Science.gov

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. The influence of microstructure on the sintering process in crystalline metal powders investigated by positron lifetime spectroscopy: II. Tungsten powders with different powder-particle sizes

    NASA Astrophysics Data System (ADS)

    Staab, T. E. M.; Krause-Rehberg, R.; Vetter, B.; Kieback, B.; Lange, G.; Klimanek, P.

    1999-02-01

    Compacts of tungsten powder with five different powder-particle sizes (from 0953-8984/11/7/010/img7 to 0953-8984/11/7/010/img8) are subjected to pressureless sintering. We investigate the change in microstructure during the sintering process by positron lifetime spectroscopy. So as to be able to distinguish between defects having the same positron lifetime, we investigate their kinetics when the sample is annealed. In particular, we consider the annealing out of vacancy clusters after low-temperature electron irradiation, as well as recovery and recrystallization of a tungsten sheet, in as-manufactured form. Making measurements on uncompacted powder, we find an increasing fraction of positrons annihilating in surface states with decreasing powder-particle size. The powder-particle and grain sizes (influencing the x-ray domain size) are monitored additionally by means of metallography and x-ray diffraction. We find that all of the methods give results in agreement with each other. The small grain sizes at lower temperature, about one fifth of the powder-particle size, cause positrons to annihilate at grain boundaries, leading to vacancy-cluster-like signals. At the intensive-shrinkage stage, there are certainly contributions from different shrinkage mechanisms. The observed shrinkage rates can be explained by Coble creep. It is possible that dislocations also play a role as vacancy sources and sinks, since the intensive-shrinkage stage occurs in a temperature region wherein recrystallization takes place.

  6. Electron momentum distribution in amorphous metals investigated by positron annihilation

    NASA Astrophysics Data System (ADS)

    Kristiakova, K.; Kristiak, J.; Galan, P.

    Electron momentum distribution in amorphous metals and the crystalline form of Ni xFe 80- xB 20 ( x = 10, 20, 30, 40) were investigated by positron annihilation. The samples were 30 mn thick ribbons, produced by rapid quenching of liquid metal on a rotating Cu wheel. The positron source was 22Na on mylar or blotting paper between two samples in sandwich arrangement. The γ-radiation was detected by a Ge(Li) detector which has a resolution at 511.9 keV ( 106Ru) of 1.6 keV. An unfolding method based on Bayes principle was applied to calculate the Doppler-broadening; S-parameter values were also determined. The calculated momentum distribution revealed a difference for the Ni 30Fe 50B 20 sample.

  7. 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.

  8. Effect of metal ions on positron annihilation characteristics in metal ion containing epoxies

    NASA Technical Reports Server (NTRS)

    Singh, J. J.; St. Clair, A. K.; Stoakley, D. M.; Holt, W. H.; Mock, W., Jr.

    1984-01-01

    In the course of developing improved moisture-resistant epoxy resins, two different types of epoxy resins containing variable mole ratios of chromium ions per polymer repeat unit were developed. Positron annihilation characteristics have been investigated in these resins as a function of their metal ion content. In both cases, the presence of metal ions reduces the lifetime as well as the intensity of the long life component. The long life component intensity reduction is considerably more pronounced than the lifetime reduction. These results have been discussed in terms of increased unpaired electron density at Ps formation sites due to the presence of chromium ions in the matrix.

  9. Development of a method to study positron diffusion in metals by the observation of positronium negative ions

    NASA Astrophysics Data System (ADS)

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

    2014-09-01

    We have developed a new method to study positron diffusion in metals. In this method, we observe positronium negative ions emitted from the sample surfaces after coating with alkali-metals to evaluate the yields of the positrons which return to the surfaces. γ-rays from the ions accelerated using an electric field are clearly distinguished from those emitted from pair-annihilation of positrons in the bulk or on the surface and self-annihilation of emitted positronium atoms. Reliable studies on positron diffusion in metals have been enabled by this method.

  10. 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.

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

    PubMed Central

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

    2012-01-01

    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). PMID:23471443

  12. 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). PMID:23471443

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

    NASA Astrophysics Data System (ADS)

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

    2006-02-01

    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+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.

  14. 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.

  15. TOXICOLOGY OF METALS. VOLUME II

    EPA Science Inventory

    The report on metal toxicology contains reviews on twenty-three metals. These have been written for inclusion in a Handbook on the Toxicology of Metals: Environmental and Occupational Aspects which is being prepared by the Scientific Committee on the Toxicology of Metals of the P...

  16. Study on the Enhanced Contribution in Noble Metals from Positron Annihilation

    NASA Astrophysics Data System (ADS)

    Hamid, A. S.; Ahmed, M. M.; Abu-Elmagd, M. S. M.; Rizk, R. A. M.

    2007-02-01

    Our motivations in the current work were to inspect various enhancement formulae along with to classify the electronic structure of noble metals Cu, Ag and Au. The measurements were performed via the two dimensional angular correlation of annihilation radiation 2D-ACAR apparatus. The electron density in momentum space ρ(p) was reconstructed and it displayed the following features. Initially, the reciprocal lattice points underscored the calculations, and they revealed Fermi surface features. Additionally, enhanced anisotropy exposed nearby Fermi momentum. They attributed to enhancement of the electronic wave function at the position of the positron. Finally, the high momentum contributions, due to interaction of positron with core-like-state, conducted the electronic structure of the metals under investigations. From another viewpoint, the features of Fermi surface of Cu, Ag and Au showed an expected analogous behavior as multiply connected sphere inside the first Brillouin zone.

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

    PubMed

    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. PMID:26931839

  18. 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.

  19. Measurements of positron scattering by hydrogen, alkali metal, and other atoms

    NASA Astrophysics Data System (ADS)

    Stein, T. S.; Harte, M.; Jiang, J.; Kauppila, W. E.; Kwan, C. K.; Li, H.; Zhou, S.

    1998-08-01

    Recent developments in measurements of total and positronium (Ps) formation cross sections for positrons (in the energy range of 1-300 eV) scattered by hydrogen, alkali metal, and other atoms are reviewed. Measurements and calculations of total and Ps formation cross section ( QPs's) for positrons scattered by hydrogen atoms are in very good agreement, and for the most part there is also good agreement for sodium, potassium, and rubidium atoms, but there is a puzzling discrepancy between measured and recently calculated QPs's for sodium. Preliminary measurements of QPs's for Mg show a very rapid rise to a large maximum value less than 2 eV above the Ps formation threshold energy (0.8 eV) which may be related to the proximity of that threshold to zero energy. It appears that structure observed in e +-Ar and Kr QPs measurements may be related to capture of inner-subshell electrons.

  20. Threshold behavior of positronium formation in positron-alkali-metal scattering

    NASA Astrophysics Data System (ADS)

    Lugovskoy, A. V.; Utamuratov, R.; Kadyrov, A. S.; Stelbovics, A. T.; Bray, I.

    2013-04-01

    We consider positron scattering on the alkali-metal atoms of Li, Na, and K at very low energies, where only the elastic scattering and positronium formation in the ground state are the two open channels. Utilizing the recently developed two-center convergent close-coupling method [Lugovskoy, Kadyrov, Bray, and Stelbovics, Phys. Rev. APLRAAN1050-294710.1103/PhysRevA.82.062708 82, 062708 (2010)] we investigate the behavior of the cross sections as the impact energy goes to zero and demonstrate their convergence. The study sets quantitative benchmarks for any rigorous theoretical treatment of the collision problems.

  1. Insight into the electron-positron correlations in metals through the looking glass

    NASA Astrophysics Data System (ADS)

    Rubaszek, Anna

    2016-05-01

    A semi-empirical analysis of the positron annihilation experimental spectra indicates for a strong sensitivity of the two-particle electron-positron (e-p) enhancement factor to the l=s, p, d, f character of the initial electronic state [1,2]. The essential discrepancy between the models consists in the dependence of the relevant correlation functions on the energy of the annihilating electron. The present contribution contains a theoretical study of the e-p enhancement factors for s, p, d and f states as a function of the electron energy. The slope of the resulting characteristics is directly related to the degree of localisation of the s, p, d and f electrons in the electron density of states. This effect occurs especially for d electrons in transition metals, in favour to the approach of Ref. [1]. The energy dependence of the two-particle correlation functions is also a source of controversy between various theoretical approaches. The energy dependent enhancement factors describe properly the positron interaction with delocalised s and p electrons, but this approach overestimates the high momentum components of the e-p momentum densities, dominated by the localised d and f states. On the contrary, the calculations that employ the energy averaged enhancement factors match better with experiment for localised d and f electrons, but they hardly reproduce experimental spectra for nearly-free electron populations. An attempt to visit two sides of the looking glass is made in the theory of the present work. The model combines the properties of both approaches. The resulting e-p momentum densities and enhancement factors are in good agreement with the experimental data for simple, noble and transition metals, both in the low and high momentum region.

  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. Microwave Transmission Measurements of the Electron Cloud Density In The Positron Ring of PEP-II

    SciTech Connect

    Pivi, M.T.F.; Krasnykh, A.K; Byrd, J.; Santis, S.De; Sonnad, K.G.; Caspers, F.; Kroyer, T.; /CERN

    2008-07-03

    Clouds of electrons in the vacuum chambers of accelerators of positively charged particle beams present a serious limitation for operation of these machines at high currents. Because of the size of these accelerators, it is difficult to probe the low energy electron clouds over substantial lengths of the beam pipe. We applied a novel technique to directly measure the electron cloud density via the phase shift induced in a TE wave which is independently excited and transmitted over a straight section of the accelerator. The modulation in the wave transmission which appear to increase in depth when the clearing solenoids are switched off, seem to be directly correlated to the electron cloud density in the section. Furthermore, we expect a larger phase shift of a wave transmitted through magnetic dipole field regions if the transmitted wave couples with the gyration motion of the electrons. We have used this technique to measure the average electron cloud density (ECD) specifically for the first time in magnetic field regions of a new 4-dipole chicane in the positron ring of the PEP-II collider at SLAC. In this paper we present and discuss the measurements taken in the Low Energy Ring (LER) between 2006 and 2008.

  4. Microwave Transmission Measurements of the Electron Cloud density In the Positron Ring of PEP-II

    SciTech Connect

    Pivi, Mauro T.F.; Krasnykh, Anatoly K.; Byrd, John; De Santis, Stefano; Sonnaad, Kiran G.; Caspers, Fritz; Kroyer, Tom

    2008-06-18

    Clouds of electrons in the vacuum chambers of accelerators of positively charged particle beams present a serious limitation for operation of these machines at high currents. Because of the size of these accelerators, it is difficult to probe the low energy electrons clouds over substantial lengths of the beam pipe. We applied a novel technique to directly measure the electron cloud density via the phase shift induced in a TE wave which is independently excited and transmitted over a straight section of the accelerator. The modulation in the wave transmission which appears to increase in depth when the clearing solenoids are switched off, seem to be directly correlated to the electron cloud density in the section. Furthermore, we expect a larger phase shift of a wave transmitted through magnetic dipole field regionsif the transmitted wave couples with the gyration motion of the electrons. We have used this technique to measure the average electron cloud density (ECD) specifically for the first time in magnetic field regions of a new 4-dipole chicane in the positron ring of the PEP-II collider at SLAC. In this paper we present and discuss the measurements taken in the Low Energy Ring (LER) between 2006 and 2008.

  5. 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.

  6. 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.

  7. Assessment of the fatigue transformation zone in bulk metallic glasses using positron annihilation spectroscopy

    NASA Astrophysics Data System (ADS)

    Liu, M.; Vallery, R. S.; Gidley, D. W.; Launey, M. E.; Kruzic, J. J.

    2009-05-01

    Depth-profiled Doppler broadening spectroscopy of positron annihilation on fatigue fracture surfaces of two amorphous Zr44Ti11Ni10Cu10Be25 metallic glass specimens reveals the presence of a layer of increased free volume induced by cyclic deformation, as compared to surfaces that have been etched to remove any surface damage. The damage layer, or fatigue transformation zone (FTZ), is generated by the propagating fatigue crack tip and the deduced size of that zone is similar to the predicted cyclic plastic zone size at a number of locations where the crack grew at different stress intensities. The presence of the FTZ is independent of the initial amount of bulk free volume, which was varied between the two specimens by structural relaxation via annealing, and the free volume sites generated in the zone are distinct from those typical of the bulk, as evidenced by the higher S parameter. Such observations support the concept that the mechanically induced free volume within the FTZ zone controls the fatigue crack growth rates rather than the initial free volume of the bulk material.

  8. Positron emission tomography during transcranial magnetic stimulation does not require mu-metal shielding.

    PubMed

    Lee, Jae Sung; Narayana, Shalini; Lancaster, Jack; Jerabek, Paul; Lee, Dong Soo; Fox, Peter

    2003-08-01

    Recording brain activity using positron emission tomography (PET) during the stimulation of different parts of the brain by transcranial magnetic stimulation (TMS) permits the mapping of neural connections in the living human brain. However, controversy remains regarding the need for micro-metal shielding of the PET scanner during magnetic stimulation. The aim of this study was to test the effects of magnetic fields generated by TMS on PET data acquisition. With TMS-on and -off in the PET field of view, transmission scans with a (68)Ge/(68)Ga pin source and emission scans with an uniform phantom filled with water and (18)F were acquired. The frequency and intensity of stimulation were set at 3-5 Hz and 70-80% of the maximum output of the stimulator, respectively. The TMS coil was placed at several locations inside the PET gantry, and the main field direction of the TMS coil was varied between parallel and perpendicular orientation to the scanner's axis. Qualitative and quantitative evaluation of the sinograms of transmission PET scans and reconstructed emission images indicated no measurable differences between TMS-on and -off and post-TMS conditions for any position or orientation. The long distance between the TMS coil and the detector block in the PET scanner, as well as the rapid reduction of the magnetic field with distance (3% of maximum field at 10 cm, in air), could explain the lack of TMS interference. The brief duration (approximately 250 micros) of the TMS pulses relative to the total PET acquisition time would also explain the lack of TMS effects. The lack of TMS effects on the PET scanner, as well as PET imaging without any shielding, has been reported by other laboratories. PMID:12948735

  9. Positron production in heavy ion collisions: Current status of the problem - II

    SciTech Connect

    Ahmad, I.; Back, B.B.; Betts, R.R.; Dunford, R.W.; Last, J.; Kutschera, W.; Rhein, M.D.; Schiffer, J.P.; Wilt, P.; Wuosmaa, A.H.

    1994-08-01

    Narrow peaks have been observed at GSI Darmstadt in the energy spectra of positrons and sum-energy spectra of positron-electron pairs, produced in collisions of very heavy ions. To date, there is no satisfactory explanation of the origin of these lines although many differing models have been proposed. In this contribution, the authors describe the features of a new experiment aimed at the study of the line phenomenon and present the results of their first experiments. The specific goals of their experiment are to clarify the experimental situation regarding the lines through high-resolution, high-statistics data and, by direct measurement of the vector momenta of the peak pairs, to determine their kinematics.

  10. 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.

  11. Slow positron beam facility for investigations of plastically deformed metals and surface crystallization of silica

    NASA Astrophysics Data System (ADS)

    Heußer, H.; Hugenschmidt, C.; Wider, T.; Maier, K.

    1999-08-01

    The simple slow positron facility at Bonn university and two recent experiments are presented. The following data briefly summarises the technical specifications of the instrument: overall size: 150×150×80 cm 3positron source: 22Na (10 mCi) moderator: Kr (solid)energy filter: magnetic solenoid at 150 eV transport energyvacuum: high vacuum (10 -6 hPa) spot size: 3 mmcount rate: 3000 s -1 in 511 keV photopeak with BGO detector in coincidence for background suppression energy range: 0.15 to 12 keV with the sample at ground potential A sapphire plate which has, at 40 K (close to the moderator temperature of 37 K), a thermal conductivity comparable to that of copper (!) ensures both the electrical isolation and the thermal contact between the positron source and the He cryostat. With the moderator directly frozen onto the 22Na source the instrument reaches an efficiency better than 10 -4. Slow positrons are extremely sensitive probes for investigations on microstructure and on the onset of surface crystallization of anorganic glasses. The formation of crystallization nuclei on the surface and the growth of the nuclei into the bulk material was investigated on amorphous SiO 2. To this end specimens of amorphous silica were isothermally tempered at a temperature of 1773 K. In another experiment the back diffusion of positrons as a function of penetration depth was studied on weakly tensile deformed aluminium polycrystals. The role of dislocations and their effect on the mobility of positrons is in the center of this investigation.

  12. A dedicated calibration tool for the MEG and MEG II positron spectrometer

    NASA Astrophysics Data System (ADS)

    Rutar, G.; Bemporad, C.; Cattaneo, P. W.; Cei, F.; Galli, L.; Kettle, P.-R.; Papa, A.

    2016-07-01

    The MEG experiment has set the latest limit of 5.7 ×10-13(90 % C.L.) on the branching ratio of the charged lepton flavor violating decay μ+ →e+ γ, making use of the most intense continuous surface muon beam in the world at the Paul Scherrer Institut (PSI), Villigen, Switzerland. High resolutions in terms of energy, timing and relative opening angle are needed in the detection of the e+ and gamma, requiring careful calibration and monitoring of the experimental apparatus. A dedicated calibration method involving Mott scattering of a monochromatic positron beam at energies close to the MEG signal energy is presented.

  13. 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.

  14. The use of divalent metal ions by type II topoisomerases.

    PubMed

    Deweese, Joseph E; Osheroff, Neil

    2010-07-01

    Type II topoisomerases are essential enzymes that regulate DNA under- and overwinding and remove knots and tangles from the genetic material. In order to carry out their critical physiological functions, these enzymes utilize a double-stranded DNA passage mechanism that requires them to generate a transient double-stranded break. Consequently, while necessary for cell survival, type II topoisomerases also have the capacity to fragment the genome. This feature of the prokaryotic and eukaryotic enzymes, respectively, is exploited to treat a variety of bacterial infections and cancers in humans. All type II topoisomerases require divalent metal ions for catalytic function. These metal ions function in two separate active sites and are necessary for the ATPase and DNA cleavage/ligation activities of the enzymes. ATPase activity is required for the strand passage process and utilizes the metal-dependent binding and hydrolysis of ATP to drive structural rearrangements in the protein. Both the DNA cleavage and ligation activities of type II topoisomerases require divalent metal ions and appear to utilize a novel variant of the canonical two-metal-ion phosphotransferase/hydrolase mechanism to facilitate these reactions. This article will focus primarily on eukaryotic type II topoisomerases and the roles of metal ions in the catalytic functions of these enzymes. PMID:20703329

  15. The Use of Divalent Metal Ions by Type II Topoisomerases

    PubMed Central

    Deweese, Joseph E.; Osheroff, Neil

    2010-01-01

    Type II topoisomerases are essential enzymes that regulate DNA under- and overwinding and remove knots and tangles from the genetic material. In order to carry out their critical physiological functions, these enzymes utilize a double-stranded DNA passage mechanism that requires them to generate a transient double-stranded break. Consequently, while necessary for cell survival, type II topoisomerases also have the capacity to fragment the genome. This feature of the prokaryotic and eukaryotic enzymes, respectively, is exploited to treat a variety of bacterial infections and cancers in humans. All type II topoisomerases require divalent metal ions for catalytic function. These metal ions function in two separate active sites and are necessary for the ATPase and DNA cleavage/ligation activities of the enzymes. ATPase activity is required for the strand passage process and utilizes the metal-dependent binding and hydrolysis of ATP to drive structural rearrangements in the protein. Both the DNA cleavage and ligation activities of type II topoisomerases require divalent metal ions and appear to utilize a novel variant of the canonical two-metal-ion phosphotransferase/hydrolase mechanism to facilitate these reactions. This article will focus primarily on eukaryotic type II topoisomerases and the roles of metal ions in the catalytic functions of these enzymes. PMID:20703329

  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. Multi-component molecular orbital study on positron attachment to alkali-metal hydride molecules: nature of chemical bonding and dissociation limits of [LiH; e+

    NASA Astrophysics Data System (ADS)

    Oyamada, Takayuki; Tachikawa, Masanori

    2014-08-01

    We have performed multi-component full-configuration interaction calculations to investigate the nature of chemical bonding of [LiH;e+] at the small and large internuclear distance. We discuss the importance of geometrical changes in positronic compounds induced by a positron attachment in terms of the virial theorem, with a comparison of the adiabatic- and vertical-positron affinity (PA). The systematic improvement of the PA values achieved by optimisation of (i) the molecular geometry and (ii) the positronic basis centre is also discussed. The stable dissociation channel of [LiH;e+] is compared with the ionic- and neutral-dissociation channels of its parent molecule LiH through the analysis of the potential energy curve and the electronic and positronic densities. The vertical PA as a function of is also presented, which is the difference between the potential energy curve of the parent molecule (LiH → Li + H) and its positronic compound ([LiH; e+] → Li + [H; e+]). Unlike the preceding study of [M. Mella et al., J. Chem. Phys. 113, 6154 (2000)], it took more than bohr to converge the vertical PA due to the long-range ionic bonding interaction.

  18. 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.

  19. 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.

  20. 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. PMID:21044814

  1. Complexity on Small Scales. II. Metallicities and Ages in the Leo II Dwarf Spheroidal Galaxy

    NASA Astrophysics Data System (ADS)

    Koch, Andreas; Grebel, Eva K.; Kleyna, Jan T.; Wilkinson, Mark I.; Harbeck, Daniel R.; Gilmore, Gerard F.; Wyse, Rosemary F. G.; Evans, N. Wyn

    2007-01-01

    We present metallicities and ages for 52 red giants in the remote Galactic dwarf spheroidal (dSph) galaxy Leo II. These stars cover the entire surface area of Leo II and are radial velocity members. We obtained medium-resolution multifiber spectroscopy with FLAMES as part of a Large Program with the Very Large Telescope at the European Southern Observatory, Chile. The metallicities were determined based on the well-established near-infrared Ca II triplet technique. This allowed us to achieve a mean random error of 0.16 dex on the metallicities, while other systematic effects, such as unknown variations in the dSph's [Ca/Fe] ratio, may introduce a further source of uncertainty of the order of 0.1 dex. The resulting metallicity distribution is asymmetric and peaks at [Fe/H]=-1.74 dex on the Carretta & Gratton scale. The full range in metallicities extends from -2.4 to -1.08 dex. As in other dSph galaxies, no extremely metal-poor red giants were found. We compare Leo II's observed metallicity distribution with model predictions for several other Galactic dSphs from the literature. Leo II clearly exhibits a lack of more metal-poor stars, analogous to the classical G dwarf problem, which may indicate a comparable ``K giant problem.'' Moreover, its evolution appears to have been affected by galactic winds. We use our inferred metallicities as an input parameter for isochrone fits to Sloan Digital Sky Survey photometry of our target stars and derive approximate ages. The resulting age-metallicity distribution covers the full age range from 2 to about 15 Gyr on our adopted isochrone scale. During the first ~7 Gyr relative to the oldest stars, the metallicity of Leo II appears to have remained almost constant, centering on the mean metallicity of this galaxy. The almost constant metallicity at higher ages and a slight drop by about 0.3 dex thereafter may be indicative of rejuvenation by low-metallicity gas. Overall, the age-metallicity relation appears to support the

  2. 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.

  3. 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.

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

    PubMed Central

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

    2008-01-01

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

  5. 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. PMID:17975286

  6. False-positive 18F-fluorodeoxyglucose positron emission tomography/computed tomography in a patient with metallic implants following chondrosarcoma resection

    PubMed Central

    ZHOU, PU; TANG, JINLIANG; ZHANG, DONG; LI, GUANGHUI

    2016-01-01

    Positron emission tomography (PET) with fluorine-18-labeled fluorodeoxyglucose (18F-FDG) has been used for the staging and evaluation of recurrence in cancer patients. We herein report a false-positive result of 18F-FDG PET/computed tomography (CT) scan in a patient following chondrosarcoma resection and metallic implanting. A 35-year-old male patient with chondrosarcoma of the left iliac bone underwent radical resection, metal brace implanting and radiotherapy. A high uptake of 18F-FDG was observed in the metallic implants and adjacent tissue during PET/CT scanning in the 5th year of follow-up. Tissue biopsy and follow-up examination identified no tumor recurrence or infection at these sites, suggesting that the results of 18F-FDG PET/CT must be interpreted with caution in cancer patients with metallic implants. PMID:27123290

  7. Nickel(II) and palladium(II) thiaethyneporphyrins. Intramolecular metal(II)-η2-CC interaction inside a porphyrinoid frame.

    PubMed

    Nojman, Elżbieta; Berlicka, Anna; Szterenberg, Ludmiła; Latos-Grażyński, Lechosław

    2012-03-01

    3,18-Diphenyl-8,13-di-p-tolyl-20-thiaethyneporphyrin ([18]thiatriphyrin(4.1.1)), which formally contains an C1-C2 ethyne moiety instead of pyrrole embedded in the macrocyclic framework of 21-thiaporphyrin, was obtained in a modification of the "3 + 1" approach using the ethyne analogue of tripyrrane (1,4-diphenyl-1,4-di(pyrrol-2-yl)but-2-yne) and 2,5-bis(p-tolylhydroxymethyl)thiophene. The spectroscopic and structural properties of 20-thiaethyneporphyrin reflect its macrocyclic aromaticity, revealing a combination of the acetylene (≥C-C≡C-C≤) and cumulene (>C═C═C═C<) character of the C18-C1-C2-C3 linker. The magnetic manifestations of aromaticity and antiaromaticity of thiaethyneporphyrin and its two-electron-oxidized derivative were observed using (1)H NMR spectroscopy and were confirmed by density functional theory calculations involving chemical shifts and nucleus-independent chemical shift analysis. Protonation of 20-thiaethyneporphyrin yielded a nonaromatic tautomer of iso-20-thiaethyneporphyrin, locating the saturated meso carbon adjacent to thiophene. Insertion of palladium(II) and nickel(II) into 20-thiaethyneporphyrin afforded planar palladium(II) thiaethyneporphyrin and low-spin diamagnetic nickel(II) 20-thiaethyneporphyrin as determined by X-ray crystallography. 20-Thiaethyneporphyrin acts as a dianionic ligand that coordinates through the two nitrogen and one sulfur donors. Metal(II) ions are uniquely exposed to form an intramolecular metal(II)-η(2)-CC bond, whereas the organometallic fragment is coplanar with the whole macrocycle. Coordination of pyridine converts diamagnetic nickel(II) thiaethyneporphyrin into its paramagnetic counterpart as determined by (1)H NMR. PMID:22356285

  8. 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.

  9. 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.

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

    NASA Astrophysics Data System (ADS)

    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. Here 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. We also found that SNe with brighter peak magnitudes have smaller pEW5018 and occur at lower Z. The data are available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (ftp://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/587/L7

  11. 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.

  12. 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.

    2016-05-01

    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.

  13. Photophysical investigation of palladium(II) ortho-metalated complexes

    SciTech Connect

    Craig, C.A.; Watts, R.J. )

    1989-01-25

    Syntheses and structural characterizations of four complexes of Pd(II) with ortho-metalated 2-phenylpyridinate (ppy{sup minus}) are reported. These complexes include a parent dimer, (Pd(ppy)Cl){sub 2}, and three derivative monomers, (Pd(ppy)(bpy))Cl, (Pd(ppy)(en))Cl, and (Pd(ppy)(CO)Cl), whereby = 2,2'-bipyridine and en = ethylenediamine. Photophysical characterizations of these species indicate low-energy absorption bands ({approximately}360 nm) and emission bands at 77 K ({approximately}460 nm) that are assigned to transitions located on the ppy{sup {minus}} ligand. Some evidence for low-energy charge-transfer states is found in trends in luminescence lifetimes. 2 tabs., 5 figs., 21 refs.

  14. 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.

  15. Ni (II), Cu (II) and Zn (II) Metal Chelates With Some Thiazole Derived Schiff-Bases: Their Synthesis, Characterization and Bactericidal Properties

    PubMed Central

    Chohan, Zahid H.

    1999-01-01

    A number of thiazole derived tridentate Schiff-bases (LH) and its metal chelates of the type [M(L)2X] where M=Ni(II), Cu(II) and Zn(II), L=substituted salicylaldehyde (5-H, 5-CH3, 5-OCH3, 5-NO2 and 5-Cl) and X=CI have been synthesized and characterized with the help of elemental analyses, conductivity measurements, magnetic moments, UV-Vis, IR and NMR spectral data. An octahedral structure for Ni(II) and Zn(II) and a distorted octahedral structure for Cu(II) chelates have been proposed. All the Schiff-bases and their metal chelates have been screened for their biological activity against Escherichia coli, Staphylococcus aureous , Pseudomonas aeruginosa and Klebsiella pneumonae and in comparison, the metal chelates have been shown to possess more antibacterial activity than the uncomplexed Schiff-bases. PMID:18475884

  16. A new chitosan biopolymer derivative as metal-complexing agent: synthesis, characterization, and metal(II) ion adsorption studies.

    PubMed

    Krishnapriya, K R; Kandaswamy, M

    2010-09-23

    In this study, a new chitosan biopolymer derivative (CTSL) has been synthesized by anchoring a new vanillin-based complexing agent or ligand, namely 4-hydroxy-3-methoxy-5-[(4-methylpiperazin-1-yl)methyl] benzaldehyde, (L) with chitosan (CTS) by means of condensation. The new material was characterized by elemental (CHN), spectral (FTIR and solid state (13)C NMR), thermal (TG-DTA and DSC), structural (powder XRD), and morphological (SEM) analyses. The CTSL was employed to study the equilibrium adsorption of various metal ions, namely, Mn(II), Fe(II), Co(II), Cu(II), Ni(II), Cd(II), and Pb(II), as functions of pH of the solutions. Its kinetics of adsorption was evaluated utilizing the pseudo first order and pseudo second order equation models and the equilibrium data were analyzed by Langmuir isotherm model. The CTSL shows good adsorption capacity for metal ions studied in the order Cu(II)>Ni(II)>Cd(II)> or =Co> or =Mn(II)>Fe(II)>Pb(II) in all studied pH ranges due to the presence of many coordinating moieties present in it. PMID:20708730

  17. 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.

  18. Galactic Temperature and Metallicity Gradients from Ultracompact H II Regions

    NASA Astrophysics Data System (ADS)

    Afflerbach, A.; Churchwell, E.; Acord, J. M.; Hofner, P.; Kurtz, S.; Depree, C. G.

    1996-10-01

    We report observations in the H42α, H66α, H76α, and H93α radio recombination lines (RRL) toward 28 ultracompact (UC) H II regions distributed in Galactocentric radius from 0 to 17 kpc. It was possible to fit the observed line intensities with a single set of electron density (ne) and temperature (Te)-values for 17 nebulae distributed in DG from 4 to 11 kpc using a non-LTE model analysis. A Galactocentric Te gradient was found of the form Te(K) = (5537±387) + (320±64)DG, where DG is the Galactocentric distance in kpc. On average, our sample is hotter than that found by Shaver et al. (1983) by approximately 1000 K. We attribute the higher average temperatures of the sources in our sample relative to those in the Shaver et al. sample to the higher density of our sample. As density increases from t0 cm-3 to 105 cm-3, metal coolants are quenched and Te increases. From the combination of photoionization-statistical equilibrium models at the densities of UC H II regions and the derived Te gradient, we find a Galactocentric oxygen abundance gradient d(O/H)/d(DG) =-0.047±0.009 dex kpc-1 under the assumption that the Te gradient is primarily determined by metal abundances. Within the uncertainties, the O/H gradient is the same as that found by Shaver et al. from optical observations. The observed line widths are correlated with density in the sense that the denser regions are more likely to have large turbulent motions and/or bulk motions such as outflows, rotation, shocks, etc. Helium RRLs were detected in a subset of six nebulae. The He+/H+ abundances are typically in the range 0.07-0.12 by number, consistent with the range found by other investigators from lower resolution observations. However, one source in our sample, G32.80A, has a ratio of 0.158±0.047, possibly indicating local enrichment of helium.

  19. 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.

  20. Determination of Strong Metal Ligands (S(II-))in Natural Waters

    NASA Astrophysics Data System (ADS)

    Kramer, J.; Smith, D. S.; Bell, R. A.; Ernste, M.

    2003-12-01

    Reduced sulfide (S(II-)) ligands have been measured in oxic freshwaters at 1-100s nM. "Group B" metals, such as Ag(I), Hg(II), Cu(I) and Pb(II) bind strongly to S(II-) ligands. Their role in aqueous metal speciation and suppression of metal toxicity make S(II-) ligands an important analytical challenge. S(II-) is probably stabilized in oxic environments as metal-sulfide (M-S) clusters within natural organic matter (NOM). S(II-) species are measured by Cr(II) reduction of M-S, acid reaction, purge and trap to capture H2S and measurement as the methylene diamine complex (CRS). But CRS may also detect other sulfur species. Silver is an excellent probe metal for determination of strong ligand sites(SLS)in NOM. A competitive ligand method, using Ag(I), is demonstrated. The bound Ag-ligand and the "free" silver ion concentration are measured during the titration. The total strong ligand (Lt) is determined by a Grans' approach. These values are used to determine the (Lt) and the conditional binding constant, K'. Measured Lt concentrations match CRS concentrations, and conditional stability constants for a 1:1 M-L stoichiometry range from log K'= 11+ to 13, consistent with known Ag-S(II-) values. Furthermore SLS and Lt correlate with water-effect ratios (WERs) for silver

  1. Results of a prospective phase II trial evaluating interim positron emission tomography-guided high dose therapy for poor prognosis diffuse large B-cell lymphoma.

    PubMed

    Stewart, Douglas A; Kloiber, Reinhard; Owen, Carolyn; Bahlis, Nizar J; Duggan, Peter; Mansoor, Adnan; Bence-Bruckler, Isabelle

    2014-09-01

    Patients with diffuse large B-cell lymphoma (DLBCL) with a poor prognosis based upon advanced stage and elevated serum lactate dehydrogenase achieve a 3-4-year progression-free survival (PFS) of only 55%. The role of interim fluoro-2-deoxy-d-glucose (FDG) positron emission tomography (PET) to guide use of upfront high dose chemotherapy (HDCT) and autologous stem cell transplant (ASCT) for patients with poor prognosis DLBCL is unproven. A prospective phase II clinical trial was designed to evaluate the outcomes of HDCT/ASCT for patients with poor prognosis DLBCL aged 18-65 years who had unfavorable interim restaging PET scans. Of the 70 eligible patients, 36 had unfavorable and 34 favorable interim PET responses, with 3-year PFS rates of 65.2% and 52.7%, respectively. In conclusion, favorable interim PET response as defined in this study is not associated with improved PFS rates for patients with poor prognosis DLBCL treated with RCHOP (rituximab, cyclophosphamide, doxorubicin, vincristine, prednisone). A phase III trial evaluating this PET-guided approach is not warranted. PMID:24188476

  2. 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.

  3. Docking of ethanamine Schiff base imines & metal (II) complexes, cytotoxicity & DNA interaction studies

    NASA Astrophysics Data System (ADS)

    Sujarani, S.; Ramu, A.

    2015-01-01

    The present study deals with a series of biologically and stereo chemically important novel transition metal (II) Schiff base chelates. The Cu (II), Co (II), Mn (II) and Ni (II) ions containing complexes were synthesized by using diphenylethanamine and 2-hydroxy/2, 4-dihydroxy/2-hydroxy-4-methoxybenzaldehydes. The synthesized complexes were characterized using micro analytical, IR, NMR, ESI-Mass, UV-Visible, cyclic voltammetry and the EPR spectroscopic techniques. The spectral data evidenced the action of ligands as a neutral bidentate Schiff bases, coordinating through azomethine nitrogen and oxygen atom of hydroxyl group. The interaction studies revealed the groove binding nature of complexes with CT-DNA. The ligand and synthesized metal complexes showed cytotoxicity against cancerous cells. The strong binding affinity of the imine and metal complexes was also confirmed by molecular docking studies.

  4. 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. PMID:27416562

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

    PubMed Central

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

    2014-01-01

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

  6. Current-induced spin polarization in transition metals and Bi/Ag bilayers observed by spin-polarized positron beam

    NASA Astrophysics Data System (ADS)

    Zhang, Hongjun; Yamamoto, Shunya; Fukaya, Yuki; Maekawa, Masaki; Li, Hui; Kawasuso, Atsuo; Seki, Takeshi; Saitoh, Eiji; Takanashi, Koki; JAEA Team; Tohoku Team

    2015-03-01

    Current-induced spin polarization (CISP) on the outermost surfaces of Au, Cu, Pt, Pd, Ta, and W films were studied by spin-polarized positron beam (SPPB). The Au and Cu surfaces showed no significant CISP. In contrast, the Pt, Pd, Ta, and W films exhibited large CISP (3 ~ 15% per charge current of 105 A/cm2) 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 outermost spin poalrization of Bi/Ag/Al2O3andAg/Bi/Al2O3 (charge currents directly connected to Ag layers) were probed by SPPB. The opposite outermost spin polarization of Bi/Ag/Al2O3andAg/Bi/Al2O3 clarified the charge-to-spin conversion in Bi/Ag bilayers. Nevertheless, the magnitudes of the outermost spin polarization of Bi(0.3 ~5)/Ag(25)/Al2O3 (numbers in parentheses denote thickness in nm) and Ag(25 ~500)/Bi(8)/Al2O3 decrease exponentially with increasing Bi thickness and Ag thickness, respectively. This provides probably the first direct evidence for spin diffusion mechanism. Financial support from JSPS Kakenhi Grant 24310072.

  7. Synthesis, characterization and biocidal activity of some transition metal(II) complexes with isatin salicylaldehyde acyldihydrazones.

    PubMed

    Singh, Vinod P; Singh, Shweta; Singh, Divya P

    2012-06-01

    Cobalt(II), nickel(II), copper(II), zinc(II) and cadmium(II) complexes with two new unsymmetrical ligands, isatin salicylaldehyde oxalic acid dihydrazide (isodh) and isatin salicylaldehyde malonic acid dihydrazide (ismdh) were synthesized and characterized by elemental analyses, electrical conductance, magnetic moments, electronic, NMR, ESR and IR spectral studies. The isodh acts as a dibasic tetra dentate ligand bonding through two >C=N-, a deprotonated phenolate and deprotonated indole enolate groups to the metal. The ismdh ligand shows monobasic tetra dentate behaviour in bonding with metal ion through two >C=N-, indole >C=O and a deprotonated phenolate group. The electronic spectral data suggest 4-coordinate square planar geometry for Co(II), Ni(II) and Cu(II) complexes of isodh, whereas, 6-coordinate octahedral structure for the ismdh complexes. The ESR studies also indicate a square planar and distorted octahedral environment around Cu(II) for isodh and ismdh complexes, respectively. Most of the metal complexes show better antifungal activity than the standard and a significant antibacterial activity against various fungi and bacteria. PMID:21679052

  8. 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,…

  9. 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.…

  10. 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

  11. 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.

  12. 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.

  13. Type Ia and II Supernovae Contributions to Metal Enrichment in the Intracluster Medium Observed with Suzaku

    NASA Astrophysics Data System (ADS)

    Sato, Kosuke; Tokoi, Kazuyo; Matsushita, Kyoko; Ishisaki, Yoshitaka; Yamasaki, Noriko Y.; Ishida, Manabu; Ohashi, Takaya

    2007-09-01

    We studied the properties of the intracluster medium (ICM) in two clusters of galaxies (AWM 7 and Abell 1060) and two groups (HCG 62 and NGC 507) with the X-ray observatory Suzaku. Based on spatially resolved energy spectra, we measured for the first time precise cumulative ICM metal masses within 0.1 and ~0.3r180. Comparing our results with supernova nucleosynthesis models, the number ratio of Type II (SNe II) to Type Ia (SNe Ia) is estimated to be ~3.5, assuming the metal mass in the ICM is represented by the sum of products synthesized in SNe Ia and SNe II. Normalized by the K-band luminosities of present galaxies, and including the metals in stars, the integrated number of past SN II explosions is estimated to be close to or somewhat higher than the star formation rate determined from Hubble Deep Field observations.

  14. 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

  15. Relativistic Configuration Interaction calculations of the atomic properties of selected transition metal positive ions; Ni II, V II and W II

    NASA Astrophysics Data System (ADS)

    Abdalmoneam, Marwa Hefny

    Relativistic Configuration Interaction (RCI) method has been used to investigate atomic properties of the singly ionized transition metals including Nickel (Ni II), Vanadium (V II), and Tungsten (W II). The methodology of RCI computations was also improved. Specifically, the method to shift the energy diagonal matrix of the reference configurations was modified which facilitated including the effects of many electronic configurations that used to be difficult to be included in the energy matrix and speeded-up the final calculations of the bound and continuum energy spectrum. RCI results were obtained for three different cases: i. Atomic moments and polarizabilities of Ni II; ii. Hyperfine structure constants of V II; iii. Lifetime, Lande g-values, and Oscillator strength of W II. Four atomic quantities of Ni II were calculated; scalar dipole polarizability, off-diagonal electric dipole polarizability, non-adiabatic scalar dipole polarizability, and quadrupole polarizability of Ni II. These quantities appear as effective parameters in an effective potential model. These quantities are computed for the first time. The two hyperfine structure (HFS) constants ; magnetic dipole interaction constant, A, and the electric quadrupole interaction constant, B, have been calculated for the V II 3d4, 3d3 4s, and 3d 2 4s2 J=1 to 5 even parity states . Analysis of the results shows the sum of HFS A of nearby energy levels to be conserved. The Lande g-value and the vector composition percentages for all the wavefunctions of those configurations have also been calculated. RCI results are in good agreement with most of the available experimental data. Lifetimes of 175 decay branches in W II have been calculated. Also, Lande g-values have been calculated for all measured W II odd parity levels J=1/2-11/2. The RCI oscillator strengths and branching fraction values of the lowest 10 energy levels for each odd parity J are presented. The calculated results are only in semi

  16. Radiative cooling II: effects of density and metallicity

    NASA Astrophysics Data System (ADS)

    Wang, Ye; Ferland, G. J.; Lykins, M. L.; Porter, R. L.; van Hoof, P. A. M.; Williams, R. J. R.

    2014-06-01

    This work follows Lykins et al. discussion of classic plasma cooling function at low density and solar metallicity. Here, we focus on how the cooling function changes over a wide range of density (nH <1012 cm-3) and metallicity (Z < 30 Z⊙). We find that high densities enhance the ionization of elements such as hydrogen and helium until they reach local thermodynamic equilibrium. By charge transfer, the metallicity changes the ionization of hydrogen when it is partially ionized. We describe the total cooling function as a sum of four parts: those due to H&He, the heavy elements, electron-electron bremsstrahlung and grains. For the first three parts, we provide a low-density limit cooling function, a density dependence function, and a metallicity-dependent function. These functions are given with numerical tables and analytical fit functions. We discuss grain cooling only in the interstellar medium case. We then obtain a total cooling function that depends on density, metallicity and temperature. As expected, collisional de-excitation suppresses the heavy elements cooling. Finally, we provide a function giving the electron fraction, which can be used to convert the cooling function into a cooling rate.

  17. 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.

  18. 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. PMID:23277183

  19. 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

    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 (L(1))-(L(5)) were derived by condensation of beta-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)(H(2)O)(4)]Cl (where M = Co(II), Cu(II), and Zn(II)) and of M : L (1 : 2) of type [M(L)(2)(H(2)O)(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

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  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. Nearby supernova host galaxies from the CALIFA survey. II. Supernova environmental metallicity

    NASA Astrophysics Data System (ADS)

    Galbany, L.; Stanishev, V.; Mourão, A. M.; Rodrigues, M.; Flores, H.; Walcher, C. J.; Sánchez, S. F.; García-Benito, R.; Mast, D.; Badenes, C.; González Delgado, R. M.; Kehrig, C.; Lyubenova, M.; Marino, R. A.; Mollá, M.; Meidt, S.; Pérez, E.; van de Ven, G.; Vílchez, J. M.

    2016-06-01

    The metallicity of a supernova progenitor, together with its mass, is one of the main parameters that can rule the progenitor's fate. We present the second study of nearby supernova (SN) host galaxies (0.005 metallicity of 115 galaxies, which hosted 132 SNe within and 10 SNe outside the field of view (FoV) of the instrument. Another 18 galaxies, which hosted only SNe outside the FoV, were also studied. Using the O3N2 calibrator that was described elsewhere, we found no statistically significant differences between the gas-phase metallicities at the locations of the three main SN types - Ia, Ib/c and II; they all have 12 + log (O/H) ≃ 8.50 within 0.02 dex. The total galaxy metallicities are also very similar, and we argue that the reason is that our sample only consists of SNe discovered in massive galaxies (log (M/M⊙) > 10 dex) by targeted searches. We neither found evidence that the metallicity at the SN location differs from the average metallicity at the galactocentric distance of the SNe. By extending our SN sample with published metallicities at the SN location, we are able to study the metallicity distributions for all SN subtypes split into SN discovered in targeted and untargeted searches. We confirm a bias toward higher host masses and metallicities in the targeted searches. By combining data from targeted and untargeted searches, we found a sequence from higher to lower local metallicity: SN Ia, Ic, and II show the highest metallicity, which is significantly higher than those of SN Ib, IIb, and Ic-BL. Our results support the scenario according to which SN Ib result from binary progenitors. Additionally, at least part of the SN Ic are the result of single massive stars that were stripped of their outer layers by metallicity-driven winds. We studied several proxies of the local metallicity that are frequently used in the literature and found that the total host

  8. 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

  9. 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.

  10. 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

  11. Vitrified metal finishing wastes II. Thermal and structural characterisation.

    PubMed

    Bingham, P A; Hand, R J; Forder, S D; Lavaysierre, A

    2005-06-30

    Waste filter cakes from two metal finishing operations were heat treated and vitrified. Substantial weight loss during heating was due to emission of water, volatile sulphur-rich and chlorine-rich compounds, and the combustion of carbonaceous components. Estimations of CO(x), SO(x) and HCl emissions were based on chemical analyses. Upon cooling from molten, one sample remained amorphous but all others partially crystallised. Crystalline nature was dependent upon waste composition and the level of P(2)O(5) addition. Thermal stabilities of the waste forms were good, but less so than MW, a borosilicate glass developed for its high temperature stability. Mossbauer and FTIR analyses showed that iron environments in the different vitrified waste forms were very similar. Iron was present predominantly as Fe(3+), although the exact redox ratio varied slightly between waste forms. Iron in both redox states occupied distorted octahedral coordination polyhedra with similar levels of site distortion. Phosphate networks in the vitreous materials were highly de-polymerised, consisting largely of (PO(4))(3-) monomer and (P(2)O(7))(2-) dimer units. This explained the high chemical durability of these waste forms and their structural insensitivity to compositional change, underlining their suitability as hosts for the immobilisation of toxic and nuclear wastes. PMID:15943935

  12. Texas Intense Positron Source (TIPS)

    NASA Astrophysics Data System (ADS)

    O'Kelly, D.

    2003-03-01

    The Texas Intense Positron Source (TIPS) is a state of the art variable energy positron beam under construction at the Nuclear Engineering Teaching Laboratory (NETL). Projected intensities on the order of the order of 10^7 e+/second using ^64Cu as the positron source are expected. Owing to is short half-life (t1/2 12.8 hrs), plans are to produce the ^64Cu isotope on-site using beam port 1 of NETL TRIGA Mark II reactor. Following tungsten moderation, the positrons will be electrostatically focused and accelerated from few 10's of eV up to 30 keV. This intensity and energy range should allow routine performance of several analytical techniques of interest to surface scientists (PALS, PADB and perhaps PAES and LEPD.) The TIPS project is being developed in parallel phases. Phase I of the project entails construction of the vacuum system, source chamber, main beam line, electrostatic/magnetic focusing and transport system as well as moderator design. Initial construction, testing and characterization of moderator and beam transport elements are underway and will use a commercially available 10 mCi ^22Na radioisotope as a source of positrons. Phase II of the project is concerned primarily with the Cu source geometry and thermal properties as well as production and physical handling of the radioisotope. Additional instrument optimizing based upon experience gained during Phase I will be incorporated in the final design. Current progress of both phases will be presented along with motivations and future directions.

