactive surface area, and retained progressively larger fractions of the initially-introduced Zn(II) and Cu(II) following the desorption step, with the copper species inhibiting the oriented aggregation of the nanoparticles into nanorods. Based on EXAFS analysis, the speciation of the sorbed metal species evolves with increasing time and temperature from surface-sorbed metal ions, which readily desorb and return to solution, to more strongly-bound, structurally-incorporated metal ions. These retained metals appear to associate intimately with the nanoparticle aggregates by substituting for iron in the nanoparticle lattice or by binding within nanoparticle aggregate pore spaces.

  20. Metal-ion exchange induced structural transformation as a way of forming novel Ni(II)- and Cu(II)-salicylaldimine structures

    NASA Astrophysics Data System (ADS)

    Wu, Jing-Yun; Tsai, Chi-Jou; Chang, Ching-Yun; Wu, Yung-Yuan

    2017-02-01

    A Zn(II)-salicylaldimine complex [Zn(Lsalpyca)(H2O)]n (1, where H2Lsalpyca=4-hydroxy-3-(((pyridin-2-yl)methylimino)methyl)benzoic acid), with a one-dimensional (1D) chain structure, has been successfully converted to a discrete Ni(II)-salicylaldimine complex [Ni(Lsalpyca)(H2O)3] (2) and an infinite Cu(II)-salicylaldimine complex {[Cu(Lsalpyca)]·3H2O}n (3) through a metal-ion exchange induced structural transformation process. However, such processes do not worked by Mn(II) and Co(II) ions. Solid-state structure analyses reveal that complexes 1-3 form comparable coordinative or supramolecular zigzag chains running along the crystallographic [201] direction. In addition, replacing Zn(II) ion by Ni(II) and Cu(II) ions caused changes in coordination environment and sphere of metal centers, from a 5-coordinate intermediate geometry of square pyramidal and trigonal bipyramidal in 1 to a 6-coordinate octahedral geometry in 2, and to a 4-coordiante square planar geometry in 3. This study shows that metal-ion exchange serves as a very efficient way of forming new coordination complexes that may not be obtained through direct synthesis.

  1. Crowe Type I and II DDH managed by large diameter metal-on-metal total hip arthroplasty.

    PubMed

    Yalcin, Nadir; Kilicarslan, Kasim; Cicek, Hakan; Kayaalp, Cetin; Yildirim, Hasan

    2011-01-01

    Large bearing metal-on-metal (MOM) total hip arthroplasty (THA) may offer advantages relating to stability and range of motion in patients with Crowe Type I and II developmental dysplasia of the hip (DDH). The purpose of this study was to provide an analysis of the clinical and radiological results of MOM THA in this context and compare the results with a cohort of patients treated with metal-on-polyethylene (MOP) bearing surfaces. 75 hips in 65 patients were treated with cementless MOM THA using large femoral heads (36-56 mm). The mean age of the patients was 47.4 years (29 to 59) and 54 were female. A group of 47 hips (41 patients) treated with conventional THA (screwed cup-polyethylene insert-28 mm head) was used for comparison. The study group was followed up for a mean of 62.1 months (32 to 76). No difference was found between the two groups in relation to improvement in Harris hip score (HHS) (43.1 to 90.3 points in the study group, 42.6 to 89.5 points in the control group, p>0.05). Although the preoperative range of motion in all planes were similar in both groups, the large head group demonstrated greater motion in all planes postoperatively, which was significant (all p=0.001). Additionally, there was a significant difference between groups in relation to the necessity for acetabular structural graft (8% and 31.9%, respectively; p=0.001). No major complications or adverse reactions to metal debris (ARMD) were observed in the study group. The results of large head MOM THA in young and active patients with DDH are similar to conventional THA at early follow-up, but the former offers the advantages of secure acetabular fixation without screws, greater range of motion, and lower risk of dislocation.

  2. Immobilization of Radionuclides and Heavy Metals through Anaerobic Bio-Oxidation of Fe(II)

    PubMed Central

    Lack, Joseph G.; Chaudhuri, Swades K.; Kelly, Shelly D.; Kemner, Kenneth M.; O'Connor, Susan M.; Coates, John D.

    2002-01-01

    Adsorption of heavy metals and radionuclides (HMR) onto iron and manganese oxides has long been recognized as an important reaction for the immobilization of these compounds. However, in environments containing elevated concentrations of these HMR the adsorptive capacity of the iron and manganese oxides may well be exceeded, and the HMR can migrate as soluble compounds in aqueous systems. Here we demonstrate the potential of a bioremediative strategy for HMR stabilization in reducing environments based on the recently described anaerobic nitrate-dependent Fe(II) oxidation by Dechlorosoma species. Bio-oxidation of 10 mM Fe(II) and precipitation of Fe(III) oxides by these organisms resulted in rapid adsorption and removal of 55 μM uranium and 81 μM cobalt from solution. The adsorptive capacity of the biogenic Fe(III) oxides was lower than that of abiotically produced Fe(III) oxides (100 μM for both metals), which may have been a result of steric hindrance by the microbial cells on the iron oxide surfaces. The binding capacity of the biogenic oxides for different heavy metals was indirectly correlated to the atomic radius of the bound element. X-ray absorption spectroscopy indicated that the uranium was bound to the biogenically produced Fe(III) oxides as U(VI) and that the U(VI) formed bidentate and tridentate inner-sphere complexes with the Fe(III) oxide surfaces. Dechlorosoma suillum oxidation was specific for Fe(II), and the organism did not enzymatically oxidize U(IV) or Co(II). Small amounts (less than 2.5 μM) of Cr(III) were reoxidized by D. suillum; however, this appeared to be inversely dependent on the initial concentration of the Cr(III). The results of this study demonstrate the potential of this novel approach for stabilization and immobilization of HMR in the environment. PMID:12039723

  3. Positron sources for Linear Colliders

    SciTech Connect

    Gai Wei; Liu Wanming

    2009-09-02

    Positron beams have many applications and there are many different concepts for positron sources. In this paper, only positron source techniques for linear colliders are covered. In order to achieve high luminosity, a linear collider positron source should have a high beam current, high beam energy, small emittance and, for some applications, a high degree of beam polarization. There are several different schemes presently being developed around the globe. Both the differences between these schemes and their common technical challenges are discussed.

  4. Spectral characterization, cyclic voltammetry, morphology, biological activities and DNA cleaving studies of amino acid Schiff base metal(II) complexes.

    PubMed

    Neelakantan, M A; Rusalraj, F; Dharmaraja, J; Johnsonraja, S; Jeyakumar, T; Sankaranarayana Pillai, M

    2008-12-15

    Metal complexes are synthesized with Schiff bases derived from o-phthalaldehyde (opa) and amino acids viz., glycine (gly) l-alanine (ala), l-phenylalanine (pal). Metal ions coordinate in a tetradentate or hexadentate manner with these N(2)O(2) donor ligands, which are characterized by elemental analysis, molar conductance, magnetic moments, IR, electronic, (1)H NMR and EPR spectral studies. The elemental analysis suggests the stoichiometry to be 1:1 (metal:ligand). Based on EPR studies, spin-Hamiltonian and bonding parameters have been calculated. The g-values calculated for copper complexes at 300K and in frozen DMSO (77K) indicate the presence of the unpaired electron in the dx2-y2 orbital. The evaluated metal-ligand bonding parameters showed strong in-plane sigma- and pi-bonding. X-ray diffraction (XRD) and scanning electron micrography (SEM) analysis provide the crystalline nature and the morphology of the metal complexes. The cyclic voltammograms of the Cu(II)/Mn(II)/VO(II) complexes investigated in DMSO solution exhibit metal centered electroactivity in the potential range -1.5 to +1.5V. The electrochemical data obtained for Cu(II) complexes explains the change of structural arrangement of the ligand around Cu(II) ions. The biological activity of the complexes has been tested on eight bacteria and three fungi. Cu(II) and Ni(II) complexes show an increased activity in comparison to the controls. The metal complexes of opapal Schiff base were evaluated for their DNA cleaving activities with calf-thymus DNA (CT DNA) under aerobic conditions. Cu(II) and VO(II) complexes show more pronounced activity in presence of the oxidant.

  5. Spectral characterization, cyclic voltammetry, morphology, biological activities and DNA cleaving studies of amino acid Schiff base metal(II) complexes

    NASA Astrophysics Data System (ADS)

    Neelakantan, M. A.; Rusalraj, F.; Dharmaraja, J.; Johnsonraja, S.; Jeyakumar, T.; Sankaranarayana Pillai, M.

    2008-12-01

    Metal complexes are synthesized with Schiff bases derived from o-phthalaldehyde (opa) and amino acids viz., glycine (gly) L-alanine (ala), L-phenylalanine (pal). Metal ions coordinate in a tetradentate or hexadentate manner with these N 2O 2 donor ligands, which are characterized by elemental analysis, molar conductance, magnetic moments, IR, electronic, 1H NMR and EPR spectral studies. The elemental analysis suggests the stoichiometry to be 1:1 (metal:ligand). Based on EPR studies, spin-Hamiltonian and bonding parameters have been calculated. The g-values calculated for copper complexes at 300 K and in frozen DMSO (77 K) indicate the presence of the unpaired electron in the d orbital. The evaluated metal-ligand bonding parameters showed strong in-plane σ- and π-bonding. X-ray diffraction (XRD) and scanning electron micrography (SEM) analysis provide the crystalline nature and the morphology of the metal complexes. The cyclic voltammograms of the Cu(II)/Mn(II)/VO(II) complexes investigated in DMSO solution exhibit metal centered electroactivity in the potential range -1.5 to +1.5 V. The electrochemical data obtained for Cu(II) complexes explains the change of structural arrangement of the ligand around Cu(II) ions. The biological activity of the complexes has been tested on eight bacteria and three fungi. Cu(II) and Ni(II) complexes show an increased activity in comparison to the controls. The metal complexes of opapal Schiff base were evaluated for their DNA cleaving activities with calf-thymus DNA (CT DNA) under aerobic conditions. Cu(II) and VO(II) complexes show more pronounced activity in presence of the oxidant.

  6. Control of metal-ion composition in the synthesis of ternary II-II'-VI nanoparticles by using a mixed-metal cluster precursor approach.

    PubMed

    DeGroot, Marty W; Rösner, Harald; Corrigan, John F

    2006-02-01

    The ternary molecular nanoclusters [Zn(x)Cd(10-x)Se4(SePh)12(PnPr3)4] (x = 1.8, 1 a; x = 2.6, 1 b) were employed as single-source precursors for the synthesis of high-quality hexagonal Zn(x)Cd(1-x)Se nanocrystals. The tellurium clusters [Zn(x)Cd(10-x)Te4(TePh)12(PnPr3)4] (x = 1.8, 2 a; x = 2.6, 2 b) are equally convenient precursors for the synthesis cubic Zn(x)Cd(1-x)E nanoparticles. The thermolysis of the cluster molecules in hexadecylamine provides an efficient system in which the inherent metal-ion stoichiometry of the clusters is retained in the nanocrystalline products, whilst also affording control of particle size within the 2-5 nm range. In all cases, the nanoparticles are monodisperse, and luminescence spectra exhibit emission energies close to the absorption edge. Analysis of the optical spectra and X-ray diffraction patterns of these materials indicates a metal-ion concentration gradient within the structures of the nanocrystals, with Zn(II) ions predominantly located near the surface of the particles.

  7. THE JHU-SDSS METAL ABSORPTION LINE CATALOG: REDSHIFT EVOLUTION AND PROPERTIES OF Mg II ABSORBERS

    SciTech Connect

    Zhu Guangtun; Menard, Brice

    2013-06-20

    We present a generic and fully automatic method aimed at detecting absorption lines in the spectra of astronomical objects. The algorithm estimates the source continuum flux using a dimensionality reduction technique and nonnegative matrix factorization, and then detects and identifies metal absorption lines. We apply it to a sample of {approx}10{sup 5} quasar spectra from the Sloan Digital Sky Survey and compile a sample of {approx}40,000 Mg II- and Fe II-absorber systems, spanning the redshift range 0.4 < z < 2.3. The corresponding catalog is publicly available. We study the statistical properties of these absorber systems and find that the rest equivalent width distribution of strong Mg II absorbers follows an exponential distribution at all redshifts, confirming previous studies. Combining our results with recent near-infrared observations of Mg II absorbers, we introduce a new parameterization that fully describes the incidence rate of these systems up to z {approx} 5. We find the redshift evolution of strong Mg II absorbers to be remarkably similar to the cosmic star formation history over 0.4 < z < 5.5 (the entire redshift range covered by observations), suggesting a physical link between these two quantities.

  8. Removal of heavy metal Cu(II) in simulated aquaculture wastewater by modified palygorskite.

    PubMed

    Cao, Jia-Shun; Wang, Cheng; Fang, Fang; Lin, Jun-Xiong

    2016-12-01

    Palygorskite (PAL) is a good heavy metal adsorbent due to its high surface area, low cost, and environmentally compatibility. But the natural PAL has limited its adsorption capacity and selectivity. In this study, a cost-effective and readily-generated absorbent, l-threonine-modified palygorskite (L-PAL), was used and its performance for Cu(II) removal in simulated aquaculture wastewater was evaluated. After preparation, L-PAL was characterized by using Fourier transform infrared spectroscopy, scanning electron microscope, energy dispersive X-ray spectroscopy, X-ray diffractometer, X-ray photoelectron spectroscopy, transmission electron microscopy and thermogravimetric analysis. The impacts of pH, adsorbent dosage, contact time, and initial Cu(II) concentration on the adsorption capacity of L-PAL were examined. The Cu(II) adsorption capacity on L-PAL was enhanced almost 10 times than that of raw PAL. The adsorption isotherms of Cu(II) fit the Langmuir isotherms, and the adsorption kinetics was dominated by the pseudo-second-order model. The thermodynamic parameters at four temperatures were calculated, which indicated that the adsorption was spontaneous and endothermic. The adsorption mechanism involves complexation, chelation, electrostatic attraction, and micro-precipitation. Furthermore, L-PAL is shown to have a high regeneration capacity. These results indicate that L-PAL is a cheap and promising absorbent for Cu(II) removal and hold potential to be used for aquaculture wastewater treatment. Copyright © 2016 Elsevier Ltd. All rights reserved.

  9. Synthesis, characterization, and anti-cancer activity of emodin-Mn(II) metal complex.

    PubMed

    Yang, Li; Tan, Jun; Wang, Bo-Chu; Zhu, Lian-Cai

    2014-12-01

    To synthesize and characterize a novel metal complex of Mn (II) with emodin, and evaluate its anti-cancer activity. The elemental analyses, IR, UV-vis, atomic absorption spectroscopy, TG-DSC, (1)H NMR, and (13)C NMR data were used to characterize the structure of the complex. The cytotoxicity of the complex against the human cancer cell lines HepG2, HeLa, MCF-7, B16, and MDA-MB-231 was tested by the MTT assay and flow cytometry. Emodin was coordinated with Mn(II) through the 9-C=O and 1-OH, and the general formula of the complex was Mn(II) (emodin)2·2H2O. In studies of the cytotoxicity, the complex exhibited significant activity, and the IC50 values of the complex against five cancer cell lines improved approximately three-fold compared with those of emodin. The complex could induce cell morphological changes, decrease the percentage of viability, and induce G0/G1 phase arrest and apoptosis in cancer cells. The coordination of emodin with Mn(II) can improve its anticancer activity, and the complex Mn(II) (emodin)2·2H2O could be studied further as a promising anticancer drug.

  10. Lifetime of combustion-generated environmentally persistent free radicals on Zn(II)O and other transition metal oxides.

    PubMed

    Vejerano, Eric; Lomnicki, Slawo; Dellinger, Barry

    2012-10-26

    Previous studies indicated that Environmentally Persistent Free Radicals (EPFRs) are formed in the post-flame, cool zone of combustion. They result from the chemisorption of gas-phase products of incomplete combustion (particularly hydroxyl- and chlorine-substituted aromatics) on Cu(II)O, Fe(III)(2)O(3), and Ni(II)O domains of particulate matter (fly ash or soot particles). This study reports our detailed laboratory investigation on the lifetime of EPFRs on Zn(II)O/silica surface. Similarly, as in the case of other transition metals, chemisorption of the adsorbate on the Zn(II)O surface and subsequent transfer of electron from the adsorbate to the metal forms a surface-bound EPFR and a reduced metal ion center. The EPFRs are stabilized by their interaction with the metal oxide domain surface. The half-lives of EPFRs formed on Zn(II)O domains were the longest observed among the transition metal oxides studied and ranged from 3 to 73 days. These half-lives were an order of magnitude longer than those formed on nickel and iron oxides, and were 2 orders of magnitude longer compared to the EPFRs on copper oxide which have half-lives only on the order of hours. The longest-lived radicals on Zn(II)O correspond to the persistency in ambient air particles of almost a year. The half-life of EPFRs was found to correlate with the standard reduction potential of the associated metal.

  11. Low-metallicity Young Clusters in the Outer Galaxy. II. Sh 2-208

    NASA Astrophysics Data System (ADS)

    Yasui, Chikako; Kobayashi, Naoto; Saito, Masao; Izumi, Natsuko

    2016-05-01

    We obtained deep near-infrared images of Sh 2-208, one of the lowest-metallicity H ii regions in the Galaxy, [O/H] = -0.8 dex. We detected a young cluster in the center of the H ii region with a limiting magnitude of K = 18.0 mag (10σ), which corresponds to a mass detection limit of ˜0.2 M⊙. This enables the comparison of star-forming properties under low metallicity with those of the solar neighborhood. We identified 89 cluster members. From the fitting of the K-band luminosity function (KLF), the age and distance of the cluster are estimated to be ˜0.5 Myr and ˜4 kpc, respectively. The estimated young age is consistent with the detection of strong CO emission in the cluster region and the estimated large extinction of cluster members (AV ˜ 4-25 mag). The observed KLF suggests that the underlying initial mass function (IMF) of the low-metallicity cluster is not significantly different from canonical IMFs in the solar neighborhood in terms of both high-mass slope and IMF peak (characteristic mass). Despite the very young age, the disk fraction of the cluster is estimated at only 27% ± 6%, which is significantly lower than those in the solar metallicity. Those results are similar to Sh 2-207, which is another star-forming region close to Sh 2-208 with a separation of 12 pc, suggesting that their star-forming activities in low-metallicity environments are essentially identical to those in the solar neighborhood, except for the disk dispersal timescale. From large-scale mid-infrared images, we suggest that sequential star formation is taking place in Sh 2-207, Sh 2-208, and the surrounding region, triggered by an expanding bubble with a ˜30 pc radius.

  12. Anti-oxidant, in vitro, in vivo anti-inflammatory activity and antiproliferative activity of mefenamic acid and its metal complexes with manganese(II), cobalt(II), nickel(II), copper(II) and zinc(II).

    PubMed

    Kovala-Demertzi, Dimitra; Hadjipavlou-Litina, Dimitra; Staninska, Malgorzata; Primikiri, Alexandra; Kotoglou, Chronis; Demertzis, Mavroudis A

    2009-06-01

    Some new complexes of mefenamic acid with potentially interesting biological activity are described. The complexes of mefenamic acid [Mn(mef)(2)(H(2)O)(2)], 1, [Co(mef)(2)(H(2)O)(2)], 2, [Ni(mef)(2)(H(2)O)(2)], 3, [Cu(mef)(2)(H(2)O)](2), 4 and [Zn(mef)(2)], 5, were prepared by the reaction of mefenamic acid, a potent anti-inflammatory drug with metal salts. Optical and infrared spectral data of these new complexes are reported. Monomeric six-coordinated species were isolated in the solid state for Mn(II), Ni(II) and Co(II), dimeric five-coordinated for Cu(II) and monomeric four-coordinated for Zn(II). In DMF or CHCl(3) solution the coordination number is retained and the coordinated molecules of water are replaced by solvent molecules. The anti-oxidant properties of the complexes were evaluated using the 1,1-diphenyl-2-picrylhydrazyl, DPPH, free radical scavenging assay. The scavenging activities of the complexes were measured and compared with those of the free drug and vitamin C. We have explored their ability to inhibit soybean lipoxygenase, beta-glucuronidase and trypsin- induced proteolysis. The complex [Mn(mef)(2)(H(2)O)(2)] exhibits the highest antioxidant activity and the highest inhibitory effect against the soybean lipogygenase (LOX), properties that are not demonstrated by mefenamic acid. Their inhibitory effects on rat paw edema induced by Carrageenan was studied and compared with those of mefenamic acid. The complex [Zn(mef)(2)] exhibited a strong inhibitory effect at 0.1 mmol/Kg B.W. (81.5 +/- 1.3% inhibition), superior to the inhibition induced by mefenamic acid at the same dose (61.5 +/- 2.3% inhibition). Mefenamic acid and its metal complexes have been evaluated for antiproliferative activity in vitro against the cells of three human cancer cell lines: MCF-7 (human breast cancer cell line), T24 (bladder cancer cell line), A-549 (non-small cell lung carcinoma) and a mouse fibroblast L-929 cell line. The copper(II) complex displays against T24, MCF-7

  13. Early evaluation of tumour metabolic response using [18F]fluorodeoxyglucose and positron emission tomography:a pilot study following the phase II chemotherapy schedule for temozolomide in recurrent high-grade gliomas

    PubMed Central

    Brock, C S; Young, H; O'Reilly, S M; Matthews, J; Osman, S; Evans, H; Newlands, E S; Price, P M

    2000-01-01

    Quantitation of metabolic changes in tumours may provide an objective measure of clinical and subclinical response to anticancer therapy. This pilot study assesses the value of quantitation of metabolic rate of glucose (MRGlu) measured in mmol min−1ml−1to assess early subclinical response to therapy in a relatively non-responsive tumour. Nine patients receiving the CRC Phase II study schedule of temozolomide were assessed with [18F]fluorodeoxyglucose ([18F]FDG) dynamic positron emission tomography (PET) scans prior to and 14 days after treatment with temozolomide given as 750–1000 mg m−2over 5 days every 28 days. Tumour MRGlu was calculated and compared with objective response at 8 weeks. Pretreatment MRGlu was higher in responders than non-responders. The responding patient group had a greater than 25% reduction in MRGlu in regions of high focal tumour uptake (HFU). Whole tumour changes in MRGlu did not correlate with response. Percentage change in HFU standardized uptake value (SUV) did discriminate the responding from the non-responding patients, but not as well as with MRGlu. Large differences also occurred in the normal brain SUV following treatment. Thus, MRGlu appeared to be a more sensitive discriminator of response than the simplified static SUV analysis. Changes in MRGlu may reflect the degree of cell kill following chemotherapy and so may provide an objective, quantitative subclinical measure of response to therapy. © 2000 Cancer Research Campaign PMID:10682673

  14. Synergistic Effects of Metals in a Promising Ru(II) -Pt(II) Assembly for a Combined Anticancer Approach: Theoretical Exploration of the Photophysical Properties.

    PubMed

    Alberto, Marta E; Russo, Nino; Adamo, Carlo

    2016-06-27

    Ru(II) -Pt(II) complexes are a class of bioactive molecules of interest as anticancer agents that combine a light-absorbing chromophore with a cisplatin-like unit. The results of a DFT and TDDFT investigation of a Ru(II) complex and its conjugate with a cis-PtCl2 moiety reveal that a synergistic effect of the metals makes the assembly a promising multitarget anticancer drug. Inspection of type I and type II photoreactions and spin-orbit coupling computations reveals that the cis-PtCl2 moiety improves the photophysical properties of the Ru(II) chromophore, ensuring efficient singlet oxygen generation and making the assembly suitable for photodynamic therapy. At the same time, the Ru(II) chromophore promotes a new alternative activation mechanism of the Pt(II) ligand via a triplet metal-to-ligand charge transfer ((3) MLCT) state, before reaching the biological target. The importance of the supramolecular architecture is accurately derived, opening interesting new perspectives on the use of bimetallic Ru(II) -Pt(II) assemblies in a combined anticancer approach. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Positron excitation of neon

    NASA Technical Reports Server (NTRS)

    Parcell, L. A.; Mceachran, R. P.; Stauffer, A. D.

    1990-01-01

    The differential and total cross section for the excitation of the 3s1P10 and 3p1P1 states of neon by positron impact were calculated using a distorted-wave approximation. The results agree well with experimental conclusions.

  16. The Japanese Positron Factory

    NASA Astrophysics Data System (ADS)

    Okada, S.; Sunaga, H.; Kaneko, H.; Takizawa, H.; Kawasuso, A.; Yotsumoto, K.; Tanaka, R.

    1999-06-01

    The Positron Factory has been planned at Japan Atomic Energy Research Institute (JAERI). The factory is expected to produce linac-based monoenergetic positron beams having world-highest intensities of more than 1010e+/sec, which will be applied for R&D of materials science, biotechnology and basic physics & chemistry. In this article, results of the design studies are demonstrated for the following essential components of the facilities: 1) Conceptual design of a high-power electron linac with 100 MeV in beam energy and 100 kW in averaged beam power, 2) Performance tests of the RF window in the high-power klystron and of the electron beam window, 3) Development of a self-driven rotating electron-to-positron converter and the performance tests, 4) Proposal of multi-channel beam generation system for monoenergetic positrons, with a series of moderator assemblies based on a newly developed Monte Carlo simulation and the demonstrative experiment, 5) Proposal of highly efficient moderator structures, 6) Conceptual design of a local shield to suppress the surrounding radiation and activation levels.

  17. Effect of biofilm coatings at metal-oxide/water interfaces I: Pb(II) and Zn(II) partitioning and speciation at Shewanella oneidensis/metal-oxide/water interfaces

    NASA Astrophysics Data System (ADS)

    Wang, Yingge; Gélabert, Alexandre; Michel, F. Marc; Choi, Yongseong; Gescher, Johannes; Ona-Nguema, Georges; Eng, Peter J.; Bargar, John R.; Farges, Francois; Spormann, Alfred M.; Brown, Gordon E.

    2016-09-01

    Microbial biofilms are often present as coatings on metal-oxide surfaces in natural and industrial environments and may induce significant changes in the partitioning behavior and speciation of aqueous metal ions, which in turn can impact their transport and fate. In this study, long-period X-ray standing wave-fluorescence yield (LP-XSW-FY) spectroscopy was used to measure under in situ conditions the partitioning of aqueous Pb(II) and Zn(II) between multilayer Shewanella oneidensis MR-1 biofilms and highly polished, oriented single-crystal surfaces of α-Al2O3 and α-Fe2O3 as a function of metal-ion concentration and time at pH 6.0. We show that after 3-h exposure time, Pb(II) binds preferentially to the α-Al2O3 (1-102) and α-Fe2O3 (0 0 0 1) surfaces at low Pb concentration ([Pb] = 10-7 M) and then increasingly partitions into the biofilm coatings at higher concentrations (10-6 to 10-4 M). In contrast, Zn(II) partitions preferentially into the biofilm coating for both surfaces at all Zn concentrations studied (10-7 to 10-4 M). In comparison, the α-Al2O3 (0 0 0 1) surface has a low affinity for both Pb(II) and Zn(II), and the biofilm coatings are the dominant sink for both ions. These findings suggest that in the presence of S. oneidensis biofilm coatings, α-Al2O3 (0 0 0 1) is the least reactive surface for Pb(II) and Zn(II) compared to α-Al2O3 (1-102) and α-Fe2O3 (0 0 0 1). They also show that Zn(II) has a lower affinity than Pb(II) for reactive sites on α-Al2O3 (1-102) and α-Fe2O3 (0 0 0 1) at [Me(II)] of 10-7 M; at 10-5 M, the bulk of the metal ions partition into the biofilm coatings. At longer exposure times (20-24 h), both Pb(II) and Zn(II) increasingly partition to the metal-oxide surfaces at [Me(II)] = 10-5 M and pH 6.0, indicating possible reaction/diffusion-controlled sorption processes. Pb LIII-edge and Zn K-edge grazing-incidence extended X-ray absorption fine structure (GI-EXAFS) measurements suggest that both Pb(II) and Zn(II) ions may be

  18. Effect of biofilm coatings at metal-oxide/water interfaces I: Pb(II) and Zn(II) partitioning and speciation at Shewanella oneidensis/metal-oxide/water interfaces

    DOE PAGES

    Wang, Yingge; Gelabert, Alexandre; Michel, F. Marc; ...

    2016-05-30

    Microbial biofilms are often present as coatings on metal-oxide surfaces in natural and industrial environments and may induce significant changes in the partitioning behavior and speciation of aqueous metal ions, which in turn can impact their transport and fate. In this study, long-period X-ray standing wave-fluorescence yield (LP-XSW-FY) spectroscopy was used to measure under in situ conditions the partitioning of aqueous Pb(II) and Zn(II) between multilayer Shewanella oneidensis MR-1 biofilms and highly polished, oriented single-crystal surfaces of α-Al2O3 and α-Fe2O3 as a function of metal-ion concentration and time at pH 6.0. We show that after 3-h exposure time, Pb(II) bindsmore » preferentially to the alpha-Al2O3 (1-102) and α-Fe2O3 (0001) surfaces at low Pb concentration ([Pb] = 10–7 M) and then increasingly partitions into the biofilm coatings at higher concentrations (10–6 to 10–4 M). In contrast, Zn(II) partitions preferentially into the biofilm coating for both surfaces at all Zn concentrations studied (10–7 to 10–4 M). In comparison, the α-Al2O3 (0001) surface has a low affinity for both Pb(II) and Zn(II), and the biofilm coatings are the dominant sink for both ions. These findings suggest that in the presence of S. oneidensis biofilm coatings, α-Al2O3 (0001) is the least reactive surface for Pb(II) and Zn(II) compared to α-Al2O3 (1-102) and α-Fe2O3 (0001). They also show that Zn(II) has a lower affinity than Pb(II) for reactive sites on α-Al2O3 (1-102) and α-Fe2O3 (0001) at [Me(II)] of 10–7 M; at 10–5 M, the bulk of the metal ions partition into the biofilm coatings. At longer exposure times (20-24 h), both Pb(II) and Zn(II) increasingly partition to the metal-oxide surfaces at [Me(II)] = 10–5 M and pH 6.0, indicating possible reaction/diffusion-controlled sorption processes. Pb L-III-edge and Zn K-edge grazing-incidence extended X-ray absorption fine structure (GI-EXAFS) measurements suggest that both Pb(II) and Zn(II

  19. Decontamination of solutions containing Cu(II) and ligands tartrate, glycine and quadrol using metallic iron.

    PubMed

    Gyliene, Ona; Vengris, Tomas; Nivinskiene, Ona; Binkiene, Rima

    2010-03-15

    Decontamination of solutions containing Cu(II) complexes with tartrate, glycine and quadrol (N,N,N'N'-tetrakis(2-hydroxypropyl)ethylenediamine) using metallic iron depends on pH and proceeds best in mildly acidic solutions. Cu(II) is completely removed from all solutions containing the ligands investigated. The degree of ligand removal from solutions considerably differs. Tartrate is relatively rapidly and completely removed from solutions. A complete removal of glycine is prolonged. The removal of quadrol from solutions using metallic iron is negligible. Electrochemical investigations showed that tartrate and glycine have inhibitory influence on anodic dissolution of iron at pH 2 and enhance it at pH 4. Quadrol does not exhibit any significant influence on iron dissolution. Chemical analysis and FT-IR investigations have shown that the content of organic compounds is the greatest in the precipitate formed in solutions containing tartrate, while it is considerably lower in glycine containing solutions. The precipitate formed in quadrol-containing solutions during the treatment with metallic iron contains only negligible amount of organics. (c) 2009 Elsevier B.V. All rights reserved.

  20. Red Sea Atlantis II brine pool nitrilase with unique thermostability profile and heavy metal tolerance.

    PubMed

    Sonbol, Sarah A; Ferreira, Ari J S; Siam, Rania

    2016-02-11

    Nitrilases, which hydrolyze nitriles in a one-step reaction into carboxylic acids and ammonia, gained increasing attention because of the abundance of nitrile compounds in nature and their use in fine chemicals and pharmaceutics. Extreme environments are potential habitats for the isolation and characterization of extremozymes including nitrilases with unique resistant properties. The Red Sea brine pools are characterized by multitude of extreme conditions. The Lower Convective Layer (LCL) of the Atlantis II Deep Brine Pool in the Red Sea is characterized by elevated temperature (68 °C), high salt concentrations (250 ‰), anoxic conditions and high heavy metal concentrations. We identified and isolated a nitrilase from the Atlantis II Deep Brine Pool in the Red Sea LCL. The isolated 338 amino-acid nitrilase (NitraS-ATII) is part of a highly conserved operon in different bacterial phyla with indiscernible function. The enzyme was cloned, expressed and purified. Characterization of the purified NitraS-ATII revealed its selectivity towards dinitriles, which suggests a possible industrial application in the synthesis of cyanocarboxylic acids. Moreover, NitraS-ATII showed higher thermal stability compared to a closely related nitrilase, in addition to its observed tolerance towards high concentrations of selected heavy metals. This enzyme sheds light on evolution of microbes in the Atlantis II Deep LCL to adapt to the diverse extreme environment and can prove to be valuable in bioremediation processes.

  1. Categoric prediction of metal ion mechanisms in the active sites of 17 select type II restriction endonucleases.

    PubMed

    Advani, Sonia; Mishra, Puneet; Dubey, Shraddha; Thakur, Samridhi

    2010-11-12

    Recently determined crystal structures of type II restriction endonucleases have produced a plethora of information on the basis for target site sequence selectivity. The positioning and role of metal ions in DNA recognition sites might reflect important properties of protein-DNA interaction. Although acidic and basic groups in the active sites can be identified, and in some cases divalent-metal binding sites delineated, a convincing picture clarifying the way in which the attacking hydroxide ion is generated, and the leaving group stabilized, has not been elucidated for any of the enzymes. We have examined the interatomic distances between metal ions and proposed key catalytic residues in the binding sites of seventeen type II restriction endonucleases whose crystal structures are documented in literature. The summary and critical evaluation of structural assignments and predictions made earlier have been useful to group these enzymes. All the enzymes used for this study have been categorized on the basis of the number of metal ions identified in their crystal structures. Among 17 experimentally characterized (not putative) type II REases, whose apparently full-length sequences are available in REBASE, we predict 8 (47%) to follow the single metal ion mechanism, 5 to follow the two metal ion mechanism, 2, the three metal ion mechanism, 1, the four metal ion mechanism and 1 the six metal ion mechanism. Copyright © 2010 Elsevier Inc. All rights reserved.

  2. 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.

  3. Synthesis, spectroscopy, and characterization of some bis-nicotinamide metal(II) dihalide complexes

    NASA Astrophysics Data System (ADS)

    Ataç, Ahmet; Yurdakul, Şenay; Berber, Savas

    2011-10-01

    We report synthesis of six new bis-nicotinamide metal(II) dihalide complexes [M(nia) 2Cl 2; M = Mn, Co; nia:nicotinamide, M(nia) 2Br 2; M = Mn, Hg; M(nia) 2I 2; M = Cd, Cu], and their characterization by combining infrared spectroscopy with density functional theory (DFT) calculations. Infrared spectra indicate that ring-nitrogen is the active donor cite, and the atomic structure of the complexes is determined to be polymeric octahedral or distorted polymeric octahedral. Spin polarized electronic ground state is obtained for Mn, Co, and Cu halide complexes. The colors of the complexes also support the conclusion of octahedral coordination around the metal atoms, in agreement with DFT results.

  4. The Reduction of Aqueous Metal Species on the Surfaces of Fe(II)-Containing Oxides: The Role of Surface Passivation

    USGS Publications Warehouse

    White, A.F.; Peterson, M.L.

    1998-01-01

    The reduction of aqueous transition metal species at the surfaces of Fe(II)- containing oxides has important ramifications in predicting the transport behavior in ground water aquifers. Experimental studies using mineral suspensions and electrodes demonstrate that structural Fe(II) heterogeneously reduces aqueous ferric, cupric, vanadate and chromate ions on magnetite and ilmenite surfaces. The rates of metal reduction on natural oxides is strongly dependent on the extent of surface passivation and redox conditions in the weathering environment. Synchrotron studies show that surface oxidation of Fe(II)-containing oxide minerals decreases their capacity for Cr(VI) reduction at hazardous waste disposal sites.

  5. Metal ion containing CXCR4 chemokine receptor antagonists: nickel(II) complexes of configurationally restricted macrocycles

    PubMed Central

    Smith, Rachel; Huskens, Dana; Daelemans, Dirk; Mewis, Ryan E.; Garcia, Courtney D.; Cain, Amy N.; Carder Freeman, TaRynn N.; Pannecouque, Christophe; De Clercq, Erik; Schols, Dominique; Hubin, Timothy J.

    2012-01-01

    Tetraazamacrocyclic complexes of transition metals provide useful units for incorporating multiple coordination interactions into a single protein binding molecule. They can be designed with available sites for protein interactions with donor atom containing amino acid side chains or have labile ligands such as H2O allowing facile exchange. Three configurationally restricted nickel(II) cyclam complexes with either one or two macrocyclic rings were synthesised and their ability to abrogate the CXCR4 chemokine receptor signalling process was assessed (IC50 = 8320, 194 and 14 nM). Analogues were characterised crystallographically to determine the geometric parameters of acetate binding as a model for aspartate. The most active nickel(II) compound was tested in several anti-HIV assays against representative viral strains showing highly potent EC50 values down to 13 nM against CXCR4 using viruses with no observed cellular cytotoxicity (CC50 > 125 μM). PMID:2289289

  6. A porous Cu(II) metal-organic framework: Synthesis, crystal structure and gas adsorption properties

    NASA Astrophysics Data System (ADS)

    Li, Wu-Wu; Guo, Ying; Zhang, Wei-Hong

    2017-09-01

    Presented here is a new porous Cu(II) metal-organic framework, namely [Cu(tdc)(H2O)]n·n(DMA) (1 H2tdc = thiophene-2,5-dicarboxylic acid, DMA = N,N‧-dimethylacetamide), which was obtained by the self-assembly reaction of CuCl2 and H2tdc under solvothermal conditions. Single crystal X-ray diffraction analysis revealed that compound 1 features a 3D porous framework based on 1D chain structure subunits, and the 1D rhombohedral channels are occupied by the lattice DMA molecules. Gas adsorption studies reveal that this desolvated sample exhibit high uptake capacity for light hydrocarbons.

  7. Amino acid positron emission tomography to monitor chemotherapy response and predict seizure control and progression-free survival in WHO grade II gliomas.

    PubMed

    Roelcke, Ulrich; Wyss, Matthias T; Nowosielski, Martha; Rudà, Roberta; Roth, Patrick; Hofer, Silvia; Galldiks, Norbert; Crippa, Flavio; Weller, Michael; Soffietti, Riccardo

    2016-05-01

    Patients with WHO grade II glioma may respond to chemotherapy that is currently not standardized regarding timing and treatment duration. Metabolic changes during chemotherapy may precede structural tumor volume reductions. We therefore compared time courses of amino acid PET and MRI responses to temozolomide (TMZ) and assessed whether responses correlated with seizure control and progression-free survival (PFS). PET and MRI were performed before and during TMZ chemotherapy. Tumor volumes were calculated using regions-of-interest analysis. Amino acid uptake was also quantified as metabolically active tumor volume and tumor-to-cerebellum uptake ratio. One hundred twenty-five PET and 125 MRI scans from 33 patients were analyzed. Twenty-five patients showed metabolic responses that exhibited an exponential time course with a 25% reduction of the active volume on average after 2.3 months. MRI responses followed a linear course with a 25% reduction after 16.8 months. Reduction of metabolically active tumor volumes, but not reduction of PET uptake ratios or MRI tumor volumes, correlated with improved seizure control following chemotherapy (P = .012). Receiver-operating-characteristic curve analysis showed that a decrease of the active tumor volume of ≥80.5% predicts a PFS of ≥60 months (P = .018) and a decrease of ≥64.5% a PFS of ≥48 months (P = .037). Amino acid PET is superior to MRI for evaluating TMZ responses in WHO grade II glioma patients. The response delay between both imaging modalities favors amino acid PET for individually tailoring the duration of chemotherapy. Additional studies should investigate whether this personalized approach is appropriate with regard to outcome. © The Author(s) 2015. Published by Oxford University Press on behalf of the Society for Neuro-Oncology. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

  8. Amino acid positron emission tomography to monitor chemotherapy response and predict seizure control and progression-free survival in WHO grade II gliomas

    PubMed Central

    Roelcke, Ulrich; Wyss, Matthias T.; Nowosielski, Martha; Rudà, Roberta; Roth, Patrick; Hofer, Silvia; Galldiks, Norbert; Crippa, Flavio; Weller, Michael; Soffietti, Riccardo

    2016-01-01

    Background Patients with WHO grade II glioma may respond to chemotherapy that is currently not standardized regarding timing and treatment duration. Metabolic changes during chemotherapy may precede structural tumor volume reductions. We therefore compared time courses of amino acid PET and MRI responses to temozolomide (TMZ) and assessed whether responses correlated with seizure control and progression-free survival (PFS). Methods PET and MRI were performed before and during TMZ chemotherapy. Tumor volumes were calculated using regions-of-interest analysis. Amino acid uptake was also quantified as metabolically active tumor volume and tumor-to-cerebellum uptake ratio. Results One hundred twenty-five PET and 125 MRI scans from 33 patients were analyzed. Twenty-five patients showed metabolic responses that exhibited an exponential time course with a 25% reduction of the active volume on average after 2.3 months. MRI responses followed a linear course with a 25% reduction after 16.8 months. Reduction of metabolically active tumor volumes, but not reduction of PET uptake ratios or MRI tumor volumes, correlated with improved seizure control following chemotherapy (P = .012). Receiver-operating-characteristic curve analysis showed that a decrease of the active tumor volume of ≥80.5% predicts a PFS of ≥60 months (P = .018) and a decrease of ≥64.5% a PFS of ≥48 months (P = .037). Conclusions Amino acid PET is superior to MRI for evaluating TMZ responses in WHO grade II glioma patients. The response delay between both imaging modalities favors amino acid PET for individually tailoring the duration of chemotherapy. Additional studies should investigate whether this personalized approach is appropriate with regard to outcome. PMID:26578622

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

    PubMed Central

    Luczak, Michal W.; Zhitkovich, Anatoly

    2013-01-01

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

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

    PubMed

    Luczak, Michal W; Zhitkovich, Anatoly

    2013-12-01

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

  11. Cardiac positron emission tomography

    SciTech Connect

    Geltman, E.M.

    1985-12-01

    Positron emission tomography (PET) is a new technique for noninvasively assessing myocardial metabolism and perfusion. It has provided new insight into the dynamics of myocardial fatty acid and glucose metabolism in normal subjects, patients with ischemic heart disease and those with cardiomyopathies, documenting regionally depressed fatty acid metabolism during myocardial ischemia and infarction and spatial heterogeneity of fatty acid metabolism in patients with cardiomyopathy. Regional myocardial perfusion has been studied with PET using water, ammonia and rubidium labeled with positron emitters, permitting the noninvasive detection of hypoperfused zones at rest and during vasodilator stress. With these techniques the relationship between perfusion and the metabolism of a variety of substrates has been studied. The great strides that have been made in developing faster high-resolution instruments and producing new labeled intermediates indicate the promise of this technique for facilitating an increase in the understanding of regional metabolism and blood flow under normal and pathophysiologic conditions. 16 references, 9 figures, 2 tables.

  12. Generation of monoenergetic positrons

    SciTech Connect

    Hulett, L.D. Jr.; Dale, J.M.; Miller, P.D. Jr.; Moak, C.D.; Pendyala, S.; Triftshaeuser, W.; Howell, R.H.; Alvarez, R.A.

    1983-01-01

    Many experiments have been performed in the generation and application of monoenergetic positron beams using annealed tungsten moderators and fast sources of /sup 58/Co, /sup 22/Na, /sup 11/C, and LINAC bremstrahlung. This paper will compare the degrees of success from our various approaches. Moderators made from both single crystal and polycrystal tungsten have been tried. Efforts to grow thin films of tungsten to be used as transmission moderators and brightness enhancement devices are in progress.

  13. IrII(ethene): metal or carbon radical? Part II: oxygenation via iridium or direct oxygenation at ethene?

    PubMed

    Hetterscheid, Dennis G H; Bens, Mariska; de Bruin, Bas

    2005-03-07

    Treatment of [(Me3tpa)IrII(ethene)]2+ (Me(3)tpa =N,N,N-tri(6-methyl-2-pyridylmethyl)amine)(1(2+)) with dioxygen in weakly coordinating solvents results in formation of [(Me3tpa)IrIII(ethene)(superoxo)]2+ (4a2+). In the presence of DMPO (DMPO = 5,5-dimethyl-2-pyrrolidine-1-oxide) DMPO is substituted for ethene, and subsequently oxidized to DMPOX by the superoxo fragment to give [(Me3tpa)IrIII(DMPOX)]2+ (7(2+); DMPOX = 5,5-dimethyl-2-pyrrolidone-1-oxide). In acetonitrile, in the absence of DMPO, oxygenation of 1(2+) to [(Me3tpa)IrIII(formylmethyl)(MeCN)]2+ (2(2+)) is observed. In the presence of DMPO the formation of 2(2+) and 7(2+) is competing. Oxygenation of 1(2+) to 2(2+) may proceed via 4a(2+), involving an insertion mechanism at the metal. However, a mechanism based on olefin ligand non-innocence seems a reasonable alternative. This involves formation of acetonitrile adduct [(Me3tpa)Ir(ethene)(MeCN)]2+ (3(2+)), which has a significant metalla-ethyl radical (IrIII-CH2CH2*) character, allowing attack of 3O2 directly at the ethene ligand. Both pathways are discussed on the basis of experimental observations and DFT geometry optimizations.

  14. Synthesis, spectroscopic characterization, DFT optimization and biological activities of Schiff bases and their metal (II) complexes

    NASA Astrophysics Data System (ADS)

    Rauf, Abdur; Shah, Afzal; Munawar, Khurram Shahzad; Khan, Abdul Aziz; Abbasi, Rashda; Yameen, Muhammad Arfat; Khan, Asad Muhammad; Khan, Abdur Rahman; Qureshi, Irfan Zia; Kraatz, Heinz-Bernhard; Zia-ur-Rehman

    2017-10-01

    A Novel Schiff base, 3-(((4-chlorophenyl)imino)methyl)benzene-1,2-diol (HL1) was successfully synthesized along with a structurally similar Schiff base 3-(((4-bromophenyl)imino)methyl)benzene-1,2-diol (HL2). Both the Schiff bases were used to synthesize their zinc (II) and cobalt (II) complexes. These compounds were characterized by FTIR, 1H NMR, 13C NMR and elemental analysis. Metal complexes were confirmed by TGA. Crystals of Schiff bases were also characterized by X-ray analysis and experimental parameters were found in line with the theoretical parameters. Quantum mechanical approach was also used to fine useful structural parameters and to ensure the geometry of metal complexes. The photometric behaviors of all the synthesized compounds were investigated in a wide pH range using BR buffers. The appearance of isosbestic points indicated the existence of Schiff bases in more than one isomeric form. Moreover, these compounds were screened for enzyme inhibition; antibacterial, cytotoxic and in vivo antidiabetic activities and compounds were found active against one or other activity. Results indicate that ZnL22 is a good inhibitor of alkaline phosphatase enzyme and possess highest potential against diabetes, blood cholesterol level and cancer cells. This effort just provides preliminary data for some biological properties. Further investigations are required to precisely determine mechanistic pathways of their use towards drug development.

  15. Synthesis, spectral characterization and biological activity of metal(II) complexes with 4-aminoantipyrine derivatives.

    PubMed

    Leelavathy, C; Arul Antony, S

    2013-09-01

    Novel metal(II) complexes derived from furfurylidene-4-aminoantipyrine and 2-aminobenzothiazole were synthesized and characterized by spectroscopic (IR, (1)H NMR, UV-Vis., ESR and DART-MS) and other analytical methods. IR spectral studies indicate the binding sites of the ligand with the metal ion. Molar conductance data and magnetic susceptibility measurements provide evidence for monomeric and neutral nature of the complexes. The X band ESR spectrum of the Cu(II) complex at 300 and 77K was recorded. The electrochemical behaviour of the complexes in MeCN at 298 K was studied. Thermal studies of the ligand and its complexes show the presence of coordinated water in the complexes. The grain size of the complex was calculated by Scherrer formula using powder XRD. The surface morphology of the complexes was studied using SEM. The in vitro biological screening of the ligand and its complexes were tested against bacterial species S. aureus, E. coli, K. pneumoniae, P. vulgaris and P. aeruginosa and fungal species A. niger, R. stolonifer, A. flavus, R. bataicola and C. albicans. The DNA binding and cleavage activity of the ligand and its complexes were studied. Super oxide dismutase (SOD) activities of the ligand and its complexes have also been measured.

  16. The effect of TiB II powder on microstructure and mechanical behavior of Al-TiB II metal matrix composites

    NASA Astrophysics Data System (ADS)

    Ehsani, N.; Abdi, F.; Abdizadeh, H.; Baharvandi, H. R.

    2007-07-01

    Cast metal matrix composites produced by stir casting method have cost advantages over the composites made by other techniques. In this study, the influence of TiB II volume fraction on microstructure and mechanical properties of Al-TiB II composites has been investigated. Three different volume fractions (5, 10, and 15) of particulate TiB II were used in production of aluminum matrix composite at 750°C. Microstructure of the composites was studied by Scanning Electron Microscopy (SEM). Composition of the samples was analyzed by X-ray diffraction (XRD). The mechanical properties of the specimens (hardness and tensile strength) were also measured. Experimental results show that the microstructure is remarkably affected by TiB II addition level. The mechanical properties were considerably improved by addition of TiB II particles.

  17. Applications and advances of positron beam spectroscopy: appendix a

    SciTech Connect

    Howell, R. H., LLNL

    1997-11-05

    Over 50 scientists from DOE-DP, DOE-ER, the national laboratories, academia and industry attended a workshop held on November 5-7, 1997 at Lawrence Livermore National Laboratory jointly sponsored by the DOE-Division of Materials Science, The Materials Research Institute at LLNL and the University of California Presidents Office. Workshop participants were charged to address two questions: Is there a need for a national center for materials analysis using positron techniques and can the capabilities at Lawrence Livermore National Laboratory serve this need. To demonstrate the need for a national center the workshop participants discussed the technical advantages enabled by high positron currents and advanced measurement techniques, the role that these techniques will play in materials analysis and the demand for the data. There were general discussions lead by review talks on positron analysis techniques, and their applications to problems in semiconductors, polymers and composites, metals and engineering materials, surface analysis and advanced techniques. These were followed by focus sessions on positron analysis opportunities in these same areas. Livermore now leads the world in materials analysis capabilities by positrons due to developments in response to demands of science based stockpile stewardship. There was a detailed discussion of the LLNL capabilities and a tour of the facilities. The Livermore facilities now include the worlds highest current beam of keV positrons, a scanning pulsed positron microprobe under development capable of three dimensional maps of defect size and concentration, an MeV positron beam for defect analysis of large samples, and electron momentum spectroscopy by positrons. This document is a supplement to the written summary report. It contains a complete schedule, list of attendees and the vuegraphs for the presentations in the review and focus sessions.

