Science.gov

Sample records for fluorescent metal halide

  1. X-ray induced fluorescence measurement of segregation in a DyI3-Hg metal-halide lamp.

    SciTech Connect

    Nimalasuriya , T.; Curry, J. J.; Sansonetti, C. J.; Ridderhof, E. J.; Shastri, S. D.; Filkweert, A. J.; Stoffels, W. W.; Haverlag, M.; van der Mullen, J. J.; Eindhoven Univ. of Technology; NIST

    2007-05-07

    Segregation of elemental Dy in a DyI{sub 3}-Hg metal-halide high-intensity discharge lamp has been observed with x-ray induced fluorescence. Significant radial and axial Dy segregation are seen, with the axial segregation characterized by a Fischer parameter value of {lambda} = 0.215 {+-} 0.002 mm{sup -1}. This is within 7% of the value ({lambda} = 0.20 {+-} 0.01 mm{sup -1}) obtained by Flikweert et al based on laser absorption by neutral Dy atoms. Elemental I is seen to exhibit considerably less axial and radial segregation. Some aspects of the observed radial segregation are compatible with a simplified fluid picture describing two main transition regions in the radial coordinate. The first transition occurs in the region where DyI{sub 3} molecules are in equilibrium with neutral Dy atoms. The second transition occurs where neutral Dy atoms are in equilibrium with ionized Dy. These measurements are part of a larger study on segregation in metal-halide lamps under a variety of conditions.

  2. Radiochemical synthesis of pure anhydrous metal halides

    NASA Technical Reports Server (NTRS)

    Philipp, W. H.; Marsik, S. J.; May, C. E.

    1973-01-01

    Method uses radiation chemistry as practical tool for inorganic preparations and in particular deposition of metals by irradiation of their aqueous metal salt solutions with high energy electrons. Higher valence metal halide is dissolved in organic liquid and exposed to high energy electrons. This causes metal halide to be reduced to a lower valence metal halide.

  3. Growth and yield characteristics of 'Waldmann's Green' leaf lettuce under different photon fluxes from metal halide or incandescent + fluorescent radiation

    NASA Technical Reports Server (NTRS)

    Knight, Sharon L.; Mitchell, Cary A.

    1988-01-01

    Growth of 'Waldmann's Green' leaf lettuce under metal halide radiation was compared with that under In = Fl at the same photosynthetic photon flux (920 micromol/s/sq m) to evaluate the influence of lamp type on growth. No differences in leaf dry weight, leaf area, relative growth rate or photosynthesis occurred after 8 days of exposure to these radiation treatments for 20 h/day.

  4. Multiple-Wavelength Metal/Halide Laser

    NASA Technical Reports Server (NTRS)

    Nerheim, N. M.

    1984-01-01

    Single device produces multiple lasing lines. Laser capable of producing many lasing lines has several reservoirs of halide lasant mixed with chlorides of copper, manganese and iron. Convection-control technique possible to rapidly change from one metal halide to another at maximum energy.

  5. TRANSURANIC METAL HALIDES AND A PROCESS FOR THE PRODUCTION THEREOF

    DOEpatents

    Fried, S.

    1951-03-20

    Halides of transuranic elements are prepared by contacting with aluminum and a halogen, or with an aluminum halide, a transuranic metal oxide, oxyhalide, halide, or mixture thereof at an elevated temperature.

  6. Dimming of metal halide lamps

    NASA Technical Reports Server (NTRS)

    Schurer, Kees

    1994-01-01

    We ran some tests on the effect of dimming of metal halide (MH) lamps upon the stability and the spectral quality of the light output. Lamps used were a new Philips lamp HPI-T 250W, a similar Philips lamp with a few thousand burning hours and a new Osram lamp HQI-T 250W/D. The ballast was a BBC type DJ 250/2KS, the starter a BAS TORGI type MZN 250 SE and the dimmer an Elstrom Control System type ERHQ-T 250. Power was derived from a Philips stabilizer, type PE 1602. Lamp output was monitored with a PAR meter. Spectra were taken at 100% and at 50% output as measured with the PAR meter. Lamps were allowed to stabilize at any setting for 30 minutes before measurements were made. Lamp manufacturers advise against dimming for fear of poor stability and intolerable changes of the spectrum. However, none of the lamps showed a decrease in stability, no flicker or wandering of the discharge, and the changes of the spectrum were not negligible, but certainly not dramatic. Lamps of either manufacture retain their white color, relative peak heights of spectral lines did shift, but no gaps in the spectrum occurred. Spectra taken at 50% with 30 minutes intervals coincided. Differences between the new and the older Philips lamp were noticeable, but not really significant.

  7. METHOD OF PREPARING METAL HALIDES

    DOEpatents

    Hendrickson, A.V.

    1958-11-18

    The conversion of plutonium halides from plutonium peroxide can be done by washing the peroxide with hydrogen peroxide, drying the peroxide, passing a dry gaseous hydrohalide over the surface of the peroxide at a temperature of about lOO icient laborato C until the reaction rate has stabillzed, and then ralsing the reaction temperature to between 400 and 600 icient laborato C until the conversion to plutonium halide is substantially complete.

  8. Method for recovering hydrocarbons from molten metal halides

    DOEpatents

    Pell, Melvyn B.

    1979-01-01

    In a process for hydrocracking heavy carbonaceous materials by contacting such carbonaceous materials with hydrogen in the presence of a molten metal halide catalyst to produce hydrocarbons having lower molecular weights and thereafter recovering the hydrocarbons so produced from the molten metal halide, an improvement comprising injecting into the spent molten metal halide, a liquid low-boiling hydrocarbon stream is disclosed.

  9. Alkali metal and alkali earth metal gadolinium halide scintillators

    DOEpatents

    Bourret-Courchesne, Edith; Derenzo, Stephen E.; Parms, Shameka; Porter-Chapman, Yetta D.; Wiggins, Latoria K.

    2016-08-02

    The present invention provides for a composition comprising an inorganic scintillator comprising a gadolinium halide, optionally cerium-doped, having the formula A.sub.nGdX.sub.m:Ce; wherein A is nothing, an alkali metal, such as Li or Na, or an alkali earth metal, such as Ba; X is F, Br, Cl, or I; n is an integer from 1 to 2; m is an integer from 4 to 7; and the molar percent of cerium is 0% to 100%. The gadolinium halides or alkali earth metal gadolinium halides are scintillators and produce a bright luminescence upon irradiation by a suitable radiation.

  10. Observation of vapor pressure enhancement of rare-earth metal-halide salts in the temperature range relevant to metal-halide lamps

    SciTech Connect

    Curry, J. J.; Henins, A.; Hardis, J. E.; Estupinan, E. G.; Lapatovich, W. P.; Shastri, S. D.

    2012-02-20

    Total vapor-phase densities of Dy in equilibrium with a DyI{sub 3}/InI condensate and Tm in equilibrium with a TmI{sub 3}/TlI condensate have been measured for temperatures between 900 K and 1400 K. The measurements show strong enhancements in rare-earth vapor densities compared to vapors in equilibrium with the pure rare-earth metal-halides. The measurements were made with x-ray induced fluorescence on the sector 1-ID beam line at the Advanced Photon Source. The temperature range and salt mixtures are relevant to the operation of metal-halide high-intensity discharge lamps.

  11. Controlling Metal-Halide Vapor Density in Lasers

    NASA Technical Reports Server (NTRS)

    Pivirotto, T. J.

    1984-01-01

    Streams of buffer gas convect and dilute metal-halide vapor. Technique uses flow of buffer gas through reservoir, which contains heated metal halide, to convect vapors into discharge tube. Second stream of buffer gas dilutes vapor. Final vapor density in laser tube controlled and changed by adjusting either one or both of buffer gas flow rates.

  12. 10 CFR 429.54 - Metal halide lamp ballasts and fixtures.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... 10 Energy 3 2012-01-01 2012-01-01 false Metal halide lamp ballasts and fixtures. 429.54 Section... CONSUMER PRODUCTS AND COMMERCIAL AND INDUSTRIAL EQUIPMENT Certification § 429.54 Metal halide lamp ballasts... are applicable to metal halide lamp ballasts; and (2) For each basic model of metal halide...

  13. 10 CFR 429.54 - Metal halide lamp ballasts and fixtures.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... 10 Energy 3 2014-01-01 2014-01-01 false Metal halide lamp ballasts and fixtures. 429.54 Section... CONSUMER PRODUCTS AND COMMERCIAL AND INDUSTRIAL EQUIPMENT Certification § 429.54 Metal halide lamp ballasts... are applicable to metal halide lamp ballasts; and (2) For each basic model of metal halide...

  14. 10 CFR 429.54 - Metal halide lamp ballasts and fixtures.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... 10 Energy 3 2013-01-01 2013-01-01 false Metal halide lamp ballasts and fixtures. 429.54 Section... CONSUMER PRODUCTS AND COMMERCIAL AND INDUSTRIAL EQUIPMENT Certification § 429.54 Metal halide lamp ballasts... are applicable to metal halide lamp ballasts; and (2) For each basic model of metal halide...

  15. Metal halide perovskites for energy applications

    NASA Astrophysics Data System (ADS)

    Zhang, Wei; Eperon, Giles E.; Snaith, Henry J.

    2016-06-01

    Exploring prospective materials for energy production and storage is one of the biggest challenges of this century. Solar energy is one of the most important renewable energy resources, due to its wide availability and low environmental impact. Metal halide perovskites have emerged as a class of semiconductor materials with unique properties, including tunable bandgap, high absorption coefficient, broad absorption spectrum, high charge carrier mobility and long charge diffusion lengths, which enable a broad range of photovoltaic and optoelectronic applications. Since the first embodiment of perovskite solar cells showing a power conversion efficiency of 3.8%, the device performance has been boosted up to a certified 22.1% within a few years. In this Perspective, we discuss differing forms of perovskite materials produced via various deposition procedures. We focus on their energy-related applications and discuss current challenges and possible solutions, with the aim of stimulating potential new applications.

  16. Indirect detection of halide ions via fluorescence quenching of quinine sulfate in microcolumn ion chromatography.

    PubMed

    Takeuchi, Toyohide; Sumida, Junichi

    2004-06-01

    Halide ions could be visualized via fluorescence quenching in microcolumn ion chromatography. The fluorescence of quinine sulfate, which was contained in an acidic eluent, was quenched by halide ions. The observed fluorescence quenching values increased in this order: iodide, bromide, and chloride. The present detection system was relatively sensitive to halide ions except for fluoride: other anions gave smaller signals than halide ions. The present detection system provided quantitative information, so it could be applied to the determination of chloride in water samples. PMID:15228124

  17. Electrolytic systems and methods for making metal halides and refining metals

    SciTech Connect

    Holland, Justin M.; Cecala, David M.

    2015-05-26

    Disclosed are electrochemical cells and methods for producing a halide of a non-alkali metal and for electrorefining the halide. The systems typically involve an electrochemical cell having a cathode structure configured for dissolving a hydrogen halide that forms the halide into a molten salt of the halogen and an alkali metal. Typically a direct current voltage is applied across the cathode and an anode that is fabricated with the non-alkali metal such that the halide of the non-alkali metal is formed adjacent the anode. Electrorefining cells and methods involve applying a direct current voltage across the anode where the halide of the non-alkali metal is formed and the cathode where the non-alkali metal is electro-deposited. In a representative embodiment the halogen is chlorine, the alkali metal is lithium and the non-alkali metal is uranium.

  18. Metal-halide mixtures for latent heat energy storage

    NASA Technical Reports Server (NTRS)

    Chen, K.; Manvi, R.

    1981-01-01

    Alkali metal and alkali halide mixtures are identified which may be suitable for thermal energy storage at temperatures above 600 C. The use of metal-halides is appropriate because of their tendency to form two immiscible melts with a density difference, which reduces scale formation and solidification on heat transfer surfaces. Also, the accumulation of phase change material along the melt interface is avoided by the self-dispersing characteristic of some metal-halides, in particular Sr-SrCl2, Ba-BaCl2, and Ba-BaBr2 mixtures. Further advantages lie in their high thermal conductivities, ability to cope with thermal shock, corrosion inhibition, and possibly higher energy densities.

  19. Low-pressure indium-halide discharges for fluorescent illumination applications

    NASA Astrophysics Data System (ADS)

    Hayashi, Daiyu; Hilbig, Rainer; Körber, Achim; Schwan, Stefan; Scholl, Robert; Boerger, Martin; Huppertz, Maria

    2010-02-01

    Low-pressure gas discharges of molecular radiators were studied for fluorescent lighting applications with a goal of reducing the energy loss due to the large Stokes shift in phosphors of conventional mercury-based fluorescent lamp technology. Indium halides (InCl, InBr, and InI) were chosen as the molecular radiators that generate ultraviolet to blue light emissions. The electrical characteristics and optical emission intensities were measured in discharges containing gaseous indium halides (InCl, InBr, and InI) as molecular radiators. The low-pressure discharges in indium halide vapor showed potential as a highly efficient gas discharge system for fluorescent lighting application.

  20. 10 CFR 431.322 - Definitions concerning metal halide lamp ballasts and fixtures.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 10 Energy 3 2010-01-01 2010-01-01 false Definitions concerning metal halide lamp ballasts and... FOR CERTAIN COMMERCIAL AND INDUSTRIAL EQUIPMENT Metal Halide Lamp Ballasts and Fixtures § 431.322 Definitions concerning metal halide lamp ballasts and fixtures. Ballast efficiency means, in the case of...

  1. 10 CFR 431.322 - Definitions concerning metal halide lamp ballasts and fixtures.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... 10 Energy 3 2012-01-01 2012-01-01 false Definitions concerning metal halide lamp ballasts and fixtures. 431.322 Section 431.322 Energy DEPARTMENT OF ENERGY ENERGY CONSERVATION ENERGY EFFICIENCY PROGRAM FOR CERTAIN COMMERCIAL AND INDUSTRIAL EQUIPMENT Metal Halide Lamp Ballasts and Fixtures § 431.322 Definitions concerning metal halide...

  2. 10 CFR 431.322 - Definitions concerning metal halide lamp ballasts and fixtures.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... 10 Energy 3 2013-01-01 2013-01-01 false Definitions concerning metal halide lamp ballasts and fixtures. 431.322 Section 431.322 Energy DEPARTMENT OF ENERGY ENERGY CONSERVATION ENERGY EFFICIENCY PROGRAM FOR CERTAIN COMMERCIAL AND INDUSTRIAL EQUIPMENT Metal Halide Lamp Ballasts and Fixtures § 431.322 Definitions concerning metal halide...

  3. 10 CFR 431.322 - Definitions concerning metal halide lamp ballasts and fixtures.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... 10 Energy 3 2011-01-01 2011-01-01 false Definitions concerning metal halide lamp ballasts and fixtures. 431.322 Section 431.322 Energy DEPARTMENT OF ENERGY ENERGY CONSERVATION ENERGY EFFICIENCY PROGRAM FOR CERTAIN COMMERCIAL AND INDUSTRIAL EQUIPMENT Metal Halide Lamp Ballasts and Fixtures § 431.322 Definitions concerning metal halide...

  4. Halide (Cl(super -)) Quenching of Quinine Sulfate Fluorescence: A Time-Resolved Fluorescence Experiment for Physical Chemistry

    ERIC Educational Resources Information Center

    Gutow, Jonathan H.

    2005-01-01

    The time-resolved fluorescence experiment investigating the halide quenching of fluorescence from quinine sulfate in water is described. The objectives of the experiment include reinforcing student understanding of the kinetics of competing pathways, making connections with microscopic theories of kinetics through comparison of experimental and…

  5. Metal-halide mixtures for latent heat energy storage

    NASA Technical Reports Server (NTRS)

    Chen, K.; Manvi, R.

    1981-01-01

    Some candidates for alkali metal and alkali halide mixtures suitable for thermal energy storage at temperatures 600 C are identified. A solar thermal system application which offer advantages such as precipitation of salt crystals away from heat transfer surfaces, increased thermal conductivity of phase change materials, corrosion inhibition, and a constant monotectic temperature, independent of mixture concentrations. By using the lighters, metal rich phase as a heat transfer medium and the denser, salt rich phase as a phase change material for latent heat storage, undesirable solidification on the heat transfer surface may be prevented, is presented.

  6. Method for producing hydrocarbon fuels from heavy polynuclear hydrocarbons by use of molten metal halide catalyst

    DOEpatents

    Gorin, Everett

    1979-01-01

    In a process for hydrocracking heavy polynuclear carbonaceous feedstocks to produce lighter hydrocarbon fuels by contacting the heavy feedstocks with hydrogen in the presence of a molten metal halide catalyst, thereafter separating at least a substantial portion of the carbonaceous material associated with the reaction mixture from the spent molten metal halide and thereafter regenerating the metal halide catalyst, an improvement comprising contacting the spent molten metal halide catalyst after removal of a major portion of the carbonaceous material therefrom with an additional quantity of hydrogen is disclosed.

  7. Fluorescence-Based Bacterial Bioreporter for Specific Detection of Methyl Halide Emissions in the Environment

    PubMed Central

    Farhan Ul Haque, Muhammad; Nadalig, Thierry; Bringel, Françoise; Schaller, Hubert

    2013-01-01

    Methyl halides are volatile one-carbon compounds responsible for substantial depletion of stratospheric ozone. Among them, chloromethane (CH3Cl) is the most abundant halogenated hydrocarbon in the atmosphere. Global budgets of methyl halides in the environment are still poorly understood due to uncertainties in their natural sources, mainly from vegetation, and their sinks, which include chloromethane-degrading bacteria. A bacterial bioreporter for the detection of methyl halides was developed on the basis of detailed knowledge of the physiology and genetics of Methylobacterium extorquens CM4, an aerobic alphaproteobacterium which utilizes chloromethane as the sole source of carbon and energy. A plasmid construct with the promoter region of the chloromethane dehalogenase gene cmuA fused to a promotorless yellow fluorescent protein gene cassette resulted in specific methyl halide-dependent fluorescence when introduced into M. extorquens CM4. The bacterial whole-cell bioreporter allowed detection of methyl halides at femtomolar levels and quantification at concentrations above 10 pM (approximately 240 ppt). As shown for the model chloromethane-producing plant Arabidopsis thaliana in particular, the bioreporter may provide an attractive alternative to analytical chemical methods to screen for natural sources of methyl halide emissions. PMID:23956392

  8. Fluorescence-based bacterial bioreporter for specific detection of methyl halide emissions in the environment.

    PubMed

    Farhan Ul Haque, Muhammad; Nadalig, Thierry; Bringel, Françoise; Schaller, Hubert; Vuilleumier, Stéphane

    2013-11-01

    Methyl halides are volatile one-carbon compounds responsible for substantial depletion of stratospheric ozone. Among them, chloromethane (CH3Cl) is the most abundant halogenated hydrocarbon in the atmosphere. Global budgets of methyl halides in the environment are still poorly understood due to uncertainties in their natural sources, mainly from vegetation, and their sinks, which include chloromethane-degrading bacteria. A bacterial bioreporter for the detection of methyl halides was developed on the basis of detailed knowledge of the physiology and genetics of Methylobacterium extorquens CM4, an aerobic alphaproteobacterium which utilizes chloromethane as the sole source of carbon and energy. A plasmid construct with the promoter region of the chloromethane dehalogenase gene cmuA fused to a promotorless yellow fluorescent protein gene cassette resulted in specific methyl halide-dependent fluorescence when introduced into M. extorquens CM4. The bacterial whole-cell bioreporter allowed detection of methyl halides at femtomolar levels and quantification at concentrations above 10 pM (approximately 240 ppt). As shown for the model chloromethane-producing plant Arabidopsis thaliana in particular, the bioreporter may provide an attractive alternative to analytical chemical methods to screen for natural sources of methyl halide emissions. PMID:23956392

  9. Ferroelectricity and Rashba-type band splittings in metal halides

    NASA Astrophysics Data System (ADS)

    Kim, Minsung; Im, Jino; Freeman, Arthur; Ihm, Jisoon; Jin, Hosub

    2014-03-01

    In this study, we investigate Rashba-type band splittings in metal halides. We use a minimal tight-binding model and first principles calculations based on density functional theory to understand the electronic structures of the materials. We find that different types of Rashba bands occur in the conduction and valence band edges in terms of the angular momentum textures. Also, the characteristics of the band splittings will be discussed in connection with the ferroelectric property. Department of Physics and Astronomy, Seoul National University, Seoul 151-747, Korea.

  10. 75 FR 5544 - Energy Conservation Program: Energy Conservation Standards for Metal Halide Lamp Fixtures: Public...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-02-03

    ... public meeting and availability of the Framework Document in the Federal Register (74 FR 69036) for... for Metal Halide Lamp Fixtures: Public Meeting and Availability of the Framework Document AGENCY... conservation standards for certain metal halide lamp fixtures. This document announces that the period...

  11. Fluorescent noble metal nanoclusters

    NASA Astrophysics Data System (ADS)

    Zheng, Jie

    Water-soluble fluorescent metallic clusters at sizes comparable to the Fermi wavelength of an electron (˜0.5 nm for gold and silver) were created and their photophysical properties were investigated at the bulk and single molecule levels. We employed biocompatible dendrimer and peptide to prepare a series of strong fluorescent gold and silver clusters with chemical or photo reduction methods. Facilitated by the well-defined dendrimer size, electrospray ionization mass spectrometry indicates that the fluorescent silver nanocluster size ranges from 2 to 8 Ag atoms. The correlation of emission energy with the number of atoms, N, in each gold nanocluster is quantitatively fit for the smallest nanoclusters with no adjustable parameters by the simple scaling relation of EFermi/N1/3, in which EFermi is the Fermi energy of bulk gold. The transition energy scaling inversely with cluster radius indicates that electronic structure can be well described with the spherical jellium model and further demonstrates that these nanomaterials are "multi-electron artificial atoms". Fluorescence from these small metal clusters can be considered protoplasmonic, molecular transitions of the free conduction electrons before the onset of collective dipole oscillations occurring when a continuous density of states is reached. In addition, very strong single molecular Stokes and anti-Stokes Raman enhancement by fluorescent silver clusters was observed. Pushing to larger sizes, we also created ˜2nm diameter glutathione encapsulated luminescent gold nanoparticles. Distinct from similarly sized but nonluminescent gold nanoparticles, these 2 nm gold nanoparticles show bright, long lifetime emission but no plasmon absorption. The emission might arise from charge transfer between gold atoms and the thiol ligand. Providing the "missing link" between atomic and nanoparticle behavior in noble metals, these highly fluorescent, water-soluble gold and silver nanoclusters offer complementary transition

  12. New generation of medium wattage metal halide lamps and spectroscopic tools for their diagnostics

    NASA Astrophysics Data System (ADS)

    Dunaevsky, A.; Tu, J.; Gibson, R.; Steere, T.; Graham, K.; van der Eyden, J.

    2010-11-01

    A new generation of ceramic metal halide high intensity discharge (HID) lamps has achieved high efficiencies by implementing new design concepts. The shape of the ceramic burner is optimized to withstand high temperatures with minimal thermal stress. Corrosion processes with the ceramic walls are slowed down via adoption of non-aggressive metal halide chemistry. Light losses over life due to tungsten deposition on the walls are minimized by maintaining a self-cleaning chemical process, known as tungsten cycle. All these advancements have made the new ceramic metal halide lamps comparable to high pressure sodium lamps for luminous efficacy, life, and maintenance while providing white light with high color rendering. Direct replacement of quartz metal halide lamps and systems results in the energy saving from 18 up to 50%. High resolution spectroscopy remains the major non-destructive tool for the ceramic metal halide lamps. Approaches to reliable measurements of relative partial pressures of the arc species are discussed.

  13. Method for producing hydrocarbon fuels and fuel gas from heavy polynuclear hydrocarbons by the use of molten metal halide catalysts

    DOEpatents

    Gorin, Everett

    1979-01-01

    In a process for hydrocracking heavy polynuclear carbonaceous feedstocks to produce lighter hydrocarbon fuels by contacting the heavy feedstocks with hydrogen in the presence of a molten metal halide catalyst in a hydrocracking zone, thereafter separating at least a major portion of the lighter hydrocarbon fuels from the spent molten metal halide and thereafter regenerating the spent molten metal halide by incinerating the spent molten metal halide by combustion of carbon and sulfur compounds in the spent molten metal halide in an incineration zone, the improvement comprising: (a) contacting the heavy feedstocks and hydrogen in the presence of the molten metal halide in the hydrocracking zone at reaction conditions effective to convert from about 60 to about 90 weight percent of the feedstock to lighter hydrocarbon fuels; (b) separating at least a major portion of the lighter hydrocarbon fuels from the spent molten metal halide; (c) contacting the spent molten metal halide with oxygen in a liquid phase gasification zone at a temperature and pressure sufficient to vaporize from about 25 to about 75 weight percent of the spent metal halide, the oxygen being introduced in an amount sufficient to remove from about 60 to about 90 weight percent of the carbon contained in the spent molten metal halide to produce a fuel gas and regenerated metal halide; and (d) incinerating the spent molten metal halide by combusting carbon and sulfur compounds contained therein.

  14. Thermal battery. [solid metal halide electrolytes with enhanced electrical conductance after a phase transition

    DOEpatents

    Carlsten, R.W.; Nissen, D.A.

    1973-03-06

    The patent describes an improved thermal battery whose novel design eliminates various disadvantages of previous such devices. Its major features include a halide cathode, a solid metal halide electrolyte which has a substantially greater electrical conductance after a phase transition at some temperature, and a means for heating its electrochemical cells to activation temperature.

  15. Spectroscopic effects of disorder and vibrational localization in mixed-halide metal-halide chain solids

    SciTech Connect

    Love, S.P.; Scott, B.; Worl, L.A.; Huckett, S.C.; Saxena, A.; Huang, X.Z.; Bishop, A.R.; Swanson, B.I.

    1993-02-01

    Resonance Raman techniques, together with lattice-dynamics and Peierls-Hubbard modelling, are used to explore the electronic and vibrational dynamics of the quasi-one-dimensional metal-halogen chain solids [Pt(en){sub 2}][R(en){sub 2}X{sub 2}](ClO{sub 4}){sub 4}, (en = C{sub 2}H{sub 8}N{sub 2} and X=Cl, Br), abbreviated ``PLX.`` The mixed-halide materials PtCl{sub 1-x}Br{sub x} and PtCl{sub 1-x}I{sub x} consist of long mixed chains with heterojunctions between segments of the two constituent materials. Thus, in addition to providing mesoscale modulation of the chain electronic states, they serve as prototypes for elucidating the properties to be expected for macroscopic heterojunctions of these highly nonlinear materials. Once a detailed understanding of the various local vibrational modes occurring in these disordered solids is developed, the electronic structure of the chain segments and junctions can be probed by tuning the Raman excitation through their various electronic resonances.

  16. Direct current ballast circuit for metal halide lamp

    NASA Technical Reports Server (NTRS)

    Lutus, P. (Inventor)

    1981-01-01

    A direct current ballast circuit for a two electrode metal halide lamp is described. Said direct current ballast circuit includes a low voltage DC input and a high frequency power amplifier and power transformer for developing a high voltage output. The output voltage is rectified by diodes and filtered by inductor and capacitor to provide a regulated DC output through commutating diodes to one terminal of the lamp at the output terminal. A feedback path from the output of the filter capacitor through the bias resistor to power the high frequency circuit which includes the power amplifier and the power transformer for sustaining circuit operations during low voltage transients on the input DC supply is described. A current sensor connected to the output of the lamp through terminal for stabilizing lamp current following breakdown of the lamp is described.

  17. Metal halide arc discharge lamp having short arc length

    NASA Technical Reports Server (NTRS)

    Muzeroll, Martin E. (Inventor)

    1994-01-01

    A metal halide arc discharge lamp includes a sealed light-transmissive outer jacket, a light-transmissive shroud located within the outer jacket and an arc tube assembly located within the shroud. The arc tube assembly includes an arc tube, electrodes mounted within the arc tube and a fill material for supporting an arc discharge. The electrodes have a spacing such that an electric field in a range of about 60 to 95 volts per centimeter is established between the electrodes. The diameter of the arc tube and the spacing of the electrodes are selected to provide an arc having an arc diameter to arc length ratio in a range of about 1.6 to 1.8. The fill material includes mercury, sodium iodide, scandium tri-iodide and a rare gas, and may include lithium iodide. The lamp exhibits a high color rendering index, high lumen output and high color temperature.

  18. Investigating Metallization in Shock-Compressed Alkali Halides

    NASA Astrophysics Data System (ADS)

    Diamond, M. R.; Ali, S. J.; Eggert, J.; Jeanloz, R.; Collins, G. W.; McWilliams, R. S.

    2014-12-01

    Laser-shock compression on four alkali halides has been used to probe the transition from insulating to metallic states, a high-pressure transition in chemical bonding that has fundamental implications for planetary formation and structure. Collectively, pressures up to 450 GPa were explored across a total of fourteen single-crystal samples of CsI, CsBr, KBr and NaCl. Velocity interferometry (VISAR) was used to record shock velocities and reflectivities at 532 nm during decaying shock compression. The data show up to three-fold increases in density as well as significant increases in optical reflectivity in response to high pressures and temperatures. Using a Drude model to estimate conductivities from the measured reflectivities, we investigate the onset of metallic conductivities for each compound. Ionic salts are simple model systems amenable to first-principles theory and serve as analog materials for predicting whether specific chemical constituents can reside in the rocky mantles or metallic cores of planets. A key objective is to disentangle the complementary roles of temperature and compression in transforming ionic into metallic bonding. Furthermore, at high pressures CsI becomes analogous to Xe: they are isoelectronic and follow matching equations of state. Therefore, studies on CsI can inform understanding of noble-gas geochemistry at conditions deep inside planets (e.g., the likelihood of Xe solubility in planetary mantles or cores). Our experiments were conducted using the Janus laser of the Jupiter Laser Facility at Lawrence Livermore National Laboratory.

  19. Reactivity of halide and pseudohalide ligands in transition-metal complexes

    SciTech Connect

    Kukushkin, Yu.N.; Kukushkin, V.Yu.

    1985-10-01

    The experimental material on the reactions of coordinated halide ligands, as well as cyanide, azido, thiocyanato, and cyanato ligands, in transition-metal complexes has been generalized in this review.

  20. High power metallic halide laser. [amplifying a copper chloride laser

    NASA Technical Reports Server (NTRS)

    Pivirotto, T. J. (Inventor)

    1982-01-01

    A laser amplification system is disclosed whereby a metallic halide vapor such as copper chloride is caused to flow through a laser amplifier and a heat exchanger in a closed loop system so that the flow rate is altered to control the temperature rise across the length of the laser amplifier. The copper atoms within the laser amplifier should not exceed a temperature of 3000 K, so that the number of copper atoms in the metastable state will not be high enough to prevent amplification in the amplifier. A molecular dissociation apparatus is provided at the input to the laser amplifier for dissociating the copper chloride into copper atoms and ions and chlorine atoms and ions. The dissociation apparatus includes a hollow cathode tube and an annular ring spaced apart from the tube end. A voltage differential is applied between the annular ring and the hollow cathode tube so that as the copper chloride flows through, it is dissociated into copper and chlorine ions and atoms.

  1. Ac electrode diagnostics in ac-operated metal halide lamps

    NASA Astrophysics Data System (ADS)

    Luijks, G. M. J. F.; van Esveld, H. A.; Nijdam, S.; Weerdesteijn, P. A. M.

    2008-07-01

    A diagnostic technique is presented to determine the electrode work function in ac-operated metal halide lamps. The heart of the experimental set-up is a high-speed photodiode array detector, which is able to follow real-time variations of electrode tip temperature and near-electrode plasma emissions in ac-operated experimental YAG lamps, enabling discrimination between the anode and cathode effects. Electrode tip temperature ripples have been measured for 100 Hz square wave operation and simulated with an existing electrode model. By using the electrode work function as main fit parameter for the simulations it is found that the measured cooling effect of the electrode tip in a NaTlDy-iodide lamp is caused by a gas-phase emitter effect of Dy. It is concluded that Dy coverage of the electrode tip causes an effective work function reduction of 0.3 eV at 100 Hz square wave operation, considerably less than the 1.0 eV reduction measured earlier for dc operation.

  2. Spectroscopic imaging of metal halide high-intensity discharge lamps

    NASA Astrophysics Data System (ADS)

    Bonvallet, Geoffrey A.

    The body of this work consists of three main research projects. An optical- and near-ultraviolet-wavelength absorption study sought to determine absolute densities of ground and excited level Sc atoms, ground level Sc + ions, and ground level Na atoms in a commercial 250 W metal halide high intensity discharge lamp during operation. These measurements also allowed the determination of the arc temperature and absolute electron density as functions of radius. Through infrared emission spectroscopy, relative densities of sodium and scandium were determined as functions of radius. Using the absolute densities gained from the optical experiment, these relative densities were calibrated. In addition, direct observation of the infrared emission allowed us to characterize the infrared power losses of the lamp. When considered as a fraction of the overall power consumption, the near-infrared spectral power losses were not substantial enough to warrant thorough investigation of their reduction in these lamps. The third project was an attempt to develop a portable x-ray diagnostic experiment. Two-dimensional spatial maps of the lamps were analyzed to determine absolute elemental mercury densities and the arc temperature as a function of radius. Two methods were used to improve the calibration of the density measurements and to correct for the spread in x-ray energy: known solutions of mercury in nitric acid, and an arc lamp which was uniformly heated to evaporate the mercury content. Although many complexities arose in this experiment, its goal was successfully completed.

  3. Electronic ballasts for metal halide lamps broaden applicability and improve efficiency

    SciTech Connect

    1992-12-31

    Metal halide lamps, typically used to light parking lots, highways, and industrial facilities, are among the most efficient and long-lived light sources available. In recent years, smaller metal halide lamps with improved color rendering have been developed, enabling these systems to gradually penetrate the commercial lighting market, with impressive efficiency gains. In a typical display lighting application, for instance, a 70-watt metal halide will produce more light than two 150-watt PAR 38 incandescents and last up to five times as long. Progress in applying metal halides in such applications has been limited, however, by the color shift that occurs as the lamp ages. New electronic ballasts for these lamps can reduce color shift by maintaining constant voltage as the lamps age, thereby broadening their application into areas like retail display, where color quality is of critical concern. Electronic ballasting can also improve efficacy by about 15 percent in comparison to electromagnetic ballasting, improve lumen maintenance and warm-up characteristics, extend lamp life, and maintain consistent power to the lamp over wide fluctuations in line voltage. Because they are smaller and lighter than electromagnetic ballasts, electronic ballasts allow metal halides to be used in track fixtures and other installations where weight might have previously been a problem.