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

    DOE PAGESBeta

    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

  16. PREFACE: The International Workshop on Positron Studies of Defects 2014

    NASA Astrophysics Data System (ADS)

    Sugita, Kazuki; Shirai, Yasuharu

    2016-01-01

    The International Workshop on Positron Studies of Defects 2014 (PSD-14) was held in Kyoto, Japan from 14-19 September, 2014. The PSD Workshop brought together positron scientists interested in studying defects to an international platform for presenting and discussing recent results and achievements, including new experimental and theoretical methods in the field. The workshop topics can be characterized as follows: • Positron studies of defects in semiconductors and oxides • Positron studies of defects in metals • New experimental methods and equipment • Theoretical calculations and simulations of momentum distributions, positron lifetimes and other characteristics for defects • Positron studies of defects in combination with complementary methods • Positron beam studies of defects at surfaces, interfaces, in sub-surface regions and thin films • Nanostructures and amorphous materials

  17. 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. PMID:21764045

  18. Liquid metal blanket module testing and design for ITER/TIBER II

    SciTech Connect

    Mattas, R.F.; Cha, Y.; Finn, P.A.; Majumdar, S.; Picologlou, B.; Stevens, H.; Turner, L.

    1988-05-01

    A major goal for ITER is the testing of nuclear components to demonstrate the integrated performance of the most attractive concepts that can lead to a commercial fusion reactor. As part of the ITER/TIBER II study, the test program and design of test models were examined for a number of blanket concepts. The work at Argonne National Laboratory focused on self-cooled liquid metal blankets. A test program for liquid metal blankets was developed based upon the ITER/TIBER II operating schedule and the specific data needs to resolve the key issues for liquid metals. Testing can begin early in reactor operation with liquid metal MHD tests to confirm predictive capability. Combined heat transfer/MHD tests can be performed during initial plasma operation. After acceptable heat transfer performance is verified, tests to determine the integrated high temperature performance in a neutron environment can begin. During the high availability phase operation, long term performance and reliability tests will be performed. It is envisioned that a companion test program will be conducted outside ITER to determine behavior under severe accident conditions and upper performance limits. A detailed design of a liquid metal test module and auxiliary equipment was also developed. The module followed the design of the TPSS blanket. Detailed analysis of the heat transfer and tritium systems were performed, and the overall layout of the systems was determined. In general, the blanket module appears to be capable of addressing most of the testing needs. 8 refs., 27 figs., 11 tabs.

  19. 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

    2015-09-01

    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. PMID:26091902

  20. Ca II triplet spectroscopy of RGB stars in NGC 6822: kinematics and metallicities

    NASA Astrophysics Data System (ADS)

    Swan, J.; Cole, A. A.; Tolstoy, E.; Irwin, M. J.

    2016-03-01

    We present a detailed analysis of the chemistry and kinematics of red giants in the dwarf irregular galaxy NGC 6822. Spectroscopy at ≈8500 Å was acquired for 72 red giant stars across two fields using FORS2 at the VLT. Line-of-sight extinction was individually estimated for each target star to accommodate the variable reddening across NGC 6822. The mean radial velocity was found to be = -52.8 ± 2.2 km s-1 with dispersion σv = 24.1 km s-1, in agreement with other studies. Ca II triplet equivalent widths were converted into [Fe/H] metallicities using a V magnitude proxy for surface gravity. The average metallicity was <[Fe/H]> = -0.84 ± 0.04 with dispersion σ = 0.31 dex and interquartile range 0.48. Our assignment of individual reddening values makes our analysis more sensitive to spatial variations in metallicity than previous studies. We divide our sample into metal-rich and metal-poor stars; the former were found to cluster towards small radii with the metal-poor stars more evenly distributed across the galaxy. The velocity dispersion of the metal-poor stars was found to be higher than that of the metal-rich stars (σ _{v_MP}=27.4 km s-1; σ _{v_MR}=21.1 km s-1); combined with the age-metallicity relation this indicates that the older populations have either been dynamically heated during their lifetimes or were born in a less disc-like distribution than the younger stars.. The low ratio vrot/σv suggests that within the inner 10 arcmin, NGC 6822's stars are dynamically decoupled from the H I gas, and possibly distributed in a thick disc or spheroid structure.

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

    PubMed

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

    2016-08-01

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

  2. 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. PMID:25194478

  3. Synthesis, spectra and DNA interactions of certain mononuclear transition metal(II) complexes of macrocyclic tetraaza diacetyl curcumin ligand

    NASA Astrophysics Data System (ADS)

    Rajesh, Jegathalaprathaban; Gubendran, Ammavasi; Rajagopal, Gurusamy; Athappan, Periyakaruppan

    2012-02-01

    A series of mononuclear transition metal(II) complexes of type [M(LL)]2+ (LL = the template condensate of orthophenylene diamine and benzilidene diacetyl curcumin (ben-diacecur) and M = Cu(II) (1) or Co(II) (2) or Ni(II) (3) or Mn(II) (4)), have been isolated and the spectral behaviors are discussed. The ligand and complexes have also been characterized by the analytical and spectral methods like UV-Visible, FT-IR, NMR and EPR. Further, the interaction of the transition metal complexes with Calf thymus (CT) DNA have also been studied by the use of physical methods like UV-Visible, emission and CD spectroscopic techniques. The electrochemical responses of these metal complexes both in presence and absence of DNA have also been demonstrated. All these findings support the hypothesis of DNA interactions of all these metal complexes through the grooves with a higher degree of interaction by complex 1 (Kb = 1.4 × 105) possibly through the interposition of the aromatic rings of the ligand compared to complexes, 2-4. The complex 1 display significant oxidative cleavage of circular plasmid pUC18 DNA in the presence of H2O2 using the singlet oxygen as a reactive species. The spectral and electrochemical response of these complexes designate that the square-planar Cu(II), Ni(II) and Co(II) complexes interact much better than the axially coordinated octahedral Mn(II) complex.

  4. Synthesis, characterization and extraction studies of some metal (II) complexes containing (hydrazoneoxime and bis-acylhydrazone) moieties.

    PubMed

    Al-Ne'aimi, Mohammed Mahmmod; Al-Khuder, Mohammed Moudar

    2013-03-15

    In this study, diacetylmonoximebenzoylhydrazone (L(1)H(2)) and 1,4-diacetylbenzene bis(benzoyl hydrazone) (L(2)H(2)) were synthesized by the condensation of benzohydrazide with diacetyl monoxime and 1,4-diacetylbenzene, respectively. Complexes of these ligands with Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) inos were prepared with a metal:ligand ratio of 1:2 for L(1)H(2) ligand, and 1:1 for L(2)H(2) ligand. The ligands and their complexes were elucidated on the basis of elemental analyses CHN, AAS, FT-IR, (1)H- and (13)C NMR spectra, UV-vis spectra and magnetic susceptibility measurements. Results show the L(1)H(2) ligand act as monoanionic O,N,N-tridentate and coordination takes place in the enol form through the oxime nitrogen, the imine nitrogen and the enolate oxygen atoms with a N(4)O(2) donor environment, while the L(2)H(2) ligand act as a dianionic O,N,N,O-tetradentate and coordination takes place in the enol form through the enolate oxygen and the azomethine nitrogen atoms with a N(2)O(2) donor environment. These results are consistent with the formation of mononuclear metal (II) complexes [M(L(1)H)(2)], and binuclear polymeric metal (II) complexes [{M(2)(L(2))}(n)]. The extraction ability of both ligands were examined in chloroform by the liquid-liquid extraction of selected transition metal [Co(2+), Ni(2+), Cu(2+), Zn(2+) and Pb(2+)] cations. The effects of pH and contact time on the percentage extraction of metal (II) ions were studied under the optimum extraction conditions. The (L(1)H(2)) ligand shows strong binding ability toward copper(II) and lead(II) ions, while the (L(2)H(2)) ligand shows strong binding ability toward nickel(II) and zinc(II) ions. PMID:23333690

  5. Synthesis, characterization and extraction studies of some metal (II) complexes containing (hydrazoneoxime and bis-acylhydrazone) moieties

    NASA Astrophysics Data System (ADS)

    Al-Ne'aimi, Mohammed Mahmmod; Al-Khuder, Mohammed Moudar

    2013-03-01

    In this study, diacetylmonoximebenzoylhydrazone (L1H2) and 1,4-diacetylbenzene bis(benzoyl hydrazone) (L2H2) were synthesized by the condensation of benzohydrazide with diacetyl monoxime and 1,4-diacetylbenzene, respectively. Complexes of these ligands with Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) inos were prepared with a metal:ligand ratio of 1:2 for L1H2 ligand, and 1:1 for L2H2 ligand. The ligands and their complexes were elucidated on the basis of elemental analyses CHN, AAS, FT-IR, 1H- and 13C NMR spectra, UV-vis spectra and magnetic susceptibility measurements. Results show the L1H2 ligand act as monoanionic O,N,N-tridentate and coordination takes place in the enol form through the oxime nitrogen, the imine nitrogen and the enolate oxygen atoms with a N4O2 donor environment, while the L2H2 ligand act as a dianionic O,N,N,O-tetradentate and coordination takes place in the enol form through the enolate oxygen and the azomethine nitrogen atoms with a N2O2 donor environment. These results are consistent with the formation of mononuclear metal (II) complexes [M(L1H)2], and binuclear polymeric metal (II) complexes [{M2(L2)}n]. The extraction ability of both ligands were examined in chloroform by the liquid-liquid extraction of selected transition metal [Co2+, Ni2+, Cu2+, Zn2+ and Pb2+] cations. The effects of pH and contact time on the percentage extraction of metal (II) ions were studied under the optimum extraction conditions. The (L1H2) ligand shows strong binding ability toward copper(II) and lead(II) ions, while the (L2H2) ligand shows strong binding ability toward nickel(II) and zinc(II) ions.

  6. 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.

  7. 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. PMID:27249166

  8. Applications of positron annihilation spectroscopy in materials research

    NASA Technical Reports Server (NTRS)

    Singh, Jag J.

    1988-01-01

    Positron Annihilation Spectroscopy (PAS) has emerged as a powerful technique for research in condensed matter. It has been used extensively in the study of metals, ionic crystals, glasses and polymers. The present review concentrates on applications of positron lifetime measurements for elucidation of the physicochemical structure of polymers.

  9. 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.

  10. 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

  11. The JHU-SDSS Metal Absorption Line Catalog: Redshift Evolution and Properties of Mg II Absorbers

    NASA Astrophysics Data System (ADS)

    Zhu, Guangtun; Ménard, Brice

    2013-06-01

    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 ~105 quasar spectra from the Sloan Digital Sky Survey and compile a sample of ~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 ~ 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.

  12. 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.

  13. Positron emission tomography.

    PubMed

    Hoffman, E J; Phelps, M E

    1979-01-01

    Conventional nuclear imaging techniques utilizing lead collimation rely on radioactive tracers with little role in human physiology. The principles of imaging based on coincidence detection of the annihilation radiation produced in positron decay indicate that this mode of detection is uniquely suited for use in emission computed tomography. The only gamma-ray-emitting isotopes of carbon, nitrogen, and oxygen are positron emitters, which yield energies too high for conventional imaging techniques. Thus development of positron emitters in nuclear medicine imaging would make possible the use of a new class of physiologically active, positron-emitting radiopharmaceuticals. The application of these principles is described in the use of a physiologically active compound labeled with a positron emitter and positron-emission computed tomography to measure the local cerebral metabolic rate in humans. PMID:440173

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

    PubMed Central

    Vejerano, Eric; Dellinger, Barry

    2014-01-01

    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)2O3, 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. PMID:22990982

  15. 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

  16. 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.

  17. 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.

  18. Metal based drugs: design, synthesis and in-vitro antimicrobial screening of Co(II), Ni(II), Cu(II) and Zn(II) complexes with some new carboxamide derived compounds: crystal structures of N-[ethyl(propan-2-yl)carbamothioyl]thiophene-2-carboxamide and its copper(II) complex.

    PubMed

    Sumrra, Sajjad H; Hanif, Muhammad; Chohan, Zahid H; Akram, Muhammad Safwan; Akhtar, Javeed; Al-Shehri, Saad M

    2016-08-01

    A new series of compounds derived from thiophene-2-carboxamide were synthesized and characterized by IR, (1)H-NMR and (13)C-NMR, mass spectrometry and elemental analysis. These compounds were further used to prepare their Co(II), Ni(II), Cu(II) and Zn(II) metal complexes. All metal(II) complexes were air and moisture stable. Physical, spectral and analytical data have shown the Ni(II) and Cu(II) complexes to exhibit distorted square-planar and Co(II) and Zn(II) complexes tetrahedral geometries. The ligand (L(1)) and its Cu(II) complex were characterized by the single-crystal X-ray diffraction method. All the ligands and their metal(II) complexes were screened for their in-vitro antimicrobial activity. The antibacterial and antifungal bioactivity data showed that the metal(II) complexes were found to be more potent than the parent ligands against one or more bacterial and fungal strains. PMID:26067080

  19. 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

  20. Atomic diffusion processes in heteroepitaxial metallic systems using SLKMC-II

    NASA Astrophysics Data System (ADS)

    Shah, Syed Islamuddin; Karim, Altaf

    We have examined the diffusion of small islands of Cu on Ag(111) surface using a self-learning kinetic Monte Carlo (SLKMC-II) method with an improved pattern recognition scheme. Due to strain generated at the interface between metals with different bulk lattice constants, interesting single atom, multi-atom and concerted diffusion processes are automatically revealed in the simulations. Here we will report various processes for small islands in the case of Cu/Ag(111) system. Key processes responsible for island diffusion and their energetics together with trends in effective energy barriers as well as diffusion constants for small islands will also be provided. In addition to 2-D diffusion processes, as an application of SLKMC-II to the 3-dimensional heteroepitaxial systems, we will also report energy barriers of some of the 3-dimensional processes including down the A- and B-steps and exchange processes

  1. Ca(II) Binding Regulates and Dominates the Reactivity of a Transition-Metal-Ion-Dependent Diesterase from Mycobacterium tuberculosis.

    PubMed

    Pedroso, Marcelo M; Larrabee, James A; Ely, Fernanda; Gwee, Shuhui E; Mitić, Nataša; Ollis, David L; Gahan, Lawrence R; Schenk, Gerhard

    2016-01-18

    The diesterase Rv0805 from Mycobacterium tuberculosis is a dinuclear metallohydrolase that plays an important role in signal transduction by controlling the intracellular levels of cyclic nucleotides. As Rv0805 is essential for mycobacterial growth it is a promising new target for the development of chemotherapeutics to treat tuberculosis. The in vivo metal-ion composition of Rv0805 is subject to debate. Here, we demonstrate that the active site accommodates two divalent transition metal ions with binding affinities ranging from approximately 50 nm for Mn(II) to about 600 nm for Zn(II) . In contrast, the enzyme GpdQ from Enterobacter aerogenes, despite having a coordination sphere identical to that of Rv0805, binds only one metal ion in the absence of substrate, thus demonstrating the significance of the outer sphere to modulate metal-ion binding and enzymatic reactivity. Ca(II) also binds tightly to Rv0805 (Kd ≈40 nm), but kinetic, calorimetric, and spectroscopic data indicate that two Ca(II) ions bind at a site different from the dinuclear transition-metal-ion binding site. Ca(II) acts as an activator of the enzymatic activity but is able to promote the hydrolysis of substrates even in the absence of transition-metal ions, thus providing an effective strategy for the regulation of the enzymatic activity. PMID:26662456

  2. Positron microprobe at LLNL

    SciTech Connect

    Asoka, P; Howell, R; Stoeffl, W

    1998-11-01

    The electron linac based positron source at Lawrence Livermore National Laboratory (LLNL) provides the world's highest current beam of keV positrons. We are building a positron microprobe that will produce a pulsed, focused positron beam for 3-dimensional scans of defect size and concentration with sub-micron resolution. The widely spaced and intense positron packets from the tungsten moderator at the end of the 100 MeV LLNL linac are captured and trapped in a magnetic bottle. The positrons are then released in 1 ns bunches at a 20 MHz repetition rate. With a three-stage re-moderation we will compress the cm-sized original beam to a 1 micro-meter diameter final spot on the target. The buncher will compress the arrival time of positrons on the target to less than 100 ps. A detector array with up to 60 BaF2 crystals in paired coincidence will measure the annihilation radiation with high efficiency and low background. The energy of the positrons can be varied from less than 1 keV up to 50 keV.

  3. Highly sensitive and selective fluorescence detection of copper (II) ion based on multi-ligand metal chelation.

    PubMed

    Zhang, Shan; Yu, Tao; Sun, Mingtai; Yu, Huan; Zhang, Zhongping; Wang, Suhua; Jiang, Hui

    2014-08-01

    A fluorescent probe was synthesized and demonstrated to be highly selective and sensitive in the reaction with copper (II) ion, generating a large variation of the fluorescence intensity in a dose-response manner. The probe contains a dansyl moiety as fluorophore and a multidentate ligand for copper (II) ion recognition. The reaction of the molecular probe with copper (II) ion proceeds rapidly and irreversibly in a 1 to 1 stoichiometric way, leading to the production of stable copper (II) complex, which subsequently results in the quenching of fluorescence. The detection limit for copper (II) ion was measured to be about 2ppb. It was also shown that the probe has high selectivity for copper (II) ion and good anti-interference ability against other transition metal ions. The herein reported very simple and reliable fluorescence probe could be employed for copper (II) ion detection in many aspects. PMID:24881551

  4. 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)

  5. Correlations between metal spin states and vibrational spectra of a trinuclear Fe(II) complex exhibiting spin crossover

    NASA Astrophysics Data System (ADS)

    Gerasimova, Tatiana P.; Katsyuba, Sergey A.; Lavrenova, Ludmila G.; Pelmenschikov, Vladimir; Kaupp, Martin

    2015-12-01

    Combined IR spectroscopic/quantum-chemical analysis of a 4-propyl-1,2,4-triazole trinuclear Fe(II) complex capable of reversible thermal spin crossover has revealed mid-IR bands of the ligand sensitive to the Fe(II) spin state. The character of the correlations found between the intensity and peak position of the triazole bands and the spin state of the metal center depends neither on the identity of the metal nor on the nuclearity of the complex. The found spectral correlations therefore allow analysis of various similar complexes. This is illustrated by the example of experimental IR spectra reported earlier for Fe(II), Co(II), Ni(II), Cu(II) and Zn(II) complexes with triazole ligands. Quantum-chemical IR spectral simulations further suggest that certain ligand bands vary between the states with the same total molecular spin, but different distribution of the spin density between the metal centers. However these variations are too subtle to discriminate between the spin transitions of the central and peripheral Fe(II) ions. The experimentally revealed mid-IR markers are therefore conclusive only for the total molecular spin.

  6. 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

  7. A position-sensitive γ-ray detector for positron annihilation 2D-ACAR based on metal package photomultiplier tubes

    NASA Astrophysics Data System (ADS)

    Inoue, Koji; Saito, Haruo; Nagashima, Yasuyuki; Hyodo, Toshio; Nagai, Yasuyoshi; Muramatsu, Shinichi; Nagai, Shota; Masuda, Keisuke

    2002-07-01

    A new position-sensitive γ-ray detector to be used in a two-dimensional angular correlation of positron annihilation radiation (2D-ACAR) apparatus has been developed. It consists of 36 compact position-sensitive photomultiplier tubes (PS-PMT: HAMAMATSU R5900-00-C8), a light guide, and 2676 Bi 4Ge 3O 12 (BGO) scintillator pieces of size 2.6 mm×2.6 mm×18 mm. A high detection efficiency for 511 keV γ-ray is achieved with the length of BGO scintillators used. The detection area is about 160 mm×160 mm. The 288 anode outputs of the PS-PMTs are wired and connected to resistor chains from which 16 outputs (8 outputs each along the X and Y directions) are taken to identify the incident position of the γ-ray. The spatial resolution is about 3 mm (FWHM). The timing signal taken from the last dynodes of the PS-PMTs gives a timing resolution of 7.7 ns (FWHM) for 511 keV positron annihilation γ-rays.

  8. 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.

  9. Synthesis, structure, and spectroscopic properties of ortho-metalated platinum(II) complexes

    SciTech Connect

    Mdleleni, M.M.; Bridgewater, J.S.; Watts, R.J.; Ford, P.C.

    1995-04-26

    The ortho-metalated Pt(II) complexes Pt(ppy)(CO)Cl (1), Pt(ptpy)(CO)Cl (2), and Pt(ppy)(Hppy)Cl (3) (where ppy and ptpy are respectively the ortho-C-deprotonated forms of 2-phenylpyridine and 2-p-tolylpyridine and Hppy is 2-phenylpyridine) have been prepared. The CO ligand is coordinated trans to the nitrogen atom of the ortho-metalated ligand and exerts a strong trans effect resulting in a relatively long Pt-N bond [2.114(19) {angstrom}]. This structure shows both the bidentate ppy ligand and the monodentate Hppy with the nitrogens of these ligands trans to each other. The UV/vis electronic absorption spectra of 1-3 have intense bands in the near-UV region ({approximately}375 nm) which have been assigned as metal to ligand charge transfer (MLCT) transitions, and higher energy bands were assigned as ligand-centered transitions. Each complex exhibits relatively long-lived structured emissions in the solid state at ambient temperature and at 77 K and 77 K glassy toluene solutions. These emissions are proposed to originate from triplet MLCT states. Notably, in solution both the lifetime and spectrum of 2 proved to be a function of the concentration, a phenomenon interpreted in terms of the propensity of square planar d{sup 8} complexes to oligomerize. In contrast, the more sterically hindered complex 3 displayed no such tendency toward oligomerization.

  10. Positron binding to molecules

    NASA Astrophysics Data System (ADS)

    Danielson, J. R.

    2011-05-01

    While there is theoretical evidence that positrons can bind to atoms, calculations for molecules are much less precise. Unfortunately, there have been no measurements of positron-atom binding, due primarily to the difficulty in forming positron-atom bound states in two-body collisions. In contrast, positrons attach to molecules via Feshbach resonances (VFR) in which a vibrational mode absorbs the excess energy. Using a high-resolution positron beam, this VFR process has been studied to measure binding energies for more than 40 molecules. New measurements will be described in two areas: positron binding to relatively simple molecules, for which theoretical calculations appear to be possible; and positron binding to molecules with large permanent dipole moments, which can be compared to analogous, weakly bound electron-molecule (negative-ion) states. Binding energies range from 75 meV for CS2 (no dipole moment) to 180 meV for acetonitrile (CH3CN). Other species studied include aldehydes and ketones, which have permanent dipole moments in the range 2.5 - 3.0 debye. The measured binding energies are surprisingly large (by a factor of 10 to 100) compared to those for the analogous negative ions, and these differences will be discussed. New theoretical calculations for positron-molecule binding are in progress, and a recent result for acetonitrile will be discussed. This ability to compare theory and experiment represents a significant step in attempts to understand positron binding to matter. In collaboration with A. C. L. Jones, J. J. Gosselin, and C. M. Surko, and supported by NSF grant PHY 07-55809.

  11. 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.

  12. 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.

  13. Theoretical study of heavy metal Cd, Cu, Hg, and Ni(II) adsorption on the kaolinite(0 0 1) surface

    NASA Astrophysics Data System (ADS)

    Zhao, Jian; He, Man-Chao

    2014-10-01

    Heavy metal pollution is currently of great concern because it has been recognized as a potential threat to air, water, and soil. Adsorption was one of the most popular methods for the removal of heavy metal. The adsorption of heavy metal Cd, Cu, Hg, and Ni(II) atoms on the hydroxylated (0 0 1) surface of kaolinite was investigated using density-functional theory within the generalized gradient approximation and a supercell approach. The coverage dependence of the adsorption structures and energetics were systematically studied for a wide range of coverage Θ [from 0.11 to 1.0 monolayers (ML)] and adsorption sites. The most stable among all possible adsorption sites for Cd(II) atom was the two-fold bridge site followed by the one-fold top site, and the top site was the most favorite adsorption site for Cu and Ni(II) atoms, while the three-fold hollow site was the most stable adsorption site for Hg(II) atom followed by the two-fold bridge site. The adsorption energy increases with the coverage for Cd, Cu, and Hg(II) atoms, thus indicating the higher stability of surface adsorption and a tendency to the formation of adsorbate islands (clusters) with increasing the coverage. However, the adsorption energy of Ni(II) atoms decreases when increasing the coverage. The adsorption capabilities of the kaolinite clay for the heavy metal atoms were in the order of Ni > Cu > Cd > Hg(II). The other properties of the Cd, Cu, Hg, and Ni(II)/kaolinite(0 0 1) system including the different charge distribution, the lattice relaxation, and the electronic density of states were also studied and discussed in detail.

  14. Nearby Spiral Galaxy Globular Cluster Systems. II. Globular Cluster Metallicities in NGC 300

    NASA Astrophysics Data System (ADS)

    Nantais, Julie B.; Huchra, John P.; Barmby, Pauline; Olsen, Knut A. G.

    2010-03-01

    We present new metallicity estimates for globular cluster (GC) candidates in the Sd spiral NGC 300, one of the nearest spiral galaxies outside the Local Group. We have obtained optical spectroscopy for 44 Sculptor Group GC candidates with the Boller and Chivens (B&C) spectrograph on the Baade Telescope at Las Campanas Observatory. There are two GCs in NGC 253 and 12 objects in NGC 300 with globular-cluster-like spectral features, nine of which have radial velocities above 0 km s-1. The remaining three, due to their radial velocities being below the expected 95% confidence limit for velocities of NGC 300 halo objects, are flagged as possible foreground stars. The non-cluster-like candidates included 13 stars, 15 galaxies, and an H II region. One GC, four galaxies, two stars, and the H II region from our sample were identified in archival Hubble Space Telescope images. For the GCs, we measure spectral indices and estimate metallicities using an empirical calibration based on Milky Way GCs. The GCs of NGC 300 appear similar to those of the Milky Way. Excluding possible stars and including clusters from the literature, the GC system (GCS) has a velocity dispersion of 68 km s-1 and has no clear evidence of rotation. The mean metallicity for our full cluster sample plus one literature object is [Fe/H] = -0.94, lying above the relationship between mean GC metallicity and overall galaxy luminosity. Excluding the three low-velocity candidates, we obtain a mean [Fe/H] = -0.98, still higher than expected, raising the possibility of significant foreground star contamination even in this sample. Visual confirmation of genuine GCs using high-resolution space-based imagery could greatly reduce the potential problem of interlopers in small samples of GCSs in low-radial-velocity galaxies. Data for this project were obtained at the Baade 6.5 m telescope, Las Campanas Observatory, Chile. This publication makes use of data products from the Two Micron All Sky Survey, which is a joint

  15. 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.

  16. 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.

  17. Advanced positron sources

    NASA Astrophysics Data System (ADS)

    Variola, A.

    2014-03-01

    Positron sources are a critical system for the future lepton colliders projects. Due to the large beam emittance at the production and the limitation given by the target heating and mechanical stress, the main collider parameters fixing the luminosity are constrained by the e+ sources. In this context also the damping ring design boundary conditions and the final performance are given by the injected positron beam. At present different schemes are being taken into account in order to increase the production and the capture yield of the positron sources, to reduce the impact of the deposited energy in the converter target and to increase the injection efficiency in the damping ring. The final results have a strong impact not only on the collider performance but also on its cost optimization. After a short introduction illustrating their fundamental role, the basic positron source scheme and the performance of the existing sources will be illustrated. The main innovative designs for the future colliders advanced sources will be reviewed and the different developed technologies presented. Finally the positrons-plasma R&D experiments and the futuristic proposals for positron sources will reviewed.

  18. Positrons from supernovae

    NASA Technical Reports Server (NTRS)

    Chan, Kai-Wing; Lingenfelter, Richard E.

    1993-01-01

    Positrons are produced in the ejecta of supernovae by the decay of nucleosynthetic Co-56, Ti-44, and Al-26. We calculate the probability that these positrons can survive without annihilating in the supernova ejecta, and we show that enough of these positrons should escape into the interstellar medium to account for the observed diffuse Galactic annihilation radiation. The surviving positrons are carried by the expanding ejecta into the interstellar medium where their annihilation lifetime of 10 exp 5 - 10 exp 6 yr is much longer than the average supernovae occurrence time of about 100 yr. Thus, annihilating positrons from thousands of supernovae throughout the Galaxy produce a steady diffuse flux of annihilation radiation. We further show that combining the calculated positron survival fractions and nucleosynthetic yields for current supernova models with the estimated supernova rates and the observed flux of diffuse Galactic annihilation radiation suggests that the present Galactic rate of Fe-56 nucleosynthesis is about 0.8 +/- 0.6 solar mass per 100 yr.

  19. Magnetic and structural properties of dinuclear singly bridged-phenoxido metal(II) complexes.

    PubMed

    Massoud, Salah S; Spell, Mark; Ledet, Catherine C; Junk, Thomas; Herchel, Radovan; Fischer, Roland C; Trávníček, Zdeněk; Mautner, Franz A

    2015-02-01

    The reaction of a methanolic solution containing the bi-compartmental phenolic ligand 2,6-bis[bis(2-pyridylmethyl)aminomethyl]-4-chlorophenol (L(Cl)-OH) with MCl2·nH2O in the presence of NH4PF6 or NaClO4 afforded the dinuclear bridged-phenoxido dichlorido-metal(ii) complexes [Co2(μ-L(Cl)O)(H2O)2Cl2][Co2(μ-L(Cl)O)(MeOH)2Cl2](PF6)2 (), [Ni2(μ-L(Cl)O)(MeOH)2Cl2]PF6 (), [Ni2(μ-L(Cl)O)(MeOH)(H2O)Cl2]ClO4·1.25H2O (), [Cu2(μ-L(Cl)O)Cl2]PF6·1/2MeOH () and [Zn2(μ-L(Cl)O)Cl2]PF6·MeOH (). The complexes were characterized by elemental microanalyses, conductivity measurements, IR and UV-Vis spectroscopy, mass spectrometry and single crystal X-ray crystallography. Each M(ii) center within the dinuclear complex cations is octahedrally coordinated in complexes , and five-coordinated distorted square pyramidal in and . Magnetic susceptibility measurements at variable temperature of the complexes revealed weak to moderate antiferromagnetic coupling with |J| values = 8.38, 39.0, 30.2 and 0.79 cm(-1), respectively. The results of DFT calculations correlate well with the experimentally determined antiferromagnetic coupling and show that the magnetic exchange coupling occurs mainly through the phenoxido bridge M-O-M. Implications of geometry around the central metal ion, MM distance, M-O-M bond angle and overlapping of magnetic orbitals on the magnetic exchange coupling are discussed. PMID:25502556

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

    PubMed

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

    2016-04-01

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

  1. Intriguing manipulation of metal-enhanced fluorescence for the detection of Cu(II) and cysteine.

    PubMed

    Ganguly, Mainak; Pal, Jaya; Mondal, Chanchal; Pal, Anjali; Pal, Tarasankar

    2014-09-22

    Commercially available salicylaldehyde, in alkaline medium, exhibits strong fluorescence after one hour of UV exposure in the presence of Ag(I) . The phenolic group of salicylaldehyde is converted into the quinone form under alkaline conditions in the presence of AgNO3 , resulting in aggregated Ag(0), which causes approximately 250 times fluorescence enhancement of the in situ produced quinone. Such high silver-enhanced-fluorescence (SEF) is selectively quenched by cysteine, arginine, histidine, methionine, and tryptophan. In contrast to the other amino acids, ageing brings selectivity of the cysteine-induced quenching effect. Interestingly, Cu(II) is found to be the only metal ion that exclusively regenerates the lost fluorescence. Thus, quenching and recovery of fluorescence (Turn Off/On) can be used for the selective and sensitive detection of cysteine as well as Cu(II) ions in one pot. Alteration of the electric field density around the fluorophore (lightening rod effect) and scattering/absorption cross-section have been proposed to account for the Off/On fluorescence. PMID:25124795

  2. Magnetic and Photochromic Properties of a Manganese(II) Metal-Zwitterionic Coordination Polymer.

    PubMed

    Gong, Teng; Yang, Xiao; Sui, Qi; Qi, Yan; Xi, Fu-Gui; Gao, En-Qing

    2016-01-01

    The solvothermal reaction of Mn(ClO4)2, NaN3, and a rigid viologen-tethered tetracarboxylic acid (1,1'-bis(3,5-dicarboxyphenyl)-4,4'-bipyridinium chloride, [H4L]Cl2) led to a coordination polymer of formula [Mn4(L)(N3)6(H2O)2]n. X-ray analysis revealed a 3D coordination structure. The Mn(II) ions are connected by mixed azide and carboxylate bridges to give 2D layers, which are pillared by the viologen tether of the zwitterionic ligand. Magnetic analyses suggested that the compound features antiferromagnetism and field-induced metamagnetism. The compound also shows photochromic and photomagnetic properties. The long-range magnetic ordering is owed to the spin-canting structure of the Mn(II)-azide-carboxylate layer; the photochromism involves the formation of viologen radicals via photoinduced electron transfer, and the photomagnetism is related to the interactions between the metal ion and the photogenerated radicals. The study demonstrates a strategy for the design of new multifunctional materials with photoresponsive properties. PMID:26671046

  3. Photostability of phosphonate-derivatized, Ru(II) polypyridyl complexes on metal oxide surfaces.

    PubMed

    Hanson, Kenneth; Brennaman, M Kyle; Luo, Hanlin; Glasson, Christopher R K; Concepcion, Javier J; Song, Wenjing; Meyer, Thomas J

    2012-03-01

    The photostability of [Ru(II)(bpy)(2)(4,4'-(PO(3)H(2))(2)bpy)]Cl(2) (bpy = 4,4'-bipyridine) on nanocrystalline TiO(2) and ZrO(2) films was investigated using a standard measurement protocol. Stability was evaluated by monitoring visible light absorbance spectral changes, in real time, during 455 nm photolysis (30 nm fwhm, 475 mW/cm(2)) in a variety of conditions relevant to dye-sensitized solar cells and dye-sensitized photoelectrosynthesis cells. Desorption (k(des)) and photochemical (k(chem)) processes were observed and found to be dependent upon solvent, anion, semiconductor, and presence of oxygen. Both processes are affected by oxygen with k(des) and k(photo) noticeably smaller in argon saturated solution. Desorption was strongly solvent and pH dependent with desorption rates increasing in the order: methanol (MeOH) ≈ acetonitrile (MeCN) < propylene carbonate (PC) < pH 1 ≪ pH 7. Photochemistry occurred in MeOH and PC but not in aqueous, 0.1 M HClO(4) and MeCN. The anion and solvent dependence of k(photo) strongly suggests the photoreaction involves ligand substitution initiated by population of metal centered d-d states. The relative stability of -PO(3)H(2)- versus -COOH-substituted [Ru(II)(bpy)(3)](2+) was also quantitatively established. PMID:22316053

  4. Communication: Photoactivation of nucleobase bound platinum(II) metal complexes: probing the influence of the nucleobase.

    PubMed

    Sen, Ananya; Dessent, Caroline E H

    2014-12-28

    We present UV laser action spectra (220-300 nm) of isolated nucleobase-bound Pt(II)(CN)4(2-) complexes, i.e., Pt(CN)4(2-)⋅M, where M = uracil, thymine, cytosine, and adenine. These metal complex-nucleobase clusters represent model systems for identifying the fundamental photophysical and photochemical processes occurring in photodynamic platinum (II) drug therapies that target DNA. This is the first study to explore the specific role of the nucleobase in the photophysics of the aggregate complex. Each of the complexes studied displays a broadly similar absorption spectra, with a strong λmax ∼ 4.7 eV absorption band (nucleobase localized chromophore) and a subsequent increase in the absorption intensity towards higher spectral-energy (Pt(CN)4(2-) localized chromophore). However, strikingly different band widths are observed across the series of complexes, decreasing in the order Pt(CN)4(2-)⋅Thymine > Pt(CN)4(2-)⋅Uracil > Pt(CN)4(2-)⋅Adenine > Pt(CN)4(2-)⋅Cytosine. Changes in the bandwidth of the ∼4.7 eV band are accompanied by distinctive changes in the photofragment product ions observed following photoexcitation, with the narrower-bandwidth complexes showing a greater propensity to decay via electron detachment decay. We discuss these observations in the context of the distinctive nucleobase-dependent excited state lifetimes. PMID:25554122

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

    PubMed

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

    2013-11-21

    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 (Fe(2+) or Co(2+)). 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 O(2-) ions in PVP-Cu2O complexes with transition metal(II) ions (Fe(2+) or Co(2+)) 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. PMID:24084833

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

    PubMed Central

    Schmidt, Sidsel Birkelund; Persson, Daniel Pergament; Powikrowska, Marta; Frydenvang, Jens; Schjoerring, Jan K.; Jensen, Poul Erik; Husted, Søren

    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

  7. Possible Role of Metal(II) Octacyanomolybdate(IV) in Chemical Evolution: Interaction with Ribose Nucleotides

    NASA Astrophysics Data System (ADS)

    Kumar, Anand; Kamaluddin

    2013-02-01

    We have proposed that double metal cyanide compounds (DMCs) might have played vital roles as catalysts in chemical evolution and the origin of life. We have synthesized a series of metal octacyanomolybdates (MOCMos) and studied their interactions with ribose nucleotides. MOCMos have been shown to be effective adsorbents for 5'-ribonucleotides. The maximum adsorption level was found to be about 50 % at neutral pH under the conditions studied. The zinc(II) octacyanomolybdate(IV) showed larger adsorption compared to other MOCMos. The surface area seems to important parameter for the adsorption of nucleotides. The adsorption followed a Langmuir adsorption isotherms with an overall adsorption trends of the order of 5'-GMP > 5'-AMP > 5'-CMP > 5'-UMP. Purine nucleotides were adsorbed more strongly than pyrimidine nucleotides on all MOCMos possibly because of the additional binding afforded by the imidazole ring in purines. Infrared spectral studies of adsorption adducts indicate that adsorption takes place through interaction between adsorbate molecules and outer divalent ions of MOCMos.

  8. Metal Binding in Photosystem II Super- and Subcomplexes from Barley Thylakoids.

    PubMed

    Schmidt, Sidsel Birkelund; Persson, Daniel Pergament; Powikrowska, Marta; Frydenvang, Jens; Schjoerring, Jan K; Jensen, Poul Erik; Husted, Søren

    2015-08-01

    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

  9. 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.

  10. BIOLOGICAL MONITORING OF TOXIC TRACE METALS. VOLUME 2. TOXIC TRACE METALS IN PLANTS AND ANIMALS OF THE WORLD. PART II

    EPA Science Inventory

    The needs and priorities in using biological accumulator organisms for monitoring toxic trace metals in plants and animals are analyzed. The toxic trace metals selected for study are antimony, arsenic, beryllium, boron, cadmium, chromium, cobalt, copper, lead, mercury, nickel, se...

  11. Novel M(II)-Hg(II) coordination polymers generated from metal-containing building blocks M(2-pyrazinecarboxylate) 2 · (H 2O) 2 (M=Cu, Ni, Co) and HgCl 2

    NASA Astrophysics Data System (ADS)

    Dong, Yu-Bin; Smith, Mark D.; zur Loye, Hans-Conrad

    2000-12-01

    A new class of M(II)-Hg(II) (M=Cu(II), Co(II), Ni(II)) mixed-metal coordination polymers, Cu(2-pyrazinecarboxylate) 2HgCl 2 ( 4), [Co(2-pyrazinecarboxylate) 2(HgCl 2) 2] · 0.61H 2O ( 5) and [Ni(2-pyrazinecarboxylate) 2(HgCl 2) 2] · 0.77H 2O ( 6), have been prepared by self assembly of metal-containing building blocks, M(2-pyrazinecarboxylate) 2 · (H 2O) 2 (M=Cu(II), Co(II), Ni(II)), with HgCl 2. Compounds 4- 6 were characterized fully by IR, elemental analysis and single crystal X-ray diffraction. Compound 4 crystallized in the monoclinic space group C2/ c, with a=17.916(5) Å, b=7.223(2) Å, c=13.335(4) Å, β=128.726(3)°, V=1346.2(6) Å 3, Z=4. It contains alternating Hg(II) and Cu(II) metal centers that are cross-linked by 2-pyrazinecarboxylate spacers and chlorine co-ligands to generate a unique three-dimensional Hg(II)-Cu(II) mixed metal framework. Compound 5 crystallized in the triclinic space group P1¯, with a=6.3879(7) Å, b=6.6626(8) Å, c=13.2286(15) Å, α=96.339(2)°, β=91.590(2)°, γ=113.462(2)°, V=511.71(10) Å 3, Z=1. Compound 6 also crystallized in the triclinic space group P1¯, with a=6.3543(8) Å, b=6.6194(8) Å, c=13.2801(16) Å, α=96.449(2)°, β=92.263(2)°, γ=113.541(2)°, V=506.67(11) Å 3, Z=1. Compounds 5 and 6 are isostructural and in the solid state the Hg(II)⋯M(II)⋯Hg(II) units are connected by Hg 2Cl 2 linkages to produce a novel M(II)-Hg(II) (MCo(II), Ni(II)) zigzag mixed-metal chain, in which a new type of M-M'-M'-M array was observed. The metal containing building blocks, M(2-pyrazinecarboxylate) 2 · (H 2O) 2 (MCu(II), Co(II), Ni(II)), exhibit different connectivities to HgCl 2 depending on the metal cation contained within them.

  12. High acetylene/ethylene separation in a microporous zinc(II) metal-organic framework with low binding energy.

    PubMed

    Wen, Hui-Min; Li, Bin; Wang, Hailong; Krishna, Rajamani; Chen, Banglin

    2016-01-21

    A novel zinc(II) metal-organic framework UTSA-67a with narrow one-dimensional (1D) pore channels and inner cages of moderate size has been developed for highly selective separation of C2H2/C2H4 mixtures at room temperature. PMID:26597048

  13. Synthesis, thermal and optical properties of metal(II) complexes with a novel ligand derived from pyrazolone-5

    NASA Astrophysics Data System (ADS)

    Li, Xiaoyi; Wu, Yiqun; Gu, Donghong; Gan, Fuxi

    2011-03-01

    Three novel metal(II) complexes, CoL2, NiL2 and CuL2 (L = (Z)-4-(2-(1,3-dimethyl-5-oxo-1H-pyrazol-4(5H)-ylidene)hydrazinyl)-1,5-dimethyl-2-phenyl-1,2-dihydropyrazol-3-one were synthesized. Their structures were postulated based on elemental analyses, 1H NMR, ESI-MS, FT-IR spectra and UV-vis spectra. The effect of different central metal(II) ions on absorption bands of the metal(II) complexes in CHCl3 solutions was researched. The result indicates that the bathochromic shift is CuL2 > NiL2 > CoL2. The absorption properties of thin films and thermal stability of these complexes are also discussed. In addition, the optical constants (complex refractive index N= n+ ik) and thickness of the complex thin films on polished single-crystal silicon substrates were measured by spectroscopic ellipsometry. Results indicate that the metal(II) complexes would be a promising recording medium candidate for blu-ray recordable optical storage system due to good absorption at 405 nm, high thermal stability and sharp thermal decomposition, and a high n values of 1.35-1.45 and a low k values of 0.33-0.39.

  14. Positron bunching and electrostatic transport system for the production and emission of dense positronium clouds into vacuum

    NASA Astrophysics Data System (ADS)

    Aghion, S.; Amsler, C.; Ariga, A.; Ariga, T.; Belov, A. S.; Bonomi, G.; Bräunig, P.; Bremer, J.; Brusa, R. S.; Cabaret, L.; Caccia, M.; Caravita, R.; Castelli, F.; Cerchiari, G.; Chlouba, K.; Cialdi, S.; Comparat, D.; Consolati, G.; Demetrio, A.; Di Noto, L.; Doser, M.; Dudarev, A.; Ereditato, A.; Evans, C.; Fesel, J.; Fontana, A.; Forslund, O. K.; Gerber, S.; Giammarchi, M.; Gligorova, A.; Gninenko, S.; Guatieri, F.; Haider, S.; Holmestad, H.; Huse, T.; Jernelv, I. L.; Jordan, E.; Kaltenbacher, T.; Kellerbauer, A.; Kimura, M.; Koetting, T.; Krasnicky, D.; Lagomarsino, V.; Lebrun, P.; Lansonneur, P.; Lehner, S.; Liberadzka, J.; Malbrunot, C.; Mariazzi, S.; Marx, L.; Matveev, V.; Mazzotta, Z.; Nebbia, G.; Nedelec, P.; Oberthaler, M.; Pacifico, N.; Pagano, D.; Penasa, L.; Petracek, V.; Pistillo, C.; Prelz, F.; Prevedelli, M.; Ravelli, L.; Rienäcker, B.; Røhne, O. M.; Rosenberger, S.; Rotondi, A.; Sacerdoti, M.; Sandaker, H.; Santoro, R.; Scampoli, P.; Sorrentino, F.; Spacek, M.; Storey, J.; Strojek, I. M.; Testera, G.; Tietje, I.; Vamosi, S.; Widmann, E.; Yzombard, P.; Zavatarelli, S.; Zmeskal, J.

    2015-11-01

    We describe a system designed to re-bunch positron pulses delivered by an accumulator supplied by a positron source and a Surko-trap. Positron pulses from the accumulator are magnetically guided in a 0.085 T field and are injected into a region free of magnetic fields through a μ -metal field terminator. Here positrons are temporally compressed, electrostatically guided and accelerated towards a porous silicon target for the production and emission of positronium into vacuum. Positrons are focused in a spot of less than 4 mm FWTM in bunches of ∼8 ns FWHM. Emission of positronium into the vacuum is shown by single shot positron annihilation lifetime spectroscopy.

  15. Direct C–H Metalation with Chromium(II) and Iron(II): Transition-Metal Host / Benzenediide Guest Magnetic Inverse-Crown Complexes**

    PubMed Central

    Alborés, Pablo; Carrella, Luca M; Clegg, William; García-Álvarez, Pablo; Kennedy, Alan R; Klett, Jan; Mulvey, Robert E; Rentschler, Eva; Russo, Luca

    2009-01-01

    Abstract Check M(etal)ate: The chessboard and the figures represent a special reaction in which different low-polarity metals can metalate arenes directly when they are brought into the right position. In a combination of queen (sodium) and knight (chromium or iron), it is possible for the knight (usually the weaker piece) to make a direct deadly hit on the king (benzene) in this game of elemental chess. PMID:19156782

  16. Development of Texas intense positron source

    NASA Astrophysics Data System (ADS)

    Köymen, A. R.; Ünlü, K.; Jacobsen, F. M.; Göktepeli, S.; Wehring, B. W.

    1999-02-01

    The Texas Intense Positron Source (TIPS) is a reactor-based low-energy positron beam facility utilizing some novel techniques in positron beam production. This facility will be located at the University of Texas (UT) at Austin Nuclear Engineering Teaching Laboratory (NETL) and is being developed by UT Austin and UT Arlington researchers. TIPS will use a large area (total area of 900-1800 cm 2) 64Cu source to supply fast β + particles for subsequent moderation to form an intense monoenergetic positron beam in the energy range of 0-50 keV with an expected intensity of 10 8 e +/s. Natural copper will be neutron activated near the core of the NETL 1 MW TRIGA Mark II research reactor to produce the 64Cu isotope. The activated source will be transported to the moderator/remoderator assembly, outside the biological shield of the reactor. This assembly combines the primary moderation and posterior remoderation of the fast β + particles into one stage using solid Kr to produce a low-energy positron source of a few eV with a diameter of 8 mm. The low-energy positron beam is then extracted by an electrostatic modified SOA gun and after further acceleration to 5 keV, the beam is focused onto the object slit of a 90° bending magnet. After further focusing and another 90° bend, the beam enters the main accelerator/decelerator that transports the beam onto the target for experimentation. The components of TIPS have been manufactured and are currently being optimized. In this communication we present some of the details of the TIPS facility and furthermore briefly discuss its intended applications.

  17. 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. PMID:26114263

  18. Position-resolved Positron Annihilation Lifetime Spectroscopy

    NASA Astrophysics Data System (ADS)

    Wagner, A.; Butterling, M.; Fiedler, F.; Fritz, F.; Kempe, M.; Cowan, T. E.