  18. Positron lifetime spectrometer using a DC positron beam

    DOEpatents

    Xu, Jun; Moxom, Jeremy

    2003-10-21

    An entrance grid is positioned in the incident beam path of a DC beam positron lifetime spectrometer. The electrical potential difference between the sample and the entrance grid provides simultaneous acceleration of both the primary positrons and the secondary electrons. The result is a reduction in the time spread induced by the energy distribution of the secondary electrons. In addition, the sample, sample holder, entrance grid, and entrance face of the multichannel plate electron detector assembly are made parallel to each other, and are arranged at a tilt angle to the axis of the positron beam to effectively separate the path of the secondary electrons from the path of the incident positrons.

  19. Clinical applications with the HIDAC positron camera

    NASA Astrophysics Data System (ADS)

    Frey, P.; Schaller, G.; Christin, A.; Townsend, D.; Tochon-Danguy, H.; Wensveen, M.; Donath, A.

    1988-06-01

    A high density avalanche chamber (HIDAC) positron camera has been used for positron emission tomographic (PET) imaging in three different human studies, including patients presenting with: (I) thyroid diseases (124 cases); (II) clinically suspected malignant tumours of the pharynx or larynx (ENT) region (23 cases); and (III) clinically suspected primary malignant and metastatic tumours of the liver (9 cases, 19 PET scans). The positron emitting radiopharmaceuticals used for the three studies were Na 124I (4.2 d half-life) for the thyroid, 55Co-bleomycin (17.5 h half-life) for the ENT-region and 68Ga-colloid (68 min half-life) for the liver. Tomographic imaging was performed: (I) 24 h after oral Na 124I administration to the thyroid patients, (II) 18 h after intraveneous administration of 55Co-bleomycin to the ENT patients and (III) 20 min following the intraveneous injection of 68Ga-colloid to the liver tumour patients. Three different imaging protocols were used with the HIDAC positron camera to perform appropriate tomographic imaging in each patient study. Promising results were obtained in all three studies, particularly in tomographic thyroid imaging, where a significant clinical contribution is made possible for diagnosis and therapy planning by the PET technique. In the other two PET studies encouraging results were obtained for the detection and precise localisation of malignant tumour disease including an estimate of the functional liver volume based on the reticulo-endothelial-system (RES) of the liver, obtained in vivo, and the three-dimensional display of liver PET data using shaded graphics techniques. The clinical significance of the overall results obtained in both the ENT and the liver PET study, however, is still uncertain and the respective role of PET as a new imaging modality in these applications is not yet clearly established. To appreciate the clinical impact made by PET in liver and ENT malignant tumour staging needs further investigation

  20. Negative interference of metal (II) ions with nucleotide excision repair in human cell-free extracts.

    PubMed

    Calsou, P; Frit, P; Bozzato, C; Salles, B

    1996-12-01

    Inhibition of the nucleotide excision repair (NER) process is believed to cause the potentiation of the genotoxic and mutagenic effects of DNA damaging agents like UV-light or cisplatin by metal ions. However, the precise underlying molecular mechanism of this phenomenon is still unknown. Using in vitro assays, we have determined the potential interference of several metal (II) ions with the lesion recognition and strand incision/displacement steps of the NER mechanism, independently from the DNA polymerization step. When combinations of an optimal Mg2+ concentration and concentrations of various metal ions in a range from 0.1 to 1 mM were tested, all combinations, with Mn2+ and Ni2+ excepted, inhibited specifically the incision repair activity by human protein extracts. There was a good correlation for Cd2+, Co2+, Fe2+, Cu2+, Hg2+, Pb2+ and Zn2+ between an inhibiting effect on the incision activity and a reduced protein binding activity to a damaged DNA probe as assessed by gel mobility shift assay.

  1. Pseudo Order Kinetics Model to Predict the Adsorption Interaction of Corn-Stalk Adsorbent Surface with Metal Ion Adsorbate Cu (II) and Fe (II)

    NASA Astrophysics Data System (ADS)

    Haryanto, B.; Singh, W. B.; Barus, E. S.; Ridho, A.; Rawa, M. R.

    2017-01-01

    The adsorption process using cornstalk as adsorbent was used to remove the single metal ion such as copper ion and cadmium ion. The adsorption kinetics of each contaminant then used to predict the interaction type of metal ion on surface of corn stalk by calculating pseudo order 1st and 2nd. The identification type as chemically or physically interaction was predicted from the quality of r2 by plotting the adsorption capacity (q) and time (t). The r2 were 0.01 and 0.99 for pseudo order 1st and 2nd respectively for Fe (II). The r2 were 0.26 and 0.999 for pseudo order 1st and 2nd respectively for Cu (II). The result of adsorption interaction of metal ion and surface function of corn stalk is chemical type. SEM/EDX confirmed the Cu2+ presence on cornstalk surface.

  2. Liquid metal reactor deactivation as applied to the experimental breeder reactor - II.

    SciTech Connect

    Earle, O. K.; Michelbacher, J. A.; Pfannenstiel, D. F.; Wells, P. B.

    1999-05-28

    The Experimental Breeder Reactor-II (EBR-II) at Argonne National Laboratory-West (ANL-W) was shutdown in September, 1994. This sodium cooled reactor had been in service since 1964, and by the US Department of Energy (DOE) mandate, was to be placed in an industrially and radiologically safe condition for ultimate decommissioning. The deactivation of a liquid metal reactor presents unique concerns. The first major task associated with the project was the removal of all fueled assemblies. In addition, sodium must be drained from systems and processed for ultimate disposal. Residual quantities of sodium remaining in systems must be deactivated or inerted to preclude future hazards associated with pyrophoricity and generation of potentially explosive hydrogen gas. A Sodium Process Facility (SPF) was designed and constructed to react the elemental sodium from the EBR-II primary and secondary systems to sodium hydroxide for disposal. This facility has a design capacity to allow the reaction of the complete inventory of sodium at ANL-W in less than two years. Additional quantities of sodium from the Fermi-1 reactor are also being treated at the SPF.

  3. Raman study of in vivo synthesized Zn(II)-metallothionein complexes: structural insight into metal clusters and protein folding.

    PubMed

    Torreggiani, Armida; Domènech, Jordi; Atrian, Sílvia; Capdevila, Mercè; Tinti, Anna

    2008-12-01

    Metallothioneins (MTs) are metal-chelating peptides that play an active role in zinc homeostasis. The participation of metal ligands other than cysteines and the presence of secondary structure elements in metal-MT complexes are fairly unknown, especially in nonvertebrate MTs. Here, four Zn(II) complexes of invertebrate MTs (mollusc, insect, nematode, and echinoderm) and the Zn(II)-MT complex of the mammalian MT1 isoform, heterologously synthesized in E. coli, were studied by analytic and spectroscopic techniques. By Raman and circular dichroism spectroscopy, new structural informations were obtained. The five analyzed MT isoforms consist largely of beta-turns with the near exclusion of alpha-helical segments. Raman spectroscopy was revealed as an useful tool, providing information about the state of the cysteine sulfur atoms (metal coordinated and oxidized), the participation of histidine in metal coordination, and the molecular environment of tyrosine residues. In all the five Zn(II)-MT studied samples, acid-labile sulfide anions were found as nonproteic ligands, since sulfide-containing and sulfide-devoid species coexisted in the corresponding preparations. Significantly, Raman bands useful as markers of sulfide bridging ligands were identified. Overall, this work illustrates how the combination of analytical and spectroscopic techniques can be a very informative approach for the analysis of in vivo-synthesized metal-MT complexes, providing new data on the metal binding behavior of MTs from the most diverse organisms.

  4. Mn Oxide Biogenesis and Metal Sequestration in the Presence of Co (II) and Cu (II) By Bacillus SG-1 Bacterial Spores

    SciTech Connect

    Bayat, N

    2004-02-05

    Mn oxides play an important role in degrading contaminants and cycling nutrients in soils and natural waters. The process in which Mn (II) oxidizes to form MnO, is slow; however, Bacillus SG-1 bacterial spores can catalyze the process and allow it to proceed up to five orders of magnitude faster. This experiment explored the affects of co-ion metal concentrations on Biogenic Mn oxide production and their ability to sequester metal cations. Spore solutions were prepared with different ratios of Metal (II): Mn (II) added over a three-week period; this was done separately for Co (II) and Cu (II). The copper solutions were analyzed with ICP/AES to check for the amount of copper and manganese left in solution after biogenic MnO, production. ICP/AES was used to analyze the ratio of Co: Mn in spores where Co was the co-ion metal. Observations showed very little dissolved Cu and Mn exist in solutions with low copper concentrations, but a large amount of Cu and Mn were left in solutions where higher Cu concentrations were used. This shows that high Cu concentration inhibits biogenic Mn oxide production and Cu sequestration. For the experiments with Co as the co-ion metal, it was observed that the ratio of Co: Mn in the spores is relatively similar to the ratios added; however, an exception to this rule was experiments where high concentrations of Co were used. The inconsistency in Co: Mn ratios at high Co concentrations showed that high Co concentrations also inhibit biogenic Mn oxide production.

  5. Nonlinear Color--Metallicity Relations of Globular Clusters. VI. On Calcium II Triplet Based Metallicities of Globular Clusters in Early-type Galaxies

    NASA Astrophysics Data System (ADS)

    Chung, Chul; Yoon, Suk-Jin; Lee, Sang-Yoon; Lee, Young-Wook

    2016-02-01

    The metallicity distribution function of globular clusters (GCs) in galaxies is a key to understanding galactic formation and evolution. The calcium II triplet (CaT) index has recently become a popular metal abundance indicator thanks to its sensitivity to GC metallicity. Here we revisit and assess the reliability of CaT as a metallicity indicator using our new stellar population synthesis simulations based on empirical high-resolution fluxes. The model shows that the CaT strength of old (>10 Gyr) GCs is proportional to [Fe/H] below -0.5. In the modest metal-rich regime, however, CaT does not increase anymore with [Fe/H] due to the little contribution from coolest red giant stars to the CaT absorption. The nonlinear nature of the color-CaT relation is confirmed by the observations of GCs in nearby early-type galaxies. This indicates that the CaT should be used carefully when deriving metallicities of metal-rich stellar populations. Our results offer an explanation for the observed sharp difference between the color and CaT distributions of GCs in the same galaxies. We take this as an analogy to the view that metallicity-color and metallicity-Lick index nonlinearity of GCs is primarily responsible for their observed “bimodal” distributions of colors and absorption indices.

  6. Adsorption of Ni(II) and Cd(II) from water by novel chelating sponge and the effect of alkali-earth metal ions on the adsorption.

    PubMed

    Cheng, Cheng; Wang, Jinnan; Yang, Xin; Li, Aimin; Philippe, Corvini

    2014-01-15

    Novel chelating sponge (PVA-M-H) was prepared with polyvinyl alcohol by graft polymerization and nucleophilic substitution. E.A, SEM, FT-IR, (13)CNMR, and XPS analyses were used to characterize PVA-M-H. The equilibrium adsorption capacities of PVA-M-H for Ni(II) and Cd(II) were 65.39 and 125.11mgg(-1), respectively. Within the range of 278-308K, the adsorption enthalpy changes of Ni(II) and Cd(II) on PVA-M-H were about 36.39-37.72kJmol(-1), and the free energy were about -13.27 to -1.7kJmol(-1). Both pseudo-first- and -second-order equations fit the adsorption kinetic curves well, and the initial adsorption rates of Ni(II) and Cd(II) onto PVA-M-H were 17.83 and 34.81mg (gmin)(-1), respectively. Although the presence of alkali-earth metal ions in solution decreased Ni(II) and Cd(II) removal, PVA-M-H still retained more than 60 and 80% of its adsorption capacity even as the concentration of Ca(2+) and Mg(2+) was up to 10mmolL(-1), respectively. Both 0.1M HCl and 0.1M EDTA solution could desorb Ni(II) and Cd(II) from PVA-M-H effectively, and the adsorption capacity of PVA-M-H for Ni(II) and Cd(II) could still maintain more than 90% level without any obvious decrease at the fifth cycle.

  7. Studies on metal-organic frameworks of Cu(II) with isophthalate linkers for hydrogen storage.

    PubMed

    Yan, Yong; Yang, Sihai; Blake, Alexander J; Schröder, Martin

    2014-02-18

    Hydrogen (H2) is a promising alternative energy carrier because of its environmental benefits, high energy density, and abundance. However, development of a practical storage system to enable the "Hydrogen Economy" remains a huge challenge. Metal-organic frameworks (MOFs) are an important class of crystalline coordination polymers constructed by bridging metal centers with organic linkers. MOFs show promise for H2 storage owing to their high surface area and tuneable properties. In this Account, we summarize our research on novel porous materials with enhanced H2 storage properties and describe frameworks derived from 3,5-substituted dicarboxylates (isophthalates) that serve as versatile molecular building blocks for the construction of a range of interesting coordination polymers with Cu(II) ions. We synthesized a series of materials by connecting linear tetracarboxylate linkers to {Cu(II)2} paddlewheel moieties. These materials exhibit high structural stability and permanent porosity. Varying the organic linker modulates the pore size, geometry, and functionality to control the overall H2 adsorption. Our top-performing material in this series has a H2 storage capacity of 77.8 mg g(-1) at 77 K, 60 bar. H2 adsorption at low, medium, and high pressures correlates with the isosteric heat of adsorption, surface area, and pore volume, respectively. Another series, using tribranched C3-symmetric hexacarboxylate ligands with Cu(II), gives highly porous (3,24)-connected frameworks incorporating {Cu(II)2} paddlewheels. Increasing the length of the hexacarboxylate struts directly tunes the porosity of the resultant material from micro- to mesoporosity. These materials show exceptionally high H2 uptakes owing to their high surface area and pore volume. The first member of this family reported adsorbs 111 mg g(-1) of H2, or 55.9 g L(-1), at 77 K, 77 bar, while at 77 K, 1 bar, the material adsorbs 2.3 wt % H2. We and others have since achieved enhanced H2 adsorption in these

  8. Synthesis, characterization and biological activity of ferrocene-based Schiff base ligands and their metal (II) complexes

    NASA Astrophysics Data System (ADS)

    Liu, Yu-Ting; Lian, Gui-Dan; Yin, Da-Wei; Su, Bao-Jun

    Metal (II) complexes derived from S-benzyl-N-(1-ferrocenyl-3-(4-methylbenzene)acrylketone) dithiocarbazate; HL1, S-benzyl-N-(1-ferrocenyl-3-(4-chlorobenzene)acrylketone)dithiocarbazate; HL2, all the compounds were characterized using various spectroscopic techniques. The molar conductance data revealed that the chelates were non-electrolytes. IR spectra showed that the Schiff bases were coordinated to the metal ions in a bidentate manner with N, S donor sites. The ligands and their metal complexes have been screened for in vitro antibacterial, antifungal properties. The result of these studies have revealed that zinc (II) complexes 6 and 13 of both the ligands and copper (II) complexes 9 of the HL2 were observed to be the most active against all bacterial strains, antifungal activity was overall enhanced after complexation of the ligands.

  9. Synthesis, characterization and biological activity of ferrocene-based Schiff base ligands and their metal (II) complexes.

    PubMed

    Liu, Yu-Ting; Lian, Gui-Dan; Yin, Da-Wei; Su, Bao-Jun

    2013-01-01

    Metal (II) complexes derived from S-benzyl-N-(1-ferrocenyl-3-(4-methylbenzene)acrylketone) dithiocarbazate; HL(1), S-benzyl-N-(1-ferrocenyl-3-(4-chlorobenzene)acrylketone)dithiocarbazate; HL(2), all the compounds were characterized using various spectroscopic techniques. The molar conductance data revealed that the chelates were non-electrolytes. IR spectra showed that the Schiff bases were coordinated to the metal ions in a bidentate manner with N, S donor sites. The ligands and their metal complexes have been screened for in vitro antibacterial, antifungal properties. The result of these studies have revealed that zinc (II) complexes 6 and 13 of both the ligands and copper (II) complexes 9 of the HL(2) were observed to be the most active against all bacterial strains, antifungal activity was overall enhanced after complexation of the ligands.

  10. Laser Created Relativistic Positron Jets

    SciTech Connect

    Chen, H; Wilks, S C; Meyerhofer, D D; Bonlie, J; Chen, C D; Chen, S N; Courtois, C; Elberson, L; Gregori, G; Kruer, W; Landoas, O; Mithen, J; Murphy, C; Nilson, P; Price, D; Scheider, M; Shepherd, R; Stoeckl, C; Tabak, M; Tommasini, R; Beiersdorder, P

    2009-10-08

    Electron-positron jets with MeV temperature are thought to be present in a wide variety of astrophysical phenomena such as active galaxies, quasars, gamma ray bursts and black holes. They have now been created in the laboratory in a controlled fashion by irradiating a gold target with an intense picosecond duration laser pulse. About 10{sup 11} MeV positrons are emitted from the rear surface of the target in a 15 to 22-degree cone for a duration comparable to the laser pulse. These positron jets are quasi-monoenergetic (E/{delta}E {approx} 5) with peak energies controllable from 3-19 MeV. They have temperatures from 1-4 MeV in the beam frame in both the longitudinal and transverse directions. Positron production has been studied extensively in recent decades at low energies (sub-MeV) in areas related to surface science, positron emission tomography, basic antimatter science such as antihydrogen experiments, Bose-Einstein condensed positronium, and basic plasma physics. However, the experimental tools to produce very high temperature positrons and high-flux positron jets needed to simulate astrophysical positron conditions have so far been absent. The MeV temperature jets of positrons and electrons produced in our experiments offer a first step to evaluate the physics models used to explain some of the most energetic phenomena in the universe.

  11. Changes in the adsorbate dipole layer with changing d-filling of the metal (II) (Co, Ni, Cu) phthalocyanines on Au(111).

    PubMed

    Xiao, Jie; Dowben, Peter A

    2009-02-04

    In combined photoemission and inverse photoemission spectroscopy studies, we observe changes in the metal phthalocyanine molecular orbital offsets with respect to the conducting gold substrate Fermi level, with the changing d-electron filling of the metal (II) (Co, Ni, Cu) phthalocyanines. The implication is that the interfacial dipole layer depends upon the choice of metal (Co, Ni, Cu) centers within the metal (II) phthalocyanines adsorbed on Au(111).

  12. A plasmid containing the human metallothionein II gene can function as an antibody-assisted electrophoretic biosensor for heavy metals.

    PubMed

    Wooten, Dennis C; Starr, Clarise R; Lyon, Wanda J

    2016-01-01

    Different forms of heavy metals affect biochemical systems in characteristic ways that cannot be detected with typical metal analysis methods like atomic absorption spectrometry. Further, using living systems to analyze interaction of heavy metals with biochemical systems can be laborious and unreliable. To generate a reliable easy-to-use biologically-based biosensor system, the entire human metallothionein-II (MT-II) gene was incorporated into a plasmid (pUC57-MT) easily replicated in Escherichia coli. In this system, a commercial polyclonal antibody raised against human metal-responsive transcription factor-1 protein (MTF-1 protein) could modify the electrophoretic migration patterns (i.e. cause specific decreases in agarose gel electrophoretic mobility) of the plasmid in the presence or absence of heavy metals other than zinc (Zn). In the study here, heavy metals, MTF-1 protein, and polyclonal anti-MTF-1 antibody were used to assess pUC57-MT plasmid antibody-assisted electrophoretic mobility. Anti-MTF-1 antibody bound both MTF-1 protein and pUC57-MT plasmid in a non-competitive fashion such that it could be used to differentiate specific heavy metal binding. The results showed that antibody-inhibited plasmid migration was heavy metal level-dependent. Zinc caused a unique mobility shift pattern opposite to that of other metals tested, i.e. Zn blocked the antibody ability to inhibit plasmid migration, despite a greatly increased affinity for DNA by the antibody when Zn was present. The Zn effect was reversed/modified by adding MTF-1 protein. Additionally, antibody inhibition of plasmid mobility was resistant to heat pre-treatment and trypsinization, indicating absence of residual DNA extraction-resistant bacterial DNA binding proteins. DNA binding by anti-DNA antibodies may be commonly enhanced by xenobiotic heavy metals and elevated levels of Zn, thus making them potentially effective tools for assessment of heavy metal bioavailability in aqueous solutions and

  13. Metal-pyrazolyl diazine interaction: synthesis, structure and electrochemistry of binuclear transition metal(II) complexes derived from an 'end-off' compartmental Schiff base ligand.

    PubMed

    Budagumpi, Srinivasa; Revankar, Vidyanand K

    2010-09-15

    Pyrazolyl diazine (mu-NN) bridged late first row transition metal(II) complexes have been prepared by the interaction of metal(II) chlorides with an 'end-off' compartmental Schiff base ligand. The ligand system has a strong diazine bridging component and obtained as a condensation product between 1H-pyrazole-3,5-dicarbohydrazide and 3-acetylcoumarin in absolute ethanol. All synthesized compounds are characterized on the basis of various spectral and analytical techniques. Complexes are found to be non-electrolytes and monomeric in nature. The magnetic exchange interactions are very weak because of the more electronegative exogenous chloride, though diazine bridging group bring metal centers in a close proximity.

  14. Synthesis, characterization, electrochemical and biological studies on some metal(II) Schiff base complexes containing quinoxaline moiety

    NASA Astrophysics Data System (ADS)

    Justin Dhanaraj, Chellaian; Johnson, Jijo

    2014-01-01

    Novel Co(II), Ni(II), Cu(II) and Zn(II) complexes of Schiff base derived from quinoxaline-2,3-(1,4H)-dione and 4-aminoantipyrine (QDAAP) were synthesized. The ligand and its complexes were characterized by elemental analyses, molar conductance, magnetic susceptibility measurements, FTIR, UV-Vis., mass and 1H NMR spectral studies. The X band ESR spectrum of the Cu(II) complex at 300 and 77 K were also recorded. Thermal studies of the ligand and its complexes show the presence of coordinated water in the Ni(II) and Zn(II) complexes. The coordination behavior of QDAAP is also discussed. All the complexes are mono nuclear and tetrahedral geometry was found for Co(II) complex. For the Ni(II) and Zn(II) complexes, octahedral geometry was assigned and for the Cu(II) complex, square planar geometry has been suggested. The grain size of the complexes was estimated using powder XRD. The surface morphology of the compounds was studied using SEM analysis. Electrochemical behavior of the synthesized complexes in DMF at room temperature was investigated by cyclic voltammetry. The in vitro biological screening of QDAAP and its metal complexes were tested against bacterial species Staphylococcus aureus, Escherichia coli and Pseudomonas aeruginosa. The fungal species include Aspergillus niger, Aspergillus flavus and Candida albicans. The DNA cleavage activity of QDAAP and its complexes were also discussed.

  15. Synthesis, characterization, electrochemical and biological studies on some metal(II) Schiff base complexes containing quinoxaline moiety.

    PubMed

    Dhanaraj, Chellaian Justin; Johnson, Jijo

    2014-01-24

    Novel Co(II), Ni(II), Cu(II) and Zn(II) complexes of Schiff base derived from quinoxaline-2,3-(1,4H)-dione and 4-aminoantipyrine (QDAAP) were synthesized. The ligand and its complexes were characterized by elemental analyses, molar conductance, magnetic susceptibility measurements, FTIR, UV-Vis., mass and (1)H NMR spectral studies. The X band ESR spectrum of the Cu(II) complex at 300 and 77K were also recorded. Thermal studies of the ligand and its complexes show the presence of coordinated water in the Ni(II) and Zn(II) complexes. The coordination behavior of QDAAP is also discussed. All the complexes are mono nuclear and tetrahedral geometry was found for Co(II) complex. For the Ni(II) and Zn(II) complexes, octahedral geometry was assigned and for the Cu(II) complex, square planar geometry has been suggested. The grain size of the complexes was estimated using powder XRD. The surface morphology of the compounds was studied using SEM analysis. Electrochemical behavior of the synthesized complexes in DMF at room temperature was investigated by cyclic voltammetry. The in vitro biological screening of QDAAP and its metal complexes were tested against bacterial species Staphylococcus aureus, Escherichia coli and Pseudomonas aeruginosa. The fungal species include Aspergillus niger, Aspergillus flavus and Candida albicans. The DNA cleavage activity of QDAAP and its complexes were also discussed.

  16. Positron Emission Tomography (PET)

    SciTech Connect

    Welch, M.J.

    1990-01-01

    Positron emission tomography (PET) assesses biochemical processes in the living subject, producing images of function rather than form. Using PET, physicians are able to obtain not the anatomical information provided by other medical imaging techniques, but pictures of physiological activity. In metaphoric terms, traditional imaging methods supply a map of the body's roadways, its, anatomy; PET shows the traffic along those paths, its biochemistry. This document discusses the principles of PET, the radiopharmaceuticals in PET, PET research, clinical applications of PET, the cost of PET, training of individuals for PET, the role of the United States Department of Energy in PET, and the futures of PET. 22 figs.

  17. Positron Emission Tomography (PET)

    DOE R&D Accomplishments Database

    Welch, M. J.

    1990-01-01

    Positron emission tomography (PET) assesses biochemical processes in the living subject, producing images of function rather than form. Using PET, physicians are able to obtain not the anatomical information provided by other medical imaging techniques, but pictures of physiological activity. In metaphoric terms, traditional imaging methods supply a map of the body's roadways, its, anatomy; PET shows the traffic along those paths, its biochemistry. This document discusses the principles of PET, the radiopharmaceuticals in PET, PET research, clinical applications of PET, the cost of PET, training of individuals for PET, the role of the United States Department of Energy in PET, and the futures of PET.

  18. Quantum positron acoustic waves

    SciTech Connect

    Metref, Hassina; Tribeche, Mouloud

    2014-12-15

    Nonlinear quantum positron-acoustic (QPA) waves are investigated for the first time, within the theoretical framework of the quantum hydrodynamic model. In the small but finite amplitude limit, both deformed Korteweg-de Vries and generalized Korteweg-de Vries equations governing, respectively, the dynamics of QPA solitary waves and double-layers are derived. Moreover, a full finite amplitude analysis is undertaken, and a numerical integration of the obtained highly nonlinear equations is carried out. The results complement our previously published results on this problem.

  19. Fabrication of hollow metal oxide nanocrystals by etching cuprous oxide with metal(ii) ions: approach to the essential driving force

    NASA Astrophysics Data System (ADS)

    Sohn, Jong Hwa; Cha, Hyun Gil; Kim, Chang Woo; Kim, Do Kyoung; Kang, Young Soo

    2013-10-01

    Hollow metal oxide nanocrystals were prepared by etching cuprous oxide with metal ions and were applied as photoelectrodes. As a hard template, polyvinylpyrrolidone stabilized cuprous oxide (PVP-Cu2O) and non-stabilized cuprous oxide (nPVP-Cu2O) were synthesized by a precipitation method. Hollow iron oxide and cobalt oxide nanocrystals with a truncated octahedral morphology were fabricated by an etching reaction with transition metal(ii) ions (Fe2+ or Co2+). In the etching reaction process, a cationic exchange reaction occurs between the divalent metal ion and Cu+ due to the higher Lewis acidity. Facet selective etching of cuprous oxide has been observed during the ionic exchange reaction of Cu+ and O2- ions in PVP-Cu2O complexes with transition metal(ii) ions (Fe2+ or Co2+) at the surface of a (110) facet. Amorphous states of hollow metal oxide products were annealed to form α-Fe2O3 (hematite) and Co3O4 and their crystal structure was examined with X-ray diffraction and HR-TEM. The optical absorption behavior of semiconductor nanocrystals was measured with UV-vis spectroscopy to define band gap energy. The hollow hematite structure has a 2.08 eV band gap and Co3O4 (Co(ii,iii) oxide) has a 1.80 eV indirect band gap. Using these hollow nanocrystals, a metal oxide monolayer film was fabricated with a secondary growth approach and was studied for its photocatalytic properties.Hollow metal oxide nanocrystals were prepared by etching cuprous oxide with metal ions and were applied as photoelectrodes. As a hard template, polyvinylpyrrolidone stabilized cuprous oxide (PVP-Cu2O) and non-stabilized cuprous oxide (nPVP-Cu2O) were synthesized by a precipitation method. Hollow iron oxide and cobalt oxide nanocrystals with a truncated octahedral morphology were fabricated by an etching reaction with transition metal(ii) ions (Fe2+ or Co2+). In the etching reaction process, a cationic exchange reaction occurs between the divalent metal ion and Cu+ due to the higher Lewis acidity

  20. Copper(II)-based metal affinity chromatography for the isolation of the anticancer agent bleomycin from Streptomyces verticillus culture.

    PubMed

    Gu, Jiesi; Codd, Rachel

    2012-10-01

    The glycopeptide-based bleomycins are structurally complex natural products produced by Streptomyces verticillus used in combination therapy against testicular and other cancers. Bleomycin has a high affinity towards a range of transition metal ions with the 1:1 Fe(II) complex relevant to its mechanism of action in vivo and the 1:1 Cu(II) complex relevant to its production from culture. The affinity between Cu(II) and bleomycin was the underlying principle for using Cu(II)-based metal affinity chromatography in this work to selectively capture bleomycin from crude S. verticillus culture. A solution of standard bleomycin was retained at a binding capacity of 300 nmol mL(-1) on a 1-mL bed volume of Cu(II)-loaded iminodiacetate (IDA) resin at pH 9 via the formation of the heteroleptic immobilized complex [Cu(IDA)(bleomycin)]. Bleomycin was eluted from the resin at pH 5 as the metal-free ligand under conditions where pK(a) (IDA)II)-loaded IDA resin at pH 9 in 50% yield from bleomycin-containing S. verticillus culture that was pre-processed using XAD-2 resin to remove endogenously bound Cu(II). The approximate 25-fold purification of bleomycin from complex culture supernatant under aqueous conditions in a single step demonstrates the potential of Cu(II)-based metal affinity chromatography as a green chemistry platform for streamlined access to this high-value therapeutic agent.

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

    PubMed

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

    2009-01-01

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

  2. A microporous Zn(II)-MOF with open metal sites: structure and selective adsorption properties.

    PubMed

    Zheng, Xiaofang; Huang, Yumei; Duan, Jingui; Wang, Chenggang; Wen, Lili; Zhao, Jinbo; Li, Dongfeng

    2014-06-14

    A three-dimensional microporous framework, Zn(II)-MOF [Zn(HPyImDC)(DMA)]n (1) (H3PyImDC = 2-(pyridine-4-yl)-1H-4,5-imidazoledicarboxylic, DMA = N,N'-dimethylacetamide), with open metal sites and small-sized pores, exhibits excellent selective capture of CO2 over N2 and CH4 at 273 K, as well as alcohols from water. The excellent CO2 adsorption selectivity of 1 allows its potential use in the capture of CO2 from industrial flue gas or the removal of CO2 from natural gas. More interestingly, compound represents the rare case of porous materials separating propanol isomers, which may be caused by the relative flexibility of the linear n-propanol considering that both n-propanol and i-propanol have similar kinetic diameters.

  3. Nickel(II) oxide nanostructure derived from metal-organic frameworks and its adsorption capability

    NASA Astrophysics Data System (ADS)

    Ru, Shuai; Xu, Lina; Xiao, Hongping; Li, Xinhua

    2016-11-01

    Nanosized nickel(II) oxide (NiO) was obtained by oxidation of ([(Ni2(nic)4(H2O)] n , nic = nicotinic acid), a metal-organic framework (MOF), at 350 °C. Nanosized NiO assembled to form block NiO having a mesoporous structure similar to the porous structure of activated carbon block. This bulk NiO exhibits excellent adsorbing capability, with 100% higher adsorption capacities than the [(Ni2(nic)4(H2O)] n MOF towards toluene and water steam; therefore, it can find potential application in gas adsorption. Moreover, this bulk NiO can be synthesized using a facile, environment-friendly, and cost-effective method, and exhibits excellent hydrothermal stability, which is not commonly observed for MOFs.

  4. HIGH-RESOLUTION SPECTROSCOPY OF EXTREMELY METAL-POOR STARS IN THE LEAST EVOLVED GALAXIES: BOÖTES II

    SciTech Connect

    Ji, Alexander P.; Frebel, Anna; Simon, Joshua D.; Geha, Marla

    2016-01-20

    We present high-resolution Magellan/MIKE spectra of the four brightest confirmed red giant stars in the ultra-faint dwarf galaxy Boötes II (Boo II). These stars all inhabit the metal-poor tail of the Boo II metallicity distribution function. The chemical abundance pattern of all detectable elements in these stars is consistent with that of the Galactic halo. However, all four stars have undetectable amounts of neutron-capture elements Sr and Ba, with upper limits comparable to the lowest ever detected in the halo or in other dwarf galaxies. One star exhibits significant radial velocity variations over time, suggesting it to be in a binary system. Its variable velocity has likely increased past determinations of the Boo II velocity dispersion. Our four stars span a limited metallicity range, but their enhanced α-abundances and low neutron-capture abundances are consistent with the interpretation that Boo II has been enriched by very few generations of stars. The chemical abundance pattern in Boo II confirms the emerging trend that the faintest dwarf galaxies have neutron-capture abundances distinct from the halo, suggesting the dominant source of neutron-capture elements in halo stars may be different than in ultra-faint dwarfs.

  5. Surface complexation of heavy metal cations on clay edges: insights from first principles molecular dynamics simulation of Ni(II)

    NASA Astrophysics Data System (ADS)

    Zhang, Chi; Liu, Xiandong; Lu, Xiancai; He, Mengjia; Jan Meijer, Evert; Wang, Rucheng

    2017-04-01

    Aiming at an atomistic mechanism of heavy metal cation complexing on clay surfaces, we carried out systematic first principles molecular dynamics (FPMD) simulations to investigate the structures, free energies and acidity constants of Ni(II) complexes formed on edge surfaces of 2:1 phyllosilicates. Three representative complexes were studied, including monodentate complex on the tbnd SiO site, bidentate complex on the tbnd Al(OH)2 site, and tetradentate complex on the octahedral vacancy where Ni(II) fits well into the lattice. The complexes structures were characterized in detail. Computed free energy values indicate that the tetradentate complex is significantly more stable than the other two. The calculated acidity constants indicate that the tetradentate complex can get deprotonated (pKa = 8.4) at the ambient conditions whereas the other two hardly deprotonate due to extremely high pKa values. By comparing with the 2 Site Protolysis Non Electrostatic Surface Complexation and Cation Exchange (2SPNE SC/CE) model, the vacant site has been assigned to the strong site and the other two to the weak site, respectively. Thus a link has been built between atomistic simulations and macroscopic experiments and it is deduced that this should also apply to other heavy metal cations based on additional simulations of Co(II) and Cu(II) and previous simulations of Fe(II) and Cd(II)). This study forms a physical basis for understanding the transport and fixation of heavy metal elements in many geologic environments.

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

    PubMed

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

    2016-06-08

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

  7. Observations of M33 H II Regions: the Ne/S ratio, metallicity, and ionization variations

    NASA Astrophysics Data System (ADS)

    Rubin, R. H.; Simpson, J. P.; McNabb, I. A.; Brunner, G.; Colgan, S. W. J.; Dufour, R. J.; Pauldrach, A. W. A.; Browne, A. D.; Zhang, R.; Csongradi, E. J.

    2009-01-01

    We have observed emission lines of [S IV] 10.51, H(7--6) 12.37, [Ne II] 12.81, [Ne III] 15.56, and [S III] 18.71 μm in a number of extragalactic H II regions with the Spitzer Space Telescope. A previous paper presented our data and analysis for the substantially face-on spiral galaxy M83. Here we report our results for the local group spiral galaxy M33. The nebulae selected cover a wide range of galactocentric radii (R_G). The observations were made with the Infrared Spectrograph with the short wavelength, high resolution module. The above set of five lines is observed cospatially, thus permitting a reliable comparison of the fluxes. From the measured fluxes, we determine the ionic abundance ratios including Ne++/Ne^+, S3+/S++, and S++/Ne^+ and find that there is a correlation of increasingly higher ionization with larger R_G. By sampling the dominant ionization states of Ne (Ne^+, Ne++) and S (S++, S3+) for H II regions, we can estimate the Ne/H, S/H, and Ne/S ratios. We find that there is a decrease in metallicity with increasing R_G. There is no apparent variation in the Ne/S ratio with R_G. Unlike our previous similar study of M83, where we conjectured that this ratio was an upper limit, for M33 the derived ratios are likely a robust indication of Ne/S. This occurs because the H II regions have lower metallicity and higher ionization than those in M83. Both Ne and S are primary elements produced in α-chain reactions, following C and O burning in stars, making their yields depend very little on the stellar metallicity. Thus, it is expected that Ne/S remains relatively constant throughout a galaxy. The median (average) Ne/S ratio derived for H II regions in M33 is 16.3 (16.9), just slightly higher than the Orion Nebula value of 14.3. These values are in sharp contrast with the much lower ``canonical", but controversial, solar value of ˜5. A recent nucleosynthesis, galactic chemical evolution model predicts a Ne/S abundance of ˜9. Our observations may also be

  8. Synthesis, structural characterization, thermal and electrochemical studies of the N,N'-bis[(3,4-dichlorophenyl)methylidene]cyclohexane-1,4-diamine and its Cu(II), Co(II) and Ni(II) metal complexes.

    PubMed

    Dolaz, Mustafa; McKee, Vickie; Gölcü, Ayşegül; Tümer, Mehmet

    2009-01-01

    In this study, N,N'-bis[(3,4-dichlorophenyl)methylidene]cyclohexane-1,4-diamine (L) and its Cu(II), Co(II) and Ni(II) complexes were prepared and characterized by the analytical and spectroscopic methods. The analytical data show the composition of the metal complex to be [M(2)L(Cl)(4)(H(2)O)(2)], where L is the Schiff base ligand. The conductance data indicate that all the complexes are non-electrolytes. The compound (L) behaves as a monodentate ligand. But, obtained complexes have binuclear nature. The electrochemical properties of the metal complexes are dependent on reversible, irreversible and quasi-reversible redox waves in the anodic and cathodic regions due to oxidation and reduction of the metal ions. The single crystal of the ligand (L) was obtained from CH(3)CN solution. Space group and crystal system of the ligand are P2(1)/C and monoclinic, respectively.

  9. Synthesis, structural characterization, thermal and electrochemical studies of the N, N'-bis[(3,4-dichlorophenyl)methylidene]cyclohexane-1,4-diamine and its Cu(II), Co(II) and Ni(II) metal complexes

    NASA Astrophysics Data System (ADS)

    Dolaz, Mustafa; McKee, Vickie; Gölcü, Ayşegül; Tümer, Mehmet

    2009-01-01

    In this study, N, N'-bis[(3,4-dichlorophenyl)methylidene]cyclohexane-1,4-diamine (L) and its Cu(II), Co(II) and Ni(II) complexes were prepared and characterized by the analytical and spectroscopic methods. The analytical data show the composition of the metal complex to be [M 2L(Cl) 4(H 2O) 2], where L is the Schiff base ligand. The conductance data indicate that all the complexes are non-electrolytes. The compound (L) behaves as a monodentate ligand. But, obtained complexes have binuclear nature. The electrochemical properties of the metal complexes are dependent on reversible, irreversible and quasi-reversible redox waves in the anodic and cathodic regions due to oxidation and reduction of the metal ions. The single crystal of the ligand (L) was obtained from CH 3CN solution. Space group and crystal system of the ligand are P2 1/ C and monoclinic, respectively.

  10. Portable Positron Measurement System (PPMS)

    SciTech Connect

    2011-01-01

    Portable Positron Measurement System (PPMS) is an automated, non-destructive inspection system based on positron annihilation, which characterizes a material's in situatomic-level properties during the manufacturing processes of formation, solidification, and heat treatment. Simultaneous manufacturing and quality monitoring now are possible. Learn more about the lab's project on our facebook site http://www.facebook.com/idahonationallaboratory.

  11. Cyclotrons and positron emitting radiopharmaceuticals

    SciTech Connect

    Wolf, A.P.; Fowler, J.S.

    1984-01-01

    The state of the art of Positron Emission Tomography (PET) technology as related to cyclotron use and radiopharmaceutical production is reviewed. The paper discusses available small cyclotrons, the positron emitters which can be produced and the yields possible, target design, and radiopharmaceutical development and application. 97 refs., 12 tabs. (ACR)

  12. Portable Positron Measurement System (PPMS)

    ScienceCinema

    None

    2016-07-12

    Portable Positron Measurement System (PPMS) is an automated, non-destructive inspection system based on positron annihilation, which characterizes a material's in situatomic-level properties during the manufacturing processes of formation, solidification, and heat treatment. Simultaneous manufacturing and quality monitoring now are possible. Learn more about the lab's project on our facebook site http://www.facebook.com/idahonationallaboratory.

  13. Undulator Production of Polarized Positrons

    SciTech Connect

    William M. Bugg

    2008-08-27

    E-166 at SLAC has demonstrated the feasibilty of production of polarized positrons for the International Linear Collider using a helical undulator to produce polarized photons which are converted in a thin target to polarized positrons. The success of the experim ent has resulted in the choice of this technique for the baseline design of ILC.

  14. Abundances of heavy elements in metal deficient stars II. Detailed spectroscopic analysis

    NASA Astrophysics Data System (ADS)

    Zhao, Gang

    1994-01-01

    In this paper, we determine the abundances of a number of neutron capture elements in metal-poor dwarfs and subgiants. The strontium, yttrium, zirconium, barium, lanthanum, cerium and europium abundances are deduced in a sample of 10 to 20 stars on the basis of high resolution, high signal-to-noise spectra. The main results are: (1) The elements of the first peak, strontium-yttrium-zirconium, show the odd-even effect: strontium and zirconium are less deficient than yttrium in Population II stars. (2) The yttrium abundance is constant ([ Y/Fe] = -0.06) for all stars with [ Fe/H] > -2.5 . (3) The barium overdeficiency increases with decreasing metallicity when [ Fe/H] < -1.7 . (4) Lanthanum and cerium are overdeficient with respect to iron. (5) Europium is overabundant for -1 > [ Fe/H] > -2 . (6) There is a real cosmic scatter in [ Y/Fe] , [ Zr/Fe] and [ Ba/Fe] , of the order of 0.1 dex.

  15. Metal Binding in Photosystem II Super- and Subcomplexes from Barley Thylakoids1

    PubMed Central

    Persson, Daniel Pergament; Powikrowska, Marta

    2015-01-01

    Metals exert important functions in the chloroplast of plants, where they act as cofactors and catalysts in the photosynthetic electron transport chain. In particular, manganese (Mn) has a key function because of its indispensable role in the water-splitting reaction of photosystem II (PSII). More and better knowledge is required on how the various complexes of PSII are affected in response to, for example, nutritional disorders and other environmental stress conditions. We here present, to our knowledge, a new method that allows the analysis of metal binding in intact photosynthetic complexes of barley (Hordeum vulgare) thylakoids. The method is based on size exclusion chromatography coupled to inductively coupled plasma triple-quadrupole mass spectrometry. Proper fractionation of PSII super- and subcomplexes was achieved by critical selection of elution buffers, detergents for protein solubilization, and stabilizers to maintain complex integrity. The applicability of the method was shown by quantification of Mn binding in PSII from thylakoids of two barley genotypes with contrasting Mn efficiency exposed to increasing levels of Mn deficiency. The amount of PSII supercomplexes was drastically reduced in response to Mn deficiency. The Mn efficient genotype bound significantly more Mn per unit of PSII under control and mild Mn deficiency conditions than the inefficient genotype, despite having lower or similar total leaf Mn concentrations. It is concluded that the new method facilitates studies of the internal use of Mn and other biometals in various PSII complexes as well as their relative dynamics according to changes in environmental conditions. PMID:26084923

  16. Interactions of aqueous selenium (-II) and (IV) with metallic sulfide surfaces.

    PubMed

    Naveau, Aude; Monteil-Rivera, Fanny; Guillon, Emmanuel; Dumonceau, Jacques

    2007-08-01

    The present study was initiated to determine the capacity of sulfide minerals (pyrite FeS2 and chalcopyrite CuFeS2) to delay the migration of inorganic selenium species in geological formations. Interactions between Se(IV) and Se(-II) and synthetic and natural sulfide minerals were investigated under anoxic conditions using the batch method. Significant sorption of selenium occurred under acidic conditions. Analysis of the solids after Se sorption using X-ray photoelectron spectroscopy (XPS) and X-ray absorption near edge structure (XANES) demonstrated the presence of reduced selenium species on the metallic sulfide surfaces, thus suggesting an oxido-reduction process coupled with sorption. Selenium reduction occurred concomitantly with the oxidation of pyritic sulfur, whereas metallic species (Fe, Cu) were not involved in the redox process. Formation of ferroselite (FeSe2) was postulated to take place on the synthetic solid while surface complexation or ionic exchange processes were more likely on the natural solids.

  17. Assembly of three novel metal (II) complexes based on polycarboxylate and 1,10-phenanthroline ligands

    NASA Astrophysics Data System (ADS)

    Chen, Xiaoli; Qiao, Yali; Gao, Loujun; Cui, Huali; Zhang, Meili; Lv, Junfang

    2013-04-01

    With the principles of crystal engineering, three novel metal(II) complexes, [Cu2(betd)(phen)4].15H2O (1), [Cd4(betd)2(phen)8]ṡ28H2O (2) and {[Co2(betd)(phen)2(H2O)2]·2H2O}n (3) (H4betd = bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic acid, phen = 1,10-phenanthroline) were synthesized and structurally characterized by elemental analyses, IR spectroscopy, single-crystal X-ray diffraction analyses, TGA, powder XRD and fluorescent measurements. Complex 1 is a binuclear structure, novel water tapes are observed to be encapsulated in the 3D open supramolecular architecture by hydrogen bond interactions. In 2, two pairs of CdII ions joined with two (betd)4- ions to form a cyclic tetranuclear structure. The neighboring tetranuclear units are linked into 2D network through π⋯π stacking interactions. Interestingly, the lattice H2O molecules are joined by strong hydrogen bond interactions generating a wavy water layer, which contacts the 2D network to form 3D supramolecular structure. 3 shows a 2D (4, 4) grid network, which are assembled in an ABAB sequence to 3D supramolecular structures via π⋯π stacking interactions between two central phen ligands from two adjacent sheets and hydrogen bond interactions.

  18. Ceramics reinforced metal base composite coatings produced by CO II laser cladding

    NASA Astrophysics Data System (ADS)

    Yang, Xichen; Wang, Yu; Yang, Nan

    2008-03-01

    Due to the excellent performance in high strength, anti-temperature and anti-wear, ceramics reinforced metal base composite material was used in some important fields of aircraft, aerospace, automobile and defense. The traditional bulk metal base composite materials are the expensive cost, which is limited in its industrial application. Development of laser coating of ceramics reinforced metal base composite is very interesting in economy. This paper is focused on three laser cladding ceramics coatings of SiC particle /Al matrix , Al IIO 3 powder/ Al matrix and WC + Co/mild steel matrix. Powder particle sizes are of 10-60μm. Chemical contents of aluminum matrix are of 3.8-4.0% Cu, 1.2-1.8% Mg, 0.3-0.99% Mn and balance Al. 5KW CO II laser, 5 axes CNC table, JKF-6 type powder feeder and co-axis feeder nozzle are used in laser cladding. Microstructure and performance of laser composite coatings have been respectively examined with OM,SEM and X-ray diffraction. Its results are as follows : Microstructures of 3C-,6H- and 5H- SiC particles + Al + Al 4SiC 4 + Si in SiC/Al composite, hexagonal α-Al IIO 3 + cubic γ-Al IIO 3 + f.c.c Al in Al IIO 3 powder/ Al composite and original WC particles + separated WC particles + eutectic WC + γ-Co solid solution + W IIC particles in WC + Co/steel coatings are respectively recognized. New microstructures of 5H-SiC in SiC/Al composite, cubic γ-Al IIO 3 in Al IIO 3 composite and W IIC in WC + Co/ steel composite by laser cladding have been respectively observed.

  19. Synthesis and characterization of transition metal 2,6-pyridinedicarboxylic acid derivatives, interactions of Cu(II) and Ni(II) complexes with DNA in vitro

    NASA Astrophysics Data System (ADS)

    Khan, Sadaf; Nami, Shahab A. A.; Siddiqi, K. S.; Husain, Eram; Naseem, Imrana

    2009-03-01

    Mononuclear complexes M(L)Cl 2 where M = Mn(II), Fe(II), Co(II), Ni(II) and Cu(II) and (L = N,N-diethylpiperazinyl,2,6-pyridinedicarboxylate), have been synthesized and characterized by elemental analysis, FT-IR, 1H NMR spectroscopy, UV-vis, magnetic moment, TGA/DSC, cyclic voltammetry and conductivity measurement data. The spectral data suggests that the dipicolinic acid acts as a bidentate ligand and is coordinated to the metal ion through the carboxylate oxygen. The cyclic voltammogram for Cu(L)Cl 2 complex was found to display two reversible Cu(II)/Cu(I) and Cu(II)/Cu(III) redox couple. The ligand exhibits a two-step thermolytic pattern while the complexes decompose in three stages respectively. An octahedral geometry has been proposed for both the complexes. The investigation of the interaction of the complexes with calf thymus DNA has been performed with absorption spectroscopy and fluorescence quenching experiments, which showed that the complexes are avid binders of calf thymus DNA. Also the interaction of the Cu(II) and Ni(II) complexes with plasmid DNA (pUC 19) was studied using agarose gel electrophoresis. The results revealed that these complexes can act as effective DNA cleaving agents resulting in the nicked form of DNA (pUC 19) under physiological conditions. The gel was run both in the absence and presence of an oxidizing agent (H 2O 2). The ligand and its complexes have also been screened against microbes in order to study their antibacterial action. The results revealed that the Cu(II) complex has activity comparable with the reference drugs gentamycin and flucanzole.

  20. Metals affect the structure and activity of human plasminogen activator inhibitor-1. II. Binding affinity and conformational changes

    PubMed Central

    Thompson, Lawrence C; Goswami, Sumit; Peterson, Cynthia B

    2011-01-01

    Human plasminogen activator inhibitor type 1 (PAI-1) is a serine protease inhibitor with a metastable active conformation. The lifespan of the active form of PAI-1 is modulated via interaction with the plasma protein, vitronectin, and various metal ions. These metal ions fall into two categories: Type I metals, including calcium, magnesium, and manganese, stabilize PAI-1 in the absence of vitronectin, whereas Type II metals, including cobalt, copper, and nickel, destabilize PAI-1 in the absence of vitronectin, but stabilize PAI-1 in its presence. To provide a mechanistic basis for understanding the unusual modulation of PAI-1 structure and activity, the binding characteristics and conformational effects of these two types of metals were further evaluated. Steady-state binding measurements using surface plasmon resonance indicated that both active and latent PAI-1 exhibit a dissociation constant in the low micromolar range for binding to immobilized nickel. Stopped-flow measurements of approach-to-equilibrium changes in intrinsic protein fluorescence indicated that the Type I and Type II metals bind in different modes that induce distinct conformational effects on PAI-1. Changes in the observed rate constants with varying concentrations of metal allowed accurate determination of binding affinities for cobalt, nickel, and copper, yielding dissociation constants of ∼40, 30, and 0.09 μM, respectively. Competition experiments that tested effects on PAI-1 stability were consistent with these measurements of affinity and indicate that copper binds tightly to PAI-1. PMID:21280128

  1. Positron Survival in Type II Supernovae

    DTIC Science & Technology

    1989-05-01

    constant annihilation rate per free electron. The temperature, ionization, direct in- flight annihilation, etc. can all be represented by time -dependent...electronsatom**/ #define Z...BOUND 24.5 #define IN_FLIGHT _FRACTION 0.0 /**Number that annihilate in flight **/ #deflne RESTMASS 0.511 #define END_. TIME 3.473495e9...smaller apertures within that same time period (see figure 1). Thus Share et al. conclude that the best explanation is a diffuse source of annihilation

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

    PubMed

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

    2016-04-04

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

  3. Synthesis, characterization and electrical properties of peripherally tetra-aldazine substituted novel metal free phthalocyanine and its zinc(II) and nickel(II) complexes.