  4. 10 CFR 431.324 - Uniform test method for the measurement of energy efficiency of metal halide ballasts.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... efficiency of metal halide ballasts. 431.324 Section 431.324 Energy DEPARTMENT OF ENERGY ENERGY CONSERVATION ENERGY EFFICIENCY PROGRAM FOR CERTAIN COMMERCIAL AND INDUSTRIAL EQUIPMENT Metal Halide Lamp Ballasts and Fixtures Test Procedures § 431.324 Uniform test method for the measurement of energy efficiency of...

  5. 10 CFR Appendix C to Subpart S of... - Enforcement for Performance Standards; Compliance Determination Procedure for Metal Halide Lamp...

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... Determination Procedure for Metal Halide Lamp Ballasts C Appendix C to Subpart S of Part 431 Energy DEPARTMENT... EQUIPMENT Metal Halide Lamp Ballasts and Fixtures Pt. 431, Subpt. S, App. C Appendix C to Subpart S of Part..., and n1 is the total number of tests. (c) Compute the standard deviation (S1) of the measured...

  6. 10 CFR Appendix B to Subpart S to... - Certification Report for Metal Halide Lamp Ballasts

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... Energy, Building Technologies Program, Mailstop EE-2J, 1000 Independence Avenue, SW., Washington, DC 20585-0121. Submit by E-mail to: U.S. Department of Energy, Buildings Technologies Program... 10 Energy 3 2011-01-01 2011-01-01 false Certification Report for Metal Halide Lamp Ballasts...

  7. 10 CFR Appendix A to Subpart S of... - Compliance Statement for Metal Halide Lamp Ballasts

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ...”) submits this Compliance Statement under 10 CFR Part 431 (Energy Efficiency Program for Certain Commercial... models of metal halide lamp ballasts subject to energy conservation standards specified in 10 CFR Part... comply with the energy conservation requirements in 10 CFR Part 431 with regard to any new basic model...

  8. Transition-metal-free, ambient-pressure carbonylative cross-coupling reactions of aryl halides with potassium aryltrifluoroborates.

    PubMed

    Jin, Fengli; Han, Wei

    2015-06-01

    We disclose an unprecedented transition-metal-free carbonylative cross coupling of aryl halides with potassium aryl trifluoroborates even at atmospheric pressure of carbon monoxide. This protocol is efficient, operationally simple, and shows wide scope with regard to both aryl halides and potassium aryl trifluoroborates containing a series of active functional groups. PMID:25939449

  9. Spectroscopic effects of disorder and vibrational localization in mixed-halide metal-halide chain solids

    SciTech Connect

    Love, S.P.; Scott, B.; Worl, L.A.; Huckett, S.C.; Saxena, A.; Huang, X.Z.; Bishop, A.R.; Swanson, B.I.

    1993-01-01

    Resonance Raman techniques, together with lattice-dynamics and Peierls-Hubbard modelling, are used to explore the electronic and vibrational dynamics of the quasi-one-dimensional metal-halogen chain solids [Pt(en)[sub 2

  10. Experimental and theoretical studies of highly emissive dinuclear Cu(I) halide complexes with delayed fluorescence.

    PubMed

    Kang, Liju; Chen, Jin; Teng, Teng; Chen, Xu-Lin; Yu, Rongmin; Lu, Can-Zhong

    2015-07-01

    A series of luminescent homo-dinuclear Cu(I) halide complexes, [PPh2PAr2Cu(μ-X)2CuPPh2PAr2] (X = I (1), Br (2), Cl (3)) (PPh2PAr2 = (1-bis(2-methylphenyl)phosphino-2-diphenylphosphino)benzene) were synthesized from the reaction of the corresponding cuprous halide and the chelating bisphosphine ligand PPh2PAr2 in CH3CN. The complexes were structurally characterized by X-ray single crystal analysis. Their photophysical properties were studied in detail. The Cu(I) atoms in these complexes are four-coordinated and adopt a tetrahedral coordination geometry. In each complex, the copper centers are bridged by two halide anions and each Cu(I) is chelated further terminally by a PPh2PAr2 ligand. The[Cu(μ-X)2Cu] cores have similar butterfly-type configurations. The distances between the Cu(I) atoms in each complex are over 2.94 Å. In the solid state, these complexes are highly emissive and exhibit bluish-green photoluminescence (emission peaks, λmax = 488 nm (1), 482 nm (2), 490 nm (3)) with short lifetimes (4.9-5.9 μs) and high quantum yields (ϕ = 0.42-0.95) at room temperature. In this series of complexes, the ligand-field strengths of the ions (I(-) < Br(-) < Cl(-)) do not have obvious effect on the emission maxima. The studies on varied temperature emission spectra and decay behaviours of these complexes indicate that the mechanism of their emissions involves two thermal-equilibrium excited states. At room temperature, the complexes display thermally activated delayed fluorescences with short decay lifetimes. With a decrease of the temperature, a significant increase of emission decay times by almost 2 orders of magnitude is observed. At temperatures below T ≈ 100 K, the decay times of the studied complexes are over one hundred microseconds long, which indicates that the emission originates mainly from the triplet state (T1 state). To interpret the varied temperature photophysics of these complexes, an equilibrated 2 excited states model S0 ← T1 ↔ S1 → S0

  11. Promotion of Organic Reactions by Ultrasound: Coupling of Alkyl and Aryl Halides in the Presence of Lithium Metal and Ultrasound.

    ERIC Educational Resources Information Center

    Lash, Timothy D.; Berry, Donna

    1985-01-01

    Experiments involving the coupling of alkyl and aryl halides in the presence of lithium metal and ultrasound are described. The experiments illustrate classical Wurtz and Fittig reactions in addition to being a convenient application of organic sonochemistry. (JN)

  12. Theory of metal atom-water interactions and alkali halide dimers

    NASA Technical Reports Server (NTRS)

    Jordan, K. D.; Kurtz, H. A.

    1982-01-01

    Theoretical studies of the interactions of metal atoms with water and some of its isoelectronic analogs, and of the properties of alkali halides and their aggregates are discussed. Results are presented of ab initio calculations of the heats of reaction of the metal-water adducts and hydroxyhydrides of Li, Be, B, Na, Mg, and Al, and of the bond lengths and angles an; the heats of reaction for the insertion of Al into HF, H2O, NH3, H2S and CH3OH, and Be and Mg into H2O. Calculations of the electron affinities and dipole moments and polarizabilities of selected gas phase alkali halide monomers and dimers are discussed, with particular attention given to results of calculations of the polarizability of LiF taking into account electron correlation effects, and the polarizability of the dimer (LiF)2.

  13. Reactions between cold methyl halide molecules and alkali-metal atoms

    SciTech Connect

    Lutz, Jesse J.; Hutson, Jeremy M.

    2014-01-07

    We investigate the potential energy surfaces and activation energies for reactions between methyl halide molecules CH{sub 3}X (X = F, Cl, Br, I) and alkali-metal atoms A (A = Li, Na, K, Rb) using high-level ab initio calculations. We examine the anisotropy of each intermolecular potential energy surface (PES) and the mechanism and energetics of the only available exothermic reaction pathway, CH{sub 3}X + A → CH{sub 3} + AX. The region of the transition state is explored using two-dimensional PES cuts and estimates of the activation energies are inferred. Nearly all combinations of methyl halide and alkali-metal atom have positive barrier heights, indicating that reactions at low temperatures will be slow.

  14. Method for hydrocracking a heavy polynuclear hydrocarbonaceous feedstock in the presence of a molten metal halide catalyst

    DOEpatents

    Gorin, Everett

    1981-01-01

    A method for hydrocracking a heavy polynuclear hydrocarbonaceous feedstock to produce lighter hydrocarbon fuels by contacting the feedstock with hydrogen in the presence of a molten metal halide catalyst, the method comprising: mixing the feedstock with a heavy naphtha fraction which has an initial boiling point from about 100.degree. to about 160.degree. C. with a boiling point difference between the initial boiling point and the final boiling point of no more than about 50.degree. C. to produce a mixture; thereafter contacting the mixture with partially spent molten metal halide and hydrogen under temperature and pressure conditions so that the temperature is near the critical temperature of the heavy naphtha fraction; separating at least a portion of the heavy naphtha fraction and lighter hydrocarbon fuels from the partially spent molten metal halide, unreacted feedstock and reaction products; thereafter contacting the partially spent molten metal halide, unreacted feedstock and reaction products with hydrogen and fresh molten metal halide in a hydrocracking zone to produce additional lighter hydrocarbon fuels and separating at least a major portion of the lighter hydrocarbon fuels from the spent molten metal halide.

  15. Method for hydrocracking a heavy polynuclear hydrocarbonaceous feedstock in the presence of a molten metal halide catalyst

    SciTech Connect

    Gorin, E.

    1981-01-27

    A method is described for hydrocracking a heavy polynuclear hydrocarbonaceous feedstock to produce lighter hydrocarbon fuels by contacting the feedstock with hydrogen in the presence of a molten metal halide catalyst. The method consists of mixing the feedstock with a heavy naphtha fraction which has an initial boiling point from about 100/sup 0/ to about 160/sup 0/C, with a boiling point difference between the initial boiling point and the final boiling point of no more than about 50/sup 0/C to produce a mixture. Thereafter the mixture is contacted with partially spent molten metal halide and hydrogen under temperature and pressure conditions so that the temperature is near the critical temperature of the heavy naphtha fraction. At least a portion of the heavy naphtha fraction and lighter hydrocarbon fuels is separated from the partially spent molten metal halide, unreacted feedstock and reaction products. The partially spent molten metal halide, unreacted feedstock and reaction products are then contacted with hydrogen and fresh molten metal halide in a hydrocracking zone to produce additional lighter hydrocarbon fuels and at least a major portion of the lighter hydrocarbon fuels are separated from the spent molten metal halide.

  16. Interface Engineering in Metal Halides Perovskites: From molecules to devices

    NASA Astrophysics Data System (ADS)

    Petrozza, Annamaria

    In this talk we review our recent studies which aim to clarify the relationship between structural and electronic properties from a molecular to mesoscopic level. First we identify the markers for local disorder at molecular level by using Raman Spectroscopy as a probe. Then, we exploit such a tool to explore the role of microstructure on the absorption and emission properties of the semiconductor looking both at polycrystalline thin films and single crystals. We address the controversy surrounding electron - hole interactions and excitonic effects. We show that in hybrid lead-halide perovskites dielectric screening also depends on the local microstructure of the hybrid crystals and not only on its chemical composition. This leads to the possibility of band gap engineering and the consequent control of the elementary photo-excitation dynamics that determine the perovskites' performances in different optoelectronic devices. Finally, the role of interface engineering, the effect of ion migration, and interface doping on charge extraction will be elucidated to provide a guideline for the design of hysteresis free solar cells. 1)G. Grancini & AR Srimath Kandada et al., Nature Photonics, 9 (10), 695-701, 2015 2) C. Tao et al,'' Energy Environ. Sci.,8, 2365-2370, 2015

  17. Sub-millimeter Spectroscopy of Astrophysically Important Molecules and Ions: Metal Hydrides, Halides, and Cyanides

    NASA Technical Reports Server (NTRS)

    Ziurys, L. M.; Flory, M. A.; Halfen, D. T.

    2006-01-01

    With the advent of SOFIA, Herschel, and SAFIR, new wavelength regions will become routinely accessible for astronomical spectroscopy, particularly at submm frequencies (0.5-1.1 THz). Molecular emission dominates the spectra of dense interstellar gas at these wavelengths. Because heterodyne detectors are major instruments of these missions, accurate knowledge of transition frequencies is crucial for their success. The Ziurys spectroscopy laboratory has been focusing on the measurement of the pure rotational transitions of astrophysically important molecules in the sub-mm regime. Of particular interest have been metal hydride species and their ions, as well as metal halides and cyanides. A new avenue of study has included metal bearing molecular ions.

  18. Development of processes for the production of solar grade silicon from halides and alkali metals

    NASA Technical Reports Server (NTRS)

    Dickson, C. R.; Gould, R. K.

    1980-01-01

    High temperature reactions of silicon halides with alkali metals for the production of solar grade silicon in volume at low cost were studied. Experiments were performed to evaluate product separation and collection processes, measure heat release parameters for scaling purposes, determine the effects of reactants and/or products on materials of reactor construction, and make preliminary engineering and economic analyses of a scaled-up process.

  19. Photokeratitis Linked to Metal Halide Bulbs in Two Gymnasiums - Philadelphia, Pennsylvania, 2011 and 2013.

    PubMed

    Finn, Lauren E; Gutowski, Jennifer; Alles, Steve; Mirowitz, Naomi; Johnson, Caroline; Osterhoudt, Kevin C; Patel, Ami

    2016-01-01

    In December 2011 and December 2013, the Philadelphia Department of Public Health (PDPH) received separate reports of clusters of photokeratitis linked to gymnasium events. Photokeratitis, a painful eye condition resulting from unprotected exposure to ultraviolet radiation, has previously been linked to metal halide lamps with broken outer envelopes (1,2). To investigate the cause of these clusters and further characterize patients with photokeratitis, PDPH administered questionnaires to potentially exposed persons, established a case definition, and conducted environmental assessments of both gymnasiums. Because event attendee registration information was available, a cohort study was conducted to evaluate the 2011 cluster of 242 persons who met the photokeratitis case definition. A case-series investigation was conducted to evaluate the 2013 cluster of 20 persons who met the photokeratitis case definition for that event. These investigations indicated that Type R metal halide bulbs with broken outer envelopes found in both gymnasiums were the probable cause of the photokeratitis. The Food and Drug Administration has made a number of recommendations regarding the use of metal halide bulbs in facilities where bulbs are at elevated risk for breaking, such as schools and indoor sports facilities (3). Because Type R metal halide lamps do not self-extinguish once the outer envelope is broken, these bulbs should be removed from settings with a high risk for outer envelope rupture, such as gymnasiums, or should be placed within enclosed fixtures. In instances where these bulbs cannot be exchanged for self-extinguishing lamps, Type R lamps with a broken outer envelope should be replaced immediately to limit exposure to ultraviolet radiation. A broken outer envelope can be detected by the presence of glass on the floor, or visual examination of the bulb when the power is turned off. A broken outer envelope is difficult to detect when the lamp is emitting light. PMID

  20. Multicolor fluorescent light-emitting diodes based on cesium lead halide perovskite quantum dots

    NASA Astrophysics Data System (ADS)

    Wang, Peng; Bai, Xue; Sun, Chun; Zhang, Xiaoyu; Zhang, Tieqiang; Zhang, Yu

    2016-08-01

    High quantum yield, narrow full width at half-maximum and tunable emission color of perovskite quantum dots (QDs) make this kind of material good prospects for light-emitting diodes (LEDs). However, the relatively poor stability under high temperature and air condition limits the device performance. To overcome this issue, the liquid-type packaging structure in combination with blue LED chip was employed to fabricate the fluorescent perovskite quantum dot-based LEDs. A variety of monochromatic LEDs with green, yellow, reddish-orange, and red emission were fabricated by utilizing the inorganic cesium lead halide perovskite quantum dots as the color-conversion layer, which exhibited the narrow full width at half-maximum (<35 nm), the relatively high luminous efficiency (reaching 75.5 lm/W), and the relatively high external quantum efficiency (14.6%), making it the best-performing perovskite LEDs so far. Compared to the solid state LED device, the liquid-type LED devices exhibited excellent color stability against the various working currents. Furthermore, we demonstrated the potential prospects of all-inorganic perovskite QDs for the liquid-type warm white LEDs.

  1. Designing mixed metal halide ammines for ammonia storage using density functional theory and genetic algorithms.

    PubMed

    Jensen, Peter Bjerre; Lysgaard, Steen; Quaade, Ulrich J; Vegge, Tejs

    2014-09-28

    Metal halide ammines have great potential as a future, high-density energy carrier in vehicles. So far known materials, e.g. Mg(NH3)6Cl2 and Sr(NH3)8Cl2, are not suitable for automotive, fuel cell applications, because the release of ammonia is a multi-step reaction, requiring too much heat to be supplied, making the total efficiency lower. Here, we apply density functional theory (DFT) calculations to predict new mixed metal halide ammines with improved storage capacities and the ability to release the stored ammonia in one step, at temperatures suitable for system integration with polymer electrolyte membrane fuel cells (PEMFC). We use genetic algorithms (GAs) to search for materials containing up to three different metals (alkaline-earth, 3d and 4d) and two different halides (Cl, Br and I) - almost 27,000 combinations, and have identified novel mixtures, with significantly improved storage capacities. The size of the search space and the chosen fitness function make it possible to verify that the found candidates are the best possible candidates in the search space, proving that the GA implementation is ideal for this kind of computational materials design, requiring calculations on less than two percent of the candidates to identify the global optimum. PMID:25115581

  2. NMR longitudinal relaxation enhancement in metal halides by heteronuclear polarization exchange during magic-angle spinning.

    PubMed

    Shmyreva, Anna A; Safdari, Majid; Furó, István; Dvinskikh, Sergey V

    2016-06-14

    Orders of magnitude decrease of (207)Pb and (199)Hg NMR longitudinal relaxation times T1 upon magic-angle-spinning (MAS) are observed and systematically investigated in solid lead and mercury halides MeX2 (Me = Pb, Hg and X = Cl, Br, I). In lead(ii) halides, the most dramatic decrease of T1 relative to that in a static sample is in PbI2, while it is smaller but still significant in PbBr2, and not detectable in PbCl2. The effect is magnetic-field dependent but independent of the spinning speed in the range 200-15 000 Hz. The observed relaxation enhancement is explained by laboratory-frame heteronuclear polarization exchange due to crossing between energy levels of spin-1/2 metal nuclei and adjacent quadrupolar-spin halogen nuclei. The enhancement effect is also present in lead-containing organometal halide perovskites. Our results demonstrate that in affected samples, it is the relaxation data recorded under non-spinning conditions that characterize the local properties at the metal sites. A practical advantage of fast relaxation at slow MAS is that spectral shapes with orientational chemical shift anisotropy information well retained can be acquired within a shorter experimental time. PMID:27306000

  3. NMR longitudinal relaxation enhancement in metal halides by heteronuclear polarization exchange during magic-angle spinning

    NASA Astrophysics Data System (ADS)

    Shmyreva, Anna A.; Safdari, Majid; Furó, István; Dvinskikh, Sergey V.

    2016-06-01

    Orders of magnitude decrease of 207Pb and 199Hg NMR longitudinal relaxation times T1 upon magic-angle-spinning (MAS) are observed and systematically investigated in solid lead and mercury halides MeX2 (Me = Pb, Hg and X = Cl, Br, I). In lead(ii) halides, the most dramatic decrease of T1 relative to that in a static sample is in PbI2, while it is smaller but still significant in PbBr2, and not detectable in PbCl2. The effect is magnetic-field dependent but independent of the spinning speed in the range 200-15 000 Hz. The observed relaxation enhancement is explained by laboratory-frame heteronuclear polarization exchange due to crossing between energy levels of spin-1/2 metal nuclei and adjacent quadrupolar-spin halogen nuclei. The enhancement effect is also present in lead-containing organometal halide perovskites. Our results demonstrate that in affected samples, it is the relaxation data recorded under non-spinning conditions that characterize the local properties at the metal sites. A practical advantage of fast relaxation at slow MAS is that spectral shapes with orientational chemical shift anisotropy information well retained can be acquired within a shorter experimental time.

  4. Metal halide solid-state surface treatment for nanocrystal materials

    DOEpatents

    Luther, Joseph M.; Crisp, Ryan; Beard, Matthew C.

    2016-04-26

    Methods of treating nanocrystal and/or quantum dot devices are described. The methods include contacting the nanocrystals and/or quantum dots with a solution including metal ions and halogen ions, such that the solution displaces native ligands present on the surface of the nanocrystals and/or quantum dots via ligand exchange.

  5. Antimicrobial properties of metal and metal-halide nanoparticles and their potential applications

    NASA Astrophysics Data System (ADS)

    Torrey, Jason Robert

    Heavy metals, including silver and copper, have been known to possess antimicrobial properties against bacterial, fungal, and viral pathogens. Metal nanoparticles (aggregations of metal atoms 1-200 nm in size) have recently become the subject of intensive study for their increased antimicrobial properties. In the current studies, metal and metal-halide nanoparticles were evaluated for their antibacterial efficacy. Silver (Ag), silver bromide (AgBr), silver iodide (AgI), and copper iodide (CuI) nanoparticles significantly reduced bacterial numbers of the Gram-negative Pseudomonas aeruginosa and the Gram-positive Staphylococcus aureus within 24 hours and were more effective against P. aeruginosa. CuI nanoparticles were found to be highly effective, reducing both organisms by >4.43 log 10 within 15 minutes at 60 ppm Cu. CuI nanoparticles formulated with different stabilizers (sodium dodecyl sulfate, SDS; polyvinyl pyrrolidone, PVP) were further tested against representative Gram-positive and Gram-negative bacteria, Mycobacteria, a fungus (Candida albicans ), and a non-enveloped virus (poliovirus). Both nanoparticles caused significant reductions in most of the Gram-negative bacteria within five minutes (>5.09-log10). The Gram-positive bacterial species and C. albicans were more sensitive to the CuI-SDS than the CuI-PVP nanoparticles. In contrast, the acid-fast Mycobacterium smegmatis was more resistant to CuI-SDS than CuI-PVP nanoparticles. Poliovirus was more resistant than the other organisms tested except for Mycobacterium fortuitum, which displayed the greatest resistance to CuI nanoparticles. As an example of a real world antimicrobial application, polymer coatings embedded with various concentrations of CuI nanoparticles were tested for antibacterial efficacy against P. aeruginosa and S. aureus. Polyester-epoxy powder coatings were found to display superior uniformity, stability and antimicrobial properties against both organisms (>4.92 log 10 after six hours at

  6. Cluster harvesting by successive reduction of a metal halide with a nonconventional reduction agent: a benefit for the exploration of metal-rich halide systems.

    PubMed

    Ströbele, Markus; Mos, Agnieszka; Meyer, Hans-Jürgen

    2013-06-17

    The preparation of thermally labile compounds is a great temptation in chemistry which requires a careful selection of reaction media and reaction conditions. With a new scanning technique denoted here as Cluster Harvesting, a whole series of metal halide compounds is detected by differential thermal analysis (DTA) in fused silica tubes and structurally characterized by X-ray powder diffraction. Experiments of the reduction of tungsten hexahalides with elemental antimony and iron are presented. A cascade of six compounds is identified during the reduction with antimony, and five compounds or phases are monitored following the reduction with iron. The crystal structure of Fe2W2Cl10 is reported, and two other phases in the Fe-W-Cl system are discussed. PMID:23718691

  7. Lead-Free Halide Double Perovskites via Heterovalent Substitution of Noble Metals.

    PubMed

    Volonakis, George; Filip, Marina R; Haghighirad, Amir Abbas; Sakai, Nobuya; Wenger, Bernard; Snaith, Henry J; Giustino, Feliciano

    2016-04-01

    Lead-based halide perovskites are emerging as the most promising class of materials for next-generation optoelectronics; however, despite the enormous success of lead-halide perovskite solar cells, the issues of stability and toxicity are yet to be resolved. Here we report on the computational design and the experimental synthesis of a new family of Pb-free inorganic halide double perovskites based on bismuth or antimony and noble metals. Using first-principles calculations we show that this hitherto unknown family of perovskites exhibits very promising optoelectronic properties, such as tunable band gaps in the visible range and low carrier effective masses. Furthermore, we successfully synthesize the double perovskite Cs2BiAgCl6, perform structural refinement using single-crystal X-ray diffraction, and characterize its optical properties via optical absorption and photoluminescence measurements. This new perovskite belongs to the Fm3̅m space group and consists of BiCl6 and AgCl6 octahedra alternating in a rock-salt face-centered cubic structure. From UV-vis and photoluminescence measurements we obtain an indirect gap of 2.2 eV. PMID:26982118

  8. Evaluation of Metal Halide, Plasma, and LED Lighting Technologies for a Hydrogen Fuel Cell Mobile Light (H 2 LT)

    DOE PAGESBeta

    Miller, L. B.; Donohoe, S. P.; Jones, M. H.; White, W. A.; Klebanoff, L. E.; Velinsky, S. A.

    2015-04-22

    This article reports on the testing and comparison of a prototype hydrogen fuel cell light tower (H2LT) and a conventional diesel-powered metal halide light trailer for use in road maintenance and construction activities. The prototype was originally outfitted with plasma lights and then with light-emitting diode (LED) luminaires. Light output and distribution, lighting energy efficiency (i.e., efficacy), power source thermal efficiency, and fuel costs are compared. The metal halide luminaires have 2.2 and 3.1 times more light output than the plasma and LED luminaires, respectively, but they require more power/lumen to provide that output. The LED luminaires have 1.6 timesmore » better light efficacy than either the metal halide or plasma luminaires. The light uniformity ratios produced by the plasma and LED towers are acceptable. The fuel cell thermal efficiency at the power required to operate the plasma lights is 48%, significantly higher than the diesel generator efficiency of 23% when operating the metal halide lights. Due to the increased efficiency of the fuel cell and the LED lighting, the fuel cost per lumen-hour of the H2LT is 62% of the metal halide diesel light tower assuming a kilogram of hydrogen is twice the cost of a gallon of diesel fuel.« less

  9. Metallotropic liquid crystals formed by surfactant templating of molten metal halides.

    PubMed

    Martin, James D; Keary, Cristin L; Thornton, Todd A; Novotnak, Mark P; Knutson, Jeremey W; Folmer, Jacob C W

    2006-04-01

    Liquid crystals consist of anisotropic molecular units, and most are organic molecules. Materials incorporating metals into anisotropic molecules, described as metallomesogens, have been prepared. Anisotropic structures such as one-dimensional chains and two-dimensional layers are frequently observed in solid-state inorganic materials, however, little is understood about structural organization in melts of such materials. Achieving liquid-crystalline behaviour in inorganic fluids should be possible if the anisotropic structure can be retained or designed into the molten phase. We demonstrated the ability to engineer zeolite-type structures into metal halide glasses and liquids. In this work we have engineered lamellar, cubic and hexagonal liquid-crystalline structure in metal-halide melts by controlling the volume fraction and nature of the inorganic block (up to 80 mol%) with respect to alkylammonium surfactants. The high metal content of these liquid-crystalline systems significantly advances the field of metallomesogens, which seeks to combine magnetic, electronic, optical, redox and catalytic properties common to inorganic materials with the fluid properties of liquid crystals. PMID:16547520

  10. Alkali metal/halide thermal energy storage systems performance evaluation

    NASA Technical Reports Server (NTRS)

    Phillips, W. M.; Stearns, J. W.

    1986-01-01

    A pseudoheat-pipe heat transfer mechanism has been demonstrated effective in terms of both total heat removal efficiency and rate, on the one hand, and system isothermal characteristics, on the other, for solar thermal energy storage systems of the kind being contemplated for spacecraft. The selection of appropriate salt and alkali metal substances for the system renders it applicable to a wide temperature range. The rapid heat transfer rate obtainable makes possible the placing of the thermal energy storage system around the solar receiver canister, and the immersing of heat transfer fluid tubes in the phase change salt to obtain an isothermal heat source.

  11. Alkali Metal Halide Salts as Interface Additives to Fabricate Hysteresis-Free Hybrid Perovskite-Based Photovoltaic Devices.

    PubMed

    Wang, Lili; Moghe, Dhanashree; Hafezian, Soroush; Chen, Pei; Young, Margaret; Elinski, Mark; Martinu, Ludvik; Kéna-Cohen, Stéphane; Lunt, Richard R

    2016-09-01

    A new method was developed for doping and fabricating hysteresis-free hybrid perovskite-based photovoltaic devices by using alkali metal halide salts as interface layer additives. Such salt layers introduced at the perovskite interface can provide excessive halide ions to fill vacancies formed during the deposition and annealing process. A range of solution-processed halide salts were investigated. The highest performance of methylammonium lead mixed-halide perovskite device was achieved with a NaI interlayer and showed a power conversion efficiency of 12.6% and a hysteresis of less than 2%. This represents a 90% improvement compared to control devices without this salt layer. Through depth-resolved mass spectrometry, optical modeling, and photoluminescence spectroscopy, this enhancement is attributed to the reduction of iodide vacancies, passivation of grain boundaries, and improved hole extraction. Our approach ultimately provides an alternative and facile route to high-performance and hysteresis-free perovskite solar cells. PMID:27532662

  12. Structural and up-conversion luminescence properties in Tm3+/Yb3+-codoped heavy metal oxide-halide glasses.

    PubMed

    Sun, Hongtao; Duan, Zhongchao; Zhou, Gang; Yu, Chunlei; Liao, Meisong; Hu, Lili; Zhang, Junjie; Jiang, Zhonghong

    2006-01-01

    Tm3+/Yb3+-codoped heavy metal oxide-halide glasses have been synthesized by conventional melting and quenching method. Structural properties were obtained based on the Raman spectra, indicating that halide ion has an important influence on the phonon density and maximum phonon energy of host glasses. Intense blue and weak red emissions centered at 477 and 650 nm, corresponding to the transitions 1G4-->3H6 and 1G4-->3H4, respectively, were observed at room temperature. The possible up-conversion mechanisms are discussed and estimated. With increasing halide content, the up-conversion luminescence intensity and blue luminescence lifetimes of Tm3+ ion increase notably. Our results show that with the substitution of halide ion for oxygen ion, the decrease of phonon density and maximum phonon energy of host glasses both contribute to the enhanced up-conversion emissions. PMID:15950531

  13. Highly Tunable Colloidal Perovskite Nanoplatelets through Variable Cation, Metal, and Halide Composition.

    PubMed

    Weidman, Mark C; Seitz, Michael; Stranks, Samuel D; Tisdale, William A

    2016-08-23

    Colloidal perovskite nanoplatelets are a promising class of semiconductor nanomaterials-exhibiting bright luminescence, tunable and spectrally narrow absorption and emission features, strongly confined excitonic states, and facile colloidal synthesis. Here, we demonstrate the high degree of spectral tunability achievable through variation of the cation, metal, and halide composition as well as nanoplatelet thickness. We synthesize nanoplatelets of the form L2[ABX3]n-1BX4, where L is an organic ligand (octylammonium, butylammonium), A is a monovalent metal or organic molecular cation (cesium, methylammonium, formamidinium), B is a divalent metal cation (lead, tin), X is a halide anion (chloride, bromide, iodide), and n-1 is the number of unit cells in thickness. We show that variation of n, B, and X leads to large changes in the absorption and emission energy, while variation of the A cation leads to only subtle changes but can significantly impact the nanoplatelet stability and photoluminescence quantum yield (with values over 20%). Furthermore, mixed halide nanoplatelets exhibit continuous spectral tunability over a 1.5 eV spectral range, from 2.2 to 3.7 eV. The nanoplatelets have relatively large lateral dimensions (100 nm to 1 μm), which promote self-assembly into stacked superlattice structures-the periodicity of which can be adjusted based on the nanoplatelet surface ligand length. These results demonstrate the versatility of colloidal perovskite nanoplatelets as a material platform, with tunability extending from the deep-UV, across the visible, into the near-IR. In particular, the tin-containing nanoplatelets represent a significant addition to the small but increasingly important family of lead- and cadmium-free colloidal semiconductors. PMID:27471862

  14. Alkaline and alkaline earth metal phosphate halides and phosphors

    SciTech Connect

    Lyons, Robert Joseph; Setlur, Anant Achyut; Cleaver, Robert John

    2012-11-13

    Compounds, phosphor materials and apparatus related to nacaphite family of materials are presented. Potassium and rubidium based nacaphite family compounds and phosphors designed by doping divalent rare earth elements in the sites of alkaline earth metals in the nacaphite material families are descried. An apparatus comprising the phosphors based on the nacaphite family materials are presented herein. The compounds presented is of formula A.sub.2B.sub.1-yR.sub.yPO.sub.4X where the elements A, B, R, X and suffix y are defined such that A is potassium, rubidium, or a combination of potassium and rubidium and B is calcium, strontium, barium, or a combination of any of calcium, strontium and barium. X is fluorine, chlorine, or a combination of fluorine and chlorine, R is europium, samarium, ytterbium, or a combination of any of europium, samarium, and ytterbium, and y ranges from 0 to about 0.1.

  15. Voltage-gated metal-enhanced fluorescence.

    PubMed

    Zhang, Yongxia; Aslan, Kadir; Geddes, Chris D

    2009-03-01

    We demonstrate the influence of electrical current on the ability of surface plasmons to amplify fluorescence signatures. An applied direct current across Silver Island Films (SIFs) of low electrical resistance perturbs the fluorescence enhancement. For a given applied current, surface plasmons in just-continuous films are sparsely available for fluorophore dipole-coupling and hence the enhanced fluorescence is gated as a function of the applied current. For thicker, low resistance films, sufficient charge carriers are now present in the metal that metal-enhanced fluorescence (MEF) is perturbed to a lesser extent, induced surface plasmons readily formed on the surface by the close-proximity dipole. PMID:19214719

  16. Metal Hydride and Alkali Halide Opacities in Extrasolar Giant Planets and Cool Stellar Atmospheres

    NASA Technical Reports Server (NTRS)

    Weck, Philippe F.; Stancil, Phillip C.; Kirby, Kate; Schweitzer, Andreas; Hauschildt, Peter H.

    2006-01-01

    The lack of accurate and complete molecular line and continuum opacity data has been a serious limitation to developing atmospheric models of cool stars and Extrasolar Giant Planets (EGPs). We report our recent calculations of molecular opacities resulting from the presence of metal hydrides and alkali halides. The resulting data have been included in the PHOENIX stellar atmosphere code (Hauschildt & Baron 1999). The new models, calculated using spherical geometry for all gravities considered, also incorporate our latest database of nearly 670 million molecular lines, and updated equations of state.

  17. Light emission of metal halide lamps under micro- and hypergravity conditions

    SciTech Connect

    Stoffels, W.W.; Kemps, P.C.M.; Beckers, J.; Kroesen, G.M.W.; Haverlag, M.

    2005-12-12

    The wavelength-integrated light output from a metal halide discharge lamp is measured for gravity conditions varying from 0 to 1.8 g during parabolic flights. The results show that the changing gravity affects the convection flow in the lamp, which in turn changes the total light output. For vertically burning lamps, the sign and magnitude of the effect can be predicted using the demixing parameter: the ratio of typical diffusion to convection times. In horizontally burning lamps at 0 g, the absence of convective mixing results in a reduced light emission.