    2013-06-01

    A new method which allows for position-resolved positron lifetime spectroscopy studies in extended volume samples is presented. In addition to the existing technique of in-situ production of positrons inside large (cm3) bulk samples using high-energy photons up to 16 MeV from bremsstrahlung production, granular position-sensitive photon detectors have been employed. A beam of intense bremsstrahlung is provided by the superconducting electron linear accelerator ELBE (Electron Linear Accelerator with high Brilliance and low Emittance) which delivers electron bunches of less than 10 ps temporal width and an adjustable bunch separation of multiples of 38 ns, average beam currents of 1 mA, and energies up to 40 MeV. Since the generation of bremsstrahlung and the transport to the sample preserves the sharp timing of the electron beam, positrons generated inside the entire sample volume by pair production feature a sharp start time stamp for positron annihilation lifetime studies with high timing resolutions and high signal to background ratios due to the coincident detection of two annihilation photons. Two commercially available detectors from a high-resolution medial positron-emission tomography system are being employed with 169 individual Lu2SiO5:Ce scintillation crystals, each. In first experiments, a positron-lifetime gated image of a planar Si/SiO2 (pieces of 12.5 mm × 25 mm size) sample and a 3-D structured metal in Teflon target could be obtained proving the feasibility of a three dimensional lifetime-gated tomographic system.

  19. 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.

  20. 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.

  1. Positron emission tomography

    NASA Astrophysics Data System (ADS)

    Yamamoto, Y. Lucas; Thompson, Christopher J.; Diksic, Mirko; Meyer, Ernest; Feindel, William H.

    One of the most exciting new technologies introduced in the last 10 yr is positron emission tomography (PET). PET provides quantitative, three-dimensional images for the study of specific biochemical and physiological processes in the human body. This approach is analogous to quantitative in-vivo autoradiography but has the added advantage of permitting non-invasive in vivo studies. PET scanning requires a small cyclotron to produce short-lived positron emitting isotopes such as oxygen-15, carbon-11, nitrogen-13 and fluorine-18. Proper radiochemical facilities and advanced computer equipment are also needed. Most important, PET requires a multidisciplinary scientific team of physicists, radiochemists, mathematicians, biochemists and physicians. This review analyzes the most recent trends in the imaging technology, radiochemistry, methodology and clinical applications of positron emission tomography.

  2. 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.

  3. Microstructure Evaluation of Fe-BASED Amorphous Alloys Investigated by Doppler Broadening Positron Annihilation Technique

    NASA Astrophysics Data System (ADS)

    Lu, Wei; Huang, Ping; Wang, Yuxin; Yan, Biao

    2013-07-01

    Microstructure of Fe-based amorphous and nanocrystalline soft magnetic alloy has been investigated by X-ray diffraction (XRD), transmission electronic microscopy (TEM) and Doppler broadening positron annihilation technique (PAT). Doppler broadening measurement reveals that amorphous alloys (Finemet, Type I) which can form a nanocrystalline phase have more defects (free volume) than alloys (Metglas, Type II) which cannot form this microstructure. XRD and TEM characterization indicates that the nanocrystallization of amorphous Finemet alloy occurs at 460°C, where nanocrystallites of α-Fe with an average grain size of a few nanometers are formed in an amorphous matrix. With increasing annealing temperature up to 500°C, the average grain size increases up to around 12 nm. During the annealing of Finemet alloy, it has been demonstrated that positron annihilates in quenched-in defect, crystalline nanophase and amorphous-nanocrystalline interfaces. The change of line shape parameter S with annealing temperature in Finemet alloy is mainly due to the structural relaxation, the pre-nucleation of Cu nucleus and the nanocrystallization of α-Fe(Si) phase during annealing. This study throws new insights into positron behavior in the nanocrystallization of metallic glasses, especially in the presence of single or multiple nanophases embedded in the amorphous matrix.

  4. 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.

  5. Static leach tests with the EBR-II metallic waste form.

    SciTech Connect

    Ebert, W. L.; Lewis, M. A.; Barber, T. L.; DiSanto, T.; Johnson, S. G.

    2004-01-09

    A metallic waste form (MWF) will be used to immobilize contaminated cladding hulls recovered after electrometallurgical treatment of spent sodium-bonded nuclear fuel from the Experimental Breeder Reactor-II (EBR-II). Tests were conducted to determine if the high-level waste (HLW) glass degradation model developed for total system performance assessment (TSPA) calculations for the Yucca Mountain repository system can be used to represent the degradation of disposed MWF. Static tests were conducted at 50, 70, and 90 C with monolithic samples of MWF in pH buffer solutions spiked with NaCl at a MWF surface-to-solution volume ratio of about 200 m{sup -1}. Test specimens were prepared from a surrogate MWF ingot containing about 10 mass% U. Solutions were exchanged after 14, 28, and 70 days. The cumulative amount of U released into solution through 70 days was used to calculate the MWF degradation rate for each test condition. The rate was independent of temperature. The rate was highest in acidic solutions, lowest in neutral solutions, and intermediate in alkaline solutions. The uranium release rate from a breached canister, which is the product of the MWF degradation rate and the surface area of two MWF ingots in a canister, was compared with the release rate calculated with the HLW glass degradation model for a glass log at the same temperature and pH values. The uranium release rates measured for MWF are less than the degradation rates calculated for HLW glass (compared on a mass per time basis).

  6. Simulations of Liquid III-V and II-VI Semiconductors: Semiconducting versus Metallic Behavior.

    NASA Astrophysics Data System (ADS)

    Godlevsky, V.

    2000-03-01

    All III-V group semiconductors exhibit metallic behavior when melted. The coordination number of these materials changes from 4 in the bulk to ~ 6 in the liquid phase. With the increase of the coordination number and compositional disorder common to liquid III-V semiconductors, the covalent bonds of these materials are predominantly replaced by metallic bonds. Electron delocalization and high atomic randomization result in a large entropy change during the solidarrowliquid transition. Unlike III-V compounds, a number of II-VI semiconductors (e.g. CdTe, ZnTe and HgS) experience a semiconductorarrowsemiconductor transition upon melting. These compounds retain their fourfold coordination in the liquid phase. In our work, we perform ab initio simulations of liquid GaAs (l-GaAs) and CdTe (l-CdTe), as representatives of III-V and II-VI materials.(V. Godlevsky, J. Derby, and J.R. Chelikowsky, Phys. Rev. Lett. 81), 4959 (1998) As opposed to the more close-packed l-GaAs, l-CdTe has an open fourfold structure. Besides the coordination number, l-CdTe also retains some of its crystalline compositional features (e.g. there are fewer ``wrong'' bond defects than in l-GaAs). In l-CdTe, the density of states has a dip at the Fermi level indicating the semiconducting character of electrical conductivity in this material. The d.c. conductivity in l-CdTe is by two orders of magnitude lower than that in l-GaAs. The small change in the structural order and electron delocalization is in good agreement with the small entropy change observed experimentally during the melting of CdTe. As the temperature increases further, l-CdTe undergoes a fourfold-sixfold transition accompanied by the disappearing of band gap. The d.c. conductivity of sixfold coordinated l-CdTe is by an order of magnitude larger than the d.c. conductivity of fourfold coordinated l-CdTe.(V. Godlevsky, M. Jain, J. Derby, and J.R. Chelikowsky, Phys. Rev. B, 60), 8640 (1999)

  7. 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

    2016-06-01

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

  8. 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.

  9. Robust Type-II Weyl Semimetal Phase in Transition Metal Diphosphides X P2 (X =Mo , W)

    NASA Astrophysics Data System (ADS)

    Autès, G.; Gresch, D.; Troyer, M.; Soluyanov, A. A.; Yazyev, O. V.

    2016-08-01

    The recently discovered type-II Weyl points appear at the boundary between electron and hole pockets. Type-II Weyl semimetals that host such points are predicted to exhibit a new type of chiral anomaly and possess thermodynamic properties very different from their type-I counterparts. In this Letter, we describe the prediction of a type-II Weyl semimetal phase in the transition metal diphosphides MoP2 and WP2 . These materials are characterized by relatively simple band structures with four pairs of type-II Weyl points. Neighboring Weyl points have the same chirality, which makes the predicted topological phase robust with respect to small perturbations of the crystalline lattice. In addition, this peculiar arrangement of the Weyl points results in long topological Fermi arcs, thus making them readily accessible in angle-resolved photoemission spectroscopy.

  10. Potato peels as solid waste for the removal of heavy metal copper(II) from waste water/industrial effluent.

    PubMed

    Aman, Tehseen; Kazi, Asrar Ahmad; Sabri, Muhammad Usman; Bano, Qudsia

    2008-05-01

    A new sorbent potato peels, which are normally discarded as solid waste for removing toxic metal ion Cu(II) from water/industrial waste water have been studied. Potato peels charcoal (PPC) was investigated as an adsorbent of Cu(II) from aqueous solutions. Kinetic and isotherm studies were carried out by studying the effects of various parameters such as temperature, pH and solid liquid ratios. The optimum pH value for Cu(II) adsorption onto potato peels charcoal (PPC) was found to be 6.0. The thermodynamic parameters such as standard Gibb's free energy (Delta G degrees ), standard enthalpy (Delta H degrees ) and standard entropy (DeltaS degrees ) were evaluated by applying the Van't Hoff equation. The thermodynamics of Cu(II) adsorption onto PPC indicates its spontaneous and exothermic nature. The equilibrium data at different temperatures were analyzed by Langmuir and Freundlich isotherms. PMID:18215510

  11. 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.

  12. Intense positron beam at KEK

    NASA Astrophysics Data System (ADS)

    Kurihara, Toshikazu; Yagishita, Akira; Enomoto, Atsushi; Kobayashi, Hitoshi; Shidara, Tetsuo; Shirakawa, Akihiro; Nakahara, Kazuo; Saitou, Haruo; Inoue, Kouji; Nagashima, Yasuyuki; Hyodo, Toshio; Nagai, Yasuyoshi; Hasegawa, Masayuki; Inoue, Yoshi; Kogure, Yoshiaki; Doyama, Masao

    2000-08-01

    A positron beam is a useful probe for investigating the electronic states in solids, especially concerning the surface states. The advantage of utilizing positron beams is in their simpler interactions with matter, owing to the absence of any exchange forces, in contrast to the case of low-energy electrons. However, such studies as low-energy positron diffraction, positron microscopy and positronium (Ps) spectroscopy, which require high intensity slow-positron beams, are very limited due to the poor intensity obtained from a conventional radioactive-isotope-based positron source. In conventional laboratories, the slow-positron intensity is restricted to 10 6 e +/s due to the strength of the available radioactive source. An accelerator based slow-positron source is a good candidate for increasing the slow-positron intensity. One of the results using a high intensity pulsed positron beam is presented as a study of the origins of a Ps emitted from SiO 2. We also describe the two-dimensional angular correlation of annihilation radiation (2D-ACAR) measurement system with slow-positron beams and a positron microscope.

  13. Local structure of the metal-organic perovskite dimethylammonium manganese(ii) formate.

    PubMed

    Duncan, Helen D; Dove, Martin T; Keen, David A; Phillips, Anthony E

    2016-03-14

    We report total neutron scattering measurements on the metal-organic perovskite analogue dimethylammonium manganese(ii) formate, (CD3)2ND2[Mn(DCO2)3]. Reverse Monte Carlo modelling shows that, in both the disordered high-temperature and ordered low-temperature phases, the ammonium moiety forms substantially shorter hydrogen bonds (N...O = 2.4 Å and 2.6 Å) than are visible in the average crystal structures. These bonds result from a pincer-like motion of two adjacent formate ions about the dimethylammonium ion in such a way that the framework can adjust independently to the positions of nearest-neighbour dimethylammonium ions. At low temperatures the shortest hydrogen bond is less favourable, apparently because it involves a greater distortion of the framework. Furthermore, in the high-temperature phase, in addition to the three disordered nitrogen positions expected from the average crystal structure, there appear to be also smaller probability maxima between these positions, corresponding to orientations in which the dimethylammonium is hydrogen-bonded to the two oxygen atoms of a single formate ion. The spontaneous strain across the phase transition reveals a contraction of the framework about the dimethylammonium cation, continuing as the material is cooled below the transition temperature. These results provide direct evidence of the local atomic structure of the guest-framework hydrogen bonding, and in particular the distortions of the framework responsible for the phase transition in this system. PMID:26763144

  14. Photocurrents from photosystem II in a metal oxide hybrid system: Electron transfer pathways.

    PubMed

    Brinkert, Katharina; Le Formal, Florian; Li, Xiaoe; Durrant, James; Rutherford, A William; Fantuzzi, Andrea

    2016-09-01

    We have investigated the nature of the photocurrent generated by Photosystem II (PSII), the water oxidizing enzyme, isolated from Thermosynechococcus elongatus, when immobilized on nanostructured titanium dioxide on an indium tin oxide electrode (TiO2/ITO). We investigated the properties of the photocurrent from PSII when immobilized as a monolayer versus multilayers, in the presence and absence of an inhibitor that binds to the site of the exchangeable quinone (QB) and in the presence and absence of exogenous mobile electron carriers (mediators). The findings indicate that electron transfer occurs from the first quinone (QA) directly to the electrode surface but that the electron transfer through the nanostructured metal oxide is the rate-limiting step. Redox mediators enhance the photocurrent by taking electrons from the nanostructured semiconductor surface to the ITO electrode surface not from PSII. This is demonstrated by photocurrent enhancement using a mediator incapable of accepting electrons from PSII. This model for electron transfer also explains anomalies reported in the literature using similar and related systems. The slow rate of the electron transfer step in the TiO2 is due to the energy level of electron injection into the semiconducting material being below the conduction band. This limits the usefulness of the present hybrid electrode. Strategies to overcome this kinetic limitation are discussed. PMID:26946088

  15. Positron spectroscopy of 2D materials using an advanced high intensity positron beam

    NASA Astrophysics Data System (ADS)

    McDonald, A.; Chirayath, V.; Lim, Z.; Gladen, R.; Chrysler, M.; Fairchild, A.; Koymen, A.; Weiss, A.

    An advanced high intensity variable energy positron beam(~1eV to 20keV) has been designed, tested and utilized for the first coincidence Doppler broadening (CDB) measurements on 6-8 layers graphene on polycrystalline Cu sample. The system is capable of simultaneous Positron annihilation induced Auger electron Spectroscopy (PAES) and CDB measurements giving it unparalleled sensitivity to chemical structure at external surfaces, interfaces and internal pore surfaces. The system has a 3m flight path up to a micro channel plate (MCP) for the Auger electrons emitted from the sample. This gives a superior energy resolution for PAES. A solid rare gas(Neon) moderator was used for the generation of the monoenergetic positron beam. The positrons were successfully transported to the sample chamber using axial magnetic field generated with a series of Helmholtz coils. We will discuss the PAES and coincidence Doppler broadening measurements on graphene -Cu sample and present an analysis of the gamma spectra which indicates that a fraction of the positrons implanted at energies 7-60eV can become trapped at the graphene/metal interface. This work was supported by NSF Grant No. DMR 1508719 and DMR 1338130.

  16. Cosmic Metallicity from ZnII-Selected QSO Absorption Line Systems Near Redshift z=1.2

    NASA Astrophysics Data System (ADS)

    Monier, Eric

    2010-09-01

    We have searched nearly 15,000 strong intervening MgII systems in SDSS quasar spectra to measure spectral regions where weak, unsaturated metal lines are predicted to exist, with the aim of finding a representative sample of the strongest metal-line column density systems in the universe. These systems are clearly damped Lyman-alpha {DLA} systems, which track cosmologically intervening neutral gas regions that fall along the sightlines to background quasars. We propose STIS G230L spectroscopy of seven strong-ZnII-selected systems from this sample in order to measure their Lyman-alpha absorption profiles and derive their HI column densities. Since Zn is not depleted onto grains, measurement of N{HI} allows a direct measurement of the metal abundance in such systems. We expect the results to be representative of the upper envelope of the distribution of neutral-gas-phase metallicities near redshift z=1.2. If these systems are high-N{HI} DLAs {e.g., 6E21 atoms/cm^2} they will have metallicities typical of those normally found in DLAs {e.g., one-tenth solar}. However, if they are low-N{HI} DLAs {e.g., 2E20 atoms/cm(2) }, they will have supersolar metallicities. Since these DLAs are selected on the basis of their extreme metal-line properties, analysis of their metallicities and dust-to-gas ratios will lead to strong constraints on the range of properties exhibited by DLA systems.

  17. 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

    2015-04-01

    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. PMID:25720308

  18. 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.

  19. 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

  20. Positron clouds within thunderstorms

    NASA Astrophysics Data System (ADS)

    Dwyer, Joseph R.; Smith, David M.; Hazelton, Bryna J.; Grefenstette, Brian W.; Kelley, Nicole A.; Lowell, Alexander W.; Schaal, Meagan M.; Rassoul, Hamid K.

    2015-08-01

    We report the observation of two isolated clouds of positrons inside an active thunderstorm. These observations were made by the Airborne Detector for Energetic Lightning Emissions (ADELE), an array of six gamma-ray detectors, which flew on a Gulfstream V jet aircraft through the top of an active thunderstorm in August 2009. ADELE recorded two 511 keV gamma-ray count rate enhancements, 35 s apart, each lasting approximately 0.2 s. The enhancements, which were approximately a factor of 12 above background, were both accompanied by electrical activity as measured by a flat-plate antenna on the underside of the aircraft. The energy spectra were consistent with a source mostly composed of positron annihilation gamma rays, with a prominent 511 keV line clearly visible in the data. Model fits to the data suggest that the aircraft was briefly immersed in clouds of positrons, more than a kilometre across. It is not clear how the positron clouds were created within the thunderstorm, but it is possible they were caused by the presence of the aircraft in the electrified environment.

  1. 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.

  2. 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.

  3. 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.

  4. The Upgrade of the Neutron Induced Positron Source NEPOMUC

    NASA Astrophysics Data System (ADS)

    Hugenschmidt, C.; Ceeh, H.; Gigl, T.; Lippert, F.; Piochacz, C.; Pikart, P.; Reiner, M.; Weber, J.; Zimnik, S.

    2013-06-01

    In summer 2012, the new NEutron induced POsitron Source MUniCh (NEPOMUC) was installed and put into operation at the research reactor FRM II. At NEPOMUC upgrade 80% 113Cd enriched Cd is used as neutron-gamma converter in order to ensure an operation time of 25 years. A structure of Pt foils inside the beam tube generates positrons by pair production. Moderated positrons leaving the Pt front foil are electrically extracted and magnetically guided to the outside of the reactor pool. The whole design, including Pt-foils, the electric lenses and the magnetic fields, has been improved in order to enhance both the intensity and the brightness of the positron beam. After adjusting the potentials and the magnetic guide and compensation fields an intensity of about 3·109 moderated positrons per second is expected. During the first start-up, the measured temperatures of about 90°C ensure a reliable operation of the positron source. Within this contribution the features and the status of NEPOMUC upgrade are elucidated. In addition, an overview of recent positron beam experiments and current developments at the spectrometers is given.

  5. 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

  6. 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. PMID:2621114

  7. 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

    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, (1)H 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

  8. 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

  9. 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.

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

    SciTech Connect

    Chen Zilu; Li Xiaoling; Liang Fupei

    2008-08-15

    Four Cd(II) and Zn(II) complexes with the in situ-generated ligand of 3-amino-1,2,4-triazolate (AmTAZ{sup -}) 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{sub 3}COO)] (1) presents a two-dimensional framework constructed from Zn(II) ions and {mu}{sub 3}-AmTAZ{sup -} ligands. A remarkable feature of [Zn{sub 4}(AmTAZ){sub 4}(SO{sub 4})(OH)(C{sub 2}O{sub 4}){sub 0.5}].2H{sub 2}O (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{sub 1}2{sub 1}2{sub 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{sub 4}] (4) behave as neutral {mu}{sub 2}-2,4-bridges to connect the two-dimensional CdSO{sub 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. - Graphical abstract: The solvothermal reactions of Cd(II) and Zn(II) salts bearing different anions with 5-amino-1H-1,2,4-triazole-3-carboxylic acid (AmTAZAc) produced four Cd(II) and Zn(II) MOFs with the in situ-generated 3-amino-1,2,4-triazolate (AmTAZ{sup -}) ion as ligand, which display different structural topologies and fluorescent properties. Display Omitted.

  11. 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

    2015-05-01

    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. PMID:25826776

  12. 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.

  13. 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. PMID:26735872

  14. 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.

  15. 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. PMID:26000741

  16. 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

  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. 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.

  19. Positrons at Jefferson Laboratory

    SciTech Connect

    Thomas, A W

    2009-09-01

    We review the compelling case for establishing a capability to accelerate positrons at Jefferson Lab. The potential appplications range from the study of two-photon exchange and deeply-virtual Compton scattering to exploiting the charge current weak interaction to probe the flavor structure of hadrons and nuclei. There are also fascinating ideas for using such a capability to discover new physics beyond the Standard Model of nuclear and particle physics.

  20. Positron fraction, electron and positron spectra measured by AMS-02

    NASA Astrophysics Data System (ADS)

    Pizzolotto, Cecilia

    2016-07-01

    A precise measurement by AMS-02 of the electron spectrum up to 700 GeV and of the positron spectrum and positron fraction in primary cosmic rays up 500 GeV are presented. The combined measurement of the cosmic-ray electron and positron energy spectra and fraction provide a unique tool to improve our understanding of the production, acceleration and propagation mechanism of cosmic rays.

  1. Preparation, characterization and solid-state emission of metal complex-cloisite nanohybrids (MC-C, M = Ru (II) and Cu (II)).

    PubMed

    Mallakpour, Shadpour; Dinari, Mohammad; Hadadzadeh, Hassan; Daryanavard, Marzieh; Roudi, Fereshteh

    2014-11-01

    The presence of Na(+) in the Cloisite Na(+) mineral allows modification of its interlayer space to achieve a better compatibility with the host matrix and ion-exchange with a cationic metal complex. The aim of this research is to prepare two new metal complex-Cloisite (MC-C) nanohybrids using reaction of Cloisite Na(+) with the cationic Ru (II) and Cu (II) complexes, [Ru (tpy) 2] (2+) and [Cu (Pir) (phen) (H2O) 2](+), in an aqueous solution for the first time. The X-ray diffraction (XRD) analysis of the modified clays has shown an increase in its interlayer distance as compared to the unmodified Cloisite Na(+). The positions of the basal reflections in the XRD patterns of the modified clays were shifted to a higher d value indicating the expansion in their interlayer distances. The field-emission scanning electron microscopy has shown a homogeneous morphology for the modified clays. The thermal behavior of these novel hybrid materials was also investigated by thermogravimetric analysis. The solid state fluorescence spectra of the modified clays have shown that both cationic complexes exhibit a significant fluorescence emission at room temperature when intercalated into Cloisite. PMID:25294183

  2. Two Dawson-templated three-dimensional metal-organic frameworks based on oxalate-bridged binuclear cobalt(II)/Nickel(II) SBUs and Bpy linkers.

    PubMed

    Zhao, Xinyu; Liang, Dadong; Liu, Shuxia; Sun, Chunyan; Cao, Ruige; Gao, Chaoying; Ren, Yuanhang; Su, Zhongmin

    2008-08-18

    The Dawson anion P 2W 18O 62 (6-) has been used as a noncoordinating polyoxoanion template for the construction of two metal-organic frameworks, namely, [M 2(bpy) 3(H 2O) 2(ox)][P 2W 18O 62]2(H 2-bpy). nH 2O (M = Co(II), n = 3 ( 1); M = Ni(II), n = 2 ( 2)) (bpy = 4,4'-bipyridine; ox = C 2O 4 (2-)). Single-crystal X-ray analysis reveals that both of the structures exhibit 3D host frameworks constructed from the oxalate-bridged binuclear superoctahedron secondary building units (SBUs) and bpy linkers and the voids of which are occupied by Dawson anions, guest bpy, and water molecules. Magnetic studies reveal that there are antiferromagnetic exchange interactions among the transition-metal centers in compounds 1 and 2. Furthermore, a compound 1-modified carbon paste electrode ( 1-CPE) displays good electrocatalytic activity toward the reduction of nitrite. PMID:18620386

  3. Three-dimensional nonlinear optical chromophores based on metal-to-ligand charge-transfer from ruthenium(II) or iron(II) centers.

    PubMed

    Coe, Benjamin J; Harris, James A; Brunschwig, Bruce S; Asselberghs, Inge; Clays, Koen; Garín, Javier; Orduna, Jesús

    2005-09-28

    In this article, we describe a series of new complex salts in which electron-rich transition-metal centers are coordinated to three electron-accepting N-methyl/aryl-2,2':4,4' ':4',4' ''-quaterpyridinium ligands. These complexes contain either Ru(II) or Fe(II) ions and have been characterized by using various techniques, including electronic absorption spectroscopy and cyclic voltammetry. Molecular quadratic nonlinear optical (NLO) responses beta have been determined by using hyper-Rayleigh scattering at 800 nm and also via Stark (electroabsorption) spectroscopic studies on the intense, visible d --> pi* metal-to-ligand charge-transfer bands. The latter experiments reveal that these putatively octupolar D(3) chromophores exhibit two substantial components of the beta tensor which are associated with transitions to dipolar excited states. Computations involving time-dependent density-functional theory and the finite field method serve to further illuminate the electronic structures and associated linear and NLO properties of the new chromophoric salts. PMID:16173774

  4. Comparative genotoxicity of 3-hydroxyanthranilic acid and anthranilic acid in the presence of a metal cofactor Cu (II) in vitro.

    PubMed

    Gadupudi, Gopi S; Chung, King-Thom

    2011-12-24

    Several clinical studies have reported that an increase in excretion of tryptophan metabolites 3-hydroxyanthranilic acid (3-OHAA), anthranilic acid (AA) and other metabolites in the urine of bladder cancer patients are implicated to play a role in the etiology of bladder cancer; however the mechanisms involved are unknown. The present study compares the genotoxicity of tryptophan metabolites AA and 3-OHAA to cause mutagenesis in vitro. The DNA damage effects of tryptophan metabolites were analyzed using plasmid relaxation assay performed with AA and 3-OHAA at various concentrations between 50μM and 400μM in the presence of plasmid DNA pSP-72. Both AA and 3-OHAA did not show any plasmid relaxation activity when tested alone. However, 3-OHAA in the presence of metal cofactor Cu (II) induced plasmid relaxation by causing nicks in the plasmid. This effect was not observed in the presence of other metal cofactors Fe (II) and Mn (III). Cu (II) at increasing concentrations between 5μM and 20μM and in the presence of 100μM 3-OHAA showed an apparent dose-response in causing DNA strand breaks. The Cu (II) mediated mutagenic activation of 3-OHAA was further investigated using Ames Salmonella/microsome mutagenicity assay with reactive oxygen species (ROS) sensitive tester strain Salmonella TA102. When 100μg of 3-OHAA per plate was incubated with Cu (II) a significant increase in TA102 revertants was observed with an increase in the concentration of Cu (II) from 2.5μg to 50μg. In contrast, AA with Cu (II) at such low concentration was unable to cause any significant increase in number of the TA102 revertants. This evidence for mutagenicity with only 3-OHAA and Cu (II) but not AA suggests the presence of hydroxyl group at ortho position to amino group in 3-OHAA structurally, is critical in reacting with Cu (II) to generate genotoxicity. PMID:22015263

  5. 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.

  6. 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

  7. The Lithium-, r- and s-Enhanced Metal-Poor Giant HK-II 17435-00532

    SciTech Connect

    Roederer, Ian U.; Prieto, Carlos Allende; Sneden, Christopher; Frebel, Anna; Shetrone, Matthew; Rhee, Jaehyon; Gallino, Roberto; Bisterzo, Sara; Beers, Timothy C.; Cowan, John J.

    2008-04-06

    We present the first detailed abundance analysis of the metal-poor giant HK-II 17435-00532. This star was observed as part of the University of Texas Long-Term Chemical Abundances of Stars in the Halo (CASH) Project. A spectrum was obtained with the High Resolution Spectrograph (HRS) on the Hobby-Eberly Telescope with a resolving power of R{approx}15000. Our analysis reveals that this star may be located on the red giant branch, red horizontal branch, or early asymptotic giant branch. We find that this metal-poor ([Fe/H] = -2.2) star has an unusually high lithium abundance (log{epsilon}(Li) = +2.1), mild carbon ([C/Fe] = +0.7) and sodium ([Na/Fe] = +0.6) enhancement, as well as enhancement of both s-process ([Ba/Fe] = +0.8) and r-process ([Eu/Fe] = +0.5) material. The high Li abundance can be explained by self-enrichment through extra mixing mechanisms that connect the convective envelope with the outer regions of the H-burning shell. If so, HK-II 17435-00532 is the most metal-poor starin which this short-lived phase of Li enrichment has been observed. The r- and s-process material was not produced in this star but was either present in the gas from which HK-II 17435-00532 formed or was transferred to it from a more massive binary companion. Despite the current non-detection of radial velocity variations (over a time span of {approx}180 days), it is possible that HK-II 17435-00532 is in a long-period binary system, similar to other stars with both r and s enrichment.

  8. 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.

  9. 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.

  10. Colorimetric filtrations of metal chelate precipitations for the quantitative determination of nickel(II) and lead(II).

    PubMed

    Feng, Liang; Zhang, Yue; Wen, Liying; Chen, Liang; Shen, Zheng; Guan, Yafeng

    2011-10-21

    A colorimetric filtration method has been developed for the highly selective and sensitive determination of Ni(2+) and Pb(2+) ions. Determinations of Ni(2+) and Pb(2+) follow the filtration using nioxime (1,2-cyclohexanedione dioxime) and rhodizonic acid disodium salt, respectively, as colorimetric reagents. Different from regular instrumentation techniques, the metal chelate precipitations are continuously pumped into a home-made flow cell at a constant flow rate, and filtered by a cellulose acetate/nitrate membrane. The color changes of the membrane are imaged using a conventional flatbed scanner, and digitized. The special selection of individual channels in the red, green, and blue channels of the images filters the influences of coexisting ions and provides a highly selective detection of Ni(2+) and Pb(2+) cations. The linear relationship between the colorimetric response of the chosen channel and Ni(2+) or Pb(2+) concentrations indicates a quantitative detection. The detection limit for Pb(2+) is 3 μM (almost half of the Chinese wastewater discharge standard concentration), and is well below the nM level (94 nM) for Ni(2+) (a quarter of the WHO drinking water safe-exposure standard for Ni(2+)). The determinations take five to ten minutes. No shelf life issue exists because the chelating indicators react with metal directly without any pre-immobilizations. PMID:21860847

  11. The effect of pH and temperature on the sorption of zinc(II), cadmium(II), and aluminum(III) onto new metal-ligand complexes of sporopollenin

    SciTech Connect

    Pehlivan, E.; Ersoz, M.; Pehlivan, M.; Yildiz, S.; Duncan, H.J.

    1995-03-15

    Sorption of metal ions from aqueous solution onto metal-ligand complexes of sporopollenin derivatives has been measured as a function of pH at several temperatures between 20 and 50 C. Novel metal-ligand exchange resins possessing oxime and carboxylic acid side arm functionality were prepared through the reaction of diaminosporopollenin with dichloro-antiglyoxime and bromoacetic acid. The pH dependencies and sorption isotherms of various metal ions such as Zn (II), Cd(II), and Al(III) on the resin were investigated from aqueous solution. The sorption behavior of these metal-ligand complexes of sporopollenin derivatives and the possibilities of selectively removing and recovering heavy metals are explained on the basis of their chemical nature and complex properties and the results are interpreted in terms of the variations of pH.

  12. 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

  13. 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.

  14. Nonlinear positron acoustic solitary waves

    SciTech Connect

    Tribeche, Mouloud; Aoutou, Kamel; Younsi, Smain; Amour, Rabia

    2009-07-15

    The problem of nonlinear positron acoustic solitary waves involving the dynamics of mobile cold positrons is addressed. A theoretical work is presented to show their existence and possible realization in a simple four-component plasma model. The results should be useful for the understanding of the localized structures that may occur in space and laboratory plasmas as new sources of cold positrons are now well developed.

  15. Positron Implantation Profile in Kapton

    NASA Astrophysics Data System (ADS)

    Dryzek, J.; Dryzek, E.

    2006-11-01

    The discussion presented in the paper focuses on processes accompanying positron implantation in condensed matter. They finally constitute the positron implantation profile which generally does not exhibit the exponential behavior as it is concluded from the Monte Carlo simulation made using the EGSnrc 4.0 code. The simulation was performed for the kapton and two commonly used positron sources 22Na and 68Ge\\68Ga. New formula for the implantation profile was proposed.

  16. 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

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

    DOE PAGESBeta

    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 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

  18. Metalation of cyclic pseudopeptidic thiosulfinates with Ni(II) and Zn(II) after ring opening: a mechanistic investigation.

    PubMed

    Galardon, Erwan; Bourles, Emilie; Artaud, Isabelle; Daran, Jean-Claude; Roussel, Pascal; Tomas, Alain

    2007-05-28

    Thiosulfinates are an emerging class of oxidized sulfur species that are frequently supposed to be involved in biochemical processes. Reaction of 12- and 10-membered ring pseudopeptidic thiosulfinates 1a (4,4,7,7-tetramethyl-1,3,4,7,8,10-hexahydro-5,6,1,10-benzodithiadiazacyclododecine-2,9-dione 5-oxide) and 1b (3,3,6,6-tetramethyl-1,8-dihydro-4,5,1,8-benzodithiadiazecine-2,7(3H,6H)-dione 4-oxide) with a Ni(II) salt leads after ring cleavage under alkaline conditions to the isolation of diamidato/thiolato/sulfinato complexes. These two thiolato/sulfinato complexes of nickel, which can also be prepared by dioxygen oxidation of the parent diamidato/dithiolato complexes, were characterized by X-ray crystallography. They show a square-planar geometry with a S-bonded sulfinato ligand. A similar reaction between 1b and a Zn(II) salt leads to a thiolato/sulfinato complex with an O-bonded sulfinate via the intermediate formation of a mixed thiolato/sulfinic ester. On the basis of 1H NMR, IR, and mass analyses, the sulfinic ester in the intermediate is proposed to be O-bonded to the zinc center. Then, an in-depth study of the cleavage of these thiosulfinates with the oxyanions RO- and HO- was performed. This led, after trapping of the open species with CH3I, to the identification of three polyfunctionalized products containing a methyl thioether, with either an isothiazolidin-3-one S-oxide, a methyl sulfone, or a methyl sulfinic ester. All of these products arise from a selective nucleophilic attack at the sulfinyl sulfur, promoted either directly by RO- or HO- or by an internal peptidic nitrogen of the thiosulfinate after deprotonation with RO- or HO-. PMID:17465540

  19. 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.

  20. The ATLAS Positron Experiment -- APEX

    SciTech Connect

    Ahmad, I.; Back, B.B.; Betts, R.R.; Dunford, R.; Kutschera, W.; Rhein, M.D.; Schiffer, J.P.; Wilt, P.; Wuosmaa, A.; Austin, S.M.; Kashy, E.; Winfield, J.S.; Yurkon, J.E.; Bazin, D.; Calaprice, F.P.; Young, A.; Chan, K.C.; Chisti, A.; Chowhury, P.; Greenberg, J.S.; Kaloskamis, N.; Lister, C.J.; Fox, J.D.; Roa, E.; Freedman, S.; Maier, M.R.; Freer, M.; Gazes, S.; Hallin, A.L.; Liu, M.; Happ, T.; Perera, A.; Wolfs, F.L.H.; Trainor, T.; Wolanski, M. |

    1994-03-01

    APEX -- the ATLAS Positron Experiment -- is designed to measure electrons and positrons emitted in heavy-ion collisions. Its scientific goal is to gain insight into the puzzling positron-line phenomena observed at the GSI Darmstadt. It is in operation at the ATLAS accelerator at Argonne National Lab. The assembly of the apparatus is finished and beginning 1993 the first positrons produced in heavy-ion collisions were observed. The first full scale experiment was carried out in December 1993, and the data are currently being analyzed. In this paper, the principles of operation are explained and a status report on the experiment is given.

  1. Metal-poor dwarf galaxies in the SIGRID galaxy sample. I. H II region observations and chemical abundances

    SciTech Connect

    Nicholls, David C.; Dopita, Michael A.; Sutherland, Ralph S.; Jerjen, Helmut; Kewley, Lisa J.; Basurah, Hassan

    2014-05-10

    In this paper we present the results of observations of 17 H II regions in thirteen galaxies from the SIGRID sample of isolated gas-rich irregular dwarf galaxies. The spectra of all but one of the galaxies exhibit the auroral [O III] 4363 Å line, from which we calculate the electron temperature, T{sub e} , and gas-phase oxygen abundance. Five of the objects are blue compact dwarf galaxies, of which four have not previously been analyzed spectroscopically. We include one unusual galaxy which exhibits no evidence of the [N II] λλ 6548,6584 Å lines, suggesting a particularly low metallicity (< Z {sub ☉}/30). We compare the electron temperature based abundances with those derived using eight of the new strong-line diagnostics presented by Dopita et al. Using a method derived from first principles for calculating total oxygen abundance, we show that the discrepancy between the T{sub e} -based and strong-line gas-phase abundances have now been reduced to within ∼0.07 dex. The chemical abundances are consistent with what is expected from the luminosity-metallicity relation. We derive estimates of the electron densities and find them to be between ∼5 and ∼100 cm{sup –3}. We find no evidence for a nitrogen plateau for objects in this sample with metallicities 0.5 > Z {sub ☉} > 0.15.

  2. 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 Central

    Hashem, Mohamed

    2007-01-01

    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

  3. 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.

  4. Positron sensing of distribution of defects in depth materials

    NASA Astrophysics Data System (ADS)

    Kupchishin, A. I.; Kupchishin, A. A.; Voronova, N. A.; Kirdyashkin, V. I.

    2016-02-01

    It was developed a non-destructive method of positron sensing, which allows to determine the distribution of defects in the depth of the material. From the analysis we can conclude that the angular distribution curves of annihilation photons (well as and on the characteristics in experiments on the lifetime, 3γ - angular correlation, Doppler effect) is influenced by three main factors: a) The distribution of defects in the depth of the material, their dimensions as well as parameters of the interaction of positrons with defects. With increasing the concentration of defects the intensity Jγ(a, ξ) varies more; b) Modification of the energy spectrum of slow positrons due to the influence of defects, wherein the spectrum of positrons becomes softer, and the average energy of the positron annihilation is reduced; c) Deformation of the momentum distribution of the electrons in the region of defect. The energy spectrum of electrons is also becomes softer, and the average energy of the electrons (on which positrons annihilate) is less. The experimentally were measured spectra of photons in the zone of annihilation and were calculated the distribution of defects in depth for a number of metals.

  5. 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.

  6. 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.

  7. 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.

  8. RHAPSODY-G simulations II - Baryonic growth and metal enrichment in massive galaxy clusters

    NASA Astrophysics Data System (ADS)

    Martizzi, Davide; Hahn, Oliver; Wu, Hao-Yi; Evrard, August E.; Teyssier, Romain; Wechsler, Risa H.

    2016-04-01

    We study the evolution of the stellar component and the metallicity of both the intracluster medium and of stars in massive (Mvir ≈ 6 × 1014 M⊙/h) simulated galaxy clusters from the RHAPSODY-G suite in detail and compare them to observational results. The simulations were performed with the AMR code RAMSES and include the effect of AGN feedback at the sub-grid level. AGN feedback is required to produce realistic galaxy and cluster properties and plays a role in mixing material in the central regions and regulating star formation in the central galaxy. In both our low and high resolution runs with fiducial stellar yields, we find that stellar and ICM metallicities are a factor of two lower than in observations. We find that cool core clusters exhibit steeper metallicity gradients than non-cool core clusters, in qualitative agreement with observations. We verify that the ICM metallicities measured in the simulation can be explained by a simple "regulator" model in which the metallicity is set by a balance of stellar yield and gas accretion. It is plausible that a combination of higher resolution and higher metal yield in AMR simulation would allow the metallicity of simulated clusters to match observed values; however this hypothesis needs to be tested with future simulations. Comparison to recent literature highlights that results concerning the metallicity of clusters and cluster galaxies might depend sensitively on the scheme chosen to solve the hydrodynamics.

  9. RHAPSODY-G simulations - II. Baryonic growth and metal enrichment in massive galaxy clusters

    NASA Astrophysics Data System (ADS)

    Martizzi, Davide; Hahn, Oliver; Wu, Hao-Yi; Evrard, August E.; Teyssier, Romain; Wechsler, Risa H.

    2016-07-01

    We study the evolution of the stellar component and the metallicity of both the intracluster medium and of stars in massive (Mvir ≈ 6 × 1014 M⊙ h-1) simulated galaxy clusters from the RHAPSODY-G suite in detail and compare them to observational results. The simulations were performed with the AMR code RAMSES and include the effect of active galactic nucleus (AGN) feedback at the subgrid level. AGN feedback is required to produce realistic galaxy and cluster properties and plays a role in mixing material in the central regions and regulating star formation in the central galaxy. In both our low- and high-resolution runs with fiducial stellar yields, we find that stellar and ICM metallicities are a factor of 2 lower than in observations. We find that cool core clusters exhibit steeper metallicity gradients than non-cool core clusters, in qualitative agreement with observations. We verify that the ICM metallicities measured in the simulation can be explained by a simple `regulator' model in which the metallicity is set by a balance of stellar yield and gas accretion. It is plausible that a combination of higher resolution and higher metal yield in AMR simulation would allow the metallicity of simulated clusters to match observed values; however, this hypothesis needs to be tested with future simulations. Comparison to recent literature highlights that results concerning the metallicity of clusters and cluster galaxies might depend sensitively on the scheme chosen to solve the hydrodynamics.

  10. 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

    2016-01-01

    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

  11. 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. PMID:23435202

  12. Global Properties of M31's Stellar Halo from the SPLASH Survey. II. Metallicity Profile

    NASA Astrophysics Data System (ADS)

    Gilbert, Karoline M.; Kalirai, Jason S.; Guhathakurta, Puragra; Beaton, Rachael L.; Geha, Marla C.; Kirby, Evan N.; Majewski, Steven R.; Patterson, Richard J.; Tollerud, Erik J.; 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-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. The data presented herein were obtained at the W. M. Keck Observatory, which is operated as a scientific partnership among the California Institute of Technology, the University of California and the National Aeronautics and Space Administration. The Observatory was made possible by the generous financial support of the W. M. Keck Foundation.

  13. 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.

  14. 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

    2015-10-01

    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. PMID:26264140

  15. 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.

  16. A curious interplay in the films of N-heterocyclic carbene PtII complexes upon deposition of alkali metals

    NASA Astrophysics Data System (ADS)

    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.

    2016-05-01

    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.

  17. 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.

  18. 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

  19. 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

    2016-01-01

    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. PMID:27151364

  20. Multi-component synthesis of 2-amino-6-(alkyllthio)pyridine-3,5-dicarbonitriles using Zn(II) and Cd(II) metal-organic frameworks (MOFs) under solvent-free conditions

    PubMed Central

    Thimmaiah, Muralidhara; Li, Peng; Regati, Sridhar; Chen, Banglin; Zhao, John Cong-Gui

    2012-01-01

    Multi-component synthesis 2-amino-3,5-dicarbonitrile-6-thio-pyridines has been developed by using the reaction of aldehydes, malononitrile, and thiophenols in the presence of a Zn (II) or a Cd(II) metal-organic framework (MOF) as the heterogeneous catalyst. This protocol tolerates different functional groups on the substrates and does not require the use of any organic solvent. Moreover, the Zn(II) and Cd (II) MOF catalysts can be recovered and reused for a number of runs without loss of activity. PMID:23002309

  1. Positron production within our atmosphere

    NASA Astrophysics Data System (ADS)

    Dwyer, Joseph

    2016-04-01

    Positrons are commonly produced within our atmosphere by cosmic rays and the decay radioactive isotopes. Energetic positrons are also produced by pair production from the gamma rays generated by relativistic runaway electrons. Indeed, such positrons have been detected in Terrestrial Electron Beams (TEBs) in the inner magnetosphere by Fermi/GBM. In addition, positrons play an important role in relativistic feedback discharges (also known as dark lightning). Relativistic feedback models suggest that these discharges may be responsible for Terrestrial Gamma-ray Flashes (TGFs) and some gamma-ray glows. When producing TGFs, relativistic feedback discharges may generate large, lightning-like currents with current moments reaching hundreds of kA-km. In addition, relativistic feedback discharges also may limit the electric field that is possible in our atmosphere, affecting other mechanisms for generating runaway electrons. It is interesting that positrons, often thought of as exotic particles, may play an important role in thunderstorm processes. In this presentation, the role of positrons in high-energy atmospheric physics will be discussed. The unusual observation of positron clouds inside a thunderstorm by the ADELE instrument on an NCAR/NSF Gulfstream V aircraft will also be described. These observations illustrate that we still have much to learn about positron production within our atmosphere.

  2. 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.

  3. 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)

  4. Portable Positron Measurement System (PPMS)

    ScienceCinema

    None

    2013-05-28

    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.

  5. Plasma Wakefield Acceleration of Positrons

    NASA Astrophysics Data System (ADS)

    Gessner, Spencer

    2016-03-01

    Recent particle beam and laser-driven plasma wakefield experiments have produced high-quality electron beams accelerated by a GeV or more in less than a meter. Efforts are underway to put these beams to work as sources for free-electron lasers. By contrast, little work has been done to demonstrate the tractability of plasma wakefield acceleration (PWFA) of positrons beams. The reasons for this are threefold: 1) positron beams are only useful for high-energy physics experiments, whereas electron beams are also useful as light sources, 2) there is a dearth of positron sources for PWFA experiments, and 3) the dynamics of accelerating positron beams in plasma is fundamentally different than that of electron beams. This talk will focus on the physics of accelerating positrons in plasma and contrast the dynamics of electron and positron beam-driven nonlinear plasma wakes. We describe recent experiments at the FACET test facility at SLAC National Accelerator Laboratory that for the first time demonstrate high-gradient acceleration of a positron beams in plasma. We also discuss an alternative acceleration technique called hollow channel acceleration that aims to symmetrize the dynamics of electron and positron beam-driven wakes.

  6. Positron research at the University of Texas at Austin

    NASA Astrophysics Data System (ADS)

    Goktepeli, Sinan

    The objective of the research presented in this dissertation is to advance the applications of positron annihilation research. An intense positron beam facility was designed and constructed, and a method was developed to better analyze the defect structure of solids. The Texas Reactor-based Intense Positron beam facility (TRIP) was designed to provide a monoenergetic/monodirectional beam of at least 108 e +/sec on a sample. This increase in beam intensity will enhance many positron research techniques both in atomic physics and materials science. The TRIP facility, the result of a collaboration between UT Austin and UT Arlington, is being developed around the concept of multiple scattering of positrons from solid krypton. A large area copper source will be irradiated in a beam port of the 1 MW TRIGA Mark-II research reactor at UT Austin. The source will form the bottom face of a cube with the remaining faces made of tungsten. All surfaces will be cooled down to 22 K and coated with krypton. The top face of the cube has a 1 cm diameter hole to allow for the passage of positrons. The fast beta particles emitted from the β+ decay of 64Cu will be moderated while passing through the krypton. The non- moderated positrons will lose their energy while interacting with the remaining walls. The positrons will be removed from the box by an electric field and electrostatically delivered to the sample. The work on the TRIP facility is ongoing. The results of early measurements at UT Arlington have shown that the facility will be able to achieve its goals. The method developed to better analyze the positron depth profiling (PDP) experiments uses the difference spectra of the measured Doppler broadened annihilation peaks. The difference spectra, which are obtained by subtracting the bulk peak shape from the peaks recorded for each incident positron energy, enhance the differences of the observed peaks, while removing the bulk annihilation term from the multi-state annihilation

  7. 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

    2016-08-01

    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

  8. Positron Emission Tomography.

    PubMed

    Lameka, Katherine; Farwell, Michael D; Ichise, Masanori

    2016-01-01

    Positron emission tomography (PET) is a minimally invasive imaging procedure with a wide range of clinical and research applications. PET allows for the three-dimensional mapping of administered positron-emitting radiopharmaceuticals such as (18)F-fluorodeoxyglucose (for imaging glucose metabolism). PET enables the study of biologic function in both health and disease, in contrast to magnetic resonance imaging (MRI) and computed tomography (CT), that are more suited to study a body's morphologic changes, although functional MRI can also be used to study certain brain functions by measuring blood flow changes during task performance. This chapter first provides an overview of the basic physics principles and instrumentation behind PET methodology, with an introduction to the merits of merging functional PET imaging with anatomic CT or MRI imaging. We then focus on clinical neurologic disorders, and reference research on relevant PET radiopharmaceuticals when applicable. We then provide an overview of PET scan interpretation and findings in several specific neurologic disorders such as dementias, epilepsy, movement disorders, infection, cerebrovascular disorders, and brain tumors. PMID:27432667

  9. Positron driven plasma wakefields

    NASA Astrophysics Data System (ADS)

    Pinkerton, S.; Shi, Y.; Huang, C.; An, W.; Mori, W. B.; Muggli, P.