    PubMed

    Bayrak, Rıza; Dumludağ, Fatih; Akçay, Hakkı Türker; Değirmencioğlu, İsmail

    2013-03-15

    The novel phthalonitrile containing azine segment and its corresponding tetra aldazine substituted metal free- and metallo-phthalocyanines (Zn(II) and Ni(II)) were synthesized and characterized by IR, (1)H NMR, Mass, UV-Vis spectroscopy and elemental analysis and addition to these techniques for substituted phthalonitrile (13)C NMR have been used. In addition, dc and ac electrical properties of the films of these novel phthalocyanines were investigated as a function of temperature (295-523 K) and frequency (40-10(5)Hz). Activation energy values of the films of the phthalocyanines were calculated from straight portions of the Arrhenius plot (lnσ(dc)-1/T curves) as 0.70 eV, 0.93 eV and 0.91 eV for the films of metal free, nickel- and zinc-phthalocyanines, respectively. From impedance spectroscopy measurements, it is observed that bulk resistance decreases with increasing temperature indicating semiconductor property.

  4. Heavy metal binding to heparin disaccharides. II. First evidence for zinc chelation.

    PubMed

    Whitfield, D M; Sarkar, B

    1992-06-01

    To map out the heavy metal binding sites of iduronic acid containing oligosaccharides isolated from human kidneys, we studied Zn(II) binding by nuclear magnetic resonance (NMR) and molecular modeling to two disaccharides isolated after nitrous acid depolymerization of heparin and two synthetic disaccharides representative of the heparin structure, namely, IdopA2S (alpha 1,4)AnManOH, 1 alpha, IdopA2S (alpha 1,4)AnManOH6S, 1b, IdopA2S-(alpha 1,4)GlcNS alpha Me, 2a, and IdopA2S (alpha 1,4)GlcNS6S alpha Me, 2b (see previous article in this series). A conformational analysis of the metal free and metal bound solutions was made by comparing calculated [(NOE)]s, [T1]s, and [J]s to experimental values. The 1C4, 4C1, and 2S0 conformations of the L-idopyranosiduronate ring and the 4E and 4T3 of the anhydro-D-mannitol ring are evaluated as are rotations about the C5-C6 hydroxymethylene of the AnManOH(6S) or GlcNS (6S) residues. The NOE between IdopA2S H1 and H3 and the known NOE between H2 and H5, as well as the T1 of IdopA2S H3, are introduced as NMR observables sensitive to the IdopA2S ring conformation. Similarly, a NOE between IdopA2S H5 and AnManOH(6S) or GlcNS(6S) H3 was observed that directly restricts the allowed interglycosidic conformational space. For all disaccharides, the Zn(II) bound spectral data are consistent with models in which these motions are partially "frozen" such that the 1C4 conformation of the IdopA2S is stabilized along with the 4T3 conformation of the AnManOH(6S) ring. The interglycosidic conformation is also stabilized in one of two minima. Electrostatic potential energy calculations gave the best overall agreement with experiment and suggest metal binding conformations with the carboxylate and ring oxygen of the IdopA2S residues (1C4 conformation) and either O3 of the GlcNS(6S) residues or the sulfate oxygens of the 6-sulphate for 2b providing additional chelating sites. These chelation models concur with the observation of marked 13C and 1H NMR

  5. Photochemical behavior of antibiotics impacted by complexation effects of concomitant metals: a case for ciprofloxacin and Cu(II).

    PubMed

    Wei, Xiaoxuan; Chen, Jingwen; Xie, Qing; Zhang, Siyu; Li, Yingjie; Zhang, Yifei; Xie, Hongbin

    2015-07-01

    Many water bodies, especially those adjacent to aquaculture and livestock breeding areas, are contaminated by both antibiotics and transition metals. However, the effects of the interaction between antibiotics and transition metals on the environmental behavior and the ecotoxicology of antibiotics are largely unknown. We hypothesized that antibiotics may coordinately bind with metal ions, and this complexation may affect the environmental photochemical behavior of antibiotics. We took ciprofloxacin (CIP) and Cu(ii) as a case, and employed simulated sunlight experiments and density functional theory calculations to investigate the underlying reaction mechanisms. The results showed that monovalent cationic ciprofloxacin (H2CIP(+)) that is predominant in the normal pH range (6-9) of surface waters can chelate with hydrated Cu(ii) to form [Cu(H2CIP)(H2O)4](3+). Compared with H2CIP(+), [Cu(H2CIP)(H2O)4](3+) has different molecular orbitals, and atomic charge distribution. As a result, [Cu(H2CIP)(H2O)4](3+) showed dissimilar light absorption properties, slower direct photolytic rates, lower (1)O2 generation ability and weaker reactivity towards (1)O2. Due to the Cu(ii) complexation, the apparent photodegradation of H2CIP(+) was inhibited, and the photolytic pathways and product distribution were altered. This study implies that for an accurate ecological risk assessment of antibiotics under transition metal co-contamination conditions, the effects of metal complexation should be considered.

  6. Spectroscopic, and thermal studies of some new binuclear transition metal(II) complexes with hydrazone ligands containing acetoacetanilide and isoxazole

    NASA Astrophysics Data System (ADS)

    Chen, Zhimin; Wu, Yiqun; Gu, Donghong; Gan, Fuxi

    2007-11-01

    A new chelating ligand, 2-(2-(5- tert-butylisoxazol-3-yl)hydrazono)- N-(2,4-dimethylphenyl)-3-oxobutanamide (HL), and its four binuclear transition metal complexes, M 2(L) 2 (μ-OCH 3) 2 [M = Ni(II), Co(II), Cu(II), Zn(II)], were synthesized using the procedure of diazotization, coupling and metallization. Their structures were postulated based on elemental analysis, 1H NMR, MALDI-MS, FT-IR spectra and UV-vis electronic absorption spectra. Smooth films of these complexes on K9 glass substrates were prepared using the spin-coating method and their absorption properties were evaluated. The thermal properties of the metal(II) complexes were investigated by thermogravimetry (TG) and differential scanning calorimetry (DSC). Different thermodynamic and kinetic parameters namely activation energy ( E*), enthalpy of activation (Δ H*), entropy of activation (Δ S*) and free energy change of activation (Δ G*) are calculated using Coats-Redfern (CR) equation.

  7. Zinc(II) and cadmium(II) metal complexes of thiamine pyrophosphate and 2-(alpha-hydroxyethyl)thiamine pyrophosphate: models for activation of pyruvate decarboxylase.

    PubMed

    Malandrinos, G; Louloudi, M; Koukkou, A I; Sovago, I; Drainas, C; Hadjiliadis, N

    2000-04-01

    Metal complexes of thiamine pyrophosphate (TPP) of the general formula [M2(TPPH)2Cl2]x4H2O (M = Zn2+, Cd2+) were isolated from methanolic solutions and characterized by elemental analysis, FT-IR, and multinuclear NMR spectroscopies. The data provide evidence for the bonding of the metals to the N(1') atom of the pyrimidine ring and to the pyrophosphate group. The stability constant measurements of TPP and 2-(alpha-hydroxyethyl)thiamine pyrophosphate (HETPP) metal complexes in aqueous solution imply the formation of dimeric complex species similar to the isolated solid products. They indicate also that HETPP forms more stable metal complexes than does TPP. To evaluate the coenzyme action of TPP and HETPP metal complexes, enzymic studies have been done using pyruvate decarboxylase apoenzyme. TPP metal complexes do not bind to the apoenzyme, unlike the Zn(II)-HETPP complex which can act as coenzyme. Considering these results, possible functional implications for thiamine involvement in catalysis are discussed.

  8. Synthesis of, characterization of, and photoinduced processes in polymetallic triad complexes containing Fe(II), Ru(II), and Rh(III) metal centers

    SciTech Connect

    Ronco, S.E. |; Thompson, D.W.; Gahan, S.L.; Petersen, J.D. |

    1998-04-20

    A series of new trimetallic mixed complexes containing Fe(II), Ru(II), and Rh(III) metal centers have been prepared and characterized, and their excited-state properties in a nanosecond time domain have been investigated. These new compounds were synthesized by following a building block strategy from monomeric Rh(III) and Ru(II) polyazines and tetracyanoferrate(II) ions. The products generated in each synthetic step were fully characterized and their excited-state properties investigated. These new trimetallic complexes, [(CN){sub 4}Fe{sup II}(BL(1))Ru{sup II}(bpy)-(BL(2))Rh{sup III}(tpy)(MQ{sup +})](PF{sub 6}){sub 4} (tpy = 2,2{prime}:6{prime}:2{double_prime}-terpyridine; BL(1) = 2,3-bis(2-pyridyl)pyrazine (dpp) or 2,2{prime}-bipyrimidine (bpm); BL(2) = dpp or bpm; MQ{sup +} = N-methyl-4,4{prime}-bipyridinium (monoquat)), consist of three fundamental parts linked by bridging ligands (1) an electron donor group, the tetracyanoferrate(II) unit; (2) an antenna fragment, the Ru(II) polypyridyl moiety; and (3) an electron acceptor group. The electron acceptor group is a Rh(III) polypyridyl that contains the ligands tpy and MQ{sup +}. No emission was observed in any of the reported complexes either in fluid solutions at room temperature or in glassy solutions at 77 K. Time-resolved experiments conducted on these triads showed formation of a transient intermediate within the laser pulse. Redox properties and transient absorption observations helped the authors to identify the nature of this intermediate as an Fe(III)/Ru(II) mixed-valence species that decays exponentially by following a first-order law with a lifetime of {tau} {le} 70 ns in fluid solution at room temperature.

  9. Positron emission mammography imaging

    SciTech Connect

    Moses, William W.

    2003-10-02

    This paper examines current trends in Positron Emission Mammography (PEM) instrumentation and the performance tradeoffs inherent in them. The most common geometry is a pair of parallel planes of detector modules. They subtend a larger solid angle around the breast than conventional PET cameras, and so have both higher efficiency and lower cost. Extensions to this geometry include encircling the breast, measuring the depth of interaction (DOI), and dual-modality imaging (PEM and x-ray mammography, as well as PEM and x-ray guided biopsy). The ultimate utility of PEM may not be decided by instrument performance, but by biological and medical factors, such as the patient to patient variation in radiotracer uptake or the as yet undetermined role of PEM in breast cancer diagnosis and treatment.

  10. Effect of biofilm coatings at metal-oxide/water interfaces I: Pb(II) and Zn(II) partitioning and speciation at Shewanella oneidensis/metal-oxide/water interfaces

    SciTech Connect

    Wang, Yingge; Gelabert, Alexandre; Michel, F. Marc; Choi, Yongseong; Gescher, Johannes; Ona-Nguema, Georges; Eng, Peter J.; Bargar, John R.; Farges, Francois; Spormann, Alfred M.; Brown, Jr., Gordon E.

    2016-05-30

    Microbial biofilms are often present as coatings on metal-oxide surfaces in natural and industrial environments and may induce significant changes in the partitioning behavior and speciation of aqueous metal ions, which in turn can impact their transport and fate. In this study, long-period X-ray standing wave-fluorescence yield (LP-XSW-FY) spectroscopy was used to measure under in situ conditions the partitioning of aqueous Pb(II) and Zn(II) between multilayer Shewanella oneidensis MR-1 biofilms and highly polished, oriented single-crystal surfaces of α-Al2O3 and α-Fe2O3 as a function of metal-ion concentration and time at pH 6.0. We show that after 3-h exposure time, Pb(II) binds preferentially to the alpha-Al2O3 (1-102) and α-Fe2O3 (0001) surfaces at low Pb concentration ([Pb] = 10–7 M) and then increasingly partitions into the biofilm coatings at higher concentrations (10–6 to 10–4 M). In contrast, Zn(II) partitions preferentially into the biofilm coating for both surfaces at all Zn concentrations studied (10–7 to 10–4 M). In comparison, the α-Al2O3 (0001) surface has a low affinity for both Pb(II) and Zn(II), and the biofilm coatings are the dominant sink for both ions. These findings suggest that in the presence of S. oneidensis biofilm coatings, α-Al2O3 (0001) is the least reactive surface for Pb(II) and Zn(II) compared to α-Al2O3 (1-102) and α-Fe2O3 (0001). They also show that Zn(II) has a lower affinity than Pb(II) for reactive sites on α-Al2O3 (1-102) and α-Fe2O3 (0001) at [Me(II)] of 10–7 M; at 10–5 M, the bulk of the metal ions partition into the biofilm coatings. At longer exposure times (20-24 h), both Pb(II) and Zn(II

  11. Effect of biofilm coatings at metal-oxide/water interfaces I: Pb(II) and Zn(II) partitioning and speciation at Shewanella oneidensis/metal-oxide/water interfaces

    SciTech Connect

    Wang, Yingge; Gelabert, Alexandre; Michel, F. Marc; Choi, Yongseong; Gescher, Johannes; Ona-Nguema, Georges; Eng, Peter J.; Bargar, John R.; Farges, Francois; Spormann, Alfred M.; Brown, Jr., Gordon E.

    2016-05-30

    Microbial biofilms are often present as coatings on metal-oxide surfaces in natural and industrial environments and may induce significant changes in the partitioning behavior and speciation of aqueous metal ions, which in turn can impact their transport and fate. In this study, long-period X-ray standing wave-fluorescence yield (LP-XSW-FY) spectroscopy was used to measure under in situ conditions the partitioning of aqueous Pb(II) and Zn(II) between multilayer Shewanella oneidensis MR-1 biofilms and highly polished, oriented single-crystal surfaces of α-Al2O3 and α-Fe2O3 as a function of metal-ion concentration and time at pH 6.0. We show that after 3-h exposure time, Pb(II) binds preferentially to the alpha-Al2O3 (1-102) and α-Fe2O3 (0001) surfaces at low Pb concentration ([Pb] = 10–7 M) and then increasingly partitions into the biofilm coatings at higher concentrations (10–6 to 10–4 M). In contrast, Zn(II) partitions preferentially into the biofilm coating for both surfaces at all Zn concentrations studied (10–7 to 10–4 M). In comparison, the α-Al2O3 (0001) surface has a low affinity for both Pb(II) and Zn(II), and the biofilm coatings are the dominant sink for both ions. These findings suggest that in the presence of S. oneidensis biofilm coatings, α-Al2O3 (0001) is the least reactive surface for Pb(II) and Zn(II) compared to α-Al2O3 (1-102) and α-Fe2O3 (0001). They also show that Zn(II) has a lower affinity than Pb(II) for reactive sites on α-Al2O3 (1-102) and α-Fe2O3 (0001) at [Me(II)] of 10–7 M; at 10–5 M, the bulk of the metal ions partition into the biofilm coatings. At longer exposure times (20-24 h), both Pb(II) and Zn(II

  12. Peripherally and non-peripherally tetra-benzothiazole substituted metal-free zinc (II) and lead (II) phthalocyanines: Synthesis, characterization, and investigation of photophysical and photochemical properties

    NASA Astrophysics Data System (ADS)

    Demirbaş, Ümit; Göl, Cem; Barut, Burak; Bayrak, Rıza; Durmuş, Mahmut; Kantekin, Halit; Değirmencioğlu, İsmail

    2017-02-01

    In this study, novel phthalonitrile compounds bearing 2-methylbenzo[d]thiazol-5-yloxy groups (4 and 5) and their peripherally and non-peripherally tetra-substituted metal-free (6 and 7), zinc (II) (8 and 9), and lead (II) (10 and 11) phthalocyanine derivatives were synthesized and characterized for the first time. These novel compounds showed extremely good solubility in most common organic solvents. The novel phthalocyanine compounds presented excellent results from photophysical and photochemical examinations in DMF solution. Especially, the singlet oxygen quantum yield (ΦΔ) values of the substituted zinc (II) phthalocyanines indicate that these compounds have significant potential as photosensitizers in cancer treatment by the photodynamic therapy (PDT) technique. The fluorescence quenching behaviour of these novel phthalocyanine compounds by 1,4-benzoquinone (BQ) was also examined in DMF solution.

  13. Transition metal complexes of neocryptolepine analogues. Part I: Synthesis, spectroscopic characterization, and invitro anticancer activity of copper(II) complexes

    NASA Astrophysics Data System (ADS)

    Emam, Sanaa Moustafa; El Sayed, Ibrahim El Tantawy; Nassar, Nagla

    2015-03-01

    New generation of copper(II) complexes with aminoalkylaminoneocryptolepine as bidentate ligands has been synthesized and it is characterized by elemental analyses, magnetic moment, spectra (IR, UV-Vis, 1H NMR and ESR) and thermal studies. The IR data suggest the coordination modes for ligands which behave as a bidentate with copper(II) ion. Based on the elemental analysis, magnetic studies, electronic and ESR data, binuclear square planar geometry was proposed for complexes 7a, 7b, square pyramidal for 9a, 9b and octahedral for 8a, 8b, 10a, 10b. The molar conductance in DMF solution indicates that all complexes are electrolyte except 7a and 7b. The ESR spectra of solid copper(II) complexes in powder form showed an axial symmetry with 2B1g as a ground state and hyperfine structure. The thermal stability and degradation of the ligands and their metal complexes were studied employing DTA and TG methods. The metal-free ligands and their copper(II) complexes were tested for their in vitro anticancer activity against human colon carcinoma (HT-29). The results showed that the synthesized copper(II) complexes exhibited higher anticancer activity than their free ligands. Of all the studied copper(II) complexes, the bromo-substituted complex 9b exhibited high anticancer activity at low micromolar inhibitory concentrations (IC50 = 0.58 μM), compared to the other complexes and the free ligands.

  14. Transition metal complexes of neocryptolepine analogues. Part I: synthesis, spectroscopic characterization, and invitro anticancer activity of copper(II) complexes.

    PubMed

    Emam, Sanaa Moustafa; El Sayed, Ibrahim El Tantawy; Nassar, Nagla

    2015-03-05

    New generation of copper(II) complexes with aminoalkylaminoneocryptolepine as bidentate ligands has been synthesized and it is characterized by elemental analyses, magnetic moment, spectra (IR, UV-Vis, (1)H NMR and ESR) and thermal studies. The IR data suggest the coordination modes for ligands which behave as a bidentate with copper(II) ion. Based on the elemental analysis, magnetic studies, electronic and ESR data, binuclear square planar geometry was proposed for complexes 7a, 7b, square pyramidal for 9a, 9b and octahedral for 8a, 8b, 10a, 10b. The molar conductance in DMF solution indicates that all complexes are electrolyte except 7a and 7b. The ESR spectra of solid copper(II) complexes in powder form showed an axial symmetry with (2)B1g as a ground state and hyperfine structure. The thermal stability and degradation of the ligands and their metal complexes were studied employing DTA and TG methods. The metal-free ligands and their copper(II) complexes were tested for their in vitro anticancer activity against human colon carcinoma (HT-29). The results showed that the synthesized copper(II) complexes exhibited higher anticancer activity than their free ligands. Of all the studied copper(II) complexes, the bromo-substituted complex 9b exhibited high anticancer activity at low micromolar inhibitory concentrations (IC50=0.58μM), compared to the other complexes and the free ligands.

  15. Surface Charge Transfer Doping via Transition Metal Oxides for Efficient p-Type Doping of II-VI Nanostructures.

    PubMed

    Xia, Feifei; Shao, Zhibin; He, Yuanyuan; Wang, Rongbin; Wu, Xiaofeng; Jiang, Tianhao; Duhm, Steffen; Zhao, Jianwei; Lee, Shuit-Tong; Jie, Jiansheng

    2016-11-22

    Wide band gap II-VI nanostructures are important building blocks for new-generation electronic and optoelectronic devices. However, the difficulty of realizing p-type conductivity in these materials via conventional doping methods has severely handicapped the fabrication of p-n homojunctions and complementary circuits, which are the fundamental components for high-performance devices. Herein, by using first-principles density functional theory calculations, we demonstrated a simple yet efficient way to achieve controlled p-type doping on II-VI nanostructures via surface charge transfer doping (SCTD) using high work function transition metal oxides such as MoO3, WO3, CrO3, and V2O5 as dopants. Our calculations revealed that these oxides were capable of drawing electrons from II-VI nanostructures, leading to accumulation of positive charges (holes injection) in the II-VI nanostructures. As a result, Fermi levels of the II-VI nanostructures were shifted toward the valence band regions after surface modifications, along with the large enhancement of work functions. In situ ultraviolet photoelectron spectroscopy and X-ray photoelectron spectroscopy characterizations verified the significant interfacial charge transfer between II-VI nanostructures and surface dopants. Both theoretical calculations and electrical transfer measurements on the II-VI nanostructure-based field-effect transistors clearly showed the p-type conductivity of the nanostructures after surface modifications. Strikingly, II-VI nanowires could undergo semiconductor-to-metal transition by further increasing the SCTD level. SCTD offers the possibility to create a variety of electronic and optoelectronic devices from the II-VI nanostructures via realization of complementary doping.

  16. Intense source of slow positrons

    NASA Astrophysics Data System (ADS)

    Perez, P.; Rosowsky, A.

    2004-10-01

    We describe a novel design for an intense source of slow positrons based on pair production with a beam of electrons from a 10 MeV accelerator hitting a thin target at a low incidence angle. The positrons are collected with a set of coils adapted to the large production angle. The collection system is designed to inject the positrons into a Greaves-Surko trap (Phys. Rev. A 46 (1992) 5696). Such a source could be the basis for a series of experiments in fundamental and applied research and would also be a prototype source for industrial applications, which concern the field of defect characterization in the nanometer scale.

  17. Cosmic Ray Positrons from Pulsars

    NASA Technical Reports Server (NTRS)

    Harding, Alice K.

    2010-01-01

    Pulsars are potential Galactic sources of positrons through pair cascades in their magnetospheres. There are, however, many uncertainties in establishing their contribution to the local primary positron flux. Among these are the local density of pulsars, the cascade pair multiplicities that determine the injection rate of positrons from the pulsar, the acceleration of the injected particles by the pulsar wind termination shock, their rate of escape from the pulsar wind nebula, and their propagation through the interstellar medium. I will discuss these issues in the context of what we are learning from the new Fermi pulsar detections and discoveries.

  18. Bond-valence model for metal cluster compounds. II. Matrix effect.

    PubMed

    Levi, Elena; Aurbach, Doron; Isnard, Olivier

    2013-10-01

    The bond-valence model was commonly considered as inappropriate to metal cluster compounds, but recently it was shown that the model provides unique information on the lattice strains and stabilization mechanisms in (TM)6-chalcohalides, Mx(TM)6Ly (TM = transition metal, L = the chalcogen and/or halogen ligands; M = counter-cation). The previous study was mainly devoted to the non-uniform distribution of the anion valences (bond-valence sums) around clusters. This and the previous paper are focused on two additional phenomena: (i) a steric conflict between counter-cations and the cluster-ligand framework resulting in `common' lattice strains [previous paper: Levi et al. (2013). Acta Cryst. B69, 419-425], and (ii) steric conflict between the small (TM)6-cluster and the large coordination polyhedron around the cluster or so-called matrix effect (this paper). It was shown that both phenomena can be well described by changes in the bond-valence parameters. This paper demonstrates that the matrix effect results in high strains in the TM-L bonds in most of the (TM)6-chalcohalides (TM = Nb, Mo, W and Re). In spite of this, the violations for the total TM valence are minimal, because the cluster stretching is fully or partially compensated by compression of the TM-L bonds. As a result, the influence of the matrix effect on the material stability is rather positive: it decreases the volume of the structural units and in many cases ensures a more favorable distribution of the bond valences around TM atoms, stabilizing the cluster compound.

  19. Syntheses, structural characterization and spectroscopic studies of cadmium(II)-metal(II) cyanide complexes with 4-(2-aminoethyl)pyridine

    NASA Astrophysics Data System (ADS)

    Karaağaç, Dursun; Kürkçüoğlu, Güneş Süheyla; Şenyel, Mustafa; Hökelek, Tuncer

    2017-02-01

    Three new cadmium(II)-metal(II) cyanide complexes, [Cd(4aepy)2(H2O)2][Ni(CN)4] (1), [Cd(4aepy)2(H2O)2][Pd(CN)4] (2) and [Cd(4aepy)2(H2O)2][Pt(CN)4] (3) [4aepy = 4-(2-aminoethyl)pyridine], have been synthesized and characterized by elemental, thermal, FT-IR and Raman spectral analyses. The crystal structures of 1 and 2 have been determined by single crystal X-ray diffraction technique, in which they crystallize in the monoclinic system and C2/c space group. The M(II) [M(II) = Ni(II), Pd(II) and Pt(II)] ions are coordinated with the carbon atoms of the four cyanide groups in the square planar geometries and the [M(CN)4]2- ions act as counter ions. The Cd(II) ions display an N4O2 coordination sphere with a distorted octahedral geometry, the nitrogen donors belonging to four molecules of the organic 4aepy that act as unidentate ligands and two oxygen atoms from aqua ligands. 3D supramolecular structures of 1 and 2 were occurred by M⋯π and hydrogen bonding (Nsbnd H⋯N and Osbnd H⋯N) interactions. Vibrational assignments of all the observed bands were given and the spectral properties were also supported the crystal structures of the complexes. A possible decompositions of the complexes were investigated in the temperature range 30-800 °C in the static atmosphere.

  20. Two ligand-functionalized Pb(II) metal-organic frameworks: structures and catalytic performances.

    PubMed

    Lin, Xiao-Ming; Li, Ting-Ting; Chen, Lian-Fen; Zhang, Li; Su, Cheng-Yong

    2012-09-14

    A microporous Pb(II) metal-organic framework (MOF) [PbL(2)]·2DMF·6H(2)O (1) has been assembled from a N-oxide and amide doubly functionalized ligand HL (= N-(4-carboxyphenyl)isonicotinamide 1-oxide). Complex 1 features a three-dimensional (3D) framework possessing one-dimensional (1D) rhombic channels with dimensions of 13 × 13 Å(2). The 3D framework is built up from 1D PbO(2) chains that link ligands in parallel fashion to construct single-wall channels. When recrystallizing 1 in a DMSO-DMF mixture (3 : 5 v/v), a new coordination polymer, [PbL(2)]·DMF·2H(2)O (2), was obtained. Complex 2 is also a 3D framework containing 1D rectangular channels, but the channel dimensions become reduced in size to 13 × 8 Å(2) due to reorganization of the Pb(ii) coordination environment. The PbO(2) chains in 2 are reformed to link ligands in a double-wall fashion, significantly reducing the channel size. Even though, the guest exchange study indicates that the DMF molecules in 2 could be replaced with benzene molecules when immersing in benzene solvent, showing single-crystal-to-single-crystal (SC-SC) guest exchange in the solid state and leading to a daughter crystal [PbL(2)]·0.5C(6)H(6)·2H(2)O (2'). Desolvated 1 and 2 display preferential adsorption behaviors of water vapour over CO(2) due to the hydrophilic nature of the channels and the strong host-guest interactions. Catalytic tests indicate that desolvated 1 and 2 have size-selective catalytic activity towards the Knoevenagel condensation reaction.

  1. Crystallographic studies of metal ion-DNA interactions: different binding modes of cobalt(II), copper(II) and barium(II) to N7 of guanines in Z-DNA and a drug-DNA complex.

    PubMed Central

    Gao, Y G; Sriram, M; Wang, A H

    1993-01-01

    Metal ion coordination to nucleic acids is not only required for charge neutralization, it is also essential for the biological function of nucleic acids. The structural impact of different metal ion coordinations of DNA helices is an open question. We carried out X-ray diffraction analyses of the interactions of the two transition metal ions Co(II) and Cu(II) and an alkaline earth metal ion Ba(II), with DNA of different conformations. In crystals, Co(II) ion binds exclusively at the N7 position of guanine bases by direct coordination. The coordination geometry around Co(II) is octahedral, although some sites have an incomplete hydration shell. The averaged Co-N7 bond distance is 2.3 A. The averaged Co-N7-C8 angle is 121 degrees, significantly smaller than the value of 128 degrees if the Co-N7 vector were to bisect the C5-N7-C8 bond angle. Model building of Co(II) binding to guanine N7 in B-DNA indicates that the coordinated waters in the axial positions would have a van der Waals clash with the neighboring base on the 5' side. In contrast, the major groove of A-DNA does not have enough room to accommodate the entire hydration shell. This suggests that Co(II) binding to either B-DNA or A-DNA may induce significant conformational changes. The Z-DNA structure of Cu(II)-soaked CGCGTG crystal revealed that the Cu(II) ion is bis-coordinated to N7 position of G10 and #G12 (# denotes a symmetry-related position) bases with a trigonal bipyramid geometry, suggesting a possible N7-Cu-N7 crosslinking mechanism. A similar bis-coordination to two guanines has also been seen in the interaction of Cu(II) in m5CGUAm5CG Z-DNA crystal and of Ba(II) with two other Z-DNA crystals. PMID:8371984

  2. Synthesis of N4 donor macrocyclic Schiff base ligands and their Ru (II), Pd (II), Pt (II) metal complexes for biological studies and catalytic oxidation of didanosine in pharmaceuticals

    NASA Astrophysics Data System (ADS)

    Ravi krishna, E.; Muralidhar Reddy, P.; Sarangapani, M.; Hanmanthu, G.; Geeta, B.; Shoba Rani, K.; Ravinder, V.

    2012-11-01

    A series of tetraaza (N4 donor) macrocyclic ligands (L1-L4) were derived from the condensation of o-phthalaldehyde (OPA) with some substituted aromatic amines/azide, and subsequently used to synthesize the metal complexes of Ru(II), Pd(II) and Pt(II). The structures of macrocyclic ligands and their metal complexes were characterized by elemental analyses, IR, 1H &13C NMR, mass and electronic spectroscopy, thermal, magnetic and conductance measurements. Both the ligands and their complexes were screened for their antibacterial activities against Gram positive and Gram negative bacteria by MIC method. Besides, these macrocyclic complexes were investigated as catalysts in the oxidation of pharmaceutical drug didanosine. The oxidized products were further treated with sulphanilic acid to develop the colored products to determine by spectrophotometrically. The current oxidation method is an environmentally friendly, simple to set-up, requires short reaction time, produces high yields and does not require co-oxidant.

  3. Synthesis, characterization, biological activity and equilibrium studies of metal(II) ion complexes with tridentate hydrazone ligand derived from hydralazine

    NASA Astrophysics Data System (ADS)

    El-Sherif, Ahmed A.; Shoukry, Mohamed M.; Abd-Elgawad, Mohamed M. A.

    2012-12-01

    In the present study, a new hydrazone ligand (2-((2-phthalazin-1-yl)hydrazono)methyl)phenol) prepared by condensation of hydralazine (1-Hydralazinophthalazine) with salicylaldehyde (SAH). The synthesized SAH-hydrazone and its metal complexes have been characterized by elemental analyses, IR, 1H NMR, solid reflectance, magnetic moment, molar conductance, mass spectra, UV-vis and thermal analysis (TGA). The analytical data of the complexes show the formation of 1:1 [M:L] ratio, where M represents Ni(II), Co(II) and Cu(II) ions, while L represents the deprotonated hydrazone ligand. IR spectra show that SAH is coordinated to the metal ions in a tridentate manner through phthalazine-N, azomethine-N and phenolic-oxygen groups. The ligand and their metal chelates have been screened for their antimicrobial activities using the disc diffusion method against the selected bacteria and fungi. Proton-ligand association constants of (SAH) and the stepwise stability constants of its metal complexes are determined potentiometrically in 0.1 M NaNO3 at different temperatures and the corresponding thermodynamic parameters were derived and discussed. The order of -ΔG° and -ΔH° were found to obey Mn2+ < Co2+ < Ni2+ < Cu2+, in accordance with the Irving-Williams order. The complexes were stabilized by enthalpy changes and the results suggest that the complexation is an enthalpy-driven process. The concentration distribution diagrams of the complexes are evaluated.

  4. Metal-catalyzed oxidation and cleavage of octopus glutathione transferase by the Cu(II)-ascorbate system.

    PubMed

    Tang, S S; Lin, C C; Chang, G G

    1996-01-01

    Glutathione transferase (GST) from octopus hepatopancreas was rapidly inactivated by micromolar concentration of Cu(II) in the presence of ascorbate at neutral pH and 0 degree C. Omitting the metal ion or ascorbate, or replacing the Cu(II) with Fe(II) did not result in any inactivation. Glutathione or the conjugation product of glutathione and 1-chloro-2,4-dinitrobenzene offered complete protection of the enzyme from Cu(II)-induced inactivation. 1-Chloro-2,4-dinitrobenzene, however, did not provide any protection. The inactivation was time and Cu(II) concentration dependent. The dependence of inactivation rate on Cu(II) concentration displayed saturation kinetics, which suggests that the inactivation occurs in two steps with Cu(II) binding with the enzyme first (KdCu = 260 microM), then the locally generated free radicals modify the essential amino acid residues in the active center, which results in enzyme inactivation. The Cu(II)-ascorbate system is, thus, an affinity reagent for the octopus GST. The enzyme inactivation was demonstrated to be followed by protein cleavage. Native octopus GST has a subunit M(r) of 24,000. The inactivated enzyme was cleaved at the C-terminal domain (domain II) of the enzyme molecule and resulted in the formation of peptide fragment of M(r) 15,300, which has the identical N-terminal amino acid sequence as the native enzyme. The other half of the peptide with M(r) approximately 7700 was visible in the gels only after silver staining, which also revealed a minor cleavage site, also located at the domain II, to produce peptide fragments of M(r) approximately 11,300 and 8300. The oxygen carrier molecule in the cephalopods' blood is the copper-containing hemocyanin, which during turnover will release Cu(II). Our results indicate that Cu(II) catalyzes a site-specific oxidation of the essential amino acid residues at the C-terminus of GST causing enzyme inactivation. The modified-enzyme is then affinity cleaved at the putative metal binding

  5. High resolution radio and optical observations of the central starburst in the low-metallicity dwarf galaxy II Zw 40

    SciTech Connect

    Kepley, Amanda A.; Reines, Amy E.; Johnson, Kelsey E.; Walker, Lisa May E-mail: areines@nrao.edu E-mail: lisamay@virginia.edu

    2014-02-01

    The extent to which star formation varies in galaxies with low masses, low metallicities, and high star formation rate surface densities is not well constrained. To gain insight into star formation under these physical conditions, this paper estimates the ionizing photon fluxes, masses, and ages for young massive clusters in the central region of II Zw 40—the prototypical low-metallicity dwarf starburst galaxy—from radio continuum and optical observations. Discrete, cluster-sized sources only account for half the total radio continuum emission; the remainder is diffuse. The young (≲ 5 Myr) central burst has a star formation rate surface density that significantly exceeds that of the Milky Way. Three of the 13 sources have ionizing photon fluxes (and thus masses) greater than R136 in 30 Doradus. Although isolating the effects of galaxy mass and metallicity is difficult, the H II region luminosity function and the internal extinction in the center of II Zw 40 appear to be primarily driven by a merger-related starburst. The relatively flat H II region luminosity function may be the result of an increase in interstellar medium pressure during the merger and the internal extinction is similar to that generated by the clumpy and porous dust in other starburst galaxies.

  6. Cu(II), Co(II), Ni(II), Mn(II), and Fe(II) metal complexes containing N,N'-(3,4-diaminobenzophenon)-3,5-Bu t2-salicylaldimine ligand: Synthesis, structural characterization, thermal properties, electrochemistry, and spectroelectrochemistry

    NASA Astrophysics Data System (ADS)

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

    2010-02-01

    The synthesis, structure, spectroscopic and electro-spectrochemical properties of steric hindered Schiff-base ligand [ N,N'-(3,4-benzophenon)-3,5-Bu t2-salicylaldimine (LH 2)] and its mononuclear Cu(II), Co(II), Ni(II), Mn(II) and Fe(II) complexes are described in this work. The new dissymmetric steric hindered Schiff-base ligand containing a donor set of NONO was prepared through reaction of 3,4-diaminobenzophenon with 3,5-Bu t2-salicylaldehyde. Certain metal complexes of this ligand were synthesized by treating an ethanolic solution of the ligand with an equimolar amount of metal salts. The ligand and its complexes were characterized by FT-IR, UV-vis, 1H NMR, elemental analysis, molar conductivity and thermal analysis methods in addition to magnetic susceptibility, electrochemistry and spectroelectrochemistry techniques. The tetradentate and mononuclear metal complexes were obtained by reacting N,N'-(3,4-benzophenon)-3,5-Bu t2-salicylaldimine (LH 2) with some metal acetate in a 1:1 mole ratio. The molar conductance data suggest metal complexes to be non-electrolytes.

  7. High Power Polarized Positron Source

    NASA Astrophysics Data System (ADS)

    Mikhailichenko, Alexander

    2009-09-01

    We discuss the basics of polarized positron production by low energy polarized electrons. Efficiency of conversion ˜0.1-1% might be interesting for the Continuous Electron Beam Accelerator Facility (CEBAF) and the International Linear Collider (ILC).

  8. Resolvability of positron decay channels

    SciTech Connect

    Fluss, M.J.; Howell, R.H.; Rosenberg, I.J.; Meyer, P.

    1985-03-07

    Many data analysis treatments of positron experiments attempt to resolve two or more positron decay or exist channels which may be open simultaneously. Examples of the need to employ such treatments of the experimental results can be found in the resolution of the constituents of a defect ensemble, or in the analysis of the complex spectra which arise from the interaction of slow positrons at or near the surfaces of solids. Experimental one- and two-dimensional angular correlation of annihilation radiation experiments in Al single crystals have shown that two defect species (mono- and divacancies) can be resolved under suitable conditions. Recent experiments at LLNL indicate that there are a variety of complex exit channels open to positrons interacting at surfaces, and ultimely these decay channels must also be suitably resolved from one another. 6 refs., 4 figs.

  9. Radial velocities and metallicities from infrared Ca ii triplet spectroscopy of open clusters. II. Berkeley 23, King 1, NGC 559, NGC 6603, and NGC 7245

    NASA Astrophysics Data System (ADS)

    Carrera, R.; Casamiquela, L.; Ospina, N.; Balaguer-Núñez, L.; Jordi, C.; Monteagudo, L.

    2015-06-01

    Context. Open clusters are key to studying the formation and evolution of the Galactic disc. However, there is a deficiency of radial velocity and chemical abundance determinations for open clusters in the literature. Aims: We intend to increase the number of determinations of radial velocities and metallicities from spectroscopy for open clusters. Methods: We acquired medium-resolution spectra (R ~ 8000) in the infrared region Ca ii triplet lines (~8500 Å) for several stars in five open clusters with the long-slit IDS spectrograph on the 2.5 m Isaac Newton Telescope (Roque de los Muchachos Observatory, Spain). Radial velocities were obtained by cross-correlation fitting techniques. The relationships available in the literature between the strength of infrared Ca ii lines and metallicity were also used to derive the metallicity for each cluster. Results: We obtain ⟨Vr⟩ = 48.6 ± 3.4, -58.4 ± 6.8, 26.0 ± 4.3, and -65.3 ± 3.2 km s-1 for Berkeley 23, NGC 559, NGC 6603, and NGC 7245, respectively. We found [ Fe/H ] = -0.25 ± 0.14 and -0.15 ± 0.18 for NGC 559 and NGC 7245, respectively. Berkeley 23 has low metallicity, [ Fe/H ] = -0.42 ± 0.13, which is similar to other open clusters in the outskirts of the Galactic disc. In contrast, we derived high metallicity ([ Fe/H ] = +0.43 ± 0.15) for NGC 6603, which places this system among the most metal-rich known open clusters. To our knowledge, this is the first determination of radial velocities and metallicities from spectroscopy for these clusters, except NGC 6603, for which radial velocities had been previously determined. We have also analysed ten stars in the line of sight to King 1. Because of the large dispersion obtained in both radial velocity and metallicity, we cannot be sure that we have sampled true cluster members. Based on observations made with the 2.5 m Isaac Newton Telescope operated on the island of La Palma by the Isaac Newton Group in the Spanish Observatorio del Roque de los Muchachos of the

  10. Isolation Of PS II Nanoparticles And Oxygen Evolution Studies In Synechococcus Spp. PCC 7942 Under Heavy Metal Stress

    NASA Astrophysics Data System (ADS)

    Ahmad, Iffat Zareen; Sundaram, Shanthy; Tripathi, Ashutosh; Soumya, K. K.

    2009-06-01

    The effect of heavy metals was seen on the oxygen evolution pattern of a unicellular, non-heterocystous cyanobacterial strain of Synechococcus spp. PCC 7942. It was grown in a BG-11 medium supplemented with heavy metals, namely, nickel, copper, cadmium and mercury. Final concentrations of the heavy metal solution used in the culture were 0.1, 0.4 and 1 μM. All the experiments were performed in the exponential phase of the culture. Oxygen-evolving photosystem II (PS II) particles were purified from Synechococcus spp. PCC 7942 by a single-step Ni2+-affinity column chromatography after solubilization of thylakoid membranes with sucrose monolaurate. Oxygen evolution was measured with Clark type oxygen electrode fitted with a circulating water jacket. The light on the surface of the vessel was 10 w/m2. The cultures were incubated in light for 15 minutes prior to the measurement of oxygen evolution. Oxygen evolution was measured in assay mixture containing phosphate buffer (pH-7.5, 0.1 M) in the presence of potassium ferricyanide as the electron acceptor. The preparation from the control showed a high oxygen-evolving activity of 2, 300-2, 500 pmol O2 (mg Chl)-1 h-1 while the activity was decreased in the cultures grown with heavy metals. The inhibition of oxygen evolution shown by the organism in the presence of different metals was in the order Hg>Ni>Cd>Cu. Such heavy metal resistant strains will find application in the construction of PS II- based biosensors for the monitoring of pollutants.

  11. Modelling Positron Interactions with Matter

    NASA Astrophysics Data System (ADS)

    Garcia, G.; Petrovic, Z.; White, R.; Buckman, S.

    2011-05-01

    In this work we link fundamental measurements of positron interactions with biomolecules, with the development of computer codes for positron transport and track structure calculations. We model positron transport in a medium from a knowledge of the fundamental scattering cross section for the atoms and molecules comprising the medium, combined with a transport analysis based on statistical mechanics and Monte-Carlo techniques. The accurate knowledge of the scattering is most important at low energies, a few tens of electron volts or less. The ultimate goal of this work is to do this in soft condensed matter, with a view to ultimately developing a dosimetry model for Positron Emission Tomography (PET). The high-energy positrons first emitted by a radionuclide in PET may well be described by standard formulas for energy loss of charged particles in matter, but it is incorrect to extrapolate these formulas to low energies. Likewise, using electron cross-sections to model positron transport at these low energies has been shown to be in serious error due to the effects of positronium formation. Work was supported by the Australian Research Council, the Serbian Government, and the Ministerio de Ciencia e Innovación, Spain.

  12. Fine tuning of copper(II)-chlorophyll interactions in organic media. Metalation versus oxidation of the macrocycle.

    PubMed

    Orzeł, Łukasz; Szmyd, Bartłomiej; Rutkowska-Żbik, Dorota; Fiedor, Leszek; van Eldik, Rudi; Stochel, Grażyna

    2015-04-07

    The nature of chlorophyll interactions with copper(II) ions varies considerably in organic solvents, depending on the dominant coordinative form. Besides formation of the metallo tetrapyrrolic complex, Cu(II) ions can cause oxidation of the pigment, reversible or irreversible, which can lead to the destruction of the macrocyclic structure. All these reaction types can be distinguished within a quite narrow range of reaction conditions. The ability to form new metallo derivatives in either metalation or transmetalation reactions is obviously limited by the concentration of the potential oxidant, but can be secured below this level via suitable composition of the reaction system. The decisive factor in the selection of a specific reaction pathway is the presence of a potential ligand that can affect the reactivity of Cu(II) for example by shifting its redox potential. Spectroscopic and electrochemical studies were performed in order to determine the predominant species of Cu(II) in methanol, nitromethane and acetonitrile in the presence of chloride and acetate ions, as well as to assign their appropriate oxidizing ability. This allowed us to estimate the boundary conditions for the electron transfer processes in chlorophyll-Cu(II) systems. Chlorophyll and its free base can undergo both types of electron transfer processes, however, they reveal different susceptibilities that make this class of ligands quite versatile markers in tuning the reactivity of metal ions in solutions.

  13. Structural and magnetic characterization of a tetranuclear copper(II) cubane stabilized by intramolecular metal cation-π interactions.

    PubMed

    Papadakis, Raffaello; Rivière, Eric; Giorgi, Michel; Jamet, Hélène; Rousselot-Pailley, Pierre; Réglier, Marius; Simaan, A Jalila; Tron, Thierry

    2013-05-20

    A novel tetranuclear copper(II) complex (1) was synthesized from the self-assembly of copper(II) perchlorate and the ligand N-benzyl-1-(2-pyridyl)methaneimine (L(1)). Single-crystal X-ray diffraction studies revealed that complex 1 consists of a Cu4(OH)4 cubane core, where the four copper(II) centers are linked by μ3-hydroxo bridges. Each copper(II) ion is in a distorted square-pyramidal geometry. X-ray analysis also evidenced an unusual metal cation-π interaction between the copper ions and phenyl substituents of the ligand. Calculations based on the density functional theory method were used to quantify the strength of this metal-π interaction, which appears as an important stabilizing parameter of the cubane core, possibly acting as a driving parameter in the self-aggregation process. In contrast, using the ligand N-phenethyl-1-(2-pyridyl)methaneimine (L(2)), which only differs from L(1) by one methylene group, the same synthetic procedure led to a binuclear bis(μ-hydroxo)copper(II) complex (2) displaying intermolecular π-π interactions or, by a slight variation of the experimental conditions, to a mononuclear complex (3). These complexes were studied by X-ray diffraction techniques. The magnetic properties of complexes 1 and 2 are reported and discussed.

  14. Self-assembly of alkynylplatinum(II) terpyridine amphiphiles into nanostructures via steric control and metal–metal interactions

    PubMed Central

    Leung, Sammual Yu-Lut; Wong, Keith Man-Chung; Yam, Vivian Wing-Wah

    2016-01-01

    A series of mono- and dinuclear alkynylplatinum(II) terpyridine complexes containing the hydrophilic oligo(para-phenylene ethynylene) with two 3,6,9-trioxadec-1-yloxy chains was designed and synthesized. The mononuclear alkynylplatinum(II) terpyridine complex was found to display a very strong tendency toward the formation of supramolecular structures. Interestingly, additional end-capping with another platinum(II) terpyridine moiety of various steric bulk at the terminal alkyne would lead to the formation of nanotubes or helical ribbons. These desirable nanostructures were found to be governed by the steric bulk on the platinum(II) terpyridine moieties, which modulates the directional metal−metal interactions and controls the formation of nanotubes or helical ribbons. Detailed analysis of temperature-dependent UV-visible absorption spectra of the nanostructured tubular aggregates also provided insights into the assembly mechanism and showed the role of metal−metal interactions in the cooperative supramolecular polymerization of the amphiphilic platinum(II) complexes. PMID:26933213

  15. Structural characterization of a metal-based perfusion tracer: copper(II) pyruvaldehyde bis(N4-methylthiosemicarbazone).

    PubMed

    John, E; Fanwick, P E; McKenzie, A T; Stowell, J G; Green, M A

    1989-01-01

    Copper(II) pyruvaldehyde bis(N4-methylthiosemicarbazone), Cu(PTSM), has been obtained as a dark red crystalline solid from EtOH-DMSO solvent mixture and structurally characterized by x-ray crystallography. The molecule possesses the expected pseudo-square planar N2S2 metal coordination sphere; however, the copper center also interacts through its axial coordination site with the sulfur atom of an adjacent Cu(PTSM) molecule in the crystal lattice. The structure of this compound is compared with the structures of other metal complexes that have been proposed in the nuclear medicine literature as perfusion tracers.

  16. Improvement of the trace metal composition of medium for nitrite-dependent anaerobic methane oxidation bacteria: Iron (II) and copper (II) make a difference.

    PubMed

    He, Zhanfei; Geng, Sha; Pan, Yawei; Cai, Chaoyang; Wang, Jiaqi; Wang, Liqiao; Liu, Shuai; Zheng, Ping; Xu, Xinhua; Hu, Baolan

    2015-11-15

    Nitrite-dependent anaerobic methane oxidation (n-damo) is a potential bioprocess for treating nitrogen-containing wastewater. This process uses methane, an inexpensive and nontoxic end-product of anaerobic digestion, as an external electron donor. However, the low turnover rate and slow growth rate of n-damo functional bacteria limit the practical application of this process. In the present study, the short- and long-term effects of variations in trace metal concentrations on n-damo bacteria were investigated, and the concentrations of trace metal elements of medium were improved. The results were subsequently verified by a group of long-term inoculations (90 days) and were applied in a sequencing batch reactor (SBR) (84 days). The results indicated that iron (Fe(II)) and copper (Cu(II)) (20 and 10 μmol L(-1), respectively) significantly stimulated the activity and the growth of n-damo bacteria, whereas other trace metal elements, including zinc (Zn), molybdenum (Mo), cobalt (Co), manganese (Mn), and nickel (Ni), had no significant effect on n-damo bacteria in the tested concentration ranges. Interestingly, fluorescence in situ hybridization (FISH) showed that a large number of dense, large aggregates (10-50 μm) of n-damo bacteria were formed by cell adhesion in the SBR reactor after using the improved medium, and to our knowledge this is the first discovery of large aggregates of n-damo bacteria.

  17. Photophysical Studies of Ru(II)tris(2,2`-bipyridine) Confined within a Zn(II)-Trimesic Acid Polyhedral Metal-Organic Framework

    SciTech Connect

    Larsen, Randy W; Wojtas, Lukasz

    2012-10-25

    The ability to confine photoactive catalysts within metal-organic framework (MOF) materials affords the opportunity to expand the functional diversity of these materials into solar based applications. Here, the confinement of Ru(II)tris(2,2'-bipyridine) (RuBpy) by a MOF material derived from Zn(II) ions and trimesic acid (hereafter, USF2) is examined. Although the encapsulated RuBpy could not be crystallographically resolved within the MOF framework, the photophysical properties of the complex are characteristic of confinement including extended triplet metal-to-ligand (3MLCT) lifetime (τethanol = 614 ns and {τUSF2 = 1.2 μs at 25 °C) and a slight hypsochromic shift in the steady-state emission spectrum relative to RuBpy in ethanol. The extended lifetime is attributed to a deactivation of a nonradiative 3dd that is antibonding with respect to the Ru(II)-bipyridine due to a confined molecular environment. These results represent one of the first examples of RuBpy encapsulation and photophysical characterization within a polyhedral MOF material.