  18. Helical instability in metal halide lamps under micro and hypergravity conditions

    SciTech Connect

    Stoffels, W.W.; Hout, F. van den; Kroesen, G.M.W.; Haverlag, M.; Keijser, R.

    2006-02-27

    The onset and rotation frequency of a helical instability in a metal halide lamp is studied for gravity conditions varying from microgravity to 1.8g during parabolic flights and at microgravity in the International Space Station. The results show that gravity-induced convection seriously alters the onset and behavior of the instability. Hypergravity and low lamp power increase the rotation frequency of the instability, which seems independent of the arc pressure. At microgravity conditions, only arc bending and no rotation has been observed. The arc bending increases with lamp power, allowing one to monitor the driving and damping forces of the instability.

  19. Solubility of alkali metal halides in the ionic liquid [C4C1im][OTf].

    PubMed

    Kuzmina, O; Bordes, E; Schmauck, J; Hunt, P A; Hallett, J P; Welton, T

    2016-06-28

    The solubilities of the metal halides LiF, LiCl, LiBr, LiI, NaF, NaCl, NaBr, NaI, KF, KCl, KBr, KI, RbCl, CsCl, CsI, were measured at temperatures ranging from 298.15 to 378.15 K in the ionic liquid 1-butyl-3-methylimidazolium trifluoromethanesulfonate ([C4C1im][OTf]). Li(+), Na(+) and K(+) salts with anions matching the ionic liquid have also been investigated to determine how well these cations dissolve in [C4C1im][OTf]. This study compares the influence of metal cation and halide anion on the solubility of salts within this ionic liquid. The highest solubility found was for iodide salts, and the lowest solubility for the three fluoride salts. There is no outstanding difference in the solubility of salts with matching anions in comparison to halide salts. The experimental data were correlated employing several phase equilibria models, including ideal mixtures, van't Hoff, the λh (Buchowski) equation, the modified Apelblat equation, and the non-random two-liquid model (NRTL). It was found that the van't Hoff model gave the best correlation results. On the basis of the experimental data the thermodynamic dissolution parameters (ΔH, ΔS, and ΔG) were determined for the studied systems together with computed gas phase metathesis parameters. Dissolution depends on the energy difference between enthalpies of fusion and dissolution of the solute salt. This demonstrates that overcoming the lattice energy of the solid matrix is the key to the solubility of inorganic salts in ionic liquids. PMID:27264676

  20. An above-room-temperature ferroelectric organo-metal halide perovskite: (3-pyrrolinium)(CdCl₃).

    PubMed

    Ye, Heng-Yun; Zhang, Yi; Fu, Da-Wei; Xiong, Ren-Gen

    2014-10-13

    Hybrid organo-metal halide perovskite materials, such as CH3NH3PbI3, have been shown to be some of the most competitive candidates for absorber materials in photovoltaic (PV) applications. However, their potential has not been completely developed, because a photovoltaic effect with an anomalously large voltage can be achieved only in a ferroelectric phase, while these materials are probably ferroelectric only at temperatures below 180 K. A new hexagonal stacking perovskite-type complex (3-pyrrolinium)(CdCl3) exhibits above-room-temperature ferroelectricity with a Curie temperature T(c)=316 K and a spontaneous polarization P(s)=5.1 μC cm(-2). The material also exhibits antiparallel 180° domains which are related to the anomalous photovoltaic effect. The open-circuit photovoltage for a 1 mm-thick bulky crystal reaches 32 V. This finding could provide a new approach to develop solar cells based on organo-metal halide perovskites in photovoltaic research. PMID:25196506

  1. Transition metal ion-assisted photochemical generation of alkyl halides and hydrocarbons from carboxylic acids

    SciTech Connect

    Carraher, Jack; Pestovsky, Oleg; Bakac, Andreja

    2012-03-14

    Near-UV photolysis of aqueous solutions of propionic acid and aqueous Fe3+ in the absence of oxygen generates a mixture of hydrocarbons (ethane, ethylene and butane), carbon dioxide, and Fe2+. The reaction becomes mildly catalytic (about five turnovers) in the presence of oxygen which converts a portion of alkyl radicals to oxidizing intermediates that reoxidize Fe2+. The photochemistry in the presence of halide ions (X− = Cl−, Br−) generates ethyl halides via halogen atom abstraction from FeXn3−n by ethyl radicals. Near-quantitative yields of C2H5X are obtained at ≥0.05 M X−. Competition experiments with Co(NH3)5Br2+ provided kinetic data for the reaction of ethyl radicals with FeCl2+ (k = (4.0 ± 0.5) × 106 M−1 s−1) and with FeBr2+ (k = (3.0 ± 0.5) × 107 M−1 s−1). Photochemical decarboxylation of propionic acid in the presence of Cu2+ generates ethylene and Cu+. Longer-chain acids also yield alpha olefins as exclusive products. These reactions become catalytic under constant purge with oxygen which plays a dual role. It reoxidizes Cu+ to Cu2+, and removes gaseous olefins to prevent accumulation of Cu+(olefin) complexes and depletion of Cu2+. The results underscore the profound effect that the choice of metal ions, the medium, and reaction conditions exert on the photochemistry of carboxylic acids.

  2. Promotion of the halide effect in the formation of shaped metal nanocrystals via a hybrid cationic, polymeric stabilizer: Octahedra, cubes, and anisotropic growth

    NASA Astrophysics Data System (ADS)

    Sneed, Brian T.; Golden, Matthew C.; Liu, Yejing; Lee, Hiang K.; Andoni, Ilektra; Young, Allison P.; McMahon, Greg; Erdman, Natasha; Shibata, Masateru; Ling, Xing Yi; Tsung, Chia-Kuang

    2016-06-01

    To promote the effect of halide ions (Cl-, Br-, and I-) in facet-selective growth of {111} and {100} of shaped metal nanocrystals, we utilize PDADMAC, a hybrid cationic, polymeric stabilizer. SERS and synthesis experiments provide evidence supporting that the higher amount of PDADMA+ at surfaces promotes the local adsorption of halides, allowing the creation of Pd cubes, octahedra, and cuboctopods.

  3. Double-ended metal halide arc discharge lamp with electrically isolated containment shroud

    NASA Technical Reports Server (NTRS)

    Muzeroll, Martin M. (Inventor)

    1994-01-01

    A double-ended arc discharge lamp includes a sealed, light-transmissive outer jacket, a light-transmissive shroud mounted within the outer jacket and directly supported by the outer jacket, and an arc discharge tube mounted within the shroud. The arc tube is typically a metal halide arc discharge tube. In a preferred embodiment, the shroud includes an outwardly flared portion at each end. The outwardly flared portions space the shroud from the outer jacket and support the shroud within the outer jacket. The outwardly flared portions of the shroud can be affixed to the outer jacket by fusing. The outer jacket can be provided with inwardly extending dimples for locating the shroud with respect to the outer jacket. In another embodiment, the outer jacket includes reduced diameter portions near each end which are attached to the shroud.

  4. Silicon Halide-alkali Metal Flames as a Source of Solar Grade Silicon

    NASA Technical Reports Server (NTRS)

    Olson, D. B.; Gould, R. K.

    1979-01-01

    A program is presented which was aimed at determining the feasibility of using high temperature reactions of alkali metals and silicon halides to produce low cost solar-grade silicon. Experiments are being conducted to evaluate product separation and collection processes, measure heat release parameters for scaling purposes, and determine the effects of the reactants and/or products on materials of reactor construction. During the current reporting period, the results of heat release experiments were used to design and construct a new type of thick-wall graphite reactor to produce larger quantities of silicon. A reactor test facility was constructed. Material compatibility tests were performed for Na in contact with graphite and several coated graphites. All samples were rapidly degraded at T = 1200K, while samples retained structural strength at 1700K. Pyrolytic graphite coatings cracked and separated from substances in all cases.

  5. Integrated Photoelectrolysis of Water Implemented On Organic Metal Halide Perovskite Photoelectrode.

    PubMed

    Hoang, Minh Tam; Pham, Ngoc Duy; Han, Ji Hun; Gardner, James M; Oh, Ilwhan

    2016-05-18

    Herein we report on integrated photoelectrolysis of water employing organic metal halide (OMH) perovskite material. Generic OMH perovskite material and device architecture are highly susceptible to degradation by moisture and water. We found that decomposition of perovskite devices proceeds by water ingress through pinholes in upper layers and is strongly affected by applied bias/light and electrolyte pH. It was also found that a pinhole-free hole transport layer (HTL) could significantly enhance the stability of the perovskite photoelectrode, thereby extending the photoelectrode lifetime to several tens of minutes, which is an unprecedented record-long operation. Furthermore, a carbon nanotube (CNT)/polymer composite layer was developed that can effectively protect the underlying perovskite layer from electrolyte molecules. PMID:27120406

  6. Radiative properties of ceramic metal-halide high intensity discharge lamps containing additives in argon plasma

    NASA Astrophysics Data System (ADS)

    Cressault, Yann; Teulet, Philippe; Zissis, Georges

    2016-07-01

    The lighting represents a consumption of about 19% of the world electricity production. We are thus searching new effective and environment-friendlier light sources. The ceramic metal-halide high intensity lamps (C-MHL) are one of the options for illuminating very high area. The new C-MHL lamps contain additives species that reduce mercury inside and lead to a richer spectrum in specific spectral intervals, a better colour temperature or colour rendering index. This work is particularly focused on the power radiated by these lamps, estimated using the net emission coefficient, and depending on several additives (calcium, sodium, tungsten, dysprosium, and thallium or strontium iodides). The results show the strong influence of the additives on the power radiated despite of their small quantity in the mixtures and the increase of visible radiation portion in presence of dysprosium.

  7. Charge Transfer Dynamics between Carbon Nanotubes and Hybrid Organic Metal Halide Perovskite Films.

    PubMed

    Schulz, Philip; Dowgiallo, Anne-Marie; Yang, Mengjin; Zhu, Kai; Blackburn, Jeffrey L; Berry, Joseph J

    2016-02-01

    In spite of the rapid rise of metal organic halide perovskites for next-generation solar cells, little quantitative information on the electronic structure of interfaces of these materials is available. The present study characterizes the electronic structure of interfaces between semiconducting single walled carbon nanotube (SWCNT) contacts and a prototypical methylammonium lead iodide (MAPbI3) absorber layer. Using photoemission spectroscopy we provide quantitative values for the energy levels at the interface and observe the formation of an interfacial dipole between SWCNTs and perovskite. This process can be ascribed to electron donation from the MAPbI3 to the adjacent SWCNT making the nanotube film n-type at the interface and inducing band bending throughout the SWCNT layer. We then use transient absorbance spectroscopy to correlate this electronic alignment with rapid and efficient photoexcited charge transfer. The results indicate that SWCNT transport and contact layers facilitate rapid charge extraction and suggest avenues for enhancing device performance. PMID:26757105

  8. Metal-halide perovskites for photovoltaic and light-emitting devices.

    PubMed

    Stranks, Samuel D; Snaith, Henry J

    2015-05-01

    Metal-halide perovskites are crystalline materials originally developed out of scientific curiosity. Unexpectedly, solar cells incorporating these perovskites are rapidly emerging as serious contenders to rival the leading photovoltaic technologies. Power conversion efficiencies have jumped from 3% to over 20% in just four years of academic research. Here, we review the rapid progress in perovskite solar cells, as well as their promising use in light-emitting devices. In particular, we describe the broad tunability and fabrication methods of these materials, the current understanding of the operation of state-of-the-art solar cells and we highlight the properties that have delivered light-emitting diodes and lasers. We discuss key thermal and operational stability challenges facing perovskites, and give an outlook of future research avenues that might bring perovskite technology to commercialization. PMID:25947963

  9. Hydrophobic Organic Hole Transporters for Improved Moisture Resistance in Metal Halide Perovskite Solar Cells.

    PubMed

    Leijtens, Tomas; Giovenzana, Tommaso; Habisreutinger, Severin N; Tinkham, Jonathan S; Noel, Nakita K; Kamino, Brett A; Sadoughi, Golnaz; Sellinger, Alan; Snaith, Henry J

    2016-03-01

    Solar cells based on organic-inorganic perovskite semiconductor materials have recently made rapid improvements in performance, with the best cells performing at over 20% efficiency. With such rapid progress, questions such as cost and solar cell stability are becoming increasingly important to address if this new technology is to reach commercial deployment. The moisture sensitivity of commonly used organic-inorganic metal halide perovskites has especially raised concerns. Here, we demonstrate that the hygroscopic lithium salt commonly used as a dopant for the hole transport material in perovskite solar cells makes the top layer of the devices hydrophilic and causes the solar cells to rapidly degrade in the presence of moisture. By using novel, low cost, and hydrophobic hole transporters in conjunction with a doping method incorporating a preoxidized salt of the respective hole transporters, we are able to prepare efficient perovskite solar cells with greatly enhanced water resistance. PMID:26859777

  10. Efficient destruction of CF4 through in situ generation of alkali metals from heated alkali halide reducing mixtures.

    PubMed

    Lee, Myung Churl; Choi, Wonyong

    2002-03-15

    Perfluorocarbons (PFCs) are the most potent green house gases that are very recalcitrant at destruction. An effective way of converting PFCs using hot solid reagents into safe products has been recently introduced. By investigating the thermal reductive destruction of tetrafluoromethane (CF4) we provided new insight and more physicochemical consideration on this novel process. The complete destruction of CF4was successfully achieved by flowing the gas through a heated reagent bed (400-950 degrees C) that contained powder mixtures of alkali halides, CaO, and Si. The silicon acted as a reducing agent of alkali halides for the in-situ production of alkali metals, and the calcium oxide played the role of a halide ion acceptor. The absence of any single component in this ternary mixture drastically reduced the destruction efficiency of CF4. The CF4 destruction efficiencies with the solid reagent containing the alkali halide, MX, increased in the order of Li approximately Na < K < Cs for alkali cations and I < Br < Cl < F for halide anions. This trend agreed with the endothermicity of the alkali metal generation reaction: the higher the endothermicity, the lower the destruction efficiency. Alkali metal generation was indirectly detected by monitoring H2 production from its reaction with water. The production of alkali metals increased with NaF, KF, and CsF in this order. The CsF/CaO/Si system exhibited the complete destruction of CF4 at as low as 600 degrees C. The solid product analysis by X-ray diffraction (XRD) showed the formation of CaF2 and the depletion of Si with black carbon particles formed in the solid reagent residue. No CO/CO2 and toxic HF and SiF4 formation were detected in the exhaust gas. PMID:11944694

  11. Fluorescence enhancement aided by metal ion displacement.

    PubMed

    Susini, Vanessa; Ienco, Andrea; Lucia Rossi, Veronica; Paolicchi, Aldo; Sanesi, Antonio

    2016-06-15

    Immunosensors are one of the most common platform used in clinical laboratories, in particular the class based on Enzyme Linked Fluorescent Assays (ELFA) takes advantage of the amplification step of the enzyme, usually the alkaline phosphatase, that catalyzes the hydrolysis of a fluorescent substrate leading it to fluoresce. Anyway, they suffer in sensitivity if compared to molecular diagnostic or more modern in vitro diagnostic devices. In our work, a simple and effective mechanism to enhance the fluorescent signal, and hence the sensitivity of the system, is presented. It is based on the metal ion displacement principle in which a second fluorophore, in our case Calcein Blue, quenched by a cobalt ion is add to the first one (4-MUP), and, in presence of inorganic phosphate, it will be progressively activated by the inorganic phosphate itself leading to the metal displacement. In this way Calcein Blue, newly free to fluoresce, contributes to global fluorescent signal generated by 4-MU. We have tested our proof of principle on a currently used immunoanalyzer, that is VIDAS® system (bioMérieux, Marcy l'Etoile, France) obtaining a fluorescence enhancement of about 50% for each concentration of hydrolyzed 4-MUP tested. PMID:26851581

  12. Transient Absorption and Time-Resolved Fluorescence Studies of Solvated Ruthenium Di-Bipyridine Pseudo-Halide Complexes

    NASA Astrophysics Data System (ADS)

    Compton, R.; Weidinger, D.; Owrutsky, J. C.

    2012-06-01

    Time-resolved IR and fluorescence measurements were performed to probe the vibrational and electronic properties, respectively, of ruthenium di-bipyridine pseudo-halide (Ru(Bpy){_2}(X){_2} (where X = CN, N{_3} or NCS)) complexes. Vibrational energy relaxation (VER) times were determined for the complexes dissolved in dimethyl sulfoxide (DMSO) with a trend in VER time of NCS > CN > N{_3}. A similar trend and comparable absolute rates for NCS- and N3- were previously observed by our group and others for simple inorganic anions in solution, suggesting a minimal contribution due to complexation. Measurements of the VER time of the CN complex in various solvents provide VER times in ethanol (42.3 ps) and DMSO (53.3 ps), which shows that protic solvents promote the relaxation. Time-resolved fluorescence measurements indicate a strong ligand dependence, with a factor of five decrease in the excited electronic state decay time from the CN (215 ns) to the NCS (39 ns) complex. A solvent dependence of the CN complex reveals a nearly 3-fold increase in the fluorescence decay time from acetonitrile (70 ns) to DMSO (215 ns).

  13. Metallic halide lights and lighting systems. (Latest citations from the US Patent Bibliographic file with exemplary claims). Published Search

    SciTech Connect

    Not Available

    1994-11-01

    The bibliography contains citations of selected patents concerning the design and operation of metallic halide lights and lighting systems. High pressure, high intensity, and low wattage discharge lamps are described. Citations discuss power sources, lamp life, lamp control circuits, thermal switches, and heat reflective coatings. Applications in sport stadium lighting, vehicle headlights, and crop-lighting are included. (Contains a minimum of 170 citations and includes a subject term index and title list.)

  14. Silicon halide-alkali metal flames as a source of solar grade silicon

    NASA Technical Reports Server (NTRS)

    Olson, D. B.; Miller, W. J.; Gould, R. K.

    1980-01-01

    The feasibility of using continuous high-temperature reactions of alkali metals and silicon halides to produce silicon in large quantities and of suitable purity for use in the production of photovoltaic solar cells was demonstrated. Low pressure experiments were performed demonstrating the production of free silicon and providing experience with the construction of reactant vapor generators. Further experiments at higher reagent flow rates were performed in a low temperature flow tube configuration with co-axial injection of reagents and relatively pure silicon was produced. A high temperature graphite flow tube was built and continuous separation of Si from NaCl was demonstrated. A larger scaled well stirred reactor was built. Experiments were performed to investigate the compatability of graphite based reactor materials of construction with sodium. At 1100 to 1200 K none of these materials were found to be suitable. At 1700 K the graphites performed well with little damage except to coatings of pyrolytic graphite and silicon carbide which were damaged.

  15. Silicon halide-alkali metal flames as a source of solar grade silicon

    NASA Technical Reports Server (NTRS)

    Olsen, D. B.; Miller, W. J.

    1979-01-01

    The feasibility of using alkali metal-silicon halide diffusion flames to produce solar-grade silicon in large quantities and at low cost is demonstrated. Prior work shows that these flames are stable and that relatively high purity silicon can be produced using Na + SiCl4 flames. Silicon of similar purity is obtained from Na + SiF4 flames although yields are lower and product separation and collection are less thermochemically favored. Continuous separation of silicon from the byproduct alkali salt was demonstrated in a heated graphite reactor. The process was scaled up to reduce heat losses and to produce larger samples of silicon. Reagent delivery systems, scaled by a factor of 25, were built and operated at a production rate of 0.5 kg Si/h. Very rapid reactor heating rates are observed with wall temperatures reaching greater than 2000 K. Heat release parameters were measured using a cooled stainless steel reactor tube. A new reactor was designed.

  16. Charge-Carrier Dynamics in Organic-Inorganic Metal Halide Perovskites.

    PubMed

    Herz, Laura M

    2016-05-27

    Hybrid organic-inorganic metal halide perovskites have recently emerged as exciting new light-harvesting and charge-transporting materials for efficient photovoltaic devices. Yet knowledge of the nature of the photogenerated excitations and their subsequent dynamics is only just emerging. This article reviews the current state of the field, focusing first on a description of the crystal and electronic band structure that give rise to the strong optical transitions that enable light harvesting. An overview is presented of the numerous experimental approaches toward determining values for exciton binding energies, which appear to be small (a few milli-electron volts to a few tens of milli-electron volts) and depend significantly on temperature because of associated changes in the dielectric function. Experimental evidence for charge-carrier relaxation dynamics within the first few picoseconds after excitation is discussed in terms of thermalization, cooling, and many-body effects. Charge-carrier recombination mechanisms are reviewed, encompassing trap-assisted nonradiative recombination that is highly specific to processing conditions, radiative bimolecular (electron-hole) recombination, and nonradiative many-body (Auger) mechanisms. PMID:26980309

  17. Metal-encapsulated organolead halide perovskite photocathode for solar-driven hydrogen evolution in water.

    PubMed

    Crespo-Quesada, Micaela; Pazos-Outón, Luis M; Warnan, Julien; Kuehnel, Moritz F; Friend, Richard H; Reisner, Erwin

    2016-01-01

    Lead-halide perovskites have triggered the latest breakthrough in photovoltaic technology. Despite the great promise shown by these materials, their instability towards water even in the presence of low amounts of moisture makes them, a priori, unsuitable for their direct use as light harvesters in aqueous solution for the production of hydrogen through water splitting. Here, we present a simple method that enables their use in photoelectrocatalytic hydrogen evolution while immersed in an aqueous solution. Field's metal, a fusible InBiSn alloy, is used to efficiently protect the perovskite from water while simultaneously allowing the photogenerated electrons to reach a Pt hydrogen evolution catalyst. A record photocurrent density of -9.8 mA cm(-2) at 0 V versus RHE with an onset potential as positive as 0.95±0.03 V versus RHE is obtained. The photoelectrodes show remarkable stability retaining more than 80% of their initial photocurrent for ∼1 h under continuous illumination. PMID:27595974

  18. A Survey of Infrared Continuum verses Line Radiation from Metal Halide

    NASA Astrophysics Data System (ADS)

    Kato, M.; Herd, M. T.; Lawler, J. E.

    2007-10-01

    Near-infrared radiation (near-IR) losses from the arc of six commercial Metal Halide High Intensity Discharge (MH-HID) lamps with various power levels and with both Na/Sc and rare earth doses were surveyed in this paper. A radiometrically calibrated Fourier transform infrared spectrometer was used. Lamps with rare earth doses have appreciably better Color Rendering Indices (CRI's) than lamps with Na/Sc doses. The ratios of near-IR continuum emission over near-IR line emission from these six lamps were compared. The near-IR continuum dominates near-IR losses from lamps with rare earth doses and the continuum is significant, but not dominant, from lamps with Na/Sc doses. There was no strong dependence of this ratio on input power or Color Temperature (Tc). Total near-IR losses were estimated using absolutely calibrated, horizontal irradiance measurements. Estimated total near-IR losses were correlated with CRI. The lamps with rare earth doses yield the best CRI's, but have appreciably higher near-IR losses due primarily to continuum processes. One of these rare earth MH-HID lamps was used in a more detailed study of the microscopic physics of the continuum mechanism[M. T. Herd & J. E. Lawler, J. Phys. D 40, 3386 (2007)].

  19. A survey of infrared continuum versus line radiation from metal halide lamps

    NASA Astrophysics Data System (ADS)

    Kato, M.; Herd, M. T.; Lawler, J. E.

    2008-07-01

    Near-infrared radiation (near-IR) losses from the arcs of six commercial metal halide high intensity discharge (MH-HID) lamps with various power levels and with both Na/Sc and rare earth doses were surveyed in this paper. A radiometrically calibrated Fourier transform infrared spectrometer was used. Lamps with rare earth doses have appreciably better color rendering indices (CRIs) than lamps with Na/Sc doses. The ratios of near-IR continuum emission over near-IR line emission from these six lamps were compared. The near-IR continuum dominates near-IR losses from lamps with rare earth doses and the continuum is significant, but not dominant, from lamps with Na/Sc doses. There was no strong dependence of this ratio on input power or color temperature (Tc). Total near-IR losses were estimated using absolutely calibrated, horizontal irradiance measurements. Estimated total near-IR losses were correlated with CRI. The lamps with rare earth doses yield the best CRIs, but have appreciably higher near-IR losses due primarily to continuum processes. One of these rare earth MH-HID lamps was used in a more detailed study of the microscopic physics of the continuum mechanism (Herd M T and Lawler E 2007 J. Phys. D: Appl. Phys. 40 3386).

  20. Polarizable intermolecular potentials for water and benzene interacting with halide and metal ions

    PubMed Central

    Archambault, Fabien; Soteras, Ignacio; Luque, F. Javier; Schulten, Klaus

    2010-01-01

    A complete derivation of polarizable intermolecular potentials based on high-level, gas-phase quantum-mechanical calculations is proposed. The importance of appreciable accuracy together with inherent simplicity represents a significant endeavor when enhancement of existing force fields for biological systems is sought. Toward this end, symmetry-adapted perturbation theory (SAPT) can provide an expansion of the total interaction energy into physically meaningful e.g. electrostatic, induction and van der Waals terms. Each contribution can be readily compared with its counterpart in classical force fields. Since the complexity of the different intermolecular terms cannot be fully embraced using a minimalist description, it is necessary to resort to polyvalent expressions capable of encapsulating overlooked contributions from the quantum-mechanical expansion. This choice results in consistent force field components that reflect the underlying physical principles of the phenomena. This simplified potential energy function is detailed and definitive guidelines are drawn. As a proof of concept, the methodology is illustrated through a series of test cases that include the interaction of water and benzene with halide and metal ions. In each case considered, the total energy is reproduced accurately over a range of biologically relevant distances. PMID:21113276

  1. Spectral Changes in Metal Halide and High-Pressure Sodium Lamps Equipped with Electronic Dimming

    NASA Technical Reports Server (NTRS)

    Bubenheim, David L.; Sargis, Raman; Wilson, David

    1995-01-01

    Electronic dimming of high-intensity discharge lamps offers control of Photosynthetic Photon Flux (PPF) but is often characterized as causing significant spectral changes. Growth chambers with 400-W Metal Halide (MH) and High-Pressure Sodium (HPS) lamps were equipped with a dimmer system using Silicon-Controlled Rectifiers (SCR) as high-speed switches. Phase control operation turned the line power off for some period of the alternating current cycle. At full power, the electrical input to HPS and MH lamps was 480 W (root mean squared) and could be decreased to 267 W and 428 W, respectively, before the arc was extinguished. Concomitant with this decrease in input power, PPF decreased by 60% in HPS and 50% in MH. The HPS lamp has characteristic spectral peaks at 589 and 595 nm. As power to the HPS lamps was decreased, the 589-nm peak remained constant while the 595-nm peak decreased, equaling the 589-nm peak at 345-W input, and 589-nm peak was almost absent at 270-W input. The MH lamp has a broader spectral output but also has a peak at 589 nm and another smaller peak at 545 nm. As input power approached 428 W, the 589-nm peak shifted to 570 nm. While the spectrum changed as input power was decreased in the MH and HPS lamps, the phytochrome equilibrium ratio (P(sub ft):P(sub tot)) remains unchanged for both lamp types.

  2. Liquid-crystal luminaire consisting of an optical shutter and a metal halide lamp.

    PubMed

    Takizawa, K; Fujii, T; Fujikake, H; Hirabayashi, T; Tanaka, Y; Hara, K; Takano, S; Asakawa, H; Kita, H

    1999-04-20

    We made a liquid-crystal (LC) luminaire for the first time to our knowledge by combining a metal halide lamp and an optical shutter composed of a compound of a very high nematic-isotropic point (172 degrees C) LC and a polymer (CLCP). The shutter can modulate high-power light independently of the state of polarization because the CLCP film becomes transparent or opalescent when either sufficiently high or no voltage is applied to it. To solve the problem, which is peculiar to CLCP films, that the color temperature of light modulated by the film changes with the film's transmittance, a pulse-width modulation method that varies the time ratio of the on and off states of the shutter was developed. The performance characteristics of the luminaire were as follows: illuminance range, 192 to 10,400 lx at a distance of 5 m from the luminaire; rise and decay times, 1.4 and 1.5 ms; color temperature, 4060-5600 K; operation room temperature, approximately 150 degrees C; stable operation time, more than 2000 h. Experimental results show the feasibility of applications of this luminaire in various fields, including television, movie, and stage lighting. PMID:18319829

  3. Microstructured hydroxyl environments and Raman spectroscopy in selected basic transition-metal halides

    NASA Astrophysics Data System (ADS)

    Liu, Xiao-Dong; Meng, Dong-Dong; Hagihala, Masato; Zheng, Xu-Guang

    2011-08-01

    Raman vibrational spectra of the selected basic (hydroxyl OH and deuteroxyl OD) transition-metal halides, geometrically frustrated material series α-, β-, γ-Cu2(OH)3Cl, α-Cu2(OH)3Br, β-Ni2(OH)3Cl, β-Co2(OH)3Cl, β-Co2(OH)3Br, γ-Cu2(OD)3Cl, and β-Co2(OD)3Cl are measured at room temperature and analysed to investigate the relationship between the microstructured OH environments and their respective Raman spectra. Among these selected samples, the last two are used to determine the OH stretching vibration region (3600 cm-1-3300 cm-1) and OH bending vibration region (1000 cm-1-600 cm-1) of OH systems in the spectra. Through the comparative analysis of the distances d(metal—O), d(O—halogen), and d(OH), the strong metal—O interaction and trimeric hydrogen bond (C3v, Cs or C1 symmetry) are found in every material, but both determine simultaneously an ultimate d(OH), and therefore an OH stretching vibration frequency. According to the approximately linear relationship between the OH stretching vibration frequency and d(OH), some unavailable d(OH) are guessed and some doubtful d(OH) are suggested to be corrected. In addition, it is demonstrated in brief that the OH bending vibration frequency is also of importance to check the more detailed crystal microstructure relating to the OH group.

  4. Spectral Changes in Metal Halide and High-pressure Sodium Lamps Equipped with Electronic Dimming

    NASA Technical Reports Server (NTRS)

    Bubenheim, David L.; Sargis, Raman; Wilson, David

    1995-01-01

    Electronic dimming of high-intensity discharge lamps offers control of photosynthetic photon flux (PPF) but is often characterized as causing significant spectral changes. Growth chambers with 400-W metal halide (MH) and high-pressure sodium (HPS) lamps were equipped with a dimmer system using silicon-controlled rectifiers (SCR) as high-speed switches. Phase control operation turned the line power off for some period of the alternating current cycle. At full power, the electrical input to HPS and MH lamps was 480 W (root mean squared) and could be decreased to 267 W and 428 W, respectively, before the arc was extinguished. Concomitant with this decrease in input power, PPF decreased by 60% in HPS and 50% in MH. The HPS lamp has characteristic spectral peaks at 589 and 595 nm. As power to the HPS lamps was decreased, the 589-nm peak remained constant while the 595-nm peak decreased, equaling the 589-nm peak at 345-W input, and the 589-nm peak was almost absent at 270-W input. The MH lamp has a broader spectral output but also has a peak at 589 nm and another smaller peak at 545 nm. As input power to the MH lamps decreased, the peak at 589 diminished to equal the 545-nm peak. As input power approached 428 W, the 589-nm peak shifted to 570 nm. While the spectrum changed as input power was decreased in the MH and HPS lamps, the phytochrome equilibrium ratio (P(sub fr):P(sub tot)) remains unchanged for both lamp types.

  5. Evaluation of Metal Halide, Plasma, and LED Lighting Technologies for a Hydrogen Fuel Cell Mobile Light (H 2 LT)

    SciTech Connect

    Miller, L. B.; Donohoe, S. P.; Jones, M. H.; White, W. A.; Klebanoff, L. E.; Velinsky, S. A.

    2015-04-22

    This article reports on the testing and comparison of a prototype hydrogen fuel cell light tower (H2LT) and a conventional diesel-powered metal halide light trailer for use in road maintenance and construction activities. The prototype was originally outfitted with plasma lights and then with light-emitting diode (LED) luminaires. Light output and distribution, lighting energy efficiency (i.e., efficacy), power source thermal efficiency, and fuel costs are compared. The metal halide luminaires have 2.2 and 3.1 times more light output than the plasma and LED luminaires, respectively, but they require more power/lumen to provide that output. The LED luminaires have 1.6 times better light efficacy than either the metal halide or plasma luminaires. The light uniformity ratios produced by the plasma and LED towers are acceptable. The fuel cell thermal efficiency at the power required to operate the plasma lights is 48%, significantly higher than the diesel generator efficiency of 23% when operating the metal halide lights. Due to the increased efficiency of the fuel cell and the LED lighting, the fuel cost per lumen-hour of the H2LT is 62% of the metal halide diesel light tower assuming a kilogram of hydrogen is twice the cost of a gallon of diesel fuel.

  6. Technetium dichloride : a new binary halide containing metal-metal multiple bonds.

    SciTech Connect

    Poineau, F.; Malliakas, C. D.; Weck, P. F.; Scott, B. L.; Johnstone, E. V.; Forster, P. M.; Kim, E.; Kanatzidis, M. G.; Czerwinski, K. R.; Sattelberger, A. P.

    2011-06-15

    Technetium dichloride has been discovered. It was synthesized from the elements and characterized by several physical techniques, including single crystal X-ray diffraction. In the solid state, technetium dichloride exhibits a new structure type consisting of infinite chains of face sharing [Tc{sub 2}Cl{sub 8}] rectangular prisms that are packed in a commensurate supercell. The metal-metal separation in the prisms is 2.127(2) {angstrom}, a distance consistent with the presence of a Tc {triple_bond} Tc triple bond that is also supported by electronic structure calculations.

  7. Technetium Dichloride: A New Binary Halide Containing Metal-Metal Multiple Bonds

    SciTech Connect

    Poineau, Frederic; Malliakas, Christos D.; Weck, Philippe F.; Scott, Brian L.; Johnstone, Erik V.; Forster, Paul M.; Kim, Eunja; Kanatzidis, Mercouri G.; Czerwinski, Kenneth R.; Sattelberge, Alfred P.

    2011-10-19

    Technetium dichloride has been discovered. It was synthesized from the elements and characterized by several physical techniques, including single crystal X-ray diffraction. In the solid state, technetium dichloride exhibits a new structure type consisting of infinite chains of face sharing [Tc{sub 2}Cl{sub 8}] rectangular prisms that are packed in a commensurate supercell. The metal-metal separation in the prisms is 2.127(2) {angstrom}, a distance consistent with the presence of a Tc {triple_bond} Tc triple bond that is also supported by electronic structure calculations.