    2010-11-01

    The LHC is producing high-energy, high-charge proton bunches (1e11 protons at 1-7 TeV each) that could be used to accelerate ``witness'' electron bunches to TeV range eneregies via a plasma wakefield accelerator (PWFA). Simulations [1] suggest that a proton ``drive'' bunch is able to excite large wakefields if the bunch size is on the order of 100 μm; however, the LHC paramters are currently on the 1 cm scale. SLAC'S FACET is able to supply positorn bunchs with the ideal parameters for driving a PWFA. Although at lower energy (2e10 positrons at 23 GeV each), initial simiulations in QuickPIC show that the physics of a positron drive bunch is very similar to that of a proton drive bunch. Differences in the physics arise from the mass difference: slower dephasing but faster transverse bunch evolution. Other considerations include driver head erosion and purity of the wakefield ion column. The physics of positive drivers for PWFA and the viability of this scheme for future high-energy colliders will be investigated at SLAC's FACET.[4pt] [1] Caldwell, et al. Nature Physics 5, 363 (2009).[0pt] [2] C.H. Huang, et al., J. Comp. Phys., 217(2), 658, (2006).

  10. Electrokinetic remediation. II. Amphoteric metals and enhancement with a weak acid

    SciTech Connect

    Wilson, D.J.; Rodriguez-Maroto, J.M.; Gomez-Lahoz, C.

    1995-09-01

    A one-dimensional model is developed for the electrokinetic treatment of aquifers contaminated with an ionic salt. Electrokinetic removal of amphoteric metals such as zinc and lead is simulated. The use of a weak acid (acetic acid) to neutralize a portion of the OH{sup {minus}} generated electrolytically in the cathode compartment is explored in connection with the electrokinetic removal of nonamphoteric metals such as copper and cadmium.

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

    NASA Astrophysics Data System (ADS)

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

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

  12. Mixed ligand two dimensional Cd(ii)/Ni(ii) metal organic frameworks containing dicarboxylate and tripodal N-donor ligands: Cd(ii) MOF is an efficient luminescent sensor for detection of picric acid in aqueous media.

    PubMed

    Rachuri, Yadagiri; Parmar, Bhavesh; Bisht, Kamal Kumar; Suresh, Eringathodi

    2016-05-01

    Two dimensional metal organic frameworks (MOFs) [Cd(5-BrIP)(TIB)]n () and [Ni2(5-BrIP)2(TIB)2]n (), involving the aromatic polycarboxylate ligand 5-bromo isophthalic acid (H2BrIP), flexible tripodal ligand 1,3,5-tris(imidazol-1-ylmethyl)benzene (TIB) and Cd(ii)/Ni(ii) metal nodes have been synthesized by different methods. These compounds were characterized by various analytical methods, and variable temperature X-ray diffraction data showed thermal stability of both MOFs up to 350 °C. Phase purity as well as water stability of the MOFs were established by powder X-ray diffraction, and the structural diversity of the compounds were investigated by single-crystal X-ray diffraction. Both the MOFs are mixed ligand 2D nets, and the topology of the network can be described as a binodal 3,5-c connected net with 3,5L2 topology having the point symbol {4(2)·6(7)·8}{4(2)·6}. Sensing of picric acid [2,4,6-trinitrophenol, TNP] by luminescence quenching among a large range of nitroanalytes in aqueous phase by the Cd(ii) luminescent MOF (LMOF) were been investigated. Structural studies on 1 : 1 co-crystals () of TIB and TNP were carried out. The selective and sensitive fluorescence quenching response of towards electron-deficient TNP over other nitro analytes in aqueous phase was demonstrated by fluorescence quenching titration. Concomitant occurrence of electron transfer/energy transfer processes and electrostatic interaction favours the selective sensing of TNP. A Cd(ii) LMOF ()-coated paper strip that we developed demonstrated fast and selective response to TNP, by the complete quenching of the blue fluorescence upon excitation of the paper strip at 365 nm radiation in its presence. PMID:27067118

  13. 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}ȯ )≈ 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.

  14. 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).

  15. 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).

  16. 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. PMID:23824307

  17. 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

  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. 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. PMID:20810212

  20. The LAMOST Spectroscopic Survey of Star Clusters in M31. II. Metallicities, Ages, and Masses

    NASA Astrophysics Data System (ADS)

    Chen, Bingqiu; Liu, Xiaowei; Xiang, Maosheng; Yuan, Haibo; Huang, Yang; Shi, Jianrong; Fan, Zhou; Huo, Zhiying; Wang, Chun; Ren, Juanjuan; Tian, Zhijia; Zhang, Huawei; Liu, Gaochao; Cao, Zihuang; Zhang, Yong; Hou, Yonghui; Wang, Yuefei

    2016-08-01

    We select from Paper I a sample of 306 massive star clusters observed with the Large Sky Area Multi–Object Fibre Spectroscopic Telescope (LAMOST) in the vicinity fields of M31 and M33, and determine their metallicities, ages, and masses. Metallicities and ages are estimated by fitting the observed integrated spectra with stellar synthesis population (SSP) models with a pixel–to–pixel spectral fitting technique. Ages for most young clusters are also derived by fitting the multi–band photometric measurements with model spectral energy distributions (SEDs). The estimated cluster ages span a wide range, from several million years to the age of the universe. The numbers of clusters younger and older than 1 Gyr are, respectively, 46 and 260. With ages and metallicities determined, cluster masses are then estimated by comparing the multi–band photometric measurements with SSP model SEDs. The derived masses range from ∼ {10}3 to ∼ {10}7 M ⊙, peaking at ∼ {10}4.3 and ∼ {10}5.7 M ⊙ for young (\\lt 1 Gyr) and old (\\gt 1 Gyr) clusters, respectively. Our estimated metallicities, ages, and masses are in good agreement with available literature values. Old clusters richer than [Fe/H] ∼ ‑0.7 dex have a wide range of ages. Those poorer than [Fe/H] ∼ ‑0.7 dex seem to be composed of two groups, as previously found for Galactic globular clusters—one of the oldest ages with all values of metallicity down to ∼ -2 dex and another with metallicity increasing with decreasing age. The old clusters in the inner disk of M 31 (0–30 kpc) show a clear metallicity gradient measured at ‑0.038 ± 0.023 dex kpc‑1.

  1. Deformation in metals after low temperature irradiation: Part II - Irradiation hardening, strain hardening, and stress ratios

    SciTech Connect

    Byun, Thak Sang; Li, Meimei

    2008-03-01

    Effects of irradiation at temperatures 200oC on tensile stress parameters are analyzed for dozens of bcc, fcc, and hcp pure metals and alloys, focusing on irradiation hardening, strain hardening, and relationships between the true stress parameters. Similar irradiation-hardening rates are observed for all the metals irrespective of crystal type; typically, the irradiation-hardening rates are large, in the range 100 - 1000 GPa/dpa, at the lowest dose of <0.0001 dpa and decrease with dose to a few tens of MPa/dpa or less at about 10 dpa. However, average irradiation-hardening rates over the dose range of 0 dpa − (the dose to plastic instability at yield) are considerably lower for stainless steels due to their high uniform ductility. It is shown that whereas low temperature irradiation increases the yield stress, it does not significantly change the strain-hardening rate of metallic materials; it decreases the fracture stress only when non-ductile failure occurs. Such dose independence in strain hardening behavior results in strong linear relationships between the true stress parameters. Average ratios of plastic instability stress to unirradiated yield stress are about 1.4, 3.9, and 1.3 for bcc metals (and precipitation hardened IN718 alloy), annealed fcc metals (and pure Zr), and Zr-4 alloy, respectively. Ratios of fracture stress to plastic instability stress are calculated to be 2.2, 1.7, and 2.1, respectively. Comparison of these values confirms that the annealed fcc metals and other soft metals have larger uniform ductility but smaller necking ductility when compared to other materials.

  2. Waste ashes for use in agricultural production: II. Contents of minor and trace metals.

    PubMed

    Zhang, Fu-Shen; Yamasaki, S; Kimura, K

    2002-03-01

    The present study was carried out to examine the contents of 18 minor and trace metals in five typical municipal waste ashes in Japan. In the waste ashes, Li, Ga, Rb, Y, Zr had relatively higher concentrations, approximately 5-300 mg kg(-1), the remaining metal concentrations were generally approximately 0.05-20 mg kg(-1). A comparison of the metal concentrations in the waste ashes and in Japanese agricultural soils indicated that the ratios for Ga, Mo, Ag, Sb, W, Bi between sewage sludge ash (SSA) and the soils were approximately 10-100 and for the remaining metals approximately 0.2-2; the ratios between food scrap ash (FSA), animal waste ash (AWA), horticulture waste ash (HWA) and incinerator bottom ash (IBA) and the soils were approximately 0.2-5. Furthermore, an overall evaluation on the waste ashes was also carried out using factor analysis with the addition of the other 21 elements examined in a companion paper. In the waste ashes, the major nutrient elements and heavy metals were mainly described by four factors: factors 1 and 2 explained the main information of the minor and trace metals while factors 3 and 4 explained that of the major nutrient elements. Factor 2 in the score plots could be used to evaluate the potential risk of the waste ashes to agricultural soils. Of the five types of waste ashes, SSA and IBA were abundant with minor and trace metals; AWA was relatively abundant with major nutrient elements especially for K; FSA was relatively abundant with major nutrient elements except for K, while HWA was not abundant with either of them. PMID:11886086

  3. The LAMOST Spectroscopic Survey of Star Clusters in M31. II. Metallicities, Ages, and Masses

    NASA Astrophysics Data System (ADS)

    Chen, Bingqiu; Liu, Xiaowei; Xiang, Maosheng; Yuan, Haibo; Huang, Yang; Shi, Jianrong; Fan, Zhou; Huo, Zhiying; Wang, Chun; Ren, Juanjuan; Tian, Zhijia; Zhang, Huawei; Liu, Gaochao; Cao, Zihuang; Zhang, Yong; Hou, Yonghui; Wang, Yuefei

    2016-08-01

    We select from Paper I a sample of 306 massive star clusters observed with the Large Sky Area Multi–Object Fibre Spectroscopic Telescope (LAMOST) in the vicinity fields of M31 and M33, and determine their metallicities, ages, and masses. Metallicities and ages are estimated by fitting the observed integrated spectra with stellar synthesis population (SSP) models with a pixel–to–pixel spectral fitting technique. Ages for most young clusters are also derived by fitting the multi–band photometric measurements with model spectral energy distributions (SEDs). The estimated cluster ages span a wide range, from several million years to the age of the universe. The numbers of clusters younger and older than 1 Gyr are, respectively, 46 and 260. With ages and metallicities determined, cluster masses are then estimated by comparing the multi–band photometric measurements with SSP model SEDs. The derived masses range from ˜ {10}3 to ˜ {10}7 M ⊙, peaking at ˜ {10}4.3 and ˜ {10}5.7 M ⊙ for young (\\lt 1 Gyr) and old (\\gt 1 Gyr) clusters, respectively. Our estimated metallicities, ages, and masses are in good agreement with available literature values. Old clusters richer than [Fe/H] ˜ ‑0.7 dex have a wide range of ages. Those poorer than [Fe/H] ˜ ‑0.7 dex seem to be composed of two groups, as previously found for Galactic globular clusters—one of the oldest ages with all values of metallicity down to ˜ -2 dex and another with metallicity increasing with decreasing age. The old clusters in the inner disk of M 31 (0–30 kpc) show a clear metallicity gradient measured at ‑0.038 ± 0.023 dex kpc‑1.

  4. Positron-acoustic solitary waves in a magnetized electron-positron-ion plasma with nonthermal electrons and positrons

    NASA Astrophysics Data System (ADS)

    Rahman, M. M.; Alam, M. S.; Mamun, A. A.

    2015-05-01

    Obliquely propagating positron-acoustic solitary waves (PASWs) in a magnetized electron-positron-ion plasma (containing nonthermal hot positrons and electrons, inertial cold positrons, and immobile positive ions) are precisely investigated by deriving the Zakharov-Kuznetsov equation. It is found that the characteristics of the PASWs are significantly modified by the effects of external magnetic field, obliqueness, nonthermality of hot positrons and electrons, temperature ratio of hot positrons and electrons, and respective number densities of hot positrons and electrons. The findings of our results can be employed in understanding the localized electrostatic structures and the characteristics of PASWs in various space and laboratory plasmas.

  5. 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

  6. 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.

  7. 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. PMID:26277654

  8. 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.

  9. 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). PMID:22469431

  10. Non-redox metal ions can promote Wacker-type oxidations even better than copper(II): a new opportunity in catalyst design.

    PubMed

    Qin, Shuhao; Dong, Lei; Chen, Zhuqi; Zhang, Sicheng; Yin, Guochuan

    2015-10-28

    In Wacker oxidation and inspired Pd(ii)/Cu(ii)-catalyzed C-H activations, copper(ii) is believed to serve in re-oxidizing of Pd(0) in the catalytic cycle. Herein we report that non-redox metal ions like Sc(iii) can promote Wacker-type oxidations even better than Cu(ii); both Sc(iii) and Cu(ii) can greatly promote Pd(ii)-catalyzed olefin isomerization in which the redox properties of Cu(ii) are not essential, indicating that the Lewis acid properties of Cu(ii) can play a significant role in Pd(ii)-catalyzed C-H activations in addition to its redox properties. Characterization of catalysts using UV-Vis and NMR indicated that adding Sc(OTf)3 to the acetonitrile solution of Pd(OAc)2 generates a new Pd(ii)/Sc(iii) bimetallic complex having a diacetate bridge which serves as the key active species for Wacker-type oxidation and olefin isomerization. Linkage of trivalent Sc(iii) to the Pd(ii) species makes it more electron-deficient, thus facilitating the coordination of olefin to the Pd(ii) cation. Due to the improved electron transfer from olefin to the Pd(ii) cation, it benefits the nucleophilic attack of water on the olefinic double bond, leading to efficient olefin oxidation. The presence of excess Sc(iii) prevents the palladium(0) black formation, which has been rationalized by the formation of the Sc(iii)H-Pd(ii) intermediate. This intermediate inhibits the reductive elimination of the H-Pd(ii) bond, and facilitates the oxygen insertion to form the HOO-Pd(ii) intermediate, and thus avoids the formation of the inactive palladium(0) black. The Lewis acid promoted Wacker-type oxidation and olefin isomerization demonstrated here may open up a new opportunity in catalyst design for versatile C-H activations. PMID:26390300

  11. Crystal growth, characterization and theoretical studies of alkaline earth metal-doped tetrakis(thiourea)nickel(II) chloride.

    PubMed

    Agilandeshwari, R; Muthu, K; Meenatchi, V; Meena, K; Rajasekar, M; Aditya Prasad, A; Meenakshisundaram, S P

    2015-02-25

    The influence of Sr(II)-doping on the properties of tetrakis(thiourea)nickel(II) chloride (TTNC) has been described. The reduction in the intensity observed in powder X-ray diffraction of doped specimen and slight shifts in vibrational frequencies of doped specimens confirm the lattice stress as a result of doping. Surface morphological changes due to doping of the Sr(II) are observed by scanning electron microscopy. The incorporation of metal into the host crystal lattice was confirmed by energy dispersive X-ray spectroscopy. Lattice parameters are determined by single crystal XRD analysis. The thermogravimetric and differential thermal analysis studies reveal the purity of the materials and no decomposition is observed up to the melting point. The nonlinear optical properties of the doped and undoped specimens were studied. Theoretical calculations were performed using the Density functional theory (DFT) method with B3LYP/LANL2DZ as the basis set. The molecular geometry and vibrational frequencies of TTNC in the ground state were calculated and the observed structural parameters of TTNC are compared with parameters obtained from single crystal X-ray studies. The atomic charge distributions are obtained by Mulliken charge population analysis. The first-order molecular hyperpolarizability, polarizability and dipole moment were derived. PMID:25233030

  12. 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.

  13. Radio frequency elevator for a pulsed positron beam

    NASA Astrophysics Data System (ADS)

    Dickmann, Marcel; Mitteneder, Johannes; Kögel, Gottfried; Egger, Werner; Sperr, Peter; Ackermann, Ulrich; Piochacz, Christian; Dollinger, Günther

    2016-06-01

    An elevator increases the potential energy of a particle beam with respect to ground potential without any alteration of kinetic energy and other beam parameters. This elevator is necessary for the implementation of the Munich Scanning Positron Microscope (SPM) at the intense positron source NEPOMUC at the research reactor FRM II in Munich. The principles of the rf elevator for pure electrostatically guided positrons are described. Measurements of beam quality behind the elevator are reported, which confirm that after the implementation of elevator and SPM at NEPOMUC the SPM can be operated at a considerably improved resolution (~ 0.3 μm) and event rate (~3.7 kHz) compared to the laboratory based β+-source.

  14. Chirality at metal and helical ligand folding in optical isomers of chiral bis(naphthaldiminato)nickel(II) complexes.

    PubMed

    Enamullah, Mohammed; Quddus, Mohammad Abdul; Hasan, Mohammad Rezabul; Pescitelli, Gennaro; Berardozzi, Roberto; Makhloufi, Gamall; Vasylyeva, Vera; Janiak, Christoph

    2016-01-14

    Enantiopure bis[{(R or S)-N-1-(Ar)ethyl-2-oxo-1-naphthaldiminato-κ(2)N,O}]nickel(ii) complexes {Ar = C6H5 ( or ), p-OMeC6H4 ( or ), and p-BrC6H4 ( or )} are synthesized from the reactions between (R or S)-N-1-(Ar)ethyl-2-oxo-1-naphthaldimine and nickel(ii) acetate. Circular-dichroism spectra and their density-functional theoretical simulation reveal the expected mirror image relationship between the enantiomeric pairs / and / in solution. CD spectra are dominated by the metal-centered Λ- or Δ-chirality of non-planar four-coordinated nickel, this latter being in turn dictated by the ligand chirality. Single crystal structure determination for and shows that there are two symmetry-independent molecules (A and B) in each asymmetric unit that give a Z' = 2 structure. Two asymmetric and chiral bidentate N^O-chelate Schiff base ligands coordinate to the nickel atom in a distorted square planar N2O2-coordination sphere. The conformational difference between the symmetry-independent molecules arises from the "up-or-down" folding of the naphthaldiminato ligand with respect to the coordination plane, which creates right- (P) or left-handed (M) helical conformations. Overall, the combination of ligand chirality, chirality at the metal and ligand folding gives rise to discrete metal helicates of preferred helicity in a selective way. Cyclic voltammograms (CV) show an oxidation wave at ca. 1.30 V for the [Ni(L)2]/[Ni(L)2](+) couple, and a reduction wave at ca. -0.35 V for the [Ni(L)2]/[Ni(L)2](-) couple in acetonitrile. PMID:26619269

  15. Metal-containing ligands for mixed-metal polymers: novel Cu(II)-Ag(I) mixed-metal coordination polymers generated from [Cu(2-methylpyrazine-5-carboxylate)2(H2O)].3H2O and silver(I) salts.

    PubMed

    Dong, Y B; Smith, M D; zur Loye, H C

    2000-05-01

    One Cu(II)-containing ligand and two Cu(II)-Ag(I) mixed-metal coordination polymers have been synthesized. [Cu(2-methylpyrazine-5-carboxylate)2(H2O)].3H2O (1) was obtained as a molecular complex with two uncoordinated nitrogen donors by the reaction of 2-methylpyrazine-5-carboxylate sodium with CuCl(2).2H2O in water. Compound 1 crystallized in the triclinic space group P1, with a = 10.498(2) A, b = 11.000(2) A, c = 8.1424(16) A, alpha = 98.33(3) degrees, beta = 101.83(3) degrees, gamma = 66.68(3) degrees, and Z = 2. Reactions of 1 with silver(I) salts have been studied. Two Cu(II)-Ag(I) mixed-metal coordination polymers, namely, Ag[Cu(2-methylpyrazine-5-carboxylate)2.(H2O)2](BF4) (2) and Ag[Cu(2-methylpyrazine-5-carboxylate)2.(H2O)2](NO3) (3), have been generated by treating 1 with AgBF4 and AgNO3, respectively. Compound 2 crystallized in the monoclinic space group C2/c, with a = 25.827(5) A, b = 9.6430(19) A, c = 7.4525(15) A, beta = 94.74(3) degrees, and Z = 4. Compound 3 also crystallized in the monoclinic space group C2/c, with a = 25.855(5) A, b = 9.782(2) A, c = 7.1201(14) A, beta = 96.90(3) degrees, and Z = 4. The main structural feature in both 2 and 3 is a zigzag Cu(II)-Ag(I) mixed-metal chain, in which the alternating Cu(II) and Ag(I) centers are linked by 2-methylpyrazine-5-carboxylate spacers. The effect of the nitrate counterion was illustrated by compound 3, in which a novel [Ag+...NO3-] coordination chain has been found which acts as the connector to cross-link the one-dimensional zigzag chains into a three-dimensional network. In addition, an identical interchain O-H...O hydrogen bonding system has been found in both 2 and 3 and has been shown to play a significant role in directing the alignment of the one-dimensional mixed-metal polymer chains in the crystalline state. The magnetic susceptibilities of 2 and 3 were measured and found to follow the Curie law (mu eff = 1.85 for 2 and 1.83 for 3). PMID:11428114

  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. 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

  18. 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

  19. Surface states and annihilation characteristics of positrons trapped at the (100) and (111) surfaces of silicon

    NASA Astrophysics Data System (ADS)

    Fazleev, N. G.; Fry, J. L.; Weiss, A. H.

    2004-10-01

    surface and compared with experimental positron spectroscopy data. These calculations reveal strong dependence of positron annihilation characteristics on the crystal face of clean Si in contrast to the much smaller face dependence found on clean metal surfaces. Annihilation probabilities of surface trapped positrons with Si2s - and 2p -core-level electrons are found to be significantly smaller for the reconstructed Si(111)-(7×7) surface when compared with the results for the reconstructed Si(100)-(2×1) surface, in agreement with experimental PAES data. These results indicate that PAES intensities, which are proportional to core annihilation probabilities, are sensitive to the crystal face and surface structure of an elemental semiconductor.

  20. 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.

  1. [Fundamentals of positron emission tomography].

    PubMed

    Ostertag, H

    1989-07-01

    Positron emission tomography is a modern radionuclide method of measuring physiological quantities or metabolic parameters in vivo. The method is based on: (1) radioactive labelling with positron emitters; (2) the coincidence technique for the measurement of the annihilation radiation following positron decay; (3) analysis of the data measured using biological models. The basic aspects and problems of the method are discussed. The main fields of future research are the synthesis of new labelled compounds and the development of mathematical models of the biological processes to be investigated. PMID:2667029

  2. 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.

  3. Studies on stannic selenoarsenate. II. Separation of uranium from numerous metal ions

    SciTech Connect

    Nabi, S.A.; Siddiqi, Z.M.; Rao, R.A.K.

    1982-12-01

    Stannic selenoarsenate has been synthesized by adding 0.05 M sodium selenite and 0.05 M sodium arsenate to a 0.05 M solution of stannic chloride in a volume ratio of 1:1:1 at pH 1. A tentative structure has been proposed on the basis of chemical composition, pH titrations, and infrared and thermogravimetric analyses. Distribution coefficients of several metal ions have been studied in hydrochloric acid, citric acid, ammonium citrate-citric acid, and water-dioxane systems. The unusual adsorption behavior or uranium has been utilized for its quantitative separation from several metal ions.

  4. Minutes of the 28th Annual Plutonium Sample Exchange Meeting. Part II: metal sample exchange

    SciTech Connect

    Not Available

    1984-01-01

    Contents of this publication include the following list of participating laboratories; agenda; attendees; minutes of October 25 and 26 meeting; and handout materials supplied by speakers. The handout materials cover the following: statistics and reporting; plutonium - chemical assay 100% minus impurities; americium neptunium, uranium, carbon and iron data; emission spectroscopy data; plutonium metal sample exchange; the calorimetry sample exchange; chlorine determination in plutonium metal using phyrohydrolysis; spectrophotometric determination of 238-plutonium in oxide; plutonium measurement capabilities at the Savannah River Plant; and robotics in radiochemical laboratory.

  5. 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.

  6. Borohydride complexes of europium(ii) and ytterbium(ii) and their conversion to metal borides. Structures of (l)4YbBh42 (L = Ch3Cn, C5H5N). (Reannouncement with new availability information)

    SciTech Connect

    White, J.P.; Deng, H.; Shore, S.G.

    1991-12-31

    Borohydride complexes of numerous metal ions are known. We have found that acetonitrile and pyridine are exceptionally good ligands for lathanide(II) ions. They promote formation of complexes with boron hydride and carborane anions. Use of these amines allows isolation of complexes that would otherwise be insoluble or unstable in other solvents. When these amines are employed as solvents, stable lanthanide(II) borohydride complexes can be isolated.

  7. 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.

  8. Supramolecular metal displacement allows on-fluorescence analysis of manganese(II) in living cells.

    PubMed

    Gruppi, Francesca; Liang, Jian; Bartelle, Benjamin B; Royzen, Maksim; Turnbull, Daniel H; Canary, James W

    2012-11-11

    Due to the importance of Mn(2+) ions in biological processes, it is of growing interest to develop protocols for analysis of Mn(2+) uptake and distribution in cells. A supramolecular metal displacement assay can provide ratiometric fluorescence detection of Mn(2+), allowing for quantitative and longitudinal analysis of Mn(2+) uptake in living cells. PMID:23023093

  9. 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. PMID:26478092

  10. THERMAL CONVERSION OF MUNICIPAL WASTEWATER SLUDGE, PHASE II: STUDY OF HEAVY METAL EMISSIONS

    EPA Science Inventory

    The object of this work was to compare and analyze heavy metal emissions associated with the thermal conversion (incineration) processes which can be conducted in a multiple-hearth furnace to dry municipal wastewater (sewage) sludge and reduce its volume by forming an ash or char...

  11. 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.

  12. 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. PMID:22995046

  13. Positron annihilation spectroscopy with magnetically analyzed beams

    NASA Technical Reports Server (NTRS)

    Singh, J. J.; Holt, W. H.; Mock, W., Jr.

    1982-01-01

    Lifetime measurements with magnetically analyzed positron beams were made in condensed media with uniform and non-uniform properties. As expected, the lifetime values with magnetically analyzed positron beams in uniform targets are similar to those obtained with conventional positron sources. The lifetime values with magnetically analyzed beams in targets which have non-uniform properties vary with positron energy and are different from the conventional positron source derived lifetime values in these targets.

  14. 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.

  15. 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).

  16. Positrons from accelerated particle interactions

    NASA Technical Reports Server (NTRS)

    Kozlovsky, B.; Lingenfelter, R. E.; Ramaty, R.

    1987-01-01

    Positron production from the decay of radioactive nuclei produced in nuclear interactions of accelerated particles is treated in detail. Laboratory data as well as theoretical considerations are used to construct energy-dependent cross sections for the production of a large number of radioactive positron emitters resulting from proton and alpha-particle interactions with ambient cosmic matter. Using these cross sections, positron production rates are calculated for a variety of energetic particle spectra, assuming solar abundances for both the energetic particles and the ambient medium. These results can be used for the study of astrophysical sites which emit annihilation radiation. In particular, the results have been applied to solar flares, where the observed 0.511 MeV line is shown to be due to positrons resulting from accelerated particle reactions.

  17. Possibilities with pulsed polarized high density slow positrons

    NASA Astrophysics Data System (ADS)

    Mills, A. P., Jr.

    2014-04-01

    A particularly bright and intense polarized slow positron beam could be formed from isotopically enriched 79Kr produced at a reactor. After moderation with solid Ne, accumulation, compression, and bunching, this type of positron beam would enable a number of experiments including: (1) Long term storage of a neutral polarized electron-positron plasma in a cold box; (2) Pulsed e+ ACAR with a pulsed magnet to measure Fermi surfaces of paramagnetic metals; (3) Single shot measurements of positron annihilation in laser-imploding plasmas; (4) Study of a spin-polarized positronium gas at a density around that of ordinary air to produce a Ps Bose-Einstein condensate at room temperature; (5) High energy polarized positron channelling experiments to study polarized electron spatial wave functions in ferromagnets; and (6) Study of supersonic free expansion spin polarized BEC Ps jets formed from, for example, 1011 m=1 triplet Ps atoms created within an open ended 1 μm diameter cylindrical cavity 100 μm in length.

  18. 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.

  19. High-Resolution Spectroscopy of Extremely Metal-Poor Stars from SDSS/SEGUE. II. Binary Fraction

    NASA Astrophysics Data System (ADS)

    Aoki, Wako; Suda, Takuma; Beers, Timothy C.; Honda, Satoshi

    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] \\lt -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.

  20. Reactivity of lithium n-butyl amidinates towards group 14 metal(II) chlorides providing series of hetero- and homoleptic tetrylenes.

    PubMed

    Chlupatý, Tomáš; Padělková, Zdeňka; Lyčka, Antonín; Brus, Jiří; Růžička, Aleš

    2012-04-28

    The new class of homo- and heteroleptic n-butyl-N,N'-disubstituted amidinato group 14 metal(II) complexes were prepared by salt elimination from starting lithium amidinates and metal(II) chlorides both in stoichiometric ratio 2:1 and 1:1, respectively. The target amidinates contain less bulky isopropyl or cyclohexyl as well as a sterically demanding aromatic substituent. Desired 1:1 Pb(II) complexes are not accessible by the described procedure. Ligand transfer from Pb to Sn is taking place if homoleptic Pb(II) compounds are reacted with SnCl(2). Prepared tetrylenes were characterized by (1)H, (13)C, (119)Sn and (207)Pb NMR spectroscopy in C(6)D(6) or THF-d(8). X-Ray diffraction studies of one heteroleptic Ge(II) monomeric where the coordination polyhedron of the three coordinated germanium atoms is a trigonal pyramid, two different dimeric structures of heteroleptic Sn(II) complexes, one amidine hydroiodide byproduct and the oxidation product of the heteroleptic chloro Sn(II) amidinate as a tetranuclear species with two Sn(IV) and two Sn(II) atoms in central Sn(2)O(2) planar ring were performed on appropriate single crystals. The dimer of one of the heteroleptic stannylenes reveals a new type of monomeric units connection, weak Sn-Cl contact and an interaction of the tin atom with delocalized N-C(C)-N system of the amidinato ligand of the second molecule. PMID:22415327

  1. 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.

  2. 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.

  3. 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

  4. 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.

  5. 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. PMID:24024515

  6. 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. PMID:6523119

  7. Engineering Short Preorganized Peptide Sequences for Metal Ion Coordination: Copper(II) a Case Study.

    PubMed

    Lima, L M P; Iranzo, O

    2016-01-01

    Peptides are multidentate chiral ligands capable of coordinating different metal ions. Nowadays, they can be obtained with high yield and purity, thanks to the advances on peptide/protein chemistry as well as in equipment (peptide synthesizers). Based on the identity and length of their amino acid sequences, peptides can present different degrees of flexibility and folding. Although short peptide sequences (<20 amino acids) usually lack structure in solution, different levels of structural preorganization can be induced by introducing conformational constraints, such as β-turn/loop template sequences and backbone cyclization. For all these reasons, and the fact that one is not restricted to use proteinogenic amino acids, small peptidic scaffolds constitute a simple and versatile platform for the development of inorganic systems with tailor-made properties and functions. Here we outline a general approach to the design of short preorganized peptide sequences (10-16 amino acids) for metal ion coordination. Based on our experience, we present a general scheme for the design, synthesis, and characterization of these peptidic scaffolds and provide protocols for the study of their metal ion coordination properties. PMID:27586340

  8. INSTRUMENTS AND METHODS OF INVESTIGATION: Positron annihilation spectroscopy in materials structure studies

    NASA Astrophysics Data System (ADS)

    Grafutin, Viktor I.; Prokop'ev, Evgenii P.

    2002-01-01

    A relatively new method of materials structure analysis — positron annihilation spectroscopy (PAS) — is reviewed. Measurements of positron lifetimes, the determination of positron 3γ- and 2γ-annihilation probabilities, and an investigation of the effects of different external factors on the fundamental characteristics of annihilation constitute the basis for this promising method. The ways in which the positron annihilation process operates in ionic crystals, semiconductors, metals and some condensed matter systems are analyzed. The scope of PAS is described and its prospects for the study of the electronic and defect structures are discussed. The applications of positron annihilation spectroscopy in radiation physics and chemistry of various substances as well as in physics and chemistry of solutions are exemplified.

  9. A modified positron lifetime spectrometer as method of non-destructive testing in materials

    NASA Astrophysics Data System (ADS)

    Chen, Z. Q.; Shi, J. J.; Jiang, J.; Liu, X. B.; Wang, R. S.; Wu, Y. C.

    2015-02-01

    This paper aims to develop a new non-destructive testing (NDT) method using positron annihilation spectroscopy, a powerful tool to detect vacancy-type defects and defect's chemical environment. A positron NDT system was designed and constructed by modifying the "sandwich" structure of sample-source-sample in the conventional positron lifetime spectrometer. The positron lifetime spectra of one single sample can be measured and analyzed by subtracting the contribution of a reference sample. The feasibility and reliability of the positron NDT system have been tested by analyzing nondestructively deformation damage caused by mechanical treatment in metals and steels. This system can be used for detecting defects and damage in thick or large-size samples without cutting off the sample materials, as well as for detecting two-dimensional distribution of defects.

  10. High elemental selectivity to Sn submonolayers embedded in Al using positron annihilation spectroscopy

    NASA Astrophysics Data System (ADS)

    Hugenschmidt, C.; Pikart, P.; Stadlbauer, M.; Schreckenbach, K.

    2008-03-01

    In the present work, we demonstrate that metal layers in the submonolayer range embedded in a matrix are revealed with unprecedented sensitivity by coincident Doppler-broadening spectroscopy of the positron annihilation using a monoenergetic positron beam. The measured electron momentum distribution specific for Sn is clearly observable in Al/Sn/Al -layered samples even at a Sn area density of as low as 7.3×10-2μg/cm2 below 200nm Al. An explanation for the high elemental selectivity for the thin Sn layers is set forward in terms of efficient positron trapping due to the changing positron affinity at the Al/Sn -interface and quantum-dot-like positron states in Sn nanoparticles.

  11. Arsenic Specitation in Multiple Metal Environments: II. Micro-Spectroscopic Investigation of a CCA Contaminated Soil

    SciTech Connect

    Grafe,M.; Tappero, R.; Marcus, M.; Sparks, D.

    2008-01-01

    The speciation of arsenic (As) in a copper-chromated-arsenate (CCA) contaminated soil was investigated using micro-focused X-ray fluorescence (microXRF) and micro-focused X-ray absorption fine structure (microXAFS) spectroscopies to determine if and how the co-contaminating metal cations (Cu, Zn, Cr) influenced the speciation of As. 15 microXRF images were collected on 30-mum polished thin sections and powder-on-tape samples from which Pearson correlation coefficients (rho) between As and various metal species were determined based on the fluorescence intensity of each element in each image pixel. 29 microXAFS and two bulk-XAFS spectra were collected from depths of 0-20 cm (LM-A) and 20-40 cm (LM-B) to determine the chemical speciation of As in the soil by target analyses of principal components with circa 52 reference spectra and linear least-square combination fitting of individual experimental spectra with a refined reference phase list (32) of likely As species. Arsenic and metal cations (Cr, Mn, Fe, Cu, Zn) accumulated in distinct, isolated areas often not larger than 50 x 50 microm in which the Pearson correlation between the elements was strongly positive (rho>0.75). The correlation of As to Zn and Cr decreased from >0.9 to <0.8 and increased to Cu from approximately 0.6 to >0.8 with depth. Arsenic occurred predominantly in the +5 oxidation state. Abstract factor analysis and linear least square combination fit analysis suggested that As occurred as a continuum of fully and poorly-ordered copper-arsenate precipitates with additional components being characterized by surface adsorption complexes on goethite and gibbsite in the presence and absence of Zn. Precipitates other than copper-based ones, e.g., scorodite, adamite and ojuelaite were also identified. The significant co-localization and chemical speciation of As with Cu suggest that the speciation of As in a contaminated soils is not solely controlled by surface adsorption reactions, but significantly

  12. 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. PMID:27249784

  13. 12-Metal 36-membered ring based W(V)-Co(II) layers showing spin-glass behavior.

    PubMed

    Zhao, Liang; Duan, Ran; Zhuang, Peng-Fei; Zheng, Hui; Jiao, Cheng-Qi; Wang, Jun-Li; He, Cheng; Liu, Tao

    2015-07-28

    The present study describes the designed synthesis, X-ray structures, and magnetic properties of two 2D cyano bridged heterobimetallic W(V)-Co(II) networks, {[W(CN)8]2[Co(phpy)4]3}·2CH3OH·2H2O (1) and {[W(CN)8]2[Co(4-spy)4]3}·6H2O (2) (phpy = 4-phenylpyridine, 4-spy = 4-styrylpyridine). Both compounds consist of cyano-bridged 12-metal 36-membered ring units, Co6W6(CN)12, joined by organic linkers into a 2D plane. The layer presents a corrugated configuration in compound 1 and a plane configuration in compound 2 due to different π-π stacking interactions. Magnetic measurements reveal that both 1 and 2 have a transition to the spin glass-like phase due to competitive magnetic interactions. PMID:26076432

  14. Liquid metal embrittlement susceptibility of welded MANET II (DIN 1.4914) in liquid Pb17Li.

    NASA Astrophysics Data System (ADS)

    Sample, T.; Fenici, P.; Kolbe, H.

    1996-10-01

    TIG welding of 12 mm thick plates of MANET II steel was accomplished using filler material of the same composition. Tensile tests, at a constant displacement rate of 0.1 mm min -1 (corresponding to an initial strain rate of 1.1 × 10 -4 s -1), were carried out on specimens consisting solely of the weld, HAZ and bulk material under vacuum and liquid Pb17Li at 250 and 400°C. The post-weld heat treatment (750°C/4 h air cooled) which was given to the welded plates was sufficient to prevent any liquid metal embrittlement. The presence of oxide inclusions and pores in the weld reduced the extent of plastic strain at rupture exhibited by some of the welds.

  15. 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.

  16. 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. PMID:26901629

  17. 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.

  18. 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.

  19. 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.

  20. 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) . PMID:26489982

  1. 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

  2. Metallation of Isatin (2,3-Indolinedione). X-Ray Structure and Solution Behavior of Bis(Isatinato)Mercury(II)

    PubMed Central

    Garcia-Raso, Angel; Fiol, Juan J.; Molins, Elies; Calafat, Antonia M.; Marzilli, Patricia A.; Marzilli, Luigi G.

    1995-01-01

    The first X-ray structure of an isatin (2,3-indolinedione, isaH) metal complex, bis(isatinato)memury(II) (C16H8N2O4Hg) (1), was determined. (1) was obtained from the reaction of isaH with mercury(II) acetate in methanol. Analogously, treatment of sodium saccharinate and mercury(II) acetate in methanol yielded Hg(saccharinato)2•0.5CH3OH (3). (1) crystallizes in the monoclinic system, space group P21/ a with a = 7.299(1) Å, b = 8.192(1) Å, c = 11.601(1) Å , β = 105.82(1)°, V = 667.4 Å3, Z = 2, Dcalc = 2.452 g cm−3, MoKα radiation(λ = 0.71073 Å), μ = 115.5 cm-1, F(000) = 460, 21(1) °C. The structure was refined on the basis of 2023 observed reflections to R= 0.044. The two deprotonated, non coplanar isa ligands are trans to each other in a head to tail orientation and bound to the Hg through the nitrogen in a linear N-Hg-N arrangement. The Hg atom is at the center of symmetry of the complex and displaced by 0.62 Å from the two planes of the isa ligands (τ Hg-N1-C2-O2= -16°). The Hg-N bond length is 2.015 Å. Noπ-aryl-memury(ll)-π-aryl stacking interaction was observed either in the solid state or in the solution state. The IR, electronic, and 1H and 13CNMR spectral data of (1) and (3) suggest binding of the memury to the heterocyclic nitrogen, in agreement with the crystal structure determination of (1). PMID:18472749

  3. Research on the Adsorption of O2 in Metal-Organic Frameworks with Open Manganese(ii) Coordination Sites

    NASA Astrophysics Data System (ADS)

    Wang, Weike; Yang, Jiangfeng; Li, Libo; Li, Jinping

    2013-02-01

    Three different metal-organic frameworks (MOFs), specifically Mn2(dobdc)(DMF)4 (H2dobdc=[2,5-dihydroxyterephthalic acid]; compound (1), Mn5(btac)4(μ3-OH)2(EtOH)2...DMF...3EtOH...3H2O (H2btac=[benzotriaole-5-carboxylicacid]; compound (2), and Mn3(2,6-ndc)3...4DMF (H2ndc=[2,6-naphthalenedicarbo-xylic acid]; compound (3), have been synthesized, the channels of which are lined with coordinatively unsaturated MnII centers. The adsorption of O2 in these MOFs has been measured using a gravimetric method at different temperatures (-78°C, -5°C, and 25°C) at a pressure of 1 bar. Gas adsorption isotherms of compounds 1 and 2 at 298 K indicated that they bind O2 by chemisorption at low pressure, with capacities of 1.2 wt.% and 2.14 wt.%, respectively, for the first cycle, with reversible oxygen binding for compound 1 and partially irreversible oxidation for compound 2. However, compound 3 binds O2 by physisorption, with a capacity of just 0.21 wt.%. This difference between the three compounds stems from the different coordination environments of the respective MnII centers, which give rise to differences in electron density. The results suggest that there must be an optimal electron density around the exposed MnII center for partial charge transfer from this center to the bound O2 molecule; if the electron density is too high or too low, reversible chemisorption of O2 is not favored.

  4. Preparation of manganese(II), chromium(III) and ferric(III) oxides nanoparticles in situ metal citraconate complexes frameworks

    NASA Astrophysics Data System (ADS)

    Refat, Moamen S.

    2014-12-01

    The new reactions of some divalent and trivalent transition metal ions (Mn(II), Cr(III), and Fe(III)) with citraconic acid has been studied. The obtained results indicate the formation of citraconic acid compounds with molar ratio of metal to citraconic acid of 2:2 or 2:3 with general formulas Mn2(C5H4O4)2 or M2(C5H4O4)3ṡnH2O where n = 6 for Cr, and Fe(III). The thermal decomposition of the crystalline solid complexes was investigated. The IR spectra of citraconate suggested that the carboxylic groups are bidentatically bridging and chelating. In the course of decomposition the complexes are dehydrated and then decompose either directly to oxides in only one step or with intermediate formation of oxocarbonates. This proposal dealing the preparation of MnO2, Fe2O3 and Cr2O3 nanoparticles. The crystalline structure of oxide products were checked by X-ray powder diffraction (XRD), and the morphology of particles by scanning electron microscopy (SEM).

  5. Preparation of manganese(II), chromium(III) and ferric(III) oxides nanoparticles in situ metal citraconate complexes frameworks.

    PubMed

    Refat, Moamen S

    2014-12-10

    The new reactions of some divalent and trivalent transition metal ions (Mn(II), Cr(III), and Fe(III)) with citraconic acid has been studied. The obtained results indicate the formation of citraconic acid compounds with molar ratio of metal to citraconic acid of 2:2 or 2:3 with general formulas Mn2(C5H4O4)2 or M2(C5H4O4)3⋅nH2O where n=6 for Cr, and Fe(III). The thermal decomposition of the crystalline solid complexes was investigated. The IR spectra of citraconate suggested that the carboxylic groups are bidentatically bridging and chelating. In the course of decomposition the complexes are dehydrated and then decompose either directly to oxides in only one step or with intermediate formation of oxocarbonates. This proposal dealing the preparation of MnO2, Fe2O3 and Cr2O3 nanoparticles. The crystalline structure of oxide products were checked by X-ray powder diffraction (XRD), and the morphology of particles by scanning electron microscopy (SEM). PMID:24952090

  6. Direct synthesis of high-valent aryl-Cu(II) and aryl-Cu(III) compounds: mechanistic insight into arene C-H bond metalation.

    PubMed

    Zhang, Hu; Yao, Bo; Zhao, Liang; Wang, De-Xian; Xu, Bo-Qing; Wang, Mei-Xiang

    2014-04-30

    Copper and its salts are abundant, inexpensive, and eco-friendly and have been used as the surrogates of noble metals to effect arene C-H bond activation and transformations. Despite of the recent significant progress of the study, syntheses of high-valent arylcopper(II-III) compounds are still very rare and mechanisms of copper(II)-catalyzed reactions remain elusive. With the use of azacalix[1]arene[3]pyridines as a platform, a number of arylcopper(II) compounds were synthesized efficiently from the reaction of Cu(ClO4)2 under ambient conditions. The resulting aryl-Cu(II) compounds, which contain an unprecedented (substituted) phenyl-Cu(II) σ-bond, were stable under atmospheric conditions and can undergo facile oxidation reaction by free copper(II) ions or oxone to afford arylcopper(III) compounds in good yields. Both arylcopper(II) and arylcopper(III) compounds were characterized unambiguously by means of XRD, XPS, and NMR methods. Experimental evidence including reaction kinetics, LFER and KIE, and theoretical calculations indicated that the Cu(ClO4)2-mediated arene C-H bond activation proceeds plausibly through an electrophilic aromatic metalation pathway. The synthesis of high-valent arylcopper compounds and the reaction mechanism reported here highlight the diversity and richness of organocopper chemistry. PMID:24730979

  7. Proton/metal-ligand stability constants of complexes of Ni(II), Cu(II), and Co(II) with diethyl 4-(substituted-phenyl)-2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylate in 70% dioxane-water mixture

    NASA Astrophysics Data System (ADS)

    Tekade, Pradip V.; Bajaj, Sonal D.; Thool, Seemita

    2015-12-01

    Physico-chemical properties viz proton-ligand and metal-ligand stability constants of complexes of diethyl 4-(substituted-phenyl)-2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylate with Ni(II), Cu(II), and Co(II) were determined in mixed solvents (70% dioxane). Presence of OH/NH group(s) in these compounds was confirmed at 0.1 M ionic strength in 70% dioxane-water mixture pH-metrically. It is observed that Ni(II), Cu(II), and Co(II) metal ions formed 1: 1 and 1: 2 complex with all the three ligands. The results show that the ratio of log K 1/log K 2 is positive in all cases. This implies that there is little or no steric hindrance to the addition of secondary molecules.

  8. 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.

  9. 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.

  10. 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.

  11. Performance of the (n,γ)-Based Positron Beam Facility NEPOMUC

    NASA Astrophysics Data System (ADS)

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

    2009-01-01

    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 9.108 e+/s is achieved (1 keV). The performance and applications of the facility are presented.

  12. Copper (II) and zinc (ii) metal-based salicyl-, furanyl-, thienyl- and pyrrolyl-derived ONNO, NNNO, ONNS & NNNS donor asymmetrically mixed schiff-bases with antibacterial and antifungal potentials.

    PubMed

    Chohan, Zahid H; Arif, M; Rashid, A

    2008-12-01

    A new series of asymmetric salicyl-, furanyl-, thienyl- and pyrrolyl-derived ONNO, NNNO, ONNS & NNNS donor antibacterial and antifungal Schiff-bases and their copper(II) and zinc(II) metal complexes have been synthesized and characterized. IR spectra indicated the ligands to act as quartdentate towards divalent metal ions via two azomethine-N, deprotonated-O of salicyl, furanyl-O, thienyl-S and/or pyrrolyl-N. The magnetic moments and electronic spectral data suggest octahedral geometry for Cu(II) and Zn(II) complexes. NMR spectral data of the ligands and their diamagnetic zinc(II) complexes well-define their proposed structures/geometries. Elemental analyses data of the ligands and metal complexes agree with their proposed structures/geometries. The synthesized ligands, along with their metal complexes were screened for their antibacterial activity against B. cereus, C. diphtheriae, E. coli, K. pneumoniae, P. mirabilis, P. aeruginosa, S. typhi, S. dysenteriae and S. aureus strains and for in-vitro antifungal activity against T. schoenleinii, C. glabrata, P. boydii, C. albicans, A. niger, M. canis and T. mentagrophytes. The results of these studies show the metal 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. Eight compounds, L(4), (1), (7), (8), (11), (17), (19) and (23) displayed potent cytotoxic activity with LD(50) = 1.445 x 10(- 3), 1.021 x 10(- 3), 7.478 x 10(- 4), 8.566 x 10(- 4), 1.028 x 10(- 3), 9.943 x 10(- 4), 8.730 x 10(- 4) and 1.124 x 10(- 3) M respectively, against Artemia salina. PMID:19005942

  13. Preliminary anti-cancer photodynamic therapeutic in vitro studies with mixed-metal binuclear ruthenium(II)-vanadium(IV) complexes.