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

    USGS Publications Warehouse

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

    2016-01-01

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

  19. Synthesis and characterization of bis (acetylacetonato κ-O, O') [zinc(ii)/copper(ii)] hybrid organic-inorganic complexes as solid metal organic precursors.

    PubMed

    Rooydell, Reza; Wang, Ruey-Chi; Brahma, Sanjaya; Ebrahimzadeh, Farzaneh; Liu, Chuan-Pu

    2015-05-07

    We have synthesized novel metal organic hybrid mixed compounds of bis (acetylacetonato κ-O, O') [zinc(ii)/copper(ii)]. Taking C10H14O4Zn0.7Cu0.3 (Z0.7C0.3AA) as an example, the crystals are composed of Z0.7C0.3AA units and uncoordinated water molecules. Single-crystal X-ray diffraction results show that the complex Z0.7C0.3AA crystallizes in the monoclinic system, space group P21/n. The unit cell dimensions are a = 10.329(4) Å, b = 4.6947(18) Å, and c = 11.369(4) Å; the angles are α = 90°, β = 91.881(6)°, and γ = 90°, the volume is 551.0(4) Å(3), and Z = 2. In this process, the M(ii) ions of Zn and Cu mix and occupy the centers of symmetrical structural units, which are coordinated to two ligands. The measured bond lengths and angles of O-M-O vary with the ratio of metal species over the entire series of the complexes synthesized. The chemistry of the as-synthesized compounds has been characterized using infrared spectroscopy, mass spectroscopy, energy-dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy analysis, and the morphology of the products has been characterized using scanning electron microscopy. The thermal decomposition of the Z0.7C0.3AA composites measured by thermogravimetric analysis suggests that these complexes are volatile. The thermal characteristics of these complexes make them attractive precursors for metal organic chemical vapor deposition.

  20. Synthesis, Spectroscopic Characterization, and Biological Evaluation Studies of 5-Bromo-3-(((hydroxy-2-methylquinolin-7-yl)methylene)hydrazono)indolin-2-one and Its Metal (II) Complexes

    PubMed Central

    Siddappa, Kuruba; Mayana, Nabiya Sultana

    2014-01-01

    The Schiff base ligand 5-bromo-3-(((8-hydroxy-2-methylquinolin-7-yl)methylene)hydrazono)indolin-2-one (BHMQMHI) was prepared via condensation of 5-bromo-3-hydrazonoindolin-2-one and 7-formyl-8-hydroxy-2-methylquinoline and its Co(II), Ni(II), Cu(II), Zn(II), Cd(II), and Hg(II) complexes have been synthesized and characterized by elemental analysis, conductance data, magnetic susceptibility measurements, IR, UV-Vis, mass spectrometry, 1H NMR, ESR, XRD, and thermal studies. By these spectral studies it is found that Co(II), Ni(II), and Cu(II) complexes have exhibited octahedral geometry whereas the Zn(II), Cd(II), and Hg(II) complexes have exhibited tetrahedral geometry. Potentiometric studies have been carried out on complexes of Schiff base (BHMQMHI) with Cu(II), Co(II), and Ni(II). Calvin-Bjerrum pH-titration technique as used by Irving and Rossotti has been applied to determine stability constants in mixed solvents at 25 ± 1°C. The present study reports the protonation constants of this ligand and stability constants of its metal complexes in dioxane-water (50%, v/v) mixtures. Metal-ligand stability constants fall in the order of Cu(II) > Co(II) > Ni(II) which is in agreement with those reported by Irving stability order. The Schiff base (BHMQMHI) and its metal complexes have been screened for their in vitro antibacterial and antifungal activities by minimum inhibitory concentration (MIC) method. The DNA cleavage activities of all the complexes were studied by agarose gel electrophoresis method. In addition, the free ligand along with its complexes has been studied for their antioxidant activity. PMID:25371658

  1. Method for photon activation positron annihilation analysis

    DOEpatents

    Akers, Douglas W.

    2006-06-06

    A non-destructive testing method comprises providing a specimen having at least one positron emitter therein; determining a threshold energy for activating the positron emitter; and determining whether a half-life of the positron emitter is less than a selected half-life. If the half-life of the positron emitter is greater than or equal to the selected half-life, then activating the positron emitter by bombarding the specimen with photons having energies greater than the threshold energy and detecting gamma rays produced by annihilation of positrons in the specimen. If the half-life of the positron emitter is less then the selected half-life, then alternately activating the positron emitter by bombarding the specimen with photons having energies greater then the threshold energy and detecting gamma rays produced by positron annihilation within the specimen.

  2. Some new nano-sized Fe(II), Cd(II) and Zn(II) Schiff base complexes as precursor for metal oxides: Sonochemical synthesis, characterization, DNA interaction, in vitro antimicrobial and anticancer activities.

    PubMed

    Abdel-Rahman, Laila H; Abu-Dief, Ahmed M; El-Khatib, Rafat M; Abdel-Fatah, Shimaa Mahdy

    2016-12-01

    The complexes of Fe(II), Cd(II) and Zn(II) with Schiff base derived from 2-amino-3-hydroxypyridine and 3-methoxysalicylaldehyde have been prepared. Melting points, decomposition temperatures, Elemental analyses, TGA, conductance measurements, infrared (IR) and UV-Visible spectrophotometric studies were utilized in characterizing the compounds. The UV-Visible spectrophotometric analysis revealed 1:1 (metal-ligand) stoichiometry for the three complexes. In addition to, the prepared complexes have been used as precursors for preparing their corresponding metal oxides nanoparticles via thermal decomposition. The structures of the nano-sized complexes and their metal oxides were characterized by X-ray powder diffraction and transmittance electron microscopy. Moreover, the prepared Schiff base ligand, its complexes and their corresponding nano-sized metal oxides have been screened in vitro for their antibacterial activity against three bacteria, gram-positive (Microccus luteus) and gram-negative (Escherichia coli, Serratia marcescence) and three strains of fungus. The metal chelates were shown to possess more antimicrobial activity than the free Schiff-base chelate and their nano-sized metal oxides have the highest activity. The binding behaviors of the complexes to calf thymus DNA have been investigated by absorption spectra, viscosity mensuration and gel electrophoresis. The DNA binding constants reveal that all these complexes interact with DNA through intercalative binding mode. Furthermore, the cytotoxic activity of the prepared Schiff base complexes on human colon carcinoma cells, (HCT-116 cell line) and hepatic cellular carcinoma cells, (HepG-2) showed potent cytotoxicity effect against growth of carcinoma cells compared to the clinically used Vinblastine standard.

  3. 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

    2017-07-01

    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.

  4. Effects of thermal aging on the microstructure of Type-II boundaries in dissimilar metal weld joints

    NASA Astrophysics Data System (ADS)

    Yoo, Seung Chang; Choi, Kyoung Joon; Bahn, Chi Bum; Kim, Si Hoon; Kim, Ju Young; Kim, Ji Hyun

    2015-04-01

    In order to investigate the effects of long-term thermal aging on the microstructural evolution of Type-II boundary regions in the weld metal of Alloy 152, a representative dissimilar metal weld was fabricated from Alloy 690, Alloy 152, and A533 Gr.B. This mock-up was thermally aged at 450 °C to accelerate the effects of thermal aging in a nuclear power plant operation condition (320 °C). The microstructure of the Type-II boundary region of the weld root, which is parallel to and within 100 μm of the fusion boundary and known to be more susceptible to material degradation, was then characterized after different aging times using a scanning electron microscope equipped with an energy dispersive X-ray spectroscope for micro-compositional analysis, electron backscattered diffraction detector for grain and grain boundary orientation analysis, and a nanoindenter for measurement of mechanical properties. Through this, it was found that a steep compositional gradient and high grain average misorientation is created in the narrow zone between the Type-II and fusion boundaries, while the concentration of chromium and number of low-angle grain boundaries increases with aging time. A high average hardness was also observed in the same region of the dissimilar metal welds, with hardness peaking with thermal aging simulating an operational time of 15 years.

  5. Synthesis, spectroscopic, thermal and anticancer studies of metal-antibiotic chelations: Ca(II), Fe(III), Pd(II) and Au(III) chloramphenicol complexes

    NASA Astrophysics Data System (ADS)

    Al-Khodir, Fatima A. I.; Refat, Moamen S.

    2016-09-01

    Four Ca(II), Fe(III), Pd(II) and Au(III) complexes of chloramphenicol drug have been synthesized and well characterized using elemental analyses, (infrared, electronic, and 1H-NMR) spectra, magnetic susceptibility measurement, and thermal analyses. Infrared spectral data show that the chloramphenicol drug coordinated to Ca(II), Pd(II) and Au(III) metal ions through two hydroxyl groups with 1:1 or 1:2 M ratios, but Fe(III) ions chelated towards chloramphenicol drug via the oxygen and nitrogen atoms of amide group with 1:2 ratio based on presence of keto↔enol form. The X-ray powder diffraction (XRD), scanning electron microscope (SEM) and transmission electron microscopy (TEM) techniques were used to identify the nano-size particles of both iron(III) and gold(III) chloramphenicol complexes. The antimicrobial assessments of the chloramphenicol complexes were scanned and collected the results against of some kind of bacteria and fungi. The cytotoxic activity of the gold(III) complex was tested against the human colon carcinoma (HCT-116) and human hepatocellular carcinoma (HepG-2) tumor cell lines.

  6. [Tau Positron Emission Tomography].

    PubMed

    Higuchi, Makoto

    2017-07-01

    Accumulation of fibrillar tau protein aggregates is a neuropathological hallmark of Alzheimer's disease (AD) and related neurodegenerative dementias, including a subgroup of frontotemporal lobar degeneration (FTLD). Visualization of tau lesions in the brains of living subjects enables a pathology-based diagnosis of dementing illnesses in the prodromal stage, and offers objective measures of disease progression and outcomes of disease-modifying therapies. With this rationale, diverse classes of low-molecular-weight chemicals capable of binding to a β-pleated sheet structure have been developed to be used for in vivo positron emission tomography (PET) of tau pathologies. Clinical PET studies of AD patients with such tau probes have provided the following insights: (1) Tau fibrils accumulate in the hippocampal formation in an age-dependent manner that is independent of amyloid-beta peptide (Aβ) pathology; (2) The deposition of Aβ may trigger a spatial expansion of tau pathology, in transition from normal aging to advanced AD; and (3) Tau accumulation is intimately associated with local neuronal loss, leading to cortical atrophy and focal symptoms. In contrast, studies of FTLD have shown a limited performance of first-generation PET probes in capturing non-AD-type tau lesions. New compounds have accordingly been developed and clinically tested, proving to yield a high contrast for tau deposits with high specificity. These second-generation probes are being evaluated primarily by pharmaceutical companies, in line with their growing demands for neuroimaging-based biomarkers serving for clinical trials of anti-Aβ and anti-tau therapies. Meanwhile, a consortium flexibly linking academia and industry to facilitate the utilization of research tools, including tau PET probes, has been established in Japan, for the ultimate purpose of elucidating the molecular etiology of tauopathies and creating diagnostic and therapeutic agents based on such an understanding.

  7. Mixed-metal supramolecular complexes coupling phosphine-containing Ru(II) light absorbers to a reactive Pt(II) through polyazine bridging ligands.

    PubMed

    Swavey, Shawn; Fang, Zhenglai; Brewer, Karen J

    2002-05-06

    Supramolecular bimetallic Ru(II)/Pt(II) complexes [(tpy)Ru(PEt(2)Ph)(BL)PtCl(2)](2+) and their synthons [(tpy)Ru(L)(BL)](n)()(+) (where L = Cl(-), CH(3)CN, or PEt(2)Ph; tpy = 2,2':6',2''-terpyridine; and BL = 2,2'-bipyrimidine (bpm) or 2,3-bis(2-pyridyl)pyrazine (dpp)) have been synthesized and studied by cyclic voltammetry, electronic absorption spectroscopy, mass spectral analysis, and (31)P NMR. The mixed-metal bimetallic complexes couple phosphine-containing Ru chromophores to a reactive Pt site. These complexes show how substitution of the monodentate ligand on the [(tpy)RuCl(BL)](+) synthons can tune the properties of these light absorbers (LA) and incorporate a (31)P NMR tag by addition of the PEt(2)Ph ligand. The redox potentials for the Ru(III/II) couples occur at values greater than 1.00 V versus the Ag/AgCl reference electrode and can be tuned to more positive potentials on going from Cl(-) to CH(3)CN or PEt(2)Ph (E(1/2) = 1.01, 1.55, and 1.56 V, respectively, for BL = bpm). The BL(0/-) couple at -1.03 (bpm) and -1.05 V (dpp) for [(tpy)Ru(PEt(2)Ph)(BL)](2+) shifts dramatically to more positive potentials upon the addition of the PtCl(2) moiety to -0.34 (bpm) and -0.50 V (dpp) for the [(tpy)Ru(PEt(2)Ph)(BL)PtCl(2)](2+) bridged complex. The lowest energy electronic absorption for these complexes is assigned as the Ru(d pi) --> BL(pi*) metal-to-ligand charge transfer (MLCT) transition. These MLCT transitions are tuned to higher energy in the monometallic synthons when Cl(-) is replaced by CH(3)CN or PEt(2)Ph (516, 452, and 450 nm, for BL = bpm, respectively) and to lower energy when Pt(II)Cl(2) is coordinated to the bridging ligand (560 and 506 nm for BL = bpm or dpp). This MLCT state displays a broad emission at room temperature for all the dpp systems with the [(tpy)Ru(PEt(2)Ph)(dpp)PtCl(2)](2+) system exhibiting an emission centered at 750 nm with a lifetime of 56 ns. These supramolecular complexes [(tpy)Ru(PEt(2)Ph)(BL)PtCl(2)](2+) represent the

  8. Zinc(II) Thiosemicarbazone Complex As a Ligand Towards Some Transition Metal Ions: Synthesis, Spectroscopic and Antimicrobial Studies.

    PubMed

    Khalil, Saied M E; Shebl, Magdy; Al-Gohani, Faizah S

    2010-09-01

    Heterobinuclear complexes have been synthesized by stepwise reactions using the mononuclear complex, [Zn(Tsc)2] • H2O, as a complex ligand towards the metal ions, vanadyl(IV), manganese(II), iron(III), cobalt(II), nickel(II) and copper(II). The complex ligand was synthesized by the reaction of zinc acetate dihydrate with salicylaldehyde followed by the condensation with thiosemicarbazide. The structures of the complex ligand and the prepared complexes were elucidated by elemental analyses, IR, electronic, mass, 1H and 13C NMR spectra as well as molar conductivity and magnetic susceptibility measurements. All the complexes exhibited octahedral geometrical arrangements formulated as [Zn(Tsc)2VO(SO4)(H2O)], [Zn(Tsc)2MCl2(H2O)2] (M = Mn, Fe and Co) and [Zn(Tsc)2Fe(ox)Cl2] except the nickel(II) and copper(II) complexes, [Zn(Tsc)2CuCl(H2O)], [Zn(Tsc)2NiCl2], which have square planar geometries. The complex ligand and some of its heterobinuclear complexes showed antibacterial activity against the sensitive organisms Staphylococcus aureus as Gram-positive bacteria, Escherichia coli as Gram-negative bacteria and antifungal activity against the fungi Candida albicans and Aspergillus flavus.

  9. Electrochemiluminescent immunosensing of prostate-specific antigen based on silver nanoparticles-doped Pb (II) metal-organic framework.

    PubMed

    Ma, Hongmin; Li, Xiaojian; Yan, Tao; Li, Yan; Zhang, Yong; Wu, Dan; Wei, Qin; Du, Bin

    2016-05-15

    In this work, silver nanoparticles-doped Pb (II) metal-organic framework (Ag-MOF) was prepared and exploited as a luminescence probe for the development of label-free electrochemiluminescence (ECL) immunosensing scheme for prostate-specific antigen (PSA). The β-cyclodextrin based MOF, Pb-β-cyclodextrin (Pb(II)-β-CD) shows excellent ECL behavior and unexpected reducing capacity towards silver ions. Silver nanoparticles could massively form on the surface of Pb(II)-β-CD (Ag@Pb(II)-β-CD) without use any additional reducing agent, while the ECL behavior of Pb(II)-β-CD still was well retained. The Ag@Pb(II)-β-CD was used as a substrate material to modify glass carbon electrodes and formed a sensing platform for the fabricating ECL immunosensor. The presence of silver nanoparticles enables the facile immobilization of capturing antibody of PSA. The specific binding of PSA onto the electrode surface induces the decrease of ECL signals. A linear range of 0.001-50 ng mL(-1) with a detection limit of 0.34 pg mL(-1) (S/N=3) was obtained after the optimization of experimental conditions. This simply fabricated immunosensor exhibits good stability, accuracy and acceptable reproducibility, which suggesting its potential applications in clinical diagnostics.

  10. Binding selectivity of vitamin K3 based chemosensors towards nickel(II) and copper(II) metal ions

    NASA Astrophysics Data System (ADS)

    Patil, Amit; Lande, Dipali N.; Nalkar, Archana; Gejji, Shridhar P.; Chakrovorty, Debamitra; Gonnade, Rajesh; Moniz, Tânia; Rangel, Maria; Pereira, Eulália; Salunke-Gawali, Sunita

    2017-09-01

    The vitamin K3 derivatives 2-methyl-3-[(pyridin-2-ylmethyl)-amino]-1,4-naphthoquinone (M-1), 2-methyl-3-[(pyridin-2-ylethyl)-amino]-1,4-naphthoquinone (M-2), 2-methyl-3-((2-(thiophen-2-yl)methyl)amino)naphthalene-1,4-dione (M-3) and 2-methyl-3-((2-(thiophen-2-yl)ethyl)amino)naphthalene-1,4-dione (M-4) have been synthesized, characterized and studied for their chemosensor abilities towards transition metal ions. Crystal structures of M-1 to M-4 revealed a variety of Nsbnd H⋯O, Csbnd H⋯O, Csbnd H⋯π and π⋯π interactions. Minor variations in such interactions by chemical stimuli such as metal ions, results in change in color that can be visualized by naked eyes. It has been shown that electronic structure and 1H NMR, vibrational as well as electronic spectra from the density functional theory agree well with the experiments. The metal ion binding in ethanol, ethanol-water and in mild base triethylamine brings forth recognizing ability of M-1 toward Ni2+ whereas M-2 exhibits large sensing ability for Cu2+ ion. Interestingly M-1 display varying metal ion binding specificity in different solvents with the association constant in ethanol being 11,786 M-1 for Ni2+ compared to 9462 M-1 for the Cu2+. A reversal in preferential binding of M-2 with the respective association constants being 4190 M-1 and 6370 M-1 is discernible.

  11. Synthesis, spectral characterization and DNA bindings of tridentate N2O donor Schiff base metal(II) complexes.

    PubMed

    Kathiresan, Sellamuthu; Anand, Thangavel; Mugesh, Subramanian; Annaraj, Jamespandi

    2015-07-01

    To evaluate the biological preference of synthetic small drugs towards DNA target, new metal based chemotherapeutic agents of Cu(II), Co(II), Ni(II) and Zn(II), 2,4-diiodo-6-((pyridin-2-ylmethylimino)methyl)phenol (L) Schiff base complexes (1, 2, 3 &4) having N,N,O donor system respectively were synthesized and thoroughly characterized. The IR results confirmed the tridentate binding of the ligand with metal centre during complexation and reflects the proposed structure. The density function theory calculations were also used to further investigate the electronic structure and properties of ligand and complexes. The preliminary investigation of herring Sperm (HS-DNA) interaction propensity of complexes 1-4 were carried out in Tris-HCl buffer at pH 7.1 to demonstrate their mode of interactions. The obtained results reveal that these complexes significantly interact with DNA on the grooves, further, this observed mode of interactions was also confirmed by molecular docking evaluations. The complexes 1-4 were also screened for antimicrobial evaluations which demonstrated that their significant activity against various human pathogens. The cleavage studies with pBR322 plasmid DNA revealed higher nuclease activity of 1 as compared to other complexes.

  12. Fluorimetric determination of copper(II) in aqueous solution using lucifer yellow CH as selective metal reagent.

    PubMed

    Mayr, T; Wencel, D; Werner, T

    2001-09-01

    Lucifer yellow CH is shown to be a highly selective fluorescent reagent for the determination of Cu(III) in the microg L(-1) concentration range. The fluorophore is statically quenched by Cu(II); the carbohydrazide group was assigned as the complexing part of the dye molecule. A total range of Cu(II) determination from 0.06 mg L(-1) (1 micromol L(-1)) to 6.3 mg L(-2) (100 micromol L(-1)) with a limit of detection of 0.019 mg L(-1) (0.3 micromol L(-1)) was obtained, along with surprisingly high selectivity. There was no interference from alkaline and earth alkaline metal ions. The cross sensitivity to heavy metal ions was evaluated by the separate solution method and by competitive binding experiments. Calibration plots are shown for Cu(II) determination at different pH and the dissociation constant was determined. The application of the reagent was demonstrated by the determination of the Cu(II) content of tap water samples.

  13. A novel curcumin assay with the metal ion Cu (II) as a simple probe by resonance light scattering technique

    NASA Astrophysics Data System (ADS)

    Chen, Zhanguang; Zhu, Li; Song, Tianhe; Chen, Junhui; Guo, Zhiming

    2009-04-01

    A fantastic resonance light scattering (RLS) enhancement phenomenon was found when the interaction between the metal ion Cu (II) and a natural antioxidant curcumin (C 21H 20O 6) occurred in certain conditions. Based on this phenomenon, a novel and convenient assay of curcumin was developed and successfully applied on the determination of curcumin in human urine samples. This assay applied the RLS technique with a common metal ion Cu (II) as the spectral probe. In the pH range of 6.5-7.5, the interaction between Cu (II) and curcumin occurred and the weak RLS intensity of Cu (II) was greatly enhanced by curcumin. The maximum peak was located at 538.5 nm. Under the optimum conditions, the enhanced RLS intensity was proportional to the concentration of curcumin ranging from 0.4 to 60 μg ml -1 with the detection limit of 0.07 μg ml -1. The synthetic and human urine samples were determined satisfactorily. Good recoveries (98.8-102.5%) were obtained in the determination of urine samples, which proved that the assay proposed was reliable and applicable in the determination of curcumin in body fluid. In this work, the RLS and fluorescence spectral characteristics of the chemicals, the optimum conditions of the reaction and the influencing factors were investigated.

  14. Distributions, equivalent widths and metallicities of the H II regions in the spiral galaxies NGC 5457 and NGC 4395

    NASA Astrophysics Data System (ADS)

    Cedrés, B.; Cepa, J.

    2002-09-01

    Using CCD observations in the narrow band filters in Hα , Hβ , [O Ii], [O Iii], [S Ii] and [S Iii] lines we have compiled a catalogue of 338 H Ii regions for the inner parts of NGC 5457 and 158 for NGC 4395. The extinction, equivalent widths, distributions, excitations, ionization hardness, ionization parameters and metallicities for these regions, a distinction being made between arm and inter-arm zones, are presented here with the first results of a study of stellar formation. Tables 3 to 8 are only available in electronic form at the CDS via anonymous ftp to cdsarc.u-strasbg.fr (130.79.128.5) or via http://cdsweb.u-strasbg.fr/cgi-bin/qcat?J/A+A/391/809

  15. I. New Techniques for the Synthesis of Metals and Alloys. II. The Properties of Rare Earth Metals and Alloys

    DTIC Science & Technology

    1974-11-01

    Evaporation Apparatus Gas Scattering Evaporation High Rate Physical Vapor Deposition Process Hafnium Carbide *** 20. ABSTRACT (Conttnu» on r...2,500 Aluminium oxide 2 100 Tungsten carbide 1,700 Quartz 820 Metals < 800 34 ^^M ■ ’ ■ The microstructure of the deposit shows a fine

  16. Investigation of Explosively Driven Fragmentation of Metals - Two Dimensional Fracture and Fragmentation of Metal Shells: Progress Report II

    SciTech Connect

    Grady, D

    2003-02-01

    High explosive enclosed by a metal case qualitatively describes an essential component of high energy systems of importance to the Department of Energy. Detonation of the high explosive causes intense transient pressure loading of the metal following arrival of normal or obliquely incident explosive detonation wave. Subsequent expansion and deformation of the metal case leads to eventual rupture and the opening of fractures and fissures. Details of the rupture process are critical to performance of the system. Consequently, it is essential that the material and kinematic issues governing the processes of dynamic loading and subsequent failure of an explosive-metal case component within a functioning system be adequately understood. Among the reasons are to quantify existing performance, characterize potential degradation of performance resulting from system aging, and optimizing or maintaining system performance through implementation of structural or material changes. The physical and engineering issues underlying this dynamic response and failure phenomena are not adequately understood. The purpose of the present program is to identify the key issues and develop theoretical, computational and experimental models needed to achieve a satisfactory theoretical and analysis framework for analysis of metal case failure in the explosive environment. Specific tasks within the present program include: (1) Models and theories currently being pursued based on physical principles of both the statistical fragmentation concepts of Mott and the energy-based concept of others show promise of providing the analytic and computational methodology capable of predicting explosion-induced fracture and fragmentation of metal components. Experimental studies initiated in the earlier effort offer promise to provide critical test data for validation. The present task shall involve the further refinement and development of the dynamic failure and fragmentation models and theories, and the

  17. Analysis of positron lifetime spectra in polymers

    NASA Technical Reports Server (NTRS)

    Singh, Jag J.; Mall, Gerald H.; Sprinkle, Danny R.

    1988-01-01

    A new procedure for analyzing multicomponent positron lifetime spectra in polymers was developed. It requires initial estimates of the lifetimes and the intensities of various components, which are readily obtainable by a standard spectrum stripping process. These initial estimates, after convolution with the timing system resolution function, are then used as the inputs for a nonlinear least squares analysis to compute the estimates that conform to a global error minimization criterion. The convolution integral uses the full experimental resolution function, in contrast to the previous studies where analytical approximations of it were utilized. These concepts were incorporated into a generalized Computer Program for Analyzing Positron Lifetime Spectra (PAPLS) in polymers. Its validity was tested using several artificially generated data sets. These data sets were also analyzed using the widely used POSITRONFIT program. In almost all cases, the PAPLS program gives closer fit to the input values. The new procedure was applied to the analysis of several lifetime spectra measured in metal ion containing Epon-828 samples. The results are described.

  18. Positron accumulation effect in particles embedded in a low-density matrix

    SciTech Connect

    Dryzek, Jerzy; Siemek, Krzysztof

    2015-02-07

    Systematic studies of the so-called positron accumulation effect for samples with particles embedded in a matrix are reported. This effect is related to energetic positrons which penetrate inhomogeneous medium. Due to differences in the linear absorption coefficient, different amounts of positrons are accumulated and annihilate in the identical volume of both materials. Positron lifetime spectroscopy and Doppler broadening of the annihilation line using Na-22 positrons were applied to the studies of the epoxy resin samples with embedded micro-sized particles of transition metals, i.e., Ni, Sn, Mo, W, and nonmetal particles, i.e., Si and NaF. The significant difference between the determined fraction of positrons annihilating in the particles and the particle volume fraction indicates the positron accumulation effect. The simple phenomenological model and Monte Carlo simulations are able to describe the main features of the obtained dependencies. The aluminum alloy with embedded Sn nanoparticles is also considered for demonstration differences between the accumulation and another related effect, i.e., the positron affinity.

  19. New fluorescent azo-Schiff base Cu(II) and Zn(II) metal chelates; spectral, structural, electrochemical, photoluminescence and computational studies

    NASA Astrophysics Data System (ADS)

    Purtas, Fatih; Sayin, Koray; Ceyhan, Gokhan; Kose, Muhammet; Kurtoglu, Mukerrem

    2017-06-01

    A new Schiff base containing azo chromophore group obtained by condensation of 2-hydroxy-4-[(E)-phenyldiazenyl]benzaldehyde with 3,4-dimethylaniline (HL) are used for the syntheses of new copper(II) and zinc(II) chelates, [Cu(L)2], and [Zn(L)2], and characterized by physico-chemical and spectroscopic methods such as 1H and 13C NMR, IR, UV.-Vis. and elemental analyses. The solid state structure of the ligand was characterized by single crystal X-ray diffraction study. X-ray diffraction data was then used to calculate the harmonic oscillator model of aromaticity (HOMA) indexes for the rings so as to investigate of enol-imine and keto-amine tautomeric forms in the solid state. The phenol ring C10-C15 shows a considerable deviation from the aromaticity with HOMA value of 0.837 suggesting the shift towards the keto-amine tautomeric form in the solid state. The analytical data show that the metal to ligand ratio in the chelates was found to be 1:2. Theoretical calculations of the possible isomers of the ligand and two metal complexes are performed by using B3LYP method. Electrochemical and photoluminescence properties of the synthesized azo-Schiff bases were also investigated.

  20. Metal transports and enrichments in iron depositions hosted in basaltic rocks. II: Metal rich fluids and Fe origin

    NASA Astrophysics Data System (ADS)

    Zhang, Ronghua; Zhang, Xuetong; Hu, Shumin

    2015-12-01

    This study focuses on revealing the mechanism of metal transport, enrichment and Fe origin of iron deposition during water basalt interactions occurred in basaltic rocks. Observations of the iron deposits (anhydrite-magnetite-pyroxene type deposits) hosted in K-rich basaltic rocks in the Mesozoic volcanic area of the Middle-Lower Yangtze River valley, China, indicate that the mechanism of metal transport and enrichment for those deposits are significant objective to scientists, and the Fe origin problem is not well resolved. Here the metal transport, enrichment and iron origin have been investigated in high temperature experiments of water basaltic interactions. These deposits were accompanying a wide zone with metal alteration. The effects of hydrothermal alteration on major rock-forming element concentrations in basaltic rock were investigated by systematically comparing the chemical compositions of altered rocks with those of fresh rocks. In the deposits, these metals are distributed throughout altered rocks that exhibit vertical zoning from the deeper to the shallow. Then, combined with the investigations of the metal-alterations, we performed kinetic experiments of water-basaltic rock interactions using flow-through reactors in open systems at temperatures from 20 °C to 550 °C, 23-34 MPa. Release rates for the rock-forming elements from the rocks have been measured. Experiments provide the release rates for various elements at a large temperature range, and indicate that the dissolution rates (release rates) for various elements vary with temperature. Si, Al, and K have high release rates at temperatures from 300 °C to 500 °C; the maximum release rates (RMX) for Si are reached at temperatures from 300 °C to 400 °C. The RMXs for Ca, Mg, and Fe are at low temperatures from 20 °C to 300 °C. Results demonstrate that Fe is not released from 400 °C to 550 °C, and indicate that when deep circling fluids passed through basaltic rocks, Fe was not mobile, and

  1. Four Zn(II)/Cd(II)-3-amino-1,2,4-triazolate frameworks constructed by in situ metal/ligand reactions: Structures and fluorescent properties

    NASA Astrophysics Data System (ADS)

    Chen, Zilu; Li, Xiaoling; Liang, Fupei

    2008-08-01

    Four Cd(II) and Zn(II) complexes with the in situ-generated ligand of 3-amino-1,2,4-triazolate (AmTAZ -) were isolated from the solvothermal reactions of the corresponding Cd(II) or Zn(II) salts with 5-amino-1H-1,2,4-triazole-3-carboxylic acid (AmTAZAc). Their structures were determined by single-crystal X-ray diffraction analysis. [Zn(AmTAZ)(CH 3COO)] ( 1) presents a two-dimensional framework constructed from Zn(II) ions and μ3-AmTAZ - ligands. A remarkable feature of [Zn 4(AmTAZ) 4(SO 4)(OH)(C 2O 4) 0.5]·2H 2O ( 2) is the construction of the building units of octagonal cylinders which interact with each other by sharing one face or overlapping, resulting in the formation of a three-dimensional framework with three kinds of 1D channels. [Cd(AmTAZ)Br] ( 3) crystallizes in a chiral space group P2 12 12 1, giving a homochiral three-dimensional framework with two types of helical channels (left- and right-handed). Different from the others, the 3-amino-1,2,4-triazole molecules in [Cd(AmTAZH)SO 4] ( 4) behave as neutral μ2-2,4-bridges to connect the two-dimensional CdSO 4 sheets into a three-dimensional framework. Of all, 2 and 3 display different fluorescent properties probably due to different metal ions, coordination environments and structural topologies.

  2. Positron emitter labeled enzyme inhibitors

    DOEpatents

    Fowler, J.S.; MacGregor, R.R.; Wolf, A.P.

    1987-05-22

    This invention involved a new strategy for imaging and mapping enzyme activity in the living human and animal body using positron emitter-labeled suicide enzyme inactivators or inhibitors which become covalently bound to the enzyme as a result of enzymatic catalysis. Two such suicide in activators for monoamine oxidase have been labeled with carbon-11 and used to map the enzyme subtypes in the living human and animal body using PET. By using positron emission tomography to image the distribution of radioactivity produced by the body penetrating radiation emitted by carbon-11, a map of functionally active monoamine oxidase activity is obtained. Clorgyline and L-deprenyl are suicide enzyme inhibitors and irreversibly inhibit monoamine oxidase. When these inhibitors are labeled with carbon-11 they provide selective probes for monoamine oxidase localization and reactivity in vivo using positron emission tomography. 2 figs.

  3. Positron-alkali atom scattering

    NASA Technical Reports Server (NTRS)

    Mceachran, R. P.; Horbatsch, M.; Stauffer, A. D.; Ward, S. J.

    1990-01-01

    Positron-alkali atom scattering was recently investigated both theoretically and experimentally in the energy range from a few eV up to 100 eV. On the theoretical side calculations of the integrated elastic and excitation cross sections as well as total cross sections for Li, Na and K were based upon either the close-coupling method or the modified Glauber approximation. These theoretical results are in good agreement with experimental measurements of the total cross section for both Na and K. Resonance structures were also found in the L = 0, 1 and 2 partial waves for positron scattering from the alkalis. The structure of these resonances appears to be quite complex and, as expected, they occur in conjunction with the atomic excitation thresholds. Currently both theoretical and experimental work is in progress on positron-Rb scattering in the same energy range.

  4. Positron emitter labeled enzyme inhibitors

    DOEpatents

    Fowler, Joanna S.; MacGregor, Robert R.; Wolf, Alfred P.; Langstrom, Bengt

    1990-01-01

    This invention involves a new strategy for imaging and mapping enzyme activity in the living human and animal body using positron emitter-labeled suicide enzyme inactivators or inhibitors which become covalently bound to the enzyme as a result of enzymatic catalysis. Two such suicide inactivators for monoamine oxidase have been labeled with carbon-11 and used to map the enzyme subtypes in the living human and animal body using PET. By using positron emission tomography to image the distribution of radioactivity produced by the body penetrating radiation emitted by carbon-11, a map of functionally active monoamine oxidase activity is obtained. Clorgyline and L-deprenyl are suicide enzyme inhibitors and irreversibly inhibit monoamine oxidase. When these inhibitors are labeled with carbon-11 they provide selective probes for monoamine oxidase localization and reactivity in vivo using positron emission tomography.

  5. Positron emitter labeled enzyme inhibitors

    SciTech Connect

    Fowler, J.S.; MacGregor, R.R.; Wolf, A.P.; Langstrom, B.

    1990-04-03

    This invention involves a new strategy for imaging and mapping enzyme activity in the living human and animal body using positron emitter-labeled suicide enzyme inactivators or inhibitors which become covalently bound to the enzyme as a result of enzymatic catalysis. Two such suicide inactivators for monoamine oxidase have been labeled with carbon-11 and used to map the enzyme subtypes in the living human and animal body using PET. By using positron emission tomography to image the distribution of radioactivity produced by the body penetrating radiation emitted by carbon-11, a map of functionally active monoamine oxidase activity is obtained. Clorgyline and L-deprenyl are suicide enzyme inhibitors and irreversibly inhibit monoamine oxidase. When these inhibitors are labeled with carbon-11 they provide selective probes for monoamine oxidase localization and reactivity in vivo using positron emission tomography.

  6. Positron scattering from simple molecules

    NASA Astrophysics Data System (ADS)

    Singh, Suvam; Dutta, Sangita; Naghma, Rahla; Antony, Bobby

    2017-07-01

    A modified version of spherical complex optical potential formalism is employed to calculate the positron scattering cross sections over a wide energy range from near positronium formation threshold to 5000 eV. In the present study, the interaction potential of the positron-target scattering system is developed under an optical potential framework for the calculation of positron scattering total cross sections for CH4, CO, CO2, H2, N2O and NO molecules. The results obtained are in good agreement with most of the available experimental and theoretical values in terms of its shape and magnitude. A characteristic increase in cross section is observed for all the molecules near the positronium formation threshold, which signifies the emergence of positronium formation along with other inelastic channels.

  7. Interaction of glutathione reductase with heavy metal: the binding of Hg(II) or Cd(II) to the reduced enzyme affects both the redox dithiol pair and the flavin.

    PubMed

    Picaud, Thierry; Desbois, Alain

    2006-12-26

    To determine the inhibition mechanism of yeast glutathione reductase (GR) by heavy metal, we have compared the electronic absorption and resonance Raman (RR) spectra of the enzyme in its oxidized (Eox) and two-electron reduced (EH2) forms, in the absence and the presence of Hg(II) or Cd(II). The spectral data clearly show a redox dependence of the metal binding. The metal ions do not affect the absorption and RR spectra of Eox. On the contrary, the EH2 spectra, generated by addition of NADPH, are strongly modified by the presence of heavy metal. The absorption changes of EH2 are metal-dependent. On the one hand, the main flavin band observed at 450 nm for EH2 is red-shifted at 455 nm for the EH2-Hg(II) complex and at 451 nm for the EH2-Cd(II) complex. On the other hand, the characteristic charge-transfer (CT) band at 540 nm is quenched upon metal binding to EH2. In NADPH excess, a new CT band is observed at 610 nm for the EH2-Hg(II)-NADPH complex and at 590 nm for EH2-Cd(II)-NADPH. The RR spectra of the EH2-metal complexes are not sensitive to the NADPH concentration. With reference to the RR spectra of EH2 in which the frequencies of bands II and III were observed at 1582 and 1547 cm-1, respectively, those of the EH2-metal complexes are detected at 1577 and 1542 cm-1, indicating an increased flavin bending upon metal coordination to EH2. From the frequency shifts of band III, a concomitant weakening of the H-bonding state of the N5 atom is also deduced. Taking into account the different chemical properties of Hg(II) and Cd(II), the coordination number of the bound metal ion was deduced to be different in GR. A mechanism of the GR inhibition is proposed. It proceeds primarily by a specific binding of the metal to the redox thiol/thiolate pair and the catalytic histidine of EH2. The bound metal ion then acts on the bending of the isoalloxazine ring of FAD as well as on the hydrophobicity of its microenvironment.

  8. Positron Emission Tomography - Computed Tomography (PET/CT)

    MedlinePlus

    ... Index A-Z Positron Emission Tomography - Computed Tomography (PET/CT) Positron emission tomography (PET) uses small amounts of ... CT)? What is Positron Emission Tomography – Computed Tomography (PET/CT) Scanning? Positron emission tomography, also called PET imaging ...

  9. Complexation abilities of neuropeptide gamma toward copper(II) ions and products of metal-catalyzed oxidation.

    PubMed

    Pietruszka, Marta; Jankowska, Elżbieta; Kowalik-Jankowska, Teresa; Szewczuk, Zbigniew; Smużyńska, Maria

    2011-08-15

    The stability constants, stoichiometry, and solution structures of copper(II) complexes of neuropeptide gamma (NPG) (D(1)-A-G-H(4)-G-Q-I-S-H(9)-K-R-H(12)-K-T-D-S-F-V-G-L-M(21)-NH(2)) and acethyl-neuropeptide gamma (Ac-D(1)-A-G-H(4)-G-Q-I-S-H(9)-K-R-H(12)-K-T-D-S-F-V-G-L-M(21)-NH(2)) were determined in aqueous solution. For both peptides the additional deprotonations were observed; therefore, the potentiometric data calculations for NPG were only made in 2.5-7.4 pH range. For Ac-NPG one additional deprotonation was observed, likely hydroxy group of Ser residue, and the potentiometric data calculations in the 2.5-10.5 pH range may be performed. The potentiometric and spectroscopic data (UV-vis, CD, EPR) for the neuropeptide gamma show that a D(1) residue stabilizes significantly the copper(II) complexes with 1N {NH(2),β-COO(-)}, 2N {NH(2),β-COO(-),N(Im)}, and 3N {NH(2),β-COO(-),2N(Im)} coordination modes as the result of coordination through the β-carboxylate group. The Ac-NPG forms with the copper(II) ions the 3N {3N(Im)} complex in a wide 4.5-7.5 pH range. At higher pH deprotonation and coordination of the sequential amide nitrogens occur. Metal-catalyzed oxidation of proteins is mainly a site-specific process in which amino acids at metal-binding sites to the protein are preferentially oxidized. To elucidate the products of the copper(II)-catalyzed oxidation of NPG and Ac-NPG the liquid chromatography-mass spectrometry method (LC-MS) and the Cu(II)/H(2)O(2) as a model oxidizing system were employed. For solutions containing a 1:4 peptide-hydrogen peroxide molar ratio oxidation of the methionine residue to methionine sulphone was observed. For the 1:1:4 Cu(II)-NPG-H(2)O(2) system oxidation of two His residues and cleavage of the G(3)-H(4) and R(11)-H(12) peptide bonds were detected, supporting involvement of His(4) and His(12) in binding of the copper(II) ions. Oxidations of three histidine residues to 2-oxohistidines and fragmentations of Ac-NPG near the His

  10. Mutational analysis of divalent metal ion binding in the active site of class II α-mannosidase from Sulfolobus solfataricus.

    PubMed

    Hansen, Dennis K; Webb, Helen; Nielsen, Jonas Willum; Harris, Pernille; Winther, Jakob R; Willemoës, Martin

    2015-03-24

    Mutational analysis of Sulfolobus solfataricus class II α-mannosidase was focused on side chains that interact with the hydroxyls of the -1 mannosyl of the substrate (Asp-534) or form ligands to the active site divalent metal ion (His-228 and His-533) judged from crystal structures of homologous enzymes. D534A and D534N appeared to be completely inactive. When compared to the wild-type enzyme, the mutant enzymes in general showed only small changes in K(M) for the substrate, p-nitrophenyl-α-mannoside, but elevated activation constants, K(A), for the divalent metal ion (Co²⁺, Zn²⁺, Mn²⁺, or Cd²⁺). Some mutant enzyme forms displayed an altered preference for the metal ion compared to that of the wild type-enzyme. Furthermore, the H228Q, H533E, and H533Q enzymes were inhibited at increasing Zn²⁺ concentrations. The catalytic rate was reduced for all enzymes compared to that of the wild-type enzyme, although less dramatically with some activating metal ions. No major differences in the pH dependence between wild-type and mutant enzymes were found in the presence of different metal ions. The pH optimum was 5, but enzyme instability was observed at pH <4.5; therefore, only the basic limb of the bell-shaped pH profile was analyzed.

  11. Particle physics. Positrons ride the wave

    DOE PAGES

    Piot, Philippe

    2015-08-26

    Here, experiments reveal that positrons — the antimatter equivalents of electrons — can be rapidly accelerated using a plasma wave. The findings pave the way to high-energy electron–positron particle colliders.

  12. Particle physics. Positrons ride the wave

    SciTech Connect

    Piot, Philippe

    2015-08-26

    Here, experiments reveal that positrons — the antimatter equivalents of electrons — can be rapidly accelerated using a plasma wave. The findings pave the way to high-energy electron–positron particle colliders.

  13. KMOS view of the Galactic Centre - II. Metallicity distribution of late-type stars

    NASA Astrophysics Data System (ADS)

    Feldmeier-Krause, A.; Kerzendorf, W.; Neumayer, N.; Schödel, R.; Nogueras-Lara, F.; Do, T.; de Zeeuw, P. T.; Kuntschner, H.

    2017-01-01

    Knowing the metallicity distribution of stars in the Galactic Centre has important implications for the formation history of the Milky Way nuclear star cluster. However, this distribution is not well known, and is currently based on a small sample of fewer than 100 stars. We obtained near-infrared K-band spectra of more than 700 late-type stars in the central 4 pc2 of the Milky Way nuclear star cluster with the integral-field spectrograph KMOS (VLT). We analyse the medium-resolution spectra using a full-spectral fitting method employing the Göttingen spectral library of synthetic PHOENIX spectra. The derived stellar metallicities range from metal-rich [M/H] > +0.3 dex to metal-poor [M/H] <-1.0 dex, with a fraction of 5.2^{+6.0}_{-3.1} per cent metal-poor ([M/H] ≤ -0.5 dex) stars. The metal-poor stars are distributed over the entire observed field. The origin of metal-poor stars remains unclear. They could originate from infalling globular clusters. For the metal-rich stellar population ([M/H] > 0 dex), a globular cluster origin can be ruled out. As there is only a very low fraction of metal-poor stars in the central 4 pc2 of the Galactic Centre, we believe that our data can discard a scenario in which the Milky Way nuclear star cluster is purely formed from infalling globular clusters.

  14. Performance of the (n,{gamma})-Based Positron Beam Facility NEPOMUC

    SciTech Connect

    Schreckenbach, K.; Hugenschmidt, C.; Piochacz, C.; Stadlbauer, M.; Loewe, B.; Maier, J.; Pikart, P.

    2009-01-28

    The in-pile positron source of NEPOMUC at the neutron source Heinz Maier-Leibnitz (FRM II) provides at the experimental site an intense beam of monoenergetic positrons with selectable energy between 15 eV and 3 keV. The principle of the source is based on neutron capture gamma rays produced by cadmium in a beam tube tip close to the reactor core. The gamma ray absorption in platinum produces positrons which are moderated and formed to the beam. An unprecedented beam intensity of 9.10{sup 8} e{sup +}/s is achieved (1 keV). The performance and applications of the facility are presented.

  15. THE ABUNDANCE SCATTER IN M33 FROM H II REGIONS: IS THERE ANY EVIDENCE FOR AZIMUTHAL METALLICITY VARIATIONS?

    SciTech Connect

    Bresolin, Fabio

    2011-04-01

    Optical spectra of 25 H II regions in the inner 2 kpc of the M33 disk have been obtained with the Gemini Multi-Object Spectrograph at the Gemini North telescope. The oxygen abundance gradient measured from the detection of the [O III] {lambda}4363 auroral line displays a scatter of approximately 0.06 dex, a much smaller value than recently reported by Rosolowsky and Simon in this galaxy. The analysis of the abundances for a large sample of H II regions derived from the R{sub 23} strong-line indicator confirms that the scatter is small over the full disk of M33, consistent with the measuring uncertainties, and comparable to what is observed in other spiral galaxies. No evidence is therefore found for significant azimuthal variations in the present-day metallicity of the interstellar medium in this galaxy on spatial scales from {approx}100 pc to a few kpc. A considerable fraction of M33 H II regions with auroral line detections show spectral features revealing sources of hard ionizing radiation (such as He II emission and large [Ne III], [O III] line fluxes). Since R{sub 23} is shown to severely underestimate the oxygen abundances in such cases, care must be taken in chemical abundance studies of extragalactic H II regions based on this strong-line indicator.

  16. The preparation of polyelectrolyte complexes carboxymethyl chitosan(CMC)-pectin by reflux method as a Pb (II) metal ion adsorbent

    NASA Astrophysics Data System (ADS)

    Hastuti, Budi; Mudasir, Siswanta, Dwi; Triyono

    2016-02-01

    Aim of this research is to synthesized a chemically stable polyelectrolyte complexs carboxymetyl chitosan CMC-pectin as Pb(II) ion adsorbent by reflux method. During synthesis process, the optimum mass ratio of CMC and pectin was pre-determined and the active groups of the CMC-pectin complex was characterized by using IR spectrofotometer. Finally, adsorption capacity of the adsorbent material for Pb (II) ions was studied under optimum condition, i.e. adsorbent mass, contact time, and pH. Result shows that CMC could be succesfully combined with pectin to produce CMC-pectin complex. The optimum mass ratio CMC: pectin to form the polyelectrolyte complexs CMC-pectin was 70% : 30%. The active groups identified in the CMC-pectin complex was a hydroxyl (OH) and carboxylate (-COOH) groups. The optimum conditions for Pb (II) ion absoprtion was 10 mg of the adsorbent mass, 75 min of contact time, and pH 5. This material can be effectively used as adsorbents for Pb (II) ions, where up to 91% Pb (II) metal ions was adsorbed from aqueous solution and the adsorption capacity of the adsorbent was 41.63 mg/g.

  17. Adsorption of Azo-Dye Orange II from Aqueous Solutions Using a Metal-Organic Framework Material: Iron- Benzenetricarboxylate

    PubMed Central

    Rojas García, Elizabeth; López Medina, Ricardo; May Lozano, Marcos; Hernández Pérez, Isaías; Valero, Maria J.; Maubert Franco, Ana M.

    2014-01-01

    A Metal-Organic Framework (MOF), iron-benzenetricarboxylate (Fe(BTC)), has been studied for the adsorptive removal of azo-dye Orange II from aqueous solutions, where the effect of various parameters was tested and isotherm and kinetic models were suggested. The adsorption capacities of Fe(BTC) were much higher than those of an activated carbon. The experimental data can be best described by the Langmuir isotherm model (R2 > 0.997) and revealed the ability of Fe(BTC) to adsorb 435 mg of Orange II per gram of adsorbent at the optimal conditions. The kinetics of Orange II adsorption followed a pseudo-second-order kinetic model, indicating the coexistence of physisorption and chemisorption, with intra-particle diffusion being the rate controlling step. The thermodynamic study revealed that the adsorption of Orange II was feasible, spontaneous and exothermic process (−25.53 kJ·mol−1). The high recovery of the dye showed that Fe(BTC) can be employed as an effective and reusable adsorbent for the removal of Orange II from aqueous solutions and showed the economic interest of this adsorbent material for environmental purposes. PMID:28788289

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

    NASA Astrophysics Data System (ADS)

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

    2017-08-01

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

  19. An environment-dependent semi-empirical tight binding model suitable for electron transport in bulk metals, metal alloys, metallic interfaces, and metallic nanostructures. II. Application—Effect of quantum confinement and homogeneous strain on Cu conductance

    SciTech Connect

    Hegde, Ganesh Povolotskyi, Michael; Kubis, Tillmann; Charles, James; Klimeck, Gerhard

    2014-03-28

    The Semi-Empirical tight binding model developed in Part I Hegde et al. [J. Appl. Phys. 115, 123703 (2014)] is applied to metal transport problems of current relevance in Part II. A systematic study of the effect of quantum confinement, transport orientation, and homogeneous strain on electronic transport properties of Cu is carried out. It is found that quantum confinement from bulk to nanowire boundary conditions leads to significant anisotropy in conductance of Cu along different transport orientations. Compressive homogeneous strain is found to reduce resistivity by increasing the density of conducting modes in Cu. The [110] transport orientation in Cu nanowires is found to be the most favorable for mitigating conductivity degradation since it shows least reduction in conductance with confinement and responds most favorably to compressive strain.