  8. Further Insights into Metal-DOM Interaction: Consideration of Both Fluorescent and Non-Fluorescent Substances

    PubMed Central

    Xu, Huacheng; Zhong, Jicheng; Yu, Guanghui; Wu, Jun; Jiang, Helong; Yang, Liuyan

    2014-01-01

    Information on metal binding with fluorescent substances has been widely studied. By contrast, information on metal binding with non-fluorescent substances remains lacking despite the dominance of these substances in aquatic systems. In this study, the metal binding properties of both fluorescent and non-fluorescent substances were investigated by using metal titration combined with two-dimensional correlation spectroscopy (2D–COS) analysis. The organic matters in the eutrophic algae-rich lake, including natural organic matters (NOM) and algae-induced extracellular polymeric substances (EPS), both contained fluorescent and non-fluorescent substances. The peaks in the one-dimensional spectra strongly overlapped, while 2D–COS can decompose the overlapped peaks and thus enhanced the spectral resolution. Moreover, 2D FTIR COS demonstrated that the binding susceptibility of organic ligands in both NOM and algal EPS matrices followed the order: 3400>1380>1650 cm−1, indicative the significant contribution of non-fluorescent ligands in metal binding. The modified Stern-Volmer equation also revealed a substantial metal binding potential for the non-fluorescent substances (logKM: 3.57∼4.92). As for the effects of organic ligands on metal binding, EPS was characterized with higher binding ability than NOM for both fluorescent and non-fluorescent ligands. Algae-induced EPS and the non-fluorescent substances in eutrophic algae-rich lakes should not be overlooked because of their high metal binding potential. PMID:25380246

  9. Release of halide ions from the buried active site of the haloalkane dehalogenase LinB revealed by stopped-flow fluorescence analysis and free energy calculations.

    PubMed

    Hladilkova, Jana; Prokop, Zbynek; Chaloupkova, Radka; Damborsky, Jiri; Jungwirth, Pavel

    2013-11-21

    Release of halide ions is an essential step of the catalytic cycle of haloalkane dehalogenases. Here we describe experimentally and computationally the process of release of a halide anion from the buried active site of the haloalkane dehalogenase LinB. Using stopped-flow fluorescence analysis and umbrella sampling free energy calculations, we show that the anion binding is ion-specific and follows the ordering I(-) > Br(-) > Cl(-). We also address the issue of the protonation state of the catalytic His272 residue and its effect on the process of halide release. While deprotonation of His272 increases binding of anions in the access tunnel, we show that the anionic ordering does not change with the switch of the protonation state. We also demonstrate that a sodium cation could relatively easily enter the active site, provided the His272 residue is singly protonated, and replace thus the missing proton. In contrast, Na(+) is strongly repelled from the active site containing the doubly protonated His272 residue. Our study contributes toward understanding of the reaction mechanism of haloalkane dehalogenase enzyme family. Determination of the protonation state of the catalytic histidine throughout the catalytic cycle remains a challenge for future studies. PMID:24151979

  10. Spectral variation of fluorescence lifetime near single metal nanoparticles

    NASA Astrophysics Data System (ADS)

    Li, Jia; Krasavin, Alexey V.; Webster, Linden; Segovia, Paulina; Zayats, Anatoly V.; Richards, David

    2016-02-01

    We explore the spectral dependence of fluorescence enhancement and the associated lifetime modification of fluorescent molecules coupled to single metal nanoparticles. Fluorescence lifetime imaging microscopy and single-particle dark-field spectroscopy are combined to correlate the dependence of fluorescence lifetime reduction on the spectral overlap between the fluorescence emission and the localised surface plasmon (LSP) spectra of individual gold nanoparticles. A maximum lifetime reduction is observed when the fluorescence and LSP resonances coincide, with good agreement provided by numerical simulations. The explicit comparison between experiment and simulation, that we obtain, offers an insight into the spectral engineering of LSP mediated fluorescence and may lead to optimized application in sensing and biomedicine.

  11. Antenna induced hot restrike of a ceramic metal halide lamp recorded by high-speed photography

    NASA Astrophysics Data System (ADS)

    Hermanns, P.; Hoebing, T.; Bergner, A.; Ruhrmann, C.; Awakowicz, P.; Mentel, J.

    2016-03-01

    The hot restrike is one of the biggest challenges in operating ceramic metal halide lamps with mercury as buffer gas. Compared to a cold lamp, the pressure within a ceramic burner is two orders of magnitude higher during steady state operation due to the high temperature of the ceramic tube and the resulting high mercury vapour pressure. Room temperature conditions are achieved after 300 s of cooling down in a commercial burner, enclosed in an evacuated outer bulb. At the beginning of the cooling down, ignition voltage rises up to more than 14 kV. A significant reduction of the hot-restrike voltage can be achieved by using a so called active antenna. It is realized by a conductive sleeve surrounding the burner at the capillary of the upper electrode. The antenna is connected to the lower electrode of the lamp, so that its potential is extended to the vicinity of the upper electrode. An increased electric field in front of the upper electrode is induced, when an ignition pulse is applied to the lamp electrodes. A symmetrically shaped ignition pulse is applied with an amplitude, which is just sufficient to re-ignite the hot lamp. The re-ignition, 60 s after switching off the lamp, when the mercury pressure starts to be saturated, is recorded for both polarities of the ignition pulse with a high-speed camera, which records four pictures within the symmetrically shaped ignition pulse with exposure times of 100 ns and throws of 100 ns. The pictures show that the high electric field and its temporal variation establish a local dielectric barrier discharge in front of the upper electrode inside the burner, which covers the inner wall of the burner with a surface charge. It forms a starting point of streamers, which may induce the lamp ignition predominantly within the second half cycle of the ignition pulse. It is found out that an active antenna is more effective when the starting point of the surface streamer in front of the sleeve is a negative surface charge on the

  12. Universal scaling of potential energy functions describing intermolecular interactions. II. The halide-water and alkali metal-water interactions

    SciTech Connect

    Werhahn, Jasper C.; Akase, Dai; Xantheas, Sotiris S.

    2014-08-14

    The scaled versions of the newly introduced [S. S. Xantheas and J. C. Werhahn, J. Chem. Phys.141, 064117 (2014)] generalized forms of some popular potential energy functions (PEFs) describing intermolecular interactions – Mie, Lennard-Jones, Morse, and Buckingham exponential-6 – have been used to fit the ab initio relaxed approach paths and fixed approach paths for the halide-water, X-(H2O), X = F, Cl, Br, I, and alkali metal-water, M+(H2O), M = Li, Na, K, Rb, Cs, interactions. The generalized forms of those PEFs have an additional parameter with respect to the original forms and produce fits to the ab initio data that are between one and two orders of magnitude better in the χ2 than the original PEFs. They were found to describe both the long-range, minimum and repulsive wall of the respective potential energy surfaces quite accurately. Overall the 4-parameter extended Morse (eM) and generalized Buckingham exponential-6 (gBe-6) potentials were found to best fit the ab initio data for these two classes of ion-water interactions. Finally, the fitted values of the parameter of the (eM) and (gBe-6) PEFs that control the repulsive wall of the potential correlate remarkably well with the ionic radii of the halide and alkali metal ions.

  13. Metal Halide Solid-State Surface Treatment for High Efficiency PbS and PbSe QD Solar Cells

    SciTech Connect

    Crisp, R. W.; Kroupa, D. M.; Marshall, A. R.; Miller, E. M.; Zhang, J.; Beard, M. C.; Luther, J. M.

    2015-04-24

    We developed a layer-by-layer method of preparing PbE (E = S or Se) quantum dot (QD) solar cells using metal halide (PbI2, PbCl2, CdI2, or CdCl2) salts dissolved in dimethylformamide to displace oleate surface ligands and form conductive QD solids. The resulting QD solids have a significant reduction in the carbon content compared to films treated with thiols and organic halides. We find that the PbI2 treatment is the most successful in removing alkyl surface ligands and also replaces most surface bound Cl- with I-. The treatment protocol results in PbS QD films exhibiting a deeper work function and band positions than other ligand exchanges reported previously. The method developed here produces solar cells that perform well even at film thicknesses approaching a micron, indicating improved carrier transport in the QD films. We demonstrate QD solar cells based on PbI2 with power conversion efficiencies above 7%.

  14. Metal Halide Solid-State Surface Treatment for High Efficiency PbS and PbSe QD Solar Cells

    DOE PAGESBeta

    Crisp, R. W.; Kroupa, D. M.; Marshall, A. R.; Miller, E. M.; Zhang, J.; Beard, M. C.; Luther, J. M.

    2015-04-24

    We developed a layer-by-layer method of preparing PbE (E = S or Se) quantum dot (QD) solar cells using metal halide (PbI2, PbCl2, CdI2, or CdCl2) salts dissolved in dimethylformamide to displace oleate surface ligands and form conductive QD solids. The resulting QD solids have a significant reduction in the carbon content compared to films treated with thiols and organic halides. We find that the PbI2 treatment is the most successful in removing alkyl surface ligands and also replaces most surface bound Cl- with I-. The treatment protocol results in PbS QD films exhibiting a deeper work function and bandmore » positions than other ligand exchanges reported previously. The method developed here produces solar cells that perform well even at film thicknesses approaching a micron, indicating improved carrier transport in the QD films. We demonstrate QD solar cells based on PbI2 with power conversion efficiencies above 7%.« less

  15. Valence and Conduction Band Densities of States of Metal Halide Perovskites: A Combined Experimental–Theoretical Study

    PubMed Central

    2016-01-01

    We report valence and conduction band densities of states measured via ultraviolet and inverse photoemission spectroscopies on three metal halide perovskites, specifically methylammonium lead iodide and bromide and cesium lead bromide (MAPbI3, MAPbBr3, CsPbBr3), grown at two different institutions on different substrates. These are compared with theoretical densities of states (DOS) calculated via density functional theory. The qualitative agreement achieved between experiment and theory leads to the identification of valence and conduction band spectral features, and allows a precise determination of the position of the band edges, ionization energy and electron affinity of the materials. The comparison reveals an unusually low DOS at the valence band maximum (VBM) of these compounds, which confirms and generalizes previous predictions of strong band dispersion and low DOS at the MAPbI3 VBM. This low DOS calls for special attention when using electron spectroscopy to determine the frontier electronic states of lead halide perovskites. PMID:27364125

  16. Valence and Conduction Band Densities of States of Metal Halide Perovskites: A Combined Experimental-Theoretical Study.

    PubMed

    Endres, James; Egger, David A; Kulbak, Michael; Kerner, Ross A; Zhao, Lianfeng; Silver, Scott H; Hodes, Gary; Rand, Barry P; Cahen, David; Kronik, Leeor; Kahn, Antoine

    2016-07-21

    We report valence and conduction band densities of states measured via ultraviolet and inverse photoemission spectroscopies on three metal halide perovskites, specifically methylammonium lead iodide and bromide and cesium lead bromide (MAPbI3, MAPbBr3, CsPbBr3), grown at two different institutions on different substrates. These are compared with theoretical densities of states (DOS) calculated via density functional theory. The qualitative agreement achieved between experiment and theory leads to the identification of valence and conduction band spectral features, and allows a precise determination of the position of the band edges, ionization energy and electron affinity of the materials. The comparison reveals an unusually low DOS at the valence band maximum (VBM) of these compounds, which confirms and generalizes previous predictions of strong band dispersion and low DOS at the MAPbI3 VBM. This low DOS calls for special attention when using electron spectroscopy to determine the frontier electronic states of lead halide perovskites. PMID:27364125

  17. Mesoscopic photosystems for solar light harvesting and conversion: facile and reversible transformation of metal-halide perovskites.

    PubMed

    Harms, Hauke Arne; Tétreault, Nicolas; Pellet, Norman; Bensimon, Michaël; Grätzel, Michael

    2014-01-01

    Recently, hybrid organic-inorganic metal halide perovskites have gained prominence as potent light harvesters in thin film solid-state photovoltaics. In particular the solar-to-electric power conversion efficiency (PCE) of devices using CH(3)NH(3)PbI(3) as sensitizer has increased from 3 to 20.1% within only a few years. This key material can be prepared by solution processing from PbI(2) and CH(3)NH(3)I in one step or by sequential deposition. In the latter case an electron capturing support such as TiO(2) is first covered with PbI(2), which upon exposure to a CH(3)NH(3)I solution is converted to the perovskite. Here we apply for the first time quartz crystal microbalance (QCMD) measurements in conjunction with X-ray diffraction and scanning electron microscopy to analyse the dynamics of the conversion of PbI(2) to CH(3)NH(3)PbI(3). Employing 200 nm thick PbI(2) films as substrates we discover that the CH(3)NH(3)I insertion in the PbI(2) is reversible, with the extraction into the solvent isopropanol occurring on the same time scale of seconds as the intercalation process. This offers an explanation for the strikingly rapid and facile exchange of halide ions in CH(3)NH(3)PbX(3) by solution processing at room temperature. PMID:25643832

  18. The impacts of new street light technologies: experimentally testing the effects on bats of changing from low-pressure sodium to white metal halide

    PubMed Central

    Stone, Emma Louise; Wakefield, Andrew; Harris, Stephen; Jones, Gareth

    2015-01-01

    Artificial light at night is a major feature of anthropogenic global change and is increasingly recognized as affecting biodiversity, often negatively. On a global scale, newer technology white lights are replacing orange sodium lights to reduce energy waste. In 2009, Cornwall County Council (UK) commenced replacement of existing low-pressure sodium (LPS) high intensity discharge (HID) street lights with new Phillips CosmoPolis white ceramic metal halide street lights to reduce energy wastage. This changeover provided a unique collaborative opportunity to implement a before-after-control-impact field experiment to investigate the ecological effects of newly installed broad spectrum light technologies. Activity of the bat species Pipistrellus pipistrellus, P. pygmaeus and Nyctalus/Eptesicus spp. was significantly higher at metal halide than LPS lights, as found in other studies of bat activity at old technology (i.e. mercury vapour) white light types. No significant difference was found in feeding attempts per bat pass between light types, though more passes overall were recorded at metal halide lights. Species-specific attraction of bats to the metal halide lights could have cascading effects at lower trophic levels. We highlight the need for further research on possible ecosystem-level effects of light technologies before they are installed on a wide scale. PMID:25780239

  19. The impacts of new street light technologies: experimentally testing the effects on bats of changing from low-pressure sodium to white metal halide.

    PubMed

    Stone, Emma Louise; Wakefield, Andrew; Harris, Stephen; Jones, Gareth

    2015-05-01

    Artificial light at night is a major feature of anthropogenic global change and is increasingly recognized as affecting biodiversity, often negatively. On a global scale, newer technology white lights are replacing orange sodium lights to reduce energy waste. In 2009, Cornwall County Council (UK) commenced replacement of existing low-pressure sodium (LPS) high intensity discharge (HID) street lights with new Phillips CosmoPolis white ceramic metal halide street lights to reduce energy wastage. This changeover provided a unique collaborative opportunity to implement a before-after-control-impact field experiment to investigate the ecological effects of newly installed broad spectrum light technologies. Activity of the bat species Pipistrellus pipistrellus, P. pygmaeus and Nyctalus/Eptesicus spp. was significantly higher at metal halide than LPS lights, as found in other studies of bat activity at old technology (i.e. mercury vapour) white light types. No significant difference was found in feeding attempts per bat pass between light types, though more passes overall were recorded at metal halide lights. Species-specific attraction of bats to the metal halide lights could have cascading effects at lower trophic levels. We highlight the need for further research on possible ecosystem-level effects of light technologies before they are installed on a wide scale. PMID:25780239

  20. An Engineered Palette of Metal Ion Quenchable Fluorescent Proteins

    PubMed Central

    Yu, Xiaozhen; Strub, Marie-Paule; Barnard, Travis J.; Noinaj, Nicholas; Piszczek, Grzegorz; Buchanan, Susan K.; Taraska, Justin W.

    2014-01-01

    Many fluorescent proteins have been created to act as genetically encoded biosensors. With these sensors, changes in fluorescence report on chemical states in living cells. Transition metal ions such as copper, nickel, and zinc are crucial in many physiological and pathophysiological pathways. Here, we engineered a spectral series of optimized transition metal ion-binding fluorescent proteins that respond to metals with large changes in fluorescence intensity. These proteins can act as metal biosensors or imaging probes whose fluorescence can be tuned by metals. Each protein is uniquely modulated by four different metals (Cu2+, Ni2+, Co2+, and Zn2+). Crystallography revealed the geometry and location of metal binding to the engineered sites. When attached to the extracellular terminal of a membrane protein VAMP2, dimeric pairs of the sensors could be used in cells as ratiometric probes for transition metal ions. Thus, these engineered fluorescent proteins act as sensitive transition metal ion-responsive genetically encoded probes that span the visible spectrum. PMID:24752441

  1. Revealing the ultrafast charge carrier dynamics in organo metal halide perovskite solar cell materials using time resolved THz spectroscopy

    NASA Astrophysics Data System (ADS)

    Ponseca, C. S., Jr.; Sundström, V.

    2016-03-01

    Ultrafast charge carrier dynamics in organo metal halide perovskite has been probed using time resolved terahertz (THz) spectroscopy (TRTS). Current literature on its early time characteristics is unanimous: sub-ps charge carrier generation, highly mobile charges and very slow recombination rationalizing the exceptionally high power conversion efficiency for a solution processed solar cell material. Electron injection from MAPbI3 to nanoparticles (NP) of TiO2 is found to be sub-ps while Al2O3 NPs do not alter charge dynamics. Charge transfer to organic electrodes, Spiro-OMeTAD and PCBM, is sub-ps and few hundreds of ps respectively, which is influenced by the alignment of energy bands. It is surmised that minimizing defects/trap states is key in optimizing charge carrier extraction from these materials.

  2. Optical emission spectroscopy of metal-halide lamps: Radially resolved atomic state distribution functions of Dy and Hg

    SciTech Connect

    Nimalasuriya, T.; Flikweert, A.J.; Stoffels, W.W.; Haverlag, M.; Mullen, J.J.A.M. van der; Pupat, N.B.M.

    2006-03-01

    Absolute line intensity measurements are performed on a metal-halide lamp. Several transitions of atomic and ionic Dy and atomic Hg are measured at different radial positions from which we obtain absolute atomic and ionic Dy intensity profiles. From these profiles we construct the radially resolved atomic state distribution function (ASDF) of the atomic and ionic Dy and the atomic Hg. From these ASDFs several quantities are determined as functions of radial position, such as the (excitation) temperature, the ion ratio Hg{sup +}/Dy{sup +}, the electron density, the ground state, and the total density of Dy atoms and ions. Moreover, these ASDFs give us insight about the departure from equilibrium. The measurements show a hollow density profile for the atoms and the ionization of atoms in the center. In the outer parts of the lamp molecules dominate.

  3. Optical emission spectroscopy of metal-halide lamps: Radially resolved atomic state distribution functions of Dy and Hg

    NASA Astrophysics Data System (ADS)

    Nimalasuriya, T.; Flikweert, A. J.; Stoffels, W. W.; Haverlag, M.; van der Mullen, J. J. A. M.; Pupat, N. B. M.

    2006-03-01

    Absolute line intensity measurements are performed on a metal-halide lamp. Several transitions of atomic and ionic Dy and atomic Hg are measured at different radial positions from which we obtain absolute atomic and ionic Dy intensity profiles. From these profiles we construct the radially resolved atomic state distribution function (ASDF) of the atomic and ionic Dy and the atomic Hg. From these ASDFs several quantities are determined as functions of radial position, such as the (excitation) temperature, the ion ratio Hg+/Dy+, the electron density, the ground state, and the total density of Dy atoms and ions. Moreover, these ASDFs give us insight about the departure from equilibrium. The measurements show a hollow density profile for the atoms and the ionization of atoms in the center. In the outer parts of the lamp molecules dominate.

  4. Three dimensional dynamic study of a metal halide thallium iodine discharge plasma powered by a sinusoidal and square signal

    NASA Astrophysics Data System (ADS)

    Bechir Ben Hamida, Mohamed; Charrada, Kamel

    2016-01-01

    The purpose of this paper is to study the dynamic of a metal halide thallium iodine discharge lamp fed by a sinusoidal and square power supply. For this, a chemical model under Local Thermodynamic Equilibrium conditions has been developed to compute the plasma composition and transport coefficients such as thermal conductivity, viscosity and electric conductivity. This is then coupled with a three-dimensional time-dependent code that solves the system of the mass, energy and momentum equations, as well as the Laplace equation for the plasma using Comsol Multiphysics with Matlab. After validation with the experimental results, this model was applied to analyze the influence of the key parameters on the discharge behavior such as frequency for an AC arc current and the atomic ratio for square arc-current wave form on the convective process.

  5. FT-IR and Raman spectroscopic and quantum chemical investigations of some metal halide complexes of 1-phenylpiperazine.

    PubMed

    Keşan, Gürkan; Bağlayan, Ozge; Parlak, Cemal; Alver, Ozgür; Senyel, Mustafa

    2012-03-01

    New metal halide complexes in the form of M(pp)(2)Cl(2) (where pp=1-phenylpiperazine and M=Pd or Hg) have been prepared for the first time and their FT-IR and FT-Raman spectra are reported in the region of 4000-10 cm(-1) and 4000-50 cm(-1), respectively. The optimized geometric parameters, normal mode frequencies and corresponding vibrational assignments of the present compounds are theoretically examined by means of B3LYP hybrid density functional theory (DFT) method together with Lanl2dz basis set. Furthermore, reliable vibrational assignments made on the basis of potential energy distribution (PED) were calculated and the thermodynamics functions, the highest occupied and the lowest unoccupied molecular orbitals (HOMO and LUMO) of these compounds have been predicted. According to the results, theoretical values have been successfully compared against experimental data. PMID:22225603

  6. FT-IR and Raman spectroscopic and quantum chemical investigations of some metal halide complexes of 1-phenylpiperazine

    NASA Astrophysics Data System (ADS)

    Keşan, Gürkan; Bağlayan, Özge; Parlak, Cemal; Alver, Özgür; Şenyel, Mustafa

    2012-03-01

    New metal halide complexes in the form of M(pp)2Cl2 (where pp = 1-phenylpiperazine and M = Pd or Hg) have been prepared for the first time and their FT-IR and FT-Raman spectra are reported in the region of 4000-10 cm-1 and 4000-50 cm-1, respectively. The optimized geometric parameters, normal mode frequencies and corresponding vibrational assignments of the present compounds are theoretically examined by means of B3LYP hybrid density functional theory (DFT) method together with Lanl2dz basis set. Furthermore, reliable vibrational assignments made on the basis of potential energy distribution (PED) were calculated and the thermodynamics functions, the highest occupied and the lowest unoccupied molecular orbitals (HOMO and LUMO) of these compounds have been predicted. According to the results, theoretical values have been successfully compared against experimental data.

  7. Development of processes for the production of solar grade silicon from halides and alkali metals, phase 1 and phase 2

    NASA Technical Reports Server (NTRS)

    Dickson, C. R.; Gould, R. K.; Felder, W.

    1981-01-01

    High temperature reactions of silicon halides with alkali metals for the production of solar grade silicon are described. Product separation and collection processes were evaluated, measure heat release parameters for scaling purposes and effects of reactants and/or products on materials of reactor construction were determined, and preliminary engineering and economic analysis of a scaled up process were made. The feasibility of the basic process to make and collect silicon was demonstrated. The jet impaction/separation process was demonstrated to be a purification process. The rate at which gas phase species from silicon particle precursors, the time required for silane decomposition to produce particles, and the competing rate of growth of silicon seed particles injected into a decomposing silane environment were determined. The extent of silane decomposition as a function of residence time, temperature, and pressure was measured by infrared absorption spectroscopy. A simplistic model is presented to explain the growth of silicon in a decomposing silane enviroment.

  8. Metal enhanced fluorescence with gold nanoparticles

    NASA Astrophysics Data System (ADS)

    Mattingly, Shaina LaRissa Strating

    A novel hybrid nanocomposite of Au nanoparticle-modified silicon nanowire was developed for surface enhanced fluorescence applications. The designed nanocomposite contained a silicon nanowire, gold nanoparticles and a silica layer doped with dye molecules. The hybrid nanomaterial was characterized using scanning electron microscopy (SEM), scanning transmission electron microscopy (STEM), fluorescence measurements, Fourier transform infrared (FT-IR) spectroscopy, and energy-dispersive X-ray spectroscopy (EDS). The results showed that the gold nanoparticles were uniformly adhered on the silicon nanowires and covered by a thin silica layer. The nanostructure exhibited strong capacity for surface enhanced fluorescence. Different enhancement factors were obtained by changing synthetic conditions. The second goal of the project was to determine if the shape of gold nanoparticles affects the extent of its fluorescence enhancement under constant external factors. Two shapes of gold nanoparticles were synthesized and characterized by SEM, STEM, zeta potential and absorbance measurements. Then they were coated with fluorescent dye-doped silica and the fluorescence intensity was measured and compared to the pure fluorescent dye. Gold nanorods enhanced fluorescence more than gold nanostars and that the fluorescent dye Alexafluor 700 showed a greater fluorescence intensity change in the presence of nanoparticles than methylene blue.

  9. Dependence of metal-enhanced fluorescence on surface roughness

    NASA Astrophysics Data System (ADS)

    François, Alexandre; Sciacca, Beniamino; Zuber, Agnieszka; Klantsataya, Elizaveta; Monro, Tanya M.

    2014-03-01

    Metal Enhanced Fluorescence (MEF) takes advantage of the coupling between surface plasmons, in either a metallic thin film or metallic nanoparticles, and fluorophores located in proximity of the metal, yielding an increase of the fluorophore emission. While MEF has been widely studied on metallic nanoparticles with the emphasis on creating brighter fluorescent labels, planar surfaces have not benefitted from the same attention. Here we investigate the influence of the surface roughness of a thin metallic film on the fluorescence enhancement. 50nm thick silver films were deposited on glass slides using either thermal evaporation with different evaporation currents or an electroless plating method based on the Tollens reaction to vary the surface roughness. Multiple layers of positively and negatively charged polyelectrolytes were deposited on top of the metallic coating to map out the enhancement factor as function of the gap between the metallic coating and fluorophore molecules covalently bound to the last polyelectrolyte layer. We show that fluorescence is enhanced by the presence of the metallic film, and in particular that the enhancement increases by a factor 3 to 40 for roughness ranging from 3 nm to 8 nm. Although these enhancement factors are modest compared to the enhancement produced by complex metallic nanoparticles or nano-patterned metallic thin films, the thin films used here are capable of supporting a plasmonic wave and offer the possibility of combining different techniques, such as surface plasmon resonance (with its higher refractive index sensitivity compared to localized plasmons) and MEF within a single device.

  10. Fluorescence imaging of metal ions implicated in diseases.

    PubMed

    Qian, Xuhong; Xu, Zhaochao

    2015-07-21

    Metal ions play an important role in various biological processes, their abnormal homeostasis in cells is related to many diseases, such as neurodegenerative disease, cancer and diabetes. Fluorescent imaging offers a unique route to detect metal ions in cells via a contactless and damage-free way with high spatial and temporal fidelity. Consequently, it represents a promising method to advance the understanding of physiological and pathological functions of metal ions in cell biology. In this highlight article, we will discuss recent advances in fluorescent imaging of metal ions by small-molecule sensors for understanding the role of metals in related diseases. We will also discuss challenges and opportunities for the design of small-molecule sensors for fluorescent detection of cellular metal ions as a potential method for disease diagnosis. PMID:25556818

  11. Spectral variation of fluorescence lifetime near single metal nanoparticles

    PubMed Central

    Li, Jia; Krasavin, Alexey V.; Webster, Linden; Segovia, Paulina; Zayats, Anatoly V.; Richards, David

    2016-01-01

    We explore the spectral dependence of fluorescence enhancement and the associated lifetime modification of fluorescent molecules coupled to single metal nanoparticles. Fluorescence lifetime imaging microscopy and single-particle dark-field spectroscopy are combined to correlate the dependence of fluorescence lifetime reduction on the spectral overlap between the fluorescence emission and the localised surface plasmon (LSP) spectra of individual gold nanoparticles. A maximum lifetime reduction is observed when the fluorescence and LSP resonances coincide, with good agreement provided by numerical simulations. The explicit comparison between experiment and simulation, that we obtain, offers an insight into the spectral engineering of LSP mediated fluorescence and may lead to optimized application in sensing and biomedicine. PMID:26876780

  12. Tuning Fluorescence Direction with Plasmonic Metal–Dielectric– Metal Substrates

    PubMed Central

    Choudhury, Sharmistha Dutta; Badugu, Ramachandram; Nowaczyk, Kazimierz; Ray, Krishanu; Lakowicz, Joseph R.

    2013-01-01

    Controlling the emission properties of fluorophores is essential for improving the performance of fluorescence-based techniques in modern biochemical research, medical diagnosis, and sensing. Fluorescence emission is isotropic in nature, which makes it difficult to capture more than a small fraction of the total emission. Metal– dielectric–metal (MDM) substrates, discussed in this Letter, convert isotropic fluorescence into beaming emission normal to the substrate. This improves fluorescence collection efficiency and also opens up new avenues for a wide range of fluorescence-based applications. We suggest that MDM substrates can be readily adapted for multiple uses, such as in microarray formats, for directional fluorescence studies of multiple probes or for molecule-specific sensing with a high degree of spatial control over the fluorescence emission. SECTION: Physical Processes in Nanomaterials and Nanostructures PMID:24013521

  13. Fluorescence enhancement in visible light: dielectric or noble metal?

    PubMed

    Sun, S; Wu, L; Bai, P; Png, C E

    2016-07-28

    A high permittivity dielectric gives the impression of outperforming plasmonic noble metal in visible light fluorescence enhancement primarily because of its small loss. Nonetheless, the performances of these two platforms in various situations remain obscure due to the different optical confinement mechanisms as well as the complexity in the fluorescence enhancement process. This study presents a comprehensive comparison between these two platforms based on nanoparticles (NPs) to evaluate their capability and applicability in fluorescence enhancement by taking into account the fluorescence excitation rate, the quantum yield, the fluorophore wavelengths and Stokes shifts as well as the far field intensity. In a low permittivity sensing medium (e.g. air), the dielectric NP can achieve comparable or higher fluorescence enhancement than the metal NP due to its decent NP-enhanced excitation rate and larger quantum yield. In a relatively high permittivity sensing medium (e.g. water), however, there is a significant decrement of the excitation rate of the dielectric NP as the permittivity contrast decreases, leading to a smaller fluorescence enhancement compared to the metallic counterpart. Combining the fluorescence enhancement and the far field intensity studies, we further conclude that for both dielectric and plasmonic NPs, the optimal situation occurs when the fluorescence excitation wavelength, the fluorescence emission wavelength and the electric-dipole-mode of the dielectric NP (or the plasmonic resonance of the metal NP) are the same and all fall in the low conductivity region of the NP material. We also find that the electric-dipole-mode of the dielectric NP performs better than the magnetic-dipole-mode for fluorescence enhancement applications because only the electric-dipole-mode can be strongly excited by the routinely used fluorescent dyes and quantum dots, which behave as electric dipoles by nature. PMID:27374052

  14. Single molecule fluorescence studies of ribosome dynamics: An application of metal enhanced fluorescence

    NASA Astrophysics Data System (ADS)

    Bharill, Shashank

    Metal enhanced fluorescence (MEF), in which a surface plasmon near a noble metal alters the spectral properties of an organic fluorophore, has been reported to increase fluorescence intensity without a concomitant increase in photobleaching rate. The fluorescence intensities of Cy3- and Cy5-labeled ribosomal initiation complexes (ICs) near 50 nm silver particles were increased 4 - 7-fold compared to ICs in the absence of silver colloids. Photobleaching lifetime was not significantly decreased, resulting in 4 - 5.5-fold enhancement in total photon emission prior to photobleaching. Fluorophores showing enhanced fluorescence were located within ˜280 nm of the colloidal particles, as detected by light scattering and scanning probe microscopy. Aggregates of silver particles or larger colloids themselves produced wavelength-shifted luminescence similar to fluorescence, presumably due to resonant extinction between nearby metal particles. Intensity fluctuations above shot noise, at 0.1 - 5 Hz, were greater from slides containing colloidal particles than from plain glass. Overall signal to noise ratio was similar or slightly better near the silver particles. Proximity to silver particles did not compromise ribosome function, as measured by codon-dependent binding of fluorescent tRNA to the A site of fluorescent labeled ribosomes, dynamics of fluorescence resonance energy transfer between adjacent tRNAs in the ribosomal A and P sites, and elongation factor G catalyzed translocation.

  15. Transition metal-mediated donor-acceptor coordination of low-oxidation state Group 14 element halides.

    PubMed

    Swarnakar, Anindya K; Ferguson, Michael J; McDonald, Robert; Rivard, Eric

    2016-03-30

    The reactivity of tungsten carbonyl adducts of Group 14 element (Ge, Sn and Pb) dihalides towards the metal-based donors (η(5)-C5H5)Rh(PMe2Ph)2 and Pt(PCy3)2 was examined. When (η(5)-C5H5)Rh(PMe2Ph)2 was treated with the Lewis acid supported Ge(ii) complex, THF·GeCl2·W(CO)5, cyclopentadienyl ring activation occurred, whereas the analogous Lewis acidic units SnCl2·W(CO)5 and PbCl2 form direct adducts with the Rh complex to yield Rh-Sn and Rh-Pb dative bonds. Attempts to prepare metal coordinated element(ii) hydrides by adding hydride sources to the above mentioned rhodium-E(ii) halide complexes were unsuccessful; in each case insoluble products were formed along with regeneration of free (η(5)-C5H5)Rh(PMe2Ph)2. In a parallel study, ECl2·W(CO)5 (E = Ge or Sn) groups were shown to participate in E-Cl oxidation addition chemistry with (Cy3P)2Pt to give the formal Pt(ii) complexes ClPt(PCy3)2ECl·W(CO)5. PMID:26373599

  16. Fluorescence Spectroscopy with Metal-Dielectric Waveguides

    PubMed Central

    Badugu, Ramachandram; Szmacinski, Henryk; Ray, Krishanu; Descrovi, Emiliano; Ricciardi, Serena; Zhang, Douguo; Chen, Junxue; Huo, Yiping; Lakowicz, Joseph R.