    PubMed

    Holder, Alvin A; Taylor, Patrick; Magnusen, Anthony R; Moffett, Erick T; Meyer, Kyle; Hong, Yiling; Ramsdale, Stuart E; Gordon, Michelle; Stubbs, Javelyn; Seymour, Luke A; Acharya, Dhiraj; Weber, Ralph T; Smith, Paul F; Dismukes, G Charles; Ji, Ping; Menocal, Laura; Bai, Fengwei; Williams, Jennie L; Cropek, Donald M; Jarrett, William L

    2013-09-01

    We report the synthesis and characterisation of mixed-metal binuclear ruthenium(II)-vanadium(IV) complexes, which were used as potential photodynamic therapeutic agents for melanoma cell growth inhibition. The novel complexes, [Ru(pbt)2(phen2DTT)](PF6)2·1.5H2O 1 (where phen2DTT = 1,4-bis(1,10-phenanthrolin-5-ylsulfanyl)butane-2,3-diol and pbt = 2-(2'-pyridyl)benzothiazole) and [Ru(pbt)2(tpphz)](PF6)2·3H2O 2 (where tpphz = tetrapyrido[3,2-a:2',3'-c:3'',2''-h:2''',3'''-j]phenazine) were synthesised and characterised. Compound 1 was reacted with [VO(sal-L-tryp)(H2O)] (where sal-L-tryp = N-salicylidene-L-tryptophanate) to produce [Ru(pbt)2(phen2DTT)VO(sal-L-tryp)](PF6)2·5H2O 4; while [VO(sal-L-tryp)(H2O)] was reacted with compound 2 to produce [Ru(pbt)2(tpphz)VO(sal-L-tryp)](PF6)2·6H2O 3. All complexes were characterised by elemental analysis, HRMS, ESI MS, UV-visible absorption, ESR spectroscopy, and cyclic voltammetry, where appropriate. In vitro cell toxicity studies (with the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) colorimetric assay) via dark and light reaction conditions were carried out with sodium diaqua-4,4',4'',4''' tetrasulfophthalocyaninecobaltate(II) (Na4[Co(tspc)(H2O)2]), [VO(sal-L-tryp)(phen)]·H2O, and the chloride salts of complexes 3 and 4. Such studies involved A431, human epidermoid carcinoma cells; human amelanotic malignant melanoma cells; and HFF, non-cancerous human skin fibroblast cells. Both chloride salts of complexes 3 and 4 were found to be more toxic to melanoma cells than to non-cancerous fibroblast cells, and preferentially led to apoptosis of the melanoma cells over non-cancerous skin cells. The anti-cancer property of the chloride salts of complexes 3 and 4 was further enhanced when treated cells were exposed to light, while no such effect was observed on non-cancerous skin fibroblast cells. ESR and (51)V NMR spectroscopic studies were also used to assess the stability of the chloride salts of complexes 3

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

    PubMed

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

    2016-04-01

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

  15. 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.

  16. Synthesis and characterization of a series of transition metal complexes with a new symmetrical polyoxaaza macroacyclic Schiff base ligand: X-ray crystal structure of cobalt(II) and nickel(II) complexes and their antibacterial properties

    NASA Astrophysics Data System (ADS)

    Keypour, Hassan; Shayesteh, Maryam; Rezaeivala, Majid; Chalabian, Firoozeh; Valencia, Laura

    2013-01-01

    A new symmetrical [N4O2] hexadentate Schiff base ligand, (E)-N-(pyridin-2-ylmethylene)-2-(3-(2-((E)-pyridin-2-lmethyleneamino)phenoxy)naphthalen-2-yloxy)benzenamine, abbreviated to L, and its complexes of Ni(II), Cu(II), Zn(II), Co(II), Cd(II) and Mn(II) have been synthesized in the presence of metal ions. The complexes were structurally characterized by elemental analyses, IR, UV-Vis, NMR and molar conductivity. The crystal structures of two complexes, [NiL(ONO2)2]·2H2O and [CoLCl2]CH3OH·0.5H2O, have been determined by a single crystal X-ray diffraction study. In these complexes, the ligand is coordinated in a neutral form via pyridine and azomethine nitrogen atoms. The metal ions complete their six coordination with two coordinated nitrate or chloride ions, forming a distorted octahedral geometry. The synthesized compounds have antibacterial activity against the three Gram-positive bacteria: Enterococcus faecalis, Bacillus cereus and Staphylococcus epid and also against the three Gram-negative bacteria: Citrobacter freundii, Enterobacter aerogenes and Salmonella typhi. The activity data show that the complexes are more potent antibacterials than the parent Schiff base.

  17. Coordination mode of pentadentate ligand derivative of 5-amino-1,3,4-thiadiazole-2-thiol with nickel(II) and copper(II) metal ions: Synthesis, spectroscopic characterization, molecular modeling and fungicidal study

    NASA Astrophysics Data System (ADS)

    Chandra, Sulekh; Gautam, Seema; Kumar, Amit; Madan, Molly

    2015-02-01

    Complexes of nickel(II), and copper(II) were synthesized with pantadentate ligand i.e. 3,3‧-thiodipropionicacid-bis(5-amino-1,3,4-thiadiazole-2-thiol) (L). The ligand was synthesized by the condensation of thiodipropionic acid and 5-amino-1,3,4-thiadiazole-2-thiol in 1:2 ratio, respectively. Synthesized ligand was characterized by elemental analysis, mass, 1H NMR, IR, and molecular modeling. All the complexes were characterized by elemental analysis, molar conductance, magnetic moment, IR, electronic spectra, ESR, and molecular modeling. The newly synthesized complexes possessed general composition [M(L)X2] where M = Ni(II), Cu(II), L = pantadentate ligand and X = Cl-, CH3COO-. The IR spectral data indicated that the ligand behaved as a pantadentate ligand and coordinated to the metal ion through N2S3 donor atoms. The molar conductance value of Ni(II), and Cu(II) complexes in DMSO corresponded to their electrolytic behavior. On the basis of spectral study, octahedral and tetragonal geometry was assigned for Ni(II) and Cu(II) complexes, respectively. In vitro fungicidal study of ligand and its complexes was investigated against fungi Candida albicans, Candida parapsilosis, Candidia krusei, and Candida tropicalis by means of well diffusion method.

  18. The interaction of zinc(II) and hydroxamic acids and a metal-triggered Lossen rearrangement.

    PubMed

    Duchácková, Lucie; Roithová, Jana

    2009-12-14

    The structure and reactivity of a complex of zinc(II), water, acetic acid, and acetohydroxamic acid, in which one of the acids is deprotonated, is investigated by means of mass spectrometry, labeling studies, and density functional calculations to unravel the exceptional binding properties of hydroxamic acids towards zinc-containing enzymes at the molecular level. It is shown that acetohydroxamic acid is deprotonated in the complex, whereas acetic acid is present in its neutral form. The binding energies of the ligands towards zinc increase in the following order: water

  19. 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.

  20. Enhancement of chitosan-graphene oxide SPR sensor with a multi-metallic layers of Au-Ag-Au nanostructure for lead(II) ion detection

    NASA Astrophysics Data System (ADS)

    Kamaruddin, Nur Hasiba; Bakar, Ahmad Ashrif A.; Yaacob, Mohd Hanif; Mahdi, Mohd Adzir; Zan, Mohd Saiful Dzulkefly; Shaari, Sahbudin

    2016-01-01

    We demonstrate the enhancement of surface plasmon resonance (SPR) technique by implementing a multi-metallic layers of Au-Ag-Au nanostructure in the chitosan-graphene oxide (CS-GO) SPR sensor for lead(II) ion detection. The performance of the sensor is analyzed via SPR measurements, from which the sensitivity, signal-to-noise ratio and repeatability are determined. The nanostructure layers are characterized using field emission scanning electron microscopy (FESEM), atomic force microscopy (AFM), X-ray diffraction (XRD), Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). We showed that the proposed structure has increased the shift in the SPR angle up to 3.5° within the range of 0.1-1 ppm due to the enhanced evanescent field at the sensing layer-analyte interface. This sensor also exhibits great repeatability which benefits from the stable multi-metallic nanostructure. The SNR value of 0.92 for 5 ppm lead(II) ion solution and reasonable linearity range up to that concentration shows that the tri-metallic CS-GO SPR sensor gives a good response towards the lead(II) ion solution. The CS-GO SPR sensor is also sensitive to at least a 10-5 change in the refractive index. The results prove that our proposed tri-metallic CS-GO SPR sensor demonstrates a strong performance and reliability for lead(II) ion detection in accordance with the standardized lead safety level for wastewater.

  1. Rational synthesis of an exceptionally stable Zn(II) metal-organic framework for the highly selective and sensitive detection of picric acid.

    PubMed

    Hu, Yingli; Ding, Meili; Liu, Xiao-Qin; Sun, Lin-Bing; Jiang, Hai-Long

    2016-04-28

    Based on an organic ligand involving both carboxylate and tetrazole groups, a chemically stable Zn(II) metal-organic framework has been rationally synthesized and behaves as a fluorescence chemosensor for the highly selective and sensitive detection of picric acid, an extremely hazardous and strong explosive. PMID:27046028

  2. Non-redox metal ion promoted oxidative coupling of indoles with olefins by the palladium(ii) acetate catalyst through dioxygen activation: experimental results with DFT calculations.

    PubMed

    Zhang, Sicheng; Chen, Zhuqi; Qin, Shuhao; Lou, Chenlin; Senan, Ahmed M; Liao, Rong-Zhen; Yin, Guochuan

    2016-04-26

    Developing new catalytic technologies through C-H bond activation to synthesize versatile pharmaceuticals has attracted much attention in recent decades. This work introduces a new strategy in catalyst design for Pd(ii)-catalyzed C-H bond activation in which non-redox metal ions serving as Lewis acids play significant roles. In the oxidative coupling of indoles with olefins using dioxygen, it was found that Pd(OAc)2 alone as the catalyst is very sluggish at ambient temperature which provided a low yield of the olefination product, whereas adding non-redox metal ions to Pd(OAc)2 substantially improves its catalytic efficiency. In particular, it provided bis(indolyl)methane derivatives as the dominant product, a category of pharmacological molecules which could not be synthesized by Pd(ii)-catalyzed oxidative coupling previously. Detailed investigations revealed that the reaction proceeds by heterobimetallic Pd(ii)/Sc(iii)-catalyzed oxidative coupling of an indole with an olefin followed by Sc(iii)-catalyzed addition with a second indole molecule. DFT calculations disclosed that the formation of heterobimetallic Pd(ii)/Sc(iii) species substantially decreases the C-H bond activation energy barrier, and shifts the rate determining step from C-H bond activation of indole to the olefination step. This non-redox metal ion promoted Pd(ii)-catalyzed C-H bond activation may offer a new opportunity for catalyst design in organic synthesis, which has not been fully recognized yet. PMID:27075840

  3. The GHOSTS survey - II. The diversity of halo colour and metallicity profiles of massive disc galaxies

    NASA Astrophysics Data System (ADS)

    Monachesi, Antonela; Bell, Eric F.; Radburn-Smith, David J.; Bailin, Jeremy; de Jong, Roelof S.; Holwerda, Benne; Streich, David; Silverstein, Grace

    2016-04-01

    We study the stellar halo colour properties of six nearby massive highly inclined disc galaxies using Hubble space telescope Advanced Camera for Surveys and Wide Field Camera 3 observations in both F606W and F814W filters from the GHOSTS (Galaxy Halos, Outer disks, Substructure, Thick disks, and Star clusters) survey. The observed fields probe the stellar outskirts out to projected distances of ˜50-70 kpc from their galactic centre along the minor axis. The 50 per cent completeness levels of the colour-magnitude diagrams are typically at 2 mag below the tip of the red giant branch (RGB). We find that all galaxies have extended stellar haloes out to ˜50 kpc and two out to ˜70 kpc. We determined the halo colour distribution and colour profile for each galaxy using the median colours of stars in the RGB. Within each galaxy, we find variations in the median colours as a function of radius which likely indicates population variations, reflecting that their outskirts were built from several small accreted objects. We find that half of the galaxies (NGC 0891, NGC 4565, and NGC 7814) present a clear negative colour gradient in their haloes, reflecting a declining metallicity; the other have no significant colour or population gradient. In addition, notwithstanding the modest sample size of galaxies, there is no strong correlation between their halo colour/metallicity or gradient with galaxy's properties such as rotational velocity or stellar mass. The diversity in halo colour profiles observed in the GHOSTS galaxies qualitatively supports the predicted galaxy-to-galaxy scatter in halo stellar properties, a consequence of the stochasticity inherent in the assembling history of galaxies.

  4. H II Region Metallicity Constraints Near the Site of the Strongly Lensed Supernova “SN Refsdal” at Redshift 1.49

    NASA Astrophysics Data System (ADS)

    Yuan, Tiantian; Kobayashi, Chiaki; Kewley, Lisa J.

    2015-05-01

    We present the local H ii region metallicity near the site of the recently discovered multiply lensed supernova (SN; “SN Refsdal”) at redshift 1.49. “SN Refsdal” is located at the outer spiral arm (˜7 kpc) of the lensed host galaxy, which we previously reported to exhibit a steep negative galactocentric metallicity gradient. Based on our updated near-infrared integral field spectroscopic data, the gas-phase metallicity averaged in an intrinsic radius of ˜550 pc surrounding an H ii region ˜200 pc away from the SN site is 12 + log(O/H)PP04N2≤slant 8.67. The metallicity averaged over nine H ii regions at similar galactocentric distances (˜5-7 kpc) as “SN Refsdal” is constrained to be 12 + log(O/H)PP04N2≤slant 8.11. Given the fortuitous discovery of “SN Refsdal” in an advantageously lensed face-on spiral, this is the first observational constraint on the local metallicity environment of an SN site at redshift z\\gt 1.

  5. Metal- and anion-directed assemblies of CuII, CoII, NiII, and ZnII coordination polymers based on a bent dipyridyl ligand 4-amino-3,5-bis(3-pyridyl)-1,2,4-triazole and malonic acid

    NASA Astrophysics Data System (ADS)

    Jiang, Cheng-Hui; Qi, Yan-Mei; Sun, Yu; Chi, Qin; Guo, Ya-Mei

    2012-06-01

    This work presents six CuII, CoII, NiII, and ZnII coordination polymers assembled from a bent dipyridyl ligand 4-amino-3,5-bis(3-pyridyl)-1,2,4-triazole (3-bpt) and malonic acid (H2mal), which have been prepared at ambient conditions in water-methanol solution. Single-crystal X-ray diffraction indicates that these complexes show a variety of 1-D (for 2-6) and 2-D (for 1) coordination patterns. The results evidently reveal the versatility of 3-bpt with different configurations and binding modes in coordination assemblies, which will be profoundly influenced by the metal ions and even inorganic counter anions. Furthermore, extended supramolecular architectures are constructed via multiple secondary interactions such as hydrogen bonding and aromatic stacking.

  6. Cooperative metal-ligand assisted E/Z isomerization and cyano activation at Cu(II) and Co(II) complexes of arylhydrazones of active methylene nitriles.

    PubMed

    Mahmudov, Kamran T; Kopylovich, Maximilian N; Sabbatini, Alessandra; Drew, Michael G B; Martins, Luísa M D R S; Pettinari, Claudio; Pombeiro, Armando J L

    2014-09-15

    New (E/Z)-2-(2-(1-cyano-2-methoxy-2-oxoethylidene)hydrazinyl)benzoic acid (H2L(4)) and known sodium 2-(2-(dicyanomethylene)hydrazinyl)benzenesulfonate (NaHL(1)), 2-(2-(dicyano-methylene)hydrazinyl)benzoic acid (H2L(2)), and sodium (E/Z)-2-(2-(1-cyano-2-methoxy-2-oxoethylidene)hydrazinyl)benzenesulfonate (NaHL(3)) were used in the template synthesis of a series of Cu(II) and Co(II) complexes [Cu(H2O)2L(1a)]·H2O (1), [Cu(H2O)(3-pyon)L(1b)]·H2O (2), [Cu(H2O)(4-pyon)L(1b)] (3), [Co(H2O)((CH3)2NCHO)(μ-L(2a))]2·(CH3)2NCHO (4), [Cu3(μ3-OH)(NO3)(CH3OH)(μ2-X)3(μ2-HL(3))] (5), [Cu(H2O)(py)L(3)]·H2O (6), [Cu(H2O)2(μ-L(4))]6·6H2O (7), [Cu(2-cnpy(b))2(L(1b))2]·2H2O (8), [Cu(2-cnpy(a))2(L(1a))2]·2H2O (9), and [Cu(H2O)(4-cnpy)(L(1a))2] (10), where 3-pyon = 1-(pyridin-3-yl)ethanone, 4-pyon = 1-(pyridin-4-yl)ethanone, py = pyridine, HX = syn-2-pyridinealdoxime, 4-cnpy = 4-cyanopyridine; 2-cnpy(a), 2-cnpy(b), L(1a), L(1b), L(2a) are the ligands derived from nucleophilic attack of methanol (a) or water (b) on a cyano group of 2-cyanopyridine (2-cnpy), L(1) or L(2), respectively, giving the corresponding iminoesters (2-cnpy(a), L(1a) or L(2a)) or carboxamides (2-cnpy(b) or L(1b)). An auxiliary ligand, namely syn-2-pyridinealdoxime or pyridine, acting cooperatively with the metal ion (Cu(II) in this case), induced an E/Z isomerization of the H2L(4) ligand; the E- and Z-isomers were isolated separately and fully characterized (compounds 9 and 10, respectively). A one-pot activation of nitrile groups in different molecules was achieved in the syntheses of 8 and 9. Complexes 1-10 are catalyst precursors for the solvent-free microwave (MW)-assisted selective oxidation of secondary alcohols to the corresponding ketones, with typical yields in the 29-99% range (TOFs up to 4.94 × 10(3) h(-1)) after 30 min of MW irradiation. PMID:25148569

  7. Metalloprotein-inhibitor binding: Human carbonic anhydrase II as a model for probing metal-ligand interactions in a metalloprotein active site

    PubMed Central

    Martin, David P.; Hann, Zachary S.; Cohen, Seth M.

    2013-01-01

    An ever increasing number of metalloproteins are being discovered that play essential roles in physiological processes. Inhibitors of these proteins have significant potential for the treatment of human disease, but clinical success of these compounds has been limited. Herein, Zn(II)-dependent metalloprotein inhibitors in clinical use are reviewed, and the potential for using novel metal-binding groups (MBGs) in the design of these inhibitors is discussed. By using human carbonic anhydrase II (hCAII) as a model system, the nuances of MBG-metal interactions in the context of a protein environment can be probed. Understanding how metal coordination influences inhibitor binding may help in the design new therapeutics targeting metalloproteins. PMID:23706138

  8. Solid state phase transitions in linear transition metal polymers: Variations of the unit cell dimension in bisglyoximato nickel (II)

    NASA Astrophysics Data System (ADS)

    Böhm, Michael C.

    1984-07-01

    The band structure of bisglyoximato nickel(II) has been studied as a function of the unit cell dimension ( c) in a staggered and an eclipsed chain conformation by means of crystal orbital (CO) calculations based on the tight-binding approximation. The crystal Hamiltonian is a semiempirical Hartree-Fock (HF) self-consistent field (SCF) operator developed in the framework of the INDO formalism. c has been modified in the interval between 3.0 and 4.2 Å, numbers that are typical for metallomacrocycles of the 3d series. The dispersion curves for metal 3d and ligand bands, the density of states distributions, charge reorganizations and the nature of intercell interactions are studied as a function of the separation between the bisglyoximato moieties. The width of the ligand bands is continuously reduced with increasing c values. This simple ε( k) pattern is not found for the “Ni 3d bands” of the low-dimensional material. The weak NiNi overlap in comparison to metal-ligand interactions of the intracell and intercell type leads to a complicated relation between the energetic width of the Ni 3d states and the unit cell dimension c. The character and the shape of the filled Ni 3d bands are analyzed in detail and are compared with the results of band structure calculations on one-dimensional materials with 5d centers (e.g. Krogmann's salt) that show broad dispersions for the metal bands. Physical phenomena in materials with injected (3d) holes, that must be expected as a result of the narrow metal bands, are shortly discussed. The interaction energies between atoms in neighbouring unit cells are decomposed into Coulomb, resonance and exchange contributions. The electrostatic potentials exceed the covalent resonance interactions as well as the exchange coupling. The interaction energy between the Ni centers is highly repulsive. General rules are formulated that give some insight into modification of the electronic structure of organometallic polymers in the 3d series as

  9. PROBING THE LOW-REDSHIFT STAR FORMATION RATE AS A FUNCTION OF METALLICITY THROUGH THE LOCAL ENVIRONMENTS OF TYPE II SUPERNOVAE

    SciTech Connect

    Stoll, R.; Stanek, K. Z.; Pogge, R. W.; Prieto, J. L.

    2013-08-10

    Type II supernovae (SNe) can be used as a star formation tracer to probe the metallicity distribution of global low-redshift star formation. We present oxygen and iron abundance distributions of Type II SN progenitor regions that avoid many previous sources of bias. Because iron abundance, rather than oxygen abundance, is of key importance for the late stage evolution of the massive stars that are the progenitors of core-collapse supernovae, and because iron enrichment lags oxygen enrichment, we find a general conversion from oxygen abundance to iron abundance. The distributions we present here are the best yet observational standard of comparison for evaluating how different classes of supernovae depend on progenitor metallicity. We spectroscopically measure the gas-phase oxygen abundance near a representative subsample of the hosts of Type II SNe from the first-year Palomar Transient Factory (PTF) SN search, using a combination of Sloan Digital Sky Survey (SDSS) spectra near the SN location (9 hosts) and new longslit spectroscopy (25 hosts). The median metallicity of these 34 hosts at or near the SN location is 12+log(O/H) = 8.65, with a median error of 0.09. The median host galaxy stellar mass from fits to SDSS photometry is 10{sup 9.9} M{sub Sun }. They do not show a systematic offset in metallicity or mass from a redshift-matched sample of the MPA/JHU value-added catalog. In contrast to previous SN host metallicity studies, this sample is drawn from a single survey. It is also drawn from an areal rather than a targeted survey, so SNe in the lowest-mass galaxies are not systematically excluded. Indeed, the PTF SN search has a slight bias toward following up transients in low mass galaxies. The progenitor region metallicity distribution we find is statistically indistinguishable from the metallicity distribution of Type II SN hosts found by targeted surveys and by samples from multiple surveys with different selection functions. Using the relationship between

  10. Next Generation Metallic Iron Nodule Technology in Electric Arc Steelmaking - Phase II

    SciTech Connect

    Donald R. Fosnacht; Iwao Iwasaki; Richard F. Kiesel; David J. Englund; David W. Hendrickson; Rodney L. Bleifuss

    2010-12-22

    The current trend in the steel industry is a gradual decline in conventional steelmaking from taconite pellets in blast furnaces, and an increasing number of alternative processes using metallic scrap iron, pig iron and metallized iron ore products. Currently, iron ores from Minnesota and Michigan are pelletized and shipped to the lower Great Lakes ports as blast furnace feed. The existing transportation system and infrastructure is geared to handling these bulk materials. In order to expand the opportunities for the existing iron ore mines beyond their blast furnace customer base, a new material is needed to satisfy the needs of the emerging steel industry while utilizing the existing infrastructure and materials handling. A recent commercial installation employing Kobe Steel’s ITmk3 process, was installed in Northeastern Minnesota. The basic process uses a moving hearth furnace to directly reduce iron oxides to metallic iron from a mixture of iron ore, coals and additives. The resulting products can be shipped using the existing infrastructure for use in various steelmaking processes. The technology reportedly saves energy by 30% over the current integrated steelmaking process and reduces emissions by more than 40%. A similar large-scale pilot plant campaign is also currently in progress using JFE Steel’s Hi-QIP process in Japan. The objective of this proposal is to build upon and improve the technology demonstrated by Kobe Steel and JFE, by further reducing cost, improving quality and creating added incentive for commercial development. This project expands previous research conducted at the University of Minnesota Duluth’s Natural Resources Research Institute and that reported by Kobe and JFE Steel. Three major issues have been identified and are addressed in this project for producing high-quality nodular reduced iron (NRI) at low cost: (1) reduce the processing temperature, (2) control the furnace gas atmosphere over the NRI, and (3) effectively use sub

  11. 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.

  12. 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.

  13. 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.

  14. Instrumentation in positron emission tomography

    SciTech Connect

    Not Available

    1988-03-11

    Positron emission tomography (PET) is a three-dimensional medical imaging technique that noninvasively measures the concentration of radiopharmaceuticals in the body that are labeled with positron emitters. With the proper compounds, PET can be used to measure metabolism, blood flow, or other physiological values in vivo. The technique is based on the physics of positron annihilation and detection and the mathematical formulations developed for x-ray computed tomography. Modern PET systems can provide three-dimensional images of the brain, the heart, and other internal organs with resolutions on the order of 4 to 6 mm. With the selectivity provided by a choice of injected compounds, PET has the power to provide unique diagnostic information that is not available with any other imaging modality. This is the first five reports on the nature and uses of PET that have been prepared for the American Medical Association's Council on Scientific Affairs by an authoritative panel.

  15. 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.

  16. Instrumentation for positron emission tomography.

    PubMed

    Budinger, T F; Derenzo, S E; Huesman, R H

    1984-01-01

    Positron emission tomography with a spatial resolution of 2 mm full width at half maximum for quantitation in regions of interest 4 mm in diameter will become possible with the development of detectors that achieve ultrahigh resolution. Improved resolution will be possible using solid-state photodetectors for crystal identification or photomultiplier tubes with many small electron multipliers . Temporal resolution of 2 seconds and gating of cyclic events can be accomplished if statistical requirements are met. The major physical considerations in achieving high-resolution positron emission tomography are the degradation in resolution resulting from positron range, emission angle, parallax error, detector sampling density, the sensitivity of various detector materials and packing schemes, and the trade off between temporal resolution and statistical accuracy. The accuracy of data required for physiological models depends primarily on the fidelity of spatial sampling independent of statistical constraints. PMID:6611124

  17. E166: Polarized Positrons & Polarimetry

    SciTech Connect

    Schuler, K.Peter; /DESY

    2011-12-06

    A proof-of-principle experiment has been carried out in the Final Focus Test Beam (FFTB) at Stanford Linear Accelerator Center (SLAC) to demonstrate production of polarized positrons in a manner suitable for implementation at the International Linear Collider (ILC). A helical undulator of 2.54 mm period and 1 -m length produced circularly polarized photons with a first harmonic endpoint energy of 8 MeV when traversed by a 46.6 GeV electron beam. The polarized photons were converted to polarized positrons in a 0.2-radiation-length tungsten target. The polarization of these positrons was measured using a Compton transmission polarimeter to have peak value in excess of 80%.

  18. Elaborated 1H NMR study for the ligitional behavior of two thiosemicarbazide derivatives towards some heavy metals (Sn(II), Sb(III), Pb(II) and Bi(III)), thermal, antibacterial and antifungal studies

    NASA Astrophysics Data System (ADS)

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

    2011-10-01

    A new series of heavy metal complexes are prepared. Sn(II), Sb(III), Pb(II) and Bi(III) are the metal ions used in complexation with two thiosemicarbazide ligands. The IR and 1H NMR spectra of the free ligands display their presence in thiole-thione forms coincide with each other. The IR spectra of the complexes support the presence of 2:2 molar ratio (M:HL) with HL 1 ligand and 1:1 beside 1:2 with HL 2. The ligand coordinates as bi molecules in some complexes and displays two tautomer forms at the same complex molecule 1H NMR spectra of Sn(II) and Sb(III) complexes were done and comes coincide with IR data. The electronic spectral analysis displays a lower shift appearance in n → π* charge transfer band in most isolated complexes. As well as, a new band is shinned in visible region with Sb(III), Bi(III) complexes and Sn(II)-HL 2. This band is pointed to its use in spectrophotometric analysis for these metal ions. The TG analysis for all isolated compounds was briefly discussed. The molecular modeling parameters support the stability of thiole form of the free ligands in comparing with their thiones by a small difference. The antibacterial and antifungal activities were studied against some organisms and reveal the priority of most investigated complexes.

  19. Bio-sensitive activities of coordination compounds containing 1,10-phenanthroline as co-ligand: Synthesis, structural elucidation and DNA binding properties of metal(II) complexes

    NASA Astrophysics Data System (ADS)

    Raman, Natarajan; Mahalakshmi, Rajkumar; Mitu, Liviu

    2014-10-01

    Present work reports the DNA binding and cleavage characteristics of a series of mixed-ligand complexes having the composition [M(L)(phen)2]Cl2 (where M = Cu(II), Ni(II), Co(II) and Zn(II) and phen as co-ligand) in detail. Their structural features and other properties have been deduced from their elemental analyses, magnetic susceptibility and molar conductivity as well as from IR, UV-Vis, 1H NMR and EPR spectral studies. The UV-Vis, magnetic susceptibility and EPR spectral data of metal complexes suggest an octahedral geometry. The binding properties of these complexes with calf thymus DNA (CT-DNA) have been explored using electronic absorption spectroscopy, viscosity measurement, cyclic voltammetry and differential pulse voltammetry. The DNA-binding constants for Cu(II), Ni(II), Co(II), and Zn(II) complexes are 6.14 × 105 M-1, 1.8 × 105 M-1, 6.7 × 104 M-1 and 2.5 × 104 M-1 respectively. Detailed analysis reveals that these complexes interact with DNA through intercalation binding. Nuclease activity has also been investigated by gel electrophoresis. Moreover, the synthesized Schiff base and its mixed-ligand complexes have been screened for antibacterial and antifungal activities. The data reveal that the complexes exhibit higher activity than the parent ligand.

  20. 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.

  1. Particle physics. Positrons ride the wave

    SciTech Connect

    Piot, Philippe

    2015-08-26

    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.

  2. Enhancing the Magnetic Anisotropy of Linear Cr(II) Chain Compounds Using Heavy Metal Substitutions.

    PubMed

    Christian, Jonathan H; Brogden, David W; Bindra, Jasleen K; Kinyon, Jared S; van Tol, Johan; Wang, Jingfang; Berry, John F; Dalal, Naresh S

    2016-07-01

    Magnetic properties of the series of three linear, trimetallic chain compounds Cr2Cr(dpa)4Cl2, 1, Mo2Cr(dpa)4Cl2, 2, and W2Cr(dpa)4Cl2, 3 (dpa = 2,2'-dipyridylamido), have been studied using variable-temperature dc and ac magnetometry and high-frequency EPR spectroscopy. All three compounds possess an S = 2 electronic ground state arising from the terminal Cr(2+) ion, which exhibits slow magnetic relaxation under an applied magnetic field, as evidenced by ac magnetic susceptibility and magnetization measurements. The slow relaxation stems from the existence of an easy-axis magnetic anisotropy, which is bolstered by the axial symmetry of the compounds and has been quantified through rigorous high-frequency EPR measurements. The magnitude of D in these compounds increases when heavier ions are substituted into the trimetallic chain; thus D = -1.640, -2.187, and -3.617 cm(-1) for Cr2Cr(dpa)4Cl2, Mo2Cr(dpa)4Cl2, and W2Cr(dpa)4Cl2, respectively. Additionally, the D value measured for W2Cr(dpa)4Cl2 is the largest yet reported for a high-spin Cr(2+) system. While earlier studies have demonstrated that ligands containing heavy atoms can enhance magnetic anisotropy, this is the first report of this phenomenon using heavy metal atoms as "ligands". PMID:26881994

  3. Mixed-metal molecular complexes: Single-molecule nanomagnets and bioinorganic models of the water oxidizing complex of photosystem II

    NASA Astrophysics Data System (ADS)

    Mishra, Abhudaya

    2006-12-01

    The current burgeoning research in high nuclearity manganese-containing carboxylate clusters is primarily due to their relevance in areas as diverse as magnetic materials and bioinorganic chemistry. In the former, the ability of single molecules to retain, below a critical temperature (T B), their magnetization vector, resulting in the observation of bulk magnetization in the absence of a field and without long-range ordering of the spins, has termed such molecules as Single-Molecule Magnets (SMMs), or molecular nanomagnets. These molecules display superparamagnet like slow magnetization relaxation arising from the combination of a large molecular spin, S, and a large and negative magnetoanisotropy, D. Traditionally, these nanomagnets have been Mn containing species. An out of the box approach towards synthesizing SMMs is engineering mixed-metal Mn-containing compounds. An attractive choice towards this end is the use of Lanthanides (Ln), which possess both a high spin, S, and a large D. A family of related MnIII8Ce IV SMMs has been synthesized. However, the Ce ion of these complexes is diamagnetic (CeIV). Thus, further investigation has led to the isolation of a family of MnIII11Ln III4 complexes in which all but the Ln = Eu complex function as single-molecule nanomagnets. The mixed-metal synthetic effort has been extended to include actinides with the successful isolation of a Mn IV10ThIV6 complex, albeit this homovalent complex is not a SMM. In the bioinorganic research, the Water Oxidizing Complex (WOC) in Photosystem II (PS II) catalyzes the oxidation of H2O to O2 in green plants, algae and cyanobacteria. Recent crystal structures of the WOC confirm it to be a Mn4CaOx cluster with primarily carboxylate ligation. To date, various multinuclear Mn complexes have been synthesized as putative models of the WOC. On the contrary, there have been no synthetic MnCa(Sr) mixed-metal complexes. Thus, in this bioinorganic modeling research of the WOC, various synthetic

  4. General synthetic approach to heterostructured nanocrystals based on noble metals and I-VI, II-VI, and I-III-VI metal chalcogenides.

    PubMed

    Liu, Minghui; Zeng, Hua Chun

    2014-08-19

    Solid metal precursors (alloys or monometals) can serve both as a starting template and as a source material for chemical transformation to metal chalcogenides. Herein, we develop a simple solution-based strategy to obtain highly monodisperse noble-metal-based heterostructured nanocrystals from such precursor seeds. By utilizing chemical and structural inhomogeneity of these metal seeds, in this work, we have synthesized a total of five I-VI (Ag2S, Ag2Se, Ag3AuS2, Ag3AuSe2, and Cu9S5), three II-VI (CdS, CdSe, and CuSe), and four I-III-VI (AgInS2, AgInSe2, CuInS2, and CuInSe2) chalcogenides, together with their fifteen associated heterodimers (Au-Ag2S, Au-Ag2Se, Au-Ag3AuS2, Au-Ag3AuSe2, Au-AgInS2, Au-AgInSe2, Au-CdS, Au-CdSe, Ag-Ag2S, Ag-AgInS2, Au-Cu9S5, Au-CuInS2, Au-CuSe, Au-CuInSe2, and Pt-AgInS2) to affirm the process generality. Briefly, by adding elemental sulfur or selenium to AuAg alloy seeds and tuning the reaction conditions, we can readily obtain phase-pure Au-Ag2S, Au-Ag2Se, Au-Ag3AuS2, and Au-Ag3AuSe2 heterostructures. Similarly, we can also fabricate Au-AgInS2 and Au-AgInSe2 heterostructures from the AuAg seeds by adding sulfur/selenium and indium precursors. Furthermore, by partial or full conversion of Ag seeds, we can prepare both single-phase Ag chalcogenide nanocrystals and Ag-based heterostructures. To demonstrate wide applicability of this strategy, we have also synthesized Au-based binary and ternary Cu chalcogenide (Au-Cu9S5, Au-CuSe, Au-CuInS2, and Au-CuInSe2) heterostructures from alloy seeds of AuCu and Pt chalcogenides (e.g., Pt-AgInS2) from alloy seeds of PtAg. The structure and composition of the above products have been confirmed with X-ray diffraction, high-resolution transmission electron microscopy, X-ray photoelectron spectroscopy, and energy-dispersive X-ray spectroscopy methods. A kinetic investigation of the formation mechanism of these heterostructures is brought forward using Au-AgInS2 and Ag-CuInS2 as model examples. PMID

  5. EPR of layered magnetic metal-amino acid salts. II. Cu(L-Met) 2

    NASA Astrophysics Data System (ADS)

    Levstein, P. R.; Steren, C. A.; Gennaro, A. M.; Calvo, R.

    1988-03-01

    Single crystals of bis(L-methioninato)copper(II), Cu(L-Met) 2, were studied by EPR at 9.7 and 33.6 GHz, at 300 K. The position and the peak-to-peak linewidth of the single observed EPR line were measured in three perpendicular planes of the samples. This single resonance is due to the collapse of the resonances of the two magnetically inequivalent copper ions in the lattice caused by the exchange interaction. The components of the molecular g tensor for isolated copper ions were obtained using a model which assumes axial symmetry. The results indicate that the unpaired electron occupies the d( x2 - y2) orbital, and the orientation of the molecule obtained from the EPR data agrees with the crystallographic result. The linewidth data support a model which assumes exchange narrowing of the magnetic dipolar interaction in a two-dimensional magnetic lattice, an incomplete collapse of the hyperfine structure, and a frequency-dependent contribution in the planes where the g factors for the two sites of copper are different. An analysis of this latter contribution, allows to evaluate an exchange coupling constant | J'| = 0.10 K between inequivalent copper neighbors. Besides, the analysis of the hyperfine contribution to the linewidth gives | J| = 0.18 K for the average value of the exchange interaction of one copper ion with its six nearest neighbors within the layer. Concerning the possible superexchange paths between inequivalent copper ions, we suggest they can be of two types: the CuNH…OCu one, involving hydrogen bonds between equatorial nitrogens and equatorial oxygens, and the other consisting of CuOCOCu carboxylate bridges involving apical and equatorial oxygens. They are discussed in view of the experimental results.

  6. Spin Forming Aluminum Crew Module (CM) Metallic Aft Pressure Vessel Bulkhead (APVBH) - Phase II

    NASA Technical Reports Server (NTRS)

    Hoffman, Eric K.; Domack, Marcia S.; Torres, Pablo D.; McGill, Preston B.; Tayon, Wesley A.; Bennett, Jay E.; Murphy, Joseph T.

    2015-01-01

    The principal focus of this project was to assist the Multi-Purpose Crew Vehicle (MPCV) Program in developing a spin forming fabrication process for manufacture of the Orion crew module (CM) aft pressure vessel bulkhead. The spin forming process will enable a single piece aluminum (Al) alloy 2219 aft bulkhead resulting in the elimination of the current multiple piece welded construction, simplify CM fabrication, and lead to an enhanced design. Phase I (NASA TM-2014-218163 (1)) of this assessment explored spin forming the single-piece CM forward pressure vessel bulkhead. The Orion MPCV Program and Lockheed Martin (LM) recently made two critical decisions relative to the NESC Phase I work scope: (1) LM selected the spin forming process to manufacture a single-piece aft bulkhead for the Orion CM, and (2) the aft bulkhead will be manufactured from Al 2219. Based on the Program's new emphasis related to the spin forming process, the NESC was asked to conduct a Phase II assessment to assist in the LM manufacture of the aft bulkhead and to conduct a feasibility study into spin forming the Orion CM cone. This activity was approved on June 19, 2013. Dr. Robert Piascik, NASA Technical Fellow for Materials at the Langley Research Center (LaRC), was selected to lead this assessment. The project plan was approved by the NASA Engineering and Safety Center (NESC) Review Board (NRB) on July 18, 2013. The primary stakeholders for this assessment were the NASA and LM MPCV Program offices. Additional benefactors are commercial launch providers developing CM concepts.

  7. Spin Forming Aluminum Crew Module (CM) Metallic Aft Pressure Vessel Bulkhead (APVBH) - Phase II

    NASA Technical Reports Server (NTRS)

    Hoffman, Eric K.; Domack, Marcia S.; Torres, Pablo D.; McGill, Preston B.; Tayon, Wesley A.; Bennett, Jay E.; Murphy, Joseph T.

    2015-01-01

    The principal focus of this project was to assist the Multi-Purpose Crew Vehicle (MPCV) program in developing a spin forming fabrication process for manufacture of the Orion crew module (CM) aft pressure vessel bulkhead. The spin forming process will enable a single piece aluminum (Al) alloy 2219 aft bulkhead resulting in the elimination of the current multiple piece welded construction, simplify CM fabrication, and lead to an enhanced design. Phase I (NASA TM-2014-218163, (1)) of this assessment explored spin forming the single-piece CM forward pressure vessel bulkhead. The MPCV Program and Lockheed Martin (LM) recently made two critical decisions relative to the NESC Phase I work scope: (1) LM selected the spin forming process to manufacture a singlepiece aft bulkhead for the Orion CM, and (2) the aft bulkhead will be manufactured from Al 2219. Based on the Program's new emphasis related to the spin forming process, the NESC was asked to conduct a Phase II assessment to assist in the LM manufacture of the aft bulkhead and to conduct a feasibility study into spin forming the Orion CM cone. This activity was approved on June 19, 2013. Dr. Robert Piascik, NASA Technical Fellow for Materials at the Langley Research Center (LaRC), was selected to lead this assessment. The project plan was approved by the NASA Engineering and Safety Center (NESC) Review Board (NRB) on July 18, 2013. The primary stakeholders for this assessment are the NASA and LM MPCV Program offices. Additional benefactors are commercial launch providers developing CM concepts.

  8. Spectral, magnetic, biocidal screening, DNA binding and photocleavage studies of mononuclear Cu(II) and Zn(II) metal complexes of tricoordinate heterocyclic Schiff base ligands of pyrazolone and semicarbazide/thiosemicarbazide based derivatives

    NASA Astrophysics Data System (ADS)

    Raman, N.; Selvan, A.; Manisankar, P.

    2010-07-01

    We depict the synthesis and characterization of copper(II) and zinc(II) coordination compounds of 4-(3',4'-dimethoxybenzaldehydene)2-3-dimethyl-1-phenyl-3-pyrazolin-5-semicarbazone ( 1a), 4-(3',4'-dimethoxybenzaldehydene)2-3-dimethyl-1-phenyl-3-pyrazolin-5-thiosemicarbazone ( 1b), 4-(3'-hydroxy-4'-nitrobenzaldehydene)2-3-dimeth yl-1-phenyl-3-pyrazolin-5-semicarbazone ( 1c) and 4-(3'-hydroxy-4'-nitrobenzal dehydene)2-3-dimethyl-1-phenyl-3-pyrazolin-5-thiosemicarbazone ( 1d). All the remote compounds have the general composition [ML 2] (M = Cu(II) and Zn(II)); L = Schiff base ( 1a- 1d). All the complexes were characterized by elemental analysis, molar conductivity, IR, 1H NMR, UV-vis, ESI-Mass, magnetic susceptibility measurements, cyclic voltammetric measurements, and EPR spectral studies. It has been originated that the Schiff bases with Cu(II) and Zn(II) ions form mononuclear complexes on 1:2 (metal:ligand) stoichiometry. Distorted octahedral environment is suggested for the metal complexes. The conductivity data confirm the non-electrolytic nature of the complexes. The interaction of CuL 21a- 1d complexes with CT DNA was investigated by spectroscopic, electrochemical and viscosity measurements. Results suggest that the copper complexes bind to DNA via an intercalative mode. Moreover, the complexes have been found to promote the photocleavage of plasmid DNA pBR322 under irradiation at 365 nm. The Schiff bases and their metal complexes were screened for their antifungal and antibacterial activities against different species of pathogenic fungi and bacteria and their biopotency has been discussed.

  9. Communication: Photoactivation of nucleobase bound platinum{sup II} metal complexes: Probing the influence of the nucleobase

    SciTech Connect

    Sen, Ananya; Dessent, Caroline E. H.

    2014-12-28

    We present UV laser action spectra (220-300 nm) of isolated nucleobase-bound Pt{sup II}(CN){sub 4}{sup 2−} complexes, i.e., Pt(CN){sub 4}{sup 2−}⋅M, where M = uracil, thymine, cytosine, and adenine. These metal complex-nucleobase clusters represent model systems for identifying the fundamental photophysical and photochemical processes occurring in photodynamic platinum (II) drug therapies that target DNA. This is the first study to explore the specific role of the nucleobase in the photophysics of the aggregate complex. Each of the complexes studied displays a broadly similar absorption spectra, with a strong λ{sub max} ∼ 4.7 eV absorption band (nucleobase localized chromophore) and a subsequent increase in the absorption intensity towards higher spectral-energy (Pt(CN){sub 4}{sup 2−} localized chromophore). However, strikingly different band widths are observed across the series of complexes, decreasing in the order Pt(CN){sub 4}{sup 2−}⋅Thymine > Pt(CN){sub 4}{sup 2−}⋅Uracil > Pt(CN){sub 4}{sup 2−}⋅Adenine > Pt(CN){sub 4}{sup 2−}⋅Cytosine. Changes in the bandwidth of the ∼4.7 eV band are accompanied by distinctive changes in the photofragment product ions observed following photoexcitation, with the narrower-bandwidth complexes showing a greater propensity to decay via electron detachment decay. We discuss these observations in the context of the distinctive nucleobase-dependent excited state lifetimes.

  10. Land application of chemically treated sewage sludge. II. Effects on soil and plant heavy metal content

    SciTech Connect

    Soon, Y.K.; Bates, T.E.; Moyer, J.R.

    1980-07-01

    Anaerobically digested sewage sludges resulting from treatment of sewage with Ca(OH)/sub 2/, Al/sub 2/(SO/sub 4/)/sub 3/, or FeCl/sub 3/ for phosphorus precipitation were applied to corn (Zea mays L.) and bromegrass (Bromus inermis Leyess) grown on a soil having an initial pH of 7.3. Rates of sludge supplied 200, 400, 800, and and 1,600 kg N/ha each year for 5 years. Treatments with NH/sub 4/NO/sub 3/ supplying 0, 100, 20, and 400 kg N/ha were included for comparison. Plant tissue was analyzed for Cu, Zn, Mn, Cd, Ni, Cr, and Pb. No toxicity or deficiency symptoms were noted. Soil Zn, Cd, and Ni extracted by NTA (nitrilotriacetic acid) were increased by continued sludge application. The NTA-extractable Zn and Cd were positively correlated with the Zn and Cd concentrations in corn stover. Soil pH was reduced by the Fe-sludge application, slightly affected by the Al-sludge, and increased by the Ca-sludge. Increases in Cu concentrations in bromegrass and corn stover were associated with increases in the N content rather than the source of N, and plant Cu concentrations remained relatively constant across years. Sewage sludge application increased Zn, Cd, and Ni concentrations in bromegrass and corn stover, and Zn and Ni concentrations in corn grain, particularly at the higher metal loadings from sludge application. Zinc and Cd concentrations, especially in corn stover, increased with continued sludge application during the 5-year period. The inclusion of soil pH as a factor, in addition to cummulative amounts of Zn or Cd added as a constituent of sludge, improved the regression equations predicting Zn or Cd uptake.

  11. Electrostatic Nonplanar Positron-Acoustic Shock Waves in Superthermal Electron-Positron-Ion Plasmas

    NASA Astrophysics Data System (ADS)

    M. J., Uddin; M. S., Alam; A. A., Mamun

    2015-06-01

    The basic properties of the nonlinear propagation of the nonplanar (cylindrical and spherical) positron-acoustic (PA) shock waves (SHWs) in an unmagnetized electron-positron-ion (e-p-i) plasma containing immobile positive ions, mobile cold positrons, and superthermal (kappa distributed) hot positrons and electrons are investigated both analytically and numerically. The modified Burgers equation (mBE) is derived by using the reductive perturbation method. The basic features of PA SHWs are significantly modified by the cold positron kinematic viscosity (η), superthermal parameter of electrons (κe), superthermal parameter of hot positrons (κp), the ratio of the electron temperature to hot positron temperature (σ), the ratio of the electron number density to cold positron number density and the ratio of the hot positron number density to cold positron number density (μph). This study could be useful to identify the basic properties of nonlinear electrostatic disturbances in dissipative space and laboratory plasmas.

  12. 21 CFR 892.1110 - Positron camera.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 8 2011-04-01 2011-04-01 false Positron camera. 892.1110 Section 892.1110 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) MEDICAL DEVICES RADIOLOGY DEVICES Diagnostic Devices § 892.1110 Positron camera. (a) Identification. A positron camera is a device intended to image...