  20. Design of ternary alkaline-earth metal Sn(II) oxides with potential good p-type conductivity

    SciTech Connect

    Du, Mao -Hua; Singh, David J.; Zhang, Lijun; Li, Yuwei; Xu, Qiaoling; Ma, Yanming; Zheng, Weitao

    2016-04-19

    Oxides with good p-type conductivity have been long sought after to achieve high performance all-oxide optoelectronic devices. Divalent Sn(II) based oxides are promising candidates because of their rather dispersive upper valence bands caused by the Sn-5s/O-2p anti-bonding hybridization. There are so far few known Sn(II) oxides being p-type conductive suitable for device applications. Here, we present via first-principles global optimization structure searches a material design study for a hitherto unexplored Sn(II)-based system, ternary alkaline-earth metal Sn(II) oxides in the stoichiometry of MSn2O3 (M = Mg, Ca, Sr, Ba). We identify two stable compounds of SrSn2O3 and BaSn2O3, which can be stabilized by Sn-rich conditions in phase stability diagrams. Their structures follow the Zintl behaviour and consist of basic structural motifs of SnO3 tetrahedra. Unexpectedly they show distinct electronic properties with band gaps ranging from 1.90 (BaSn2O3) to 3.15 (SrSn2O3) eV, and hole effective masses ranging from 0.87 (BaSn2O3) to above 6.0 (SrSn2O3) m0. Further exploration of metastable phases indicates a wide tunability of electronic properties controlled by the details of the bonding between the basic structural motifs. Lastly, this suggests further exploration of alkaline-earth metal Sn(II) oxides for potential applications requiring good p-type conductivity such as transparent conductors and photovoltaic absorbers.

  1. Design of ternary alkaline-earth metal Sn(II) oxides with potential good p-type conductivity

    SciTech Connect

    Du, Mao -Hua; Singh, David J.; Zhang, Lijun; Li, Yuwei; Xu, Qiaoling; Ma, Yanming; Zheng, Weitao

    2016-04-19

    Oxides with good p-type conductivity have been long sought after to achieve high performance all-oxide optoelectronic devices. Divalent Sn(II) based oxides are promising candidates because of their rather dispersive upper valence bands caused by the Sn-5s/O-2p anti-bonding hybridization. There are so far few known Sn(II) oxides being p-type conductive suitable for device applications. Here, we present via first-principles global optimization structure searches a material design study for a hitherto unexplored Sn(II)-based system, ternary alkaline-earth metal Sn(II) oxides in the stoichiometry of MSn2O3 (M = Mg, Ca, Sr, Ba). We identify two stable compounds of SrSn2O3 and BaSn2O3, which can be stabilized by Sn-rich conditions in phase stability diagrams. Their structures follow the Zintl behaviour and consist of basic structural motifs of SnO3 tetrahedra. Unexpectedly they show distinct electronic properties with band gaps ranging from 1.90 (BaSn2O3) to 3.15 (SrSn2O3) eV, and hole effective masses ranging from 0.87 (BaSn2O3) to above 6.0 (SrSn2O3) m0. Further exploration of metastable phases indicates a wide tunability of electronic properties controlled by the details of the bonding between the basic structural motifs. Lastly, this suggests further exploration of alkaline-earth metal Sn(II) oxides for potential applications requiring good p-type conductivity such as transparent conductors and photovoltaic absorbers.

  2. Design of ternary alkaline-earth metal Sn(II) oxides with potential good p-type conductivity

    DOE PAGES

    Du, Mao -Hua; Singh, David J.; Zhang, Lijun; ...

    2016-04-19

    Oxides with good p-type conductivity have been long sought after to achieve high performance all-oxide optoelectronic devices. Divalent Sn(II) based oxides are promising candidates because of their rather dispersive upper valence bands caused by the Sn-5s/O-2p anti-bonding hybridization. There are so far few known Sn(II) oxides being p-type conductive suitable for device applications. Here, we present via first-principles global optimization structure searches a material design study for a hitherto unexplored Sn(II)-based system, ternary alkaline-earth metal Sn(II) oxides in the stoichiometry of MSn2O3 (M = Mg, Ca, Sr, Ba). We identify two stable compounds of SrSn2O3 and BaSn2O3, which can bemore » stabilized by Sn-rich conditions in phase stability diagrams. Their structures follow the Zintl behaviour and consist of basic structural motifs of SnO3 tetrahedra. Unexpectedly they show distinct electronic properties with band gaps ranging from 1.90 (BaSn2O3) to 3.15 (SrSn2O3) eV, and hole effective masses ranging from 0.87 (BaSn2O3) to above 6.0 (SrSn2O3) m0. Further exploration of metastable phases indicates a wide tunability of electronic properties controlled by the details of the bonding between the basic structural motifs. Lastly, this suggests further exploration of alkaline-earth metal Sn(II) oxides for potential applications requiring good p-type conductivity such as transparent conductors and photovoltaic absorbers.« less

  3. Effect of metal oxides on the reactivity of persulfate/Fe(II) in the remediation of diesel-contaminated soil and sand.

    PubMed

    Do, Si-Hyun; Kwon, Yong-Jae; Kong, Sung-Ho

    2010-10-15

    The effect of metal oxides on the ability of persulfate (PS) with Fe(II) to remediate diesel-contaminated soil was investigated. In both natural soil and purchased sand, the highest diesel degradation occurred at pH 3 and the optimum molar ratio of PS/Fe(II) was 100:1 (i.e. 500 mM PS to 5 mM Fe(II)). Moreover, adding Fe(II) increased PS reactivity more in soil than it did in sand, indicating the involvement of metal oxides in the soil matrix. Evaluating the effects of metal oxides (i.e. goethite, hematite, magnetite, and manganese oxide) on the reactivity of PS with/without Fe(II) in a system containing diesel-contaminated sand revealed that manganese oxide increased PS activity the most and that the highest diesel degradation by PS occurred when both manganese oxide and Fe(II) were used as activators. XRD did not show the transformation of manganese oxide in the presence of Fe(II). SEM-EDS showed the association of Fe(II) on the surface of manganese oxide, and ICP analysis revealed that almost all the added Fe(II) adsorbed to manganese oxide but almost none adsorbed to iron oxides under acidic conditions. Therefore, the high reactivity of PS could be due to the high density of Fe(II) over the surface of manganese oxide. 2010 Elsevier B.V. All rights reserved.

  4. Study on low-energy positron polarimetry

    NASA Astrophysics Data System (ADS)

    Schälicke, A.; Alexander, G.; Dollan, R.; Laihem, K.; Lohse, T.; Riemann, S.; Starovoitov, P.; Ushakov, A.

    2007-12-01

    A polarised positron source has been proposed for the design of the international linear collider (ILC). In order to optimise the positron beam, a measurement of its degree of polarisation close to the positron creation point is desired. In this contribution, methods for determining the positron polarisation at low energies are reviewed. A newly developed polarisation extension to GEANT4 will provide the basis for further polarimeter investigations.

  5. Binding of kinetically inert metal ions to RNA: the case of platinum(II).

    PubMed

    Chapman, Erich G; Hostetter, Alethia A; Osborn, Maire F; Miller, Amanda L; DeRose, Victoria J

    2011-01-01

    In this chapter several aspects of Pt(II) are highlighted that focus on the properties of Pt(II)-RNA adducts and the possibility that they influence RNA-based processes in cells. Cellular distribution of Pt(II) complexes results in significant platination of RNA, and localization studies find Pt(II) in the nucleus, nucleolus, and a distribution of other sites in cells. Treatment with Pt(II) compounds disrupts RNA-based processes including enzymatic processing, splicing, and translation, and this disruption may be indicative of structural changes to RNA or RNA-protein complexes. Several RNA-Pt(II) adducts have been characterized in vitro by biochemical and other methods. Evidence for Pt(II) binding in non-helical regions and for Pt(II) cross-linking of internal loops has been found. Although platinated sites have been identified, there currently exists very little in the way of detailed structural characterization of RNA-Pt(II) adducts. Some insight into the details of Pt(II) coordination to RNA, especially RNA helices, can be gained from DNA model systems. Many RNA structures, however, contain complex tertiary folds and common, purine-rich structural elements that present suitable Pt(II) nucleophiles in unique arrangements which may hold the potential for novel types of platinum-RNA adducts. Future research aimed at structural characterization of platinum-RNA adducts may provide further insights into platinum-nucleic acid binding motifs, and perhaps provide a rationale for the observed inhibition by Pt(II) complexes of splicing, translation, and enzymatic processing.

  6. Binding of Kinetically Inert Metal Ions to RNA: The Case of Platinum(II)

    PubMed Central

    Chapman, Erich G.; Hostetter, Alethia A.; Osborn, Maire F.; Miller, Amanda L.; DeRose, Victoria J.

    2014-01-01

    In this chapter several aspects of Pt(II) are highlighted that focus on the properties of Pt(II)-RNA adducts and the possibility that they influence RNA-based processes in cells. Cellular distribution of Pt(II) complexes results in significant platination of RNA, and localization studies find Pt(II) in the nucleus, nucleolus, and a distribution of other sites in cells. Treatment with Pt(II) compounds disrupts RNA-based processes including enzymatic processing, splicing, and translation, and this disruption may be indicative of structural changes to RNA or RNA-protein complexes. Several RNA-Pt(II) adducts have been characterized in vitro by biochemical and other methods. Evidence for Pt(II) binding in non-helical regions and for Pt(II) cross-linking of internal loops has been found. Although platinated sites have been identified, there currently exists very little in the way of detailed structural characterization of RNA-Pt(II) adducts. Some insight into the details of Pt(II) coordination to RNA, especially RNA helices, can be gained from DNA model systems. Many RNA structures, however, contain complex tertiary folds and common, purine-rich structural elements that present suitable Pt(II) nucleophiles in unique arrangements which may hold the potential for novel types of platinum-RNA adducts. Future research aimed at structural characterization of platinum-RNA adducts may provide further insights into platinum-nucleic acid binding motifs, and perhaps provide a rationale for the observed inhibition by Pt(II) complexes of splicing, translation, and enzymatic processing. PMID:22010278

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

    PubMed Central

    Scozzafava, Andrea

    1997-01-01

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

  8. Biological Low-pH Mn(II) Oxidation in a Manganese Deposit Influenced by Metal-Rich Groundwater

    PubMed Central

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

    2016-01-01

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

  9. ON-OFF mechanism of a fluorescent sensor for the detection of Zn(II), Cd(II), and Cu(II)transition metal ions.

    PubMed

    Su, Huizhen; Chen, Xuebo; Fang, Weihai

    2014-01-07

    An ab initio multiconfigurational (CASPT2//CASSCF) approach has been employed to map radiative and nonradiative relaxation pathways for a cyclam-methylbenzimidazole fluorescent sensor and its metal ion (Zn(2+), Cd(2+), and Cu(2+)) complexes to provide an universal understanding of ON-OFF fluorescent mechanisms for the selective identification of these metal ions. The photoinduced electron transfer (PET) between the receptor and the signaling unit is quantitatively attributed for the first time to a newly generated transition of S0→SCT((1)nπ*), which is a typical (1)nπ* excitation but exhibits a significant charge transfer character and zwitterionic radical configuration. The present study contributes the two theoretical models of the competitive coexistence of radiative/nonradiative decay channel in (1)ππ*/SCT((1)nπ*) states for the detection of metal ions with d(10) configuration (i.e., Zn(2+), Cd(2+), etc.) and a downhill ladder relaxation pathway through multi nona-diabatic relays for the probing of d(9) cations (Cu(2+), etc.). These computational results will establish a benchmark for ON-OFF mechanisms of a fluorescent sensor that coordinates various transition metal ions with different electron configuration and radius.

  10. Synthesis, characterization and anti-microbial activity of phenylurea-formaldehyde resin (PUF) and its polymer metal complexes (PUF-Mn(II)

    NASA Astrophysics Data System (ADS)

    Ahamad, Tansir; Alshehri, Saad M.

    2012-10-01

    Phenylurea-formaldehyde polymer (PUF) was synthesized via polycondensation of phenylurea and formaldehyde in basic medium, its polymer-metal complexes [PUF-M(II)] were prepared with Mn(II), Co(II), Ni(II), Cu(II), and Zn(II) ions. PUF and PUF-M(II) were characterized with magnetic moment measurements, elemental and spectral (UV-visible, FTIR, 1H-NMR, 13C-NMR and ESR) analysis. The thermal behaviors of all the synthesized polymers were carried out using thermogravimetric analysis (TGA) and differential thermal analysis (DTA). The thermal data revealed that all of the PUF-M(II) showed higher thermal stabilities than the PUF and also ascribed that the PUF-Cu(II) showed better thermal stability than the other PUF-M(II). The kinetic parameters such as activation energy, pre-exponential factor etc., were evaluated for these polymer metal complexes using Coats-Redfern equation. In addition, the antimicrobial activity of the synthesized polymers was tested against several microorganisms using agar well diffusion methods. Among all of the PUF-M(II), the antimicrobial activity of the PUF-Cu(II) showed the highest zone of inhibition because of its higher stability constant and may be used in biomedical applications.

  11. Selective extraction of histidine derivatives by metal affinity with a copper(II)-chelating ligand complex in an aqueous two-phase system.

    PubMed

    Oshima, Tatsuya; Oshima, Chinatsu; Baba, Yoshinari

    2015-05-15

    Affinity extraction based on the interaction between a target molecule and a specific affinity ligand offers a novel separation system for biomolecules in an aqueous two-phase system, however, most of affinity ligands are expensive. In the present study, metal affinity extraction of histidine (His) derivatives using a complex between Cu(II) and a commercially available chelating ligand was studied in a poly(ethylene glycol) (PEG)/Li2SO4 ATPS. Alizarin complexone (3-[N,N-bis(carboxymethyl)amino methyl]-1,2-dihydroxy anthraquinone, AC) was selected as the chelating ligand because of the good extractability of Cu(II) into the upper PEG-rich phase. On the basis of coordinate bonding with Cu(II), the extraction of His in the presence of the Cu(II)-AC complex under neutral condition was 73%, which was much higher than that under Cu(II) free condition (13%). Among a series of divalent transition metal ions (Cu(II), Ni(II), Co(II), and Zn(II)), Cu(II) was the most effective for the extraction of His. Derivatives of His were selectively extracted in the presence of many other amino acids because of the specificity of the interaction between Cu(II) and imidazole group of His. Extracted His was quantitatively stripped from the Cu(II)-AC complex using competitive complexation with agents such as iminodiacetic acid and imidazole. Copyright © 2015 Elsevier B.V. All rights reserved.

  12. Synthesis, characterization and anti-microbial activity of phenylurea-formaldehyde resin (PUF) and its polymer metal complexes (PUF-Mn(II).

    PubMed

    Ahamad, Tansir; Alshehri, Saad M

    2012-10-01

    Phenylurea-formaldehyde polymer (PUF) was synthesized via polycondensation of phenylurea and formaldehyde in basic medium, its polymer-metal complexes [PUF-M(II)] were prepared with Mn(II), Co(II), Ni(II), Cu(II), and Zn(II) ions. PUF and PUF-M(II) were characterized with magnetic moment measurements, elemental and spectral (UV-visible, FTIR, 1H-NMR, 13C-NMR and ESR) analysis. The thermal behaviors of all the synthesized polymers were carried out using thermogravimetric analysis (TGA) and differential thermal analysis (DTA). The thermal data revealed that all of the PUF-M(II) showed higher thermal stabilities than the PUF and also ascribed that the PUF-Cu(II) showed better thermal stability than the other PUF-M(II). The kinetic parameters such as activation energy, pre-exponential factor etc., were evaluated for these polymer metal complexes using Coats-Redfern equation. In addition, the antimicrobial activity of the synthesized polymers was tested against several microorganisms using agar well diffusion methods. Among all of the PUF-M(II), the antimicrobial activity of the PUF-Cu(II) showed the highest zone of inhibition because of its higher stability constant and may be used in biomedical applications.

  13. Effect of Cr(VI) and Ni(II) metal ions on human adipose derived stem cells.

    PubMed

    Indra, R; Purna Sai, K; Rajaram, A; Rajaram, Rama

    2015-02-01

    Environmental exposure of Cr(VI) and Ni(II) due to rapid industrialization causes adverse effects in living tissues. Small quantities of these ions also find their way into tissues when metal alloys are used as implants. Even though considerable research has been done on the effects due to their exposure in animal cells, there are only very few reports on how they can affect stem cells which have been shown to be found in adult tissues as well, albeit in small quantities. Hence this study was aimed at understanding how Cr(VI) and Ni(II) affect human adipose derived stem cells (hADSCs) in a cell culture environment. Our results indicate that both ions induce apoptosis in a concentration and time dependent manner with loss of mitochondrial membrane potential (MMP) and corresponding increase in caspase-3 activity. With regard to Ni(II), apoptosis seems to occur only in a small percentage of cells while necrosis is predominant. It can be inferred that the long term exposure of these metals may cause adverse effects in stem cell proliferation and differentiation.

  14. Studies of positron induced luminescence from polymers

    SciTech Connect

    Xu, J.; Hulett, L.D. Jr.; Lewis, T.A.; Tolk, N.H.

    1994-06-01

    Light emission from polymers (anthracene dissolved in polystryrene) induced by low-energy positrons and electrons has been studied. Results indicate a clear difference between optical emissions under positron and electron bombardment. The positron-induced luminescence spectrum is believed to be generated by both collisional and annihilation processes.

  15. A spin-canted Ni(II)4-based metal-organic framework with gas sorption properties and high adsorptive selectivity for light hydrocarbons.

    PubMed

    Li, Jia; Guo, Ying; Fu, Hong-Ru; Zhang, Jian; Huang, Rong-Bin; Zheng, Lan-Sun; Tao, Jun

    2014-08-21

    The reaction of nickel(II) nitrate with isonicotinic acid and 2,6-dimethyl-pyridine-3,5-dicarboxylic acid affords a novel, tetranuclear nickel(II)-based metal-organic framework that exhibits spin-canted antiferromagnetism with a canted angle of 1.65° and high adsorptive selectivity for light hydrocarbons.

  16. Heavy metal pollution among autoworkers. II. Cadmium, chromium, copper, manganese, and nickel.

    PubMed Central

    Clausen, J; Rastogi, S C

    1977-01-01

    Garages and auto-repair workshops may be polluted with other heavy metals besides lead. Blood of autoworkers with high lead content was analysed for cadmium, chromium, copper manganese, nickel, ALAD activity and carboxyhaemoglobin level. Cadmium and copper levels in blood of autoworkers were comparable with those of the control subjects while chroimium and nickel levels were significantly higher (P less than 0-01 for both metals), and scattered raised values of manganese were found. There was no significant mutual correlation between levels of various heavy metals determined in whole blood. High copper levels were slightly related to decreasing ALAD activity (P less than 0-1). Nineteen per cent of autoworkers were found to have an abnormally blood level of carboxyhaemoglobin. The amount of particulate heavy metal in autoworkshop air was not related to biochemical abnormalities found in the autoworkers. Various sources of pollution of these heavy metals in autoworkshops are discussed. PMID:71915

  17. Removal Efficiency of the Heavy Metals Zn(II), Pb(II) and Cd(II) by Saprolegnia delica and Trichoderma viride at Different pH Values and Temperature Degrees.

    PubMed

    Ali, Esam H; Hashem, Mohamed

    2007-09-01

    The removal efficiency of the heavy metals Zn, Pb and Cd by the zoosporic fungal species Saprolegnia delica and the terrestrial fungus Trichoderma viride, isolated from polluted water drainages in the Delta of Nile in Egypt, as affected by various ranges of pH values and different temperature degrees,was extensively investigated. The maximum removal efficiency of S. delica for Zn(II) and Cd(II) was obtained at pH 8 and for Pb(II) was at pH 6 whilst the removal efficiency of T. viride was found to be optimum at pH 6 for the three applied heavy metals. Regardless the median lethal doses of the three heavy metals, Zn recorded the highest bioaccumulation potency by S. delica at all pH values except at pH 4, followed by Pb whereas Cd showed the lowest removal potency by the fungal species and vice versa in case of T. viride. The optimum biomass dry weight production by S. delica was found when the fungus was grown in the medium treated with the heavy metal Pb at pH 6, followed by Zn at pH 8 and Cd at pH 8. The optimum biomass dry weight yield by T. viride amended with Zn,Pb and Cd was obtained at pH 6 for the three heavy metals with the maximum value at Zn. The highest yield of biomass dry weight was found when T. viride treated with Cd at all different pH values followed by Pb whilst Zn output was the lowest and this result was reversed in case of S. delica. The maximum removal efficiency and the biomass dry weight production for the three tested heavy metals was obtained at the incubation temperature 20℃ in case of S. delica while it was 25℃ for T. viride. Incubation of T. viride at higher temperatures (30℃ and 35℃) enhanced the removal efficiency of Pb and Cd than low temperatures (15℃ and 20℃) and vice versa in case of Zn removal. At all tested incubation temperatures, the maximum yield of biomass dry weight was attained at Zn treatment by the two tested fungal species. The bioaccumulation potency of S. delica for Zn was higher than that for Pb at all

  18. Global properties of M31's stellar halo from the splash survey. II. Metallicity profile

    SciTech Connect

    Gilbert, Karoline M.; Kalirai, Jason S.; Guhathakurta, Puragra; Geha, Marla C.; Tollerud, Erik J.; Kirby, Evan N.; Bullock, James S.; Tanaka, Mikito; Chiba, Masashi

    2014-12-01

    We present the metallicity distribution of red giant branch (RGB) stars in M31's stellar halo, derived from photometric metallicity estimates for over 1500 spectroscopically confirmed RGB halo stars. The stellar sample comes from 38 halo fields observed with the Keck/DEIMOS spectrograph, ranging from 9 to 175 kpc in projected distance from M31's center, and includes 52 confirmed M31 halo stars beyond 100 kpc. While a wide range of metallicities is seen throughout the halo, the metal-rich peak of the metallicity distribution function becomes significantly less prominent with increasing radius. The metallicity profile of M31's stellar halo shows a continuous gradient from 9 to ∼100 kpc, with a magnitude of ∼ – 0.01 dex kpc{sup –1}. The stellar velocity distributions in each field are used to identify stars that are likely associated with tidal debris features. The removal of tidal debris features does not significantly alter the metallicity gradient in M31's halo: a gradient is maintained in fields spanning 10-90 kpc. We analyze the halo metallicity profile, as well as the relative metallicities of stars associated with tidal debris features and the underlying halo population, in the context of current simulations of stellar halo formation. We argue that the large-scale gradient in M31's halo implies M31 accreted at least one relatively massive progenitor in the past, while the field to field variation seen in the metallicity profile indicates that multiple smaller progenitors are likely to have contributed substantially to M31's outer halo.

  19. Synthesis, characterisation and catalytic activity of 4, 5-imidazoledicarboxylate ligated Co(II) and Cd(II) metal-organic coordination complexes

    NASA Astrophysics Data System (ADS)

    Gangu, Kranthi Kumar; Maddila, Suresh; Mukkamala, Saratchandra Babu; Jonnalagadda, Sreekantha B.

    2017-09-01

    Two mono nuclear coordination complexes, namely, [Co(4,5-Imdc)2 (H2O)2] (1) and [Cd(4,5-Imdc)2(H2O)3]·H2O (2) were constructed using Co(II) and Cd(II) metal salts with 4,5-Imidazoledicarboxylic acid (4,5-Imdc) as organic ligand. Both 1, 2 were structurally characterized by single crystal XRD and the results reveal that 1 belongs to P21/n space group with unit cell parameters [a = 5.0514(3) Å, b = 22.5786(9) Å, c = 6.5377(3) Å, β = 111.5°] whereas, 2 belongs to P21/c space group with unit cell parameters [a = 6.9116(1) Å, b = 17.4579(2) Å, c = 13.8941(2) Å, β = 97.7°]. While Co(II) in 1 exhibited a six coordination geometry with 4,5-Imdc and water molecules, Cd(II) ion in 2 showed a seven coordination with the same ligand and solvent. In both 1 and 2, the hydrogen bond interactions with mononuclear unit generated 3D-supramolecular structures. Both complexes exhibit solid state fluorescent emission at room temperature. The efficacy of both the complexes as heterogeneous catalysts was examined in the green synthesis of six pyrano[2,3,c]pyrazole derivatives with ethanol as solvent via one-pot reaction between four components, a mixture of aromatic aldehyde, malononitrile, hydrazine hydrate and dimethyl acetylenedicarboxylate. Both 1 and 2 have produced pyrano [2,3,c]pyrazoles in impressive yields (92-98%) at room temperature in short interval of times (<20 min), with no need for any chromatographic separations. With good stability, ease of preparation and recovery plus reusability up to six cycles, both 1 and 2 prove to be excellent environmental friendly catalysts for the value-added organic transformations using green principles.

  20. Positron-acoustic shock waves associated with cold viscous positron fluid in superthermal electron-positron-ion plasmas

    SciTech Connect

    Uddin, M. J. Alam, M. S.; Mamun, A. A.

    2015-06-15

    A theoretical investigation is made on the positron-acoustic (PA) shock waves (SHWs) in an unmagnetized electron-positron-ion plasma containing immobile positive ions, cold mobile positrons, and hot positrons and electrons following the kappa (κ) distribution. The cold positron kinematic viscosity is taken into account, and the reductive perturbation method is used to derive the Burgers equation. It is found that the viscous force acting on cold mobile positron fluid is a source of dissipation and is responsible for the formation of the PA SHWs. It is also observed that the fundamental properties of the PA SHWs are significantly modified by the effects of different parameters associated with superthermal (κ distributed) hot positrons and electrons.

  1. Removal of Hg(II) from aqueous solution using sodium humate as heavy metal capturing agent.

    PubMed

    Wang, Shixiang; Liu, Yong; Fan, Qin; Zhou, Anlan; Fan, Lu; Mu, Yulan

    2016-12-01

    An environmental friendly and economic natural biopolymer-sodium humate (HA-Na) was used to capture Hg(II) from aqueous solutions, and the trapped Hg(II) (HA-Na-Hg) was then removed by aluminium coagulation. The best Hg(II) capturing performance (90.60%) was observed under the following conditions: initial pH of 7.0, coagulation pH of 6.0, HA-Na dosage of 5.0 g L(-1), Al2(SO4)3.18H2O dosage of 4.0 g L(-1), initial Hg(II) concentration of 50 mg L(-1) and capturing time of 30 min. The HA-Na compositions with the molecular weight beyond 70 kDa showed the most intense affinity toward Hg(II). The results showed that the reaction equilibrium was achieved within 10 min (pH 7.0), and could be well fitted by the pseudo-second-order kinetics model. The capturing process could be well described by the Langmuir isotherm model and the maximum capturing capacity of Hg(II) was high up to 9.80 mg g(-1) at 298 K (pH 7.0). The Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) analysis showed that the redox reaction between Hg(II) and HA-Na and the coordination reaction of carboxyl and hydroxy groups of HA-Na with Hg(II) were responsible for Hg(II) removal. The successive regeneration experiment showed that the capturing efficiency of humates for Hg(II) was maintained at about 51% after five capture-regeneration recycles.

  2. Alginate and Algal-Based Beads for the Sorption of Metal Cations: Cu(II) and Pb(II)

    PubMed Central

    Wang, Shengye; Vincent, Thierry; Faur, Catherine; Guibal, Eric

    2016-01-01

    Alginate and algal-biomass (Laminaria digitata) beads were prepared by homogeneous Ca ionotropic gelation. In addition, glutaraldehyde-crosslinked poly (ethyleneimine) (PEI) was incorporated into algal beads. The three sorbents were characterized by scanning electron microscopy (SEM) coupled with energy dispersive X-ray analysis (EDX): the sorption occurs in the whole mass of the sorbents. Sorption experiments were conducted to evaluate the impact of pH, sorption isotherms, and uptake kinetics. A special attention was paid to the effect of drying (air-drying vs. freeze-drying) on the mass transfer properties. For alginate, freeze drying is required for maintaining the porosity of the hydrogel, while for algal-based sorbents the swelling of the material minimizes the impact of the drying procedure. The maximum sorption capacities observed from experiments were 415, 296 and 218 mg Pb g−1 and 112, 77 and 67 mg Cu g−1 for alginate, algal and algal/PEI beads respectively. Though the sorption capacities of algal-beads decreased slightly (compared to alginate beads), the greener and cheaper one-pot synthesis of algal beads makes this sorbent more competitive for environmental applications. PEI in algal beads decreases the sorption properties in the case of the sorption of metal cations under selected experimental conditions. PMID:27598128

  3. Alginate and Algal-Based Beads for the Sorption of Metal Cations: Cu(II) and Pb(II).

    PubMed

    Wang, Shengye; Vincent, Thierry; Faur, Catherine; Guibal, Eric

    2016-09-01

    Alginate and algal-biomass (Laminaria digitata) beads were prepared by homogeneous Ca ionotropic gelation. In addition, glutaraldehyde-crosslinked poly (ethyleneimine) (PEI) was incorporated into algal beads. The three sorbents were characterized by scanning electron microscopy (SEM) coupled with energy dispersive X-ray analysis (EDX): the sorption occurs in the whole mass of the sorbents. Sorption experiments were conducted to evaluate the impact of pH, sorption isotherms, and uptake kinetics. A special attention was paid to the effect of drying (air-drying vs. freeze-drying) on the mass transfer properties. For alginate, freeze drying is required for maintaining the porosity of the hydrogel, while for algal-based sorbents the swelling of the material minimizes the impact of the drying procedure. The maximum sorption capacities observed from experiments were 415, 296 and 218 mg Pb g(-1) and 112, 77 and 67 mg Cu g(-1) for alginate, algal and algal/PEI beads respectively. Though the sorption capacities of algal-beads decreased slightly (compared to alginate beads), the greener and cheaper one-pot synthesis of algal beads makes this sorbent more competitive for environmental applications. PEI in algal beads decreases the sorption properties in the case of the sorption of metal cations under selected experimental conditions.

  4. Modification and characterization of PET fibers for fast removal of Hg(II), Cu(II) and Co(II) metal ions from aqueous solutions.

    PubMed

    Monier, M; Abdel-Latif, D A

    2013-04-15

    A new chelating fiber (PET-TSC) was prepared with PET for fast removal of Hg(2+), Cu(2+) and Co(2+) from water. Elemental analysis, SEM, BET surface area, (13)C NMR, FTIR and X-ray diffraction spectra were used to characterize PET-TSC. The higher uptake capacity of the studied metal ions was observed at higher pH values. Kinetic study indicated that the adsorption of Hg(2+), Cu(2+) and Co(2+) followed the pseudo-second-order equation, suggesting chemical sorption as the rate-limiting step of the adsorption process. The best interpretation for the equilibrium data was given by Langmuir isotherm, and the maximum adsorption capacities were 120.02, 96.81 and 78.08 mg/g for Hg(2+), Cu(2+) and Co(2+) ions, respectively. 1M HCl or 0.1M EDTA could be used as effective eluant to desorb the Hg(2+), Cu(2+) and Co(2+) adsorbed by PET-TSC, and the adsorption capacity of PET-TSC for the three heavy metal ions could still be maintained at about 90% level at the 5th cycle. Accordingly, it is expected that PET-TSC could be used as a promising adsorbent for fast removal of heavy metal ions from water, and the present work also might provide a simple and effective method to reuse the waste PET fibers. Copyright © 2013 Elsevier B.V. All rights reserved.

  5. Anticandidal cytotoxicity, antitumor activities, and purified cell wall modulation by novel Schiff base ligand and its metal (II) complexes against some pathogenic yeasts.

    PubMed

    Geweely, Neveen S

    2009-09-01

    The preparation of metal (II) complexes [CoCl(2).6H(2)O, Ni(CH(3)COO)(2).4H(2)O, Cu(CH(3)COO)(2).2H(2)O, and Zn (CH3COO)(2) .2H(2)O] with 2[N-(cinnamlidene) amino]-5-nitro phenol as a novel ligands and their biological evaluation against candida species was studied. The inhibitory effects of the tested metal complexes were tested against six pathogenic yeasts (Candida albicans, C. fructus, C. glabrata, C. oleophila, C. parapsilosis, and C. tropicalis). The effect of the most efficient metal complex (Zn(II) complex) was more pronounced at 1.25 microg/ml, while Ni(II) complex was exhibited the least suppressive effect. Co(II) and Zn(II) complexes act as potential antitumor agents, while Zn(II) complex has shown promising cytotoxic activity with slow candidal respiration rate. Addition of Zn(II) complex leading to suppression of cell wall components in all candidal cells accompanied with leaking out of amino acids. Purification of the cell wall mannoprotein of C. glabrata treated with Zn(II) complex was established, resulting one pure fissured protein peak. Cell wall protein modulation was showed by appearance of two new protein bands with molecular weights of 72 and 39 KDa in C. glabrata cells treated with Zn(II) complex compared with one pure protein band 55.6 KDa in the non treated yeast cell.

  6. Isotopic studies of the metal-ligand vibrations in histamine complexes with Copper(II)

    NASA Astrophysics Data System (ADS)

    Drożdżewski, Piotr; Kordon, Ewa

    2000-06-01

    Two known copper complexes of the formulae Cu(hm) 2(ClO 4) 2, Cu(hm)Cl 2 and new, Cu(hm)Br 2 (hm=histamine) have been investigated in the 600-50 cm -1 far-infrared region. Assignments of vibrations related to metal-ligand bonds have been made based on metal isotope substitution, partial deuteration and halogen sensitivity. Copper-hm stretching vibrations have been localised at 420, 417 and 411 cm -1 for modes involving amine nitrogen and at 282, 270, 259 cm -1 for those of imidazole nitrogen. Vibrational coupling between some metal-ligand modes has been postulated.

  7. Solid-Phase Equilibria for Metal-Silicon-Oxygen Ternary Systems. II. Sc, Y, and La

    DTIC Science & Technology

    1991-02-28

    Organization: Regents of the University of California TECHNICAL REPORT No. 9 SOLID- PHASE EQUILIBRIA FOR METAL-SILICON-OXYGEN TERNARY SYSTEMS: 11: Sc, Y, AND La...34’ SOLID- PHASE EQUILIBRIA FOR METAL-SILICON-OXYGEN TERNARY SYSTEMS: 11: Sc, Y, AND 1a 13 0911OtiA AUTHORCS) Haojie Yuan and R. Stanley Williams lI" TV...0660te tCLhSSWI=) Solid phase equilibria for metal-silicon-oxygen ternary systems I1: Sc, Y and La Haojie Yuan and R. Stanley Williams Department of

  8. Theoretical study of the Pb(II)-catechol system in dilute aqueous solution: Complex structure and metal coordination sphere determination

    NASA Astrophysics Data System (ADS)

    Lapouge, Christine; Cornard, Jean-Paul

    2010-04-01

    We investigated the unknown interaction of Pb(II) with catechol ligand in diluted aqueous solution by electronic spectroscopies combined with quantum chemical calculations. The aim of this work is the determination of the complete structure of the complex formed and particularly the metal coordination sphere. Three successive steps have been necessary to reach this goal: (i) the comparison of the experimental electronic absorption spectrum with theoretical spectra calculated from various hypothetical structures, (ii) complexation reaction pathways calculations in vacuum and with taking into account the solvent effects and finally (iii) the fluorescence emission wavelength calculations. All these investigations led to identify a monodentate complex with the monodeprotonated ligand, in which the Pb atom presents a coordination number of five. The formula of the complex is [Pb(Hcat)(HO)4]mono+.

  9. Modeling ecological data in soil ecosystems: A demonstration for heavy metal transport by earthworms using Stella II{trademark}

    SciTech Connect

    Johnston, J.M.; Tomlin, A.D.; Protz, R. ||

    1995-06-01

    Various modeling approaches have been developed for use in aquatic systems, but few exist for terrestrial systems. Using the modeling application software, Stella II{trademark}, we incorporated field data to parameterize the storage compartments and flux rates amongst compartments. This software is intuitive and easy to master yet robust in its application to many types of ecological systems. The applicability of Stella II{trademark} to modeling field data was demonstrated using contaminant cadmium residues as tracers of sludge applications to land near Guelph, Canada. Earthworms were found to be very significant in transporting the Cd (and the sludge) in this soil ecosystem. The utility of this modeling procedure can be extended to carbon and nutrient cycling as well as xenobiotics such as heavy metals and pesticides to predict their transport in soil ecosystems.

  10. A porous Cd(II) metal-organic framework with high adsorption selectivity for CO2 over CH4

    NASA Astrophysics Data System (ADS)

    Zhu, Chunlan

    2017-05-01

    Metal-organic frameworks (MOFs) have attracted a lot of attention in recent decades. We applied a semi-rigid four-carboxylic acid linker to assemble with Cd(II) ions to generate a novel microporous Cd(II) MOF material. Single crystal X-ray diffraction study reveals the different two dimension (2D) layers can be further packed together with an AB fashion by hydrogen bonds (O4sbnd H4⋯O7 = 1.863 Å) to construct a three dimension (3D) supermolecular architecture. The resulting sample can be synthesized under solvothermal reactions successfully, which exhibits high selectivity adsorption of CO2 over CH4 at room temperature. In addition, the obtained sample was characterized by thermal gravimetric analyses (TGA), Fourier-transform infrared spectra (FT-IR), elemental analysis (CHN) and powder X-ray diffraction (PXRD).

  11. Calcium (II) - and dipicolinic acid mediated-biostimulation of oil-bioremediation under multiple stresses by heat, oil and heavy metals.

    PubMed

    Radwan, Samir S; Al-Mailem, Dina M; Kansour, Mayada K

    2017-08-25

    The oil-producing Arabian Gulf states have hot summer seasons of about 7-month in length. Therefore, environmental oil spills should be bioremediated by the activity of indigenous, hydrocarbonoclastic (hydrocarbon-degrading) microorganisms with optimum growth at about 50 °C. Soils in such arid countries harbor thermophilic bacteria, whose oil-consumption potential is enhanced by calcium (II) - and dipicolinic acid (DPA)-supplement. Those organisms are, however, subjected to additional stresses including toxic effects of heavy metals that may be associated with the spilled oil. Our study highlighted the resistance of indigenous, thermophilic isolates to the heavy metals, mercury (II), cadmium (II), arsenic (II) and lead (II) at 50 °C. We also detected the uptake of heavy metals by 15 isolates at 50 °C, and identified the merA genes coding for Hg(2+)-resistance in 4 of the studied Hg(2+)-resistant isolates. Hg(2+) was the most toxic metal and the metal toxicity was commonly higher in the presence of oil. The addition of Ca(2+) and DPA enhanced the Hg(2+)-resistance among most of the isolates at 50 °C. Crude oil consumption at 50 °C by 4 selected isolates was inhibited by the tested heavy metals. However, Ca(2+) and DPA limited this inhibition and enhanced oil-consumption, which exceeded by far the values in the control cultures.

  12. Applications of RIGAKU Dmax Rapid II micro-X-ray diffractometer in the analysis of archaeological metal objects

    NASA Astrophysics Data System (ADS)

    Mozgai, Viktória; Szabó, Máté; Bajnóczi, Bernadett; Weiszburg, Tamás G.; Fórizs, István; Mráv, Zsolt; Tóth, Mária

    2017-04-01

    During material analysis of archaeological metal objects, especially their inlays or corrosion products, not only microstructure and chemical composition, but mineralogical composition is necessary to be determined. X-ray powder diffraction (XRD) is a widely-used method to specify the mineralogical composition. However, when sampling is not or limitedly allowed due to e.g. the high value of the object, the conventional XRD analysis can hardly be used. Laboratory micro-XRD instruments provide good alternatives, like the RIGAKU Dmax Rapid II micro-X-ray diffractometer, which is a unique combination of a MicroMax-003 third generation microfocus, sealed tube X-ray generator and a curved 'image plate' detector. With this instrument it is possible to measure as small as 10 µm area in diameter on the object. Here we present case studies for the application of the micro-XRD technique in the study of archaeological metal objects. In the first case niello inlay of a Late Roman silver augur staff was analysed. Due to the high value of the object, since it is the only piece known from the Roman Empire, only non-destructive analyses were allowed. To reconstruct the preparation of the niello, SEM-EDX analysis was performed on the niello inlays to characterise their chemical composition and microstructure. Two types of niello are present: a homogeneous, silver sulphide niello (acanthite) and an inhomogeneous silver-copper sulphide niello (exsolution of acanthite and jalpaite or jalpaite and stromeyerite). The micro-X-ray diffractometer was used to verify the mineralogical composition of the niello, supposed on the base of SEM results. In the second case corrosion products of a Late Roman copper cauldron with uncertain provenance were examined, since they may hold clues about the burial conditions (pH, Eh, etc.) of the object. A layer by layer analysis was performed in cross sections of small metal samples by using electron microprobe and micro-X-ray diffractometer. The results

  13. X-ray absorption spectroscopy of metal site speciation in the metallo-β-lactamase BcII from Bacillus cereus.

    PubMed

    Breece, Robert M; Llarrull, Leticia I; Tioni, Mariana F; Vila, Alejandro J; Tierney, David L

    2012-06-01

    Cobalt and zinc binding by the subclass B1 metallo-β-lactamase BcII from Bacillus cereus is examined by X-ray absorption spectroscopy, at various levels of metal loading. The data show that a significant amount of the dinuclear enzyme is formed, even at substoichiometric levels of metal loading, whether the added metal is Zn(II) or Co(II). Increasing metal addition, from 0.5 to 1.0 to 2.0eq/mol of enzyme, are shown to result in a more ordered active site. While Zn(II) appears to show no preference for the Zn(1) (3H) or Zn(2) (DCH) sites, the extended X-ray absorption fine structure (EXAFS) suggests that Co(II) shows a slight preference for the DCH site at low levels of added Co(II). The results are discussed in the context of similar metal-binding studies of other B1 metallo-β-lactamases. Copyright © 2012 Elsevier Inc. All rights reserved.

  14. Solution equilibria between ethylenediamine-N,N'-di-3-propionate and some transition metal(II) ions.

    PubMed

    Disic, J; Trifunovic, S; Grujic, S; Djurdjevic, P

    1999-06-14

    Solution equilibria between the ligand ethylenediamine-N,N'-di-3-propionate (eddp(2-)) and copper(II), nickel(II) or cobalt(II) ions were studied by glass electrode pH-metric and spectrophotometric measurements in 0.1 M NaCl ionic medium at 298.0+/-0.2 K. In the concentration limits 1.0metal(II)]

  15. Half-sandwich iron(ii) complexes with protic acyclic diaminocarbene ligands: synthesis, deprotonation and metalation reactions.

    PubMed

    Ruiz, Javier; García, Lucía; Vivanco, Marilín; Sol, Daniel; García-Granda, Santiago

    2017-08-08

    A variety of half-sandwich iron(ii) complexes with diprotic acyclic diaminocarbene ligands (pADCs) have been obtained by reaction of the cationic complexes [Fe(Cp)(CO)2(CNR)](+) and [Fe(Cp)(CO)(CNR)2](+) with methylamine, and their acid-base behaviour was studied, revealing an easy reversible deprotonation reaction of both N-H moieties of the carbene ligands. The deprotonation process is frequently followed by a nucleophilic attack of the nitrogen atom on a vicinal carbonyl or isocyanide ligand, affording the corresponding metallacycles. Metalation of one or two N-H groups of the pADC ligands can be accomplished by reaction of the carbene complexes with either [AuCl(PPh3)] or [Ru(p-cym)Cl2]2 in the presence of KOH or LiHMDS as deprotonating agents. A number of Fe(ii)/Au(i) and Fe(ii)/Ru(ii) heterometallic complexes have been prepared in this way, some of them formally containing unique metalla-N-heterocyclic carbene ligands.

  16. A curious interplay in the films of N-heterocyclic carbene PtII complexes upon deposition of alkali metals

    PubMed Central

    Makarova, Anna A.; Grachova, Elena V.; Niedzialek, Dorota; Solomatina, Anastasia I.; Sonntag, Simon; Fedorov, Alexander V.; Vilkov, Oleg Yu.; Neudachina, Vera S.; Laubschat, Clemens; Tunik, Sergey P.; Vyalikh, Denis V.

    2016-01-01

    The recently synthesized series of PtII complexes containing cyclometallating (phenylpyridine or benzoquinoline) and N-heterocyclic carbene ligands possess intriguing structures, topologies, and light emitting properties. Here, we report curious physicochemical interactions between in situ PVD-grown films of a typical representative of the aforementioned PtII complex compounds and Li, Na, K and Cs atoms. Based on a combination of detailed core-level photoelectron spectroscopy and quantum-chemical calculations at the density functional theory level, we found that the deposition of alkali atoms onto the molecular film leads to unusual redistribution of electron density: essential modification of nitrogen sites, reduction of the coordination PtII centre to Pt0 and decrease of electron density on the bromine atoms. A possible explanation for this is formation of a supramolecular system “Pt complex-alkali metal ion”; the latter is supported by restoration of the system to the initial state upon subsequent oxygen treatment. The discovered properties highlight a considerable potential of the PtII complexes for a variety of biomedical, sensing, chemical, and electronic applications. PMID:27151364

  17. A curious interplay in the films of N-heterocyclic carbene Pt(II) complexes upon deposition of alkali metals.

    PubMed

    Makarova, Anna A; Grachova, Elena V; Niedzialek, Dorota; Solomatina, Anastasia I; Sonntag, Simon; Fedorov, Alexander V; Vilkov, Oleg Yu; Neudachina, Vera S; Laubschat, Clemens; Tunik, Sergey P; Vyalikh, Denis V

    2016-05-06

    The recently synthesized series of Pt(II) complexes containing cyclometallating (phenylpyridine or benzoquinoline) and N-heterocyclic carbene ligands possess intriguing structures, topologies, and light emitting properties. Here, we report curious physicochemical interactions between in situ PVD-grown films of a typical representative of the aforementioned Pt(II) complex compounds and Li, Na, K and Cs atoms. Based on a combination of detailed core-level photoelectron spectroscopy and quantum-chemical calculations at the density functional theory level, we found that the deposition of alkali atoms onto the molecular film leads to unusual redistribution of electron density: essential modification of nitrogen sites, reduction of the coordination Pt(II) centre to Pt(0) and decrease of electron density on the bromine atoms. A possible explanation for this is formation of a supramolecular system "Pt complex-alkali metal ion"; the latter is supported by restoration of the system to the initial state upon subsequent oxygen treatment. The discovered properties highlight a considerable potential of the Pt(II) complexes for a variety of biomedical, sensing, chemical, and electronic applications.

  18. Spectral characterization, electrochemical and anticancer studies on some metal(II) complexes containing tridentate quinoxaline Schiff base

    NASA Astrophysics Data System (ADS)

    Chellaian, Justin Dhanaraj; Johnson, Jijo

    2014-06-01

    Co(II), Ni(II), Cu(II) and Zn(II) complexes of a tridentate ONO donor Schiff base ligand derived from 3-(2-aminoethylamino)quinoxalin-2(1H)-one were synthesized. The ligand and its metal complexes were characterized using elemental analysis, molar conductance, IR, 1H NMR, mass, magnetic susceptibility, electronic spectra and ESR spectral studies. Electrochemical behavior of the synthesized compounds was studied using cyclic voltammetry. The grain size of the synthesized compounds was determined by powder XRD. The Schiff base and its complexes have been screened for their antimicrobial activities against the bacterial species E. coli, K. pneumoniae, P. aeruginosa and S. aureus; fungal species include, A. niger, and C. albicans by disc diffusion method. The results show that the complexes have higher activity than the free ligand. The interaction of the complexes with calf thymus DNA (CT DNA) has been investigated by electronic absorption method. Furthermore, the DNA cleavage activity of the complexes was studied using agarose gel electrophoresis. In vitro anticancer studies of the ligand and its complexes using MTT assay was also done.

  19. The Metal Abundances across Cosmic Time (MACT) Survey. II. Evolution of the Mass-metallicity Relation over 8 Billion Years, Using [OIII]4363AA-based Metallicities

    NASA Astrophysics Data System (ADS)

    Ly, Chun; Malkan, Matthew A.; Rigby, Jane R.; Nagao, Tohru

    2016-09-01

    We present the first results from MMT and Keck spectroscopy for a large sample of 0.1≤slant z≤slant 1 emission-line galaxies selected from our narrowband imaging in the Subaru Deep Field. We measured the weak [O iii] λ4363 emission line for 164 galaxies (66 with at least 3σ detections, and 98 with significant upper limits). The strength of this line is set by the electron temperature for the ionized gas. Because the gas temperature is regulated by the metal content, the gas-phase oxygen abundance is inversely correlated with [O iii] λ4363 line strength. Our temperature-based metallicity study is the first to span ≈ 8 Gyr of cosmic time and ≈ 3 dex in stellar mass for low-mass galaxies, {log}({M}\\star /{M}⊙ )≈ 6.0-9.0. Using extensive multi-wavelength photometry, we measure the evolution of the stellar mass-gas metallicity relation and its dependence on dust-corrected star formation rate (SFR). The latter is obtained from high signal-to-noise Balmer emission-line measurements. Our mass-metallicity relation is consistent with Andrews & Martini at z≤slant 0.3, and evolves toward lower abundances at a given stellar mass, {log}{({{O/H}})\\propto (1+z)}-{2.32-0.26+0.52}. We find that galaxies with lower metallicities have higher SFRs at a given stellar mass and redshift, although the scatter is large (≈ 0.3 dex) and the trend is weaker than seen in local studies. We also compare our mass-metallicity relation against predictions from high-resolution galaxy formation simulations, and find good agreement with models that adopt energy- and momentum-driven stellar feedback. We identified 16 extremely metal-poor galaxies with abundances of less than a tenth of solar; our most metal-poor galaxy at z≈ 0.84 is similar to I Zw 18.

  20. Solvent-Mediated Transformation from Achiral to Chiral Nickel(II) Metal-Organic Frameworks and Reassembly in Solution.

    PubMed

    Li, Xiaoju; Yu, Zhenjiang; Li, Xinxiong; Guo, Xiaofang

    2015-11-09

    Reactions of 5-nitroisophthalic acid (NO2 -H2 ip), 1,4-bis(imidazol-1'-yl)butane (bimb), and Ni(NO3 )2 ⋅6 H2 O gave rise to four metal-organic frameworks (MOFs), [Ni2 (NO2 -ip)2 (bimb)1.5 ]n (1), [Ni4 (NO2 -ip)3 (bimb)2 (OH)2 (H2 O)]n ⋅(CH3 CH2 OH)0.5 n (2), [Ni(NO2 -ip)(bimb)1.5 (H2 O)]n ⋅(H2 O)n ⋅(CH3 CH2 OH)0.5 n (3), and [Ni(NO2 -ip) (bimb)(μ-H2 O)]n ⋅(H2 O)n (4). The metal/ligand ratio, pH value, and solvent exerted a subtle but crucial influence on the formation of complexes 1-4, which possess different visual color and crystal structures. Complex 1 exhibits a twofold interpenetrating 3D pillared bilayer framework composed of binuclear and mononuclear Ni(II) units, whereas complex 2 is a 3D chiral network that consists of asymmetric tetranuclear Ni(II) units. Complexes 3 and 4 are 3D layer-pillared frameworks that consist of mononuclear Ni(II) ions and a 3D six-connected network of μ-water-bridged dinuclear Ni(II) units, respectively. Interestingly, achiral 4 can be transformed into chiral 2 by using a solvent-mediated single-crystal-to-single-crystal process without any chiral auxiliary. Magnetic analyses of 2 and 4 show the occurrence of antiferromagnetic interactions. Complex 3 is difficult to obtain directly as a single solid phase, but it can be homogeneously formed by solvent-mediated transformations from 1, 2, and 4. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. [Emergent treatment process for raw water polluted by heavy metal Pb (II)].