    2015-01-01

    We describe a hybrid metal-dielectric waveguide structures (MDWs) with numerous potential applications in the biosciences. These structures consist of a thin metal film coated with a dielectric layer. Depending on the thickness of the dielectric layer, the modes can be localized near the metal, within the dielectric, or at the top surface of the dielectric. The optical modes in a metal-dielectric waveguide can have either S (TE) or P (TM) polarization. The dielectric spacer avoids the quenching, which usually occurs for fluorophores within about 5 nm from the metal. Additionally, the resonances display a sharp angular dependence and can exhibit several hundred-fold increases in intensity (E2) at the silica-air interface relative to the incident intensity. Fluorophores placed on top of the silica layer couple efficiently with the metal, resulting in a sharp angular distribution of emission through the metal and down from the bottom of the structure. This coupling occurs over large distances to several hundred nm away from the metal and was found to be consistent with simulations of the reflectivity of the metal-dielectric waveguides. Remarkably, for some silica thicknesses, the emission is almost completely coupled through the structure with little free-space emission away from the metal-dielectric waveguide. The efficiency of fluorophore coupling is related to the quality of the resonant modes sustained by the metal-dielectric waveguide, resulting in coupling of most of the emission through the metal into the underlying glass substrates. Metal-dielectric waveguides also provide a method to resolve the emission from surface-bound fluorophores from the bulk-phase fluorophores. Metal-dielectric waveguides are simple to fabricate for large surface areas, the resonance wavelength can be adjusted by the dielectric thickness, and the silica surface is suitable for coupling to biomolecules. Metal-dielectric waveguides can have numerous applications in diagnostics and high

  17. Metal ion influence on eumelanin fluorescence and structure

    NASA Astrophysics Data System (ADS)

    Sutter, Jens-Uwe; Birch, David J. S.

    2014-06-01

    Melanin has long been thought to have an unworkably weak and complex fluorescence, but here we study its intrinsic fluorescence in order to demonstrate how metal ions can be used to control the rate of formation, constituents and structure of eumelanin formed from the well-known laboratory auto-oxidation of 3,4-dihydroxy-L-phenylalanine (L-DOPA). The effect on eumelanin absorption and fluorescence of a range of solvated metal ions is reported including Cu, Zn, Ni, Na and K. Monovalent cations and Zn have little effect, but the effect of transition metal cations can be considerable. For example, at pH 10, copper ions are shown to accelerate the onset of eumelanin formation, but not the rate of formation once it commences, and simplify the usual complex structure and intrinsic fluorescence of eumelanin in a way that is consistent with an increased abundance of 5,5-dihydroxyindole-2-carboxylic acid (DHICA). The presence of a dominant 6 ns fluorescence decay time at 480 nm, when excited at 450 nm describes a distinct photophysical species, which we tentatively assign to small oligomers. Copper is well-known to normally quench fluorescence, but increasing amounts of copper surprisingly leads to an increase in the fluorescence decay time of eumelanin, while reducing the fluorescence intensity, suggesting copper modification of the excited state. Such results have bearing on diverse areas. The most accepted morphology for melanin is that of a graphite-like sheet structure, and one which readily binds metal ions, an interaction that is thought to have an important, though as yet unclear bearing on several areas of medicine including neurology. There is also increasing interest in bio-mimicry by preparing and labelling sheet structures with metal ions for new electronic and photonic materials.

  18. Plasmon-enhanced fluorescence near metallic nanostructures: biochemical applications

    NASA Astrophysics Data System (ADS)

    Goldys, E. M.; Barnett, A.; Xie, F.; Drozdowicz-Tomsia, K.; Gryczynski, I.; Matveeva, E. G.; Gryczynski, Z.; Shtoyko, T.

    2007-11-01

    Amplification of fluorescence is a nanoscale phenomenon which is particularly pronounced in close proximity to metal nanostructures. Due to its sharp distance dependence, it is ideally suited to monitor biorecognition reactions. Using this effect we have been able to demonstrate ultrasensitive bioassays. Two types of metal nanostructures have been employed, nanometric silver islands deposited over an ultrathin metal mirror and silver fractal structures. For the first type, metal mirrors (aluminum, gold, or silver protected with a thin silica layer) were coated with SIFs and an immunoassay (model assay for rabbit IgG or myoglobin immunoassay) was performed on this surface using fluorescently labeled antibodies. Our results show that SIFs alone (on a glass surface not coated with metal) enhance the immunoassay signal approximately 3 to 10-fold. Using a metal mirror instead of glass as support for SIFs leads to up to 50-fold signal enhancement. The second type of metal nanostructures, silver fractals, were produced by electrochemical reduction of silver nitrate deposited on sapphire covered with a thin conductive film of indium tin oxide. These structures were used as a substrate for a model rabbit IgG bioassay. The fluorescence resulting from the binding of antibody labeled with Rhodamine was highly nonuniform with distinctive hot spots. These highly fluorescent regions were correlated with areas of higher Ag thickness and coverage. Such high values of fluorescence amplification in both types of nanostructures have been interpreted by using time-resolved fluorescence data and by considering the radiative properties of plasmons in the environments which promote plasmon coupling.

  19. Fluorescence biosensing strategy based on energy transfer between fluorescently labeled receptors and a metallic surface.

    PubMed

    Pérez-Luna, Víctor H; Yang, Saipeng; Rabinovich, Emmanuil M; Buranda, Tione; Sklar, Larry A; Hampton, Philip D; López, Gabriel P

    2002-01-01

    A new fluorescence-based biosensor is presented. The biosensing scheme is based on the fact that a fluorophore in close proximity to a metal film (<100 A) experiences strong quenching of fluorescence and a dramatic reduction in the lifetime of the excited state. By immobilizing the analyte of interest (or a structural analog of the analyte) to a metal surface and exposing it to a labeled receptor (e.g. antibody), the fluorescence of the labeled receptor becomes quenched upon binding because of the close proximity to the metal. Upon exposure to free analyte, the labeled receptor dissociates from the surface and diffuses into the bulk of the solution. This increases its separation from the metal and an increase of fluorescence intensity and/or lifetime of the excited state is observed that indicates the presence of the soluble analyte. By enclosing this system within a small volume with a semipermeable membrane, a reversible device is obtained. We demonstrate this scheme using a biotinylated self-assembled monolayer (SAM) on gold as our surface immobilized analyte analog, fluorescently labeled anti-biotin as a receptor, and a solution of biotin in PBS as a model analyte. This scheme could easily be extended to transduce a wide variety of protein-ligand interactions and other biorecognition phenomena (e.g. DNA hybridization) that result in changes in the architecture of surface immobilized biomolecules such that a change in the separation distance between fluorophores and the metal film is obtained. PMID:11742737

  20. Diode-Pumped Organo-Lead Halide Perovskite Lasing in a Metal-Clad Distributed Feedback Resonator.

    PubMed

    Jia, Yufei; Kerner, Ross A; Grede, Alex J; Brigeman, Alyssa N; Rand, Barry P; Giebink, Noel C

    2016-07-13

    Organic-inorganic lead halide perovskite semiconductors have recently reignited the prospect of a tunable, solution-processed diode laser, which has the potential to impact a wide range of optoelectronic applications. Here, we demonstrate a metal-clad, second-order distributed feedback methylammonium lead iodide perovskite laser that marks a significant step toward this goal. Optically pumping this device with an InGaN diode laser at low temperature, we achieve lasing above a threshold pump intensity of 5 kW/cm(2) for durations up to ∼25 ns at repetition rates exceeding 2 MHz. We show that the lasing duration is not limited by thermal runaway and propose instead that lasing ceases under continuous pumping due to a photoinduced structural change in the perovskite that reduces the gain on a submicrosecond time scale. Our results indicate that the architecture demonstrated here could provide the foundation for electrically pumped lasing with a threshold current density Jth < 5 kA/cm(2) under sub-20 ns pulsed drive. PMID:27331618

  1. Structure characterization of 1:1 adducts of metal(II) halides and piperazine

    SciTech Connect

    Yu Jiehui Hou Qin; Wang Tiegang; Zhang Xiao; Xu Jiqing

    2007-02-15

    From the simple hydro/solvothermal reactions, two 1:1 adducts of MX{sub 2} and piperazine (pip) [CdI{sub 2}(pip)] 1 and [CoCl{sub 2}(pip)] 2 were prepared. Both were characterized by elemental analyses, IR spectra, ultra-violet visible spectra, thermogravimetric analyses and X-ray single-crystal diffraction. With pip as the bridges, the 1-D linear CdI{sub 2} chains are extended into a 2-D layered compound 1, while the mononuclear CoCl{sub 2} units are linked into a 1-D zigzag-type chain compound 2. The fluorescence emission spectrum indicates that compound 1 possesses fluorescence property with the peaks at 373nm ({lambda}{sub ex}=212nm) and 410nm ({lambda}{sub ex}=293nm)

  2. Interface Energetics in Organo-Metallic Halide Perovskite-based Photovoltaic Cells

    NASA Astrophysics Data System (ADS)

    Schulz, Philip

    2015-03-01

    In my presentation I will talk about the most recent findings on the electronic structure of methylammonium lead tri-halide (MAPbX3, X =I, Br) perovskite films and their interfaces to adjacent transport layers. Intricate knowledge of the electronic alignment at the contact interfaces in perovskite solar cells is essential for the understanding of the working principle as well as improving design and thus performance of respective devices. In our studies we employ ultra-violet, X-ray and inverse photoemission spectroscopy (UPS, XPS, IPES) to directly determine valence and conduction band offsets. In this way we are able to report a direct measurement of the electronic band gap as well as ionization energy and electron affinity found for perovskite surfaces. Furthermore, our findings indicate that the electronic energy level alignment of adjacent organic hole transport layers, such as spiro-MeOTAD, can limit the maximum attainable open circuit voltage (Voc) in solar cells if the highest occupied molecular orbital of the hole transport material is not well aligned to the valence band maximum of the perovskite layer. Using better suited hole transporters, like CBP, values for Voc larger than 1.5 V could be achieved in the case of MAPbBr3 based devices. More recently, inverted perovskite solar cells based on nickel oxide bottom anodes have been reported to yield viable power conversion efficiencies and stability. We find that the interface between the p-doped NiO surface and the MAPbI3 layer on top lead to p-type perovskite filsm while the same material deposited on TiO2 in the conventional cell geometry turns out to be n-type. A further investigation of a C60 layer deposited on top of p-type perovskite films reveals an ideal alignment between the lowest unoccupied molecular orbital of the organic electron transport materials and the conduction band minimum of the perovskite film underneath. These results explain why the inverted solar cell structure could achieve

  3. Metal-Enhanced Fluorescence: Ultrafast Energy Transfer from Dyes in a Polymer Film to Metal Nanoparticles.

    PubMed

    Lee, Jaebeom; Pang, Yoonsoo

    2016-02-01

    Fluorescence from dye molecules dispersed in thin polymer layers increases by 20-25 times when a silver island film exists beneath the layer. Polymer layers of <100 nm thick cover the silver island film to minimize emission quenching from direct contact and also keep the dye molecules in close proximity to the metal nanosurface for possible fluorescence enhancements by silver island film. We report an ultrafast radiation process of ~400 ps lifetime from the surface plasmons of silver nanoparticles observed in time-resolved fluorescence of rhodamine 6G and DCM in thin polymer films coated on silver island surface. The ultrafast energy transfer and fluorescence from metal nanoparticles might be strongly related to the efficiency of metal-enhanced fluorescence. PMID:27433635

  4. Steering Fluorescence Emission with Metal-Dielectric-Metal Structures of Au, Ag and Al

    PubMed Central

    Dutta Choudhury, Sharmistha; Badugu, Ramachandram; Ray, Krishanu; Lakowicz, Joseph R.

    2014-01-01

    Directional control over fluorescence emission is important for improving the sensitivity of fluorescence based techniques. In recent years, plasmonic and photonic structures have shown great promise in shaping the spectral and spatial distribution of fluorescence, which otherwise is typically isotropic in nature and independent of the observation direction. In this work we have explored the potential of metal-dielectric-metal (MDM) structures composed of Au, Ag or Al in steering the fluorescence emission from various probes emitting in the NIR, Visible or UV/blue region. We show that depending on the optical properties of the metal and the thickness of the dielectric layer, the emission from randomly oriented fluorophores embedded within the MDM substrate is transformed into beaming emission normal to the substrate. Agreement of the observed angular emission patterns with reflectivity calculations reveals that the directional emission is due to the coupling of the fluorescence with the electromagnetic modes supported by the MDM structure. PMID:25126154

  5. Halide ion controlled shape dependent gold nanoparticle synthesis with tryptophan as reducing agent: Enhanced fluorescent properties and white light emission

    NASA Astrophysics Data System (ADS)

    Kasture, Manasi; Sastry, Murali; Prasad, B. L. V.

    2010-01-01

    We report the synthesis of Au nanoparticles in presence of two surfactants cetyltrimethyl ammonium chloride (CTAC) and cetyltrimethyl ammonium bromide (CTAB) by reducing Au 3+ ions with tryptophan. Interestingly, triangular shaped particles were seen to form in presence of CTAB, while spherical nanoparticles resulted with CTAC. The highlight of this result is the white light emission from the Au triangles obtained when CTAB is used. These results are supported by lifetime measurements and fluorescence.

  6. Spectral dependence of fluorescence near plasmon resonant metal nanoparticles

    NASA Astrophysics Data System (ADS)

    Chen, Yeechi

    The optical properties of fluorophores are significantly modified when placed within the near field (0--100 nm) of plasmon resonant metal nanostructures, due to the competition between increased decay rates and "hotspots" of concentrated electric fields. The decay rates and effective electric field intensities are highly dependent on the relative position of dye and metal and the overlap between plasmon resonance and dye absorption and emission. Understanding these dependencies can greatly improve the performance of biosensing and nanophotonic devices. In this dissertation, the fluorescence intensity of organic dyes and CdSe quantum dots near single metal nanoparticles is studied as a function of the local surface plasmon resonance (LSPR) of the nanoparticle. Single metal nanoparticles have narrow, well-defined, intense local surface plasmon resonances that are tunable across the visible spectrum by changes in size and shape. First, we show that organic dyes can be self-assembled on single silver nanoprisms into known configurations by the hybridization of thiolated DNA oligomers. We correlate the fluorescence intensity of the dyes to the LSPR of the individual nanoprism to which they are attached. For each of three different organic dyes, we observe a strong correlation between the fluorescence intensity of the dye and the degree of spectral overlap with the plasmon resonance of the nanoparticle. On average, we observe the brightest fluorescence from dyes attached to metal nanoparticles that have a LSPR scattering peak 40--120 meV higher in energy than the emission peak of the fluorophore. Second, the plasmon-enhanced fluorescence from CdSe/CdS/CdZnS/ZnS core/shell quantum dots is studied near a variety of silver and gold nanoparticles. With single-particle scattering spectroscopy, the localized surface plasmon resonance spectra of single metal nanoparticles is correlated with the photoluminescence excitation (PLE) spectra of the nearby quantum dots. The PLE

  7. Fluorescent probes and bioimaging: alkali metals, alkaline earth metals and pH.

    PubMed

    Yin, Jun; Hu, Ying; Yoon, Juyoung

    2015-07-21

    All living species and life forms have an absolute requirement for bio-functional metals and acid-base equilibrium chemistry owing to the critical roles they play in biological processes. Hence, a great need exists for efficient methods to detect and monitor biometals and acids. In the last few years, great attention has been paid to the development of organic molecule based fluorescent chemosensors. The availability of new synthetic fluorescent probes has made fluorescence microscopy an indispensable tool for tracing biologically important molecules and in the area of clinical diagnostics. This review highlights the recent advances that have been made in the design and bioimaging applications of fluorescent probes for alkali metals and alkaline earth metal cations, including lithium, sodium and potassium, magnesium and calcium, and for pH determination within biological systems. PMID:25317749

  8. A Cell-Permeable Fluorescent Prochelator Responds to Hydrogen Peroxide and Metal Ions by Decreasing Fluorescence

    PubMed Central

    Hyman, Lynne M.; Franz, Katherine J.

    2011-01-01

    Described here is the development of two boronic ester-based fluorescent prochelators, FloB (2-(6-hydroxy-3-oxo-3H-xanthen-9-yl)-4(5)-[2-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-benzylidene-hydrazinocarbonyl]-benzoic acid) and FloB-SI (2-(6-hydroxy-3-oxo-3Hxanthen-9-yl)-4(5)-[2-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzyloxy)-benzylidene-hydrazinocarbonyl]-benzoic acid) that show a fluorescence response to a variety of transition metal ions only after reaction with H2O2. Both prochelators’ boronic ester masks are oxidized by H2O2 to reveal a fluorescein-tagged metal chelator, FloS (4(5)-(2-hydroxy-benzylidenehydrazinocarbonyl)-2-(6-hydroxy-3-oxo-3H-xanthen-9-yl)-benzoic acid). Chelation of Fe3+ or Cu2+ elicits a 70% decrease in the emission signal of FloS, while Zn2+, Ni2+, and Co2+ produce a more modest fluorescence decrease. The conversion of FloB to FloS proceeds in organic solvents, but hydrolytic decomposition of its hydrazone backbone is observed in aqueous solution. However, FloB-SI oxidizes cleanly with H2O2 within 1 h in aqueous solutions to produce FloS. Fluorescence microscopy studies in HeLa cells with FloB-SI show that the sensor’s fluorescence intensity remains unchanged until incubation with exogenous H2O2, which results in a decreased fluorescent signal. Incubation with a competitive chelator restores the emission response, thus suggesting that FloB-SI can effectively report on a H2O2-induced increase in intracellular labilized metal. PMID:22287796

  9. Sensing Metal Ions with DNA Building Blocks: Fluorescent Pyridobenzimidazole Nucleosides

    PubMed Central

    Kim, Su Jeong; Kool, Eric T.

    2008-01-01

    We describe novel fluorescent N-deoxyribosides (1 and 2) having 2-pyrido-2-benzimidazole and 2-quino-2-benzimidazole as aglycones. The compounds were prepared from the previously unknown heterocyclic precursors and Hoffer’s chlorosugar, yielding alpha anomers as the chief products. X-ray crystal structures confirmed the geometry, and showed that the pyridine and benzimidazole ring systems deviated from coplanarity in the solid state by 154° and 140°, respectively. In methanol the compounds 1 and 2 had absorption maxima at 360 and 370 nm respectively, and emission maxima at 494 and 539 nm. Experiments revealed varied fluorescence responses of the nucleosides to a panel of seventeen monovalent, divalent and trivalent metal ions in methanol. One or both of the nucleosides showed significant changes with ten of the metal ions. The most pronounced spectral changes for ligand-nucleoside 1 included red shifts in fluorescence (Au+, Au3+), strong quenching (Cu2+, Ni2+, Pt2+), and in substantial enhancements in emission intensity coupled with redshifts (Ag+, Cd2+, Zn2+). The greatest spectral changes for ligand-nucleoside 2 included a redshift in fluorescence (Ag+), a blueshift (Cd2+), strong quenching (Pd2+, Pt2+), and in substantial enhancements in emission intensity coupled with a blueshift (Zn2+). The compounds could be readily incorporated into oligodeoxynucleotides, where an initial study revealed that they retained sensitivity to metal ions in aqueous solution, and demonstrated possible cooperative sensing behavior with several ions. The two free nucleosides alone can act as differential sensors for at multiple metal ions, and they are potentially useful monomers for contributing metal ion sensing capability to DNAs. PMID:16669686

  10. A study of the convective flow as a function of external parameters in a high-pressure metal halide discharge lamp (HgDyI3)

    NASA Astrophysics Data System (ADS)

    Hajji, S.; HadjSalah, S.; Benhalima, A.; Charrada, K.; Zissis, G.

    2016-06-01

    This paper deals with the modelling of the convection processes in metal-halide lamp discharges (HgDyI3). For this, we realized a 3D model, a steady, direct current powered and time-depending model for the solution of conservation equations relative to mass, momentum, and energy. After validation, this model was applied to the study of the effect of some parameters that have appeared on major transport phenomena of mass and energy in studying the lamp. Indeed, the electric current, the atomic ratio (Hg/Dy), and the effect of the convective transport have been studied.

  11. Pathways toward high-performance perovskite solar cells: review of recent advances in organo-metal halide perovskites for photovoltaic applications

    NASA Astrophysics Data System (ADS)

    Song, Zhaoning; Watthage, Suneth C.; Phillips, Adam B.; Heben, Michael J.

    2016-04-01

    Organo-metal halide perovskite-based solar cells have been the focus of intense research over the past five years, and power conversion efficiencies have rapidly been improved from 3.8 to >21%. This article reviews major advances in perovskite solar cells that have contributed to the recent efficiency enhancements, including the evolution of device architecture, the development of material deposition processes, and the advanced device engineering techniques aiming to improve control over morphology, crystallinity, composition, and the interface properties of the perovskite thin films. The challenges and future directions for perovskite solar cell research and development are also discussed.

  12. Metal-atom fluorescence from the quenching of metastable rare gases by metal carbonyls

    SciTech Connect

    Hollingsworth, W.E.

    1982-11-01

    A flowing afterglow apparatus was used to study the metal fluorescence resulting from the quenching of metastable rare-gas states by metal carbonyls. The data from the quenching or argon, neon, and helium by iron and nickel carbonyl agreed well with a restricted degree of freedom model indicating a concerted bond-breaking dissociation.

  13. Designer metal-nanoantennae/dye complexes for maximum fluorescence enhancement

    NASA Astrophysics Data System (ADS)

    Meng, Xiang; Yang, Hao; Grote, Richard R.; Dadap, Jerry I.; Panoiu, Nicolae C.; Osgood, Richard M.

    2015-09-01

    We theoretically investigate the fluorescence enhancement of a representative set of dye-molecules excited by three classes of nanoantennae, using a fully vectorial three-dimensional finite-difference time-domain (3D FDTD) method. Through these 3D FDTD calculations, in conjunction with analytic guidance using temporal coupled-mode (TCM) theory, we develop a design procedure for antennae assemblies that allow achieving fluorescence enhancements of 200-900 over the emission intensity in the bare dye molecule. The enhancement from these commercially available fluorochrome conjugates, namely, CFTM568, CFTM660R and CFTM790 are fully investigated using spherical-dimer, elliptical-dimer, and bowtie nanoantennae. These results demonstrate a method for rationally designing arbitrary metallic nanoparticle/emitter assemblies prior to their synthesis and assembly to achieve optimum fluorescence enhancement.

  14. In Vivo Metal Ion Imaging Using Fluorescent Sensors.

    PubMed

    Van de Bittner, Genevieve C; Hirayama, Tasuku

    2016-01-01

    In vivo imaging in living animals provides the ability to monitor alterations of signaling molecules, ions, and other biological components during various life stages and in disease. The data gained from in vivo imaging can be used for biological discovery or to determine elements of disease progression and can inform the development and translation of therapeutics. Herein, we present theories behind small-molecule, fluorescent, metal ion sensors as well as the methods for their successful application to in vivo metal ion imaging, including ex vivo validation. PMID:27283424

  15. Electronic line-up in light-emitting diodes with alkali-halide/metal cathodes

    NASA Astrophysics Data System (ADS)

    Brown, T. M.; Friend, R. H.; Millard, I. S.; Lacey, D. J.; Butler, T.; Burroughes, J. H.; Cacialli, F.

    2003-05-01

    The electronic nature of metal-semiconductor contacts is a fundamental issue in the understanding of semiconductor device physics, because such contacts control charge injection, and therefore play a major role in determining the electron/hole population in the semiconductor itself. This role is particularly important for organic semiconductors as they are generally used in their pristine, undoped form. Here, we review our progress in the understanding of the energy level line-up in finished, blue-emitting, polyfluorene-based light-emitting diodes, which exploit LiF and CsF thin films in combination with Ca and Al to obtain cathodes with low injection barriers. We have used electroabsorption measurements, as they allow the noninvasive determination of the built-in potential when changing the cathode. This provides precious experimental information on the alteration of the polymer/cathode interfacial energy level line-up. The latter is found to depend strongly on the electrode work function. Thus, the Schottky-Mott model for the energy level alignment is found to be a better first-order approximation than those models where strong pinning or large interface dipoles determine the alignment (e.g., Bardeen model), except for electrodes that extensively react with the polymer, and introduce deep gap states. In addition, we show results that validate the approximation of rigid tilting of polymer energy levels with bias (for biases for which no significant injection of carriers occurs). To investigate further the consequences of the electronic line-up on device operation, we complemented the electroabsorption measurements with characterization of the emissive and transport properties of the light-emitting diodes, and confirmed that the cathodic barrier lowering in CsF/Ca/Al and LiF/Ca/Al electrodes leads to the best improvements in electron injection. We found that luminance and overall current are greatly affected by the barrier-reducing cathodes, indicating a truly

  16. Interpulse kinetics in copper and copper halide lasers

    NASA Technical Reports Server (NTRS)

    Harstad, K. G.

    1983-01-01

    The various rate processes that govern the interpulse relaxation in metal vapor and metal halide vapor lasers are considered. Computer calculations indicate that the rapid metastable levels relaxation observed in copper and copper halide laser experiments requires the existence of a relatively small resonance in the cross section for metastable excitation or deexcitation near threshold. The accurate calculation of interpulse relaxation requires knowledge of rate constants presently not well known; this is especially so for metal halide lasers.

  17. The electronic structure of metal oxide/organo metal halide perovskite junctions in perovskite based solar cells

    PubMed Central

    Dymshits, Alex; Henning, Alex; Segev, Gideon; Rosenwaks, Yossi; Etgar, Lioz

    2015-01-01

    Cross-sections of a hole-conductor-free CH3NH3PbI3 perovskite solar cell were characterized with Kelvin probe force microscopy. A depletion region width of about 45 nm was determined from the measured potential profiles at the interface between CH3NH3PbI3 and nanocrystalline TiO2, whereas a negligible depletion was measured at the CH3NH3PbI3/Al2O3 interface. A complete solar cell can be realized with the CH3NH3PbI3 that functions both as light harvester and hole conductor in combination with a metal oxide. The band diagrams were estimated from the measured potential profile at the interfaces, and are critical findings for a better understanding and further improvement of perovskite based solar cells. PMID:25731963

  18. Bimetallic Nanoshells for Metal - Enhanced Fluorescence with Broad Band Fluorophores.

    PubMed

    Zhang, Jian; Fu, Yi; Mahdavi, Farhad

    2012-11-15

    In this article, we reported the near-field interactions between the Ru(bpy)(3) (2+) complexes and plasmon resonances from the bimetallic nanoshells. The metallic nanoshells were fabricated on 20 nm silica spheres as cores by depositing 10 nm monometallic or bimetallic shells. There were approx. 15 Ru(bpy)(3) (2+) complexes in the silica core. The metal shells were constituted of silver or/and gold. The bimetallic shells could be generated in homogeneous or heterogeneous geometries. The homogeneous bimetallic shells contained 10 nm silver-gold alloys. The heterogeneous bimetallic shells contained successive 5 nm gold and 5 nm silver shells, or alternatively, 5 nm silver and 5 nm gold shells. Optical properties of metal nanoshells were studied on both the ensemble spectra and single nanoparticle imaging measurements. The heterogeneous bimetallic shells were found to have a large scale of metal-enhanced emission relative to the monometallic or homogeneous bimetallic shells. It is because the heterogeneous bimetallic shells may display split dual plasmon resonances which can interact with the excitation and emission bands of the Ru(bpy)(3) (2+) complexes in the silica cores leading to more efficient near-field interactions. The prediction can be demonstrated by the lifetimes. Therefore, it is suggested that both the compositions and geometries of the metal shells can influence the interactions with the fluorophores in the cores. This observation also offers us an opportunity for developing plasmon-based fluorescence metal nanoparticles as novel nanoparticle imaging agents which have high performances in fluorescence cell or tissue imaging. PMID:23230456

  19. Toxicity of organometal halide perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Babayigit, Aslihan; Ethirajan, Anitha; Muller, Marc; Conings, Bert

    2016-03-01

    In the last few years, the advent of metal halide perovskite solar cells has revolutionized the prospects of next-generation photovoltaics. As this technology is maturing at an exceptional rate, research on its environmental impact is becoming increasingly relevant.

  20. Noble metal superparticles and methods of preparation thereof

    DOEpatents

    Sun, Yugang; Hu, Yongxing

    2016-07-12

    A method comprises heating an aqueous solution of colloidal silver particles. A soluble noble metal halide salt is added to the aqueous solution which undergoes a redox reaction on a surface of the silver particles to form noble metal/silver halide SPs, noble metal halide/silver halide SPs or noble metal oxide/silver halide SPs on the surface of the silver particles. The heat is maintained for a predetermined time to consume the silver particles and release the noble metal/silver halide SPs, the noble metal halide/silver halide SPs or the noble metal oxide/silver halide SPs into the aqueous solution. The aqueous solution is cooled. The noble metal/silver halide SPs, the noble metal halide/silver halide SPs or noble metal oxide/silver halide SPs are separated from the aqueous solution. The method optionally includes adding a soluble halide salt to the aqueous solution.

  1. Metal-induced fluorescence properties of three-dimensionally ordered macroporous silver inverse opal platforms

    NASA Astrophysics Data System (ADS)

    Chae, Weon-Sik; Lee, Myung-Jin; Kim, Kisun; Hyun, Jerome K.; Jeon, Seokwoo

    2016-02-01

    This study examined the metal-induced fluorescence properties of three-dimensionally ordered macroporous silver inverse opal (IO) films. Electrochemically synthesized silver IO films with a micrometer cavity exhibited notable fluorescence enhancement at the silver frame, and a decrease in fluorescence lifetime. Numerical calculations supported the observations of a higher fluorescence efficiency at the frame than in the cavity.

  2. 40 CFR Table 3 to Subpart Ffff of... - Emission Limits for Hydrogen Halide and Halogen HAP Emissions or HAP Metals Emissions From...

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 13 2013-07-01 2012-07-01 true Emission Limits for Hydrogen Halide and..., Table 3 Table 3 to Subpart FFFF of Part 63—Emission Limits for Hydrogen Halide and Halogen HAP Emissions... limit in the following table that applies to your process vents that contain hydrogen halide and...

  3. 40 CFR Table 3 to Subpart Ffff of... - Emission Limits for Hydrogen Halide and Halogen HAP Emissions or HAP Metals Emissions From...

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 13 2012-07-01 2012-07-01 false Emission Limits for Hydrogen Halide.... FFFF, Table 3 Table 3 to Subpart FFFF of Part 63—Emission Limits for Hydrogen Halide and Halogen HAP... limit in the following table that applies to your process vents that contain hydrogen halide and...

  4. 40 CFR Table 3 to Subpart Ffff of... - Emission Limits for Hydrogen Halide and Halogen HAP Emissions or HAP Metals Emissions From...

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 12 2011-07-01 2009-07-01 true Emission Limits for Hydrogen Halide and... to Subpart FFFF of Part 63—Emission Limits for Hydrogen Halide and Halogen HAP Emissions or HAP... following table that applies to your process vents that contain hydrogen halide and halogen HAP emissions...

  5. 40 CFR Table 3 to Subpart Ffff of... - Emission Limits for Hydrogen Halide and Halogen HAP Emissions or HAP Metals Emissions From...

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 13 2014-07-01 2014-07-01 false Emission Limits for Hydrogen Halide.... FFFF, Table 3 Table 3 to Subpart FFFF of Part 63—Emission Limits for Hydrogen Halide and Halogen HAP... limit in the following table that applies to your process vents that contain hydrogen halide and...

  6. 40 CFR Table 3 to Subpart Ffff of... - Emission Limits for Hydrogen Halide and Halogen HAP Emissions or HAP Metals Emissions From...

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 12 2010-07-01 2010-07-01 true Emission Limits for Hydrogen Halide and... to Subpart FFFF of Part 63—Emission Limits for Hydrogen Halide and Halogen HAP Emissions or HAP... following table that applies to your process vents that contain hydrogen halide and halogen HAP emissions...

  7. Fluorescence from a quantum dot and metallic nanosphere hybrid system

    SciTech Connect

    Schindel, Daniel G.; Singh, Mahi R.

    2014-03-31

    We present energy absorption and interference in a quantum dot-metallic nanosphere system embedded on a dielectric substrate. A control field is applied to induce dipole moments in the nanosphere and the quantum dot, and a probe field is applied to monitor absorption. Dipole moments in the quantum dot or the metal nanosphere are induced, both by the external fields and by each other's dipole fields. Thus, in addition to direct polarization, the metal nanosphere and the quantum dot will sense one another via the dipole-dipole interaction. The density matrix method was used to show that the absorption spectrum can be split from one peak to two peaks by the control field, and this can also be done by placing the metal sphere close to the quantum dot. When the two are extremely close together, a self-interaction in the quantum dot produces an asymmetry in the absorption peaks. In addition, the fluorescence efficiency can be quenched by the addition of a metal nanosphere. This hybrid system could be used to create ultra-fast switching and sensing nanodevices.

  8. Colorimetric Fluorescent Nanosensor Based on Hexamethylene Diisocyanate for Fluorescent Responses and Adsorption of Heavy Metal Ions.

    PubMed

    Xu, Yaohui; Zhou, Yang; Li, Ruixing

    2016-03-01

    An inorganic-organic hybrid material based on magnetic Fe3O4@SiO2 nanoparticles was synthesized for fluorescent responses and removal of heavy metal ions, in which superparamagnetic Fe3O4@SiO2 nanoparticles were firstly prepared and modified with hexamethylene diisocyanate (HDI) instead of 3-isocyanatopropyltriethoxysilane (IPTES) as the organic coupling agent, and then a rhodamine derivative with spirolactam structure (Rho-en) was conjugated on the HDI functionalized Fe3O4@SiO2 nanoparticles through isocyanate groups. Both of functionalized Fe3O4@SiO2 nanoparticles based on IPTES and HDI were characterized by FT-IR and XPS, and the results indicated that HDI was a good alternative as chemical bridge for surface modification on the surface of Fe3O4@SiO2 nanoparticles. The inorganic-organic hybrid composites synthesized based HDI showed naked-eye color changes and fluorescent responses towards Zn2+, Cd2+, Mn2+, Pb2+, Hg2+ and Fe3+, which could serve as the available proofs for the qualitative analysis. Moreover, the as-obtained composites not only had excellent adsorption capability for Pb2+ and Hg2+, but also showed strong magnetic sensitivity, which could help to the removal and separation of functionalized magnetic nanocomposites after capturing the heavy metal ions. In addition, the plausible interaction mode of functionalized Fe3O4@SiO2 nanoparticles with heavy metal ions was discussed. PMID:27455720

  9. Formation of Metal Clusters or Nitrogen-Bridged Adducts by Reaction of a Bis(amino)stannylene with Halides of Two-Valent Transition Metals.