  13. Reversible CO Scavenging via Adsorbate-Dependent Spin State Transitions in an Iron(II)-Triazolate Metal-Organic Framework.

    PubMed

    Reed, Douglas A; Xiao, Dianne J; Gonzalez, Miguel I; Darago, Lucy E; Herm, Zoey R; Grandjean, Fernande; Long, Jeffrey R

    2016-05-01

    A new metal-organic framework, Fe-BTTri (Fe3[(Fe4Cl)3(BTTri)8]2·18CH3OH, H3BTTri =1,3,5-tris(1H-1,2,3-triazol-5-yl)benzene)), is found to be highly selective in the adsorption of CO over a variety of other gas molecules, making it extremely effective, for example, in the removal of trace CO from mixtures with H2, N2, and CH4. This framework not only displays significant CO adsorption capacity at very low pressures (1.45 mmol/g at just 100 μbar), but, importantly, also exhibits readily reversible CO binding. Fe-BTTri utilizes a unique spin state change mechanism to bind CO in which the coordinatively unsaturated, high-spin Fe(II) centers of the framework convert to octahedral, low-spin Fe(II) centers upon CO coordination. Desorption of CO converts the Fe(II) sites back to a high-spin ground state, enabling the facile regeneration and recyclability of the material. This spin state change is supported by characterization via infrared spectroscopy, single crystal X-ray analysis, Mössbauer spectroscopy, and magnetic susceptibility measurements. Importantly, the spin state change is selective for CO and is not observed in the presence of other gases, such as H2, N2, CO2, CH4, or other hydrocarbons, resulting in unprecedentedly high selectivities for CO adsorption for use in CO/H2, CO/N2, and CO/CH4 separations and in preferential CO adsorption over typical strongly adsorbing gases like CO2 and ethylene. While adsorbate-induced spin state transitions are well-known in molecular chemistry, particularly for CO, to our knowledge this is the first time such behavior has been observed in a porous material suitable for use in a gas separation process. Potentially, this effect can be extended to selective separations involving other π-acids. PMID:27097297

  14. LSQ13fn: A type II-Plateau supernova with a possibly low metallicity progenitor that breaks the standardised candle relation

    NASA Astrophysics Data System (ADS)

    Polshaw, J.; Kotak, R.; Dessart, L.; Fraser, M.; Gal-Yam, A.; Inserra, C.; Sim, S. A.; Smartt, S. J.; Sollerman, J.; Baltay, C.; Rabinowitz, D.; Benetti, S.; Botticella, M. T.; Campbell, H.; Chen, T.-W.; Galbany, L.; McKinnon, R.; Nicholl, M.; Smith, K. W.; Sullivan, M.; Takáts, K.; Valenti, S.; Young, D. R.

    2016-04-01

    We present optical imaging and spectroscopy of supernova (SN) LSQ13fn, a type II supernova with several hitherto-unseen properties. Although it initially showed strong symmetric spectral emission features attributable to He ii, N iii, and C iii, reminiscent of some interacting SNe, it transitioned into an object that would fall more naturally under a type II-Plateau (IIP) classification. However, its spectral evolution revealed several unusual properties: metal lines appeared later than expected, were weak, and some species were conspicuous by their absence. Furthermore, the line velocities were found to be lower than expected given the plateau brightness, breaking the SN IIP standardised candle method for distance estimates. We found that, in combination with a short phase of early-time ejecta-circumstellar material interaction, metal-poor ejecta, and a large progenitor radius could reasonably account for the observed behaviour. Comparisons with synthetic model spectra of SNe IIP of a given progenitor mass would imply a progenitor star metallicity as low as 0.1 Z⊙. LSQ13fn highlights the diversity of SNe II and the many competing physical effects that come into play towards the final stages of massive star evolution immediately preceding core-collapse. The reduced spectra are only available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (ftp://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/588/A1

  15. Optical and electrochemical characteristics of ethylenediamine complexes of Pt(II) and Ir(III) with metalated 2-phenyl- and 2-naphthylbenzothiazole

    NASA Astrophysics Data System (ADS)

    Katlenok, E. A.; Balashev, K. P.

    2016-05-01

    The cyclometalated complexes [Pt(C^N)En]PF6 and [Ir(C^N)2En]PF6 ((C^N)- are deprotonated forms of 2-phenylbenzothiazole or 2-naphthylbenzothiazole and En is ethylenediamine) are studied by 1H NMR, IR, electronic absorption, and emission spectroscopy, as well as by voltammetry. Metalation of heterocyclic ligands leads to the formation of five-membered {M(C^N)} cycles in the composition of squareplanar Pt(II) complexes and octahedral Ir(III) complexes of the cis-C,C structure. A bathochromic shift of the metal-to-cyclometalated ligand charge transfer bands and a decrease in the potential difference between the single-electron waves of metal-centered oxidation and ligand-centered reduction of complexes upon substitution of 2-phenylbenzothiazole by 2-naphthylbenzothiazole and of Pt(II) by Ir(II) are shown. The phosphorescence of complexes in the visible region is assigned to the radiative transition from the metal-modified intraligand electronic excited state.

  16. Versatile Tailoring of Paddle-Wheel Zn(II) Metal-Organic Frameworks through Single-Crystal-to-Single-Crystal Transformations.

    PubMed

    Pal, Tapan K; Neogi, Subhadip; Bharadwaj, Parimal K

    2015-11-01

    A new tetracarboxylate ligand having short and long arms formed 2D layer Zn(II) coordination polymer 1 with paddle-wheel secondary building units under solvothermal conditions. The framework undergoes solvent-specific single crystal-to-single crystal (SC-SC) transmetalation to produce 1Cu . With a sterically encumbered dipyridyl linker, the same ligand forms non-interpenetrated, 3D, pillared-layer Zn(II) metal-organic framework (MOF) 2, which takes part in SC-SC linker-exchange reactions to produce three daughter frameworks. The parent MOF 2 shows preferential incorporation of the longest linker in competitive linker-exchange experiments. All the 3D MOFs undergo complete SC-SC transmetalation with Cu(II) , whereby metal exchange in different solvents and monitoring of X-ray structures revealed that bulky solvated metal ions lead to ordering of the shortest linker in the framework, which confirms that the solvated metal ions enter through the pores along the linker axis. PMID:26383591

  17. 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.

  18. Positron-acoustic shock waves associated with cold viscous positron fluid in superthermal electron-positron-ion plasmas

    NASA Astrophysics Data System (ADS)

    Uddin, M. J.; Alam, M. S.; Mamun, A. A.

    2015-06-01

    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.

  19. Magnetic structure and dynamics of a strongly one-dimensional cobaltII metal-organic framework

    NASA Astrophysics Data System (ADS)

    Sibille, Romain; Lhotel, Elsa; Mazet, Thomas; Malaman, Bernard; Ritter, Clemens; Ban, Voraksmy; François, Michel

    2014-03-01

    We investigate the magnetism of the CoII4(OH)2(C10H16O4)3 metal-organic framework, which displays complex inorganic chains separated from each other by distances of 1 to 2 nm and orders at 5.4 K. The zero-field magnetic structure is determined using neutron powder diffraction: it is mainly antiferromagnetic but possesses a ferromagnetic component along the c axis. This magnetic structure persists in presence of a magnetic field. Alternating current susceptibility measurements confirm the existence of a single thermally activated regime over seven decades in frequency (E /kB≈64 K), whereas time-dependent relaxation of the magnetization after saturation in an external field leads to a two times smaller energy barrier. These experiments probe the slow dynamics of domain walls within the chains: we propose that the ac measurements are sensitive to the motion of existing domain walls within the chains, while the magnetization measurements are governed by the creation of domain walls.

  20. Role of the crystal field stabilization energy in the formation of metal(II) formate mixed crystals

    NASA Astrophysics Data System (ADS)

    Balarew, Christo; Stoilova, Donka; Vassileva, Violeta

    A relationship between the distribution coefficient values and the factors determining the isomorphous substitution of some metal(II) formates (Mg, Mn, Fe, Co, Ni, Cu, Zn, Cd) has been found, given by D=[exp⁡{aṡf[ΔR/R]+bṡϕ(Δɛ)+cṡψ(Δs)}/{RT}, where Δ R/R is the relative difference in the ionic radii of the intersubstituting ions, Δɛ is the difference in the Me sbnd O bond energy, Δ s is the difference in the crystal field stabilization energy. The pre-exponential term represents the balance in bonding factors between the ions in the crystal and in the aqueous solution, in the case of ideally mixing in the solid state. The exponential term takes into account the enthalpy of mixing in the solid state. For the isostructural formate salts in which the substitution of a given cation by another one occurs in equivalent octahedral positions, the difference in the crystal field stabilization energy exerts the most important influence on the enthalpy of mixing.

  1. Synthesis of new piperazine derived Cu(II)/Zn(II) metal complexes, their DNA binding studies, electrochemistry and anti-microbial activity: Validation for specific recognition of Zn(II) complex to DNA helix by interaction with thymine base

    NASA Astrophysics Data System (ADS)

    Bhat, Irshad-ul-Haq; Tabassum, Sartaj

    2009-06-01

    New 3,4:9,10-dibenzo-2,11-dihydroxy-1,12-bispiperazine-5,8-dioxododecane complexes [C 24H 36N 4O 6Cu] ( 1), [C 24H 32N 4O 4Zn] ( 2) have been synthesized and characterized by elemental analysis, IR, NMR, Mass, EPR, UV-vis spectroscopy and molar conductance measurements. The complexes are non-ionic in nature and possess octahedral geometry around Cu 2+, Zn 2+ central metal ions. The binding studies of 1 and 2 with calf thymus DNA (CT-DNA) were investigated by UV-vis, fluorescence, cyclic voltammetery and viscosity measurements. The calculated binding constant Kb for 1 and 2 obtained from UV-vis absorption studies was 7.6 × 10 3 M -1, 80.8 × 10 4 M -1, respectively. The intrinsic binding constants were also estimated to be 7.0 × 10 4 M -1 and 7.53 × 10 5 M -1 for 1 and 2, respectively by using emission titrations. These experimental results suggest that complexes are groove binders and interact to CT-DNA with different affinities. Both the complexes in presence and absence of CT-DNA show quasireversible wave corresponding to Cu II/Cu I and Zn II/Zn I redox couple. The changes in E1/2, Δ E, Ipa/ Ipc ascertain the interaction of 1 and 2 with CT-DNA. Further, decrease in viscosity of CT-DNA with increasing concentration of complexes was observed. In vitro, antimicrobial activity against fungi A. brassicicola, A. niger and bacteria E. coli, P. aeruginosa of complexes were carried out, which indicate that complex 2 is more active against both fungal and bacterial strains as shown by % inhibition data.

  2. 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.

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

    SciTech Connect

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

    2014-03-15

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

  4. 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.

  5. Development of a transport system for the copper source of the Texas Intense Positron Source facility

    NASA Astrophysics Data System (ADS)

    Doron, O.; Biegalski, S. R.; O'Kelly, S.; Hurst, B. J.

    2006-01-01

    The transport system design and construction for The Texas Intense Positron Source (TIPS) facility has been completed. This facility is located on beam port 1 of The University of Texas at Austin TRIGA Mark II 1.1 MW research reactor. The TIPS will provide a high intensity, variable energy positron beam for use in material studies. The natural copper source is transported into beam port 1 of the reactor where it is irradiated at close proximity to the reactor core. The transport system is an L-shaped aluminum channel that utilizes pulleys to drive a source cart. The copper source is transported on the cart into and out of the beam port for irradiation. After removal from the beam port, the activated copper positron source will be placed into a vacuum chamber where the positrons are moderated with annealed tungsten foil and electrostatically extracted.

  6. Non-bonding interactions and non-covalent delocalization effects play a critical role in the relative stability of group 12 complexes arising from interaction of diethanoldithiocarbamate with the cations of transition metals Zn(II), Cd(II), and Hg(II): a theoretical study.

    PubMed

    Bahrami, Homayoon; Farhadi, Saeed; Siadatnasab, Firouzeh

    2016-07-01

    The chelating properties of diethanoldithiocarbamate (DEDC) and π-electron flow from the nitrogen atom to the sulfur atom via a plane-delocalized π-orbital system (quasi ring) was studied using a density functional theory method. The molecular structure of DEDC and its complexes with Zn(II), Cd(II), and Hg(II) were also considered. First, the geometries of this ligand and DEDC-Zn(II), DEDC-Cd(II), and DEDC-Hg(II) were optimized, and the formation energies of these complexes were then calculated based on the electronic energy, or sum of electronic energies, with the zero point energy of each species. Formation energies indicated the DEDC-Zn(II) complex as the most stable complex, and DEDC-Cd(II) as the least stable. Structural data showed that the N1-C2 π-bond was localized in the complexes rather than the ligand, and a delocalized π-bond over S7-C2-S8 was also present. The stability of DEDC-Zn(II), DEDC-Cd(II), and DEDC-Hg(II) complexes increased in the presence of the non-specific effects of the solvent (PCM model), and their relative stability did not change. There was π-electron flow or resonance along N1-C2-S7 and along S7-C2-S8 in the ligand. The π-electron flow or resonance along N1-C2-S7 was abolished when the metal interacted with sulfur atoms. Energy belonging to van der Waals interactions and non-covalent delocalization effects between the metal and sulfur atoms of the ligand was calculated for each complex. The results of nucleus-independent chemical shift (NICS) indicated a decreasing trend as Zn(II) < Cd(II) < Hg(II) for the aromaticity of the quasi-rings. Finally, by ignoring van der Waals interactions and non-covalent delocalization effects between the metal and sulfur atoms of the ligand, the relative stability of the complexes was changed as follows:[Formula: see text] Graphical Abstract Huge electronic cloud localized on Hg(II) in the Hg(II)-DEDC complex. PMID:27299888

  7. Controlled Fabrication of Silk Protein Sericin Mediated Hierarchical Hybrid Flowers and Their Excellent Adsorption Capability of Heavy Metal Ions of Pb(II), Cd(II) and Hg(II).

    PubMed

    Koley, Pradyot; Sakurai, Makoto; Aono, Masakazu

    2016-01-27

    Fabrication of protein-inorganic hybrid materials of innumerable hierarchical patterns plays a major role in the development of multifunctional advanced materials with their improved features in synergistic way. However, effective fabrication and applications of the hybrid structures is limited due to the difficulty in control and production cost. Here, we report the controlled fabrication of complex hybrid flowers with hierarchical porosity through a green and facile coprecipitation method by using industrial waste natural silk protein sericin. The large surface areas and porosity of the microsize hybrid flowers enable water purification through adsorption of different heavy metal ions. The high adsorption capacity depends on their morphology, which is changed largely by sericin concentration in their fabrication. Superior adsorption and greater selectivity of the Pb(II) ions have been confirmed by the characteristic growth of needle-shaped nanowires on the hierarchical surface of the hybrid flowers. These hybrid flowers show excellent thermal stability even after complete evaporation of the protein molecules, significantly increasing the porosity of the flower petals. A simple, cost-effective and environmental friendly fabrication method of the porous flowers will lead to a new solution to water pollution required in the modern industrial society. PMID:26736132

  8. Synthesis, crystal structures and luminescent properties of zinc(II) metal-organic frameworks constructed from terpyridyl derivative ligand

    NASA Astrophysics Data System (ADS)

    Yang, Xiao-Le; Shangguan, Yi-Qing; Hu, Huai-Ming; Xu, Bing; Wang, Bao-Cheng; Xie, Juan; Yuan, Fei; Yang, Meng-Lin; Dong, Fa-Xin; Xue, Gang-Lin

    2014-08-01

    Five zinc(II) metal-organic frameworks, [Zn3(344-pytpy)2Cl6]n·n(H2O) (1), [Zn(344-pytpy)(ox)]n (2), [Zn2(344-pytpy)(bdc)2]n·1.5n(H2O) (3), [Zn2(344-pytpy)2 (sfdb)2]n·1.5n(H2O) (4) and [Zn3(344-pytpy)2(btc)2]n·2n(H2O) (5), (344-pytpy=4‧-(3-pyridyl)-4,2‧:6‧,4″-terpyridine, H2ox=oxalic acid, H2bdc=1,4-benzenedi-carboxylic acid, H2sfdb=4,4‧-sulfonyldibenzoic acid and H3btc=1,3,5-benzene-tricarboxylic acid) have been prepared by hydrothermal reactions. Compound 1 is a 1D chain structure, in which 344-pytpy ligand links three ZnII centers through three of terminal N-donors. Compound 2 is a 4-connected 3D framework with the dia topological net and the Schläfli symbol of 66. Compound 3 displays a unusual 3-fold interpenetrating 3D coordination network which exhibits a new intriguing (3,3,4)-connected topological net with the Schläfli symbol of (4.82)(4.85)(83). Compound 4 features a two-fold interpenetrating 4-connected 2D framework with the sql topological net and the Schläfli symbol of (44.62). Compound 5 is a new self-interpenetrating (3,3,4,4)-connected topological net with the Schläfli symbol of (6.82)2(62.82.10.12)(62.83.10)2(62.8)2. The luminescence properties of 1-5 have been investigated by emission spectra and they possess great thermal stabilities which can be stable up to around 400 °C.

  9. 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.

  10. 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.

  11. Understanding of the low temperature auto-oxidation scheme of sec-alcohols based on a Cu(II)-MOF with open metal sites.

    PubMed

    Ma, Jian-Ping; Zhao, Chao-Wei; Wang, Shen-Qing; Zhang, Jin-Ping; Niu, Xue; Dong, Yu-Bin

    2015-10-01

    A Cu(II)-MOF (1') with open metal sites was readily obtained by removing the coordinated water molecule at 120 °C. It can be used as a probe to evidence the sec-alkyl hydroperoxide species generated from room temperature sec-alcohol auto-oxidation in air. The formed alkyl hydroperoxides can be effectively catalyzed by 1' to decompose into molecular oxygen and corresponding sec-alcohols under ambient conditions. PMID:26216657

  12. 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.

  13. Effects of oxidation state on metal ion binding by Medicago sativa (alfalfa): Atomic and X-ray absorption spectroscopic studies with Fe(II) and Fe(III)

    SciTech Connect

    Tiemann, K.J.; Gardea-Torresdey, J.L.; Gamez, G.; Dokken, K.; Cano-Aguilera, I.; Renner, M.W.; Furenlid, L.R.

    2000-02-15

    The authors present here experimental results that investigate the effects of metal-ion binding on iron-ion sorption to and recovery from alfalfa biomass. Fe(II)- and Fe(III)-ion binding were measured in order to ascertain the differences in binding strengths due to changes in oxidation state. Stronger binding was found for iron(III)-biomass as compared to iron(II)-biomass. The optimal pH for iron uptake was determined to be 5. The results of pH binding profile, orion desorption, and temperature-dependent binding experiments as well as X-ray spectroscopic (XAS) measurements all suggest that binding of iron by alfalfa biomass may be occurring through carboxyl ligands. The XAS experiments further demonstrate that the metal binding proceeds without an oxidation state change, and both iron(II) and iron(III) have similar coordination environments. The information presented will assist in understanding the binding of other metals to alfalfa biomass and in developing methods for their recovery.

  14. Post-annealing treatment for Cu-TiO2 nanotubes and their use in photocatalytic methyl orange degradation and Pb(II) heavy metal ions removal

    NASA Astrophysics Data System (ADS)

    Sreekantan, Srimala; Mohd Zaki, Syazwani; Lai, Chin Wei; Tzu, Teoh Wah

    2014-07-01

    TiO2 nanotubes were synthesized via electrochemical anodization of Ti foil at 60 V for 1 h in a bath with electrolytes composed of ethylene glycol containing 5 wt.% of NH4F and 1 vol.% of H2O2. The incorporation of optimum Cu2+ ions (1.30 at.%) into TiO2 nanotubes were prepared by using wet impregnation method to improve their photocatalytic methyl orange degradation and Pb(II) heavy metal removal. The small Cu2+ ions were successfully diffused into lattice of TiO2 nanotubes by conducting post-annealing treatment at 400 °C for 4 h in argon atmosphere after wet impregnation. In this manner, optimum Cu2+ ions played a crucial role in suppressing the recombination of charge carriers by forming inter-band states (mismatch of the band energies) within the lattice of Cu-TiO2. The experimental results showed that a maximum of 80% methyl orange removal and 97.3% Pb(II) heavy metal removal at pH 11 under UV irradiation for 5 h. Besides, it was noticed that photocatalytic Pb(II) heavy metal removal was strong dependence on pH of the solution because of the amphoteric character of Cu-TiO2 in an aqueous medium.

  15. Covalent attachment of diphosphine ligands to glassy carbon electrodes via Cu-catalyzed alkyne-azide cycloaddition. Metallation with Ni(II).

    PubMed

    Das, Atanu K; Engelhard, Mark H; Lense, Sheri; Roberts, John A S; Bullock, R Morris

    2015-07-21

    Covalent tethering of P(Ph)2N(C6H4C≡CH)2 ligands (P(Ph)2N(C6H4C≡CH)2 = 1,5-di-(4-ethynylphenyl)-3,7-diphenyl-1,5-diaza-3,7-diphosphacyclooctane) to planar, azide-terminated glassy carbon electrode surfaces has been accomplished using a Cu(I)-catalyzed alkyne-azide cycloaddition (CuAAC) coupling reaction, using a BH3←P protection-deprotection strategy. Deprotected, surface-confined ligands were metallated using [Ni(II)(MeCN)6](BF4)2. X-ray photoelectron spectroscopic measurements demonstrate that metallation introduced 1.3 equivalents Ni(II) per diphosphine onto the electrode surface. Exposure of the surface to a second diphosphine ligand, P(Ph)2N(Ph)2, resulted in the removal of Ni from the surface. Protection, coupling, deprotection, and metallation conditions were optimized using solution-phase model systems, with benzyl azide as a model for the azide-terminated carbon surface; these reactions generate a [Ni(II)(diphosphine)2](2+) complex. PMID:25811536

  16. THE DISCOVERY OF A LARGE Ly{alpha}+He II NEBULA AT z {approx} 1.67: A CANDIDATE LOW METALLICITY REGION?

    SciTech Connect

    Prescott, Moire K. M.; Dey, Arjun; Jannuzi, Buell T. E-mail: dey@noao.edu

    2009-09-01

    We have discovered a {approx}45 kpc Ly{alpha} nebula (or Ly{alpha} 'blob') at z {approx} 1.67 which exhibits strong, spatially extended He II emission and very weak C IV and C III] emission. This is the first spatially extended Ly{alpha}+He II emitter observed and the lowest redshift Ly{alpha} blob yet found. Strong Ly{alpha} and He II{lambda}1640 emission in the absence of metal lines has been proposed as a unique observational signature of primordial galaxy formation (e.g., from gravitational cooling radiation or Population III star formation), but no convincing examples of spatially extended Ly{alpha}+He II emitters have surfaced either in Ly{alpha}-emitting galaxy surveys at high redshifts (z > 4) or in studies of Ly{alpha} nebulae at lower redshifts. From comparisons with photoionization models, we find that the observed line ratios in this nebula are consistent with low metallicity gas (Z {approx}< 10{sup -2}-10{sup -3} Z{sub sun}), but that this conclusion depends on the unknown ionization parameter of the system. The large He II equivalent width ({approx}37 {+-} 10 A) and the large He II/Ly{alpha} ratio (0.12 {+-} 0.04) suggest that the cloud is being illuminated by a hard ionizing continuum, either an active galactic nucleus (AGN) or very low metallicity stars, or perhaps powered by gravitational cooling radiation. Thus far there is no obvious sign of a powerful AGN in or near the system, so in order to power the nebula while remaining hidden from view even in the mid-infrared, the AGN would need to be heavily obscured. Despite the strong Ly{alpha}+He II emission, it is not yet clear what is the dominant power source for this nebula. The system therefore serves as an instructive example of how the complexities of true astrophysical sources will complicate matters when attempting to use a strong Ly{alpha}+He II signature as a unique tracer of primordial galaxy formation.

  17. Positron annihilation in transparent ceramics

    NASA Astrophysics Data System (ADS)

    Husband, P.; Bartošová, I.; Slugeň, V.; Selim, F. A.

    2016-01-01

    Transparent ceramics are emerging as excellent candidates for many photonic applications including laser, scintillation and illumination. However achieving perfect transparency is essential in these applications and requires high technology processing and complete understanding for the ceramic microstructure and its effect on the optical properties. Positron annihilation spectroscopy (PAS) is the perfect tool to study porosity and defects. It has been applied to investigate many ceramic structures; and transparent ceramics field may be greatly advanced by applying PAS. In this work positron lifetime (PLT) measurements were carried out in parallel with optical studies on yttrium aluminum garnet transparent ceramics in order to gain an understanding for their structure at the atomic level and its effect on the transparency and light scattering. The study confirmed that PAS can provide useful information on their microstructure and guide the technology of manufacturing and advancing transparent ceramics.

  18. Positron scattering from vinyl acetate

    NASA Astrophysics Data System (ADS)

    Chiari, L.; Zecca, A.; Blanco, F.; García, G.; Brunger, M. J.

    2014-09-01

    Using a Beer-Lambert attenuation approach, we report measured total cross sections (TCSs) for positron scattering from vinyl acetate (C4H6O2) in the incident positron energy range 0.15-50 eV. In addition, we also report an independent atom model with screening corrected additivity rule computation results for the TCSs, differential and integral elastic cross sections, the positronium formation cross section and inelastic integral cross sections. The energy range of these calculations is 1-1000 eV. While there is a reasonable qualitative correspondence between measurement and calculation for the TCSs, in terms of the energy dependence of those cross sections, the theory was found to be a factor of ˜2 larger in magnitude at the lower energies, even after the measured data were corrected for the forward angle scattering effect.

  19. The integrated calcium II triplet as a metallicity indicator: comparisons with high-resolution [Fe/H] in M31 globular clusters

    NASA Astrophysics Data System (ADS)

    Sakari, Charli M.; Wallerstein, George

    2016-02-01

    Medium resolution (R = 4000-9000) spectra of the near infrared Ca II lines (at 8498, 8542, and 8662 Å) in M31 globular cluster (GC) integrated light spectra are presented. In individual stars the Ca II triplet (CaT) traces stellar metallicity; this paper compares integrated CaT strengths to well determined, high-precision [Fe/H] values from high-resolution integrated light spectra. The target GCs cover a wide range in metallicity (from [Fe/H] ˜ -2.1 to -0.2). While most are older than ˜10 Gyr, some may be of intermediate age (2-6 Gyr). A handful (3-6) have detailed abundances (e.g. low [Ca/Fe]) that indicate they may have been accreted from dwarf galaxies. Using various measurements and definitions of CaT strength, it is confirmed that for GCs with [Fe/H] ≲ -0.4 and older than ˜2 Gyr the integrated CaT traces cluster [Fe/H] to within ˜0.2 dex, independent of age. CaT lines in metal-rich GCs are very sensitive to nearby atomic lines (and TiO molecular lines in the most metal-rich GCs), largely due to line blanketing in continuum regions. The [Ca/Fe] ratio has a mild effect on the integrated CaT strength in metal poor GCs. The integrated CaT can therefore be safely used to determine rough metallicities for distant, unresolved clusters, provided that attention is paid to the limits of the measurement techniques.

  20. Precious Metals in SDSS Quasar Spectra. II. Tracking the Evolution of Strong, 0.4 < z < 2.3 Mg II Absorbers with Thousands of Systems

    NASA Astrophysics Data System (ADS)

    Seyffert, Eduardo N.; Cooksey, Kathy L.; Simcoe, Robert A.; O'Meara, John M.; Kao, Melodie M.; Prochaska, J. Xavier

    2013-12-01

    We have performed an analysis of over 34,000 Mg II doublets at 0.36 < z < 2.29 in Sloan Digital Sky Survey (SDSS) Data Release 7 quasar spectra; the catalog, advanced data products, and tools for analysis are publicly available. The catalog was divided into 14 small redshift bins with roughly 2500 doublets in each and from Monte Carlo simulations, we estimate 50% completeness at rest equivalent width W r ≈ 0.8 Å. The equivalent width frequency distribution is described well by an exponential model at all redshifts, and the distribution becomes flatter with increasing redshift, i.e., there are more strong systems relative to weak ones. Direct comparison with previous SDSS Mg II surveys reveals that we recover at least 70% of the doublets in these other catalogs, in addition to detecting thousands of new systems. We discuss how these surveys came by their different results, which qualitatively agree but because of the very small uncertainties, differ by a statistically significant amount. The estimated physical cross section of Mg II-absorbing galaxy halos increased approximately threefold from z = 0.4 to z = 2.3, while the W r >= 1 Å absorber line density, d {N}_{{Mg}\\,\\scriptsize{II}}/d X, grew by roughly 45%. Finally, we explore the different evolution of various absorber populations—damped Lyα absorbers, Lyman limit systems, strong C IV absorbers, and strong and weaker Mg II systems—across cosmic time (0 < z < 6).

  1. 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.

  2. PEP-II Status

    SciTech Connect

    Sullivan, M.; Bertsche, K.; Browne, M.; Cai, Y.; Cheng, W.; Colocho, W.; Decker, F.-J.; Donald, M.; Ecklund, S.; Erickson, R.; Fisher, A.S.; Fox, J.; Heifets, S.; Himel, T.; Iverson, R.; Kulikov, A.; Novokhatski, A.; Pacak, V.; Pivi, M.; Rivetta, C.; Ross, M.; /SLAC /Saclay /Frascati

    2008-07-25

    PEP-II and BaBar have just finished run 7, the last run of the SLAC B-factory. PEP-II was one of the few high-current e+e- colliding accelerators and holds the present world record for stored electrons and stored positrons. It has stored 2.07 A of electrons, nearly 3 times the design current of 0.75 A and it has stored 3.21 A of positrons, 1.5 times more than the design current of 2.14 A. High-current beams require careful design of several systems. The feedback systems that control instabilities, the RF system stability loops, and especially the vacuum systems have to handle the higher power demands. We present here some of the accomplishments of the PEP-II accelerator and some of the problems we encountered while running high-current beams.

  3. Positron annihilation in the interstellar medium

    NASA Technical Reports Server (NTRS)

    Guessoum, Nidhal; Ramaty, Reuven; Lingenfelter, Richard E.

    1991-01-01

    Positronium formation and annihilation are studied in a model for the interstellar medium consisting of cold cloud cores, warm partially ionized cloud envelopes, and hot intercloud gas. The gamma-ray spectra resulting from positron annihilation in these components of the interstellar medium are calculated. The spectra from the individual components are then combined, using two limiting assumptions for the propagation of the positrons, namely, that the positrons propagate freely throughout the interstellar medium, and that the positrons are excluded from the cold cloud cores. In the first case, the bulk of the positrons annihilate in the cloud cores and the annihilation line exhibits broad wings resulting from the annihilation of positronium formed by charge exchange in flight. In the second case, the positrons annihilate mainly in the warm envelopes, and the line wings are suppressed.

  4. Development of a transmission positron microscope

    NASA Astrophysics Data System (ADS)

    Matsuya, M.; Jinno, S.; Ootsuka, T.; Inoue, M.; Kurihara, T.; Doyama, M.; Inoue, M.; Fujinami, M.

    2011-07-01

    A practical transmission positron microscope (TPM) JEM-1011B has been developed to survey differences in the interaction of positron and electron beams with materials, and is installed in the Slow Positron Facility of High Energy Accelerator Research Organization (KEK). The TPM can share positron and electron beams, and can also be used as a transmission electron microscope (TEM). Positron transmission images up to magnification 10,000× (resolution: 50 nm) and positron diffraction patterns up to 044 family were successfully obtained by the TPM comparing them with those of electrons. The differences in material transmittances for both beams have been measured, and can be explained by the calculated results of the Monte Carlo simulation code PENELOPE-2008.

  5. 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.

  6. HIGH-RESOLUTION SPECTROSCOPY OF EXTREMELY METAL-POOR STARS IN THE LEAST EVOLVED GALAXIES: URSA MAJOR II and COMA BERENICES

    SciTech Connect

    Frebel, Anna; Simon, Joshua D.; Geha, Maria; Willman, Beth E-mail: jsimon@ociw.ed E-mail: bwillman@haverford.ed

    2010-01-01

    We present spectra of six metal-poor stars in two of the ultra-faint dwarf galaxies orbiting the Milky Way (MW), Ursa Major II, and Coma Berenices obtained with the Keck/High Resolution Echelle Spectrometer (HIRES). These observations include the first high-resolution spectroscopic observations of extremely metal-poor ([Fe/H] < -3.0) stars not belonging to the MW halo field star population. We obtain abundance measurements and upper limits for 26 elements between carbon and europium. The entire sample of stars spans a range of -3.2 < [Fe/H] < -2.3, and we confirm that each galaxy contains a large intrinsic spread of Fe abundances. A comparison with MW halo stars of similar metallicities reveals substantial agreement between the abundance patterns of the ultra-faint dwarf galaxies and the MW halo for the light, alpha, and iron-peak elements (C to Zn). This agreement contrasts with the results of earlier studies of more metal-rich stars (-2.5 approx< [Fe/H] approx< -1.0) in more luminous dwarf spheroidal galaxies, which found significant abundance discrepancies with respect to the MW halo data. The abundances of neutron-capture elements (Sr to Eu) in the ultra-faint dwarf galaxies are extremely low, consistent with the most metal-poor halo stars, but not with the typical halo abundance pattern at [Fe/H] approx> -3.0. Not only are our results broadly consistent with a galaxy formation model that predicts that massive dwarf galaxies are the source of the metal-rich component ([Fe/H]> - 2.5) of the MW halo, but they also suggest that the faintest known dwarfs may be the primary contributors to the metal-poor end of the MW halo metallicity distribution.

  7. Removal and mechanism of Cu (II) and Cd (II) from aqueous single-metal solutions by a novel biosorbent from waste-activated sludge.

    PubMed

    Zhang, Zhiqiang; Wang, Pan; Zhang, Jiao; Xia, Siqing

    2014-09-01

    The removal and mechanism of Cu(2+) and Cd(2+) from aqueous single-metal solutions were investigated by using a novel biosorbent from waste-activated sludge. A series of adsorption experiments was designed to disclose the effects of the key factors on the adsorption capacity of the biosorbent for the metal ions. The mass ratio of the biosorbent to metal ion was optimized as 2 to balance the adsorption capacity and the removal efficiency. A right shaking speed (150 r/min) not only ensured enough contact frequency between the sorbent and the adsorbate but also reduced the mass transfer resistance. The natural pH value (about 5.5) of the metal solutions benefited a high adsorption capacity of the biosorbent and avoided the consumption of acid or base for pH adjustment. The adsorption reactions belonged to the endothermic process between 15 and 45 °C. As the scanning electron microscopy (SEM) images showed, the meshy structure with long chains and many branches was ideal for the biosorbent to quickly capture the metal ions. The energy-dispersive X-ray (EDX) spectra confirmed that the adsorbed metal ions lay in the precipitates of the adsorption reactions. According to the FTIR analyses, the functional groups responsible for Cu(2+) adsorption majorly consisted of O-H, N-H, COOH, CONH2, and the groups containing sulfur and phosphorus, while those for Cd(2+) adsorption contained O-H, N-H, COOH, and CONH2. The differences in the responsible functional groups explained the phenomenon that the adsorption capacity of the biosorbent for Cu(2+) was higher than that for Cd(2+). PMID:24878552

  8. Synthesis, characterization and properties of some divalent metal(II) complexes: Their electrochemical, catalytic, thermal and antimicrobial activity studies

    NASA Astrophysics Data System (ADS)

    Tümer, Mehmet; Ekinci, Duygu; Tümer, Ferhan; Bulut, Akif

    2007-07-01

    In this study, we synthesized the amine compound 2-(2-aminoethyliminomethyl)phenol (H 3A) as the starting material, and then we prepared the polydentate Schiff base ligands from the reactions of the amine compound (H 3A) with phtaldialdehyde (H 2L), 4-methyl-2,6-di-formlyphenol (H 3L 1) and 4- t-butyl-2,6-di-formylphenol (H 3L 2) in the ethanol solution. Moreover, the complexes Cd(II), Cu(II), Co(II), Ni(II), Zn(II) and Sn(II) of the ligands H 2L, H 3L 1 and H 3L 2 have been prepared. All compounds have been characterized by the analytical and spectroscopic methods. In addition, the magnetic susceptibility and molar conductance measurements have been made. The catalytic properties of the mono- and binuclear Co(II) and Cu(II) complexes have been studied on the 3,5-di- tert-butylcatechol (3,5-DTBC) and ascorbic acid (aa) as a substrate. The oxidative C-C coupling properties of the Co(II) and Cu(II) complexes have been investigated on the sterically hindered 2,6-di- tert-butylphenol (dtbp). The antimicrobial activity properties of the ligands and their mono- and binuclear complexes have been studied against the bacteria and fungi. The results have been compared to the antibacterial and fungi drugs. The TGA curves show that the decomposition takes place in three steps for all complexes. Electrochemical properties of the complexes Cu(II) and Ni(II) have been investigated for the first time in acetonitrile by cyclic voltammetry.

  9. 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.

  10. 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.

  11. Intrinsic disorder and metal binding in UreG proteins from Archae hyperthermophiles: GTPase enzymes involved in the activation of Ni(II) dependent urease.

    PubMed

    Miraula, Manfredi; Ciurli, Stefano; Zambelli, Barbara

    2015-06-01

    Urease is a Ni(II) enzyme present in every domain of life, in charge for nitrogen recycling through urea hydrolysis. Its activity requires the presence of two Ni(II) ions in the active site. These are delivered by the concerted action of four accessory proteins, named UreD, UreF, UreG and UreE. This process requires protein flexibility at different levels and some disorder-to-order transition events that coordinate the mechanism of protein-protein interaction. In particular, UreG, the GTPase in charge of nucleotide hydrolysis required for urease activation, presents a significant degree of intrinsic disorder, existing as a conformational ensemble featuring characteristics that recall a molten globule. Here, the folding properties of UreG were explored in Archaea hyperthermophiles, known to generally feature significantly low level of structural disorder in their proteome. UreG proteins from Methanocaldococcus jannaschii (Mj) and Metallosphaera sedula (Ms) were structurally and functionally analyzed by integrating circular dichroism, NMR, light scattering and enzymatic assays. Metal-binding properties were studied using isothermal titration calorimetry. The results indicate that, as the mesophilic counterparts, both proteins contain a significant amount of secondary structure but maintain a flexible fold and a low GTPase activity. As opposed to other UreGs, secondary structure is lost at high temperatures (68 and 75 °C, respectively) with an apparent two-state mechanism. Both proteins bind Zn(II) and Ni(II), with affinities two orders of magnitude higher for Zn(II) than for Ni(II). No major modifications of the average conformational ensemble are observed, but binding of Zn(II) yields a more compact dimeric form in MsUreG. PMID:25846143

  12. The PEP-II design

    SciTech Connect

    Sullivan, M.K.

    1995-05-01

    The Stanford Linear Accelerator Center (SLAC), Lawrence Berkeley Laboratory (LBL), Lawrence Livermore National Laboratory (LLNL) Positron Electron Project-II (PEP-II) is a design for a high-luminosity, asymmetric energy, electron-positron colliding beam accelerator that will operate at the center-of-mass energy of the {Upsilon}4S (10.58 GeV). The goal of the design is to achieve a large enough integrated luminosity with a moving center-of-mass reference frame to he able to observe the predicted rare decay modes of the {Upsilon}4S that do not conserve charge parity (CP).

  13. [PHEMA/PEI]-Cu(II) based immobilized metal affinity chromatography cryogels: Application on the separation of IgG from human plasma.

    PubMed

    Bakhshpour, Monireh; Derazshamshir, Ali; Bereli, Nilay; Elkak, Assem; Denizli, Adil

    2016-04-01

    The immobilized metal-affinity chromatography (IMAC) has gained significant interest as a widespread separation and purification tool for therapeutic proteins, nucleic acids and other biological molecules. The enormous potential of IMAC for proteins with natural surface exposed-histidine residues and for recombinant proteins with histidine clusters. Cryogels as monolithic materials have recently been proposed as promising chromatographic adsorbents for the separation of biomolecules in downstream processing. In the present study, IMAC cryogels have been synthesized and utilized for the adsorption and separation of immunoglobulin G (IgG) from IgG solution and whole human plasma. For this purpose, Cu(II)-ions were coupled to poly(hydroxyethyl methacrylate) PHEMA using poly(ethylene imine) (PEI) as the chelating ligand. In this study the cryogels formation optimized by the varied proportion of PEI from 1% to 15% along with different amounts of Cu (II) as chelating metal. The prepared cryogels were characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, and thermogravimetric analysis. The [PHEMA/PEI]-Cu(II) cryogels were assayed for their capability to bind the human IgG from aqueous solutions. The IMAC cryogels were found to have high affinity toward human IgG. The adsorption of human IgG was investigated onto the PHEMA/PEI cryogels with (10% PEI) and the concentration of Cu (II) varied as 10, 50, 100 and 150 mg/L. The separation of human IgG was achieved in one purification step at pH7.4. The maximum adsorption capacity was observed at the [PHEMA/PEI]-Cu(II) (10% PEI) with 72.28 mg/g of human IgG. The purification efficiency and human IgG purity were investigated by sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS-PAGE). PMID:26838913

  14. Precious metals in SDSS quasar spectra. II. Tracking the evolution of strong, 0.4 < z < 2.3 Mg II absorbers with thousands of systems

    SciTech Connect

    Seyffert, Eduardo N.; Simcoe, Robert A.; Cooksey, Kathy L.; O'Meara, John M.; Kao, Melodie M.; Prochaska, J. Xavier E-mail: simcoe@space.mit.edu E-mail: jomeara@smcvt.edu E-mail: xavier@ucolick.org

    2013-12-20

    We have performed an analysis of over 34,000 Mg II doublets at 0.36 < z < 2.29 in Sloan Digital Sky Survey (SDSS) Data Release 7 quasar spectra; the catalog, advanced data products, and tools for analysis are publicly available. The catalog was divided into 14 small redshift bins with roughly 2500 doublets in each and from Monte Carlo simulations, we estimate 50% completeness at rest equivalent width W {sub r} ≈ 0.8 Å. The equivalent width frequency distribution is described well by an exponential model at all redshifts, and the distribution becomes flatter with increasing redshift, i.e., there are more strong systems relative to weak ones. Direct comparison with previous SDSS Mg II surveys reveals that we recover at least 70% of the doublets in these other catalogs, in addition to detecting thousands of new systems. We discuss how these surveys came by their different results, which qualitatively agree but because of the very small uncertainties, differ by a statistically significant amount. The estimated physical cross section of Mg II-absorbing galaxy halos increased approximately threefold from z = 0.4 to z = 2.3, while the W {sub r} ≥ 1 Å absorber line density, dN{sub MgII}/dX, grew by roughly 45%. Finally, we explore the different evolution of various absorber populations—damped Lyα absorbers, Lyman limit systems, strong C IV absorbers, and strong and weaker Mg II systems—across cosmic time (0 < z < 6).

  15. Stability analysis of an inline peptide-based conjugate for metal delivery: nickel(II)-claMP Tag epidermal growth factor as a model system.

    PubMed

    Mills, Brittney J; Laurence, Jennifer S

    2015-02-01

    Metals are a key component of many diagnostic imaging and biotechnology applications, and the majority of cancer patients receive a platinum-based drug as part of their treatment. Significant effort has been devoted to developing tight binding synthetic chelators to enable effective targeted delivery of metal-based conjugates, with most successes involving lanthanides rather than transition metals for diagnostic imaging. Chemical conjugation modifies the protein's properties and generates a heterogeneous mixture of products. Chelator attachment is typically carried out by converting the amino group on lysines to an amide, which can impact the stability and solubility of the targeting protein and these properties vary among the set of individual conjugate species. Site-specific attachment is sought to reduce complexity and control stability. Here, the metal abstraction peptide technology was applied to create the claMP Tag, an inline platform for generating site-specific conjugates involving transition metals. The claMP Tag was genetically encoded into epidermal growth factor (EGF) and loaded with nickel(II) as a model system to demonstrate that the tag within the homogeneous inline conjugate presents sufficient solution stability to enable biotechnology applications. The structure and disulfide network of the protein and chemical stability of the claMP Tag and EGF components were characterized. PMID:25212829

  16. THE MOST METAL-POOR STARS. II. CHEMICAL ABUNDANCES OF 190 METAL-POOR STARS INCLUDING 10 NEW STARS WITH [Fe/H] {<=} -3.5 , ,

    SciTech Connect

    Yong, David; Norris, John E.; Bessell, M. S.; Asplund, M.; Christlieb, N.; Beers, Timothy C.; Barklem, P. S.; Frebel, Anna; Ryan, S. G. E-mail: jen@mso.anu.edu.au E-mail: martin@mso.anu.edu.au E-mail: beers@pa.msu.edu E-mail: afrebel@mit.edu

    2013-01-01

    We present a homogeneous chemical abundance analysis of 16 elements in 190 metal-poor Galactic halo stars (38 program and 152 literature objects). The sample includes 171 stars with [Fe/H] {<=} -2.5, of which 86 are extremely metal poor, [Fe/H] {<=} -3.0. Our program stars include 10 new objects with [Fe/H] {<=} -3.5. We identify a sample of 'normal' metal-poor stars and measure the trends between [X/Fe] and [Fe/H], as well as the dispersion about the mean trend for this sample. Using this mean trend, we identify objects that are chemically peculiar relative to 'normal' stars at the same metallicity. These chemically unusual stars include CEMP-no objects, one star with high [Si/Fe], another with high [Ba/Sr], and one with unusually low [X/Fe] for all elements heavier than Na. The Sr and Ba abundances indicate that there may be two nucleosynthetic processes at lowest metallicity that are distinct from the main r-process. Finally, for many elements, we find a significant trend between [X/Fe] versus T {sub eff}, which likely reflects non-LTE and/or three-dimensional effects. Such trends demonstrate that care must be exercised when using abundance measurements in metal-poor stars to constrain chemical evolution and/or nucleosynthesis predictions.

  17. Copper(II)-mediated thermolysis of alginates: a model kinetic study on the influence of metal ions in the thermochemical processing of macroalgae.

    PubMed

    Rowbotham, J S; Dyer, P W; Greenwell, H C; Selby, D; Theodorou, M K

    2013-02-01

    Thermochemical processing methods such as pyrolysis are of growing interest as a means of converting biomass into fuels and commodity chemicals in a sustainable manner. Macroalgae, or seaweed, represent a novel class of feedstock for pyrolysis that, owing to the nature of the environments in which they grow coupled with their biochemistry, naturally possess high metal contents. Although the impact of metals upon the pyrolysis of terrestrial biomass is well documented, their influence on the thermochemical conversion of marine-derived feeds is largely unknown. Furthermore, these effects are inherently difficult to study, owing to the heterogeneous character of natural seaweed samples. The work described in this paper uses copper(II) alginate, together with alginic acid and sodium alginate as model compounds for exploring the effects of metals upon macroalgae thermolysis. A thermogravimetric analysis-Fourier transform infrared spectroscopic study revealed that, unusually, Cu(2+) ions promote the onset of pyrolysis in the alginate polymer, with copper(II) alginate initiating rapid devolatilization at 143°C, 14°C lower than alginic acid and 61°C below the equivalent point for sodium alginate. Moreover, this effect was mirrored in a sample of wild Laminaria digitata that had been doped with Cu(2+) ions prior to pyrolysis, thus validating the use of alginates as model compounds with which to study the thermolysis of macroalgae. These observations indicate the varying impact of different metal species on thermochemical behaviour of seaweeds and offer an insight into the pyrolysis of brown macroalgae used in phytoremediation of metal-containing waste streams. PMID:24427515

  18. Copper(II)-mediated thermolysis of alginates: a model kinetic study on the influence of metal ions in the thermochemical processing of macroalgae

    PubMed Central

    Rowbotham, J. S.; Dyer, P. W.; Greenwell, H. C.; Selby, D.; Theodorou, M. K.