    PubMed

    Chu, Wen-Hai; Gao, Nai-Yun; Yao, Juan-Juan; Shang, Ya-Bo; Qin, Zhu-Qun

    2008-10-01

    Based on two common coagulants-polyferric sulfate (PFS) and polyaluminum chloride (PACl), some measurements and processes in the background of Pb (II) concentration sudden increase in water were studied. The removal efficiency of Pb(II) was compared between PAC and diatomite absorption with coagulation. The effect of coagulant dosage, initial concentration of Pb(II), pH value and KMnO4 preoxidation on coagulation were investigated. The results showed that using PFS was better than PACl for the removal of Pb(II). The regulating pH value up to 9 could improve the removal efficiency of Pb(II) up to 95% by coagulation under the optimum dosage of coagulant PFS of 10 mg/L. KMnO4 preoxidation could improve the removal efficacy of Pb(II) by coagulation of PACl only. The Pb(II) removal efficiency of PAC and diatomite absorption with coagulation were almost equal. Pb(II) concentration could be lowered from 402 microg/L to below 10 microg/L under the condition that dosages of PAC or diatomite were 10 mg/L or 25 mg/L by using PFS. The same effect could be got under the condition that dosages of PAC or diatomite were 20 mg/L or 50 mg/L by using PACl. KMnO4 and diatomite are dosed at the same time would weaken their function each other. Therefore, diatomite adsorption coupled with coagulation is the simplest and most effective method for removing Pb(II).

  2. Galaxy evolution in cosmological simulations with outflows - II. Metallicities and gas fractions

    NASA Astrophysics Data System (ADS)

    Davé, Romeel; Finlator, Kristian; Oppenheimer, Benjamin D.

    2011-09-01

    We use cosmological hydrodynamic simulations to investigate how inflows, star formation and outflows govern the gaseous and metal content of galaxies within a hierarchical structure formation context. In our simulations, galaxy metallicities are established by a balance between inflows and outflows as governed by the mass outflow rate, implying that the mass-metallicity relation reflects how the outflow rate varies with stellar mass. Gas content, meanwhile, is set by a competition between inflow into and gas consumption within the interstellar medium, the latter being governed by the star formation law, while the former is impacted by both wind recycling and preventive feedback. Stochastic variations in the inflow rate move galaxies off the equilibrium mass-metallicity and mass-gas fraction relations in a manner correlated with the star formation rate, and the scatter is set by the time-scale to re-equilibrate. The evolution of both relations from z= 3 → 0 is slow, as individual galaxies tend to evolve mostly along the relations. Gas fractions at a given stellar mass slowly decrease with time because the cosmic inflow rate diminishes faster than the consumption rate, while metallicities slowly increase as infalling gas becomes more enriched. Observations from z˜ 3 → 0 are better matched by simulations employing momentum-driven wind scalings rather than constant wind speeds, but all models predict too low gas fractions at low masses and too high metallicities at high masses. All our models reproduce observed second-parameter trends of the mass-metallicity relation with the star formation rate and environment, indicating that these are a consequence of equilibrium and not feedback. Overall, the analytical framework of our equilibrium scenario broadly captures the relevant physics establishing the galaxy gas and metal content in simulations, which suggests that the cycle of baryonic inflows and outflows centrally governs the cosmic evolution of these properties

  3. Positron microanalysis with high intensity beams

    SciTech Connect

    Hulett, L.D. Jr.; Donohue, D.L.

    1990-01-01

    One of the more common applications for a high intensity slow positron facility will be microanalysis of solid materials. In the first section of this paper some examples are given of procedures that can be developed. Since most of the attendees of this workshop are experts in positron spectroscopy, comprehensive descriptions will be omitted. With the exception of positron emission microscopy, most of the procedures will be based on those already in common use with broad beams. The utility of the methods have all been demonstrated, but material scientists use very few of them because positron microbeams are not generally available. A high intensity positron facility will make microbeams easier to obtain and partially alleviate this situation. All microanalysis techniques listed below will have a common requirement, which is the ability to locate the microscopic detail or area of interest and to focus the positron beam exclusively on it. The last section of this paper is a suggestion of how a high intensity positron facility might be designed so as to have this capability built in. The method will involve locating the specimen by scanning it with the microbeam of positrons and inducing a secondary electron image that will immediately reveal whether or not the positron beam is striking the proper portion of the specimen. This scanning positron microscope' will be a somewhat prosaic analog of the conventional SEM. It will, however, be an indispensable utility that will enhance the practicality of positron microanalysis techniques. 6 refs., 1 fig.

  4. High intensity positron program at LLNL

    SciTech Connect

    Asoka-Kumar, P.; Howell, R.H.; Stoeffl, W.

    1998-09-23

    Lawrence Livermore National Laboratory (LLNL) is the home of the world's highest current beam of keV positrons. The potential for establishing a national center for materials analysis using positron annihilation techniques around this capability is being actively pursued. The high LLNL beam current will enable investigations in several new areas. We are developing a positron microprobe that will produce a pulsed, focused positron beam for 3-dimensional scans of defect size and concentration with submicron resolution. Below we summarize the important design features of this microprobe. Several experimental end stations will be available that can utilize the high current beam with a time distribution determined by the electron linac pulse structure, quasi-continuous, or bunched at 20 MHz, and can operate in an electrostatic or (and) magnetostatic environment. Some of the planned early experiments are: two-dimensional angular correlation of annihilation radiation of thin films and buried interfaces, positron diffraction holography, positron induced desorption, and positron induced Auger spectra.

  5. Slow positron beam generator for lifetime studies

    NASA Technical Reports Server (NTRS)

    Singh, Jag J. (Inventor); Eftekhari, Abe (Inventor); St.clair, Terry L. (Inventor)

    1991-01-01

    A slow positron beam generator uses a conductive source residing between two test films. Moderator pieces are placed next to the test film on the opposite side of the conductive source. A voltage potential is applied between the moderator pieces and the conductive source. Incident energetic positrons: (1) are emitted from the conductive source; (2) are passed through test film; and (3) isotropically strike moderator pieces before diffusing out of the moderator pieces as slow positrons, respectively. The slow positrons diffusing out of moderator pieces are attracted to the conductive source which is held at an appropriate potential below the moderator pieces. The slow positrons have to pass through the test films before reaching the conductive source. A voltage is adjusted so that the potential difference between the moderator pieces and the conductive source forces the positrons to stop in the test films. Measurable annihilation radiation is emitted from the test film when positrons annihilate (combine) with electrons in the test film.

  6. Spin polarized low-energy positron source

    NASA Astrophysics Data System (ADS)

    Petrov, V. N.; Samarin, S. N.; Sudarshan, K.; Pravica, L.; Guagliardo, P.; Williams, J. F.

    2015-06-01

    This paper presents an investigation of spin polarization of positrons from a source based on the decay of 22Na isotopes. Positrons are moderated by transmission through a tungsten film and electrostatically focussed and transported through a 90 deg deflector to produce a slow positron beam with polarization vector normal to the linear momentum. The polarization of the beam was determined to be about 10% by comparison with polarized electron scattering asymmetries from a thin Fe film on W(110) at 10-10 Torr. Low energy electron emission from Fe layer on W(100) surfaces under positron impact is explored. It is shown that the intensity asymmetry of the electron emission as a function of the incident positron energy can be used to estimate the polarization of the positron beam. Also several materials with long mean free paths for spin relaxation are considered as possible moderators with increased polarization of the emergent positrons.

  7. Design of the NLC positron source

    SciTech Connect

    Tang, H.; Emma, P.; Gross, G.; Kulikov, A.; Li, Z.; Miller, R.; Rinolfi, L.; Turner, J.; Yeremian, D.

    1996-08-01

    The design of the positron source for the Next Linear Collider (NLC) is presented. The key features of this design include accelerating positrons at an L-band frequency (1428 MHz) and using a rotating positron target with multi-stage differential pumping. Positron yield simulations show that the L-band design yields at the source 2.5 times the beam intensity required at the interaction point and is easily upgrade to higher intensities required for the 1 TeV NLC upgrade. Multi-bunch beam loading compensation schemes in the positron capture and booster accelerators and the optics design of the positron booster accelerator are described. For improved source efficiency, the design boasts two parallel positron vaults adequately shielded from each other such that one serves as an on-line spare.

  8. Heavy metals in urban soils of East St. Louis, IL. Part II: Leaching characteristics and modeling.

    PubMed

    Kaminski, M D; Landsberger, S

    2000-09-01

    The city of East St. Louis, IL, has a history of abundant industrial activities including smelters of ferrous and non-ferrous metals, a coal-fired power plant, companies that produced organic and inorganic chemicals, and petroleum refineries. Following a gross assessment of heavy metals in the community soils (see Part I of this two-part series), leaching tests were performed on specific soils to elucidate heavy metal-associated mineral fractions and general leachability. Leaching experiments, including the Toxicity Characteristic Leaching Procedure (TLCP) and column tests, and sequential extractions, illustrated the low leachability of metals in East St. Louis soils. The column leachate results were modeled using a formulation developed for fly ash leaching. The importance of instantaneous dissolution was evident from the model. By incorporating desorption/adsorption terms into the source term, the model was adapted very well to the time-dependent heavy metal leachate concentrations. The results demonstrate the utility of a simple model to describe heavy metal leaching from contaminated soils.

  9. Heavy Metals in Urban Soils of East St. Louis, IL Part II: Leaching Characteristics and Modeling.

    PubMed

    Kaminski, Michael D; Landsberger, Sheldon

    2000-09-01

    The city of East St. Louis, IL, has a history of abundant industrial activities including smelters of ferrous and non-ferrous metals, a coal-fired power plant, companies that produced organic and inorganic chemicals, and petroleum refineries. Following a gross assessment of heavy metals in the community soils (see Part I of this two-part series), leaching tests were performed on specific soils to elucidate heavy metal-associated mineral fractions and general leachability. Leaching experiments, including the Toxicity Characteristic Leaching Procedure (TLCP) and column tests, and sequential extractions, illustrated the low leachability of metals in East St. Louis soils. The column leachate results were modeled using a formulation developed for fly ash leaching. The importance of instantaneous dissolution was evident from the model. By incorporating desorption/adsorption terms into the source term, the model was adapted very well to the time-dependent heavy metal leachate concentrations. The results demonstrate the utility of a simple model to describe heavy metal leaching from contaminated soils.

  10. Dinuclear metal(ii)-acetato complexes based on bicompartmental 4-chlorophenolate: syntheses, structures, magnetic properties, DNA interactions and phosphodiester hydrolysis.

    PubMed

    Massoud, Salah S; Ledet, Catherine C; Junk, Thomas; Bosch, Simone; Comba, Peter; Herchel, Radovan; Hošek, Jan; Trávníček, Zdeněk; Fischer, Roland C; Mautner, Franz A

    2016-08-09

    A series of dinuclear metal(ii)-acetato complexes: [Ni2(μ-L(Cl)O)(μ2-OAc)2](PF6)·3H2O (1), [Ni2(μ-L(Cl)O)(μ2-OAc)2](ClO4)·CH3COCH3 (2), [Cu2(μ-L(Cl)O)(μ2-OAc)(ClO4)](ClO4) (3), [Cu2(μ-L(Cl)O)(OAc)2](PF6)·H2O (4), [Zn2(μ-L(Cl)O)(μ2-OAc)2](PF6) (5) and [Mn2(L(Cl)-O)(μ2-OAc)2](ClO4)·H2O (6), where L(Cl)O(-) = 2,6-bis[bis(2-pyridylmethyl)aminomethyl]-4-chlorophenolate, were synthesized. The complexes were structurally characterized by spectroscopic techniques and single crystal X-ray crystallography. Six-coordinate geometries with doubly bridged acetato ligands were found in Ni(ii), Zn(ii) and Mn(ii) complexes 1, 2, 5 and 6, whereas with Cu(ii) complexes a five-coordinate species was obtained with 4, and mixed five- and six-coordinate geometries with a doubly bridged dimetal core were observed in 3. The magnetic properties of complexes 1-4 and 6 were studied at variable temperatures and revealed weak to very weak antiferromagnetic interactions in 1, 2, 4 and 6 (J = -0.55 to -9.4 cm(-1)) and ferromagnetic coupling in 3 (J = 15.4 cm(-1)). These results are consistent with DFT calculations performed at the B3LYP/def2-TZVP(-f) level of theory. Under physiological conditions, the interaction of the dinculear complexes 1-5 with supercoiled plasmid ds-DNA did not show any pronounced nuclease activity, but Ni(ii) complexes 1 and 2 revealed a strong ability to unwind the supercoiled conformation of ds-DNA. The mechanistic studies performed on the interaction of the Ni(ii) complexes with DNA demonstrated the important impact of the nickel(ii) ion in the unwinding process. In combination with the DNA study, the phosphatase activity of complexes 1, 3, and 5 was examined by the phosphodiester hydrolysis of bis(2,4-dinitrophenol)phosphate (BDNPP) in the pH range of 5.5-10.5 at 25 °C. The Michaelis-Menten kinetics performed at pH 7 and 10.7 showed that catalytic efficiencies kcat/KM (kcat = catalytic rate constant, KM = substrate binding constant) decrease in the order

  11. Type-II antiferromagnetism in compounds of iron with 4d metals

    NASA Astrophysics Data System (ADS)

    Marcus, P. M.; Moruzzi, V. L.; Qiu, S. L.

    1996-11-01

    Previous first-principles calculations on the magnetic phases of nine FeX and Fe2XY compounds in the CsCl structure, where X and Y are 4d elements from Tc to Ag, are extended to include type-II as well as type-I antiferromagnetism. The antiferromagnetism of FeRh and Fe2RuRh is greatly enhanced in the type-II phase and FeRu in the type-II phase becomes the fifth such compound with an antiferromagnetic ground state. However in the weaker antiferromagnets FePd and Fe2RhPd the equilibrium state of the type-II phase has a higher energy than the type-I phase.

  12. Multi-component synthesis of 2-amino-6-(alkyllthio)pyridine-3,5-dicarbonitriles using Zn(II) and Cd(II) metal-organic frameworks (MOFs) under solvent-free conditions.

    PubMed

    Thimmaiah, Muralidhara; Li, Peng; Regati, Sridhar; Chen, Banglin; Zhao, John Cong-Gui

    2012-09-05

    Multi-component synthesis 2-amino-3,5-dicarbonitrile-6-thio-pyridines has been developed by using the reaction of aldehydes, malononitrile, and thiophenols in the presence of a Zn (II) or a Cd(II) metal-organic framework (MOF) as the heterogeneous catalyst. This protocol tolerates different functional groups on the substrates and does not require the use of any organic solvent. Moreover, the Zn(II) and Cd (II) MOF catalysts can be recovered and reused for a number of runs without loss of activity.

  13. Synthesis, crystal structure and magnetic characterization of metal(II) coordination polymers based on 2-carboxyethylphosphonic acid and 1,10-phenanthroline (metal=Cu, Co, Cd)

    SciTech Connect

    Fernandez-Zapico, Eva; Montejo-Bernardo, Jose Manuel; D'Vries, Richard; Garcia, Jose R.; Garcia-Granda, Santiago; Rodriguez Fernandez, Jesus; Pedro, Imanol de; Blanco, Jesus A.

    2011-12-15

    Three non-isostructural metal(II) coordination polymers (metal=copper, cobalt, cadmium) were synthesized under the same mild hydrothermal conditions (T=408 K) by mixture of the corresponding metal acetate with 2-carboxyethylphosphonic acid and 1,10-phenanthroline (1:1:1 M ratio) and their structures were determined by single-crystal X-ray diffraction. Cu{sub 2}(HO{sub 3}PCH{sub 2}CH{sub 2}COO){sub 2}(C{sub 12}H{sub 8}N{sub 2}){sub 2}(H{sub 2}O){sub 2} and Cd{sub 2}(HO{sub 3}PCH{sub 2}CH{sub 2}COO){sub 2}(C{sub 12}H{sub 8}N{sub 2}){sub 2} are triclinic (space group P-1) with a=7.908(5) A, b=10.373(5) A, c=11.515(5) A, {alpha}=111.683(5) Degree-Sign , {beta}=95.801(5) Degree-Sign , {gamma}=110.212(5) Degree-Sign (T=120 K), and a=8.162(5) A, b=9.500(5) A, c=11.148(5) A, {alpha}=102.623(5) Degree-Sign , {beta}=98.607(5) Degree-Sign , {gamma}=113.004(5) Degree-Sign (T=293 K), respectively. In contrast, [Co{sub 2}(HO{sub 3}PCH{sub 2}CH{sub 2}COO){sub 2}(C{sub 12}H{sub 8}N{sub 2}){sub 2}({mu}-OH{sub 2})](H{sub 2}O) is orthorhombic (space group Pbcn) with a=21.1057(2) A, b=9.8231(1) A, c=15.4251(1) A (T=120 K). For these three compounds, structural features, including H-bond network and the {pi}-{pi} stacking interactions, and thermal stability are reported and discussed. None of the materials present a long-range magnetic order in the range of temperatures investigated from 300 K down to 1.8 K. - Graphical abstract: In same synthetic conditions, both the chemical and structural features of three transition metal(II) coordination polymers based on 2-carboxyethylphosphonate and 1-10 Prime -phenanthroline are influenced by the metal cation characteristics, leading to non-homologous materials with different properties, which show the high chemical versatility of this interesting system. Highlights: Black-Right-Pointing-Pointer Non-isostructural metal coordination polymers were synthesized under mild hydrothermal conditions. Black-Right-Pointing-Pointer Ligand's flexibility

  14. Lorentz-violating type-II Dirac fermions in transition metal dichalcogenide PtTe2.

    PubMed

    Yan, Mingzhe; Huang, Huaqing; Zhang, Kenan; Wang, Eryin; Yao, Wei; Deng, Ke; Wan, Guoliang; Zhang, Hongyun; Arita, Masashi; Yang, Haitao; Sun, Zhe; Yao, Hong; Wu, Yang; Fan, Shoushan; Duan, Wenhui; Zhou, Shuyun

    2017-08-15

    Topological semimetals have recently attracted extensive research interests as host materials to condensed matter physics counterparts of Dirac and Weyl fermions originally proposed in high energy physics. Although Lorentz invariance is required in high energy physics, it is not necessarily obeyed in condensed matter physics, and thus Lorentz-violating type-II Weyl/Dirac fermions could be realized in topological semimetals. The recent realization of type-II Weyl fermions raises the question whether their spin-degenerate counterpart-type-II Dirac fermions-can be experimentally realized too. Here, we report the experimental evidence of type-II Dirac fermions in bulk stoichiometric PtTe2 single crystal. Angle-resolved photoemission spectroscopy measurements and first-principles calculations reveal a pair of strongly tilted Dirac cones along the Γ-A direction, confirming PtTe2 as a type-II Dirac semimetal. Our results provide opportunities for investigating novel quantum phenomena (e.g., anisotropic magneto-transport) and topological phase transition.Whether the spin-degenerate counterpart of Lorentz-violating Weyl fermions, the Dirac fermions, can be realized remains as an open question. Here, Yan et al. report experimental evidence of such type-II Dirac fermions in bulk PtTe2 single crystal with a pair of strongly tilted Dirac cones.

  15. Efficient Removal of Heavy Metals from Polluted Water with High Selectivity for Mercury(II) by 2-Imino-4-thiobiuret-Partially Reduced Graphene Oxide (IT-PRGO).

    PubMed

    Awad, Fathi S; AbouZeid, Khaled M; El-Maaty, Weam M Abou; El-Wakil, Ahmad M; El-Shall, M Samy

    2017-10-04

    A novel chelating adsorbent, based on the chemical modification of graphene oxide by functionalization amidinothiourea to form 2-imino-4-thiobiuret-partially reduced graphene oxide (IT-PRGO), is used for the effective extraction of the toxic metal ions Hg(II), Cu(II), Pb(II), Cr(VI), and As(V) from wastewater. FTIR and Raman spectroscopy, XRD, and XPS confirm the successful incorporation of the amidinothiourea groups within the partially reduced GO nanosheets through nucleophilic substitution reactions with the acyl chloride groups in the chemically modified GO. The IT-PRGO adsorbent shows exceptional selectivity for the extraction of Hg(II) with a capacity of 624 mg/g, placing it among the top of carbon-based materials known for the high capacity of Hg(II) removal from aqueous solutions. The maximum sorption capacities for As(V), Cu(II), Cr(VI), and Pb(II) are 19.0, 37.0, 63.0, and 101.5 mg/g, respectively. The IT-PRGO displays a 100% removal of Hg(II) at concentrations up to 100 ppm with 90%, 95%, and 100% removal within 15, 30, and 90 min, respectively, at 50 ppm concentration. In a mixture of six heavy metal ions containing 10 ppm of each ion, the IT-PRGO shows a removal of 3% Zn(II), 4% Ni(II), 9% Cd(II), 21% Cu(II), 63% Pb(II), and 100% Hg(II). A monolayer adsorption behavior is suggested based on the excellent agreement of the experimental sorption isotherms with the Langmuir model. The sorption kinetics can be fitted well to a pseudo-second-order kinetic model which suggests a chemisorption mechanism via the amidinothiourea groups grafted on the reduced graphene oxide nanosheets. Desorption studies demonstrate that the IT-PRGO is easily regenerated with the desorption of the metal ions Hg(II), Cu(II), Pb(II), Cr(VI), and As(V) reaching 96%, 100%, 100%, 96%, and 100%, respectively, from their maximum sorption capacities using different eluents. The IT-PRGO is proposed as a top performing remediation adsorbent for the extraction of heavy metals from waste and

  16. In situ reactive zone with modified Mg(OH)2 for remediation of heavy metal polluted groundwater: Immobilization and interaction of Cr(III), Pb(II) and Cd(II).

    PubMed

    Dong, Jun; Li, Bowen; Bao, Qiburi

    2017-04-01

    Mg(OH)2 dissolves slowly and can provide a long-term source of alkalinity, thus a promising alternative reagent for the in situ remediation of heavy metal polluted groundwater. However, the application of Mg(OH)2 on in situ reactive zone (IRZ) for heavy metal polluted groundwater has never been investigated. In this study, the behaviors of heavy metals in a Mg(OH)2 IRZ were monitored for 45d. The heavy metals show a sequential precipitation by modified Mg(OH)2 due to the difference of Ksp. Column tests were conducted to investigate the temporal and spatial distribution of heavy metals in Mg(OH)2 IRZ and evaluate the stabilization effect for multi-heavy metal polluted groundwater. Experimental results indicate that there exist interactions between different heavy metals, and their zoning distribution is attributed either to the competitive adsorption onto porous media (control column) or to the sequential precipitation of heavy metal ions (IRZ column). In contrast with the control column, heavy metal contaminated area in Mg(OH)2 IRZ significantly shrinks. According to the chemical speciation analysis, when water containing Pb(II), Cd(II) and Cr(III) flows through Mg(OH)2 IRZ, exchangeable fraction of total concentration significantly reduce and the proportion of carbonate and Fe/Mn oxides fraction increase, indicating the decrease of their mobility and toxicity. Copyright © 2017 Elsevier B.V. All rights reserved.

  17. In situ reactive zone with modified Mg(OH)2 for remediation of heavy metal polluted groundwater: Immobilization and interaction of Cr(III), Pb(II) and Cd(II)

    NASA Astrophysics Data System (ADS)

    Dong, Jun; Li, Bowen; Bao, Qiburi

    2017-04-01

    Mg(OH)2 dissolves slowly and can provide a long-term source of alkalinity, thus a promising alternative reagent for the in situ remediation of heavy metal polluted groundwater. However, the application of Mg(OH)2 on in situ reactive zone (IRZ) for heavy metal polluted groundwater has never been investigated. In this study, the behaviors of heavy metals in a Mg(OH)2 IRZ were monitored for 45 d. The heavy metals show a sequential precipitation by modified Mg(OH)2 due to the difference of Ksp. Column tests were conducted to investigate the temporal and spatial distribution of heavy metals in Mg(OH)2 IRZ and evaluate the stabilization effect for multi-heavy metal polluted groundwater. Experimental results indicate that there exist interactions between different heavy metals, and their zoning distribution is attributed either to the competitive adsorption onto porous media (control column) or to the sequential precipitation of heavy metal ions (IRZ column). In contrast with the control column, heavy metal contaminated area in Mg(OH)2 IRZ significantly shrinks. According to the chemical speciation analysis, when water containing Pb(II), Cd(II) and Cr(III) flows through Mg(OH)2 IRZ, exchangeable fraction of total concentration significantly reduce and the proportion of carbonate and Fe/Mn oxides fraction increase, indicating the decrease of their mobility and toxicity.

  18. Gastrointestinal transit of undigestible solids measured by metal detector EAS II.

    PubMed

    Ewe, K; Press, A G; Dederer, W

    1989-06-01

    A new method was developed to measure gastrointestinal transit: a metal particle is followed on its way through the gastrointestinal tract by means of a portable metal detector. Deviation of measured localization of the metal particle from the exact site was 0.5-1.0 cm depending on its size and distance from the search probe. A metal sphere of 6 mm diameter can be located accurately in the body at a distance of 2-12 cm from the abdominal surface. Emptying of a metal particle from the stomach, its arrival at the caecal area and its passage through the colon into the rectum can be registered and hence, gastric residence time, small intestinal transit and transit through different parts of the colon were determined. Gastric residence time at the interdigestive phase was (mean +/- SD) 67 +/- 52 min in 20 persons with a range of 9-185 min. When gastric emptying was recorded by pH sensitive radiotelemetering capsule in 10 persons, correlation of both methods was r = 0.99. Small intestinal transit averaged 110 +/- 56 min in six healthy volunteers when breakfast was eaten after the marker had left the stomach. It was delayed to 218 +/- 34 min (P less than 0.01) when fasting was continued. Large intestinal transit of the metal marker was compared to whole body transit of radio-opaque ('Hinton') markers. In nine normal persons, 70% of the Hinton markers were excreted together with the metal particle. It is concluded that this new method is suitable for studying a large variety of physiological, pathophysiological and pharmacological questions concerning gastrointestinal transit.(ABSTRACT TRUNCATED AT 250 WORDS)

  19. Surface and bulk investigations at the high intensity positron beam facility NEPOMUC

    NASA Astrophysics Data System (ADS)

    Hugenschmidt, C.; Dollinger, G.; Egger, W.; Kögel, G.; Löwe, B.; Mayer, J.; Pikart, P.; Piochacz, C.; Repper, R.; Schreckenbach, K.; Sperr, P.; Stadlbauer, M.

    2008-10-01

    The NEutron-induced POsitron source MUniCh (NEPOMUC) at the research reactor FRM II delivers a low-energy positron beam ( E = 15-1000 eV) of high intensity in the range between 4 × 10 7 and 5 × 10 8 moderated positrons per second. At present four experimental facilities are in operation at NEPOMUC: a coincident Doppler-broadening spectrometer (CDBS) for defect spectroscopy and investigations of the chemical vicinity of defects, a positron annihilation-induced Auger-electron spectrometer (PAES) for surface studies and an apparatus for the production of the negatively charged positronium ion Ps -. Recently, the pulsed low-energy positron system (PLEPS) has been connected to the NEPOMUC beam line, and first positron lifetime spectra were recorded within short measurement times. A positron remoderation unit which is operated with a tungsten single crystal in back reflection geometry has been implemented in order to improve the beam brilliance. An overview of NEPOMUC's status, experimental results and recent developments at the running spectrometers are presented.

  20. Gas adsorption and structural diversity in a family of Cu(II) pyridyl-isophthalate metal-organic framework materials

    NASA Astrophysics Data System (ADS)

    Gould, Jamie A.; Athwal, Harprit Singh; Blake, Alexander J.; Lewis, William; Hubberstey, Peter; Champness, Neil R.; Schröder, Martin

    2017-01-01

    A family of Cu(II)-based metal-organic frameworks (MOFs) has been synthesized using three pyridyl-isophthalate ligands, H2L1 (4'-(pyridin-4-yl)biphenyl-3,5-dicarboxylic acid), H2L2 (4''-(pyridin-4-yl)-1,1':4',1''-terphenyl-3,5-dicarboxylic acid) and H2L3 (5-[4-(pyridin-4-yl)naphthalen-1-yl]benzene-1,3-dicarboxylic acid). Although in each case the pyridyl-isophthalate ligands adopt the same pseudo-octahedral [Cu2(O2CR)4N2] paddlewheel coordination modes, the resulting frameworks are structurally diverse, particularly in the case of the complex of Cu(II) with H2L3, which leads to three distinct supramolecular isomers, each derived from Kagomé and square nets. In contrast to [Cu(L2)] and the isomers of [Cu(L3)], [Cu(L1)] exhibits permanent porosity. Thus, the gas adsorption properties of [Cu(L1)] were investigated with N2, CO2 and H2, and the material exhibits an isosteric heat of adsorption competitive with leading MOF sorbents for CO2. [Cu(L1)] displays high H2 adsorption, with the density in the pores approaching that of liquid H2. This article is part of the themed issue 'Coordination polymers and metal-organic frameworks: materials by design'.

  1. Confinement of a bioinspired nonheme Fe(II) complex in 2D hexagonal mesoporous silica with metal site isolation.

    PubMed

    Jollet, Véronique; Albela, Belén; Sénéchal-David, Katell; Jégou, Pascale; Kolodziej, Emilie; Sainton, Joëlle; Bonneviot, Laurent; Banse, Frédéric

    2013-08-28

    A mixed amine pyridine polydentate Fe(II) complex was covalently tethered in hexagonal mesoporous silica of the MCM-41 type. Metal site isolation was generated using adsorbed tetramethylammonium cations acting as a patterned silanol protecting mask and trimethylsilylazane as a capping agent. Then, the amine/pyridine ligand bearing a tethering triethoxysilane group was either grafted to such a pretreated silica surface prior to or after complexation to Fe(II). These two synthetic routes, denoted as two-step and one-step, respectively, were also applied to fumed silica for comparison, except that the silanol groups were capped after tethering the metal unit. The coordination of the targeted complex was monitored using UV-visible spectrophotometry and, according to XPS, the best control was achieved inside the channels of the mesoporous silica for the two-step route. For the solid prepared according to the one-step route, tethering of the complex occurred mainly at the entrance of the channel.

  2. Gas adsorption and structural diversity in a family of Cu(II) pyridyl-isophthalate metal-organic framework materials.

    PubMed

    Gould, Jamie A; Athwal, Harprit Singh; Blake, Alexander J; Lewis, William; Hubberstey, Peter; Champness, Neil R; Schröder, Martin

    2017-01-13

    A family of Cu(II)-based metal-organic frameworks (MOFs) has been synthesized using three pyridyl-isophthalate ligands, H2L(1) (4'-(pyridin-4-yl)biphenyl-3,5-dicarboxylic acid), H2L(2) (4''-(pyridin-4-yl)-1,1':4',1''-terphenyl-3,5-dicarboxylic acid) and H2L(3) (5-[4-(pyridin-4-yl)naphthalen-1-yl]benzene-1,3-dicarboxylic acid). Although in each case the pyridyl-isophthalate ligands adopt the same pseudo-octahedral [Cu2(O2CR)4N2] paddlewheel coordination modes, the resulting frameworks are structurally diverse, particularly in the case of the complex of Cu(II) with H2L(3), which leads to three distinct supramolecular isomers, each derived from Kagomé and square nets. In contrast to [Cu(L(2))] and the isomers of [Cu(L(3))], [Cu(L(1))] exhibits permanent porosity. Thus, the gas adsorption properties of [Cu(L(1))] were investigated with N2, CO2 and H2, and the material exhibits an isosteric heat of adsorption competitive with leading MOF sorbents for CO2 [Cu(L(1))] displays high H2 adsorption, with the density in the pores approaching that of liquid H2This article is part of the themed issue 'Coordination polymers and metal-organic frameworks: materials by design'. © 2016 The Author(s).

  3. Infrared Multiple-Photon Dissociation spectroscopy of group II metal complexes with salicylate

    SciTech Connect

    Ryan P. Dain; Gary Gresham; Gary S. Groenewold; Jeffrey D. Steill; Jos Oomens; Michael J. van Stipdonk

    2011-07-01

    Ion-trap tandem mass spectrometry with collision-induced dissociation, and the combination of infrared multiple-photon dissociation (IRMPD) spectroscopy and density functional theory (DFT) calculations were used to characterize singly-charged, 1:1 complexes of Ca2+, Sr2+ and Ba2+ with salicylate. For each metal-salicylate complex, the CID pathways are: (a) elimination of CO2 and (b) formation of [MOH]+ where M=Ca2+, Sr2+ or Ba2+. DFT calculations predict three minima for the cation-salicylate complexes which differ in the mode of metal binding. In the first, the metal ion is coordinated by O atoms of the (neutral) phenol and carboxylate groups of salicylate. In the second, the cation is coordinated by phenoxide and (neutral) carboxylic acid groups. The third mode involves coordination by the carboxylate group alone. The infrared spectrum for the metal-salicylate complexes contains a number of absorptions between 1000 – 1650 cm-1, and the best correlation between theoretical and experimental spectra for the structure that features coordination of the metal ion by phenoxide and the carbonyl group of the carboxylic acid group, consistent with calculated energies for the respective species.

  4. Effect of heavy metals on the stabilization of mercury(II) by DTCR in desulfurization solutions.

    PubMed

    Hou, Jiaai; Lu, Rongjie; Sun, Mingyang; Baig, Shams Ali; Tang, Tingmei; Cheng, Lihua; Xu, Xinhua

    2012-05-30

    Several heavy metals, including Cu(2+), Ni(2+), Pb(2+), and Zn(2+), were investigated in simulated desulfurization solutions to evaluate their interferences with Hg(2+) during the reaction with dithiocarbamate type chelating resin (DTCR). Appropriate DTCR dosage and the effect of pH were also explored with respect to restoration of high Hg(2+) precipitation efficiency and reduction of mercury concentrations. The experimental results suggested that increasing heavy metal concentration inhibited Hg(2+) precipitation efficiency to a considerable extent and the inhibition order of the four heavy metals was Cu(2+)>Ni(2+)>Pb(2+)>Zn(2+). However, the coordination ability was closely related to the configuration and the orbital hybridization of each metal. In the cases of Cu(2+) and Pb(2+), increased DTCR dosage was beneficial to Hg(2+) precipitation, which could lay the foundation of practical applications of DTCR dosage for industrial wastewater treatment. The enhanced Hg(2+) precipitation performance seen for increasing pH might have come from the deprotonation of sulfur atoms on the DTCR functional groups and the formation of metal hydroxides (M(OH)(2), M=Cu, Pb, Hg).

  5. Metallicity of the Intergalactic Medium Using Pixel Statistics. II. The Distribution of Metals as Traced by C IV

    NASA Astrophysics Data System (ADS)

    Schaye, Joop; Aguirre, Anthony; Kim, Tae-Sun; Theuns, Tom; Rauch, Michael; Sargent, Wallace L. W.

    2003-10-01

    We measure the distribution of carbon in the intergalactic medium as a function of redshift z and overdensity δ. Using a hydrodynamical simulation to link the H I absorption to the density and temperature of the absorbing gas, and a model for the UV background radiation, we convert ratios of C IV to H I pixel optical depths into carbon abundances. For the median metallicity this technique was described and tested in Paper I of this series. Here we generalize it to reconstruct the full probability distribution of the carbon abundance and apply it to 19 high-quality quasar absorption spectra. We find that the carbon abundance is spatially highly inhomogeneous and is well described by a lognormal distribution for fixed δ and z. Using data in the range logδ=-0.5-1.8 and z=1.8-4.1, and a renormalized version of the 2001 Haardt & Madau model for the UV background radiation from galaxies and quasars, we measure a median metallicity of [C/H]=-3.47+0.07-0.06+0.08+0.09-0.10(z-3)+0.65+0.10-0.14(logδ-0.5) and a lognormal scatter of σ([C/H])=0.76+0.05-0.08+0.02+0.08-0.12(z-3)-0.23+0.09-0.07(logδ-0.5). Thus, we find significant trends with overdensity but no evidence for evolution. These measurements imply that gas in this density range accounts for a cosmic carbon abundance of [C/H]=-2.80+/-0.13 (ΩC~2×10-7), with no evidence for evolution. The dominant source of systematic error is the spectral shape of the UV background, with harder spectra yielding higher carbon abundances. While the systematic errors due to uncertainties in the spectral hardness may exceed the quoted statistical errors for δ<10, we stress that UV backgrounds that differ significantly from our fiducial model give unphysical results. The measured lognormal scatter is strictly independent of the spectral shape, provided the background radiation is uniform. We also present measurements of the C III/C IV ratio (which rule out temperatures high enough for collisional ionization to be important for the

  6. Infrared multiple photon dissociation spectroscopy of group I and group II metal complexes with Boc-hydroxylamine.

    PubMed

    Dain, Ryan P; Gresham, Gary; Groenewold, Gary S; Steill, Jeffrey D; Oomens, Jos; Van Stipdonk, Michael J

    2013-08-30

    Hydroxamates are essential growth factors for some microbes, acting primarily as siderophores that solubilize iron for transport into a cell. Here we determined the intrinsic structure of 1:1 complexes between Boc-protected hydroxylamine and group I ([M(L)](+)) and group II ([M(L-H)](+)) cations, where M and L are the cation and ligand, respectively, which are convenient models for the functional unit of hydroxamate siderphores. The relevant complex ions were generated by electrospray ionization (ESI) and isolated and stored in a Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer. Infrared spectra of the isolated complexes were collected by monitoring (infrared) photodissociation yield as a function of photon energy. Experimental spectra were then compared to those predicted by density functional theory (DFT) calculations. The infrared multiple photon dissociation (IRMPD) spectra collected are in good agreement with those predicted to be lowest-energy by DFT. The spectra for the group I complexes contain six resolved absorptions that can be attributed to amide I and II type and hydroxylamine N-OH vibrations. Similar absorptions are observed for the group II cation complexes, with shifts of the amide I and amide II vibrations due to the change in structure with deprotonation of the hydroxylamine group. IRMPD spectroscopy unequivocally shows that the intrinsic binding mode for the group I cations involves the O atoms of the amide carbonyl and hydroxylamine groups of Boc-hydroxylamine. A similar binding mode is preferred for the group II cations, except that in this case the metal ion is coordinated by the O atom of the deprotonated hydroxylamine group. Copyright © 2013 John Wiley & Sons, Ltd.

  7. The Abundance Scatter in M33 from H II Regions: Is There Any Evidence for Azimuthal Metallicity Variations?

    NASA Astrophysics Data System (ADS)

    Bresolin, Fabio

    2011-04-01

    Optical spectra of 25 H II regions in the inner 2 kpc of the M33 disk have been obtained with the Gemini Multi-Object Spectrograph at the Gemini North telescope. The oxygen abundance gradient measured from the detection of the [O III] λ4363 auroral line displays a scatter of approximately 0.06 dex, a much smaller value than recently reported by Rosolowsky & Simon in this galaxy. The analysis of the abundances for a large sample of H II regions derived from the R 23 strong-line indicator confirms that the scatter is small over the full disk of M33, consistent with the measuring uncertainties, and comparable to what is observed in other spiral galaxies. No evidence is therefore found for significant azimuthal variations in the present-day metallicity of the interstellar medium in this galaxy on spatial scales from ~100 pc to a few kpc. A considerable fraction of M33 H II regions with auroral line detections show spectral features revealing sources of hard ionizing radiation (such as He II emission and large [Ne III], [O III] line fluxes). Since R 23 is shown to severely underestimate the oxygen abundances in such cases, care must be taken in chemical abundance studies of extragalactic H II regions based on this strong-line indicator. Based on observations obtained at the Gemini Observatory, which is operated by the Association of Universities for Research in Astronomy, Inc., under a cooperative agreement with the NSF on behalf of the Gemini partnership: the National Science Foundation (United States), the Science and Technology Facilities Council (United Kingdom), the National Research Council (Canada), CONICYT (Chile), the Australian Research Council (Australia), Ministério da Ciência e Tecnologia (Brazil) and Ministerio de Ciencia, Tecnología e Innovación Productiva (Argentina).

  8. 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).

  9. INFRARED MULTIPLE-PHOTON PHOTODISSOCIATION OF GAS-PHASE GROUP II METAL-NITRATE ANIONS

    SciTech Connect

    Jos Oomens; Linda Myers; Ryan Dain; Chris Leavitt; Vy Pham; Garold Gresham; Gary Groenewold; Mike Van Stipdonk

    2008-06-01

    Infrared spectra of gas-phase metal-nitrate anions M(NO3)3-, where M=Mg2+, Ca2+, Sr2+ and Ba2+, were recorded by infrared multiple photon dissociation (IRMPD) spectroscopy. Photodissociation of each of the precursors produces NO3- through the elimination of a neutral M(NO3)2 unit. An absorption pattern characteristic of metal nitrates is observed in the IRMPD spectra, including the symmetric and antisymmetric NO3 stretches. The latter is split into high and low frequency components as a result of perturbation of the nitrate symmetry by complexation to the metal ion, and the magnitude of the splitting decreases following the trend Mg2+ > Ca2+ > Sr2+ ? Ba2+. The experimental spectra are in good general agreement with those obtained from density functional theory calculations.

  10. Synthesis, spectral and magnetic susceptibility studies on tetrachloro metal(II)phthalocyanines

    NASA Astrophysics Data System (ADS)

    Somashekarappa, M. P.; Venugopala Reddy, K. R.; Harish, M. N. K.; Keshavayya, J.

    2005-10-01

    The present paper describes a simple method for the synthesis of symmetrically substituted 1,8,15,22-tetrachloro phthalocyanines of copper, cobalt, nickel and zinc. The title complexes are synthesized from the corresponding tetraamino metal phthalocyanines by modified Sandmeyers method and in turn the tetraamino metal phthalocyanines are prepared from 3-nitrophthalic acid. The bluish-green coloured tetrachloro metal phthalocyanine complexes are characterized by elemental, electronic, IR, magnetic susceptibility and X-ray powder diffraction studies to check the purity and the structural integrity. The magnetic susceptibility studies revealed that, the experimental values are higher than that of the spin only value magnetic moment, and the presence of intermolecular co-operative effects.

  11. Capture and polarization of positrons in a proposed NLC polarized positron source

    SciTech Connect

    Batygin, Yuri K

    2003-05-28

    A proposed NLC polarized positron source utilizes a 150 GeV electron beam passing through a helical undulator. The resulting flux of polarized photons is converted in a thin positron production target. Spin polarized positrons are captured using a high field flux concentrator followed by an accelerator section immersed in a solenoidal field. Positron tracking through the accelerating and focusing systems is done together with integration of spin precession. Optimization of the collection system is performed to insure high positron yield into the 6-dimensional acceptance of the subsequent pre-damping ring while keeping the high value of positron beam polarization.

  12. Influence of group II metals on Radium-226 concentration ratios in the native green plum (Buchanania obovata) from the Alligator Rivers Region, Northern Territory, Australia.

    PubMed

    Medley, Peter; Bollhöfer, Andreas

    2016-01-01

    In this study, uptake of Ra from soil, and the influence of group II metals on Ra uptake, into the stones and edible flesh of the fruit of the wild green plum, Buchanania obovata, was investigated. Selective extraction of the exchangeable fraction of the soil samples was undertaken but was not shown to more reliably predict Ra uptake than total soil Ra activity concentration. Comparison of the group II metal to Ca ratios (i.e. Sr/Ca, Ba/Ca, Ra/Ca) in the flesh with exchangeable Ca shows that Ca outcompetes group II metals for root uptake and that the uptake pathway discriminated against group II metals relative to ionic radius, with uptake of Ca > Sr > Ba > Ra. Flesh and stone analysis showed that movement of group II metals to these components of the plant, after root uptake, was strongly related. This supports the hypothesis that Sr, Ba and Ra are being taken up as analogue elements, and follow the same uptake and translocation pathways, with Ca. Comparison with previously reported data from a native passion fruit supports the use of total soil CRs on natural, undisturbed sites. As exchangeable CRs for Ra reach a saturation value it may be possible to make more precise predictions using selective extraction techniques for contaminated or disturbed sites.

  13. Phytostabilization of a metal contaminated sandy soil. II: Influence of compost and/or inorganic metal immobilizing soil amendments on metal leaching.

    PubMed

    Ruttens, A; Colpaert, J V; Mench, M; Boisson, J; Carleer, R; Vangronsveld, J

    2006-11-01

    A lysimeter approach (under natural climatologic conditions) was used to evaluate the effect of four metal immobilizing soil treatments [compost (C), compost+cyclonic ashes (C+CA), compost+cyclonic ashes+steel shots (C+CA+SS)) and cyclonic ashes+steel shots (CA+SS)] on metal leaching through an industrially contaminated soil. All treatments decreased Zn and Cd leaching. Strongest reductions occurred after CA+SS and C+CA+SS treatments (Zn: -99.0% and -99.2% respectively; Cd: -97.2% and -98.3% respectively). Copper and Pb leaching increased after C (17 and >30 times for Cu and Pb respectively) and C+CA treatment (4.4 and >3.7 times for Cu and Pb respectively). C+CA+SS or CA+SS addition did not increase Cu leaching; the effect on Pb leaching was not completely clear. Our results demonstrate that attention should be paid to Cu and Pb leaching when organic matter additions are considered for phytostabilization of metal contaminated soils.

  14. Ecological Risk Assessment of a Metal-Contaminated Area in the Tropics. Tier II: Detailed Assessment

    PubMed Central

    Niemeyer, Júlia Carina; Moreira-Santos, Matilde; Ribeiro, Rui; Rutgers, Michiel; Nogueira, Marco Antonio; da Silva, Eduardo Mendes; Sousa, José Paulo

    2015-01-01

    This study presents data on the detailed evaluation (tier 2) of a site-specific ecological risk assessment (ssERA) in a former smelter area contaminated with metals (Santo Amaro, Bahia, Brazil). Combining information from three lines of evidence (LoE), chemical (ChemLoE), ecotoxicological (EcotoxLoE) and ecological (EcoLoE), in the Triad approach, integrated risk values were calculated to rank sites and confirm the potential risk disclosed with tier 1. Risk values were calculated for the habitat and for the retention functions in each sampling point. Habitat function included the ChemLoE calculated from total metal concentrations. The EcotoxLoE was based on reproduction tests with terrestrial invertebrates (Folsomia candida, Enchytraeus crypticus, Eisenia andrei), shoot length and plant biomass (Avena sativa, Brassica rapa). For the EcoLoE, ecological parameters (microbial parameters, soil invertebrate community, litter breakdown) were used to derive risk values. Retention function included the ChemLoE, calculated from extractable metal concentrations, and the EcotoxLoE based on eluate tests with aquatic organisms (Daphnia magna reproduction and Pseudokirchneriella subcapitata growth). Results related to the habitat function indicated that the metal residues are sufficient to cause risk to biota, while the low metal levels in extracts and the general lack of toxicity in aquatic tests indicated a high soil retention capacity in most sampling points. Integrated risk of tier 2 showed the same trend of tier 1, suggesting the need to proceed with remediation actions. The high risk levels were related to direct toxicity to organisms and indirect effects, such as failure in the establishment of vegetation and the consequent loss of habitat quality for microorganisms and soil fauna. This study shed some light on the selection of tools for the tier 2 of an ssERA in tropical metal-contaminated sites, focusing on ecological receptors at risk and using available chemical

  15. Ecological Risk Assessment of a Metal-Contaminated Area in the Tropics. Tier II: Detailed Assessment.

    PubMed

    Niemeyer, Júlia Carina; Moreira-Santos, Matilde; Ribeiro, Rui; Rutgers, Michiel; Nogueira, Marco Antonio; da Silva, Eduardo Mendes; Sousa, José Paulo

    2015-01-01

    This study presents data on the detailed evaluation (tier 2) of a site-specific ecological risk assessment (ssERA) in a former smelter area contaminated with metals (Santo Amaro, Bahia, Brazil). Combining information from three lines of evidence (LoE), chemical (ChemLoE), ecotoxicological (EcotoxLoE) and ecological (EcoLoE), in the Triad approach, integrated risk values were calculated to rank sites and confirm the potential risk disclosed with tier 1. Risk values were calculated for the habitat and for the retention functions in each sampling point. Habitat function included the ChemLoE calculated from total metal concentrations. The EcotoxLoE was based on reproduction tests with terrestrial invertebrates (Folsomia candida, Enchytraeus crypticus, Eisenia andrei), shoot length and plant biomass (Avena sativa, Brassica rapa). For the EcoLoE, ecological parameters (microbial parameters, soil invertebrate community, litter breakdown) were used to derive risk values. Retention function included the ChemLoE, calculated from extractable metal concentrations, and the EcotoxLoE based on eluate tests with aquatic organisms (Daphnia magna reproduction and Pseudokirchneriella subcapitata growth). Results related to the habitat function indicated that the metal residues are sufficient to cause risk to biota, while the low metal levels in extracts and the general lack of toxicity in aquatic tests indicated a high soil retention capacity in most sampling points. Integrated risk of tier 2 showed the same trend of tier 1, suggesting the need to proceed with remediation actions. The high risk levels were related to direct toxicity to organisms and indirect effects, such as failure in the establishment of vegetation and the consequent loss of habitat quality for microorganisms and soil fauna. This study shed some light on the selection of tools for the tier 2 of an ssERA in tropical metal-contaminated sites, focusing on ecological receptors at risk and using available chemical

  16. NUMERICAL SIMULATIONS OF SUPERNOVA DUST DESTRUCTION. II. METAL-ENRICHED EJECTA KNOTS

    SciTech Connect

    Silvia, Devin W.; Smith, Britton D.; Shull, J. Michael E-mail: michael.shull@colorado.edu

    2012-03-20

    Following our previous work, we investigate through hydrodynamic simulations the destruction of newly formed dust grains by sputtering in the reverse shocks of supernova remnants. Using an idealized setup of a planar shock impacting a dense, spherical clump, we implant a population of Lagrangian particles into the clump to represent a distribution of dust grains in size and composition. We vary the relative velocity between the reverse shock and ejecta clump to explore the effects of shock heating and cloud compression. Because supernova ejecta will be metal-enriched, we consider gas metallicities from Z/Z{sub Sun} = 1 to 100 and their influence on the cooling properties of the cloud and the thermal sputtering rates of embedded dust grains. We post-process the simulation output to calculate grain sputtering for a variety of species and size distributions. In the metallicity regime considered in this paper, the balance between increased radiative cooling and increased grain erosion depends on the impact velocity of the reverse shock. For slow shocks (v{sub shock} {<=} 3000 km s{sup -1}), the amount of dust destruction is comparable across metallicities or in some cases is decreased with increased metallicity. For higher shock velocities (v{sub shock} {>=} 5000 km s{sup -1}), an increase in metallicity from Z/Z{sub Sun} = 10 to 100 can lead to an additional 24% destruction of the initial dust mass. While the total dust destruction varies widely across grain species and simulation parameters, our most extreme cases result in complete destruction for some grain species and only 44% dust mass survival for the most robust species. These survival rates are important in understanding how early supernovae contribute to the observed dust masses in high-redshift galaxies.

  17. Preparation and characterization of chelating fibers based on natural wool for removal of Hg(II), Cu(II) and Co(II) metal ions from aqueous solutions.