    PubMed

    Veith, Michael; Müller, Alice; Stahl, Lothar; Nötzel, Martin; Jarczyk, Maria; Huch, Volker

    1996-06-19

    When the cyclic bis(amino)stannylene Me(2)Si(NtBu)(2)Sn is allowed to react with metal halides MX(2) (M = Cr, Fe, Co, Zn; X = Cl, Br [Zn]) adducts of the general formula [Me(2)Si(NtBu)(2)Sn.MX(2)](n) are obtained. The compounds are generally dimeric (n = 2) except the ZnBr(2) adduct, which is monomeric in benzene. The crystal structures of [Me(2)Si(NtBu)(2)Sn.CoCl(2)](2) (triclinic, space group &Pmacr;1; a = 8.620(9) Å, b = 9.160(9) Å, c = 12.280(9) Å, alpha = 101.2(1) degrees, beta = 97.6(1) degrees, gamma = 105.9(1) degrees, Z = 1) and of [Me(2)Si(NtBu)(2)Sn.ZnCl(2)](2) (monoclinic, space group P2(1)/c; a = 8.156(9) Å, b = 16.835(12) Å, c = 13.206(9) Å, beta = 94.27(6) degrees, Z = 2) were determined by X-ray diffraction techniques. The two compounds form similar polycyclic, centrosymmetrical assemblies of metal atoms bridged by chlorine or nitrogen atoms. While in the case of the cobalt compound Co is pentacoordinated by three chlorine and two nitrogen atoms, in the zinc derivative Zn is almost tetrahedrally coordinated by three chlorine atoms and one nitrogen atom. The iron derivative [Me(2)Si(NtBu)(2)Sn.FeCl(2)](2) seems to be isostructural with the cobalt compound as can be deduced from the crystal data (triclinic, a = 8.622(7) Å, b = 9.158(8) Å, c = 12.353(8) Å, alpha = 101.8(1) degrees, beta = 96.9(1) degrees, gamma = 105.9(1) degrees, Z = 1). If NiBr(2), PdCl(2), or PtCl(2) is combined with the stannylene, the reaction product is totally different: 4 equiv of the stannylene are coordinating per metal halide, forming the molecular compound [Me(2)Si(NtBu)(2)Sn](4)MX(2), which crystallizes with half a mole of benzene per molecular formula. The crystal structures of [Me(2)Si(NtBu)(2)Sn](4).NiBr(2).(1)/(2)C(6)H(6) (tetragonal, space group I4(1)/a, a = b = 43.86(4) Å, c = 14.32(2) Å, Z = 16) and [Me(2)Si(NtBu)(2)Sn](4).PdCl(2).(1)/(2)C(6)H(6) (tetragonal, space group I4(1)/a, a = b = 43.99(4) Å, c = 14.318(14) Å, Z = 16) reveal the two compounds to

  10. A Strained Disilane-Promoted Carboxylation of Organic Halides with CO2 under Transition-Metal-Free Conditions.

    PubMed

    Mita, Tsuyoshi; Suga, Kenta; Sato, Kaori; Sato, Yoshihiro

    2015-11-01

    By using a strained four-membered ring disilane (3,4-benzo-1,1,2,2-tetraethyldisilacyclobutene) and CsF, a wide range of aryl, alkenyl, alkynyl, benzyl, allyl, and alkyl halides was successfully carboxylated under an ambient CO2 atmosphere (CO2 balloon) at room temperature within 2 h. In this carboxylation, a highly reactive silyl anion, which is generated from the disilane and CsF, is a key to facilitating the formation of a carbanion equivalent. The resulting anionic species can be trapped with CO2 to produce carboxylic acids with high efficiency. PMID:26451945

  11. Effect of metal cation replacement on the electronic structure of metalorganic halide perovskites: Replacement of lead with alkaline-earth metals

    NASA Astrophysics Data System (ADS)

    Pazoki, Meysam; Jacobsson, T. Jesper; Hagfeldt, Anders; Boschloo, Gerrit; Edvinsson, Tomas

    2016-04-01

    Organic and inorganic lead halogen perovskites, and in particular, C H3N H3Pb I3 , have during the last years emerged as a class of highly efficient solar cell materials. Herein we introduce metalorganic halogen perovskite materials for energy-relevant applications based on alkaline-earth metals. Based on the classical notion of Goldschmidt's rules and quantum mechanical considerations, the three alkaline-earth metals, Ca, Sr, and Ba, are shown to be able to exchange lead in the perovskite structure. The three alkaline-earth perovskites, C H3N H3Ca I3,C H3N H3Sr I3 , and C H3N H3Ba I3 , as well as the reference compound, C H3N H3Pb I3 , are in this paper investigated with density functional theory (DFT) calculations, which predict these compounds to exist as stable perovskite materials, and their electronic properties are explored. A detailed analysis of the projected molecular orbital density of states and electronic band structure from DFT calculations were used for interpretation of the band-gap variations in these materials and for estimation of the effective masses of the electrons and holes. Neglecting spin-orbit effects, the band gap of MACa I3,MASr I3 , and MABa I3 were estimated to be 2.95, 3.6, and 3.3 eV, respectively, showing the relative change expected for metal cation exchange. The shifts in the conduction band (CB) edges for the alkaline-earth perovskites were quantified using scalar relativistic DFT calculations and tight-binding analysis, and were compared to the situation in the more extensively studied lead halide perovskite, C H3N H3Pb I3 , where the change in the work function of the metal is the single most important factor in tuning the CB edge and band gap. The results show that alkaline-earth-based organometallic perovskites will not work as an efficient light absorber in photovoltaic applications but instead could be applicable as charge-selective contact materials. The rather high CB edge and the wide band gap together with the large

  12. The Silver Halides

    ERIC Educational Resources Information Center

    Sahyun, M. R. V.

    1977-01-01

    Illustrates the type of fractional bonding for solid silver halides. Treats the silver halides as electron excess compounds, and develops a model of a localized bonding unit that may be iterated in three dimensions to describe the bulk phase. (MLH)

  13. Process and composition for drying of gaseous hydrogen halides

    DOEpatents

    Tom, Glenn M.; Brown, Duncan W.

    1989-08-01

    A process for drying a gaseous hydrogen halide of the formula HX, wherein X is selected from the group consisting of bromine, chlorine, fluorine, and iodine, to remove water impurity therefrom, comprising: contacting the water impurity-containing gaseous hydrogen halide with a scavenger including a support having associated therewith one or more members of the group consisting of: (a) an active scavenging moiety selected from one or more members of the group consisting of: (i) metal halide compounds dispersed in the support, of the formula MX.sub.y ; and (ii) metal halide pendant functional groups of the formula -MX.sub.y-1 covalently bonded to the support, wherein M is a y-valent metal, and y is an integer whose value is from 1 to 3; (b) corresponding partially or fully alkylated compounds and/or pendant functional groups, of the metal halide compounds and/or pendant functional groups of (a); wherein the alkylated compounds and/or pendant functional groups, when present, are reactive with the gaseous hydrogen halide to form the corresponding halide compounds and/or pendant functional groups of (a); and M being selected such that the heat of formation, .DELTA.H.sub.f of its hydrated halide, MX.sub.y.(H.sub.2 O).sub.n, is governed by the relationship: .DELTA.H.sub.f .gtoreq.n.times.10.1 kilocalories/mole of such hydrated halide compound wherein n is the number of water molecules bound to the metal halide in the metal halide hydrate. Also disclosed is an appertaining scavenger composition and a contacting apparatus wherein the scavenger is deployed in a bed for contacting with the water impurity-containing gaseous hydrogen halide.

  14. Oxidation of hydrogen halides to elemental halogens

    DOEpatents

    Rohrmann, Charles A.; Fullam, Harold T.

    1985-01-01

    A process for oxidizing hydrogen halides having substantially no sulfur impurities by means of a catalytically active molten salt is disclosed. A mixture of the subject hydrogen halide and an oxygen bearing gas is contacted with a molten salt containing an oxidizing catalyst and alkali metal normal sulfates and pyrosulfates to produce an effluent gas stream rich in the elemental halogen and substantially free of sulfur oxide gases.

  15. Fluorescent chelates for monitoring metal binding with macromolecules.

    PubMed

    Islam, M; Khanin, M; Sadik, O A

    2003-01-01

    Metals and radionuclides are usually coupled with proteins together with suitable ligands for therapeutic, tumor-imaging, pharmaceuticals, and biocompatibility applications. Several ligands that can strongly coordinate a given nuclide in a specific valency are already known. However, the demand for bifunctionality has limited the applications of these ligands. We hereby report the molecular design of a receptor system based on the linkage of protein to monoazo ligands. By use of basic coordination chemistry, 4-(3-quinolinoazo)hydroxybenzoic acid (QABA) and derivatives were successfully conjugated to ovalbumin, bovine serum albumin, and alkaline phosphatase at a site that was distinct from the metal binding site. The presence of carboxylic acid linkage in the QABA served as a convenient bridge for protein conjugation and may allow the generic application of these ligands for bioconjugate synthesis while ensuring a high in vivo stability. The ligand-protein conjugates were characterized using UV-vis spectroscopy, Fourier transform infrared spectroscopy, thin layer chromatography, NMR, and surface-enhanced laser desorption ionization time-of-flight mass spectrometry. The conjugate was tested for the ability to recognize nonradioactive Ga(3+) at a physiological pH, and a binding constant of 1 x 10(20) was recorded. Also, the in vitro testing results indicated that the fluorescent conjugates exhibited significant selectivity for gallium compared to Pb(2+), Hg(2+), Zn(2+), Cu(2+), Fe(3+), and Co(2+) while no responses were obtained for alkaline and alkaline earth metals. These attributes could allow these conjugates to be used as a model for imaging sensors and for metal detection. PMID:12523855

  16. Selective fluorescence sensors for detection of nitroaniline and metal Ions based on ligand-based luminescent metal-organic frameworks

    NASA Astrophysics Data System (ADS)

    Yu, Zongchao; Wang, Fengqin; Lin, Xiangyi; Wang, Chengmiao; Fu, Yiyuan; Wang, Xiaojun; Zhao, Yongnan; Li, Guodong

    2015-12-01

    Metal-organic frameworks (MOFs) are porous crystalline materials with high potential for applications in fluorescence sensors. In this work, two solvent-induced Zn(II)-based metal-organic frameworks, Zn3L3(DMF)2 (1) and Zn3L3(DMA)2(H2O)3 (2) (L=4,4‧-stilbenedicarboxylic acid), were investigated as selective sensing materials for detection of nitroaromatic compounds and metal ions. The sensing experiments show that 1 and 2 both exhibit selective fluorescence quenching toward nitroaniline with a low detection limit. In addition, 1 exhibits high selectivity for detection of Fe3+ and Al3+ by significant fluorescence quenching or enhancement effect. While for 2, it only exhibits significant fluorescence quenching effect for Fe3+. The results indicate that 1 and 2 are both promising fluorescence sensors for detecting and recognizing nitroaniline and metal ions with high sensitivity and selectivity.

  17. Fluorescence quenching of water-soluble conjugated polymer by metal cations and its application in sensor

    NASA Astrophysics Data System (ADS)

    Chen, Yan-Guo; Zhao, Dan; He, Zhi-Ke; Ai, Xin-Ping

    2007-02-01

    The effects of different metal cations on the fluorescence of water-soluble conjugated polymer (CP) and their quenching mechanism have been explored. Most transition metal cations, especially noble metal cations, such as Pd 2+, Ru 3+, and Pt 2+ possessed higher quenching efficiency to CP fluorescence than that of the main group metal cations and other transition metal cations, which have filled or half-full outmost electron layer configurations. Base on this, rapid, sensitive detection of noble metal cations can be realized and a novel quencher-tether-ligand (QTL) probe was developed to detect avidin and streptavidin.

  18. The gas phase emitter effect of lanthanum within ceramic metal halide lamps and its dependence on the La vapor pressure and operating frequency

    SciTech Connect

    Ruhrmann, C.; Hoebing, T.; Bergner, A.; Groeger, S.; Awakowicz, P.; Mentel, J.; Denissen, C.; Suijker, J.

    2015-08-07

    The gas phase emitter effect increases the lamp lifetime by lowering the work function and, with it, the temperature of the tungsten electrodes of metal halide lamps especially for lamps in ceramic vessels due to their high rare earth pressures. It is generated by a monolayer on the electrode surface of electropositive atoms of certain emitter elements, which are inserted into the lamp bulb by metal iodide salts. They are vaporized, dissociated, ionized, and deposited by an emitter ion current onto the electrode surface within the cathodic phase of lamp operation with a switched-dc or ac-current. The gas phase emitter effect of La and the influence of Na on the emitter effect of La are studied by spatially and phase-resolved pyrometric measurements of the electrode tip temperature, La atom, and ion densities by optical emission spectroscopy as well as optical broadband absorption spectroscopy and arc attachment images by short time photography. An addition of Na to the lamp filling increases the La vapor pressure within the lamp considerably, resulting in an improved gas phase emitter effect of La. Furthermore, the La vapor pressure is raised by a heating of the cold spot. In this way, conditions depending on the La vapor pressure and operating frequency are identified, at which the temperature of the electrodes becomes a minimum.

  19. The gas phase emitter effect of lanthanum within ceramic metal halide lamps and its dependence on the La vapor pressure and operating frequency

    NASA Astrophysics Data System (ADS)

    Ruhrmann, C.; Hoebing, T.; Bergner, A.; Groeger, S.; Denissen, C.; Suijker, J.; Awakowicz, P.; Mentel, J.

    2015-08-01

    The gas phase emitter effect increases the lamp lifetime by lowering the work function and, with it, the temperature of the tungsten electrodes of metal halide lamps especially for lamps in ceramic vessels due to their high rare earth pressures. It is generated by a monolayer on the electrode surface of electropositive atoms of certain emitter elements, which are inserted into the lamp bulb by metal iodide salts. They are vaporized, dissociated, ionized, and deposited by an emitter ion current onto the electrode surface within the cathodic phase of lamp operation with a switched-dc or ac-current. The gas phase emitter effect of La and the influence of Na on the emitter effect of La are studied by spatially and phase-resolved pyrometric measurements of the electrode tip temperature, La atom, and ion densities by optical emission spectroscopy as well as optical broadband absorption spectroscopy and arc attachment images by short time photography. An addition of Na to the lamp filling increases the La vapor pressure within the lamp considerably, resulting in an improved gas phase emitter effect of La. Furthermore, the La vapor pressure is raised by a heating of the cold spot. In this way, conditions depending on the La vapor pressure and operating frequency are identified, at which the temperature of the electrodes becomes a minimum.

  20. Analysis of molecular structure, spectroscopic properties (FT-IR, micro-Raman and UV-vis) and quantum chemical calculations of free and ligand 2-thiopheneglyoxylic acid in metal halides (Cd, Co, Cu, Ni and Zn)

    NASA Astrophysics Data System (ADS)

    Gökce, Halil; Bahçeli, Semiha

    2013-12-01

    In this study, molecular geometries, experimental vibrational wavenumbers, electronic properties and quantum chemical calculations of 2-thiopheneglyoxylic acid molecule, (C6H4O3S), and its metal halides (Cd, Co, Cu, Ni and Zn) which are used as pharmacologic agents have been investigated experimentally by FT-IR, micro-Raman and UV-visible spectroscopies and elemental analysis. Meanwhile the vibrational calculations were verified by DFT/B3LYP method with 6-311++G(d,p) and LANL2DZ basis sets in the ground state, for free TPGA molecule and its metal halide complexes, respectively, for the first time. The calculated fundamental vibrational frequencies for the title compounds are in a good agreement with the experimental data.

  1. Fluorescent metal ion chemosensors via cation exchange reactions of complexes, quantum dots, and metal-organic frameworks.

    PubMed

    Cheng, Jinghui; Zhou, Xiangge; Xiang, Haifeng

    2015-11-01

    Due to their wide range of applications and biological significance, fluorescent sensors have been an active research area in the past few years. In the present review, recent research developments on fluorescent chemosensors that detect metal ions via cation exchange reactions (transmetalation, metal displacement, or metal exchange reactions) of complexes, quantum dots, and metal-organic frameworks are described. These complex-based chemosensors might have a much better selectivity than the corresponding free ligands/receptors because of the shielding function of the filled-in metal ions. Moreover, not only the chemical structure of the ligands/receptors but also the identity of the central metal ions have a tremendous impact on the sensing performances. Therefore, sensing via cation exchange reactions potentially provides a new, simple, and powerful way to design fluorescent chemosensors. PMID:26375420

  2. Oxidative addition of group 13 and 14 metal halides and Alkyls to Ga(DDP) (DDP = bulky bisimidinate).

    PubMed

    Kempter, Andreas; Gemel, Christian; Fischer, Roland A

    2008-08-18

    The oxidative addition of a variety of group 13 and group 14 halides and alkyls R aMX to the mono valent group 13 bis-imidinate Ga(DDP) (DDP = 2-{(2,6-diisopropyl-phenyl)amino}-4-{(2,6-diisopropylphenyl)imino}-2-pentene) is reported. Accordingly, the insertion of Ga(DDP) into the Ga-Me bond of GaMe 3 yield in the complexes [{(DDP)GaMe}GaMe 2] ( 1) and [{(DDP)GaMe} 2GaMe] ( 2), respectively, which show a temperature-dependent equilibrium between 1 at higher temperatures and 2 at lower temperatures. In the case of GaCl 3, the only isolable product is [{(DDP)GaCl} 2GaCl] ( 3). The related reaction of SnMe 2Cl 2 with Ga(DDP) yields the compound [Me 2Sn{ClGa(DDP)} 2] ( 4), whereas SnMe 4 behaves inert. In the case of SiCl 4, only the monoinsertion product [Cl 3Si{ClGa(DDP)}] ( 5) was observed. Finally, [(CH 3) 3C{ClGa(DDP)}] ( 6) is synthesized by insertion of Ga(DDP) into the C-Cl bond of ClC(CH 3) 3. All new compounds were fully characterized by elemental analysis, NMR-spectroscopy, and single-crystal X-ray diffraction analysis. PMID:18630902

  3. Metal-clad optical waveguide fluorescence device for the detection of heavy metal ions

    NASA Astrophysics Data System (ADS)

    Margheri, Giancarlo; Giorgetti, Emilia; Marsili, Paolo; Zoppi, Angela; Lascialfari, Luisa; Cicchi, Stefano

    2014-07-01

    We developed Hg-sensing chips by decorating the external surface of metal-clad optical waveguides with a monolayer of Hg-sensitive fluorescent molecular probes. The emission properties of the original water-soluble form of the molecule were previously found to be selectively quenched in the presence of Hg ions. The fabricated samples were tested with optical waveguide fluorescence spectroscopy by putting them in contact with a 5-μM water solution of Hg ions and recording the emission spectra versus incubation time. The estimate of the limit of detection was 150 nM. A preliminary evaluation of the selectivity of the structure was also performed by using Cd as possible interfering analytes.

  4. A combined metal-halide/metal flux synthetic route towards type-I clathrates: crystal structures and thermoelectric properties of A8Al8Si38 (A = K, Rb, and Cs).

    PubMed

    Baran, Volodymyr; Senyshyn, Anatoliy; Karttunen, Antti J; Fischer, Andreas; Scherer, Wolfgang; Raudaschl-Sieber, Gabriele; Fässler, Thomas F

    2014-11-10

    Single-phase samples of the compounds K8Al8Si38 (1), Rb8Al8Si38 (2), and Cs7.9Al7.9Si38.1 (3) were obtained with high crystallinity and in good quantities by using a novel flux method with two different flux materials, such as Al and the respective alkali-metal halide salt (KBr, RbCl, and CsCl). This approach facilitates the removal of the product mixture from the container and also allows convenient extraction of the flux media due to the good solubility of the halide salts in water. The products were analyzed by means of single-crystal X-ray structure determination, powder X-ray and neutron diffraction experiments, (27)Al-MAS NMR spectroscopy measurements, quantum chemical calculations, as well as magnetic and transport measurements (thermal conductivity, electrical resistivity, and Seebeck coefficient). Due to the excellent quality of the neutron diffraction data, the difference between the nuclear scattering factors of silicon and aluminum atoms was sufficient to refine their mixed occupancy at specific sites. The role of variable-range hopping for the interpretation of the resistivity and the Seebeck coefficient is discussed. PMID:25267571

  5. Actinide halide complexes

    DOEpatents

    Avens, L.R.; Zwick, B.D.; Sattelberger, A.P.; Clark, D.L.; Watkin, J.G.

    1992-11-24

    A compound is described of the formula MX[sub n]L[sub m] wherein M is a metal atom selected from the group consisting of thorium, plutonium, neptunium or americium, X is a halide atom, n is an integer selected from the group of three or four, L is a coordinating ligand selected from the group consisting of aprotic Lewis bases having an oxygen-, nitrogen-, sulfur-, or phosphorus-donor, and m is an integer selected from the group of three or four for monodentate ligands or is the integer two for bidentate ligands, where the sum of n+m equals seven or eight for monodentate ligands or five or six for bidentate ligands. A compound of the formula MX[sub n] wherein M, X, and n are as previously defined, and a process of preparing such actinide metal compounds are described including admixing the actinide metal in an aprotic Lewis base as a coordinating solvent in the presence of a halogen-containing oxidant.

  6. Actinide halide complexes

    DOEpatents

    Avens, Larry R.; Zwick, Bill D.; Sattelberger, Alfred P.; Clark, David L.; Watkin, John G.

    1992-01-01

    A compound of the formula MX.sub.n L.sub.m wherein M is a metal atom selected from the group consisting of thorium, plutonium, neptunium or americium, X is a halide atom, n is an integer selected from the group of three or four, L is a coordinating ligand selected from the group consisting of aprotic Lewis bases having an oxygen-, nitrogen-, sulfur-, or phosphorus-donor, and m is an integer selected from the group of three or four for monodentate ligands or is the integer two for bidentate ligands, where the sum of n+m equals seven or eight for monodentate ligands or five or six for bidentate ligands, a compound of the formula MX.sub.n wherein M, X, and n are as previously defined, and a process of preparing such actinide metal compounds including admixing the actinide metal in an aprotic Lewis base as a coordinating solvent in the presence of a halogen-containing oxidant, are provided.

  7. Recent advances in technetium halide chemistry.

    PubMed

    Poineau, Frederic; Johnstone, Erik V; Czerwinski, Kenneth R; Sattelberger, Alfred P

    2014-02-18

    Transition metal binary halides are fundamental compounds, and the study of their structure, bonding, and other properties gives chemists a better understanding of physicochemical trends across the periodic table. One transition metal whose halide chemistry is underdeveloped is technetium, the lightest radioelement. For half a century, the halide chemistry of technetium has been defined by three compounds: TcF6, TcF5, and TcCl4. The absence of Tc binary bromides and iodides in the literature was surprising considering the existence of such compounds for all of the elements surrounding technetium. The common synthetic routes that scientists use to obtain binary halides of the neighboring elements, such as sealed tube reactions between elements and flowing gas reactions between a molecular complex and HX gas (X = Cl, Br, or I), had not been reported for technetium. In this Account, we discuss how we used these routes to revisit the halide chemistry of technetium. We report seven new phases: TcBr4, TcBr3, α/β-TcCl3, α/β-TcCl2, and TcI3. Technetium tetrachloride and tetrabromide are isostructural to PtX4 (X = Cl or Br) and consist of infinite chains of edge-sharing TcX6 octahedra. Trivalent technetium halides are isostructural to ruthenium and molybdenum (β-TcCl3, TcBr3, and TcI3) and to rhenium (α-TcCl3). Technetium tribromide and triiodide exhibit the TiI3 structure-type and consist of infinite chains of face-sharing TcX6 (X = Br or I) octahedra. Concerning the trichlorides, β-TcCl3 crystallizes with the AlCl3 structure-type and consists of infinite layers of edge-sharing TcCl6 octahedra, while α-TcCl3 consists of infinite layers of Tc3Cl9 units. Both phases of technetium dichloride exhibit new structure-types that consist of infinite chains of [Tc2Cl8] units. For the technetium binary halides, we studied the metal-metal interaction by theoretical methods and magnetic measurements. The change of the electronic configuration of the metal atom from d(3) (Tc

  8. Selective Fischer-Tropsch synthesis on metal powder catalysts prepared by the potassium reduction of halides in THF

    SciTech Connect

    Miyake, M.; Takebe, K.; Nomura, M.

    1987-06-01

    Metal powders such as Fe, Co, Ni, Fe-Co, and Fe-Ni prepared by reducing metal iodides or bromides with potassium metal in refluxing THF were used as catalysts for Fischer-Tropsch syntheses. These metal powders contained very small particles and have BET surface areas (28-36 m/sup 2//g). The metal powder catalysts, such as Fe and Fe-Co (80:20), gave 1-butene with more than 35 wt% selectivity at a rather high CO conversion of over 10 wt% at 533-553 K, while products on the Co catalyst obeyed conventional Schulz-Flory type distribution. The Ni catalyst showed little activity. Effects of reaction variables (temperature, H/sub 2//CO feed gas ratio, and composition of Fe-Co) were investigated.

  9. Complete-velocity-range description of negative-ion conversion of neutral atoms on an alkali-metal-halide surface under grazing geometry

    NASA Astrophysics Data System (ADS)

    Zhou, Hu; Zhou, Wang; Zhang, Meixiao; Zhou, Lihua; Ma, Yulong; Wang, Guangyi; Wu, Yong; Li, Bowen; Chen, Ximeng

    2016-06-01

    We propose a simple theoretical approach to consider negative-ion conversion of neutral atoms grazing on alkali-metal-halide crystal surfaces over the complete velocity range. The conversion process is viewed as a series of successive binary collisions between the projectile and the negatively charged sites on the surface along their trajectories due to localization of valence-band electrons at the anionic sites of the crystal. Conversion from F0 to F- via grazing scattering in LiF(100) and KI(100) is demonstrated with this model, which incorporates the key factors of image interaction and Mott-Littleton polarization interaction for electron capture. It also incorporates the decrease in the electron affinity due to Coulomb barrier tunneling of large-velocity negative ions to the vacuum level near surface anion sites. The pronounced differences in the efficiency of F- formation at LiF(100) and KI(100) surfaces are well explained by the proposed model. The relative efficiency and related saturation of the negative-ion formation for LiF and KI crystals compare well with experimental results.

  10. Mechanism of Charge Transfer and Recombination Dynamics in Organo Metal Halide Perovskites and Organic Electrodes, PCBM, and Spiro-OMeTAD: Role of Dark Carriers.

    PubMed

    Ponseca, Carlito S; Hutter, Eline M; Piatkowski, Piotr; Cohen, Boiko; Pascher, Torbjörn; Douhal, Abderrazzak; Yartsev, Arkady; Sundström, Villy; Savenije, Tom J

    2015-12-30

    Despite the unprecedented interest in organic-inorganic metal halide perovskite solar cells, quantitative information on the charge transfer dynamics into selective electrodes is still lacking. In this paper, we report the time scales and mechanisms of electron and hole injection and recombination dynamics at organic PCBM and Spiro-OMeTAD electrode interfaces. On the one hand, hole transfer is complete on the subpicosecond time scale in MAPbI3/Spiro-OMeTAD, and its recombination rate is similar to that in neat MAPbI3. This was found to be due to a high concentration of dark charges, i.e., holes brought about by unintentional p-type doping of MAPbI3. Hence, the total concentration of holes in the perovskite is hardly affected by optical excitation, which manifested as similar decay kinetics. On the other hand, the decay of the photoinduced conductivity in MAPbI3/PCBM is on the time scale of hundreds of picoseconds to several nanoseconds, due to electron injection into PCBM and electron-hole recombination at the interface occurring at similar rates. These results highlight the importance of understanding the role of dark carriers in deconvoluting the complex photophysical processes in these materials. Moreover, optimizing the preparation processes wherein undesired doping is minimized could prompt the use of organic molecules as a more viable electrode substitute for perovskite solar cell devices. PMID:26636183

  11. Chemistry of soluble β-diketiminatoalkaline-earth metal complexes with M-X bonds (M=Mg, Ca, Sr; X=OH, Halides, H).

    PubMed

    Sarish, Sankaranarayana Pillai; Nembenna, Sharanappa; Nagendran, Selvarajan; Roesky, Herbert W

    2011-03-15

    Victor Grignard's Nobel Prize-winning preparation of organomagnesium halides (Grignard reagents) marked the formal beginning of organometallic chemistry with alkaline earth metals. Further development of this invaluable synthetic route, RX+Mg→RMgX, with the heavier alkaline earth metals (Ca and Sr) was hampered by limitations in synthetic methodologies. Moreover, the lack of suitable ligands for stabilizing the reactive target molecules, particularly with the more electropositive Ca and Sr, was another obstacle. The absence in the literature, until just recently, of fundamental alkaline earth metal complexes with M-H, M-F, and M-OH (where M is the Group 2 metal Mg, Ca, or Sr) bonds amenable for organometallic reactions is remarkable. The progress in isolating various unstable compounds of p-block elements with β-diketiminate ligands was recently applied to Group 2 chemistry. The monoanionic β-diketiminate ligands are versatile tools for addressing synthetic challenges, as amply demonstrated with alkaline earth complexes: the synthesis and structural characterization of soluble β-diketiminatocalcium hydroxide, β-diketiminatostrontium hydroxide, and β-diketiminatocalcium fluoride are just a few examples of our contribution to this area of research. To advance the chemistry beyond synthesis, we have investigated the reactivity and potential for applications of these species, for example, through the demonstration of dip coating surfaces with CaCO(3) and CaF(2) with solutions of the calcium hydroxide and calcium fluoride complexes, respectively. In this Account, we summarize some recent developments in alkaline earth metal complex chemistry, particularly of Mg, Ca, and Sr, through the utilization of β-diketiminate ligands. We focus on results generated in our laboratory but give due mention to work from other groups as well. We also highlight the closely related chemistry of the Group 12 element Zn, as well as the important chemistry developed by other groups

  12. Rigidifying Fluorescent Linkers by Metal-Organic Framework Formation for Fluorescence Blue Shift and Quantum Yield Enhancement

    SciTech Connect

    Wei, ZW; Gu, ZY; Arvapally, RK; Chen, YP; McDougald, RN; Ivy, JF; Yakovenko, AA; Feng, DW; Omary, MA; Zhou, HC

    2014-06-11

    We demonstrate that rigidifying the structure of fluorescent linkers by structurally constraining them in metal-organic frameworks (MOFs) to control their conformation effectively tunes the fluorescence energy and enhances the quantum yield. Thus, a new tetraphenylethylene-based zirconium MOF exhibits a deep-blue fluorescent emission at 470 nm with a unity quantum yield (99.9 +/- 0.5%) under Ar, representing ca. 3600 cm(-1) blue shift and doubled radiative decay efficiency vs the linker precursor. An anomalous increase in the fluorescence lifetime and relative intensity takes place upon heating the solid MOF from cryogenic to ambient temperatures. The origin of these unusual photoluminescence properties is attributed to twisted linker conformation, intramolecular hindrance, and framework rigidity.

  13. Fluorescent metal nanoshell and CK19 detection on single cell image

    SciTech Connect

    Zhang, Jian; Fu, Yi; Li, Ge; Lakowicz, Joseph R.; Zhao, Richard Y.

    2011-09-16

    Highlights: {yields} Novel metal nanoshell as fluorescence imaging agent. {yields} Fluorescent mAb-metal complex with enhanced intensity and shortened lifetime. {yields} Immuno-interactions of mAb-metal complexes with CK19 molecules on CNCAP and HeLa cell surfaces. {yields} Isolation of conjugated mAb-metal complexes from cellular autofluorescence on cell image. -- Abstract: In this article, we report the synthesis strategy and optical properties of a novel type of fluorescence metal nanoshell when it was used as imaging agent for fluorescence cell imaging. The metal nanoshells were made with 40 nm silica cores and 10 nm silver shells. Unlike typical fluorescence metal nanoshells which contain the organic dyes in the cores, novel metal nanoshells were composed of Cy5-labelled monoclonal anti-CK19 antibodies (mAbs) on the external surfaces of shells. Optical measurements to the single nanoparticles showed that in comparison with the metal free labelled mAbs, the mAb-Ag complexes displayed significantly enhanced emission intensity and dramatically shortened lifetime due to near-field interactions of fluorophores with metal. These metal nanoshells were found to be able to immunoreact with target cytokeratin 19 (CK19) molecules on the surfaces of LNCAP and HeLa cells. Fluorescence cell images were recorded on a time-resolved confocal microscope. The emissions from the metal nanoprobes could be clearly isolated from the cellular autofluorescence backgrounds on the cell images as either individuals or small clusters due to their stronger emission intensities and shorter lifetimes. These emission signals could also be precisely counted on single cell images. The count number may provide an approach for quantifying the target molecules in the cells.

  14. APPARATUS FOR THE PRODUCTION OF LITHIUM METAL

    DOEpatents

    Baker, P.S.; Duncan, F.R.; Greene, H.B.

    1961-08-22

    Methods and apparatus for the production of high-purity lithium from lithium halides are described. The apparatus is provided for continuously contacting a molten lithium halide with molten barium, thereby forming lithium metal and a barium halide, establishing separate layers of these reaction products and unreacted barium and lithium halide, and continuously withdrawing lithium and barium halide from the reaction zone. (AEC)

  15. An artificial tongue fluorescent sensor array for identification and quantitation of various heavy metal ions.

    PubMed

    Xu, Wang; Ren, Changliang; Teoh, Chai Lean; Peng, Juanjuan; Gadre, Shubhankar Haribhau; Rhee, Hyun-Woo; Lee, Chi-Lik Ken; Chang, Young-Tae

    2014-09-01

    Herein, a small-molecule fluorescent sensor array for rapid identification of seven heavy metal ions was designed and synthesized, with its sensing mechanism mimicking that of a tongue. The photoinduced electron transfer and intramolecular charge transfer mechanism result in combinatorial interactions between sensor array and heavy metal ions, which lead to diversified fluorescence wavelength shifts and emission intensity changes. Upon principle component analysis (PCA), this result renders clear identification of each heavy metal ion on a 3D spatial dispersion graph. Further exploration provides a concentration-dependent pattern, allowing both qualitative and quantitative measurements of heavy metal ions. On the basis of this information, a "safe-zone" concept was proposed, which provides rapid exclusion of versatile hazardous species from clean water samples based on toxicity characteristic leaching procedure standards. This type of small-molecule fluorescent sensor array could open a new avenue for multiple heavy metal ion detection and simplified water quality analysis. PMID:25144824

  16. Maximizing dye fluorescence via incorporation of metallic nanoparticles in solution

    NASA Astrophysics Data System (ADS)

    Xu, Yang; Lei, Guangyin; Booker, Annette C.; Linares, Katherine A.; Fleming, Dara L.; Meehan, Kathleen; Lu, Guo-Quan; Love, Nancy G.; Love, Brian J.