    2013-01-01

    Thermochemical processing methods such as pyrolysis are of growing interest as a means of converting biomass into fuels and commodity chemicals in a sustainable manner. Macroalgae, or seaweed, represent a novel class of feedstock for pyrolysis that, owing to the nature of the environments in which they grow coupled with their biochemistry, naturally possess high metal contents. Although the impact of metals upon the pyrolysis of terrestrial biomass is well documented, their influence on the thermochemical conversion of marine-derived feeds is largely unknown. Furthermore, these effects are inherently difficult to study, owing to the heterogeneous character of natural seaweed samples. The work described in this paper uses copper(II) alginate, together with alginic acid and sodium alginate as model compounds for exploring the effects of metals upon macroalgae thermolysis. A thermogravimetric analysis–Fourier transform infrared spectroscopic study revealed that, unusually, Cu2+ ions promote the onset of pyrolysis in the alginate polymer, with copper(II) alginate initiating rapid devolatilization at 143°C, 14°C lower than alginic acid and 61°C below the equivalent point for sodium alginate. Moreover, this effect was mirrored in a sample of wild Laminaria digitata that had been doped with Cu2+ ions prior to pyrolysis, thus validating the use of alginates as model compounds with which to study the thermolysis of macroalgae. These observations indicate the varying impact of different metal species on thermochemical behaviour of seaweeds and offer an insight into the pyrolysis of brown macroalgae used in phytoremediation of metal-containing waste streams. PMID:24427515

  19. IMPROVED Ti II log(gf) VALUES AND ABUNDANCE DETERMINATIONS IN THE PHOTOSPHERES OF THE SUN AND METAL-POOR STAR HD 84937

    SciTech Connect

    Wood, M. P.; Lawler, J. E.; Sneden, C.; Cowan, J. J. E-mail: jelawler@wisc.edu E-mail: cowan@nhn.ou.edu

    2013-10-01

    Atomic transition probability measurements for 364 lines of Ti II in the UV through near-IR are reported. Branching fractions from data recorded using a Fourier transform spectrometer (FTS) and a new echelle spectrometer are combined with published radiative lifetimes to determine these transition probabilities. The new results are in generally good agreement with previously reported FTS measurements. Use of the new echelle spectrometer, independent radiometric calibration methods, and independent data analysis routines enables a reduction of systematic errors and overall improvement in transition probability accuracy over previous measurements. The new Ti II data are applied to high-resolution visible and UV spectra of the Sun and metal-poor star HD 84937 to derive new, more accurate Ti abundances. Lines covering a range of wavelength and excitation potential are used to search for non-LTE effects. The Ti abundances derived using Ti II for these two stars match those derived using Ti I and support the relative Ti/Fe abundance ratio versus metallicity seen in previous studies.

  20. The population of planetary nebulae and H II regions in M 81. A study of radial metallicity gradients and chemical evolution

    NASA Astrophysics Data System (ADS)

    Stanghellini, L.; Magrini, L.; Villaver, E.; Galli, D.

    2010-10-01

    Context. M 81 is an ideal laboratory to investigate the galactic chemical and dynamical evolution through the study of its young and old stellar populations. Aims: We analyze the chemical abundances of planetary nebulae and H ii regions in the M 81 disk for insight on galactic evolution, and compare it with that of other galaxies, including the Milky Way. Methods: We acquired Hectospec/MMT spectra of 39 PNe and 20 H ii regions, with 33 spectra viable for temperature and abundance analysis. Our PN observations represent the first PN spectra in M 81 ever published, while several H ii region spectra have been published before, although without a direct electron temperature determination. We determine elemental abundances of helium, nitrogen, oxygen, neon, sulfur, and argon in PNe and H ii regions, and determine their averages and radial gradients. Results: The average O/H ratio of PNe compared to that of the H ii regions indicates a general oxygen enrichment in M 81 in the last ~10 Gyr. The PN metallicity gradient in the disk of M 81 is Δlog(O/H)/ΔRG = -0.055 ± 0.02 dex/kpc. Neon and sulfur in PNe have a radial distribution similar to that of oxygen, with similar gradient slopes. If we combine our H ii sample with the one in the literature we find a possible mild evolution of the gradient slope, with results consistent with gradient steepening with time. Additional spectroscopy is needed to confirm this trend. There are no type I PNe in our M 81 sample, consistently with the observation of only the brightest bins of the PNLF, the galaxy metallicity, and the evolution of post-AGB shells. Conclusions: Both the young and the old populations of M 81 disclose shallow but detectable negative radial metallicity gradient, which could be slightly steeper for the young population, thus not excluding a mild gradients steepening with the time since galaxy formation. During its evolution M 81 has been producing oxygen; its total oxygen enrichment exceeds that of other nearby

  1. Noble metal (Ru{sup III}, Pd{sup II}, Pt{sup II}) substituted {open_quotes}sandwich{close_quotes} type polyoxometalates: Preparation, characterization, and catalytic activity in oxidations of alkanes and alkenes by peroxides

    SciTech Connect

    Neumann, R.; Khenkin, A.M.

    1995-11-08

    The polyoxometalates substituted with noble metals, Pd(II), Pt(II) and Ru(III), K{sub 12}([WZnPd{sup II}{sub 2}(H{sub 2}O){sub 2}](ZnW{sub 9}O{sub 34}){sub 2}){center_dot}38H{sub 2}O, K{sub 12}[WZnPt{sup II}{sub 2}(H{sub 2}O){sub 2}][(ZnW{sub 9}O{sub 34}){sub 2}]{center_dot}36H{sub 2}O, and Na{sub 11}[WZnRu{sup III}{sub 2}(OH)(H{sub 2}O)][(ZnW{sub 9}O{sub 34}){sub 2}]{center_dot}42H{sub 2}O, were prepared by exchange of labile zinc atoms with noble metal atoms from the isostructural starting material, N{sub 12}-[WZn{sub 3}(H{sub 2}O){sub 2}][(ZnW{sub 9}O{sub 34}){sub 2}]{center_dot}46H{sub 2}O. Magnetic susceptibility studies as a function of temperature provide convincing evidence of two ruthenium (III) centers with no magnetic interaction between them. The catalytic activity of these compounds was tested for the oxidation of alkenes and alkanes using aqueous 30% hydrogen peroxide and 70% tert-butyl hydroperoxide as oxidants. The alkene oxidation proceeded in high reactivity and moderate selectivity to the epoxide product using 30% H{sub 2}O{sub 2}. Kinetic profiles as well as UV-vis and IR spectra before, during and after the reaction indicate that the catalysts are stable throughout the reaction. Formation of epoxides rather than ketonization in the reaction of terminal alkenes as well as low reactivity with iodosobenzene indicates that the reaction is tungsten centered and not noble metal centered. Oxidation of alkenes with tert-butyl hydroperoxide gave mostly allylic oxidation and/or addition of tert-butyl alcohol to the double bond. Oxidation of cyclic alkanes such as cyclohexane and adamantane was successful with tert-butyl hydroperoxide with catalytic activity 10 times higher than previously found for transition metal substituted Keggin compounds. Ratios of hydroxylation of adamantane at tertiary vs secondary positions indicates different active species in the palladium-, platinum-, and ruthenium substituted-polyoxometalates.

  2. Positron emission tomography and autoradiography

    SciTech Connect

    Mazziotta, J.; Schelbert, H.R.

    1985-01-01

    This a text on cerebral and myocardial imaging using positron emission tomography and autoradiography. Authorities in nuclear medicine and biophysics define the central principles of these complex and rapidly evolving imagine technologies-their theoretical foundations, the nature of the biochemical events being measured, the basis for constructing tracer kinetic models, the criteria governing radiopharmaceutical design, and the rationale for PET in the clinical setting. After reviewing the characteristics of cerebral and myocardial hemodynamics, transport, and metabolism, the contributors detail the theory of PET and autoradiography, the instrumentation required, and the procedures involved.

  3. Positron scattering and annihilation in hydrogenlike ions

    NASA Astrophysics Data System (ADS)

    Green, D. G.; Gribakin, G. F.

    2013-09-01

    Diagrammatic many-body theory is used to calculate the scattering phase shifts, normalized annihilation rates Zeff, and annihilation γ spectra for positron collisions with the hydrogenlike ions He+, Li2+, B4+, and F8+. Short-range electron-positron correlations and longer-range positron-ion correlations are accounted for by evaluating nonlocal corrections to the annihilation vertex and the exact positron self-energy. The numerical calculation of the many-body theory diagrams is performed using B-spline basis sets. To elucidate the role of the positron-ion repulsion, the annihilation rate is also estimated analytically in the Coulomb-Born approximation. It is found that the energy dependence and magnitude of Zeff are governed by the Gamow factor that characterizes the suppression of the positron wave function near the ion. For all of the H-like ions, the correlation enhancement of the annihilation rate is found to be predominantly due to corrections to the annihilation vertex, while the corrections to the positron wave function play only a minor role. Results of the calculations for s-, p-, and d-wave incident positrons of energies up to the positronium-formation threshold are presented. Where comparison is possible, our values are in excellent agreement with the results obtained using other, e.g., variational, methods. The annihilation-vertex enhancement factors obtained in the present calculations are found to scale approximately as 1+(1.6+0.46ℓ)/Zi, where Zi is the net charge of the ion and ℓ is the positron orbital angular momentum. Our results for positron annihilation in H-like ions provide insights into the problem of positron annihilation with core electrons in atoms and condensed matter systems, which have similar binding energies.

  4. Low energy positron interactions with biological molecules

    NASA Astrophysics Data System (ADS)

    Wanniarachchi, Indika L.

    Calculations of the positron density distribution which can be used for positrons bound to midsize and larger molecules have been tested for smaller molecules and subsequently applied to investigate the most likely e +e-- annihilation sites for positrons interacting with biological molecules containing C, H, O, and N. In order to allow consideration of positrons bound to extended molecules with regions of different character and no particular symmetry, atom-centered positron basis sets of Gaussian-type functions were developed for positrons bound to molecules containing O, N, C, H, Li, Na, and Be. Testing shows that there is no need to scale the positron basis functions to take into account different effective charges on the atoms in different molecules. Even at the HF level of theory the calculated positron and the contact density of e+LiH system is in qualitative agreement with the most accurate calculation was done in ECG method. Also it has been found that for larger biological molecules such as derivation of formaldehyde can leave out positron basis sets centered on H atoms and still get qualitatively acceptable contact density distribution. According to our results, the electronic and positronic wavefunctions have the most overlap in the regions of most negative electrostatic potential in the parent molecule, and we can expect that a positron bound to the molecule will be more likely to annihilate with one of the electrons in these regions. Also we find that the highest energy occupied electronic orbital often does not make the largest contribution to e+e -- annihilation, and that the energy liberated by subsequent electronic relaxation is sufficient to break the backbone in several places in di-peptides and other organic molecules.

  5. Theoretical investigation, biological evaluation and VEGFR2 kinase studies of metal(II) complexes derived from hydrotris(methimazolyl)borate.

    PubMed

    Jayakumar, S; Mahendiran, D; Srinivasan, T; Mohanraj, G; Kalilur Rahiman, A

    2016-02-01

    The reaction of soft tripodal scorpionate ligand, sodium hydrotris(methimazolyl)borate with M(ClO4)2·6H2O [MMn(II), Ni(II), Cu(II) or Zn(II)] in methanol leads to the cleavage of B-N bond followed by the formation of complexes of the type [M(MeimzH)4](ClO4)2·H2O (1-4), where MeimzH=methimazole. All the complexes were fully characterized by spectro-analytical techniques. The molecular structure of the zinc(II) complex (4) was determined by X-ray crystallography, which supports the observed deboronation reaction in the scorpionate ligand with tetrahedral geometry around zinc(II) ion. The electronic spectra of complexes suggested tetrahedral geometry for manganese(II) and nickel(II) complexes, and square-planar geometry for copper(II) complex. Frontier molecular orbital analysis (HOMO-LUMO) was carried out by B3LYP/6-31G(d) to understand the charge transfer occurring in the molecules. All the complexes exhibit significant antimicrobial activity against Gram (-ve) and Gram (+ve) bacterial as well as fungal strains, which are quite comparable to standard drugs streptomycin and clotrimazole. The copper(II) complex (3) showed excellent free radical scavenging activity against DPPH in all concentration with IC50 value of 30μg/mL, when compared to the other complexes. In the molecular docking studies, all the complexes showed hydrophobic, π-π and hydrogen bonding interactions with BSA. The cytotoxic activity of the complexes against human hepatocellular liver carcinoma (HepG2) cells was assessed by MTT assay, which showed exponential responses toward increasing concentration of complexes. PMID:26735002

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

    NASA Astrophysics Data System (ADS)

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

    2012-08-01

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

  7. IUPAC-NIST Solubility Data Series. 92. Metal Carbonates. Part 1. Solubility and Related Thermodynamic Quantities of Cadmium(II) Carbonate in Aqueous Systems

    NASA Astrophysics Data System (ADS)

    Gamsjäger, H.

    2011-12-01

    This paper, devoted to cadmium(II) carbonate, is the first in a series dedicated to the solubility of compounds relevant to mobility of metals in the environment. Here, we present compilations and critical evaluation of the experimental solubility data for cadmium(II) carbonate, otavite, in aqueous ternary and higher-order systems. The solubility of cadmium(II) carbonate depends on temperature, carbon dioxide partial pressure, pH, the presence of complexing ions, and ionic strength of the solution. Papers referring to solubility of cadmium(II) carbonate have been published since 1901; the thorough search of the literature in this field covered the period from 1901 through 2009. The compilation of the available experimental data is introduced with a critical evaluation. The evaluation of the experimental data considers the possible correlation between the data obtained under similar experimental conditions of temperature, carbon dioxide partial pressure, electrolyte, and ionic strength. Those experiments where the solid phase was well identified and the interactions between the electrolyte and the dissolved cadmium(II) ion were considered practically negligible were used to determine the thermodynamic properties of the solid cadmium(II) carbonate. Recommended values for the thermodynamic quantities are lg*Kps0\\convolu = 6.11 +/- 0.10, ΔfG°(CdCO3, cr, 298.15 K) = -(674.3 +/- 0.6) kJ mol-1, ΔfH°(CdCO3, cr, 298.15 K) = -(752.2 +/- 0.8) kJ mol-1, S°(CdCO3, cr, 298.15 K) = (103.9 +/- 0.2) J K-1 mol-1.

  8. IUPAC-NIST Solubility Data Series. 92. Metal Carbonates. Part 1. Solubility and Related Thermodynamic Quantities of Cadmium(II) Carbonate in Aqueous Systems

    NASA Astrophysics Data System (ADS)

    Churagulov, B. R.; Schmidt, P.; Zeng, D.

    2011-12-01

    This paper, devoted to cadmium(II) carbonate, is the first in a series dedicated to the solubility of compounds relevant to mobility of metals in the environment. Here, we present compilations and critical evaluation of the experimental solubility data for cadmium(II) carbonate, otavite, in aqueous ternary and higher-order systems. The solubility of cadmium(II) carbonate depends on temperature, carbon dioxide partial pressure, pH, the presence of complexing ions, and ionic strength of the solution. Papers referring to solubility of cadmium(II) carbonate have been published since 1901; the thorough search of the literature in this field covered the period from 1901 through 2009. The compilation of the available experimental data is introduced with a critical evaluation. The evaluation of the experimental data considers the possible correlation between the data obtained under similar experimental conditions of temperature, carbon dioxide partial pressure, electrolyte, and ionic strength. Those experiments where the solid phase was well identified and the interactions between the electrolyte and the dissolved cadmium(II) ion were considered practically negligible were used to determine the thermodynamic properties of the solid cadmium(II) carbonate. Recommended values for the thermodynamic quantities are lg*Kps0∘ = 6.11 ± 0.10, ΔfG°(CdCO3, cr, 298.15 K) = -(674.3 ± 0.6) kJ mol-1, ΔfH°(CdCO3, cr, 298.15 K) = -(752.2 ± 0.8) kJ mol-1, S°(CdCO3, cr, 298.15 K) = (103.9 ± 0.2) J K-1 mol-1.

  9. Fe(III) hydroxide nucleation and growth on quartz in the presence of Cu(II), Pb(II), and Cr(III): metal hydrolysis and adsorption.

    PubMed

    Dai, Chong; Hu, Yandi

    2015-01-01

    Fe(III) hydroxide nanoparticles are an essential carrier for aqueous heavy metals. Particularly, iron hydroxide precipitation on mineral surfaces can immobilize aqueous heavy metals. Here, we used grazing-incidence small-angle X-ray scattering (GISAXS) to quantify nucleation and growth of iron hydroxide on quartz in 0.1 mM Fe(NO3)3 solution in the presence of Na(+), Cu(2+), Pb(2+), or Cr(3+) at pH = 3.7 ± 0.1. In 30 min, the average radii of gyration (R(g)) of particles on quartz grew from around 2 to 6 nm in the presence of Na(+) and Cu(2+). Interestingly, the particle sizes remained 3.3 ± 0.3 nm in the presence of Pb(2+), and few particles formed in the presence of Cr(3+). Quartz crystal microbalance dissipation (QCM-D) measurements showed that only Cr(3+) adsorbed onto quartz, while Cu(2+) and Pb(2+) did not. Cr(3+) adsorption changed the surface charge of quartz from negative to positive, thus inhibiting the precipitation of positively charged iron hydroxide on quartz. Masses and compositions of the precipitates were also quantified. This study provided new insights on interactions among quartz, iron hydroxide, and metal ions. Such information is helpful not only for environmental remediation but also for the doping design of iron oxide catalysts. PMID:25496643

  10. Quantification of Outer-Sphere Macrochelate Formation in the Ternary cis-Diammine-Platinum(II)-Bis-2'-deoxyguanosine 5'-Monophosphate Complex, cis-(NH(3))(2)Pt(dGMP)(2)(2)(-), and Formation of Quaternary Mixed Metal Ion Species with Magnesium(II), Copper(II), or Zinc(II) in Aqueous Solution.

    PubMed

    Song, Bin; Oswald, Gerda; Zhao, Jing; Lippert, Bernhard; Sigel, Helmut

    1998-09-21

    The acid-base properties of cis-(NH(3))(2)Pt(dG)(2)(2)(-), where both dG(2)(-) (=2'-deoxyguanosine 5'-monophosphate) are N7-coordinated to the same Pt(II) [the complex is abbreviated as Pt(dG)(2)(2)(-)], are summarized [on the basis of potentiometric pH titration data from B. Song et al. (Metal-Based Drugs 1996, 3, 131-141)] and a micro acidity constant scheme is developed which allows quantification of the intrinsic acidity of the two P(O)(2)(OH)(-) groups present in this ternary complex (I = 0.1 M, NaNO(3); 25 degrees C). On the basis of comparisons with the corresponding acid-base properties of cis-(NH(3))(2)Pt(dCMP.H-N3)(2) [(dCMP.H)(-) = phosphate-monoprotonated 2'-deoxycytidine 5'-monophosphate] it is concluded that intramolecular, outer-sphere macrochelates form via Pt(NH(3)).O(3)P hydrogen bonds. The formation degree of these macrochelates is quantified; it amounts in aqueous solution in each case (in its lower limit) to about 40% for the various possibilities which exist for the formation of these chelates in the cis-(NH(3))(2)Pt(dG)(2) complexes. The stability constants of the mixed metal ion complexes, M[Pt(H;dG)(dG)](+) and M[Pt(dG)(2)], were also determined via potentiometric pH titrations. On the basis of previous measurements with simple phosphate monoesters and phosphonate derivatives, i.e., R-PO(3)(2)(-) with R being a noncoordinating residue (Sigel, H.; et al., Helv. Chim. Acta 1992, 75, 2634-2656), it is shown that the stability of the two mixed metal ion complexes is largely governed by the basicity of the phosphate groups (as quantified via the mentioned microconstants) indicating that the effect of the N7-bound Pt(II) on the phosphate-metal ion binding properties is relatively small. These results suggest that, e.g., a metal ion bound to a nucleobase residue in a nucleotide or in a nucleic acid affects only slightly the metal ion binding capabilities of its phosphate residue or its phosphate backbone. PMID:11670649

  11. Ionisation of atomic hydrogen by positron impact

    NASA Technical Reports Server (NTRS)

    Spicher, Gottfried; Olsson, Bjorn; Raith, Wilhelm; Sinapius, Guenther; Sperber, Wolfgang

    1990-01-01

    With the crossed beam apparatus the relative impact-ionization cross section of atomic hydrogen by positron impact was measured. A layout of the scattering region is given. The first measurements on the ionization of atomic hydrogen by positron impact are also given.

  12. Gas Permeations Studied by Positron Annihilation

    NASA Astrophysics Data System (ADS)

    Yuan, Jen-Pwu; Cao, Huimin; Jean, X.; Yang, Y. C.

    1997-03-01

    The hole volumes and fractions of PC and PET polymers are measured by positron annihilation lifetime spectroscopy. Direct correlations between the measured hole properties and gas permeabilities are observed. Applications of positron annihilation spectroscopy to study gas transport and separation of polymeric materials will be discussed.

  13. Positron Emission Mammotomography with Dual Planar Detectors

    SciTech Connect

    Mark Smith; Raymond Raylman; Stanislaw Majewski

    2003-06-29

    Positron emission mammography (PEM) is usually performed with two stationary planar detectors above and below a compressed breast. There is image blurring normal to the detectors due to the limited angular range of the lines of response. Positron emission mammotomography (PEM-T) with dual planar detectors rotating about the breast can obtain complete angular sampling and has the potential to improve activity estimation.

  14. On the method of positron lifetime measurement

    NASA Technical Reports Server (NTRS)

    Nishiyama, F.; Shizuma, K.; Nasai, H.; Nishi, M.

    1983-01-01

    A fast-slow coincidence system was constructed for the measurement of positron lifetimes in material. The time resolution of this system was 270 ps for the (60)Co gamma rays. Positron lifetime spectra for 14 kinds of alkali halides were measured with this system. Two lifetime components and their intensities were derived from analyses of the lifetime spectra.

  15. Electron and Positron Stopping Powers of Materials

    National Institute of Standards and Technology Data Gateway

    SRD 7 NIST Electron and Positron Stopping Powers of Materials (PC database for purchase)   The EPSTAR database provides rapid calculations of stopping powers (collisional, radiative, and total), CSDA ranges, radiation yields and density effect corrections for incident electrons or positrons with kinetic energies from 1 keV to 10 GeV, and for any chemically defined target material.

  16. 21 CFR 892.1110 - Positron camera.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Positron camera. 892.1110 Section 892.1110 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) MEDICAL DEVICES RADIOLOGY DEVICES Diagnostic Devices § 892.1110 Positron camera. (a) Identification. A...

  17. 21 CFR 892.1110 - Positron camera.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 8 2013-04-01 2013-04-01 false Positron camera. 892.1110 Section 892.1110 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) MEDICAL DEVICES RADIOLOGY DEVICES Diagnostic Devices § 892.1110 Positron camera. (a) Identification. A...

  18. 21 CFR 892.1110 - Positron camera.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 8 2012-04-01 2012-04-01 false Positron camera. 892.1110 Section 892.1110 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) MEDICAL DEVICES RADIOLOGY DEVICES Diagnostic Devices § 892.1110 Positron camera. (a) Identification. A...

  19. 21 CFR 892.1110 - Positron camera.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 8 2014-04-01 2014-04-01 false Positron camera. 892.1110 Section 892.1110 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) MEDICAL DEVICES RADIOLOGY DEVICES Diagnostic Devices § 892.1110 Positron camera. (a) Identification. A...

  20. Transient ions in electron and positron scattering

    NASA Astrophysics Data System (ADS)

    d'A Sanchez, Sergio; de Oliveira, Eliane M.; dos Santos, Josué S.; da Costa, Romarly F.; Bettega, Márcio H. F.; Lima, Marco A. P.; Varella, Márcio T. do N.

    2009-11-01

    We report on recent advances in studies of transient ions formed in electron and positron scattering by molecules. We briefly discuss elastic electron collisions against pyrrole and glycine, as well as electron affinities of glycine-water clusters. Positron scattering and annihilation on small molecules is also discussed.

  1. The Most Metal-poor Stars. II. Chemical Abundances of 190 Metal-poor Stars Including 10 New Stars with [Fe/H] <= -3.5

    NASA Astrophysics Data System (ADS)

    Yong, David; Norris, John E.; Bessell, M. S.; Christlieb, N.; Asplund, M.; Beers, Timothy C.; Barklem, P. S.; Frebel, Anna; Ryan, S. G.

    2013-01-01

    We present a homogeneous chemical abundance analysis of 16 elements in 190 metal-poor Galactic halo stars (38 program and 152 literature objects). The sample includes 171 stars with [Fe/H] <= -2.5, of which 86 are extremely metal poor, [Fe/H] <= -3.0. Our program stars include 10 new objects with [Fe/H] <= -3.5. We identify a sample of "normal" metal-poor stars and measure the trends between [X/Fe] and [Fe/H], as well as the dispersion about the mean trend for this sample. Using this mean trend, we identify objects that are chemically peculiar relative to "normal" stars at the same metallicity. These chemically unusual stars include CEMP-no objects, one star with high [Si/Fe], another with high [Ba/Sr], and one with unusually low [X/Fe] for all elements heavier than Na. The Sr and Ba abundances indicate that there may be two nucleosynthetic processes at lowest metallicity that are distinct from the main r-process. Finally, for many elements, we find a significant trend between [X/Fe] versus T eff, which likely reflects non-LTE and/or three-dimensional effects. Such trends demonstrate that care must be exercised when using abundance measurements in metal-poor stars to constrain chemical evolution and/or nucleosynthesis predictions. This paper includes data gathered with the 6.5 m Magellan Telescopes located at Las Campanas Observatory, Chile. Based on observations collected at the European Organisation for Astronomical Research in the Southern Hemisphere, Chile (proposal 281.D-5015).

  2. Applications of slow positrons to cancer research: Search for selectivity of positron annihilation to skin cancer

    NASA Astrophysics Data System (ADS)

    Jean, Y. C.; Li, Ying; Liu, Gaung; Chen, Hongmin; Zhang, Junjie; Gadzia, Joseph E.

    2006-02-01

    Slow positrons and positron annihilation spectroscopy (PAS) have been applied to medical research in searching for positron annihilation selectivity to cancer cells. We report the results of positron lifetime and Doppler broadening energy spectroscopies in human skin samples with and without cancer as a function of positron incident energy (up to 8 μm depth) and found that the positronium annihilates at a significantly lower rate and forms at a lower probability in the samples having either basal cell carcinoma (BCC) or squamous cell carcinoma (SCC) than in the normal skin. The significant selectivity of positron annihilation to skin cancer may open a new research area of developing positron annihilation spectroscopy as a novel medical tool to detect cancer formation externally and non-invasively at the early stages.

  3. Gaseous Positronics - Positron interactions with atoms and molecules and their applications

    NASA Astrophysics Data System (ADS)

    Buckman, Stephen

    2011-05-01

    The advent of new technologies for accumulating, trapping and cooling positrons has led to a range of new experimental measurements of low energy positron interactions, and also prompted new, state-of-the-art theoretical advances in describing such interactions. This talk will present some of the recent experimental highlights of our program including the observation of threshold Wigner cusps, a search for quasi-bound positronic complexes or ``resonances,'' and measurements of positron interactions with biologically relevant molecules. The latter are an important precursor to the development of models of positron transport in soft matter and, ultimately, a positron dosimetry for techniques such as Positron Emission Tomography. Supported by the Australian Research Council's Centre of Excellence Program.

  4. Positron acoustic shock waves in four-component plasmas with nonthermal electrons and positrons

    NASA Astrophysics Data System (ADS)

    Rahman, M. M.; Mamun, A. A.; Alam, M. S.

    2014-06-01

    Positron acoustic shock waves (PASWs) in an unmagnetized four-component plasma system consisting of a cold mobile viscous positron fluid, hot positrons and electrons following the nonthermal distributions of Cairns et al. [Geophys. Res. Lett. 22, 2709 (1995)], and immobile positive ions are studied both analytically and numerically. The well-known reductive perturbation method is used to derive the Burgers equation. The basic features of the PASWs are significantly modified by the effects of the kinematic viscosity, the nonthermal electrons and hot positrons, the ratio of the electron temperature to the hot positron temperature σ, and the ratio of the hot positron (electron) number density to the cold positron number density μ 1 ( μ 2). The importance of our results to various astrophysical and laboratory plasmas are concisely discussed.

  5. Anchoring of Cu(II) onto surface of porous metal-organic framework through post-synthesis modification for the synthesis of benzimidazoles and benzothiazoles

    NASA Astrophysics Data System (ADS)

    Kardanpour, Reihaneh; Tangestaninejad, Shahram; Mirkhani, Valiollah; Moghadam, Majid; Mohammadpoor-Baltork, Iraj; Zadehahmadi, Farnaz

    2016-03-01

    Efficient synthesis of various benzimidazoles and benzothiazoles under mild conditions catalyzed by Cu(II) anchored onto UiO-66-NH2 metal organic framework is reported. In this manner, first, the aminated UiO-66 was modified with thiophene-2-carbaldehyde and then the prepared Schiff base was reacted with CuCl2. The prepared catalyst was characterized by FT-IR, UV-vis, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), N2 adsorption, inductively coupled plasma atomic emission spectroscopy (ICP-AES) and field emission scanning electron microscopy (FE-SEM). The UiO-66-NH2-TC-Cu was applied as a highly efficient catalyst for synthesis of benzimidazole and benzothiazole derivatives by the reaction of aldehydes with 1,2-diaminobenzene or 2-aminothiophenol. The Cu(II)-containing MOF was reused several times without any appreciable loss of its efficiency.

  6. Uncovering multiple Wolf-Rayet star clusters and the ionized ISM in Mrk 178: the closest metal-poor Wolf-Rayet H II galaxy

    NASA Astrophysics Data System (ADS)

    Kehrig, C.; Pérez-Montero, E.; Vílchez, J. M.; Brinchmann, J.; Kunth, D.; García-Benito, R.; Crowther, P. A.; Hernández-Fernández, J.; Durret, F.; Contini, T.; Fernández-Martín, A.; James, B. L.

    2013-07-01

    New integral field spectroscopy (IFS) has been obtained for the nearby metal-poor Wolf-Rayet (WR) galaxy Mrk 178 to examine the spatial correlation between its WR stars and the neighbouring ionized interstellar medium (ISM). The strength of the broad WR features and its low metallicity make Mrk 178 an intriguing object. We have detected the blue and red WR bumps in different locations across the field of view (˜300 pc × 230 pc) in Mrk 178. The study of the WR content has been extended, for the first time, beyond its brightest star-forming knot uncovering new WR star clusters. Using Large/Small Magellanic Cloud-template WR stars, we empirically estimate a minimum of ˜20 WR stars within the region sampled. Maps of the spatial distribution of the emission lines and of the physical-chemical properties of the ionized ISM have been created and analysed. Here, we refine the statistical methodology by Pérez-Montero et al. (2011) to probe the presence of variations in the ISM properties. An error-weighted mean of 12+log(O/H) = 7.72 ± 0.01 is taken as the representative oxygen abundance for Mrk 178. A localized N and He enrichment, spatially correlated with WR stars, is suggested by this analysis. Nebular He II λ4686 emission is shown to be spatially extended reaching well beyond the location of the WR stars. This spatial offset between WRs and He II emission can be explained based on the mechanical energy input into the ISM by the WR star winds, and does not rule out WR stars as the He II ionization source. We study systematic aperture effects on the detection and measurement of the WR features, using Sloan Digital Sky Survey spectra combined with the power of IFS. In this regard, the importance of targeting low metallicity nearby systems is discussed.

  7. Visible-Light-Assisted Photocatalytic Reduction of Nitroaromatics by Recyclable Ni(II)-Porphyrin Metal-Organic Framework (MOF) at RT.

    PubMed

    Deenadayalan, M S; Sharma, Nayuesh; Verma, Praveen Kumar; Nagaraja, C M

    2016-06-01

    A microporous Ni(II)-porphyrin metal-organic framework (MOF), [Ni3(Ni-HTCPP)2(μ2-H2O)2(H2O)4(DMF)2]·2DMF, (MOF1) (where, Ni-HTCPP = 5,10,15,20-tetrakis(4-benzoate) porphyrinato-Ni(II)) has been synthesized by the solvothermal route. Single-crystal X-ray diffraction study of 1 reveals a 2D network structure constituted by Ni3 cluster and [Ni-HTCPP](3-) metalloligand having (3, 6)-connected binodal net with {4(3)}2{4(6)·6(6)·8(3)}-kgd net topology. The 2D layers are further stacked together through π-π interactions between the porphyrin linkers to generate a 3D supramolecular framework which houses 1D channels with dimension of ∼5.0 × 9.0 Å(2) running along the crystallographic a-axis. Visible-light-assisted photocatalytic investigation of MOF1 for heterogeneous reduction of various nitroaromatics at room temperature resulted in the corresponding amines with high yield and selectivity. On the contrary, the Ni(II)-centered porphyrin tetracarboxylic acid [Ni-H4TCPP] metalloligand does not show the photocatalytic activity under similar conditions. The remarkably high catalytic performance of MOF1 over [Ni-H4TCPP] metalloligand has been attributed due to cooperative catalysis involving the Ni-centered porphyrin secendary building units (SBUs) and the Ni3-oxo node. Further, the MOF1 was recycled and reused up to three cycles without any significant loss of catalytic activity as well as structural rigidity. To the best of our knowledge, MOF1 represents the first example of MOF based on 3d metal ion exhibiting visible-light-assisted reduction of nitroaromatics under mild conditions without the assistance of noble metal cocatalysts. PMID:27191376

  8. Improved V II Log(gf) Values, Hyperfine Structure Constants, and Abundance Determinations in the Photospheres of the Sun and Metal-poor Star HD 84937

    NASA Astrophysics Data System (ADS)

    Wood, M. P.; Lawler, J. E.; Den Hartog, E. A.; Sneden, C.; Cowan, J. J.

    2014-10-01

    New experimental absolute atomic transition probabilities are reported for 203 lines of V II. Branching fractions are measured from spectra recorded using a Fourier transform spectrometer and an echelle spectrometer. The branching fractions are normalized with radiative lifetime measurements to determine the new transition probabilities. Generally good agreement is found between this work and previously reported V II transition probabilities. Two spectrometers, independent radiometric calibration methods, and independent data analysis routines enable a reduction in systematic uncertainties, in particular those due to optical depth errors. In addition, new hyperfine structure constants are measured for selected levels by least squares fitting line profiles in the FTS spectra. The new V II data are applied to high resolution visible and UV spectra of the Sun and metal-poor star HD 84937 to determine new, more accurate V abundances. Lines covering a range of wavelength and excitation potential are used to search for non-LTE effects. Very good agreement is found between our new solar photospheric V abundance, log ɛ(V) = 3.95 from 15 V II lines, and the solar-system meteoritic value. In HD 84937, we derive [V/H] = -2.08 from 68 lines, leading to a value of [V/Fe] = 0.24.

  9. Improved log(gf) Values for Lines of V I and V II, New Vanadium Abundances in the Sun and the Metal-Poor Star HD 84937

    NASA Astrophysics Data System (ADS)

    Lawler, James E.; Wood, Michael P.; Den Hartog, Elizabeth; Feigenson, Thomas; Sneden, Chris; Cowan, John J.

    2015-01-01

    New emission branching fraction measurements for 836 lines of the first spectrum of vanadium (V I) and 203 lines of V II are determined from hollow cathode lamp spectra recorded with the National Solar Observatory 1m Fourier transform spectrometer (FTS) and a high resolution echelle spectrometer. The branching fractions are combined with new radiative lifetimes from laser induced fluorescence measurements to determine accurate absolute atomic transition probabilities for 1039 lines of V I and V II. The FTS data are also used to extract new hyperfine structure A coefficients for both spectra. These new laboratory data are applied to determine the V abundance in the Sun and metal-poor star HD 84937, yielding log ɛ(V) = 3.96 (σ = 0.04) based on 93 V I lines and log ɛ(V) = 1.89 (σ = 0.07) based on nine V I lines respectively, and yielding log ɛ(V) = 3.95 (σ = 0.05) based on 15 V II lines and log ɛ(V) = 1.87 (σ = 0.07) based on 68 V II lines respectively1-3.1. Wood et al., ApJS 214:18 (2014), 2. Den Hartog et al. ApJS in press (2014), 3. Lawler et al. ApJS submitted (2014). This work is supported by NASA grant NNX10AN93G (JEL), NSF AST-1211055 (EDH & JEL), and NSF AST-1211585 (CS).

  10. IMPROVED V II log(gf) VALUES, HYPERFINE STRUCTURE CONSTANTS, AND ABUNDANCE DETERMINATIONS IN THE PHOTOSPHERES OF THE SUN AND METAL-POOR STAR HD 84937

    SciTech Connect

    Wood, M. P.; Lawler, J. E.; Den Hartog, E. A.; Sneden, C.; Cowan, J. J. E-mail: jelawler@wisc.edu E-mail: chris@verdi.as.utexas.edu

    2014-10-01

    New experimental absolute atomic transition probabilities are reported for 203 lines of V II. Branching fractions are measured from spectra recorded using a Fourier transform spectrometer and an echelle spectrometer. The branching fractions are normalized with radiative lifetime measurements to determine the new transition probabilities. Generally good agreement is found between this work and previously reported V II transition probabilities. Two spectrometers, independent radiometric calibration methods, and independent data analysis routines enable a reduction in systematic uncertainties, in particular those due to optical depth errors. In addition, new hyperfine structure constants are measured for selected levels by least squares fitting line profiles in the FTS spectra. The new V II data are applied to high resolution visible and UV spectra of the Sun and metal-poor star HD 84937 to determine new, more accurate V abundances. Lines covering a range of wavelength and excitation potential are used to search for non-LTE effects. Very good agreement is found between our new solar photospheric V abundance, log ε(V) = 3.95 from 15 V II lines, and the solar-system meteoritic value. In HD 84937, we derive [V/H] = –2.08 from 68 lines, leading to a value of [V/Fe] = 0.24.

  11. Molecular assemblies of 4-(hexadecyloxy)-n-(pyridinylmethylene)anilines at the air-water interface and Cu(II)-promoted vesicle formation via metal coordination.

    PubMed

    Wang, Haibo; Miao, Wangen; Liu, Huijin; Zhang, Xianfeng; Du, Xuezhong

    2010-09-01

    The molecular assemblies of 4-(hexadecyloxy)-N-(pyridinylmethylene)anilines (HPA) at the air-water interface on pure water and aqueous Cu(II) subphases have been investigated using in situ infrared reflection absorption spectroscopy (IRRAS). The Schiff base units were oriented with their long axes almost perpendicular to the water surface, and both imine and pyridinyl nitrogen atoms of the Schiff base units were coordinated to Cu(II) ions together with their geometrical conversions. The alkyl chains in the monolayers were quantitatively determined on the assumption that the HPA monolayers at the air-water interface were composed of sublayers of alkyl chains and Schiff base units, and the chain orientation angle on pure water was 30 +/- 2 degrees and increased to 37 +/- 2 degrees on the aqueous Cu(II) subphase. The HPA amphiphiles could not be dispersed in pure water but could self-organize into vesicles with metal-coordinated headgroups and interdigitated-packed alkyl chains in the presence of Cu(II) ions in aqueous solution. Transmission electron microscopy (TEM), differential scanning calorimetry (DSC), UV-vis spectroscopy, and small-angle X-ray diffraction (XRD) were used to investigate the aggregate structures and specific properties of the coordinated vesicles. PMID:20698514

  12. 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 (in hartree) are found to be 8.17x10{sup -4}, 4.42x10{sup -4}, 15.14x10{sup -4}, and 21.80x10{sup -4}, respectively. These states are constructed by first coupling the two electrons into a configuration which is predominantly {sup 3}P{sup e}, and then adding a p-wave positron. All the active particles are in states in which the relative angular momentum between any pair of particles is at least L=1. The LiPs state is Borromean since there are no three-body bound subsystems (of the correct symmetry) of the (Li{sup +}, e{sup -}, e{sup -}, e{sup +}) particles that make up the system. The dominant decay mode of these states will be radiative decay into a configuration that autoionizes or undergoes positron annihilation.

  13. Effect of Garlic (Allium sativum) on Heavy Metal (Nickel II and ChromiumVI) Induced Alteration of Serum Lipid Profile in Male Albino Rats

    PubMed Central

    Gupta, Amrita Das; Das, Swastika N.; Dhundasi, Salim A.; Das, Kusal K.

    2008-01-01

    We have studied the effect of simultaneous oral treatment of aqueous garlic extract (Allium sativum) on heavy metal (nickel II and chromium VI) induced changes in serum lipid profile. Nickel sulfate and potassium dichromate treated rats showed a significant increase in serum low density lipoprotein-cholesterol (LDL-C), very low density lipoprotein-cholesterol (VLDL-C) and triglyceride (TG) level as well as decrease in serum high density lipoprotein-cholesterol (HDL-C) level. Simultaneous garlic administration with nickel sulfate showed improvement in serum LDL-C, HDL-C, VLDL-C and TG level. But in case of potassium dichromate, garlic administration did not show satisfactory improvement in lipid profile except VLDL-C and TG level. The results indicate that garlic (Allium sativum) has some beneficial effect in preventing heavy metal (nickel and chromium VI) induced alteration of lipid profile. PMID:19139532

  14. Sonochemical synthesis of nanoplates of two Cd(II) based metal-organic frameworks and their applications as precursors for preparation of nano-materials.

    PubMed

    Masoomi, Mohammad Yaser; Morsali, Ali

    2016-01-01

    Nano plates of two Cd(II)-based metal-organic frameworks, [Cd2(oba)2(4-bpdb)2]n ·(DMF)x(TMU-8) and [Cd(oba)(4,4'-bipy)]n ·(DMF)y (TMU-9) were synthesized via sonochemical reaction by using various time and concentrations of initial reagents and power of irradiation and characterized by scanning electron microscopy, X-ray powder diffraction and IR spectroscopy. Moreover, the effect of triethylamine on speed of nucleation during the synthesis was investigated. Thermolysis of these MOFs at 550°C under air atmosphere yields CdO nanoparticles. PMID:26384904

  15. Crystal structure and characterization of a novel luminescent 2D metal-organic framework, poly[aquaitaconatocalcium(II)] possessing an open framework structure with hydrophobic channels

    NASA Astrophysics Data System (ADS)

    Nair, Remya M.; Sudarsanakumar, M. R.; Suma, S.; Prathapachandra Kurup, M. R.

    2016-02-01

    A novel 2D metal-organic framework poly[aquaitaconatocalcium(II)] with an open framework structure has been successfully grown by single gel diffusion technique. Sodium metasilicate was used for gel preparation. The structure was determined by single crystal X-ray diffraction. The compound crystallizes in monoclinic space group P21/c with hydrophobic 1D channels. The obtained crystals were further characterized by elemental analysis, FT-IR and UV-Visible spectroscopy, powder X-ray diffraction and thermogravimetry. The luminescent property of the complex was also discussed.

  16. Synthesis and X-ray structural studies of novel metal-organic complex: Diiodobis(2-aminopyridine)cadmium(II) single crystal

    NASA Astrophysics Data System (ADS)

    Venkatesan, G.; Anandha, G. Babu; Ramasamy, P.

    2013-02-01

    A new metal-organic hybrid complex, [Cd(ap)2I2] (DIAC), (ap = 2-aminopyridine) was synthesized and characterized by single crystal X-ray diffraction, High resolution X-ray diffraction(HRXRD) and UV-Vis-NIR transmission. The DIAC crystallize in monoclinic crystal system, space group P21/n. The coordination geometry around the Cd(II) centre is a distorted tetrahedral. The high resolution X-ray diffraction studies (HRXRD) reveals that the crystalline perfection of as grown single crystal is fairly good.

  17. Harnessing the bone-seeking ability of Ca(ii)-like metal ions in the treatment of metastatic cancer and resorption disorders.

    PubMed

    Weekes, D M; Orvig, C

    2016-04-21

    Metal ions are naturally retained by skeletal tissues in living systems because of their high affinity for the hydroxyapatite-like mineral matrix that makes up cortical bone. This is particularly true for metal ions that bear a close resemblance to calcium(ii) (such as the lanthanides or alkaline earth metals), and in a few key cases this targeting ability has been exploited in order to develop medicinal agents that are intended to treat bones which have become diseased. In this review, we focus on two areas where this has been particularly effective: first is in the diagnosis and therapy of metastatic bone cancer, in which radioactive metal ions including (99m)Tc, (153)Sm, and (223)Ra are used to image, alleviate, and ablate harmful cancerous legions with good specificity versus healthy tissues; second is the use of trivalent lanthanides to treat osteoporosis, an emerging concept which has gathered significance over the last 15 years, and is now entering preclinical trials with carefully designed systems. PMID:26853513

  18. STROeMGREN PHOTOMETRY OF GALACTIC GLOBULAR CLUSTERS. II. METALLICITY DISTRIBUTION OF RED GIANTS IN omega CENTAURI

    SciTech Connect

    Calamida, A.; Hilker, M.; Bono, G. E-mail: mhilker@eso.or

    2009-12-01

    We present new intermediate-band Stroemgren photometry based on more than 300 u, v, b, y images of the Galactic globular cluster omega Cen. Optical data were supplemented with new multiband near-infrared (NIR) photometry (350 J, H, K{sub s} images). The final optical-NIR catalog covers a region of more than 20 x 20 arcmin squared across the cluster center. We use different optical-NIR color-color planes together with proper-motion data available in the literature to identify candidate cluster red-giant (RG) stars. By adopting different Stroemgren metallicity indices, we estimate the photometric metallicity for approx4000 RGs, the largest sample ever collected. The metallicity distributions show multiple peaks ([Fe/H]{sub phot} = -1.73 +- 0.08, -1.29 +- 0.03, -1.05 +- 0.02, -0.80 +- 0.04, -0.42 +- 0.12, and -0.07 +- 0.08 dex) and a sharp cutoff in the metal-poor (MP) tail ([Fe/H]{sub phot} approx< -2 dex) that agree quite well with spectroscopic measurements. We identify four distinct subpopulations, namely, MP ([Fe/H] <= -1.49), metal-intermediate (MI; -1.49 < [Fe/H] <= -0.93), metal-rich (MR; -0.95 < [Fe/H] <= -0.15), and solar metallicity ([Fe/H] approx 0). The last group includes only a small fraction of stars (approx8% +- 5%) and should be confirmed spectroscopically. Moreover, using the difference in metallicity based on different photometric indices, we find that the 19% +- 1% of RGs are candidate CN-strong stars. This fraction agrees quite well with recent spectroscopic estimates and could imply a large fraction of binary stars. The Stroemgren metallicity indices display a robust correlation with alpha-elements ([Ca+Si/H]) when moving from the MI to the MR regime ([Fe/H] approx> -1.7 dex).

  19. Sonochemical synthesis, DNA binding, antimicrobial evaluation and in vitro anticancer activity of three new nano-sized Cu(II), Co(II) and Ni(II) chelates based on tri-dentate NOO imine ligands as precursors for metal oxides.

    PubMed

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

    2016-09-01

    Three new nano sized Cu(II), Co(II) and Ni(II) complexes of imine ligand derived from the condensation of 2-amino-3-hydroxypyridine and 3-methoxysalicylaldehyde have been prepared and investigated using various chemical techniques such as NMR, elemental analysis, molar conductance, IR, electronic spectra, TGA and magnetic moment measurements. The obtained chemical analysis data showed that the synthesis of 1:1 (metal:ligand) ratio and octahedral geometry was proposed on the basis of magnetic moment and spectral data studies except the Cu(II) complex which is tetrahedral geometry. Nano-sized particles of the investigated complexes were prepared by sonochemistry method. Furthermore, metal oxides nanoparticles were gained by calcination of the prepared corresponding complexes at 500°C and their structures were characterized by powder x-ray and transmittance electron microscopy. Moreover, the free ligand, its complexes and their metal oxides have been checked in vitro against a number of bacteria and fungi in order to assess their antimicrobial activities. In addition to that, DNA binding of the prepared complexes was tested by many routes such as electronic spectra, viscosity and gel electrophoresis. The results showed that the investigated complexes could bind to DNA via an intercalative mode. The cytotoxicity of the Schiff base complexes on human colon carcinoma cells, (HCT-116 cell line) and Breast carcinoma cells, (MCF-7 cell line) showed potent cytotoxicity effect against growth of carcinoma cells compared to the clinically used Vinblastine standard. PMID:27395793

  20. Visible and dark matter genesis and cosmic positron and electron excesses

    SciTech Connect

    Gu Peihong; Sarkar, Utpal; Zhang Xinmin

    2009-10-01

    Dark and baryonic matter contribute comparable energy density to the present universe. The dark matter may also be responsible for the cosmic positron and electron excesses. We connect these phenomena with the Dirac seesaw for neutrino masses. In our model (i) the dark matter relic density is a dark matter asymmetry generated simultaneously with the baryon asymmetry so that we can naturally understand the coincidence between the dark and baryonic matter and (ii) the dark matter mostly decays into the leptons so that its decay can interpret the anomalous cosmic rays with positron and electron excesses.