    PubMed

    Monier, M; Nawar, N; Abdel-Latif, D A

    2010-12-15

    The graft copolymerization of acrylonitrile (AN) onto natural wool fibers initiated by KMnO(4) and oxalic acid combined redox initiator system in limited aqueous medium was carried out in heterogeneous media. Moreover, modification of the grafted wool fibers was done by changing the nitrile group (-CN) into cyano-acetic acid α-amino-acrylic-hydrazide through the reaction with hydrazine hydrate followed by ethylcyanoacetate which eventually produce wool-grafted-poly(cyano-acetic acid α-amino-acrylic-hydrazide) (wool-g-PCAH) chelating fibers. The application of the modified fibers for metal ion uptake was studied using Hg(2+), Cu(2+) and Co(2+). The modified chelating fibers were characterized using FTIR spectroscopy, SEM and X-ray diffraction. Copyright © 2010 Elsevier B.V. All rights reserved.

  18. Iron metal production in silicate melts through the direct reduction of Fe/II/ by Ti/III/, Cr/II/, and Eu/II/. [in lunar basalts

    NASA Technical Reports Server (NTRS)

    Schreiber, H. D.; Balazs, G. B.; Shaffer, A. P.; Jamison, P. L.

    1982-01-01

    The production of metallic iron in silicate melts by chemical reactions of Ti(3+), Cr(2+), and Eu(2+) with Fe(2+) is demonstrated under experimental conditions in a simplified basaltic liquid. These reactions form a basis for interpreting the role of isochemical valency exchange models in explanations for the reduced nature of lunar basalts. The redox couples are individually investigated in the silicate melt to ascertain reference redox ratios that are independent of mutual interactions. These studies also provide calibrations of spectral absorptions of the Fe(2+) and Ti(2+) species in these glasses. Subsequent spectrophotometric analyses of Fe(2+) and Ti(2+) in glasses doped with both iron and titanium and of Fe(2+) in glasses doped with either iron and chromium or iron and europium ascertain the degree of mutual interactions in these dual-doped glasses.

  19. Subcellular compartmentalization of Cd and Zn in two bivalves. II. Significance of trophically available metal (TAM)

    USGS Publications Warehouse

    Wallace, W.G.; Luoma, S.N.

    2003-01-01

    This paper examines how the subcellular partitioning of Cd and Zn in the bivalves Macoma balthica and Potamocorbula amurensis may affect the trophic transfer of metal to predators. Results show that the partitioning of metals to organelles, 'enzymes' and metallothioneins (MT) comprise a subcellular compartment containing trophically available metal (TAM; i.e. metal trophically available to predators), and that because this partitioning varies with species, animal size and metal, TAM is similarly influenced. Clams from San Francisco Bay, California, were exposed for 14 d to 3.5 ??g 1-1 Cd and 20.5 ??g 1-1 Zn, including 109Cd and 65Zn as radiotracers, and were used in feeding experiments with grass shrimp Palaemon macrodatylus, or used to investigate the subcellular partitioning of metal. Grass shrimp fed Cd-contaminated P. amurensis absorbed ???60% of ingested Cd, which was in accordance with the partitioning of Cd to the bivalve's TAM compartment (i.e. Cd associated with organelles, 'enzymes' and MT); a similar relationship was found in previous studies with grass shrimp fed Cd-contaminated oligochaetes. Thus, TAM may be used as a tool to predict the trophic transfer of at least Cd. Subcellular fractionation revealed that ???34% of both the Cd and Zn accumulated by M. balthica was associated with TAM, while partitioning to TAM in P. amurensis was metal-dependent (???60% for TAM-Cd%, ???73% for TAM-Zn%). The greater TAM-Cd% of P. amurensis than M. balthica is due to preferential binding of Cd to MT and 'enzymes', while enhanced TAM-Zn% of P. amurensis results from a greater binding of Zn to organelles. TAM for most species-metal combinations was size-dependent, decreasing with increased clam size. Based on field data, it is estimated that of the 2 bivalves, P. amurensis poses the greater threat of Cd exposure to predators because of higher tissue concentrations and greater partitioning as TAM; exposure of Zn to predators would be similar between these species.

  20. The influence of anions and inhibitors on the catalytic metal ion in Co(II)-substituted horse liver alcohol dehydrogenase.

    PubMed

    Bertini, I; Lanini, G; Luchinat, C; Haas, C; Maret, W; Zeppezauer, M

    1987-01-01

    1H-NMR and electronic spectroscopic data are reported for the interaction of the effector molecule imidazole and the inhibitor molecule pyrazole with horse liver alcohol dehydrogenase whose catalytic zinc ions were replaced by Co(II). In addition 13C-NMR and optical data are given for the binding of acetate to this enzyme species. For the binary complex with imidazole an assignment of the protons of the metal-coordinated imidazole has been made and it was found that the rate of exchange of the effector molecule is slow on the NMR time scale. In the presence of NADH which is bound to the open conformation of the binary complex, the most pronounced change is a shift of the beta-CH2 protons of the metal-coordinated cysteine residues which is attributed to hydrogen bonding interactions between the carboxamide group of the nicotinamide moiety with cysteine 46. The 1H-NMR spectra of the binary complex of Co(II)-HLADH with pyrazole show resonances assigned to the protons in the 3- and 4-positions of the bound inhibitor, the NH proton resonance is not detectable. In the ternary complex with pyrazole and NAD+ only the resonances of the beta-CH2 protons (beyond 150 ppm) are changed whereas the protons of histidine 67 and the bound inhibitor are unchanged. The data demonstrate that the coordination environment of the catalytic metal ion is changed very little when the protein changes from the open to the closed conformation.(ABSTRACT TRUNCATED AT 250 WORDS)

  1. Positron confinement in embedded lithium nanoclusters

    NASA Astrophysics Data System (ADS)

    van Huis, M. A.; van Veen, A.; Schut, H.; Falub, C. V.; Eijt, S. W.; Mijnarends, P. E.; Kuriplach, J.

    2002-02-01

    Quantum confinement of positrons in nanoclusters offers the opportunity to obtain detailed information on the electronic structure of nanoclusters by application of positron annihilation spectroscopy techniques. In this work, positron confinement is investigated in lithium nanoclusters embedded in monocrystalline MgO. These nanoclusters were created by means of ion implantation and subsequent annealing. It was found from the results of Doppler broadening positron beam analysis that approximately 92% of the implanted positrons annihilate in lithium nanoclusters rather than in the embedding MgO, while the local fraction of lithium at the implantation depth is only 1.3 at. %. The results of two-dimensional angular correlation of annihilation radiation confirm the presence of crystalline bulk lithium. The confinement of positrons is ascribed to the difference in positron affinity between lithium and MgO. The nanocluster acts as a potential well for positrons, where the depth of the potential well is equal to the difference in the positron affinities of lithium and MgO. These affinities were calculated using the linear muffin-tin orbital atomic sphere approximation method. This yields a positronic potential step at the MgO||Li interface of 1.8 eV using the generalized gradient approximation and 2.8 eV using the insulator model.

  2. Sonochemical synthesis and structural determination of novel the nano-card house Cu(II) metal-organic coordination system.

    PubMed

    Mojtabazade, Faeze; Mirtamizdoust, Babak; Morsali, Ali; Talemi, Pejman

    2017-03-01

    A sonochemical method by using various time and concentrations of initial reagents and power of irradiation, was used to synthesize nano-card house of a new copper(II) metal-organic coordination system, {[Cu2(p-2yeinh)2Cl2]·(H2O)}n (1), where p-2yeinh=pyridin-2-yl ethylidene-isonicotinohydrazide. The compound was characterized by scanning electron microscopy (SEM), elemental analysis, IR spectroscopy, X-ray powder diffraction (XPRD), and single crystal X-ray analysis. The X-ray structure revealed that the Cu(II) atom is coordinated by one oxygen and three nitrogen atoms from two p-2yeinh ligands and one chloride anion with a CuN3OCl donor set with square pyramid geometry. This arrangement produces a large quadric nuclear square ring composed of four square pyramid Cu(II) moieties linked together by two p-2yeinh units (M4L4). The adjacent frameworks connected by strong hydrogen bonding interactions of methanol molecules that interact together and with the rings and π-π interactions of adjacent aromatic rings of p-2yeinh and other weak interactions. Consequently, the labile interactions also allow the discrete structure to form a 3D metal-organic coordination network. CuO nanoparticles were obtained by thermolysis of 1 at 180°C with oleic acid as a surfactant. The average diameter of the nanoparticles was estimated by XPRD to be 38nm. The morphology and size of the prepared CuO nanoparticles were further studied using SEM.

  3. Structural and magnetic properties of layered copper(II) coordination polymers intercalating s and f metal ions.

    PubMed

    Navarro, Jorge A R; Barea, Elisa; Salas, Juan M; Masciocchi, Norberto; Galli, Simona; Sironi, Angelo

    2007-04-16

    The nanoporous coordination polymer [Cu(pyrimidin-2-olate-N1,N3)2]n (1C) of the sodalite zeotype sorbs a variety of metal nitrates [M(NO3)m, M = Na+, K+, Rb+, Tl+, Ca2+, Sr2+, Ba2+, Pb2+, La3+, Nd3+, Gd3+, Er3+] from H2O/MeOH solutions, with a concomitant structural change to a layered [Cu(pyrimidin-2-olate-N1,N3)2]n.[M(NO3)m]n/2 (MNO3@1L) coordination framework. Single-crystal X-ray diffraction analyses revealed that the layers are based on Cu4(pyrimidin-2-olate-N1,N3)4 square grids of copper(II) ions bridged by N1,N3 exobidentate ligands, displaying a structural motif of the metallacalix[4]arene type in pinched cone conformation. The interlayer space is occupied by the guest metal nitrates, each metal being coordinated by (at least) the four oxygen atoms of a metallacalix[4]arene. Magnetic measurements on the MNO3@1L series denoted a weak ferromagnetic ordering taking place below the Néel temperatures (typically close to 35 K), arising from spin-canting phenomena of the antiferromagnetically coupled copper centers. When M = Nd3+, Gd3+, or Er3+, additional magnetic ordering is observed at lower temperatures, which, on the basis of static and dynamic magnetic susceptibility measurements, can be attributed to copper- lanthanide interactions.

  4. Synthesis, structure and electrochemical behavior of a 3D crystalline copper(II) metal-organic framework

    NASA Astrophysics Data System (ADS)

    Bai, Hong-Ye; Fan, Wei-Qiang; Liu, Chun-Bo; Shi, Wei-Dong; Yan, Yong-Sheng

    2014-05-01

    Using an flexible amide-type tripodal ligand N,N‧,N″-tris(3-pyridyl)-1,3,5-benzenetricarboxamide (L) and 1,4-benzenedicarboxylic acid (H2bdc), a three-dimensional copper(II) metal-organic framework (MOF) formulated as [Cu(bdc)(L)]n has been hydrothermally synthesized and structurally characterized by IR, elemental, X-ray single-crystal diffraction and thermal analysis. The complex crystallizes in the triclinic, space group P - 1, a = 8.891(2) Å, b = 11.760(2) Å, c = 15.348(3) Å, α = 96.73(3)°, β = 105.96(3)°, γ = 106.47(3)°, V = 1446.2(5) Å3, Mr = 666.10, Dc = 1.530 g/cm3, Z = 2, F(000) = 682, GOOF = 1.0560, μ(MoKα) = 0.817 mm-1, R = 0.0366 and wR = 0.0885. The structural analyses reveal that the title compound consists of one Cu(II) atom, two halves of bdc, and one L ligand. Each Cu(II) atom is linked by two bdc ligands and three L ligands to form a three-dimensional network. In addition, the electrochemical behavior of title compound has been studied. CCDC No. 990526.

  5. Positron-annihilation 2D-ACAR studies of disordered and defected alloys

    SciTech Connect

    Bansil, A.; Prasad, R.; Smedskjaer, L.C.; Benedek, R.; Mijnarends, P.E.

    1987-09-01

    Theoretical and experimental progess in connection with 2D-ACAR positron annihilation studies of ordered, disordered, and defected alloys is discussed. We present, in particular, some of the recent developments concerning the electronic structure of disordered alloys, and the work in the area of annihilation from positrons trapped at vacancy-type defects in metals and alloys. The electronic structure and properties of a number of compounds are also discussed briefly; we comment specifically on high T/sub c/ ceramic superconductors, Heusler alloys, and transition-metal aluminides. 58 refs., 116 figs.

  6. Development of spin-polarized positron source using high energy proton beam

    NASA Astrophysics Data System (ADS)

    Maekawa, M.; Fukaya, Y.; Yabuuchi, Y.; Kawasuso, A.

    2011-01-01

    To obtain a highly spin polarized positron beam, 68Ge isotope have been produced using a nuclear reaction of 69Ga(p,2n)68Ge. As target materials, we examined a metal form 69Ga stable isotope and a GaN substrate. By 20 MeV proton irradiation, the production of 68Ge source was confirmed in both targets. The production rates of 68Ge were 0.16 and 0.53 MBq/μA/h for the metal Ga and GaN target, respectively. The spin polarizations of positrons emitted from 68Ge was estimated to be approximately 50 to 70%.

  7. Coordination of two high-affinity hexamer peptides to copper(II) and palladium(II) models of the peptide-metal chelation site on IMAC resins

    SciTech Connect

    Chen, Y.; Pasquinelli, R.; Ataai, M.; Koepsel, R.R.; Kortes, R.A.; Shepherd, R.E.

    2000-03-20

    The coordination of peptides Ser-Pro-His-His-Gly-Gly (SPHHGG) and (His){sub 6} (HHHHHH) to [Pd{sup II}(mida)(D{sub 2}O)] (mida{sup 2{minus}} = N-methyliminodiacetate) was studied by {sup 1}H NMR as model reactions for Cu{sup II}(iminodiacetate)-immobilized metal affinity chromatography (IMAC) sites. This is the first direct physical description of peptide coordination for IMAC. A three-site coordination is observed which involves the first, third, and fourth residues along the peptide chain. The presence of proline in position 2 of SPHHGG achieves the best molecular mechanics and bonding angles in the coordinated peptide and enhances the interaction of the serine amino nitrogen. Histidine coordination of H{sub 1}, H{sub 3}, and H{sub 4} of (His){sub 6} and H{sub 3} and H{sub 4} of SPHHGG was detected by {sup 1}H NMR contact shifts and H/D exchange of histidyl protons. The EPR spectra of SPHHGG and HHHHHH attached to the [Cu{sup II}(mida)] unit were obtained for additional modeling of IMAC sites. EPR parameters of the parent [Cu(mida)(H{sub 2}O){sub 2}] complex are representative: g{sub zz} = 2.31; g{sub yy} = 2.086; g{sub xx} = 2.053; A{sub {vert_bar}{vert_bar}} = 161 G; A{sub N} = 19G (three line, one N coupling). Increased rhombic distortion is detected relative to the starting aqua complex in the order of [Cu(mida)L] for distortion of HHHHHH > SPHHGG > (H{sub 2}O){sub 2}. The lowering of symmetry is also seen in the decrease in the N-shf coupling, presumably to the imino nitrogen of mida{sup 2{minus}} in the order 19 G (H{sub 2}O), 16 G (SPHHGG) and 11 G (HHHHHH). Visible spectra of the [Cu(mida)(SPHHGG)] and [Cu(mida)(HHHHHH)] as a function of pH indicate coordination of one histidyl donor at ca. 4.5, two in the range of pH 5--7, and two chelate ring attachments involving the terminal amino donor for SPHHGG or another histidyl donor of HHHHHH in the pH domain of 7--8 in agreement with the [Pd{sup II}(mida)L] derivatives which form the two

  8. Low-metallicity Star Formation and Pop III-II Transition

    NASA Astrophysics Data System (ADS)

    Omukai, Kazuyuki

    2010-10-01

    The first stars in the universe were typically very massive, but those near us are not. The metallicity in the star-forming gas is thought to have played a key role in this transition of characteristic stellar mass scale. By studying the evolution of low-metallicity star-forming clouds up to the formation of protostars by way of radiation hydrodynamics with spherical symmetry, we discuss their fragmentation mass scales. The critical metallicity for low-mass fragmentation is in the range of Zcr = 10-6-10-5Zsolar. Although the exact value is still unknown due to uncertain dust nature in the early universe, the small value of Zcr means that low-mass star formation begun just after the first episode of metal enrichment. We also evaluate the upper limit on the stellar mass by the stellar feedback. Owing to the higher density in the envelope and thus higher protostellar accretion rate, the upper limit of stellar mass increases toward lower matallicity.

  9. Abundance correlations in mildly metal-poor stars. II. Light elements (C to Ca)

    NASA Astrophysics Data System (ADS)

    Decauwer, H.; Jehin, E.; Parmentier, G.; Magain, P.

    2005-04-01

    Accurate relative abundances have been obtained for carbon, oxygen, sodium, aluminium, silicon, and calcium in a sample of mildly metal-poor stars. This analysis complements a previous study carried out by Jehin et al. ([CITE], A&A, 341, 241), which provided the basis for the EASE scenario. This scenario postulates that field metal-poor stars were born in self-enriched proto-globular cluster clouds. By further investigating the correlations between the different α-element abundances, we propose a modified scenario for the formation of intermediate metallicity stars, in which the stars exhibiting lower than average α/Fe abundance ratios would form in low mass clouds, unable to sustain the formation of very massive stars (M ⪆ 30~M_⊙). Moreover, the carbon-to-iron ratio is found to decrease as one climbs the so-called Population IIb branch, i.e. when the s-element abundance increases. In the framework of the EASE scenario, we interpret this anticorrelation between the carbon and the s-element abundances as a signature of a hot bottom burning process in the metal-poor AGB stars which expelled the matter subsequently accreted by our Population IIb stars. Based on observations collected at the European Southern Observatory, La Silla, Chile (ESO Programmes 56.E-0384, 57.E-0400 and 59.E-0257).

  10. Synthesis and antimicrobial activity of polysaccharide alginate derived cationic surfactant-metal(II) complexes.

    PubMed

    Tawfik, Salah M; Hefni, Hassan H

    2016-01-01

    New natural polysaccharide carbohydrate derivatives of sodium alginate surfactant and its cobalt, copper and zinc complexes were synthesized. Structures of the synthesized compounds are reported using FTIR, (1)H NMR and UV-vis. The critical micelle concentration (CMC) value of the alginate surfactant and its metal complexes in aqueous solution was found out from surface tension measurements. Surface tension data at different temperatures served for the evaluation of the temperature-dependent CMC and the thermodynamics of micellization (ΔGmic, ΔHmic, ΔSmic) and adsorption (ΔGads, ΔGads, ΔSads). The surface activities of the synthesized polymeric surfactant and its metal complexes were influenced by their chemical structures and the type of the transition metals. These compounds were evaluated against Gram-positive bacteria (Bacillus subtilis and Staphylococcus aureus), Gram-negative bacteria (Escherichia coli and Pseudomonas aeruginosa) and fungi (Candida albicans and Asperigllus niger). The antibacterial and antifungal screening tests of the alginate surfactant metal complexes have shown good results compared to its precursor alginate surfactant.

  11. Investigation of simultaneous biosorption of copper(II) and chromium(VI) on dried Chlorella vulgaris from binary metal mixtures: Application of multicomponent adsorption isotherms

    SciTech Connect

    Aksu, Z.; Acikel, U.; Kutsal, T.

    1999-02-01

    Although the biosorption of single metal ions to various kinds of microorganisms has been extensively studied and the adsorption isotherms have been developed for only the single metal ion situation, very little attention has been given to the bioremoval and expression of adsorption isotherms of multimetal ions systems. In this study the simultaneous biosorption of copper(II) and chromium(VI) to Chlorella vulgaris from a binary metal mixture was studied and compared with the single metal ion situation in a batch stirred system. The effects of pH and single- and dual-metal ion concentrations on the equilibrium uptakes were investigated. In previous studies the optimum biosorption pH had been determined as 4.0 for copper(II) and as 2.0 for chromium(VI). Multimetal ion biosorption studies were performed at these two pH values. It was observed that the equilibrium uptakes of copper(II) or chromium(VI) ions were changed due to the biosorption pH and the presence of other metal ions. Adsorption isotherms were developed for both single- and dual-metal ions systems at these two pH values, and expressed by the mono- and multicomponent Langmuir and Freundlich adsorption models. Model parameters were estimated by nonlinear regression. It was seen that the adsorption equilibrium data fitted very well to the competitive Freundlich model in the concentration ranges studied.

  12. Image enhancement in positron emission mammography

    NASA Astrophysics Data System (ADS)

    Slavine, Nikolai V.; Seiler, Stephen; McColl, Roderick W.; Lenkinski, Robert E.

    2017-02-01

    Purpose: To evaluate an efficient iterative deconvolution method (RSEMD) for improving the quantitative accuracy of previously reconstructed breast images by commercial positron emission mammography (PEM) scanner. Materials and Methods: The RSEMD method was tested on breast phantom data and clinical PEM imaging data. Data acquisition was performed on a commercial Naviscan Flex Solo II PEM camera. This method was applied to patient breast images previously reconstructed with Naviscan software (MLEM) to determine improvements in resolution, signal to noise ratio (SNR) and contrast to noise ratio (CNR.) Results: In all of the patients' breast studies the post-processed images proved to have higher resolution and lower noise as compared with images reconstructed by conventional methods. In general, the values of SNR reached a plateau at around 6 iterations with an improvement factor of about 2 for post-processed Flex Solo II PEM images. Improvements in image resolution after the application of RSEMD have also been demonstrated. Conclusions: A rapidly converging, iterative deconvolution algorithm with a novel resolution subsets-based approach RSEMD that operates on patient DICOM images has been used for quantitative improvement in breast imaging. The RSEMD method can be applied to clinical PEM images to improve image quality to diagnostically acceptable levels and will be crucial in order to facilitate diagnosis of tumor progression at the earliest stages. The RSEMD method can be considered as an extended Richardson-Lucy algorithm with multiple resolution levels (resolution subsets).

  13. Detection of metal residues on bone using SEM-EDS--part II: Sharp force injury.

    PubMed

    Gibelli, D; Mazzarelli, D; Porta, D; Rizzi, A; Cattaneo, C

    2012-11-30

    Scanning electron microscopy coupled with X-ray energy dispersive spectrometry (SEM-EDS) is extensively seen in the literature for the improvement of the macroscopic analysis of sharp lesions, but very few indications concerning its real potential in the forensic context, particularly in forensic anthropology, are at the moment available. This paper represents a pilot study for the analysis of the behaviour of metallic residues found on bone after sharp force injury. Fourteen lesions were made on human bone (radius), cleaned of all soft tissues, with seven different sharp tools (three metal instruments, three metal saws and a baked-clay knife). Tools and lesions underwent SEM-EDS. From 3 to 18 particles were detected on each lesion, whose diameter was included between 0.5 and 150 μm. In 58% of cases, particle composition was concordant with the instrument used. The results seem to suggest that sharp force injury frequently leaves relatively few residues on bone, particularly in the case of common types of metal. Saws showed slightly more contamination with other residues than knives, which may be explained by the capability of the saw's teeth to retain the residues of previously encountered material. In addition, metal residues related to the tool used to cut the bone were located on the edges/walls of lesions in the case of saw marks, whereas they were more frequently found on the kerf floor in the case of knives/scissors, with the exception of the baked clay knife which when it leaves residues at all, seemed to leave them equally divided between the floor, the edges and the surrounding bone.

  14. Bruno Touschek: From Betatrons to Electron-Positron Colliders

    NASA Astrophysics Data System (ADS)

    Bernardini, Carlo; Pancheri, Giulia; Pellegrini, Claudio

    Bruno Touschek’s life as a physicist spanned the period from World War II to the 1970s. He was a key figure in the developments of electron-positron colliders and storage rings, and made important contributions to theoretical high energy physics. Storage rings, initially developed for high energy physics, are being widely used in many countries as synchrotron radiation sources and are a tool for research in physics, chemistry, biology, environmental sciences and cultural heritage studies. We describe Touschek’s life in Austria, where he was born, in Germany, where he participated in the construction of a betatron during WWII, and in Italy, where he proposed and led to completion the first electron-positron storage ring in 1960, in Frascati. We highlight how his central European culture influenced his lifestyle and work, and his main contributions to physics, such as the discovery of the Touschek effect and beam instabilities in the larger storage ring ADONE.

  15. Bruno Touschek: From Betatrons to Electron-Positron Colliders

    NASA Astrophysics Data System (ADS)

    Bernardini, Carlo; Pancheri, Giulia; Pellegrini, Claudio

    Bruno Touschek's life as a physicist spanned the period from World War II to the 1970s. He was a key figure in the developments of electron-positron colliders and storage rings, and made important contributions to theoretical high energy physics. Storage rings, initially developed for high energy physics, are being widely used in many countries as synchrotron radiation sources and are a tool for research in physics, chemistry, biology, environmental sciences and cultural heritage studies. We describe Touschek's life in Austria, where he was born, in Germany, where he participated in the construction of a betatron during WWII, and in Italy, where he proposed and led to completion the first electron-positron storage ring in 1960, in Frascati. We highlight how his central European culture influenced his lifestyle and work, and his main contributions to physics, such as the discovery of the Touschek effect and beam instabilities in the larger storage ring ADONE.

  16. Intervening Metal Systems in GRB and QSO Sight Lines: The Mg II and C IV Question

    NASA Astrophysics Data System (ADS)

    Sudilovsky, Vladimir; Savaglio, Sandra; Vreeswijk, Paul; Ledoux, Cédric; Smette, Alain; Greiner, Jochen

    2007-11-01

    Prochter and coworkers recently found that the number density of strong intervening 0.5II absorbers detected in gamma-ray burst (GRB) afterglow spectra is nearly 4 times larger than those in QSO spectra. We have conducted a similar study using C IV absorbers. Our C IV sample, consisting of a total of 19 systems, is drawn from three high-resolution and high to moderate signal-to-noise ratio VLT UVES spectra of three long-duration GRB afterglows, covering the redshift interval 1.6II absorbers and conclude that a higher dust extinction in the Mg II QSO samples studied up to now would give the most straightforward solution. However, this effect is only important for the strong Mg II absorbers. Regardless of the reasons for this discrepancy, this result confirms once more that GRBs can be used to detect a side of the universe that was unknown before, not necessarily connected with GRBs themselves, providing an alternative and fundamental investigative tool of the cosmic evolution of the universe. Based on observations collected at the European Southern Observatory, Chile; proposals 75.A-0385, 75.A-0603, and 77.D-0661.

  17. Nonplanar positron-acoustic Gardner solitary waves in electron-positron-ion plasmas with superthermal electrons and positrons

    NASA Astrophysics Data System (ADS)

    Uddin, M. J.; Alam, M. S.; Mamun, A. A.

    2015-02-01

    Nonplanar (cylindrical and spherical) positron-acoustic (PA) Gardner solitary waves (SWs) in an unmagnetized plasma system consisting of immobile positive ions, mobile cold positrons, and superthermal (kappa distributed) hot positrons and electrons are investigated. The modified Gardner equation is derived by using the reductive perturbation technique. The effects of cylindrical and spherical geometries, superthermal parameter of hot positrons and electrons, relative temperature ratios, and relative number density ratios on the PA Gardner SWs are studied by using the numerical simulations. The implications of our results in various space and laboratory plasma environments are briefly discussed.

  18. Nonplanar positron-acoustic Gardner solitary waves in electron-positron-ion plasmas with superthermal electrons and positrons

    SciTech Connect

    Uddin, M. J. Alam, M. S.; Mamun, A. A.

    2015-02-15

    Nonplanar (cylindrical and spherical) positron-acoustic (PA) Gardner solitary waves (SWs) in an unmagnetized plasma system consisting of immobile positive ions, mobile cold positrons, and superthermal (kappa distributed) hot positrons and electrons are investigated. The modified Gardner equation is derived by using the reductive perturbation technique. The effects of cylindrical and spherical geometries, superthermal parameter of hot positrons and electrons, relative temperature ratios, and relative number density ratios on the PA Gardner SWs are studied by using the numerical simulations. The implications of our results in various space and laboratory plasma environments are briefly discussed.

  19. [Studies on the mechanism of the interaction between hydrazide-podophyllic Ni(II), Co(II), Zn(II) metal complexes and DNA].

    PubMed

    Wang, Ping-Hong; Zhang, Qi; Yuan, Wen-Bing; Wang, Liu-Fang; Song, Yu-Min; Liu, Hui-Hong

    2006-07-01

    The mechanism of the interaction between hydrazide-podophyllic (HDPP) metal (Me) complexes and calf thymus (ct) DNA in Tris buffer (pH 7.08) was studied by viscosity measurements, electronic absorption, gel electrophoresis, and ethidium bromide (EB) fluorescence spectroscopy. The results from varied experiments show that the intensity of the maximal absorption peaks from absorption spectra is weakened in the presence of DNA compared with that in the absence of DNA. Meanwhile, DNA can remarkably quench the emission intensity of the complex Me-HDPP system. The Me-HDPP complexes can increase the viscosity of ct DNA slightly and catalyze the cleavage of super coiled pBR322 DNA to the nicked form. The complexes of Ni-HDPP and Co-HDPP can be bound to ct DNA mainly by interaction, while the partial interaction of Zn-HDPP and ct DNA is the major modes. The binding constant of Me-HDPP complexes with ct DNA was determined.

  20. High-resolution spectroscopy of extremely metal-poor stars from SDSS/Segue. II. Binary fraction

    SciTech Connect

    Aoki, Wako; Suda, Takuma; Beers, Timothy C.; Honda, Satoshi E-mail: takuma.suda@nao.ac.jp E-mail: honda@nhao.jp

    2015-02-01

    The fraction of binary systems in various stellar populations of the Galaxy and the distribution of their orbital parameters are important but not well-determined factors in studies of star formation, stellar evolution, and Galactic chemical evolution. While observational studies have been carried out for a large sample of nearby stars, including some metal-poor Population II stars, almost no constraints on the binary nature for extremely metal-poor (EMP; [Fe/H] <−3.0) stars have yet been obtained. Here we investigate the fraction of double-lined spectroscopic binaries and carbon-enhanced metal-poor (CEMP) stars, many of which could have formed as pairs of low-mass and intermediate-mass stars, to estimate the lower limit of the fraction of binary systems having short periods. The estimate is based on a sample of very metal-poor stars selected from the Sloan Digital Sky Survey and observed at high spectral resolution in a previous study by Aoki et al. That survey reported 3 double-lined spectroscopic binaries and 11 CEMP stars, which we consider along with a sample of EMP stars from the literature compiled in the SAGA database. We have conducted measurements of the velocity components for stacked absorption features of different spectral lines for each double-lined spectroscopic binary. Our estimate indicates that the fraction of binary stars having orbital periods shorter than 1000 days is at least 10%, and possibly as high as 20% if the majority of CEMP stars are formed in such short-period binaries. This result suggests that the period distribution of EMP binary systems is biased toward short periods, unless the binary fraction of low-mass EMP stars is significantly higher than that of other nearby stars.

  1. Positron annihilation induced Auger electron spectroscopy

    NASA Technical Reports Server (NTRS)

    Weiss, Alex; Koymen, A. R.; Mehl, David; Jensen, K. O.; Lei, Chun; Lee, K. H.

    1990-01-01

    Recently, Weiss et al. have demonstrated that it is possible to excite Auger transitions by annihilating core electrons using a low energy (less than 30eV) beam of positrons. This mechanism makes possible a new electron spectroscopy, Positron annihilation induced Auger Electron Spectroscopy (PAES). The probability of exciting an Auger transition is proportional to the overlap of the positron wavefunction with atomic core levels. Since the Auger electron energy provides a signature of the atomic species making the transition, PAES makes it possible to determine the overlap of the positron wavefunction with a particular element. PAES may therefore provide a means of detecting positron-atom complexes. Measurements of PAES intensities from clean and adsorbate covered Cu surfaces are presented which indicate that approx. 5 percent of positrons injected into CU at 25eV produce core annihilations that result in Auger transitions.

  2. Spectral, mechanical, thermal, optical and solid state parameters, of metal-organic bis(hydrogenmaleate)-CO(II) tetrahydrate crystal

    SciTech Connect

    Chandran, Senthilkumar; Jagan, R.; Paulraj, Rajesh; Ramasamy, P.

    2015-10-15

    Metal-organic bis(hydrogenmaleate)-Co(II) tetrahydrate single crystals have been grown by slow evaporation solution growth technique at room temperature. The crystal structure and the unit cell parameters were analyzed from the X-ray diffraction studies. Single-crystal X-ray diffraction analyses reveal that the grown crystal belongs to triclinic system with the space group P-1. Functional groups in bis(hydrogenmaleate)-Co(II) tetrahydrate were identified by Fourier transform infrared spectral analysis. The peak observed at 663 cm{sup −1} is assigned to the (Co–O) stretching vibrations. The optical transmission of the crystal was studied by UV–vis–NIR spectral analysis. The photoluminescence emission studies were carried out for the title compound in a wide wavelength range between 350 nm and 550 nm at 303 K. Mechanical strength was tested by Vickers microhardness test. The laser damage threshold value has been determined using Nd:YAG laser operating at 1064 nm. At various frequencies and temperatures the dielectric behavior of the material was investigated. Solid state parameters such as plasma energy, Penn gap, Fermi energy and electronic polarizability were evaluated. Photoconductivity measurements were carried out for the grown crystal in the presence of DC electric field at room temperature. Thermal stability and decomposition of the crystal were studied by TG–DTA. The weight loss of the title compound occurs in different steps. - Graphical abstract: Molecular structure of the bis(hydrogenmaleate)-Co(II) tetrahydrate drawn at 40% ellipsoid probability level. - Highlights: • Bis(hydrogenmaleate)-Co(II) tetrahydrate single crystal is grown by slow evaporation method. • Structural and optical properties were discussed. • The title complex crystal is thermally stable up to 91 °C. • Plasma energy, Fermi energy and electronic polarizability are evaluated. • It exhibits positive photoconductivity.

  3. Synthesis and photodynamic activity of unsymmetrical A3B tetraarylporphyrins functionalized with l-glutamate and their Zn(II) and Cu(II) metal complex derivatives.

    PubMed

    Arredondo-Espinoza, Eder U; López-Cortina, Susana T; Ramírez-Cabrera, Mónica A; Balderas-Rentería, Isaías

    2016-08-01

    Four novel unsymmetrical A3B porphyrins 1, 2, 3 and 4 were synthesized following Lindsey procedure. Porphyrins 3 and 4 include one and three l-glutamate groups, respectively, and all porphyrins were metallated with Zn(II) (1a-4a) or Cu(II) (1b-4b). Porphyrins and metalloporphyrins presented values of singlet oxygen quantum yields (ΦD) ranging from 0.21 to 0.67. The tetraaryl derivatives in this study showed phototoxicity in SiHa cells with IC50 values ranging from <0.01 to 6.56±0.11μM, the metalloporphyrin 4a showed the lowest IC50 value. Comparing the phototoxic activity between all porphyrins, functionalization of porphyrins with glutamate increased 100 times phototoxic activity (1 (IC50 4.81±0.34μM) vs. 3 (IC50 0.04±0.02μM) and 2 (IC50 5.19±0.42μM) vs. 4 (IC50 0.05±0.01μM)). This increased activity could be attributed to reduced hydrophobicity and increased ΦΔ, given by functionalization with l-glutamate. Metalloporphyrins 3a (IC50 0.04±0.01μM) and 4a (IC50<0.01μM) presented the best values ​​of phototoxic activity. Therefore, functionalization and zinc metalation increased the phototoxic activity. SiHa cells treated with porphyrins 3, 4, 3a and 4a at a final concentration of 10μM, showed increased activity of caspase-3 enzyme compared to the negative control; indicating the induction of apoptosis. Differential gene expression pattern in SiHa cells was determined; treatments with metalloporphyrins 4a and 4b were performed, respectively, comparing the expression with untreated control. Treatments in both cases showed similar gene expression pattern in upregulated genes, since they share about 25 biological pathways and a large number of genes. According to the new photophysical properties related to the structural improvement and phototoxic activity, these molecules may have the potential application as photosensitizers in the photodynamic therapy.

  4. Recent Advances in Electron and Positron Sources

    SciTech Connect

    Clendenin, James E

    2000-07-20

    Recent advances in electron and positron sources have resulted in new capabilities driven in most cases by the increasing demands of advanced accelerating systems. Electron sources for brighter beams and for high average-current beams are described. The status and remaining challenges for polarized electron beams are also discussed. For positron sources, recent activity in the development of polarized positron beams for future colliders is reviewed. Finally, a new proposal for combining laser cooling with beam polarization is presented.

  5. Positron study of annealing of gallium arsenide

    SciTech Connect

    Rice-Evans, P.C.; Smith, D.L.; Evans, H.E.; Gledhill, G.A. )

    1991-02-01

    A positron beam has been used to investigate the sub-surface changes in semi-insulating gallium arsenide which had been annealed to a range of temperatures. The variations of the Doppler S parameter as a function of positron implantation energy, when subjected to a diffusion analysis, indicate variations in positron trapping at different depths. The results indicate the changes in the type of point defect that accompany the annealing.

  6. Analysis of metal-matrix composite structures. I - Micromechanics constitutive theory. II - Laminate analyses

    NASA Technical Reports Server (NTRS)

    Arenburg, R. T.; Reddy, J. N.

    1991-01-01

    The micromechanical constitutive theory is used to examine the nonlinear behavior of continuous-fiber-reinforced metal-matrix composite structures. Effective lamina constitutive relations based on the Abouli micromechanics theory are presented. The inelastic matrix behavior is modeled by the unified viscoplasticity theory of Bodner and Partom. The laminate constitutive relations are incorporated into a first-order deformation plate theory. The resulting boundary value problem is solved by utilizing the finite element method. Attention is also given to computational aspects of the numerical solution, including the temporal integration of the inelastic strains and the spatial integration of bending moments. Numerical results the nonlinear response of metal matrix composites subjected to extensional and bending loads are presented.

  7. Perylenetetracarboxylic-metal assemblies and anisotropic charge transport in a CuII assembly

    NASA Astrophysics Data System (ADS)

    Bai, Linyi; Xia, Youyi; Jana, Avijit; Ang, Chung Yen; Zhao, Lingzhi; Fan, Zhi; Zhao, Yanli

    2016-04-01

    Structural diversity and uniformity of nanomaterials are usually prerequisites for many practical applications involving the oriented fabrication of various devices with full control over their desired physiochemical properties. Particularly in the optoelectronic field, ordered assembly inside cells is required not only for obtaining attractive configurations but also for playing an important role in the characteristics of photoconduction and conductivity. Here, we present a synergetic self-assembly driven by coordination and intermolecular interactions for the construction of organic-inorganic hybrids with multi-morphologies and tunable physical properties. 3,4,9,10-Perylenetetracarboxylic dianhydride was treated with base to produce various assemblies by coordination with metal ions, showing morphologies of nanowires, nanosheets, nanoribbons and nanorods. The organic π-spacer affords an extension in different directions through the suitable incorporation of metal ions with different coordination modes for the formation of metal-ligand complexes. Interestingly, the obtained nanorods were twisted rods with obvious screw threads on the rod wall, supporting the synergetic self-assembly. Then, anisotropic mobility measurements of the obtained Cu2+-ligand assembly were carried out to show the importance of the size- and shape-confined synthesis of the hybrids. By presenting a series of ordered metal-ligand complex superstructures driven by synergetic self-assembly, this work is expected to pave the way for future anisotropic measurements of complex assemblies.Structural diversity and uniformity of nanomaterials are usually prerequisites for many practical applications involving the oriented fabrication of various devices with full control over their desired physiochemical properties. Particularly in the optoelectronic field, ordered assembly inside cells is required not only for obtaining attractive configurations but also for playing an important role in the

  8. Analysis of metal-matrix composite structures. I - Micromechanics constitutive theory. II - Laminate analyses

    NASA Technical Reports Server (NTRS)

    Arenburg, R. T.; Reddy, J. N.

    1991-01-01

    The micromechanical constitutive theory is used to examine the nonlinear behavior of continuous-fiber-reinforced metal-matrix composite structures. Effective lamina constitutive relations based on the Abouli micromechanics theory are presented. The inelastic matrix behavior is modeled by the unified viscoplasticity theory of Bodner and Partom. The laminate constitutive relations are incorporated into a first-order deformation plate theory. The resulting boundary value problem is solved by utilizing the finite element method. Attention is also given to computational aspects of the numerical solution, including the temporal integration of the inelastic strains and the spatial integration of bending moments. Numerical results the nonlinear response of metal matrix composites subjected to extensional and bending loads are presented.

  9. Palladium(II)-catalyzed direct alkoxylation of arenes: evidence for solvent-assisted concerted metalation deprotonation.

    PubMed

    Anand, Megha; Sunoj, Raghavan B

    2011-09-16

    Density functional theory investigations on the mechanism of palladium acetate catalyzed direct alkoxylation of N-methoxybenzamide in methanol reveal that the key steps involve solvent-assisted N-H as well as C-H bond activations. The transition state for the critical palladium-carbon bond formation through a concerted metalation deprotonation (CMD) process leading to a palladacycle intermediate has been found to be more stable in the methanol-assisted pathway as compared to an unassisted route.

  10. Metallic nanoparticles and their medicinal potential. Part II: aluminosilicates, nanobiomagnets, quantum dots and cochleates.

    PubMed

    Loomba, Leena; Scarabelli, Tiziano

    2013-09-01

    Metallic miniaturization techniques have taken metals to nanoscale size where they can display fascinating properties and their potential applications in medicine. In recent years, metal nanoparticles such as aluminium, silicon, iron, cadmium, selenium, indium and calcium, which find their presence in aluminosilicates, nanobiomagnets, quantum dots (Q-dots) and cochleates, have caught attention of medical industries. The increasing impact of metallic nanoparticles in life sciences has significantly advanced the production techniques for these nanoparticles. In this Review, the various methods for the synthesis of nanoparticles are outlined, followed by their physicochemical properties, some recent applications in wound healing, diagnostic imaging, biosensing, assay labeling, antimicrobial activity, cancer therapy and drug delivery are listed, and finally their toxicological impacts are revised. The first half of this article describes the medicinal uses of two noble nanoparticles - gold and silver. This Review provides further information on the ability of aluminum, silicon, iron, selenium, indium, calcium and zinc to be used as nanoparticles in biomedical sciences. Aluminosilicates find their utility in wound healing and antibacterial growth. Iron-oxide nanoparticles enhance the properties of MRI contrast agents and are also used as biomagnets. Cadmium, selenium, tellurium and indium form the core nanostructures of tiny Q-dots used in cellular assay labeling, high-resolution cell imaging and biosensing. Cochleates have the bivalent nano ions calcium, magnesium or zinc imbedded in their structures and are considered to be highly effective agents for drug and gene delivery. The aluminosilicates, nanobiomagnets, Q-dots and cochleates are discussed in the light of their properties, synthesis and utility.

  11. Bright Metal-Poor Stars from the Hamburg/ESO Survey. II. A Chemodynamical Analysis

    NASA Astrophysics Data System (ADS)

    Beers, Timothy C.; Placco, Vinicius M.; Carollo, Daniela; Rossi, Silvia; Lee, Young Sun; Frebel, Anna; Norris, John E.; Dietz, Sarah; Masseron, Thomas

    2017-01-01

    We obtain estimates of stellar atmospheric parameters for a previously published sample of 1777 relatively bright (9< B< 14) metal-poor candidates from the Hamburg/ESO Survey. The original Frebel et al. analysis of these stars was able to derive estimates of [Fe/H] and [C/Fe] only for a subset of the sample, due to limitations in the methodology then available. A new spectroscopic analysis pipeline has been used to obtain estimates of {T}{eff}, {log} g, [Fe/H], and [C/Fe] for almost the entire data set. This sample is very local—about 90% of the stars are located within 0.5 kpc of the Sun. We consider the chemodynamical properties of these stars in concert with a similarly local sample of stars from a recent analysis of the Bidelman and MacConnell “weak metal” candidates by Beers et al. We use this combined sample to identify possible members of the halo stream of stars suggested by Helmi et al. and Chiba & Beers, as well as stars that may be associated with stripped debris from the putative parent dwarf of the globular cluster Omega Centauri, suggested to exist by previous authors. We identify a clear increase in the cumulative frequency of carbon-enhanced metal-poor (CEMP) stars with declining metallicity, as well as an increase in the fraction of CEMP stars with distance from the Galactic plane, consistent with previous results. We also identify a relatively large number of CEMP stars with kinematics consistent with the metal-weak thick-disk population, with possible implications for its origin.

  12. Pollutants in harp seals (Phoca groenlandica). II. Heavy metals and selenium.

    PubMed

    Ronald, K; Frank, R J; Dougan, J; Frank, R; Braun, H E

    1984-09-01

    Between 1976 and 1978, 249 harp seals were sampled from five locations in the Northwest Atlantic and Arctic for heavy metal and selenium residue analyses in tissue. Significant loading was apparent only in blood, brain, kidney, liver and muscle. Samples were analysed for mercury (Hg), selenium (Se), copper (Cu), cadmium (Cd) and lead (Pb). The seals carried higher levels of Cd than of the other metals. Residue levels of Cd were highest in kidney tissue; levels of other metals were highest in liver. Both males and females bioaccumulated Cd, Hg and Se. Cd, Hg, Se and Cu residues were detected in tissue from neonatal seals, indicating that transplacental and transmammary transfer of these elements had occurred. Despite the passage of residues from mother to pup, females bore significantly higher levels of Hg and Cd than males. Conversely, levels of Cu, Se or Pb did not appear to differ significantly between sexes. There was considerable individual variation in residue levels. This, coupled with the extensive annual migration undergone by these animals, made it difficult to arrive at definite conclusions regarding geographic accumulation patterns.

  13. Application of zeolite prepared from Egyptian kaolin for the removal of heavy metals: II. Isotherm models.

    PubMed

    Ibrahim, Hanan S; Jamil, Tarek S; Hegazy, Eman Z

    2010-10-15

    In this study, the adsorption behavior of zeolites A and X, which are prepared from very cheap local Egyptian clay (kaolin), with respect to Cu(2+), Cd(+2), Cr(+2), Ni(+2) and Zn(2+) has been studied. The batch method has been employed, using metal solutions ranging from 100 to 400 mg/L. The distribution coefficients (K(d)) and adsorption percent were determined for the adsorption system as a function of sorbate concentration. In the uptake evaluation part of the study, adsorption ratios of metal cations on zeolites A and X match to Langmuir, Freundlich, and Dubinin-Kaganer-Radushkevich (DKR) adsorption isotherm data. Also, every cation exchange capacity for metals has been calculated. According to the equilibrium studies, the selectivity sequence can be given as Pb(2+)>Cd(2+)>Cu(2+)>Zn(2+)>Ni(2+). It was found that the uptake depend on hydrated ion diameter. This study may attract more interest due to the presence of large reservoirs of very cheap kaolin in Egypt from which both zeolite types were prepared.

  14. Initial results of positron ionization mass spectrometry

    NASA Technical Reports Server (NTRS)

    Donohue, D. L.; Hulett, L. D., Jr.; Mcluckey, S. A.; Glish, G. L.; Eckenrode, B. A.

    1990-01-01

    The use of monoenergetic positrons for the ionization of organic molecules in the gas phase is described. The ionic products are analyzed with a time-of-flight mass spectrometer and detected to produce a mass spectrum. The ionization mechanisms which can be studied in this way include positron impact at energies above the ionization limit of the target molecules, positronium formation in the Ore gap energy range, and positron attachment at energies less than 1eV. The technique of positron ionization mass spectrometry (PIMS) may have analytical utility in that chemical selectivity is observed for one or more of these processes.

  15. KEK-IMSS Slow Positron Facility

    NASA Astrophysics Data System (ADS)

    Hyodo, T.; Wada, K.; Yagishita, A.; Kosuge, T.; Saito, Y.; Kurihara, T.; Kikuchi, T.; Shirakawa, A.; Sanami, T.; Ikeda, M.; Ohsawa, S.; Kakihara, K.; Shidara, T.

    2011-12-01

    The Slow Positron Facility at the Institute of Material Structure Science (IMSS) of High Energy Accelerator Research Organization (KEK) is a user dedicated facility with an energy tunable (0.1 - 35 keV) slow positron beam produced by a dedicated 55MeV linac. The present beam line branches have been used for the positronium time-of-flight (Ps-TOF) measurements, the transmission positron microscope (TPM) and the photo-detachment of Ps negative ions (Ps-). During the year 2010, a reflection high-energy positron diffraction (RHEPD) measurement station is going to be installed. The slow positron generator (converter/ moderator) system will be modified to get a higher slow positron intensity, and a new user-friendly beam line power-supply control and vacuum monitoring system is being developed. Another plan for this year is the transfer of a 22Na-based slow positron beam from RIKEN. This machine will be used for the continuous slow positron beam applications and for the orientation training of those who are interested in beginning researches with a slow positron beam.

  16. Applications and advances of positron beam spectroscopy

    SciTech Connect

    Howell, R., LLNL

    1998-03-18

    Over 50 scientists from DOE-DP, DOE-ER, the national laboratories, academia and industry attended a workshop held on November 5-7, 1997 at Lawrence Livermore National Laboratory. Workshop participants were charged to address two questions: Is there a need for a national center for materials analysis using positron techniques and can the capabilities at Lawrence Livermore National Laboratory serve this need. To demonstrate the need for a national center, the workshop participants discussed the technical advantages enabled by high positron currents and advanced measurement techniques, the role that these techniques would play in materials analysis and the demand for the data. Livermore now leads the world in materials analysis capabilities by positrons due to developments in response to demands of stockpile stewardship. The Livermore facilities now include the world`s highest current beam of keV positrons, a scanning pulsed positron microprobe under development capable of three dimensional maps of defect size and concentration, an MeV positron beam for defect analysis of large samples, and electron momentum spectroscopy by positrons. It was concluded that the positron microprobe under development at LLNL and other new instruments that would be relocated at LLNL at the high current keV source are an exciting step forward in providing results for the positron technique. These new data will impact a wide variety of applications.

  17. Performance Oriented Packaging Requirements of Wirebound Box for Small Caliber Ammunition Packed in PA108 Metal Container for Packing Group II Solid Hazardous Materials

    DTIC Science & Technology

    1993-11-05

    amunition. This wirebound box contains two PA108 metal containers containing 5.56= mall caliber wmuiticx for Squad Automatic Weapons . Tests were...REQUIREMENTS OF WIREBOUND BOX FOR SMALL CALIBER AMMUNITION PACKED IN PA108 METAL CONTAINER =0 QUALCTYI"’D 5 FOR Acl For PACKING GROUP II OTNC TAB...Squad Automatic Weapon . This box contains a maximum gross weight of 54 kg. POP tests were conducted using additional weight(62 kg test weight) to insure

  18. Unexpected metal ion-assisted transformations leading to unexplored bridging ligands in Ni(II) coordination chemistry: the case of PO3F(2-) group.

    PubMed

    Dermitzaki, Despina; Raptopoulou, Catherine P; Psycharis, Vassilis; Escuer, Albert; Perlepes, Spyros P; Stamatatos, Theocharis C

    2014-10-21

    The initial 'accidental', metal ion-assisted hydrolysis of PF6(-) to PO3F(2-) has been evolved in a systematic investigation of the bridging affinity of the latter group in Ni(II)/oximate chemistry; mono-, di- and trinuclear complexes have been prepared and confirmed both the rich reactivity of PO3F(2-) and its potential for further use as bridging ligand in high-nuclearity 3d-metal cluster chemistry.