    2004-12-01

    Gram-negative bacteria initiate a stress response in which the cells efflux potassium when electrophilic toxins are introduced into their environment. Hence, measurement of K+ concentration in the surrounding water using a fluorescence-based potassium-selective optode has been proposed for environmental and homeland security applications. Unfortunately, the fluorophore commonly used in such an optode is inefficient. Surface enhanced fluorescence (SEF) can be used to increase its fluorescence efficiency, which will improve the sensor's performance. To understand this phenomenon before applying it to the optode system, Rose Bengal (RB), an inexpensive and well characterized dye, in solution with gold and silver nanoparticles was studied. As expected, fluorescence from RB-gold solutions was low since alignment of gold's surface plasmon resonance (SPR) peak and absorption and fluorescence energies in RB favored energy transfer from RB to the gold nanoparticles. The alignment of the silver's SPR peak and the RB transitions favored transfer from silver to RB. SEF was observed in solutions with large dye-to-silver separation. However, little fluorescence was observed when the solution was pumped at the silver's SPR peak. Fluorescence from the dye decreased as dye-to-silver separation decreased. An explanation for these observations is presented; additional research is needed to develop a complete understanding.

  17. Recognition- and Reactivity-Based Fluorescent Probes for Studying Transition Metal Signaling in Living Systems

    PubMed Central

    2015-01-01

    Conspectus Metals are essential for life, playing critical roles in all aspects of the central dogma of biology (e.g., the transcription and translation of nucleic acids and synthesis of proteins). Redox-inactive alkali, alkaline earth, and transition metals such as sodium, potassium, calcium, and zinc are widely recognized as dynamic signals, whereas redox-active transition metals such as copper and iron are traditionally thought of as sequestered by protein ligands, including as static enzyme cofactors, in part because of their potential to trigger oxidative stress and damage via Fenton chemistry. Metals in biology can be broadly categorized into two pools: static and labile. In the former, proteins and other macromolecules tightly bind metals; in the latter, metals are bound relatively weakly to cellular ligands, including proteins and low molecular weight ligands. Fluorescent probes can be useful tools for studying the roles of transition metals in their labile forms. Probes for imaging transition metal dynamics in living systems must meet several stringent criteria. In addition to exhibiting desirable photophysical properties and biocompatibility, they must be selective and show a fluorescence turn-on response to the metal of interest. To meet this challenge, we have pursued two general strategies for metal detection, termed “recognition” and “reactivity”. Our design of transition metal probes makes use of a recognition-based approach for copper and nickel and a reactivity-based approach for cobalt and iron. This Account summarizes progress in our laboratory on both the development and application of fluorescent probes to identify and study the signaling roles of transition metals in biology. In conjunction with complementary methods for direct metal detection and genetic and/or pharmacological manipulations, fluorescent probes for transition metals have helped reveal a number of principles underlying transition metal dynamics. In this Account, we give

  18. Recognition- and reactivity-based fluorescent probes for studying transition metal signaling in living systems.

    PubMed

    Aron, Allegra T; Ramos-Torres, Karla M; Cotruvo, Joseph A; Chang, Christopher J

    2015-08-18

    Metals are essential for life, playing critical roles in all aspects of the central dogma of biology (e.g., the transcription and translation of nucleic acids and synthesis of proteins). Redox-inactive alkali, alkaline earth, and transition metals such as sodium, potassium, calcium, and zinc are widely recognized as dynamic signals, whereas redox-active transition metals such as copper and iron are traditionally thought of as sequestered by protein ligands, including as static enzyme cofactors, in part because of their potential to trigger oxidative stress and damage via Fenton chemistry. Metals in biology can be broadly categorized into two pools: static and labile. In the former, proteins and other macromolecules tightly bind metals; in the latter, metals are bound relatively weakly to cellular ligands, including proteins and low molecular weight ligands. Fluorescent probes can be useful tools for studying the roles of transition metals in their labile forms. Probes for imaging transition metal dynamics in living systems must meet several stringent criteria. In addition to exhibiting desirable photophysical properties and biocompatibility, they must be selective and show a fluorescence turn-on response to the metal of interest. To meet this challenge, we have pursued two general strategies for metal detection, termed "recognition" and "reactivity". Our design of transition metal probes makes use of a recognition-based approach for copper and nickel and a reactivity-based approach for cobalt and iron. This Account summarizes progress in our laboratory on both the development and application of fluorescent probes to identify and study the signaling roles of transition metals in biology. In conjunction with complementary methods for direct metal detection and genetic and/or pharmacological manipulations, fluorescent probes for transition metals have helped reveal a number of principles underlying transition metal dynamics. In this Account, we give three recent

  19. Investigating the gas phase emitter effect of caesium and cerium in ceramic metal halide lamps in dependence on the operating frequency

    NASA Astrophysics Data System (ADS)

    Ruhrmann, C.; Westermeier, M.; Bergner, A.; Luijks, G. M. J. F.; Awakowicz, P.; Mentel, J.

    2011-09-01

    The work function and with it the temperature of tungsten electrodes in HID lamps can be lowered and the lifetime of lamps increased by the gas phase emitter effect. A determination of the emitter effect of Cs and Ce is performed by phase resolved measurements of the electrode tip temperature Ttip(phiv), plasma temperature Tpl(phiv) and particle densities N(phiv) by means of pyrometric, optical emission and broadband absorption spectroscopy in dependence on the operating frequency. The investigated HID lamps are ceramic metal halide lamps with transparent discharge vessels made of YAG, filled with a buffer gas consisting of Ar, Kr and predominantly Hg and seeded with CsI or CeI3. In the YAG lamp seeded with CsI and CeI3 as well as in a YAG lamp seeded with DyI3 (corresponding results can be found in a preceding paper) a gas phase emitter effect is observed in the cathodic phase due to a Cs, Ce or Dy ion current. In the YAG lamp seeded with CsI the phase averaged coverage of the electrode surface with emitter atoms decreases and the electrode temperature rises with increasing frequency, whereas the emitter effect of Ce and Dy is extended to the anodic phase, which leads to a decreased average temperature Ttip(phiv) with increasing frequency. This different behaviour of the averaged values of Ttip(phiv) for increasing frequency is caused by the differing adsorption energies Ea of the respective emitter materials. In spite of the influence of Ea on the coverage of the electrode with emitter atoms, the cathodic gas phase emitter effect produces in the YAG lamps seeded with CsI, CeI3 and DyI3 a general reduction in the electrode tip temperature Ttip(phiv) in comparison with a YAG lamp with Hg filling only.

  20. Ce53Fe12S90X3 (X = Cl, Br, I): the first rare-earth transition-metal sulfide halides.

    PubMed

    Mills, Allison M; Ruck, Michael

    2006-06-26

    The compounds Ce53Fe12S90X3 (X = Cl, Br, I), which represent the first examples of rare-earth transition-metal sulfide halides, were prepared using the reactive-flux method, through reaction of Ce2S3, FeS, or Fe and S in a CeX3 flux at 1320 K. Their structures were determined by single-crystal X-ray diffraction. The compounds are isostructural, crystallizing in the trigonal space group Rm with Z = 1 [Ce53Fe12S90Cl3, a = 13.9094(9) A, c = 21.604(2) A, V = 3619.7(4) A3; Ce(53)Fe(12)S(90)Br(3), a = 13.916(1) A, c = 21.824(2) A, V = 3660.0(5) A3; Ce53Fe12S90I3, a = 13.863(3) A, c = 21.944(6) A, V = 3652(2) A3]. The structure adopted is a stuffed variant of the La52Fe12S90 structure type. Fe2S9 dimers of face-sharing octahedra are linked by face- and vertex-sharing capped CeS6 trigonal prisms, forming a three-dimensional framework containing cuboctahedral cavities of two sizes. The smaller cavities accommodate alternative sites for disordered cerium atoms. The larger cavities, which remain empty in the parent structure, are filled by halogen atoms in Ce53Fe12S90X3. Alternatively, the structure can be described as a 9-fold superstructure of the Mn5Si3 structure type (P6(3)/mcm), with a = a' and c = 3c'. Temperature-dependent magnetic susceptibility measurements suggest that Ce53Fe12S90I3 may order antiferromagnetically at low temperatures. PMID:16780341

  1. Fluorescent metal nanoshell and CK19 detection on single cell image.

    PubMed

    Zhang, Jian; Fu, Yi; Li, Ge; Lakowicz, Joseph R; Zhao, Richard Y

    2011-09-16

    In this article, we report the synthesis strategy and optical properties of a novel type of fluorescence metal nanoshell when it was used as imaging agent for fluorescence cell imaging. The metal nanoshells were made with 40 nm silica cores and 10nm silver shells. Unlike typical fluorescence metal nanoshells which contain the organic dyes in the cores, novel metal nanoshells were composed of Cy5-labelled monoclonal anti-CK19 antibodies (mAbs) on the external surfaces of shells. Optical measurements to the single nanoparticles showed that in comparison with the metal free labelled mAbs, the mAb-Ag complexes displayed significantly enhanced emission intensity and dramatically shortened lifetime due to near-field interactions of fluorophores with metal. These metal nanoshells were found to be able to immunoreact with target cytokeratin 19 (CK19) molecules on the surfaces of LNCAP and HeLa cells. Fluorescence cell images were recorded on a time-resolved confocal microscope. The emissions from the metal nanoprobes could be clearly isolated from the cellular autofluorescence backgrounds on the cell images as either individuals or small clusters due to their stronger emission intensities and shorter lifetimes. These emission signals could also be precisely counted on single cell images. The count number may provide an approach for quantifying the target molecules in the cells. PMID:21867692

  2. Molecular compressibility of some halides in alcohols

    NASA Technical Reports Server (NTRS)

    Serban, C.; Auslaender, D.

    1974-01-01

    After measuring ultrasonic velocity and density, the molecular compressibility values from Wada's formula were calculated, for alkali metal halide solutions in methyl, ethyl, butyl, and glycol alcohol. The temperature and concentration dependence were studied, finding deviations due to the hydrogen bonds of the solvent.

  3. Floating AC-DEP (dielectrophoretic) manipulations of fluorescent nanoparticle at metal nanostructure for plasmonic applications

    NASA Astrophysics Data System (ADS)

    Kim, J.; Shin, H. J.; Hwang, K. S.; Park, J. H.

    2014-11-01

    We propose the fluorescent nanoparticle manipulations at nano-metal structures with floating AC-DEP force for plasmonic applications. The electrode gap was optimized to induce enough DEP force around the nano-structure for manipulation of the nanoparticles. 10um wide gap of electrode was acquired to apply the floating AC-DEP force at various designed metal nano-structure such as nanowire, y-branch and vortex. The all shape of nano-metal structures are formed at the gap of microelectrode and not connected with microelectrode. The gold nano-structures in the gap of microelectrode were fabricated with e-beam lithography and lift-off process. Before the formation of metal nanostructure, micro electrodes for applying the electric field around the metal nano-structures were fabricated with photolithography and lift-off process. Cadmium selenide (CdSe/ZnS) QDs (0.8 nM, emission wavelength of 605 nm) with a 25 nm zinc sulfide capping layer and 100nm polystyrene nano bead (1 nM, emission wavelength of 610nm) were used as fluorescent nanoparticles. We applied the 8 Vpp, 3 MHz sine wave for the positive DEP force, and it resulted in 108 V/m electric field and 1011 V/m electric field gradient around gold nanowire with floating AC. The fluorescent nanoparticle's attachment at the nanowire is confirmed by the fluorescent optical analysis. The fluorescent nanoparticles are located successfully at designed metal nano-structures for plasmonic applications.

  4. Determination of metal ions by fluorescence anisotropy exhibits a broad dynamic range

    NASA Astrophysics Data System (ADS)

    Thompson, Richard B.; Maliwal, Badri P.; Fierke, Carol A.

    1998-05-01

    Recently, we have shown that metal ions free in solution may be determined at low levels by fluorescence anisotropy (polarization) measurements. Anisotropy measurements enjoy the advantages of wavelength ratiometric techniques for determining metal ions such as calcium, because anisotropy measurements are ratiometric as well. Furthermore, fluorescence anisotropy may be imaged in the microscope. An advantage of anisotropy not demonstrated for wavelength ratiometric approaches using indicators such as Fura-2 and Indo-1 is that under favorable circumstances anisotropy-based determinations exhibit a much broader dynamic range in metal ion concentration. Determinations of free Zn(II) in the picomolar range are demonstrated.

  5. High-power metal halide vapour lasers oscillating in deep ultraviolet, visible and middle infrared spectral ranges

    NASA Astrophysics Data System (ADS)

    Temelkov, K. A.; Slaveeva, S. I.; Kirilov, V. I.; Kostadinov, I. K.; Vuchkov, N. K.

    2012-05-01

    Middle infrared and deep ultraviolet high-power high-beam-quality stable-operating He-SrBr2 and Cu+ Ne-CuBr lasers excited in nanosecond pulsed longitudinal discharge are developed, patented and studied. Optimal discharge conditions, such as active zone diameter, vapour pressure, buffer-gas pressure, electrical excitation scheme parameters, average input power and pulse repetition frequency, are found. The highest output laser parameters are obtained for the Sr atom and Cu+ lasers, respectively. These lasers equipped with optical systems for the control of laser radiation parameters are used in a large variety of applications, such as precise material microprocessing, including biological tissues, determination of linear optical properties of different newly developed materials, laser-induced modification of conductive polymers and laser-induced fluorescence in wide-gap semiconductors, instead of free electron and excimer lasers, respectively. A master oscillator-power amplifier system, which is based on a high-beam-quality high-power CuBr vapour laser and is equipped with an optic system for laser beam control and with the X-Y stage controlled by adequate software as well, is developed and used in high-precision micromachining of samples made of nickel and tool steel.

  6. Strong dependence of fluorescence quenching on the transition metal in layered transition metal dichalcogenide nanoflakes for nucleic acid detection.

    PubMed

    Loo, Adeline Huiling; Bonanni, Alessandra; Pumera, Martin

    2016-08-01

    In recent years, the application of transition metal dichalcogenides for the development of biosensors has been receiving widespread attention from researchers, as demonstrated by the surge in studies present in the field. While different transition metal dichalcogenide materials have been employed for the fabrication of fluorescent biosensors with superior performance, no research has been conducted to draw comparisons across materials containing different transition metals. Herein, the performance of MoS2 and WS2 nanoflakes for the fluorescence detection of nucleic acids is assessed. It is discovered that, at the optimal amount, MoS2 and WS2 nanoflakes exhibit a similar degree of fluorescence quenching, at 75% and 71% respectively. However, MoS2 nanoflakes have better performance in the areas of detection range and selectivity than WS2 nanoflakes. The detection range achieved with MoS2 nanoflakes is 9.60-366 nM while 13.3-143 nM with WS2 nanoflakes. In the context of selectivity, MoS2 nanoflakes display a signal difference of 97.8% between complementary and non-complementary DNA targets, whereas WS2 nanoflakes only exhibit 44.3%. Such research is highly beneficial as it delivers vital insights on how the performance of a fluorescent biosensor can be affected by the transition metal present. Furthermore, these insights can assist in the selection of suitable transition metal dichalcogenide materials for utilization in biosensor development. PMID:27241269

  7. Oligomeric rare-earth-metal halide clusters. Three structures built of (Y{sub 16}Z{sub 4})Br{sub 36} units (Z = Ru, Ir)

    SciTech Connect

    Steinward, S.J.; Corbett, J.D.

    1996-11-20

    Suitable reactions in sealed Nb tubing at 850-950 {degrees}C gave good yields of a family of oligomeric cluster phases that were characterized by single-crystal X-ray diffraction means. The basic Y{sub 16}Z{sub 4} units ({approximately}{bar 4} symmetry) can be derived from 2+2 condensation of centered Y{sub 6}Br{sub 12}Z-type clusters or as tetracapped truncated tetrahedra Y{sub 16} that are centered by a large tetrahedral Z{sub 4}. These are surrounded by 36 bromine atoms which bridge edges or cap faces of the Y{sub 16}Z{sub 4} nuclei and, in part, bridge to metal atoms in other clusters. The principal bonding appears to be Y-Z and Y-Br, with weaker Y-Y ({bar d} {approximately} 3.70 {angstrom}) and negligible Z-Z interactions. The phase Y{sub 16}Br{sub 20}Ru{sub 4} (P4{sub 2}/nnm, Z = 2; a = 11.662(1) {angstrom}, c = 16.992 (2) {angstrom}) is isostructural with Y{sub 16}I{sub 20}Ru{sub 4} and with the new Sc{sub 16-} Br{sub 20}Z{sub 4} (Z = Fe, Os). Syntheses only in the presence of Ir and ABr-YBr{sub 3} fluxes (A = K-Cs) produce Y{sub 16-} Br{sub 24}Ir{sub 4} (Fddd, Z = 8; a = 11.718(3) {angstrom}, b = 22.361(7) {angstrom}, c = 44.702(2) {angstrom}), in which the electron-richer Ir interstitials are compensated by four additional bromine atoms and altered bridging between macroclusters. Larger amounts of YBr{sub 3} yield a third example, Y{sub 20}Br{sub 36}Ir{sub 4} (Y{sub 16}Br{sub 24}Ir{sub 4}{center_dot}4YBr{sub 3}, I4{sub 1}a, Z = 4; a = 12.699(1) {angstrom}, c = 45.11- (1){angstrom}). Here infinite zigzag chains of YBr{sub 6/2} octahedra that share cis edges lie between and bridge to the Y{sub 16}Ir{sub 4} clusters. All of these phases contain 60-electron, closed-shell macroclusters. Y{sub 16}Br{sub 20}Ru{sub 4} and Y{sub 20}Br{sub 36}ir{sub 4} were found to exhibit temperature-independent (Van Vleck) paramagnetism with values typical of those found for other rare-earth-metal, zirconium, niobium, and tantalum cluster halides.

  8. Heavy metal chelator TPEN attenuates fura-2 fluorescence changes induced by cadmium, mercury and methylmercury

    PubMed Central

    OHKUBO, Masato; MIYAMOTO, Atsushi; SHIRAISHI, Mitsuya

    2016-01-01

    Stimulation with heavy metals is known to induce calcium (Ca2+) mobilization in many cell types. Interference with the measurement of intracellular Ca2+ concentration by the heavy metals in cells loaded with Ca2+ indicator fura-2 is an ongoing problem. In this study, we analyzed the effect of heavy metals on the fura-2 fluorescence ratio in human SH-SY5Y neuroblastoma cells by using TPEN, a specific cell-permeable heavy metal chelator. Manganese chloride (30–300 µM) did not cause significant changes in the fura-2 fluorescence ratio. A high concentration (300 µM) of lead acetate induced a slight elevation in the fura-2 fluorescence ratio. In contrast, stimulation with cadmium chloride, mercury chloride or MeHg (3–30 µM) elicited an apparent elevation of the fura-2 fluorescence ratio in a dose-dependent manner. In cells stimulated with 10 or 30 µM cadmium chloride, the addition of TPEN decreased the elevated fura-2 fluorescence ratio to basal levels. In cells stimulated with mercury or MeHg, the addition of TPEN significantly decreased the elevation of the fura-2 fluorescence ratio induced by lower concentrations (10 µM) of mercury or MeHg, but not by higher concentrations (30 µM). Pretreatment with Ca2+ channel blockers, such as verapamil, 2-APB or lanthanum chloride, resulted in different effects on the fura-2 fluorescence ratio. Our study provides a characterization of the effects of several heavy metals on the mobilization of divalent cations and the toxicity of heavy metals to neuronal cells. PMID:26781706

  9. Heavy metal chelator TPEN attenuates fura-2 fluorescence changes induced by cadmium, mercury and methylmercury.

    PubMed

    Ohkubo, Masato; Miyamoto, Atsushi; Shiraishi, Mitsuya

    2016-06-01

    Stimulation with heavy metals is known to induce calcium (Ca(2+)) mobilization in many cell types. Interference with the measurement of intracellular Ca(2+) concentration by the heavy metals in cells loaded with Ca(2+) indicator fura-2 is an ongoing problem. In this study, we analyzed the effect of heavy metals on the fura-2 fluorescence ratio in human SH-SY5Y neuroblastoma cells by using TPEN, a specific cell-permeable heavy metal chelator. Manganese chloride (30-300 µM) did not cause significant changes in the fura-2 fluorescence ratio. A high concentration (300 µM) of lead acetate induced a slight elevation in the fura-2 fluorescence ratio. In contrast, stimulation with cadmium chloride, mercury chloride or MeHg (3-30 µM) elicited an apparent elevation of the fura-2 fluorescence ratio in a dose-dependent manner. In cells stimulated with 10 or 30 µM cadmium chloride, the addition of TPEN decreased the elevated fura-2 fluorescence ratio to basal levels. In cells stimulated with mercury or MeHg, the addition of TPEN significantly decreased the elevation of the fura-2 fluorescence ratio induced by lower concentrations (10 µM) of mercury or MeHg, but not by higher concentrations (30 µM). Pretreatment with Ca(2+) channel blockers, such as verapamil, 2-APB or lanthanum chloride, resulted in different effects on the fura-2 fluorescence ratio. Our study provides a characterization of the effects of several heavy metals on the mobilization of divalent cations and the toxicity of heavy metals to neuronal cells. PMID:26781706

  10. Metal-enhanced chemiluminescence from chromium, copper, nickel, and zinc nanodeposits: Evidence for a second enhancement mechanism in metal-enhanced fluorescence

    SciTech Connect

    Weisenberg, Micah; Zhang Yongxia; Geddes, Chris D.

    2010-09-27

    Over the past decade metal-fluorophore interactions, metal-enhanced fluorescence, have attracted significant research attention, with the technology now becoming common place in life science applications. In this paper, we address the underlying mechanisms of metal-enhanced fluorescence (MEF) and experimentally show using chemiluminescence solutions that MEF is indeed underpinned by two complimentary mechanisms, consistent with the recent reports by Geddes and co-workers [Zhang et al., J. Phys. Chem. C 113, 12095 (2009)] and their enhanced fluorescence hypothesis.

  11. Metal vapor Raman frequency shifter

    SciTech Connect

    Feldman, D.W.; Liu, C.; Weaver, L.A.

    1980-12-16

    Shifted Raman radiation for an all-hot Raman discharge cell is produced by external laser pumping of a metal halide medium in the cell during an afterglow period following dissociation of the metal halide medium into metal atoms and before recombination to form the original species of the metal halide medium.

  12. Quenching of tryptophan fluorescence of bovine serum albumin under the effect of ions of heavy metals

    NASA Astrophysics Data System (ADS)

    Plotnikova, O. A.; Mel'nikov, A. G.; Mel'nikov, G. V.; Gubina, T. I.

    2016-01-01

    The interaction of heavy metals with bovine serum albumin (BSA) has been studied using data of quenching of intrinsic fluorescence of the protein by the ions of the heavy metals. Under the assumption of static quenching with formation of nonfluorescent complexes of fluorophores of BSA with heavy metals, conclusions have been drawn on the peculiarities of binding of the heavy metals to the protein. The values of the Stern-Volmer constants of association and those of the constants of BSA binding to the heavy metals decrease in the order Cu(II) > Pb(II) > Cd(II). It has been experimentally found that the copper ions have greater capacity to bind to the protein with the formation of the nonfluorescent complexes, which results in a significant decrease in the fluorescence intensity of the protein.

  13. Ratiometric Fluorescent Detection of Phosphate in Aqueous Solution Based on Near Infrared Fluorescent Silver Nanoclusters/Metal-Organic Shell Composite.

    PubMed

    Dai, Cong; Yang, Cheng-Xiong; Yan, Xiu-Ping

    2015-11-17

    Synthesis of near-infrared (NIR) fluorescent AgNCs with high quantum yield and stability is challenging but important for sensing and bioimaging application. Here, we report the fabrication of AgNCs/metal-organic shell composite via the deposition of metal-organic (zinc-nitrogen) coordination shell around AgNCs for ratiometric detection of phosphate. The composite exhibits NIR emission at 720 nm with 30 nm red-shift in comparison to bare AgNCs and a weak emission at 510 nm from the shell. The absolute quantum yield of NIR fluorescence of the composite is 15%, owing to FRET from the shell to the AgNCs core under the excitation at 430 nm. Besides, the composite is stable due to the protection of the shell. On the basis of the composite, a novel ratiometric fluorescence probe for the detection of phosphate in aqueous solution with good sensitivity and selectivity was developed. The limit of detection (3s) is 0.06 μM, and the relative standard deviation for 10 replicate detections of 10 μM phosphate was 0.6%. The recoveries of spiked phosphate in water, human urine, and serum samples ranged from 94.1% to 103.4%. PMID:26489902

  14. Metal-enhanced intrinsic fluorescence of nucleic acids using platinum nanostructured substrates

    NASA Astrophysics Data System (ADS)

    Akbay, Nuriye; Mahdavi, Farhad; Lakowicz, Joseph R.; Ray, Krishanu

    2012-10-01

    We investigated the feasibility of using platinum nanostructures to accomplish the metal-enhanced fluorescence (MEF) in the UV spectral region. We examine the possibility for detection of the intrinsic fluorescence from nucleotides and G-quadruplex DNA on platinum nanoparticles. Guanosine monophosphate (GMP) showed significant increases (˜20-fold) in fluorescence intensities in the presence of platinum nanostructures when compared to quartz controls. G-quadruplex DNA demonstrated ˜5-fold increase in fluorescence intensity and higher photostability in the presence of Pt nanostructures. We performed Finite Element Method simulations to explore how Pt nanoparticles interact with plane waves and conformed that the Pt nanostructures are promising for enhancing the fluorescence emission in the UV region.

  15. UV-Fluorescent Sensing for Primary Selection of Metal-rich Seafloor Massive Sulfide Ore

    NASA Astrophysics Data System (ADS)

    Yamazaki, T.; Nakatani, T.; Nakatani, N.; Arai, R.

    2012-12-01

    Seafloor massive sulfides (SMS) in the western Pacific have received much attention as resources for Au, Ag, Cu, Zn, and Pb. Because of the higher metal contents, the venture commercial mining project may start in 2013 in the East Manus Basin, Papua New Guinea. One of important problems to be solved is reducing the waste rock disposal costs for the economy. The best location for the reducing is on seafloor just after the excavation of SMS ores. The authors select UV-fluorescent sensing for primary selection of the ores, because no additional environmental impact is created with the application of the method. First of all, the effectiveness of the UV-fluorescent sensing by a combination system with a UV-light and a camera (See attached figure) in deep water condition is clarified. Then many UV-fluorescent data of SMS ore, SMS accompanied rock, and seafloor rock samples are collected. In the analyses phase, the ore and rock samples are classified into some groups by applying the cluster analysis to the metal contents at first. Then, using the UV fluorescent color brightness and contrasts of the ore and rock samples, the discriminant analysis based on Mahalanobis distance is applied. The higher possibility to identify the SMS ores containing valuable metals from camera image is suggested from the analyses. When additional UV-fluorescent and chemical assay data are obtained, the renewal of discriminant analysis is necessary. Therefore, the results and conclusions described in this study are tentative ones.; UV-fluorescent sensing

  16. Transition-metal ions in Nd-doped glasses: spectra and effects on Nd fluorescence

    SciTech Connect

    Stokowski, S.E.; Krashkevich, D.

    1985-12-19

    We have measured transition-metal ion (Ti, V, Cr, Mn, Fe, Co, Ni, Cu) spectra and their effects on Nd fluorescence quenching in Nd-doped phosphate and silicate glasses. Our purpose was to determine the maximum allowable impurity content given particular limits on the absorption loss at 1053 nm and the Nd fluorescence quenching rate. To keep the absorption loss <0.1 m/sup -1/ the transition-metal impurity content should be kept below 0.5 ppMw. To keep the increase in the Nd fluorescence decay rate below 1%, the impurity content should be <3 ppMw. We have also found that the Nd quenching rates do not scale as predicted by the Forster-Dexter dipole-dipole energy transfer theory if we assume that the dominant variation with transition metal is the overlap integral of the Nd fluorescence spectrum and the transition-metal absorption. We suggest that phonon-assisted energy transfer to transition metals is effective in quenching Nd. We find that quenching rates increase 1.5 to 4 times as the Nd concentration increases from 0.5 to 10 x 10/sup 20/ cm/sup -3/.

  17. Large-scale detection of metals with a small set of fluorescent DNA-like chemosensors.

    PubMed

    Yuen, Lik Hang; Franzini, Raphael M; Tan, Samuel S; Kool, Eric T

    2014-10-15

    An important advantage of pattern-based chemosensor sets is their potential to detect and differentiate a large number of analytes with only few sensors. Here we test this principle at a conceptual limit by analyzing a large set of metal ion analytes covering essentially the entire periodic table, employing fluorescent DNA-like chemosensors on solid support. A tetrameric "oligodeoxyfluoroside" (ODF) library of 6561 members containing metal-binding monomers was screened for strong responders to 57 metal ions in solution. Our results show that a set of 9 chemosensors could successfully discriminate the 57 species, including alkali, alkaline earth, post-transition, transition, and lanthanide metals. As few as 6 ODF chemosensors could detect and differentiate 50 metals at 100 μM; sensitivity for some metals was achieved at midnanomolar ranges. A blind test with 50 metals further confirmed the discriminating power of the ODFs. PMID:25255102

  18. Tryptophan fluorescence quenching by alkaline earth metal cations in deionized bacteriorhodopsin.

    PubMed

    Wang, G; Wang, A J; Hu, K S

    2000-12-01

    Tryptophan quenching by the addition of alkaline earth metal cations to deionized bacteriorhodopsin suspensions was determined. The results show that the addition of cation primarily quenches fluorescence from surface tryptophan residues. The quenched intensity exhibits a 1/R dependence, where R is the ionic radius of the corresponding metal ion. This observation results from a stronger energy transfer coupling between the tryptophan and the retinal. The membrane curvature may be involved as a result of cations motion and correlated conformational changes. PMID:11332888

  19. Ensemble and Single-Molecule Studies on Fluorescence Quenching in Transition Metal Bipyridine-Complexes

    PubMed Central

    Brox, Dominik; Kiel, Alexander; Wörner, Svenja Johanna; Pernpointner, Markus; Comba, Peter; Martin, Bodo; Herten, Dirk-Peter

    2013-01-01

    Beyond their use in analytical chemistry fluorescent probes continuously gain importance because of recent applications of single-molecule fluorescence spectroscopy to monitor elementary reaction steps. In this context, we characterized quenching of a fluorescent probe by different metal ions with fluorescence spectroscopy in the bulk and at the single-molecule level. We apply a quantitative model to explain deviations from existing standard models for fluorescence quenching. The model is based on a reversible transition from a bright to a dim state upon binding of the metal ion. We use the model to estimate the stability constants of complexes with different metal ions and the change of the relative quantum yield of different reporter dye labels. We found ensemble data to agree widely with results from single-molecule experiments. Our data indicates a mechanism involving close molecular contact of dye and quenching moiety which we also found in molecular dynamics simulations. We close the manuscript with a discussion of possible mechanisms based on Förster distances and electrochemical potentials which renders photo-induced electron transfer to be more likely than Förster resonance energy transfer. PMID:23483966

  20. Metal chelate fluorescence enhancement in micellar media and its applications to niobium and tantalum ultratrace determinations

    SciTech Connect

    Sanz-Medel, A.; Alonso, J.I.G.; Gonzalez, E.B.

    1985-07-01

    The fluorescence intensities of niobium and tantalum complexes with several fluorimetric organic reagents enhanced by micellar solutions have been examined. Flavone derivatives (morin and quercetin) produced the more intense fluorescing reactions in a cationic micellar medium and are studied in detail. Effects upon fluorescence of the nature of the tensoactive material used have been investigated. The charge of the micelle, presence of homomicelles in solution, and chemical structure of the cationic surfactant and lumophoric reagent proved to be the decisive factors which influence enhancement of fluorescence of a metal chelate by a surfactant. The dramatic effects of the appropriate organizing medium and of sulfate ions on fluorescence of the Nb(V) and Ta(V) complexes with morin and quercetin are discussed in an effort to elucidate what trends may exist in the fluorescence enhancement of metal chelates by micelles. A general reaction mechanism, for those systems studied, is proposed. Analytical applications of such micelle-enhanced reactions to the fluorimetric determination of ultratraces of Nb(V) and Ta(V) are also shown. 24 references, 10 figures, 3 tables.

  1. 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

  2. A fluorescent, photochromic and thermochromic trifunctional material based on a layered metal-viologen complex.

    PubMed

    Wan, Fang; Qiu, Li-Xia; Zhou, Liang-Liang; Sun, Yan-Qiong; You, Yi

    2015-11-14

    The azide anion as an energy acceptor and an electron donor has been introduced into a metal-viologen compound to form a 2D layered viologen-based trifunctional material, which exhibits the rare discolored function of reversible photochromism and thermochromism. Interestingly, its fluorescence can be switched by visible light irradiation and heating in air. PMID:26445888

  3. Laser-induced fluorescence of metal-atom impurities in a neutral beam

    SciTech Connect

    Burrell, C.F.; Pyle, R.V.; Sabetimani, Z.; Schlachter, A.S.

    1984-10-01

    The need to limit impurities in fusion devices to low levels is well known. We have investigated, by the technique of laser-induced fluorescence, the concentration of heavy-metal atoms in a neutral beam caused by their evaporation from the hot filaments in a conventional high-current multifilament hydrogen-ion source.

  4. Enhanced fluorescent resonant energy transfer of DNA conjugates complexed with surfactants and divalent metal ions.

    PubMed

    Oh, Taeseok; Choi, Jae-Young; Heller, Michael J

    2016-04-21

    Dimerization and resultant quenching of donor and acceptor dyes conjugated on DNA causes loss of fluorescent resonant energy transfer (FRET) efficiency. However, when complexed with surfactants and divalent metal ions, sheathing effects insulate and shield the DNA structures, reducing dimerization and quenching which leads to significant enhancement of FRET efficiency. PMID:26985458

  5. Use of algal fluorescence for determination of phytotoxicity of heavy metals and pesticides as environmental pollutants

    SciTech Connect

    Samson, G.; Popovic, R.