  1. A KECK HIRES DOPPLER SEARCH FOR PLANETS ORBITING METAL-POOR DWARFS. II. ON THE FREQUENCY OF GIANT PLANETS IN THE METAL-POOR REGIME

    SciTech Connect

    Sozzetti, Alessandro; Torres, Guillermo; Latham, David W.; Stefanik, Robert P.; Korzennik, Sylvain G.; Boss, Alan P.; Carney, Bruce W.; Laird, John B. E-mail: gtorres@cfa.harvard.edu E-mail: skorzennik@cfa.harvard.edu E-mail: boss@dtm.ciw.edu E-mail: laird@bgsu.edu

    2009-05-20

    We present an analysis of three years of precision radial velocity (RV) measurements of 160 metal-poor stars observed with HIRES on the Keck 1 telescope. We report on variability and long-term velocity trends for each star in our sample. We identify several long-term, low-amplitude RV variables worthy of followup with direct imaging techniques. We place lower limits on the detectable companion mass as a function of orbital period. Our survey would have detected, with a 99.5% confidence level, over 95% of all companions on low-eccentricity orbits with velocity semiamplitude K {approx}> 100 m s{sup -1}, or M{sub p} sin i {approx}> 3.0 M {sub J}(P/yr){sup (1/3)}, for orbital periods P {approx}< 3 yr. None of the stars in our sample exhibits RV variations compatible with the presence of Jovian planets with periods shorter than the survey duration. The resulting average frequency of gas giants orbiting metal-poor dwarfs with -2.0{approx}<[Fe/H]{approx}<-0.6 is f{sub p} < 0.67% (at the 1{sigma} confidence level). We examine the implications of this null result in the context of the observed correlation between the rate of occurrence of giant planets and the metallicity of their main-sequence solar-type stellar hosts. By combining our data set with the Fischer and Valenti (2005) uniform sample, we confirm that the likelihood of a star to harbor a planet more massive than Jupiter within 2 AU is a steeply rising function of the host's metallicity. However, the data for stars with -1.0{approx}<[Fe/H]{approx}<0.0 are compatible, in a statistical sense, with a constant occurrence rate f{sub p} {approx_equal} 1%. Our results can usefully inform theoretical studies of the process of giant-planet formation across two orders of magnitude in metallicity.

  2. Metal-ion directed synthesis of N2O2 type chelate complexes of Ni(II), Cu(II) and Zn(II): spectral, thermal and single crystal studies.

    PubMed

    Yadav, Seema; Ahmad, Musheer; Siddiqi, K S

    2012-12-01

    A set of Ni(II), Cu(II) and Zn(II) complexes of Schiff base have been synthesized by one pot condensation reaction of 2-hydroxy-4-methoxybenzophenone with 1,3-diaminopropane in 1:2:1 molar ratio. They have been characterized by elemental analysis, conductance measurement, thermal analysis (TGA/DTA), FT-IR, (1)H-NMR, EPR spectra, ESI-MS and electronic spectral studies. In order to establish the geometry, a single crystal X-ray structure for [Ni(L)] complex was determined. It crystallizes in monoclinic system having unit cell parameters a=14.015(5)Å, b=13.391(5)Å, c=14.931(5)Å and α=90.000(5)(o), β=112.237(5)(o), γ=90.000(5)(o) with P 2(1)/c space group. No π-π stacking interaction was obtained in molecular packing diagram. A square-planar geometry has been confirmed for Ni(II) complex. Furthermore, on the basis of elemental analysis, IR, UV-visible and EPR data a square-planar geometry for Cu(II) and a distorted octahedral geometry for the Zn(II) complex has been established. In case of Zn(II) complex NO(3)(-) group was found to be coordinated in monodentate fashion. The low molar conductivity values of the complexes measured in chloroform and DMSO suggest their non-ionic nature. PMID:22960327

  3. Metal-ion directed synthesis of N2O2 type chelate complexes of Ni(II), Cu(II) and Zn(II): Spectral, thermal and single crystal studies

    NASA Astrophysics Data System (ADS)

    Yadav, Seema; Ahmad, Musheer; Siddiqi, K. S.

    2012-12-01

    A set of Ni(II), Cu(II) and Zn(II) complexes of Schiff base have been synthesized by one pot condensation reaction of 2-hydroxy-4-methoxybenzophenone with 1,3-diaminopropane in 1:2:1 molar ratio. They have been characterized by elemental analysis, conductance measurement, thermal analysis (TGA/DTA), FT-IR, 1H-NMR, EPR spectra, ESI-MS and electronic spectral studies. In order to establish the geometry, a single crystal X-ray structure for [Ni(L)] complex was determined. It crystallizes in monoclinic system having unit cell parameters a = 14.015(5) Å, b = 13.391(5) Å, c = 14.931(5) Å and α = 90.000(5)o, β = 112.237(5)o, γ = 90.000(5)o with P 21/c space group. No π-π stacking interaction was obtained in molecular packing diagram. A square-planar geometry has been confirmed for Ni(II) complex. Furthermore, on the basis of elemental analysis, IR, UV-visible and EPR data a square-planar geometry for Cu(II) and a distorted octahedral geometry for the Zn(II) complex has been established. In case of Zn(II) complex NO3- group was found to be coordinated in monodentate fashion. The low molar conductivity values of the complexes measured in chloroform and DMSO suggest their non-ionic nature.

  4. Crystallographic, Electrochemical, and Pulsed EPR Study of Copper(II) Polyimidazole Complexes Relevant to the Metal Sites of Copper Proteins(,).

    PubMed

    Place, Christophe; Zimmermann, Jean-Luc; Mulliez, Etienne; Guillot, Geneviève; Bois, Claudette; Chottard, Jean-Claude

    1998-08-10

    , T = 291 K; R = 0.043, R(w) = 0.049 for 2305 reflections; Cu-N = 1.984(5), 1.989(5), 2.012(5), and 1.979(5) Å, Cu-Cl = 2.796(2) Å, in a distorted bipyramidal geometry. In methanol solution, the perchlorato complexes 1, 2, Cu(TRIM)(ClO(4))(2) (3), 4, and Cu(TIK)(ClO(4))(2) (5) exhibited redox potentials from -215 to +284 mV vs NHE together with a visible absorption from 604 to 728 nm. Electron spin-echo envelope modulation (ESEEM) spectroscopy data, particularly the nuclear quadrupole interaction (NQI) parameters e(2)qQ and eta of the remote nitrogen (N1H), were analyzed and interpreted according to the model devised by Jiang et al. (J. Am. Chem. Soc. 1990, 112, 9035) with reference to Cu(HIm)(4)(ClO(4))(2). The results are the following: (i) C2 substitution of the imidazole ring, next to the remote nitrogen (1, 2) decreases the asymmetry parameter eta to ca. 0.75 compared to 1.00 for Cu(HIm)(4)(ClO(4))(2); this effect of C2 substitution on the symmetry of the electric field gradient at N1H appears similar for both the electron-donating methylene substituents (1) and the electron-withdrawing carbonyl group (2). (ii) The electron-donating or -withdrawing properties of the substituent are reflected by the variation of the e(2)qQ parameter, increasing from 1.43 to 1.75 MHz (1) or decreasing to 1.38 MHz (2), and by the nu(+) transition shifting toward higher frequencies from 1.49 to 1.65 MHz (1, 3, 4) or to lower frequencies to 1.29 MHz (2, 5). The use of the eta and nu(+) parameters to assign the Ndelta vs Nepsilon coordination of histidine to the metal and to detect modified histidine in copper-binding proteins is discussed. PMID:11670520

  5. Evidence for a conserved binding motif of the dinuclear metal site in mammalian and plant purple acid phosphatases: 1H NMR studies of the di-iron derivative of the Fe(III)Zn(II) enzyme from kidney bean.

    PubMed Central

    Battistuzzi, G; Dietrich, M; Löcke, R; Witzel, H

    1997-01-01

    The di-iron core of mammalian purple acid phosphatases has been reproduced in the plant enzyme from kidney bean (Mr 111000) upon insertion of an Fe(II) ion in place of the native zinc(II) in the dinuclear Fe(III)Zn(II) core. The shortening of the electronic relaxation time of the metal centre allows detection of hyperfine-shifted 1H NMR resonances, although severe broadening due to Curie relaxation prevents independent signal assignment. Nevertheless, comparison of the spectral features of the structurally characterized plant enzyme with those of the mammalian species, which were previously extensively assigned, is consistent with a close similarity of the metal-binding sites, also suggested by previous sequence-alignment studies. Some differences appear to be mainly localized at the M(II) site. Spectral comparison was also carried out on the Fe(III)Co(II) derivatives. PMID:9169589

  6. Cyanide bridged hetero-metallic polymeric complexes: Syntheses, vibrational spectra, thermal analyses and crystal structures of complexes [M(1,2-dmi)2Ni(μ-CN)4]n (M = Zn(II) and Cd(II))

    NASA Astrophysics Data System (ADS)

    Kürkçüoğlu, Güneş Süheyla; Sayın, Elvan; Şahin, Onur

    2015-12-01

    Two cyanide bridged hetero-metallic complexes of general formula, [M(1,2-dmi)2Ni(μ-CN)4]n (1,2-dmi = 1,2-dimethylimidazole and M = Zn(II) or Cd(II)) have been synthesized and characterized by vibrational (FT-IR and Raman) spectroscopy, single crystal X-ray diffraction, thermal analyses and elemental analyses. The crystallographic analyses reveal that the complexes, [Zn(1,2-dmi)2Ni(μ-CN)4] (1) and [Cd(1,2-dmi)2Ni(μ-CN)4] (2), have polymeric 2D networks. In the complexes, four cyanide groups of [Ni(CN)4]2- coordinated to the adjacent M(II) ions and distorted octahedral geometries of complexes are completed by two nitrogen atoms of trans 1,2-dmi ligands. The structures of 1 and 2 are similar and linked via intermolecular hydrogen bonding, C-H⋯Ni interactions to give rise to 3D networks. Vibration assignments are given for all the observed bands and the spectral features also supported to the crystal structures of heteronuclear complexes. The FT-IR and Raman spectra of the complexes are very much consistent with the structural data presented.

  7. Schwertmannite and Fe oxides formed by biological low-pH Fe(II) oxidation versus abiotic neutralization: Impact on trace metal sequestration

    NASA Astrophysics Data System (ADS)

    Burgos, William D.; Borch, Thomas; Troyer, Lyndsay D.; Luan, Fubo; Larson, Lance N.; Brown, Juliana F.; Lambson, Janna; Shimizu, Masayuki

    2012-01-01

    Three low-pH coal mine drainage (CMD) sites in central Pennsylvania were studied to determine similarities in sediment composition, mineralogy, and morphology. Water from one site was used in discontinuous titration/neutralization experiments to produce Fe(III) minerals by abiotic oxidative hydrolysis for comparison with the field precipitates that were produced by biological low-pH Fe(II) oxidation. Even though the hydrology and concentration of dissolved metals of the CMD varied considerably between the three field sites, the mineralogy of the three iron mounds was very similar. Schwertmannite was the predominant mineral precipitated at low-pH (2.5-4.0) along with lesser amounts of goethite. Trace metals such as Zn, Ni and Co were only detected at μmol/g concentrations in the field sediments, and no metals (other than Fe) were removed from the CMD at any of the field sites. Metal cations were not lost from solution in the field because of unfavorable electrostatic attraction to the iron mound minerals. Ferrihydrite was the predominant mineral formed by abiotic neutralization (pH 4.4-8.4, 4 d aging) with lesser amounts of schwertmannite and goethite. In contrast to low-pH precipitation, substantial metal removal occurred in the neutralized CMD. Al was likely removed as hydrobasaluminite and Al(OH) 3, and as a co-precipitate into schwertmannite or ferrihydrite. Zn, Ni and Co were likely removed via adsorption onto and co-precipitation into the freshly formed Fe and Al solids. Mn was likely removed by co-precipitation and, at the highest final pH values, as a Mn oxide. Biological low-pH Fe(II) oxidation can be cost-effectively used to pre-treat CMD and remove Fe and acidity prior to conventional neutralization techniques. A further benefit is that solids formed under these conditions may be of industrial value because they do not contain trace metal or metalloid contaminants.

  8. Positron deposition in plasmas by positronium beam ionization and transport of positrons in tokamak plasmas

    SciTech Connect

    Murphy, T.J.

    1986-11-01

    In a recently proposed positron transport experiment, positrons would be deposited in a fusion plasma by forming a positronium (Ps) beam and passing it through the plasma. Positrons would be deposited as the beam is ionized by plasma ions and electrons. Radial transport of the positrons to the limiter could then be measured by detecting the gamma radiation produced by annihilation of positrons with electrons in the limiter. This would allow measurements of the transport of electron-mass particles and might shed some light on the mechanisms of electron transport in fusion plasmas. In this paper, the deposition and transport of positrons in a tokamak are simulated and the annihilation signal determined for several transport models. Calculations of the expected signals are necessary for the optimal design of a positron transport experiment. There are several mechanisms for the loss of positrons besides transport to the limiter. Annihilation with plasma electrons and reformation of positronium in positron-hydrogen collisions are two such processes. These processes can alter the signal and place restrictions ons on the plasma conditions in which positron transport experiments can be effectively performed.

  9. A bis(amine-carboxylate) copper(II) coordination compound forms a two-dimensional metal-organic framework when crystallized from water and methanol.

    PubMed

    Munro, Orde Q; Akerman, Matthew P; Gillham, Kate

    2009-09-01

    When {2,2'-[(2-methyl-2-nitropropane-1,3-diyl)diimino]diacetato}copper(II), [Cu(C(8)H(13)N(3)O(6))], (I), was crystallized from a binary mixture of methanol and water, a monoclinic two-dimensional water- and methanol-solvated metal-organic framework (MOF) structure, distinctly different from the known orthorhombic one-dimensional coordination polymer of (I), was isolated, namely catena-poly[[copper(II)-mu(3)-2,2'-[(2-methyl-2-nitropropane-1,3-diyl)diimino]diacetato] methanol 0.45-solvate 0.55-hydrate], {[Cu(C(8)H(13)N(3)O(6))].0.45CH(3)OH.0.55H(2)O}(n), (II). The monoclinic structure of (II) comprises centrosymmetric dimers stabilized by a dative covalent Cu(2)O(2) core and intramolecular N-H...O hydrogen bonds. Each dimer is linked to four neighbouring dimers via symmetry-related (opposing) pairs of bridging carboxylate O atoms to generate a ;diamondoid' net or two-dimensional coordination network. Tight voids of 166 A(3) are located between these two-dimensional MOF sheets and contain a mixture of water and methanol with fractional occupancies of 0.55 and 0.45, respectively. The two-dimensional MOF sheets have nanometre-scale spacings (11.2 A) in the crystal structure. Hydrogen-bonding between the methanol/water hydroxy groups and a Cu-bound bridging carboxylate O atom apparently negates thermal desolvation of the structure below 358 K in an uncrushed crystal of (II). PMID:19726848

  10. Experimental Determination of Heat Transfer Within the Metal/Mold Gap in a DC Casting Mold: Part II. Effect of Casting Metal, Mold Material, and Other Casting Parameters

    NASA Astrophysics Data System (ADS)

    Prasad, Arvind; Bainbridge, Ian F.

    2013-07-01

    Extensive experimental studies were conducted to quantify the effect of different parameters that can affect the heat transfer from the metal to the mold during the steady-state phase of DC casting. In the first part previously published, the experimental technique was established and results were reported for the effect of gas type (atmosphere within the mold) and the gap between the metal and the mold. The results showed the significant effect of gas thermal conductivity and the metal-mold gap on the mold wall heat transfer coefficient. In this second publication on heat transfer in the mold wall region of a DC casting mold, the results from the effect of casting temperature, gas flow rate, casting alloy, mold material, and the mold insert material on the mold wall heat transfer coefficient are described. The experiments reported in the current paper show that these additional factors tested do not affect the heat flux through the mold wall to the same extent as the gap size or the gas type. The heat transfer coefficient changes by less than 5 pct when casting temperature is changed by ±25 K, less than 15 pct when the gas flow rate within the metal-mold gap flows at up to 3 LPM, and approximately 30 pct when the mold material is changed from stainless steel to AA601 to copper. Similar results were obtained when different insert materials were used. These results are explained with the help of an electrical analogy of heat transfer and are consistent with the heat transfer theory.

  11. Positron emission tomography: An overview

    PubMed Central

    Shukla, A. K.; Kumar, Utham

    2006-01-01

    The rate of glucose utilization in tumor cells is significantly enhanced as compared to normal cells and this biochemical characteristic is utilized in PET imaging using FDG as a major workhorse. The PET systems as well as cyclotrons producing positron emitting radiopharmaceuticals have undergone continuous technological refinements. While PET (CT) systems enable fusion images as well as precise attenuation correction, the self-shielded cyclotrons developed provide dedicated systems for in-house production of a large number of PET radiopharmaceuticals. The application of PET images in oncology includes those of pulmonary, colorectal, breast, lymphoma, head & neck, bone, ovarian and GI cancers. The PET has been recognized as promising diagnostic tool to predict biological and physiological changes at the molecular level and hence offer a potential area for future applications including Stem Cell research. PMID:21206635

  12. Positron emission tomography wrist detector

    DOEpatents

    Schlyer, David J.; O'Connor, Paul; Woody, Craig; Junnarkar, Sachin Shrirang; Radeka, Veljko; Vaska, Paul; Pratte, Jean-Francois

    2006-08-15

    A method of serially transferring annihilation information in a compact positron emission tomography (PET) scanner includes generating a time signal representing a time-of-occurrence of an annihilation event, generating an address signal representing a channel detecting the annihilation event, and generating a channel signal including the time and address signals. The method also includes generating a composite signal including the channel signal and another similarly generated channel signal concerning another annihilation event. An apparatus that serially transfers annihilation information includes a time signal generator, address signal generator, channel signal generator, and composite signal generator. The time signal is asynchronous and the address signal is synchronous to a clock signal. A PET scanner includes a scintillation array, detection array, front-end array, and a serial encoder. The serial encoders include the time signal generator, address signal generator, channel signal generator, and composite signal generator.

  13. Scintillators for positron emission tomography

    SciTech Connect

    Moses, W.W.; Derenzo, S.E.

    1995-09-01

    Like most applications that utilize scintillators for gamma detection, Positron Emission Tomography (PET) desires materials with high light output, short decay time, and excellent stopping power that are also inexpensive, mechanically rugged, and chemically inert. Realizing that this ``ultimate`` scintillator may not exist, this paper evaluates the relative importance of these qualities and describes their impact on the imaging performance of PET. The most important PET scintillator quality is the ability to absorb 511 keV photons in a small volume, which affects the spatial resolution of the camera. The dominant factor is a short attenuation length ({le} 1.5 cm is required), although a high photoelectric fraction is also important (> 30% is desired). The next most important quality is a short decay time, which affects both the dead time and the coincidence timing resolution. Detection rates for single 511 keV photons can be extremely high, so decay times {le} 500 ns are essential to avoid dead time losses. In addition, positron annihilations are identified by time coincidence so {le}5 ns fwhm coincidence pair timing resolution is required to identify events with narrow coincidence windows, reducing contamination due to accidental coincidences. Current trends in PET cameras are toward septaless, ``fully-3D`` cameras, which have significantly higher count rates than conventional 2-D cameras and so place higher demands on scintillator decay time. Light output affects energy resolution, and thus the ability of the camera to identify and reject events where the initial 511 keV photon has undergone Compton scatter in the patient. The scatter to true event fraction is much higher in fully-3D cameras than in 2-D cameras, so future PET cameras would benefit from scintillators with a 511 keV energy resolution < 10--12% fwhm.

  14. Search for Extremely Metal-poor Galaxies in the Sloan Digital Sky Survey. (II). High Electron Temperature Objects

    NASA Astrophysics Data System (ADS)

    Sánchez Almeida, J.; Pérez-Montero, E.; Morales-Luis, A. B.; Muñoz-Tuñón, C.; García-Benito, R.; Nuza, S. E.; Kitaura, F. S.

    2016-03-01

    Extremely metal-poor (XMP) galaxies are defined to have a gas-phase metallicity smaller than a tenth of the solar value (12+{log}[{{O/H}}]< 7.69). They are uncommon, chemically and possibly dynamically primitive, with physical conditions characteristic of earlier phases of the universe. We search for new XMPs in the Sloan Digital Sky Survey (SDSS) in a work that complements Paper I. This time, high electron temperature objects are selected; metals are a main coolant of the gas, so metal-poor objects contain high-temperature gas. Using the algorithm k-means, we classify 788,677 spectra to select 1281 galaxies that have particularly intense [O III]λ4363 with respect to [O III]λ5007, which is a proxy for high electron temperature. The metallicity of these candidates was computed using a hybrid technique consistent with the direct method, rendering 196 XMPs. A less restrictive noise constraint provides a larger set with 332 candidates. Both lists are provided in electronic format. The selected XMP sample has a mean stellar mass around {10}8 {M}⊙ , with the dust mass ∼ {10}3{M}⊙ for typical star-forming regions. In agreement with previous findings, XMPs show a tendency to be tadpole-like or cometary. Their underlying stellar continuum corresponds to a fairly young stellar population (< 1 {{Gyr}}), although young and aged stellar populations coexist at the low-metallicity starbursts. About 10% of the XMPs show large N/O. Based on their location in constrained cosmological numerical simulations, XMPs have a strong tendency to appear in voids and to avoid galaxy clusters. The puzzling 2%-solar low-metallicity threshold exhibited by XMPs remains.

  15. Dark matter with multiannihilation channels and the AMS-02 positron excess and antiproton data

    NASA Astrophysics Data System (ADS)

    Chen, Yu-Heng; Cheung, Kingman; Tseng, Po-Yan

    2016-01-01

    AMS-02 provided the unprecedented statistics in the measurement of the positron fraction from cosmic rays. That may offer a unique opportunity to distinguish the positron spectrum coming from various dark matter (DM) annihilation channels, if DM is the source of this positron excess. Therefore, we consider the scenario that the DM can annihilate into leptonic, quark, and massive gauge-boson channels simultaneously with floating branching ratios to test this hypothesis. We also study the impacts from MAX, MED, MIN, and DC diffusion models as well as from isothermal, NFW, and Einasto DM density profiles on our results. We found two parameter regions that can satisfy both AMS-02 e/+ e++e- and p ¯/p data sets at 95% C.L.: (i) under the NFW-MIN combination with Mχ⊂[10 ,30 ] TeV , and (ii) under the Einasto-DC combination with Mχ⊂[500 ,1500 ] GeV .

  16. Launch Vehicle Fire Accident Preliminary Analysis of a Liquid-Metal Cooled Thermionic Nuclear Reactor: TOPAZ-II

    NASA Astrophysics Data System (ADS)

    Hu, G.; Zhao, S.; Ruan, K.

    2012-01-01

    In this paper, launch vehicle propellant fire accident analysis of TOPAZ-II reactor has been done by a thermionic reactor core analytic code-TATRHG(A) developed by author. When a rocket explodes on a launch pad, its payload-TOPAZ-II can be subjected to a severe thermal environment from the resulting fireball. The extreme temperatures associated with propellant fires can create a destructive environment in or near the fireball. Different kind of propellants - liquid propellant and solid propellant which will lead to different fire temperature are considered. Preliminary analysis shows that the solid propellant fires can melt the whole toxic beryllium radial reflector.

  17. THE CHEMICAL ABUNDANCES OF STARS IN THE HALO (CASH) PROJECT. II. A SAMPLE OF 14 EXTREMELY METAL-POOR STARS ,

    SciTech Connect

    Hollek, Julie K.; Sneden, Christopher; Shetrone, Matthew; Frebel, Anna; Roederer, Ian U.; Beers, Timothy C.; Kang, Sung-ju; Thom, Christopher E-mail: chris@astro.as.utexas.edu E-mail: afrebel@cfa.harvard.edu E-mail: beers@pa.msu.edu E-mail: cthom@stsci.edu

    2011-11-20

    We present a comprehensive abundance analysis of 20 elements for 16 new low-metallicity stars from the Chemical Abundances of Stars in the Halo (CASH) project. The abundances have been derived from both Hobby-Eberly Telescope High Resolution Spectrograph snapshot spectra (R {approx}15, 000) and corresponding high-resolution (R {approx}35, 000) Magellan Inamori Kyocera Echelle spectra. The stars span a metallicity range from [Fe/H] from -2.9 to -3.9, including four new stars with [Fe/H] < -3.7. We find four stars to be carbon-enhanced metal-poor (CEMP) stars, confirming the trend of increasing [C/Fe] abundance ratios with decreasing metallicity. Two of these objects can be classified as CEMP-no stars, adding to the growing number of these objects at [Fe/H]< - 3. We also find four neutron-capture-enhanced stars in the sample, one of which has [Eu/Fe] of 0.8 with clear r-process signatures. These pilot sample stars are the most metal-poor ([Fe/H] {approx}< -3.0) of the brightest stars included in CASH and are used to calibrate a newly developed, automated stellar parameter and abundance determination pipeline. This code will be used for the entire {approx}500 star CASH snapshot sample. We find that the pipeline results are statistically identical for snapshot spectra when compared to a traditional, manual analysis from a high-resolution spectrum.

  18. Prototyping of the ILC Baseline Positron Target

    SciTech Connect

    Gronberg, J; Brooksby, C; Piggott, T; Abbott, R; Javedani, J; Cook, E

    2012-02-29

    The ILC positron system uses novel helical undulators to create a powerful photon beam from the main electron beam. This beam is passed through a titanium target to convert it into electron-positron pairs. The target is constructed as a 1 m diameter wheel spinning at 2000 RPM to smear the 1 ms ILC pulse train over 10 cm. A pulsed flux concentrating magnet is used to increase the positron capture efficiency. It is cooled to liquid nitrogen temperatures to maximize the flatness of the magnetic field over the 1 ms ILC pulse train. We report on prototyping effort on this system.

  19. Update on the Argonne positron accumulator ring

    SciTech Connect

    Borland, M.

    1993-07-01

    The injector for the Advanced Photon Source incorporates a 450-MeV positron accumulator ring (PAR) to decrease the filling time with the 2-Hz synchrotron. In addition to accumulating positrons from the linac, the PAR damps the beam and reduces the bunch length. The PAR lattice has been redesigned to use zero-gradient dipoles, while retaining essentially the same damping partition. Extensive simulations have been performed to set tolerances that will give high capture efficiency, in spite of the large momentum spread of the incoming positron beam.

  20. Slow-Positron Generator For Studying Polymer Films

    NASA Technical Reports Server (NTRS)

    Singh, Jag J.; St. Clair, Terry L.; Eftekhari, Abe

    1992-01-01

    Aspects of molecular structures probed by positron-annihilation spectroscopy (PAS). Slow-positron-beam generator suitable for PAS measurements in thin polymer films. Includes Na22 source of positrons and two moderators made of well-annealed tungsten foil. With proper choice of voltage, positrons emitted by inward-facing surfaces of moderators made to stop in polymer films tested.

  1. Synthesis, Characterization, Antioxidant, and Antibacterial Studies of Some Metal(II) Complexes of Tetradentate Schiff Base Ligand: (4E)-4-[(2-{(E)-[1-(2,4-Dihydroxyphenyl)ethylidene]amino}ethyl)imino]pentan-2-one

    PubMed Central

    Ejidike, Ikechukwu P.; Ajibade, Peter A.

    2015-01-01

    Co(II), Ni(II), Cu(II), and Zn(II) complexes of (4E)-4-[(2-{(E)-[1-(2,4-dihydroxyphenyl)ethylidene]amino}ethyl)imino]pentan-2-one have been synthesized and characterized by elemental analyses, molar conductance, electronic and IR spectral studies, and XRD. FTIR confirmed the ligand coordinates the metal ion to form mononuclear complex via the oxygen and nitrogen atoms of the phenolic group and azomethine group, respectively. Tetrahedral geometry is proposed for Co(II) complex and square-planar geometry for Ni(II) and Cu(II) complexes. The antibacterial studies of the compounds were determined and they show that the metal complexes are more active than the free ligands. The antioxidant activity by DPPH and ABTS method was examined and it shows Cu(II); IC50 = 2.31 ± 1.54 µM for DPPH and Co(II); IC50 = 1.83 ± 1.08 µM for ABTS were the most active. PMID:26074738

  2. Light-induced copper(II) coordination by a bicyclic tetraaza chelator through a ligand-to-metal charge-transfer reaction.

    PubMed

    Holm-Jørgensen, Jacob R; Jensen, Mikael; Bjerrum, Morten J

    2011-12-19

    To enable utilization of the broad potential of copper isotopes in nuclear medicine, rapid and robust chelation of the copper is required. Bowl adamanzanes (bicyclic tetraaza ligands) can form kinetically stable copper complexes, but they are usually formed at low rates unless high pH values and high temperatures are applied. We have investigated the effects of the variation in the pH, different anions, and UV irradiation on the chelation rate. UV spectra of mixtures of Cu(2+) and [2(4).3(1)]adz in water show the existence of a long-lived two-coordinated copper(II) intermediate (only counting coordinated amine groups) at pH above 6. These findings are supported by pH titrations of mixtures of Cu(2+) and [2(4).3(1)]adz in water. Irradiation of this complex in the ligand-to-metal charge-transfer (LMCT) band by a diode-array spectrophotometer leads to photodeprotonation and subsequently to formation of the four-coordinated copper(II) complex at a rate up to 7800-fold higher at 25 °C than in the dark. Anions in the solution were found to have three major effects: competitive inhibition due to Cu(II) binding anions, inhibition of the photoinduced transchelation from UV-absorbing anions, and photoredox inhibition from acido ligands capable of acting as electron donors in LMCT reactions. Dissolved O(2) was also found to result in photoredox inhibition. PMID:22074363

  3. Hydrolysis mechanisms of BNPP mediated by facial copper(II) complexes bearing single alkyl guanidine pendants: cooperation between the metal centers and the guanidine pendants.

    PubMed

    Zhang, Xuepeng; Liu, Xueping; Phillips, David Lee; Zhao, Cunyuan

    2016-01-28

    The hydrolysis mechanisms of DNA dinucleotide analogue BNPP(-) (bis(p-nitrophenyl) phosphate) catalyzed by mononuclear/dinuclear facial copper(ii) complexes bearing single alkyl guanidine pendants were investigated using density functional theory (DFT) calculations. Active catalyst forms have been investigated and four different reaction modes are proposed accordingly. The [Cu2(L(1))2(μ-OH)](3+) (L(1) is 1-(2-guanidinoethyl)-1,4,7-triazacyclononane) complex features a strong μ-hydroxo mediated antiferromagnetic coupling between the bimetallic centers and the corresponding more stable open-shell singlet state. Three different reaction modes involving two catalysts and a substrate were proposed for L(1) entries and the mode 1 in which an inter-complex nucleophilic attack by a metal bound hydroxide was found to be more favorable. In the L(3)-involved reactions (L(3) is 1-(4-guanidinobutyl)-1,4,7-triazacyclononane), the reaction mode in which an in-plane intracomplex scissoring-like nucleophilic attack by a Cu(ii)-bound hydroxide was found to be more competitive. The protonated guanidine pendants in each proposed mechanism were found to play crucial roles in stabilizing the reaction structures via hydrogen bonds and in facilitating the departure of the leaving group via electrostatic attraction. The calculated results are consistent with the experimental observations that the Cu(ii)-L(3) complexes are hydrolytically more favorable than their L(1)-involved counterparts. PMID:26688285

  4. On the role of mercury in the non-covalent stabilisation of consecutive U-Hg(II)-U metal-mediated nucleic acid base pairs: metallophilic attraction enters the world of nucleic acids.

    PubMed

    Benda, Ladislav; Straka, Michal; Tanaka, Yoshiyuki; Sychrovský, Vladimír

    2011-01-01

    Metal atoms with a closed-shell electronic structure and positive charge as for example the Au(I), Pt(II), Ag(I), Tl(I) or Hg(II) atoms do not in some compounds repel each other due to the so-called metallophilic attraction (P. Pyykkö, Chem. Rev., 1997, 97, 597-636). Here we highlight the role of the Hg(II)Hg(II) metallophilic attraction between the consecutive metal-mediated mismatched base pairs of nucleic acids. Usually, the base stacking dominates the non-covalent interactions between steps of native nucleic acids. In the presence of metal-mediated base pairs these non-covalent interactions are enriched by the metal-base interactions and the metallophilic attraction. The two interactions arising due to the metal linkage of the mismatches were found in this study to have a stabilizing effect on nucleic acid structure. The calculated data are consistent with recent experimental observations. The stabilization due to the metallophilic attraction seems to be a generally important concept for the nucleic acids containing heavy metals with short contacts. PMID:21049099

  5. The Buffer-Gas Positron Accumulator and Resonances in Positron-Molecule Interactions

    NASA Technical Reports Server (NTRS)

    Surko, C.M.

    2007-01-01

    This is a personal account of the development of our buffer-gas positron trap and the new generation of cold beams that these traps enabled. Dick Drachman provided much appreciated advice to us from the time we started the project. The physics underlying trap operation is related to resonances (or apparent resonances) in positron-molecule interactions. Amusingly, experiments enabled by the trap allowed us to understand these processes. The positron-resonance "box score" to date is one resounding "yes," namely vibrational Feshbach resonances in positron annihilation on hydrocarbons; a "probably" for positron-impact electronic excitation of CO and NZ;an d a "maybe" for vibrational excitation of selected molecules. Two of these processes enabled the efficient operation of the trap, and one almost killed it in infancy. We conclude with a brief overview of further applications of the trapping technology discussed here, such as "massive" positron storage and beams with meV energy resolution.

  6. Synthesis, characterization and biological activities of metal(II) dipicolinate complexes derived from pyridine-2,6-dicarboxylic acid and 2-(piperazin-1-yl)ethanol

    NASA Astrophysics Data System (ADS)

    Büyükkıdan, Nurgün; Yenikaya, Cengiz; İlkimen, Halil; Karahan, Ceyda; Darcan, Cihan; Korkmaz, Tülin; Süzen, Yasemin

    2015-12-01

    The new water-soluble and air stable compounds (H2ppz)[Co(dipic)2]·6H2O (1), (H2ppz)[Ni(dipic)2]·6H2O (2) and (H2ppz)[Zn(dipic)2]·6H2O (3) were prepared by the reaction of corresponding metal(II) acetates and a proton transfer salt, (H2ppz) (Hdipic)2, (4) of pyridine-2,6-dicarboxylic acid (H2dipic) and 2-(piperazin-1-yl)ethanol (ppz). The compounds 1-3 were characterized by elemental, IR, UV-vis. thermal analyses, magnetic measurement and single crystal X-ray diffraction studies. The molecular structures of the title compounds consist of one 1-(2-hydroxyethyl)piperazine-1,4-diium (H2ppz+2) cation, one bis(pyridine-2,6-dicarboxylate)metal(II) [M(dipic)2]2- anion, and six uncoordinated water molecules. In compounds 1-3 the metal ions coordinate to two oxygen and one nitrogen atoms of two pyridine-2,6-dicarboxylate molecules forming an octahedral environment. Antimicrobial activities against Gram (-) wild type (Escherichia coli and Pseudomonas aeruginosa), Gram (+) wild type (Staphylococcus aureus, Staphylococcus epidermidis, Bacillus cereus and Bacillus subtilis) and clinical isolate (Morganella morganii, Proteus vulgaris and Enterobacter aeruginosa) were also studied. The results were reported, discussed and compared with the corresponding starting materials ((H2ppz) (Hdipic)2 (4), H2dipic and ppz). MIC (Minimal Inhibition Concentration) values of the newly synthesized compounds were determined as 4000 μg/ml (except B. subtilis and clinical isolate E. aeruginosa, >4000 μg/ml).

  7. Structural chemistry of peroxo compounds of group VI transition metals: II. Peroxo complexes of molybdenum and tungsten: A review

    SciTech Connect

    Sergienko, V. S.

    2008-01-15

    The specific features revealed in the structure of the molybdenum and tungsten peroxo complexes with the ratios M: O{sub 2} = 1: 1, 1: 2, and 1: 4 are considered. It is demonstrated that the geometry of the coordination polyhedron of the metal atom is primarily determined by the 'metal: peroxo ligand' ratio. Formally, the pentagonal bipyramidal coordination polyhedra of the Mo(VI) and W(VI) oxo monoperoxo and oxo diperoxo complexes (the coordination numbers of the metal atoms are equal to seven) have different geometries, namely, the MO(O{sub 2})A{sub 4} pseudooctahedral and MO(O{sub 2}){sub 2}A{sub 2} pseudotrigonal bipyramidal configurations.

  8. Time-dependent behavior of positrons in noble gases

    SciTech Connect

    Wadehra, J.M. . Dept. of Physics and Astronomy); Drallos, P.J. )

    1990-01-01

    Both equilibrium and nonequilibrium behaviors of positrons in several noble gases are reviewed. Our novel procedure for obtaining the time-dependent behavior of various swarm parameters -- such as the positron drift velocity, average positron energy, positron annihilation rate (or equivalently Z{sub eff}) etc. -- for positrons in pure ambient gases subjected to external electrostatic fields is described. Summaries of time-dependent as well as electric field-dependent results for positron swarms in various noble gases are presented. New time-dependent results for positron swarms in neon are also described in detail. 36 refs., 4 figs., 3 tabs.

  9. Ab initio calculations in heterogeneous and homogeneous catalysis: I. Methanol to gasoline with ZSM-5. II. Carbonyl ligand effects on metal-metal bonds

    SciTech Connect

    Miller, A.E.

    1993-01-01

    This thesis is composed of two studies in catalysis. The first is an exploration, using computational techniques, of the mechanism for the first carbon-carbon bond formation in the methanol to gasoline (MTG) reaction. The second is a study of the factors important to the understanding of ligand effects on metal-metal bonds, and in particular, to metal clusters. Three possibilities were considered as ways to activate a carbon in the MTG process prior to formation of C2 or higher hydrocarbons. These were a free radical mechanism, a surface ylide mechanism, and a possible defect site which might lead to steric crowding of CH[sub 2] groups. Although the free radical mechanism was found to be thermodynamically within the parameters of the MTG process, it contained a high transition state. Consideration of the molecules available prior to hydrocarbon build-up and their specific electronic structure, led to the view that the available carbon atoms (methanol, dimethyl ether, etc.) were unlikely to be activated by a free radical intermediate. The surface-stabilized ylide which has been proposed as an intermediate by many was studied to determine if in fact the ylide was stabilized. The total energy of the ylide was compared to that of the naked site on the zeolite and free methylene. Free methylene ranged, depending on the geometry of the ylide, between 50 and 80 kcal more stable. These numbers are qualitatively correct, but more electron correlation would have to be incorporated in the calculation to get an accurate value for the destabilization. Starting from a defect site, two CH[sub 2] groups were each attached to two oxygen atoms. It was thought that two CH[sub 2] groups would take up considerably more space than either than original Al atom or the four hydrogens. Molecular Mechanics calculations showed the zeolite to be sufficiently flexible to prevent crowding of the CH[sub 2]'s.

  10. A field-assisted moderator for low-energy positron beams

    NASA Astrophysics Data System (ADS)

    Beling, C. D.; Simpson, R. I.; Charlton, M.; Jacobsen, F. M.; Griffith, T. C.; Moriarty, P.; Fung, S.

    1987-01-01

    A new positron field-assisted (FA) moderator based on the drift of positrons across a cooled silicon crystal is proposed. Using estimates for both the β + implantation profile and attainable drift velocities, the efficiency of drift to a slow e+ emitting surface is calculated using a diffusion equation which incorporates terms describing positron drift and annihilation. It is conjectured that efficiencies of up to 10% can be achieved. The use of epitaxially grown metallic suicide contacts to facilitate the application of the electric field is described and the consequences of using such contacts are fully discussed. Applications of the FA transmission mode moderator described here to produce timed brightness enhanced beams are briefly discussed.

  11. The binding energies of one and two water molecules to the first transition-row metal positive ions. II

    NASA Technical Reports Server (NTRS)

    Rosi, Marzio; Bauschlicher, Charles W., Jr.

    1990-01-01

    The present investigation of H2O's binding energy to transition-metal ions proceeds from the D(2h) structure and bends the two water molecules out of plane. The molecule is constrained to have C(2v) symmetry, so that each water molecule and metal ion lies on a plane. The ground states are bent only for Mn(H2O)2(+) and Zn(H2O)2(+), where only 4s4p hybridization is energetically favorable; 4s4p hybridization reduces repulsion.

  12. Influence of activated-carbon-supported transition metals on the decomposition of polychlorobiphenyls. Part II: Chemical and physical characterization and mechanistic study.

    PubMed

    Sun, Yifei; Liu, Lina; Oshita, Kazuyuki; Zeng, Xiaolan; Wang, Wei; Zhang, Yibo

    2016-09-01

    This paper studies the synergism between transition metals (TMs) and activated carbon (AC) as a catalyst support used in the catalytic decomposition of PCBs. A series of AC-supported TM catalysts was prepared according to two distinct methods: impregnation and ion exchange which were defined as LaTM-C and IRTM-C, respectively. The catalytic reactions between 2,2',4,4',5,5'-hexachlorobiphenyl (PCB-153) and AC-supported Fe, Ni, Cu and Zn catalysts were conducted under N2 atmosphere. Changes in the nature of the catalysts as well as the decomposition mechanism of PCB-153 are discussed. Important findings include: (i) a higher metal concentration and a better metal distribution on AC is realized using ion-exchange, despite a lower AC specific surface area, (ii) IRTM-C had better effects on the decomposition of PCB-153 than LaTM-C, (iii) the role of Ni, Cu, and Fe as electron donors in PCB dechlorination was evaluated vs. the stability of Zn, and (iv) both temperature and chemical composition of TM catalysts influenced the decomposition efficiency of PCBs. PMID:27320438

  13. Insights into dehydrogenative coupling of alcohols and amines catalyzed by a (PNN)-Ru(II) hydride complex: unusual metal-ligand cooperation.

    PubMed

    Zeng, Guixiang; Li, Shuhua

    2011-11-01

    Density functional theory calculations were performed to elucidate the mechanism of dehydrogenative coupling of primary alcohols and amines mediated by a PNN-Ru(II) hydride complex (PNN = (2-(di-tert-butylphosphinomethyl)-6-(diethylaminomethyl)pyridine)). A plausible reaction pathway was proposed which contains three stages: (1) The alcohol dehydrogenation reaction to generate the aldehyde and H(2); (2) The aldehyde-amine condensation reaction to form the hemiaminal intermediate; (3) The dehydrogenation process of the hemiaminal intermediate to yield the final amide product with the liberation of H(2). The first and third stages occur via a similar pathway: (a) Proton transfer from the substrate to the PNN ligand; (b) Intramolecular rearrangement of the deprotonated substrate to form an anagostic complex; (c) Hydride transfer from the deprotonated substrate to the Ru center to yield the trans-dihydride intermediate and the aldehyde (or amide); (d) Benzylic proton migration from the PNN ligand to the metal center forming a dihydrogen complex and subsequent H(2) liberation to regenerate the catalyst. In all these steps, the metal-ligand cooperation plays an essential role. In proton transfer steps (a) and (d), the metal-ligand cooperation is achieved through the aromatization/dearomatization processes of the PNN ligand. While in steps (b) and (c), their collaboration are demonstrated by the formation of an anagostic interaction between Ru and the C-H bond and two ionic hydrogen bonds supported by the PNN ligand. PMID:21942421

  14. Recovery and concentration of metal ions. 4: Uphill transport of Zn(II) in a multimembrane hybrid system

    SciTech Connect

    Wodzki, R.; Sionkowski, G.; Pozniak, G.

    1999-02-01

    A study has been made on the uphill transport of zinc cations across a multimembrane hybrid system (MHS) composed of two ion-exchange membranes (IEM) separated by a bulk liquid membrane (BLM). The fluxes of the Zn(II)/H countertransport were investigated as dependent on the composition and structure of ion-exchange polymer membranes (i), the solvent of a liquid membrane (II), the feed and strip membrane area ratio (iii), and the pH of the feed solution (iv). The IEMs of various ionogenic groups (sulfonic acid, carboxylic acid, quaternized amine) and of various structure (clustered, gelatinous, porous) were examined in the MHS containing the BLM with di(2-ethylhexyl)phosphoric acid as a carrier of Zn(II) cations. It has been found that the Zn(II) fluxes are dependent on the properties of both the BLM and polymer membranes, i.e., on the BLM solvent viscosity (i), the nature and concentration of the IEM ion-exchange sites (ii), and the IEM thickness (iii). The best results were obtained when using hexane as the BLM solvent and the Nafion-117 membrane (perfluorinated polymer, sulfonic acid groups) as the cation-exchange membrane (CEM). The influence of the area ratio (feed-to-strip interface) has been checked for A{sub f}/A{sub g} equal to 3:1, 1:1, and 1:3. It was found that the asymmetry of the system leads mainly to some changes in the accumulation of transported species in a liquid membrane phase.

  15. Scanning tunneling microscopy, orbital-mediated tunneling spectroscopy, and ultraviolet photoelectron spectroscopy of metal(II) tetraphenylporphyrins deposited from vapor.

    PubMed

    Scudiero, L; Barlow, D E; Mazur, U; Hipps, K W

    2001-05-01

    Thin films of vapor-deposited Ni(II) and Co(II) complexes of tetraphenylporphyrin (NiTPP and CoTPP) were studied supported on gold and embedded in Al-Al(2)O(3)-MTPP-Pb tunnel diodes, where M = Ni or Co. Thin films deposited onto polycrystalline gold were analyzed by ultraviolet photoelectron spectroscopy (UPS) using He I radiation. Scanning tunneling microscopy (STM) and orbital-mediated tunneling spectroscopy (STM-OMTS) were performed on submonolayer films of CoTPP and NiTPP supported on Au(111). Inelastic electron tunneling spectroscopy (IETS) and OMTS were measured in conventional tunnel diode structures. The highest occupied pi molecular orbital of the porphyrin ring was seen in both STM-OMTS and UPS at about 6.4 eV below the vacuum level. The lowest unoccupied pi molecular orbital of the porphyrin ring was observed by STM-OMTS and by IETS-OMTS to be located near 3.4 eV below the vacuum level. The OMTS spectra of CoTPP had a band near 5.2 eV (below the vacuum level) that was attributed to transient oxidation of the central Co(II) ion. That is, it is due to electron OMT via the half-filled d(z)(2) orbital present in Co(II) of CoTPP. The NiTPP OMTS spectra show no such band, consistent with the known difficulty of oxidation of the Ni(II) ion. The STM-based OMTS allowed these two porphyrin complexes to be easily distinguished. The present work is the first report of the observation of STM-OMTS, tunnel junction OMTS, and UPS of the same compounds. Scanning tunneling microscope-based orbital-mediated tunneling provides more information than UPS or tunnel junction-based OMTS and does so with molecular-scale resolution. PMID:11457159

  16. Sewage sludge ash to phosphorus fertiliser (II): Influences of ash and granulate type on heavy metal removal.

    PubMed

    Mattenberger, H; Fraissler, G; Jöller, M; Brunner, T; Obernberger, I; Herk, P; Hermann, L

    2010-01-01

    Ashes from monoincineration of sewage sludge suggest themselves as an ideal base for inorganic fertiliser production due to their relatively high phosphorus (P)-content. However, previously they need to be detoxified by reducing their heavy metal content. The core process considered in this paper consists of three steps: mixing of the ashes with suitable chlorine-containing additives, granulation of the mixture and thermochemical treatment in a rotary kiln. Here relevant heavy metal compounds are first transformed into volatile species with the help of the additives and then evaporated from the granules. In this study two chemically different ashes and their mixture were agglomerated to two different granulate types, briquettes and rolled pellets. The resulting six different materials were subjected to thermal treatment at different temperatures. The heavy metals examined were Cu and Zn due to their strong dependence on treatment conditions and their relevance concerning thermal treatment of sewage sludge ashes. Besides, the behaviour of Cl and K was monitored and evaluated. The experiments showed that ash type and temperature are more influential on Cl and heavy metal chemistry than granulate type. Temperature is a primary variable for controlling removal in both cases. Cu removal was less dependent on both ash and granulate type than Zn. The Cl utilization was more effective for Cu than for Zn. Depending on the treatment conditions some K could be retained, whereas always a