  19. Phototoxicity of strained Ru(ii) complexes: is it the metal complex or the dissociating ligand?

    PubMed

    Azar, Daniel F; Audi, Hassib; Farhat, Stephanie; El-Sibai, Mirvat; Abi-Habib, Ralph J; Khnayzer, Rony S

    2017-09-12

    A photochemically dissociating ligand in Ru(bpy)2(dmphen)Cl2 [bpy = 2,2'-bipyridine; dmphen = 2,9-dimethyl-1,10-phenanthroline] was found to be more cytotoxic on the ML-2 Acute Myeloid Leukemia cell line than Ru(bpy)2(H2O)2(2+) and prototypical cisplatin. Our findings illustrate the potential potency of diimine ligands in photoactivatable Ru(ii) complexes.

  20. Metallation of ethylenediamine based Schiff base with biologically active Cu(II), Ni(II) and Zn(II) ions: synthesis, spectroscopic characterization, electrochemical behaviour, DNA binding, photonuclease activity and in vitro antimicrobial efficacy.

    PubMed

    Raman, N; Selvan, A; Sudharsan, S

    2011-09-01

    A new ligand [C28H20N6O8] (L2) has been synthesized by the condensation reaction of 3-hydroxy-4-nitrobenzaldehydenephenylhydrazine (L1) with diethyloxalate. This ligand L2 is allowed to react with bis(ethylenediamine)Cu(II)/Ni(II)/Zn(II) complexes. It affords [(L2)Cu(en)2]Cl2(1)/[(L2)Ni(en)2]Cl2(2)/[(L2)Zn(en)2]Cl2(3) complexes, respectively. These complexes (1-3) have been characterized by the spectral and analytical techniques. The interaction of these complexes with calf thymus (CT) DNA is characterized by the absorption spectra which exhibit a slight red shift with hypochromic effect. Electrochemical analyses and viscosity measurements have also been carried out to determine the mode of binding. The shift in ΔEp, E1/2 and Ipc values explores the interaction of CT DNA with the above metal complexes. The slight increase in the viscosity of CT DNA indicates that these complexes bind to CT DNA through a partial non-classical intercalative mode. Cleavage experiments using pBR322 DNA in presence of H2O2 indicate that these complexes behave as efficient artificial chemical nucleases in the order of 1>2>3. Moreover, the antibacterial and antifungal studies reveal that complex 1 is highly active against the bacterial and fungal growth.

  1. 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

  2. Crystal structure of nonadentate tricompartmental ligand derived from pyridine-2,6-dicarboxylic acid: Spectroscopic, electrochemical and thermal investigations of its transition metal(II) complexes

    NASA Astrophysics Data System (ADS)

    Vadavi, Ramesh S.; Shenoy, Rashmi V.; Badiger, Dayananda S.; Gudasi, Kalagouda B.; Devi, L. Gomathi; Nethaji, Munirathinam

    2011-07-01

    The coordinating behavior of a new dihydrazone ligand, 2,6-bis[(3-methoxysalicylidene)hydrazinocarbonyl]pyridine towards manganese(II), cobalt(II), nickel(II), copper(II), zinc(II) and cadmium(II) has been described. The metal complexes were characterized by magnetic moments, conductivity measurements, spectral (IR, NMR, UV-Vis, FAB-Mass and EPR) and thermal studies. The ligand crystallizes in triclinic system, space group P-1, with α = 98.491(10)°, β = 110.820(10)° and γ = 92.228(10)°. The cell dimensions are a = 10.196(7) Å, b = 10.814(7) Å, c = 10.017(7) Å, Z = 2 and V = 1117.4(12). IR spectral studies reveal the nonadentate behavior of the ligand. All the complexes are neutral in nature and possess six-coordinate geometry around each metal center. The X-band EPR spectra of copper(II) complex at both room temperature and liquid nitrogen temperature showed unresolved broad signals with giso = 2.106. Cyclic voltametric studies of copper(II) complex at different scan rates reveal that all the reaction occurring are irreversible.

  3. Synthesis, characterization and biological relevance of some metal (II) complexes with oxygen, nitrogen and oxygen (ONO) donor Schiff base ligand derived from thiazole and 2-hydroxy-1-naphthaldehyde

    NASA Astrophysics Data System (ADS)

    Nagesh, G. Y.; Mruthyunjayaswamy, B. H. M.

    2015-04-01

    The novel Schiff base ligand 2-((2-hydroxynaphthalen-1-yl)methylene)-N-(4-phenylthiazol-2-yl)hydrazinecarboxamide (L) obtained by the condensation of N-(4-phenylthiazol-2-yl)hydrazinecarboxamide with 2-hydroxy-1-naphthaldehyde and its newly synthesized Cu(II), Co(II), Ni(II), Zn(II) and Cd(II) complexes have been characterized by microanalysis, molar conductance, IR, 1H NMR, ESI-mass, UV-Visible, TGA/DTA, ESR and powder X-ray diffraction data to explicate their structures. The IR results confirmed the tridentate binding of the ligand involving oxygen atom of amide carbonyl, azomethine nitrogen and naphthol oxygen. 1H NMR spectral data of the ligand (L) and its Zn(II) complex agreed well with the proposed structures. Thermogravimetric studies for Cu(II) and Ni(II) complexes indicated the presence of coordinated water molecules and the final product is the metal oxide. In order to appraise the effect of antimicrobial activity of metal ions upon chelation, the newly synthesized ligand and its metal complexes were screened for their antimicrobial activity by minimum inhibitory concentration (MIC) method. The DNA cleavage activities were studied using plasmid DNA pBR322 (Bangal re Genei, Bengaluru, Cat. No 105850) as a target molecule by agarose gel electrophoresis method. The brine shrimp bioassay was also carried out to study the in vitro cytotoxicity properties against Artemia salina. Furthermore, the antioxidant activity were determined in vitro by reduction of 1,1-diphenyl-2-picryl hydrazyl (DPPH). The ligand exhibited better in vitro-antioxidant activity than its metal complexes.

  4. Globular Cluster Abundances from High-resolution, Integrated-light Spectroscopy. II. Expanding the Metallicity Range for Old Clusters and Updated Analysis Techniques

    NASA Astrophysics Data System (ADS)

    Colucci, Janet E.; Bernstein, Rebecca A.; McWilliam, Andrew

    2017-01-01

    We present abundances of globular clusters (GCs) in the Milky Way and Fornax from integrated-light (IL) spectra. Our goal is to evaluate the consistency of the IL analysis relative to standard abundance analysis for individual stars in those same clusters. This sample includes an updated analysis of seven clusters from our previous publications and results for five new clusters that expand the metallicity range over which our technique has been tested. We find that the [Fe/H] measured from IL spectra agrees to ∼0.1 dex for GCs with metallicities as high as [Fe/H] = ‑0.3, but the abundances measured for more metal-rich clusters may be underestimated. In addition we systematically evaluate the accuracy of abundance ratios, [X/Fe], for Na i, Mg i, Al i, Si i, Ca i, Ti i, Ti ii, Sc ii, V i, Cr i, Mn i, Co i, Ni i, Cu i, Y ii, Zr i, Ba ii, La ii, Nd ii, and Eu ii. The elements for which the IL analysis gives results that are most similar to analysis of individual stellar spectra are Fe i, Ca i, Si i, Ni i, and Ba ii. The elements that show the greatest differences include Mg i and Zr i. Some elements show good agreement only over a limited range in metallicity. More stellar abundance data in these clusters would enable more complete evaluation of the IL results for other important elements. This paper includes data gathered with the 6.5 m Magellan Telescopes located at Las Campanas Observatory, Chile.

  5. Impact of Lewis base on chemical reactivity and separation efficiency for hydrated fourth-row transition metal (II) complexes: an ONIOM DFT/MM study.

    PubMed

    He, Dingsheng; Ma, Ming

    2014-04-24

    In this paper, two-layer ONIOM combinations of high-level quantum mechanics (QM) and inexpensive molecular mechanics (MM) are successfully used to investigate the structural characters of metal (M, all the transition metals in the fourth period)-H2O-Lewis base (A(-)) complexes. Global and local descriptors of chemical reactivity and selectivity from conceptual density functional theory are employed to show the properties of the active complexes of M(H2O)2A2 and to study the effect of the Lewis base for the separation of transition metal ions. It is shown that chemical potential, hardness, electrophilicity, as well as the dual and multiphilic descriptors are adequate for characterizing the global and local reactivity trends of the M(H2O)2A2 complex. It is found that the reactivity is well localized at the metallic center in M(H2O)2A2 and the dual descriptor (ΔfM(r)) can also be used to characterize the directional attack of the electrophile and nucleophile except for the selectivity of the reaction. On the basis of the values of ωM and Δsk, and the sign of ΔfM(r), the selectivity of the nucleophilic reagent (R(-)) for M(II) in M(H2O)2A2 (from high to low) follows this order: Cu(II) > Ni(II) > Co(II) > Fe(II) ≫ Mn(II) > Zn(II) > Cr(II). The Lewis base (A(-)) improves chemical reactivity and selectivity because of changing the reaction path and forming an intermediate, which possesses the higher antibonding character and the larger HOMO/LUMO gap. NBO or AIMALL analysis and Frontier orbital theory results presented here provided more theoretical support for the above reactivity and selectivity studies.

  6. Identification of a neuropeptide precursor protein that gives rise to a "cocktail" of peptides that bind Cu(II) and generate metal-linked dimers.

    PubMed

    Jones, Christopher E; Zandawala, Meet; Semmens, Dean C; Anderson, Sarah; Hanson, Graeme R; Janies, Daniel A; Elphick, Maurice R

    2016-01-01

    Neuropeptides with an Amino Terminal Cu(II), Ni(II) Binding (ATCUN) motif (H2N-xxH) bind Cu(II)/Ni(II) ions. Here we report the novel discovery of a neuropeptide precursor that gives rise to a "cocktail" of peptides that bind Cu(II)/Ni(II) and form ternary complexes--the L-type SALMFamide precursor in the starfish Asterias rubens. Echinoderm transcriptome sequence data were analysed to identify transcripts encoding precursors of SALMFamide-type neuropeptides. The sequence of the L-type SALMFamide precursor in the starfish Asterias rubens was confirmed by cDNA sequencing and peptides derived from this precursor (e.g. AYHSALPF-NH2, GYHSGLPF-NH2 and LHSALPF-NH2) were synthesized. The ability of these peptides to bind metals was investigated using UV/Vis, NMR, circular dichroism and EPR spectroscopy. AYHSALPF-NH2 and GYHSGLPF-NH2 bind Cu(II) and Ni(II) and generate metal-linked dimers to form ternary complexes with LHSALPF-NH2. Investigation of the evolutionary history of the histidine residue that confers these properties revealed that it can be traced to the common ancestor of echinoderms, which is estimated to have lived ~500 million years ago. However, L-type precursors comprising multiple SALMFamides with the histidine residue forming an ATCUN motif appears to be a feature that has evolved uniquely in starfish (Asteroidea). The discovery of a SALMFamide-type neuropeptide precursor protein that gives rise to a "cocktail" of peptides that bind metal ions and generate metal-linked dimers provides a new insight on ATCUN motif-containing neuropeptides. This property of L-type SALMFamides in the Asteroidea may be associated with a role in regulation of the unusual extra-oral feeding behaviour of starfish. Copyright © 2015 Elsevier B.V. All rights reserved.

  7. Hydrogen Storage and Selective, Reversible O2 Adsorption in a Metal-Organic Framework with Open Chromium(II) Sites.

    PubMed

    Bloch, Eric D; Queen, Wendy L; Hudson, Matthew R; Mason, Jarad A; Xiao, Dianne J; Murray, Leslie J; Flacau, Roxana; Brown, Craig M; Long, Jeffrey R

    2016-07-18

    A chromium(II)-based metal-organic framework Cr3 [(Cr4 Cl)3 (BTT)8 ]2 (Cr-BTT; BTT(3-) =1,3,5-benzenetristetrazolate), featuring coordinatively unsaturated, redox-active Cr(2+) cation sites, was synthesized and investigated for potential applications in H2 storage and O2 production. Low-pressure H2 adsorption and neutron powder diffraction experiments reveal moderately strong Cr-H2 interactions, in line with results from previously reported M-BTT frameworks. Notably, gas adsorption measurements also reveal excellent O2 /N2 selectivity with substantial O2 reversibility at room temperature, based on selective electron transfer to form Cr(III) superoxide moieties. Infrared spectroscopy and powder neutron diffraction experiments were used to confirm this mechanism of selective O2 binding. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. High-z QSO Absorption Systems: Metal-Poor Cold Flows and Mg II Absorber Host Galaxies

    NASA Astrophysics Data System (ADS)

    Cooper, Thomas; Simcoe, R. A.; Cooksey, K.; O'Meara, J.

    2014-01-01

    Cosmological simulations have suggested a new model for gas accretion in young galaxies, in which baryons flow into the star-forming disk along filamentary streams without shock heating at the dark matter halo virial radius. Observationally, these cold flows manifest as Lyman Limit Systems with low heavy element abundances. To search for cold flows in the early Universe, we have obtained echellette-resolution spectra of an HI-selected sample of LLS at z>3.5 from the Sloan Digital Sky Survey. The sightlines were selected to exhibit no heavy element absorption at the resolution afforded by SDSS, and the higher resolution data provides metallicity measurements precise enough to determine if they exhibit cold flow accretion characteristics. In a parallel program, we use the Magellan Telescopes and HST/WFC-3 to investigate the connection between Mg II absorbers and proximate galaxies at 3, extending fruitful studies of the circumgalactic medium to larger redshift.

  9. Nonvolatile Memory Effect in Indium Gallium Arsenide-Based Metal-Oxide-Semiconductor Devices Using II-VI Tunnel Insulators

    NASA Astrophysics Data System (ADS)

    Chan, P.-Y.; Gogna, M.; Suarez, E.; Karmakar, S.; Al-Amoody, F.; Miller, B. I.; Jain, F. C.

    2011-08-01

    This paper reports the successful use of ZnSe/ZnS/ZnMgS/ZnS/ZnSe as a gate insulator stack for an InGaAs-based metal-oxide-semiconductor (MOS) device, and demonstrates the threshold voltage shift required in nonvolatile memory devices using a floating gate quantum dot layer. An InGaAs-based nonvolatile memory MOS device was fabricated using a high- κ II-VI tunnel insulator stack and self-assembled GeO x -cladded Ge quantum dots as the charge storage units. A Si3N4 layer was used as the control gate insulator. Capacitance-voltage data showed that, after applying a positive voltage to the gate of a MOS device, charges were being stored in the quantum dots. This was shown by the shift in the flat-band/threshold voltage, simulating the write process of a nonvolatile memory device.

  10. Demonstration of a high-field short-period superconducting helical undulator suitable for future TeV-scale linear collider positron sources.

    PubMed

    Scott, D J; Clarke, J A; Baynham, D E; Bayliss, V; Bradshaw, T; Burton, G; Brummitt, A; Carr, S; Lintern, A; Rochford, J; Taylor, O; Ivanyushenkov, Y

    2011-10-21

    The first demonstration of a full-scale working undulator module suitable for future TeV-scale positron-electron linear collider positron sources is presented. Generating sufficient positrons is an important challenge for these colliders, and using polarized e(+) would enhance the machine's capabilities. In an undulator-based source polarized positrons are generated in a metallic target via pair production initiated by circularly polarized photons produced in a helical undulator. We show how the undulator design is developed by considering impedance effects on the electron beam, modeling and constructing short prototypes before the successful fabrication, and testing of a final module. © 2011 American Physical Society

  11. Dinuclear ruthenium(ii) complexes containing one inert metal centre and one coordinatively-labile metal centre: syntheses and biological activities.

    PubMed

    Li, Xin; Heimann, Kirsten; Li, Fangfei; Warner, Jeffrey M; Richard Keene, F; Grant Collins, J

    2016-03-07

    A series of non-symmetric dinuclear polypyridylruthenium(ii) complexes (Rubbn-Cl) that contain one inert metal centre and one coordinatively-labile metal centre, linked by the bis[4(4'-methyl-2,2'-bipyridyl)]-1,n-alkane ligand ("bbn" for n = 7, 12 and 16), have been synthesised and their potential as antimicrobial agents examined. The minimum inhibitory concentrations (MIC) of the ruthenium(II) complexes were determined against four strains of bacteria--Gram-positive Staphylococcus aureus (S. aureus) and methicillin-resistant S. aureus (MRSA), and Gram-negative Escherichia coli (E. coli) and Pseudomonas aeruginosa (P. aeruginosa). The Rubbn-Cl complexes displayed good antimicrobial activity, with Rubb12-Cl being the most active complex against both Gram-positive and Gram-negative strains. Interestingly, Rubb7-Cl was found to be eight- and sixteen-fold more active towards E. coli than against S. aureus and MRSA, respectively. The cytotoxicities of the Rubbn-Cl complexes against three eukaryotic cell lines--two kidney cell lines (BHK and HEK-293) and one liver cell line (HepG2)--were examined. The Rubbn-Cl complexes were found to be considerably less toxic towards eukaryotic cells than S. aureus, MRSA and E. coli, with Rubb12-Cl being thirty- to eighty-times more toxic to the bacteria than to BHK, HEK-293 or HepG2 cells. Unexpectedly, Rubb7-Cl was far more toxic to HepG2 cells (24 h-IC50 = 3.7 μM) and far less toxic to BHK cells (24 h-IC50 = 238 μM) than the Rubb12-Cl and Rubb16-Cl complexes. In order to understand the unexpected large differences in the cytotoxicities of the Rubbn-Cl complexes towards eukaryotic cells, a confocal microscopic study of their intracellular localisation was undertaken. The results suggest that the observed cytotoxicity might be related to the extent of DNA binding.

  12. Enhanced metal ion selectivity of 2,9-di-(pyrid-2-yl)-1,10-phenanthroline and its use as a fluorescent sensor for cadmium(II).

    PubMed

    Cockrell, Gregory M; Zhang, Gang; VanDerveer, Donald G; Thummel, Randolph P; Hancock, Robert D

    2008-01-30

    The metal ion complexing properties of the ligand DPP (2,9-di-(pyrid-2-yl)-1,10-phenanthroline) were studied by crystallography, fluorimetry, and UV-visible spectroscopy. Because DPP forms five-membered chelate rings, it will favor complexation with metal ions of an ionic radius close to 1.0 A. Metal ion complexation and accompanying selectivity of DPP is enhanced by the rigidity of the aromatic backbone of the ligand. Cd2+, with an ionic radius of 0.96 A, exhibits a strong CHEF (chelation enhanced fluorescence) effect with 10(-8) M DPP, and Cd2+ concentrations down to 10(-9) M can be detected. Other metal ions that cause a significant CHEF effect with DPP are Ca2+ (10(-3) M) and Na+ (1.0 M), whereas metal ions such as Zn2+, Pb2+, and Hg2+ cause no CHEF effect with DPP. The lack of a CHEF effect for Zn2+ relates to the inability of this small ion to contact all four donor atoms of DPP. The structures of [Cd(DPP)2](ClO4)2 (1), [Pb(DPP)(ClO4)2H2O] (2), and [Hg(DPP)(ClO4)2] (3) are reported. The Cd(II) in 1 is 8-coordinate with the Cd-N bonds to the outer pyridyl groups stretched by steric clashes between the o-hydrogens on these outer pyridyl groups and the central aromatic ring of the second DPP ligand. The 8-coordinate Pb(II) in 2 has two short Pb-N bonds to the two central nitrogens of DPP, with longer bonds to the outer N-donors. The coordination sphere around the Pb(II) is completed by a coordinated water molecule, and two coordinated ClO4(-) ions, with long Pb-O bonds to ClO4(-) oxygens, typical of a sterically active lone pair on Pb(II). The Hg(II) in 3 shows an 8-coordinate structure with the Hg(II) forming short Hg-N bonds to the outer pyridyl groups of DPP, whereas the other Hg-N and Hg-O bonds are rather long. The structures are discussed in terms of the fit of large metal ions to DPP with minimal steric strain. The UV-visible studies of the equilibria involving DPP and metal ions gave formation constants that show that DPP has a higher affinity for metal

  13. A compendium of sources of fracture toughness and fatigue crack growth data for metallic alloys. II

    NASA Technical Reports Server (NTRS)

    Hudson, C. M.; Seward, S. K.

    1982-01-01

    A compendium is presented of sources for metallic alloy fracture toughness and fatigue crack growth data, which concentrates on technical reports as the primary source of references and updates the previous Hudson and Seward (1978) compendium references on technical journals. Where available, the accession numbers which are used as code numbers for the ordering of the reports from their publishers are given. The sources of these reports include the AIAA Technical Information Service, the Defense Technical Information Center, the National Technical Information Service, and NASA.

  14. PHASE-FIELD SIMULATION OF IRRADIATED METALS: PART II: GAS BUBBLE KINETICS

    SciTech Connect

    Paul C Millett; Anter El-Azab

    2011-01-01

    We present a phase-field model for inert gas bubble formation and evolution in irradiated metals. The model evolves vacancy, self-interstitial, and fission gas atoms through a coupled set of Cahn-Hilliard and Allen-Cahn equations, capturing the processes of defect generation, recombination, annihilation at GB sinks, as well as intragranular and intergranular bubble nucleation and growth in polycrystalline microstructures. Illustrative results are presented that characterize bubble growth and shrinkage, as well as the bubble density, size and nucleation rate as a function of varying irradiation conditions. Finally, intergranular bubble characteristics such as shape, pinning energy on GB motion, and bubble density are investigated.

  15. Unusual composition dependence of magnetic relaxation for Co(II)(1-x)Ni(II)(x) chain-based metal-organic frameworks.

    PubMed

    Wang, Yan-Qin; Cheng, Ai-Ling; Liu, Pei-Pei; Gao, En-Qing

    2013-08-11

    A series of isomorphous 3D Co(II)(1-x)Ni(II)(x) MOFs based on ferromagnetic chains show SCM-type slow relaxation and the Co-rich system can exhibit a higher blocking temperature than both Co(II) and Ni(II) parent materials.

  16. The intra-annular acylamide chelate-coordinated compound: The keto-tautomer of metal (II) milrinone complex

    NASA Astrophysics Data System (ADS)

    Gong, Yun; Liu, Jinzhi; Tang, Wang; Hu, Changwen

    2008-03-01

    In the presence of N, N'-dimethyllformamide (DMF), two isostructural metal (II)-milrinone complexes formulated as M(C 12H 8N 3O) 2 (M = Co 1 and Ni 2) have been synthesized and characterized by elemental analysis, IR, TG and single crystal X-ray diffraction. The two compounds crystallize in the tetragonal system, chiral space group P4 32 12. They exhibit similar two dimensional (2D) square grid-like framework, in which milrinone acts as a ditopic ligand with its terminal pyridine and intra-annular acylamide groups covalently bridging different metal centers. The intra-annular acylamide ligand shows a chelate-coordinated mode. Compounds 1 and 2 are stable under 200 °C. Compound 3 formulated as (C 12H 9N 3O) 4·H 2O was obtained in the presence of water, the water molecule in the structure leads to the racemization of compound 3 and it crystallizes in the monoclinic system, non-chiral space group P2 1/ c. Milrinone exhibits a keto-form in the three compounds and compounds 1- 3 exhibit different photoluminescence properties.

  17. Changes of Multiple Metal Accumulation (MMA) in New Orleans Soil: Preliminary Evaluation of Differences between Survey I (1992) and Survey II (2000)

    PubMed Central

    Mielke, Howard W.; Gonzales, Christopher; Powell, Eric; MielkeJr, Paul W.

    2005-01-01

    Soil metal surveys were conducted in Baltimore, MD (1976–1979), Minnesota (1981–1988) and most recently, New Orleans, LA (1989-present). The unique characteristic of New Orleans is that it has two surveys; Survey I was completed in 1992 and Survey II was completed in 2000. This paper seeks to determine if there is a perceptible change in the amount of metals during less than a decade that separated these surveys. The Survey I collection was 4,026 samples stratified by 283 census tracts. All samples were collected in residential neighborhoods at least one block from a busy street. The Survey II collection was 5,467 samples stratified by 286 census tracts (plus City Park). The Survey II collection included busy streets as a category of samples. For comparison, the busy street category of 1,078 samples was excluded from Survey II for a total of 4,388 samples. The extraction methods of the two surveys used the same protocol for strength of acid (1 M HNO3), shaker-time (2 hours), and room temperature (~22ºC). However, Survey II differed in amount of sample used in extraction. For Surveys I and II, 4.0g and 0.4g were used respectively. The same ICP-AES was used to measure 8 metals in both surveys. To evaluate the analytical results of the two methods, reference soil samples (n=36) from the Wageningen Evaluating Programs for Analytical Laboratories, International Soil-analytical Exchange (WEPAL; ISE) were used. The relationship between the 4.0 and 0.4 g results were linear and the Survey I results were adjusted for sample:acid ratio. Further evaluation was done by creating interpolated Multiple Metal Accumulation (MMA) maps based on the median MMA for each census tract. A new map was created by dividing Survey II MMA by Survey I MMA. The ratio indicates increases of soil metals in the inner city and decreases of soil metals in the outlying areas of Metropolitan New Orleans. Comparing fresh parent alluvium from the Mississippi River with urban soil metal quantities

  18. A novel route for the removal of bodily heavy metal lead (II)

    NASA Astrophysics Data System (ADS)

    Huang, Weirong; Zhang, Penghua; Xu, Hui; Chang, Shengli; He, Yongju; Wang, Fei; Liang, Gaowei

    2015-09-01

    The lead ion concentration in bile is considerably higher than in blood, and bile is released into the alimentary tract. Thiol-modified SBA-15 administered orally can combine with lead ions in the alimentary tract. In this paper, the in vitro lead absorption of bile was investigated. This thiol-modified SBA-15 material was used in pharmacodynamics studies on rabbits. The result that the lead content in faeces was notably higher indicates that thiol-modified SBA-15 can efficiently remove lead. The mechanism could include the following: thiol-modified SBA-15 material cuts off the heavy metal lead recirculation in the process of bile enterohepatic circulation by chelating the lead in the alimentary tract, causing a certain proportion of lead to be removed by the thiol mesoporous material, and the lead is subsequently egested out of the body in faeces. The results indicate that this material might be a potential non-injection material for the removal bodily heavy metal lead in the alimentary tract. This material may also be a useful means of lead removal, especially for non-acute sub-poisoning symptoms.

  19. Cylindrical Wire Electrical Discharge Machining of Metal Bond Diamond Wheels- Part II: Wheel Wear Mechanism

    SciTech Connect

    McSpadden, SB

    2002-01-22

    The use of stereo scanning Electron Microscopy (SEM) to investigate the wear mechanism of the wire EDM true metal bond diamond wheel for ceramic grinding is presented. On the grinding wheel, a wedge-shape removal part was machined to enable the examination and measurement of the worn wheel surfaces using the stereo SEM. The stereo SEM was calibrated by comparing results of depth profile of a wear groove with the profilometer measurements. On the surface of the grinding wheel after wire EDM truing and before grinding, the diamond protruding heights were measured in the level of 35 {micro}m, comparing to the 54 {micro}m average size of the diamond in the grinding wheel. The gap between the EDM wire and rotating grinding wheel is estimated to be about 35 to 40 {micro}m. This observation indicates that, during the wire EDM, electrical sparks occur between the metal bond and EDM wire, which leaves the diamond protruding in the gap between the wire and wheel. The protruding diamond is immediately fractured at the start of the grinding process, even under a light grinding condition. After heavy grinding, the grinding wheel surface and the diamond protrusion heights are also investigated using the stereo SEM. The height of diamond protrusion was estimated in the 5 to 15 {micro}m range. This study has demonstrated the use of stereo SEM as a metrology tool to study the grinding wheel surface.

  20. A novel route for the removal of bodily heavy metal lead (II).

    PubMed

    Huang, Weirong; Zhang, Penghua; Xu, Hui; Chang, Shengli; He, Yongju; Wang, Fei; Liang, Gaowei

    2015-09-25

    The lead ion concentration in bile is considerably higher than in blood, and bile is released into the alimentary tract. Thiol-modified SBA-15 administered orally can combine with lead ions in the alimentary tract. In this paper, the in vitro lead absorption of bile was investigated. This thiol-modified SBA-15 material was used in pharmacodynamics studies on rabbits. The result that the lead content in faeces was notably higher indicates that thiol-modified SBA-15 can efficiently remove lead. The mechanism could include the following: thiol-modified SBA-15 material cuts off the heavy metal lead recirculation in the process of bile enterohepatic circulation by chelating the lead in the alimentary tract, causing a certain proportion of lead to be removed by the thiol mesoporous material, and the lead is subsequently egested out of the body in faeces. The results indicate that this material might be a potential non-injection material for the removal bodily heavy metal lead in the alimentary tract. This material may also be a useful means of lead removal, especially for non-acute sub-poisoning symptoms.

  1. Mn(II)-based porous metal-organic framework showing metamagnetic properties and high hydrogen adsorption at low pressure.

    PubMed

    Han, Zheng-Bo; Lu, Rui-Yun; Liang, Yan-Fang; Zhou, Yan-Ling; Chen, Qing; Zeng, Ming-Hua

    2012-01-02

    A Mn(II)-based homometallic porous metal-organic framework, Mn(5)(btac)(4)(μ(3)-OH)(2)(EtOH)(2)·DMF·3EtOH·3H(2)O (1, btac = benzotriazole-5-carboxylate), has been solvothermally synthesized and structurally characterized by elemental analysis, thermogravimetric analysis, and X-ray crystallographic study. 1 is a 3D neutral framework featuring 1D porous channels constructed by {Mn-OH-Mn}(n) chains and btac linkers. Magnetic studies show that 1 is a 3D metamagnet containing 1D {Mn-OH-Mn}(n) ferrimagnetic chains. High-pressure H(2) adsorption measurement at 77 K reveals that activated 1 can absorb 0.99 wt % H(2) at 0.5 atm and reaches a maximum of 1.03 wt % at 5.5 atm. The steep H(2) absorption at lower pressure (98.2% of the storage capacity at 0.5 atm) is higher than the corresponding values of some MOFs (MIL-100 (16.1%), MOF-177 (57.1%), and MOF-5 (22.2%)). Furthermore, activated 1 can adsorb CO(2) at room temperature and 275 K. The adsorption enthalpy is 22.0 kJ mol(-1), which reveals the high binding ability for CO(2). Detailed gas sorption implies that the exposed Mn(II) coordination sites in the activated 1 play an important role to improve its adsorption capacities.

  2. A Noble-Metal-Free Nickel(II) Polypyridyl Catalyst for Visible-Light-Driven Hydrogen Production from Water.

    PubMed

    Yuan, Yong-Jun; Lu, Hong-Wei; Tu, Ji-Ren; Fang, Yong; Yu, Zhen-Tao; Fan, Xiao-Xing; Zou, Zhi-Gang

    2015-10-05

    The complex [Ni(bpy)3](2+) (bpy=2,2'-bipyridine) is an active catalyst for visible-light-driven H2 production from water when employed with [Ir(dfppy)2 (Hdcbpy)] [dfppy=2-(3,4-difluorophenyl)pyridine, Hdcbpy=4-carboxy-2,2'-bipyridine-4'-carboxylate] as the photosensitizer and triethanolamine as the sacrificial electron donor. The highest turnover number of 520 with respect to the nickel(II) catalyst is obtained in a 8:2 acetonitrile/water solution at pH 9. The H2 -evolution system is more stable after the addition of an extra free bpy ligand, owing to faster catalyst regeneration. The photocatalytic results demonstrate that the nickel(II) polypyridyl catalyst can act as a more effective catalyst than the commonly utilized [Co(bpy)3 ](2+). This study may offer a new paradigm for constructing simple and noble-metal-free catalysts for photocatalytic hydrogen production. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Nanosheets of Two-Dimensional Magnetic and Conducting Fe(II)/Fe(III) Mixed-Valence Metal-Organic Frameworks.

    PubMed

    Benmansour, Samia; Abhervé, Alexandre; Gómez-Claramunt, Patricia; Vallés-García, Cristina; Gómez-García, Carlos J

    2017-08-09

    We report the synthesis, magnetic properties, electrical conductivity, and delamination into thin nanosheets of two anilato-based Fe(II)/Fe(III) mixed-valence two-dimensional metal-organic frameworks (MOFs). Compounds [(H3O)(H2O)(phenazine)3][Fe(II)Fe(III)(C6O4X2)3]·12H2O [X = Cl (1) and Br (2)] present a honeycomb layered structure with an eclipsed packing that generates hexagonal channels containing the water molecules. Both compounds show ferrimagnetic ordering at ca. 2 K coexisting with electrical conductivity (with room temperature conductivities of 0.03 and 0.003 S/cm). Changing the X group from Cl to Br leads to a decrease in the ordering temperature and room temperature conductivity that is correlated with the decrease of the electronegativity of X. Despite the ionic charge of the anilato-based layers, these MOFs can be easily delaminated in thin nanosheets with the thickness of a few monolayers.

  4. Proton conduction and long-range ferrimagnetic ordering in two isostructural Copper(II) mesoxalate metal-organic frameworks.

    PubMed

    Gil-Hernández, Beatriz; Savvin, Stanislav; Makhloufi, Gamall; Núñez, Pedro; Janiak, Christoph; Sanchiz, Joaquín

    2015-02-16

    Two compounds of formula {(H3O)[Cu7(Hmesox)5(H2O)7]·9H2O}n (1a) and {(NH4)0.6(H3O)0.4[Cu7(Hmesox)5(H2O)7]·11H2O}n (1b) were prepared and structurally characterized by single-crystal X-ray diffraction (H4mesox = mesoxalic acid, 2-dihydroxymalonic acid). The compounds are crystalline functional metal-organic frameworks exhibiting proton conduction and magnetic ordering. Variable-temperature magnetic susceptibility measurements reveal that the copper(II) ions are strongly ferro- and antiferromagnetically coupled by the alkoxide and carboxylate bridges of the mesoxalate linker to yield long-range magnetic ordering with a Tc of 17.6 K, which is reached by a rare mechanism known as topologic ferrimagnetism. Electric conductivity, measured by impedance methods, shows values as high as 6.5 × 10(-5) S cm(-1) and occurs by proton exchange among the hydronium/ammonium and water molecules of crystallization, which fill the voids left by the three-dimensional copper(II) mesoxalate anionic network.

  5. Mercury (II) reduction and co-precipitation of metallic mercury on hydrous ferric oxide in contaminated groundwater.

    PubMed

    Richard, Jan-Helge; Bischoff, Cornelia; Ahrens, Christian G M; Biester, Harald

    2016-01-01

    Mercury (Hg) speciation and sorption analyses in contaminated aquifers are useful for understanding transformation, retention, and mobility of Hg in groundwater. In most aquifers hydrous ferric oxides (HFOs) are among the most important sorbents for trace metals; however, their role in sorption or mobilization of Hg in aquifers has been rarely analyzed. In this study, we investigated Hg chemistry and Hg sorption to HFO under changing redox conditions in a highly HgCl2-contaminated aquifer (up to 870μgL(-1) Hg). Results from aqueous and solid phase Hg measurements were compared to modeled (PHREEQC) data. Speciation analyses of dissolved mercury indicated that Hg(II) forms were reduced to Hg(0) under anoxic conditions, and adsorbed to or co-precipitated with HFO. Solid phase Hg thermo-desorption measurements revealed that between 55 and 93% of Hg bound to HFO was elemental Hg (Hg(0)). Hg concentrations in precipitates reached more than 4 weight %, up to 7000 times higher than predicted by geochemical models that do not consider unspecific sorption to and co-precipitation of elemental Hg with HFO. The observed process of Hg(II) reduction and Hg(0) formation, and its retention and co-precipitation by HFO is thought to be crucial in HgCl2-contaminated aquifers with variable redox-conditions regarding the related decrease in Hg solubility (factor of ~10(6)), and retention of Hg in the aquifer.

  6. Temperature dependence of probability of absorption of. gamma. -quanta by Sn(II)-containing complexes of transition metals

    SciTech Connect

    Yurchenko, E.N.; Kuznetsov, v.I.; Burgina, E.B.

    1985-09-01

    A study has been made of the relationship f'(T) (T = 77-300/sup 0/K) for platinum-group metal complexes containing Sn(II)-X (X= F, Cl, Br); these data have been used to determine the mean-square amplitudes of vibrations of the Sn atom in the anions and together with the anion, and their temperature dependences have been found. The observed relationships at f'(T) depend to a considerable degree on the vibrations of the first type, i.e., on the rigidity of the bonds between the Sn and the immediate environment. The different Sn-X ligands have their own characteristic relationships f'(T), so that they can be used for identification of types of Sn(II)-containing complexes. The normal vibrations of the different complexes have been calculated, and it has been established that the observed changes in their f'(T) in the series of halides can be explained by the increase in the number of low-frequency vibrations in the series Br > Cl > F and by their effective inclusion in the absorption of the recoil energy given up by the Sn atom. Within the framework of the analysis, an explanation has been found for the increase in f' of the complexes when they are supported on the surface of substances containing acidic OH groups.

  7. Spectral, mechanical, thermal, optical and solid state parameters, of metal-organic bis(hydrogenmaleate)-CO(II) tetrahydrate crystal

    NASA Astrophysics Data System (ADS)

    Chandran, Senthilkumar; Jagan, R.; Paulraj, Rajesh; Ramasamy, P.

    2015-10-01

    Metal-organic bis(hydrogenmaleate)-Co(II) tetrahydrate single crystals have been grown by slow evaporation solution growth technique at room temperature. The crystal structure and the unit cell parameters were analyzed from the X-ray diffraction studies. Single-crystal X-ray diffraction analyses reveal that the grown crystal belongs to triclinic system with the space group P-1. Functional groups in bis(hydrogenmaleate)-Co(II) tetrahydrate were identified by Fourier transform infrared spectral analysis. The peak observed at 663 cm-1 is assigned to the (Co-O) stretching vibrations. The optical transmission of the crystal was studied by UV-vis-NIR spectral analysis. The photoluminescence emission studies were carried out for the title compound in a wide wavelength range between 350 nm and 550 nm at 303 K. Mechanical strength was tested by Vickers microhardness test. The laser damage threshold value has been determined using Nd:YAG laser operating at 1064 nm. At various frequencies and temperatures the dielectric behavior of the material was investigated. Solid state parameters such as plasma energy, Penn gap, Fermi energy and electronic polarizability were evaluated. Photoconductivity measurements were carried out for the grown crystal in the presence of DC electric field at room temperature. Thermal stability and decomposition of the crystal were studied by TG-DTA. The weight loss of the title compound occurs in different steps.

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

    NASA Astrophysics Data System (ADS)

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

    2016-03-01

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

  9. Unbound position II in MXCXXC metallochaperone model peptides impacts metal binding mode and reactivity: Distinct similarities to whole proteins.

    PubMed

    Shoshan, Michal S; Dekel, Noa; Goch, Wojciech; Shalev, Deborah E; Danieli, Tsafi; Lebendiker, Mario; Bal, Wojciech; Tshuva, Edit Y

    2016-06-01

    The effect of position II in the binding sequence of copper metallochaperones, which varies between Thr and His, was investigated through structural analysis and affinity and oxidation kinetic studies of model peptides. A first Cys-Cu(I)-Cys model obtained for the His peptide at acidic and neutral pH, correlated with higher affinity and more rapid oxidation of its complex; in contrast, the Thr peptide with the Cys-Cu(I)-Met coordination under neutral conditions demonstrated weaker and pH dependent binding. Studies with human antioxidant protein 1 (Atox1) and three of its mutants where S residues were replaced with Ala suggested that (a) the binding affinity is influenced more by the binding sequence than by the protein fold (b) pH may play a role in binding reactivity, and (c) mutating the Met impacted the affinity and oxidation rate more drastically than did mutating one of the Cys, supporting its important role in protein function. Position II thus plays a dominant role in metal binding and transport.

  10. Effects of metallic or translucent matrices for Class II composite restorations: 4-year clinical follow-up findings.

    PubMed

    Demarco, Flávio Fernando; Pereira-Cenci, Tatiana; de Almeida André, Dárvi; de Sousa Barbosa, Renata Pereira; Piva, Evandro; Cenci, Maximiliano Sérgio

    2011-02-01

    This study evaluated the performance of composite restorations placed with two matrix and wedge systems 4 years after placement. In a split-mouth design, 23 patients were selected and received at least two class II restorations, one with metallic matrix and wooden wedge and the other with polyester matrix and reflective wedge. One dentist placed the 109 restorations, and all cavities were restored using Single Bond and P-60 (3M ESPE) according to the manufacturer's instructions. Polymerization was performed through occlusal (metallic matrices) or through the reflective wedge (polyester matrices). Restorations were evaluated and categorized as alpha (A), bravo (B), charlie (C), and delta (D; modified United States Public Health System criteria) at baseline and 4 years after placement. Both clinical aspects and interproximal radiographs were considered in the evaluation. Data were analyzed with Mann-Whitney and Friedman tests (α = 0.05). Fifteen subjects (78 teeth/102 proximal surfaces) were reassessed after 4 years. Considering comparisons within matrices in different evaluation time points, no significant differences were observed (p > 0.05). Comparing 4-year to baseline results, the quality of marginal adaptation (40% and 40.4 %, score A), marginal staining (31.3% and 28.8%, score A), and roughness (56% and 46.2%, score A) decreased for metallic and translucent matrices, respectively (p < 0.05), while color match (9.6%, score A), occlusal contacts (75%, score A), and proximal contacts (71.7%, score A) also decreased in quality for translucent matrices (p < 0.001). Although the matrix and wedge systems evaluated showed similar clinical performance, there was clinical quality loss after 4 years, with most of the restorations being still acceptable, and no intervention was necessary.

  11. Metal-ion mutagenesis: conversion of a purple acid phosphatase from sweet potato to a neutral phosphatase with the formation of an unprecedented catalytically competent Mn(II)Mn(II) active site.

    PubMed

    Mitić, Natasa; Noble, Christopher J; Gahan, Lawrence R; Hanson, Graeme R; Schenk, Gerhard

    2009-06-17

    The currently accepted paradigm is that the purple acid phosphatases (PAPs) require a heterovalent, dinuclear metal-ion center for catalysis. It is believed that this is an essential feature for these enzymes in order for them to operate under acidic conditions. A PAP from sweet potato is unusual in that it appears to have a specific requirement for manganese, forming a unique Fe(III)-mu-(O)-Mn(II) center under catalytically optimal conditions (Schenk et al. Proc. Natl. Acad. Sci. U.S.A. 2005, 102, 273). Herein, we demonstrate, with detailed electron paramagnetic resonance (EPR) spectroscopic and kinetic studies, that in this enzyme the chromophoric Fe(III) can be replaced by Mn(II), forming a catalytically active, unprecedented antiferromagnetically coupled homodivalent Mn(II)-mu-(H)OH-mu-carboxylato-Mn(II) center in a PAP. However, although the enzyme is still active, it no longer functions as an acid phosphatase, having optimal activity at neutral pH. Thus, PAPs may have evolved from distantly related divalent dinuclear metallohydrolases that operate under pH neutral conditions by stabilization of a trivalent-divalent metal-ion core. The present Mn(II)-Mn(II) system models these distant relatives, and the results herein make a significant contribution to our understanding of the role of the chromophoric metal ion as an activator of the nucleophile. In addition, the detailed analysis of strain broadened EPR spectra from exchange-coupled dinuclear Mn(II)-Mn(II) centers described herein provides the basis for the full interpretation of the EPR spectra from other dinuclear Mn metalloenzymes.

  12. A GMOS-N IFU study of the central H ii region in the blue compact dwarf galaxy NGC 4449: kinematics, nebular metallicity and star formation

    NASA Astrophysics Data System (ADS)

    Kumari, Nimisha; James, Bethan L.; Irwin, Mike J.

    2017-10-01

    We use integral field spectroscopic (IFS) observations from the Gemini Multi-Object Spectrograph North (GMOS-N) to study the central H ii region in a nearby blue compact dwarf (BCD) galaxy NGC 4449. The IFS data enable us to explore the variation of physical and chemical conditions of the star-forming region and the surrounding gas on spatial scales as small as 5.5 pc. Our kinematical analysis shows possible signatures of shock ionization and shell structures in the surroundings of the star-forming region. The metallicity maps of the region, created using direct Te and indirect strong line methods (R23, O3N2 and N2), do not show any chemical variation. From the integrated spectrum of the central H ii region, we find a metallicity of 12 + log(O/H) = 7.88 ± 0.14 ({˜ }0.15^{+0.06}_{-0.04} Z⊙) using the direct method. Comparing the central H ii region metallicity derived here with those of H ii regions throughout this galaxy from previous studies, we find evidence of increasing metallicity with distance from the central nucleus. Such chemical inhomogeneities can be due to several mechanisms, including gas loss via supernova blowout, galactic winds or metal-poor gas accretion. However, we find that the localized area of decreased metallicity aligns spatially with the peak of star-forming activity in the galaxy, suggesting that gas accretion may be at play here. Spatially resolved IFS data for the entire galaxy are required to confirm the metallicity inhomogeneity found in this study and determine its possible cause.

  13. Transition metal(II) complexes of vitamin B13 with monodentate orotate(1-) ligands

    NASA Astrophysics Data System (ADS)

    Köse, Dursun Ali; Zümreoglu-Karan, Birgül; Şahin, Onur; Büyükgüngör, Orhan

    2006-05-01

    The formation of bisorotate(1-) complexes of the type [M(C 5H 3N 2O 4) 2(H 2O) 4]· nH 2O (M=Co, Ni, Zn and n=2, 4) was achieved by the reaction of ammonium orotate with the corresponding M(II) ions. The crystal structure of [Co(C 5H 3N 2O 4) 2(H 2O) 4]·2H 2O was determined by single crystal X-ray diffraction analysis. Each Co(II) ion in the monomeric Co(C 5H 3N 2O 4) 2(H 2O) 4 units adapts a slightly distorted octahedral geometry comprised of two monodentate orotate anions and four H 2O ligands. Columnar packing of pyrimidine rings along the c axis leads to the formation of layers that propagate parallel to the b axis and the adjacent layers are linked by hydrogen bonds forming a 3D lattice. Complexes of nickel and zinc were assumed to contain monodentate bound orotate ligands as well on the basis of physical and spectroscopic data.

  14. Platinum(II) metal complexes as potential anti-Trypanosoma cruzi agents.

    PubMed

    Vieites, Marisol; Otero, Lucía; Santos, Diego; Toloza, Jeannette; Figueroa, Roberto; Norambuena, Ester; Olea-Azar, Claudio; Aguirre, Gabriela; Cerecetto, Hugo; González, Mercedes; Morello, Antonio; Maya, Juan Diego; Garat, Beatriz; Gambino, Dinorah

    2008-01-01

    In the search for new therapeutic tools against Chagas' disease (American Trypanosomiasis) two series of new platinum(II) complexes with bioactive 5-nitrofuryl containing thiosemicarbazones as ligands were synthesized, characterized and in vitro evaluated. Most of the complexes showed IC50 values in the muM range against two different strains of Trypanosoma cruzi, causative agent of the disease, being as active as the anti-trypanosomal drug Nifurtimox. In particular, the coordination of L3 (4-ethyl-1-(5-nitrofurfurylidene)thiosemicarbazide) to Pt(II) forming [Pt(L3)2] lead to almost a five-fold activity increase in respect to the free ligand. Trying to get an insight into the trypanocidal mechanism of action of these compounds, DNA and redox metabolism (intra-parasite free radical production) were evaluated as potential parasite targets. Results suggest that the complexes could inhibit parasite growth through a dual mechanism of action involving production of toxic free radicals by bioreduction and DNA interaction.

  15. Design of Lead(II) Metal-Organic Frameworks Based on Covalent and Tetrel Bonding.

    PubMed

    Servati Gargari, Masoumeh; Stilinović, Vladimir; Bauzá, Antonio; Frontera, Antonio; McArdle, Patrick; Van Derveer, Donald; Ng, Seik Weng; Mahmoudi, Ghodrat

    2015-12-01

    Three solid materials, [Pb(HL)(SCN)2 ]⋅CH3 OH (1), [Pb(HL)(SCN)2 ] (2), and [Pb(L)(SCN)]n (3), were obtained from Pb(SCN)2 and an unsymmetrical bis-pyridyl hydrazone ligand that can act both as a bridging and as a chelating ligand. In all three the lead center is hemidirectionally coordinated and is thus sterically optimal for participation in tetrel bonding. In the crystal structures of all three compounds, the lead atoms participate in short contacts with thiocyanate sulfur or nitrogen atoms. These contacts are shorter than the sums of the van der Waals radii (3.04-3.47 Å for Pb⋅⋅⋅S and 3.54 Å for Pb⋅⋅⋅N) and interconnect the covalently bonded units (monomers, dimers, and 2D polymers) into supramolecular assemblies (chains and 3D structures). DFT calculations showed these contacts to be tetrel bonds of considerable energy (6.5-10.5 kcal mol(-1) for Pb⋅⋅⋅S and 16.5 kcal mol(-1) for Pb⋅⋅⋅N). A survey of structures in the CSD showed that similar contacts often appear in crystals of Pb(II) complexes with regular geometries, which leads to the conclusion that tetrel bonding plays a significant role in the supramolecular chemistry of Pb(II) .

  16. Ternary complexes metal [Co(II), Ni(II), Cu(II) and Zn(II)]--ortho-iodohippurate (I-hip)--acyclovir. X-ray characterization of isostructural [(Co, Ni or Zn)(I-hip)(2)(ACV)(H(2)O)(3)] with stacking as a recognition factor.

    PubMed

    Barceló-Oliver, M; Terrón, A; García-Raso, A; Fiol, J J; Molins, E; Miravitlles, C

    2004-11-01

    Four ternary metal--ortho-iodohippurate (I-hip)--acyclovir (ACV) complexes, [M(I-hip)(2)(ACV)(H(2)O)(3)] where M is Co(II) (1), Ni(II) (2), Cu (3) and Zn(II) have been obtained by reaction between the corresponding binary complexes M(II)(I-hip)(2)xnH(2)O and ACV. Three ternary complexes (M=Co, Ni and Zn) and the corresponding Zn(II)--ortho-iodohippurate binary derivative have been structurally characterized by X-ray diffraction: The studies show these three ternary complexes are isostructural and present, in solid state, an interesting stacking between the nucleobase and the aryl ring of the hippurate moiety, which probably promotes the formation of ternary complexes. Moreover, the two different ligands interact between them by means of ancillary hydrogen bonds with water molecules coordinated to the metal ion. It must be mentioned that these two recognition factors, hydrogen bonds plus stacking, could explain the reason for the isostructurality of these ternary derivatives with so different three metal ions, with diverses trends in coordination numbers and geometries. In solid state, there are two enantiomeric molecules that are related by an inversion center as the crystal-building unit (as a translational motif) for the ternary complexes.

  17. Positronic complexes with unnatural parity

    SciTech Connect

    Bromley, M. W. J.; Mitroy, J.; Varga, K.

    2007-06-15

    The structure of the unnatural parity states of PsH, LiPs, NaPs, and KPs are investigated with the configuration interaction and stochastic variational methods. The binding energies