    1988-12-01

    The phytotoxicity of heavy metals and pesticides was studied by using the fluorescence induction from the alga Dunaliella tertiolecta. The complementary area calculated from the variable fluorescence induction was used as a direct parameter to estimate phytotoxicity. The value of this parameter was affected when algae were treated with different concentrations of mercury, copper, atrazine, DCMU, Dutox, and Soilgard. The toxic effect of these pollutants was estimated by monitoring the decrease in the complementary area, which reflects photosystem II photochemistry. Further, the authors have demonstrated the advantage of using the complementary area as a parameter of phytotoxicity over using variable fluorescence yield. The complementary area of algal fluorescence can be used as a simple and sensitive parameter in the estimation of the phytotoxicity of polluted water.

  6. Metal plasmon-coupled fluorescence imaging and label free coenzyme detection in cells

    SciTech Connect

    Zhang, Jian; Fu, Yi; Li, Ge; Zhao, Richard Y.

    2012-08-31

    Highlights: Black-Right-Pointing-Pointer Metal nanoparticle for fluorescence cell imaging. Black-Right-Pointing-Pointer Non-invasive emission detection of coenzyme in cell on time-resolved confocal microscope. Black-Right-Pointing-Pointer Near-field interaction of flavin adenine dinucleotide with silver substrate. Black-Right-Pointing-Pointer Isolation of emissions by coenzymes from cellular autofluorescence on fluorescence cell imaging. -- Abstract: Flavin adenine dinucleotide (FAD) is a key metabolite in cellular energy conversion. Flavin can also bind with some enzymes in the metabolic pathway and the binding sites may be changed due to the disease progression. Thus, there is interest on studying its expression level, distribution, and redox state within the cells. FAD is naturally fluorescent, but it has a modest extinction coefficient and quantum yield. Hence the intrinsic emission from FAD is generally too weak to be isolated distinctly from the cellular backgrounds in fluorescence cell imaging. In this article, the metal nanostructures on the glass coverslips were used as substrates to measure FAD in cells. Particulate silver films were fabricated with an optical resonance near the absorption and the emission wavelengths of FAD which can lead to efficient coupling interactions. As a result, the emission intensity and quantum yield by FAD were greatly increased and the lifetime was dramatically shortened resulting in less interference from the longer lived cellular background. This feature may overcome the technical limits that hinder the direct observation of intrinsically fluorescent coenzymes in the cells by fluorescence microscopy. Fluorescence cell imaging on the metallic particle substrates may provide a non-invasive strategy for collecting the information of coenzymes in cells.

  7. Mapping metals in Parkinson's and normal brain using rapid-scanning x-ray fluorescence

    NASA Astrophysics Data System (ADS)

    Popescu, Bogdan F. Gh; George, Martin J.; Bergmann, Uwe; Garachtchenko, Alex V.; Kelly, Michael E.; McCrea, Richard P. E.; Lüning, Katharina; Devon, Richard M.; George, Graham N.; Hanson, Akela D.; Harder, Sheri M.; Chapman, L. Dean; Pickering, Ingrid J.; Nichol, Helen

    2009-02-01

    Rapid-scanning x-ray fluorescence (RS-XRF) is a synchrotron technology that maps multiple metals in tissues by employing unique hardware and software to increase scanning speed. RS-XRF was validated by mapping and quantifying iron, zinc and copper in brain slices from Parkinson's disease (PD) and unaffected subjects. Regions and structures in the brain were readily identified by their metal complement and each metal had a unique distribution. Many zinc-rich brain regions were low in iron and vice versa. The location and amount of iron in brain regions known to be affected in PD agreed with analyses using other methods. Sample preparation is simple and standard formalin-fixed autopsy slices are suitable. RS-XRF can simultaneously and non-destructively map and quantify multiple metals and holds great promise to reveal metal pathologies associated with PD and other neurodegenerative diseases as well as diseases of metal metabolism.

  8. Fluorescent copper nanoparticles: recent advances in synthesis and applications for sensing metal ions

    NASA Astrophysics Data System (ADS)

    Guo, Yongming; Cao, Fengpu; Lei, Xiaoling; Mang, Lianghong; Cheng, Shengjuan; Song, Jintong

    2016-02-01

    Fluorescent copper nanoparticles (F-CuNPs) have received great attention due to their attractive features, such as water solubility, wide availability, ease of functionalization and good biocompatibility, and considerable efforts have been devoted to the preparation and applications of F-CuNPs. This review article comprises three main parts. In the first part, we briefly present the fluorescence properties of F-CuNPs. Then we cover the fabrication strategies of various F-CuNPs functionalized by different ligands. In the third part, we focus on the applications of F-CuNPs for sensing metal ions, including Hg2+, Pb2+, Cu2+, Fe3+ and other metal ions. Lastly, we further discuss the opportunities and challenges of F-CuNPs in the synthetic strategies and applications for sensing metal ions.

  9. Application of three-coordinate copper(I) complexes with halide ligands in organic light-emitting diodes that exhibit delayed fluorescence.

    PubMed

    Osawa, Masahisa; Hoshino, Mikio; Hashimoto, Masashi; Kawata, Isao; Igawa, Satoshi; Yashima, Masataka

    2015-05-14

    A series of three-coordinate copper(I) complexes (L(Me))CuX [X = Cl (1), Br (2), I (3)], (L(Et))CuBr (4), and (L(iPr))CuBr (5) [L(Me) = 1,2-bis[bis(2-methylphenyl)phosphino]benzene, L(Et) = 1,2-bis[bis(2-ethylphenyl)phosphino]benzene, and L(iPr) = 1,2-bis[bis(2-isopropylphenyl)phosphino]benzene] exhibit efficient blue-green emission in the solid state at ambient temperature with peak wavelengths between 473 and 517 nm. The emission quantum yields were 0.38-0.95. The emission lifetimes were measured in the temperature range of 77-295 K using a nanosecond laser technique. The temperature dependence of the emission lifetimes was explained using a model with two excited states: a singlet and a triplet state. The small energy gaps (<830 cm(-1)) between the two states suggest that efficient emission from 1-5 was thermally activated delayed fluorescence (TADF). Alkyl substituents at ortho positions of peripheral phenyl groups were found to have little effect on the electronic excited states. Because the origin of the emission of complexes 2, 4, and 5 was thought to be a (σ + Br)→π* transition, photoluminescence characteristics of these complexes were dominated by the diphosphine ligands. Complexes 2, 4, and 5 had similar emission properties. Complexes 1-5 had efficient green TADF in amorphous films at 293 K with maximum emission wavelengths of 508-520 nm and quantum yields of 0.61-0.71. Organic light-emitting devices that contained complexes 1-5 and exhibited TADF exhibit bright green luminescence with current efficiencies of 55.6-69.4 cd A(-1) and maximum external quantum efficiencies of 18.6-22.5%. PMID:25470470

  10. Atomic layer deposition to prevent metal transfer from implants: An X-ray fluorescence study

    NASA Astrophysics Data System (ADS)

    Bilo, Fabjola; Borgese, Laura; Prost, Josef; Rauwolf, Mirjam; Turyanskaya, Anna; Wobrauschek, Peter; Kregsamer, Peter; Streli, Christina; Pazzaglia, Ugo; Depero, Laura E.

    2015-12-01

    We show that Atomic Layer Deposition is a suitable coating technique to prevent metal diffusion from medical implants. The metal distribution in animal bone tissue with inserted bare and coated Co-Cr alloys was evaluated by means of micro X-ray fluorescence mapping. In the uncoated implant, the migration of Co and Cr particles from the bare alloy in the biological tissues is observed just after one month and the number of particles significantly increases after two months. In contrast, no metal diffusion was detected in the implant coated with TiO2. Instead, a gradient distribution of the metals was found, from the alloy surface going into the tissue. No significant change was detected after two months of aging. As expected, the thicker is the TiO2 layer, the lower is the metal migration.

  11. Quenching of photoexcited states of the proteins chromophores and introduced into the protein macromolecules fluorescent probes by heavy metal ions

    NASA Astrophysics Data System (ADS)

    Melnikov, A. G.; Dyachuk, O. A.; Melnikov, G. V.

    2015-03-01

    We have studied the processes of quenching of photoexcited states of fluorescent probes and quenching of the fluorescence of the chromophores of human serum albumin (HSA) by heavy metal ions (HM): cations Tl+, Pb2+, Cu2+, Cd2+, and the anion of iodine (I-). We used the dye from xanthene series - eosin as a fluorescent probe. By quenching of the fluorescence of protein chromophores we found an influence of HM on the structure of proteins, resulting in a shift of the peak of the fluorescence of HSA tryptophanyl. This can be explained by proteins denaturation under the influence of heavy metals and penetration of water into the inner environment of HSA tryptophan. It was established that the constant of the quenching of the probe phosphorescence is much higher than the fluorescence, which is explained by significantly longer lifetime of the photoexcited states of fluorescent probes in the triplet state than in the singlet.

  12. Noninvasive Evaluation of Heavy Metal Uptake and Storage in Micoralgae Using a Fluorescence Resonance Energy Transfer-Based Heavy Metal Biosensor1[C][W][OPEN

    PubMed Central

    Rajamani, Sathish; Torres, Moacir; Falcao, Vanessa; Ewalt Gray, Jaime; Coury, Daniel A.; Colepicolo, Pio; Sayre, Richard

    2014-01-01

    We have developed a fluorescence resonance energy transfer (FRET)-based heavy metal biosensor for the quantification of bioavailable free heavy metals in the cytoplasm of the microalga Chlamydomonas reinhardtii. The biosensor is composed of an end-to-end fusion of cyan fluorescent protein (CFP), chicken metallothionein II (MT-II), and yellow fluorescent protein (YFP). In vitro measurements of YFP/CFP fluorescence emission ratios indicated that the addition of metals to the purified biosensor enhanced FRET between CFP and YFP, consistent with heavy metal-induced folding of MT-II. A maximum YFP/CFP FRET ratio of 2.8 was observed in the presence of saturating concentrations of heavy metals. The sensitivity of the biosensor was greatest for Hg2+ followed by Cd2+ ≈ Pb2+ > Zn2+ > Cu2+. The heavy metal biosensor was unresponsive to metals that do not bind to MT-II (Na+ and Mg2+). When expressed in C. reinhardtii, we observed a differential metal-dependent response to saturating external concentrations (1.6 mm) of heavy metals (Pb2+ > Cd2+) that was unlike that observed for the isolated biosensor (in vitro). Significantly, analysis of metal uptake kinetics indicated that equilibration of the cytoplasm with externally applied heavy metals occurred within seconds. Our results also indicated that algae have substantial buffering capacity for free heavy metals in their cytosol, even at high external metal concentrations. PMID:24368336

  13. 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

  14. Epi-Fluorescence Microscopy

    PubMed Central

    Webb, Donna J.; Brown, Claire M.

    2012-01-01

    Epi-fluorescence microscopy is available in most life sciences research laboratories, and when optimized can be a central laboratory tool. In this chapter, the epi-fluorescence light path is introduced and the various components are discussed in detail. Recommendations are made for incident lamp light sources, excitation and emission filters, dichroic mirrors, objective lenses, and charge-coupled device (CCD) cameras in order to obtain the most sensitive epi-fluorescence microscope. The even illumination of metal-halide lamps combined with new “hard” coated filters and mirrors, a high resolution monochrome CCD camera, and a high NA objective lens are all recommended for high resolution and high sensitivity fluorescence imaging. Recommendations are also made for multicolor imaging with the use of monochrome cameras, motorized filter turrets, individual filter cubes, and corresponding dyes that are the best choice for sensitive, high resolution multicolor imaging. Images should be collected using Nyquist sampling and should be corrected for background intensity contributions and nonuniform illumination across the field of view. Photostable fluorescent probes and proteins that absorb a lot of light (i.e., high extinction co-efficients) and generate a lot of fluorescence signal (i.e., high quantum yields) are optimal. A neuronal immune-fluorescence labeling protocol is also presented. Finally, in order to maximize the utility of sensitive wide-field microscopes and generate the highest resolution images with high signal-to-noise, advice for combining wide-field epi-fluorescence imaging with restorative image deconvolution is presented. PMID:23026996

  15. Mapping Metal Elements of Shuangbai Dinosaur Fossil by Synchrotron X-ray Fluorescence Microprobe

    SciTech Connect

    Wang, Y.; Qun, Y; Ablett, J

    2008-01-01

    The metal elements mapping of Shuangbai dinosaur fossil, was obtained by synchrotron x-ray fluorescence (SXRF). Eight elements, Ca, Mn, Fe, Cu, Zn, As, Y and Sr were determined. Elements As and Y were detected for the first time in the dinosaur fossil. The data indicated that metal elements are asymmetrical on fossil section. This is different from common minerals. Mapping metals showed that metal element As is few. The dinosaur most likely belongs to natural death. This is different from Zigong dinosaurs which were found dead from poisoning. This method has been used to find that metals Fe and Mn are accrete, and the same is true for Sr and Y. This study indicated that colloid granule Fe and Mn, as well as Sr and Y had opposite electric charges in lithification process of fossils. By this analysis, compound forms can be ascertained. Synchrotron light source x-ray fluorescence is a complementary method that shows mapping of metal elements at the dinosaur fossil, and is rapid, exact and intuitionist. This study shows that dinosaur fossil mineral imaging has a potential in reconstructing the paleoenvironment and ancient geology.

  16. Systematic analysis of the unique band gap modulation of mixed halide perovskites.

    PubMed

    Kim, Jongseob; Lee, Sung-Hoon; Chung, Choong-Heui; Hong, Ki-Ha

    2016-02-14

    Solar cells based on organic-inorganic hybrid metal halide perovskites have been proven to be one of the most promising candidates for the next generation thin film photovoltaic cells. Mixing Br or Cl into I-based perovskites has been frequently tried to enhance the cell efficiency and stability. One of the advantages of mixed halides is the modulation of band gap by controlling the composition of the incorporated halides. However, the reported band gap transition behavior has not been resolved yet. Here a theoretical model is presented to understand the electronic structure variation of metal mixed-halide perovskites through hybrid density functional theory. Comparative calculations in this work suggest that the band gap correction including spin-orbit interaction is essential to describe the band gap changes of mixed halides. In our model, both the lattice variation and the orbital interactions between metal and halides play key roles to determine band gap changes and band alignments of mixed halides. It is also presented that the band gap of mixed halide thin films can be significantly affected by the distribution of halide composition. PMID:26791587

  17. Visible-light-mediated, nitrogen-centered radical amination of tertiary alkyl halides under metal-free conditions to form α-tertiary amines.

    PubMed

    Brueckner, Alexander C; Hancock, Erin N; Anders, Evan J; Tierney, Matthew M; Morgan, Heather R; Scott, Kristina A; Lamar, Angus A

    2016-05-11

    A mild and operationally convenient amino-functionalization of a range of tertiary alkyl halides by reaction with iminoiodinanes (PhI[double bond, length as m-dash]NNs) and I2 has been developed. According to the mechanistic experiments described within, the reaction is speculated to proceed through a light-promoted, N-centered radical pathway involving a N,N-diiodosulfonamide reactive species. This method of direct N-incorporation offers an attractive alternative to the production of α-tertiary amines, a synthetically challenging structural class found in a variety of bioactive molecules. PMID:27113972

  18. FT-IR, Micro-Raman and UV-vis spectroscopic and quantum chemical investigations of free 2,2'-dithiodipyridine and its metal (Co, Cu and Zn) halide complexes

    NASA Astrophysics Data System (ADS)

    Gökce, Halil; Bahçeli, Semiha

    2013-10-01

    In this study the elemental analysis results, molecular geometries, vibrational and electronic absorption spectra of free 2,2'-dithiodipyridine(C10H8N2S2), (or DTDP) (with synonym, 2,2'-dipyridyl disulfide) and M(C10H8N2S2)Cl2 (M = Co, Cu and Zn) complexes have been reported. Vibrational wavenumbers of free DTDP and its metal halide complexes have been calculated by using DFT/B3LYP calculation method with 6-31++G(d,p) and Lanl2DZ basis sets, respectively, in the ground state, for the first time. The calculated fundamental vibrational frequencies are in a good agreement with experimental data. The HOMO, LUMO and MEP analyses of all compounds are performed by DFT method.

  19. METAL-CONTAINING CONJUGATED POLYMERS AS FLUORESCENT CHEMOSENSORS IN THE DETECTION OF TOXICANTS.

    PubMed

    Fegley, Megan E A; Pinnock, Sherryllene S; Malele, Catherine N; Jones, Wayne E

    2012-02-15

    Fluorescent conjugated polymers have received a great deal of recent interest due to their ability to act as chemosensors to detect various chemical species in both environmental and biological systems with sensitivity and selectivity. Examples from the literature include polymer chemosensors that operate on either fluorescence "turn-on" or "turn-off" as mechanisms of sensor response. These responses can be related to either photoinduced electron transfer or electronic energy transfer mechanisms. Recently, a series of metal-containing polymers or metallopolymers have been explored by various research groups for their use as chemosensors. In many cases, these metallopolymers have been shown to be more sensitive and selective for specific chemical species. This review focuses on fluorescent conjugated polymers as chemosensors, with a specific concentration on recent advances in metallopolymer chemosensors. PMID:22711916

  20. METAL-CONTAINING CONJUGATED POLYMERS AS FLUORESCENT CHEMOSENSORS IN THE DETECTION OF TOXICANTS

    PubMed Central

    Fegley, Megan E. A.; Pinnock, Sherryllene S.; Malele, Catherine N.; Jones, Wayne E.

    2012-01-01

    Fluorescent conjugated polymers have received a great deal of recent interest due to their ability to act as chemosensors to detect various chemical species in both environmental and biological systems with sensitivity and selectivity. Examples from the literature include polymer chemosensors that operate on either fluorescence “turn-on” or “turn-off” as mechanisms of sensor response. These responses can be related to either photoinduced electron transfer or electronic energy transfer mechanisms. Recently, a series of metal-containing polymers or metallopolymers have been explored by various research groups for their use as chemosensors. In many cases, these metallopolymers have been shown to be more sensitive and selective for specific chemical species. This review focuses on fluorescent conjugated polymers as chemosensors, with a specific concentration on recent advances in metallopolymer chemosensors. PMID:22711916

  1. Relation between the electroforming voltage in alkali halide-polymer diodes and the bandgap of the alkali halide

    SciTech Connect

    Bory, Benjamin F.; Wang, Jingxin; Janssen, René A. J.; Meskers, Stefan C. J.; Gomes, Henrique L.; De Leeuw, Dago M.

    2014-12-08

    Electroforming of indium-tin-oxide/alkali halide/poly(spirofluorene)/Ba/Al diodes has been investigated by bias dependent reflectivity measurements. The threshold voltages for electrocoloration and electroforming are independent of layer thickness and correlate with the bandgap of the alkali halide. We argue that the origin is voltage induced defect formation. Frenkel defect pairs are formed by electron–hole recombination in the alkali halide. This self-accelerating process mitigates injection barriers. The dynamic junction formation is compared to that of a light emitting electrochemical cell. A critical defect density for electroforming is 10{sup 25}/m{sup 3}. The electroformed alkali halide layer can be considered as a highly doped semiconductor with metallic transport characteristics.

  2. Resonance fluorescence spectrum of a Λ -type quantum emitter close to a metallic nanoparticle

    NASA Astrophysics Data System (ADS)

    Carreño, F.; Antón, M. A.; Yannopapas, V.; Paspalakis, E.

    2016-07-01

    We theoretically study the resonance fluorescence spectrum of a three-level quantum emitter coupled to a spherical metallic nanoparticle. We consider the case in which the quantum emitter is driven by a single laser field along one of the optical transitions. We show that the development of the spectrum depends on the relative orientation of the dipole moments of the optical transitions in relation to the metal nanoparticle. In addition, we demonstrate that the location and width of the peaks in the spectrum are strongly modified by the exciton-plasmon coupling and the laser detuning, allowing one to achieve a controlled strongly subnatural spectral line. A strong antibunching of the fluorescent photons along the undriven transition is also obtained. Our results may be used for creating a tunable source of photons which could be used for a probabilistic entanglement scheme in the field of quantum information processing.

  3. Novel laser atomic fluorescence spectrometer for environmental and biomedical analyses of heavy metals

    NASA Astrophysics Data System (ADS)

    Dergachev, Alex Y.; Mirov, Sergey B.; Pitt, Robert E.; Parmer, Keith D.

    1997-05-01

    We report on the development of a novel experimental set-up using laser atomic fluorescence for detection and concentration measurements of heavy metal atoms for environmental and biomedical analyses. This spectrometer is based on the application of tunable LiF:F2+** and LiF:F2- color center and alexandrite lasers with nonlinear converters for narrowband excitation of atomic fluorescence and the use of gated multichannel CCD detectors for fluorescence measurements. A standard graphite furnace module was used for sample atomization. The laser sources used provide narrowband selective laser excitation continuously tunable in the 200 - 400 nm range and are therefore suitable for resonant excitation of atomic transitions in practically all known heavy metal atoms. In the first experiments, water samples containing Cu, Pb and Fe impurities were studied and detection levels of less than 1 ppb were observed. Comparison of the results of atomic laser fluorescence analysis and traditional atomic absorption spectrometry showed good qualitative agreement between these two methods. It is projected that full optimization of our experimental set up will allow for improved detection levels of several orders of magnitude. Possible optimization and simplification of the spectrometer are discussed in the context of developing a portable instrument for field use.

  4. Metal enhanced fluorescence in rare earth doped plasmonic core-shell nanoparticles

    NASA Astrophysics Data System (ADS)

    Derom, S.; Berthelot, A.; Pillonnet, A.; Benamara, O.; Jurdyc, A. M.; Girard, C.; Colas des Francs, G.

    2013-12-01

    We theoretically and numerically investigate metal enhanced fluorescence of plasmonic core-shell nanoparticles doped with rare earth (RE) ions. Particle shape and size are engineered to maximize the average enhancement factor (AEF) of the overall doped shell. We show that the highest enhancement (11 in the visible and 7 in the near-infrared) is achieved by tuning either the dipolar or the quadrupolar particle resonance to the rare earth ion’s excitation wavelength. Additionally, the calculated AEFs are compared to experimental data reported in the literature, obtained in similar conditions (plasmon mediated enhancement) or when a metal-RE energy transfer mechanism is involved.

  5. Visualizing Metal Content and Intracellular Distribution in Primary Hippocampal Neurons with Synchrotron X-Ray Fluorescence

    PubMed Central

    2016-01-01

    Increasing evidence suggests that metal dyshomeostasis plays an important role in human neurodegenerative diseases. Although distinctive metal distributions are described for mature hippocampus and cortex, much less is known about metal levels and intracellular distribution in individual hippocampal neuronal somata. To solve this problem, we conducted quantitative metal analyses utilizing synchrotron radiation X-Ray fluorescence on frozen hydrated primary cultured neurons derived from rat embryonic cortex (CTX) and two regions of the hippocampus: dentate gyrus (DG) and CA1. Comparing average metal contents showed that the most abundant metals were calcium, iron, and zinc, whereas metals such as copper and manganese were less than 10% of zinc. Average metal contents were generally similar when compared across neurons cultured from CTX, DG, and CA1, except for manganese that was larger in CA1. However, each metal showed a characteristic spatial distribution in individual neuronal somata. Zinc was uniformly distributed throughout the cytosol, with no evidence for the existence of previously identified zinc-enriched organelles, zincosomes. Calcium showed a peri-nuclear distribution consistent with accumulation in endoplasmic reticulum and/or mitochondria. Iron showed 2–3 distinct highly concentrated puncta only in peri-nuclear locations. Notwithstanding the small sample size, these analyses demonstrate that primary cultured neurons show characteristic metal signatures. The iron puncta probably represent iron-accumulating organelles, siderosomes. Thus, the metal distributions observed in mature brain structures are likely the result of both intrinsic neuronal factors that control cellular metal content and extrinsic factors related to the synaptic organization, function, and contacts formed and maintained in each region. PMID:27434052

  6. Visualizing Metal Content and Intracellular Distribution in Primary Hippocampal Neurons with Synchrotron X-Ray Fluorescence.

    PubMed

    Colvin, Robert A; Jin, Qiaoling; Lai, Barry; Kiedrowski, Lech

    2016-01-01

    Increasing evidence suggests that metal dyshomeostasis plays an important role in human neurodegenerative diseases. Although distinctive metal distributions are described for mature hippocampus and cortex, much less is known about metal levels and intracellular distribution in individual hippocampal neuronal somata. To solve this problem, we conducted quantitative metal analyses utilizing synchrotron radiation X-Ray fluorescence on frozen hydrated primary cultured neurons derived from rat embryonic cortex (CTX) and two regions of the hippocampus: dentate gyrus (DG) and CA1. Comparing average metal contents showed that the most abundant metals were calcium, iron, and zinc, whereas metals such as copper and manganese were less than 10% of zinc. Average metal contents were generally similar when compared across neurons cultured from CTX, DG, and CA1, except for manganese that was larger in CA1. However, each metal showed a characteristic spatial distribution in individual neuronal somata. Zinc was uniformly distributed throughout the cytosol, with no evidence for the existence of previously identified zinc-enriched organelles, zincosomes. Calcium showed a peri-nuclear distribution consistent with accumulation in endoplasmic reticulum and/or mitochondria. Iron showed 2-3 distinct highly concentrated puncta only in peri-nuclear locations. Notwithstanding the small sample size, these analyses demonstrate that primary cultured neurons show characteristic metal signatures. The iron puncta probably represent iron-accumulating organelles, siderosomes. Thus, the metal distributions observed in mature brain structures are likely the result of both intrinsic neuronal factors that control cellular metal content and extrinsic factors related to the synaptic organization, function, and contacts formed and maintained in each region. PMID:27434052

  7. Fluorescent, MRI, and colorimetric chemical sensors for the first-row d-block metal ions.

    PubMed

    Zhu, Hao; Fan, Jiangli; Wang, Benhua; Peng, Xiaojun

    2015-07-01

    Transition metals (d-blocks) are recognized as playing critical roles in biology, and they most often act as cofactors in diverse enzymes; however, improper regulation of transition metal stores is also connected to serious disorders. Therefore, the monitoring and imaging of transition metals are significant for biological research as well as clinical diagnosis. In this article, efforts have been made to review the chemical sensors that have been developed for the detection of the first-row d-block metals (except Cu and Zn): Cr, Mn, Fe, Co, and Ni. We focus on the development of fluorescent sensors (fall into three classes: "turn-off", "turn-on", and ratiometric), colorimetric sensors, and responsive MRI contrast agents for these transition metals (242 references). Future work will be likely to fill in the blanks: (1) sensors for Sc, Ti, and V; (2) MRI sensors for Cr, Mn, Co, Ni; (3) ratiometric fluorescent sensors for Cr(6+), Mn(2+), and Ni(2+), explore new ways of sensing Fe(3+) or Cr(3+) without the proton interference, as well as extend applications of MRI sensors to living systems. PMID:25406612

  8. Heavy Metals Effect on Cyanobacteria Synechocystis aquatilis Study Using Absorption, Fluorescence, Flow Cytometry, and Photothermal Measurements

    NASA Astrophysics Data System (ADS)

    Dudkowiak, A.; Olejarz, B.; Łukasiewicz, J.; Banaszek, J.; Sikora, J.; Wiktorowicz, K.

    2011-04-01

    The toxic effect of six heavy metals on cyanobacteria Synechocystis aquatilis was studied by absorption, fluorescence, flow cytometry, and photothermal measurements. This study indicates that at the concentration used, the cyanobacteria are more sensitive to silver, copper, and mercury than to cadmium, lead, and zinc metals. Disregarding the decrease in the yields of the related radiative processes caused by photochemical processes and/or damage to phycobilisomes, no changes were detected in the efficiency of thermal deactivation processes within a few microseconds, which can indicate the lack of disturbances in the photosynthetic light reaction and the lack of damage to the photosystem caused by the heavy metal ions in the concentrations used. The results demonstrate that the relative values of fluorescence yield as well as promptly generated heat calculated for the metal-affected and unaffected (reference) bacteria are sensitive indicators of environmental pollution with heavy metal ions, whereas the complementary methods proposed could be used as a noninvasive and fast procedure for in vivo assessment of their toxicity.

  9. Algal photosynthetic responses to toxic metals and herbicides assessed by chlorophyll a fluorescence.

    PubMed

    Kumar, K Suresh; Dahms, Hans-Uwe; Lee, Jae-Seong; Kim, Hyung Chul; Lee, Won Chan; Shin, Kyung-Hoon

    2014-06-01

    Chlorophyll a fluorescence is established as a rapid, non-intrusive technique to monitor photosynthetic performance of plants and algae, as well as to analyze their protective responses. Apart from its utility in determining the physiological status of photosynthesizers in the natural environment, chlorophyll a fluorescence-based methods are applied in ecophysiological and toxicological studies to examine the effect of environmental changes and pollutants on plants and algae (microalgae and seaweeds). Pollutants or environmental changes cause alteration of the photosynthetic capacity which could be evaluated by fluorescence kinetics. Hence, evaluating key fluorescence parameters and assessing photosynthetic performances would provide an insight regarding the probable causes of changes in photosynthetic performances. This technique quintessentially provides non-invasive determination of changes in the photosynthetic apparatus prior to the appearance of visible damage. It is reliable, economically feasible, time-saving, highly sensitive, versatile, accurate, non-invasive and portable; thereby comprising an excellent alternative for detecting pollution. The present review demonstrates the applicability of chlorophyll a fluorescence in determining photochemical responses of algae exposed to environmental toxicants (such as toxic metals and herbicides). PMID:24632123

  10. Upconversion fluorescence metal-organic frameworks thermo-sensitive imprinted polymer for enrichment and sensing protein.

    PubMed

    Guo, Ting; Deng, Qiliang; Fang, Guozhen; Gu, Dahai; Yang, Yukun; Wang, Shuo

    2016-05-15

    A novel fluorescence material with thermo-sensitive for the enrichment and sensing of protein was successfully prepared by combining molecular imprinting technology with upconversion nanoparticles (UCNPs) and metal-organic frameworks (MOFs). Herein, the UCNPs acted as signal reporter for composite materials because of its excellent fluorescence property and chemical stability. MOFs were introduced to molecularly imprinted polymer (MIP) due to its high specific surface area which increases the rate of mass transfer relative to that of traditional bulk MIP. The thermo-sensitive imprinted material which allows for swelling and shrinking with response to temperature changes was prepared by choosing Bovine hemoglobin (BHB) as the template, N-isopropyl acrylamide (NIPAAM) as the temperature-sensitive functional monomer and N,N-methylenebisacrylamide (MBA) as the cross-linker. The recognition characterizations of imprinted material-coated UCNPs/MOFs (UCNPs/MOFs/MIP) were evaluated, and the results showed that the fluorescence intensity of UCNPs/MOFs/MIP reduced gradually with the increase of BHB concentration. The fluorescence material was response to the temperature. The adsorption capacity was as much as 167.6 mg/g at 28°C and 101.2mg/g at 44°C, which was higher than that of traditional MIP. Therefore, this new fluorescence material for enrichment and sensing protein is very promising for future applications. PMID:26722764

  11. Using synchrotron X-ray fluorescence microprobes in the study of metal homeostasis in plants

    PubMed Central

    Punshon, Tracy; Guerinot, Mary Lou; Lanzirotti, Antonio

    2009-01-01

    Background and Aims This Botanical Briefing reviews the application of synchrotron X-ray fluorescence (SXRF) microprobes to the plant sciences; how the technique has expanded our knowledge of metal(loid) homeostasis, and how it can be used in the future. Scope The use of SXRF microspectroscopy and microtomography in research on metal homeostasis in plants is reviewed. The potential use of SXRF as part of the ionomics toolbox, where it is able to provide fundamental information on the way that plants control metal homeostasis, is recommended. Conclusions SXRF is one of the few techniques capable of providing spatially resolved in-vivo metal abundance data on a sub-micrometre scale, without the need for chemical fixation, coating, drying or even sectioning of samples. This gives researchers the ability to uncover mechanisms of plant metal homeostasis that can potentially be obscured by the artefacts of sample preparation. Further, new generation synchrotrons with smaller beam sizes and more sensitive detection systems will allow for the imaging of metal distribution within single living plant cells. Even greater advances in our understanding of metal homeostasis in plants can be gained by overcoming some of the practical boundaries that exist in the use of SXRF analysis. PMID:19182222

  12. Using Synchrotron X-ray Fluorescence Microprobes in the Study of Metal Homeostasis in Plants

    SciTech Connect

    Punshon, T.; Guerinot, M; Lanzirotti, A

    2009-01-01

    Background and Aims: This Botanical Briefing reviews the application of synchrotron X-ray fluorescence (SXRF) microprobes to the plant sciences; how the technique has expanded our knowledge of metal(loid) homeostasis, and how it can be used in the future. Scope: The use of SXRF microspectroscopy and microtomography in research on metal homeostasis in plants is reviewed. The potential use of SXRF as part of the ionomics toolbox, where it is able to provide fundamental information on the way that plants control metal homeostasis, is recommended. Conclusions: SXRF is one of the few techniques capable of providing spatially resolved in-vivo metal abundance data on a sub-micrometre scale, without the need for chemical fixation, coating, drying or even sectioning of samples. This gives researchers the ability to uncover mechanisms of plant metal homeostasis that can potentially be obscured by the artefacts of sample preparation. Further, new generation synchrotrons with smaller beam sizes and more sensitive detection systems will allow for the imaging of metal distribution within single living plant cells. Even greater advances in our understanding of metal homeostasis in plants can be gained by overcoming some of the practical boundaries that exist in the use of SXRF analysis.

  13. Laser-induced fluorescence in doped metal oxide planar waveguides deposited from aqueous solutions

    SciTech Connect

    Hess, N.J.; Exarhos, G.J. ); Wood, S.M. . Shock Dynamics Lab.)

    1991-12-01

    An aqueous route to the deposition of complex metal oxide films is based upton the complexation of the corresponding metal nitrate salts by glycine, followed by spin-casting the concentrated solution onto silica substrates. The presence of glycine serves to frustrate precipitation and leads to the formation of a glassy matrix through which metal cations are homogeneously dispersed. Subsequent heating of coated substrates initiates an oxidation-reduction reaction which removes the organic matrix and residual nitrate leaving behind a film of the desired oxide composition. Using this method, ruby (Cr:Al{sub 2}O{sub 3}) and Sm:YAG (Sm:Y{sub 3}Al{sub 5}O{sub 12}) films on the order of 150 nm thick have been deposited. The respective phase have been confirmed by XRD data and from the measured fluorescence spectra. The red fluorescence exhibited by these materials under 488 nm excitation is dependent upon the ambient temperature and pressure. A marked shift in wavelength is observed as a function of increasing pressure. Ruby also exhibits a temperature dependent wavelength shift in contrast to Sm:YAG where a negligible shift is seen to temperatures near 1200 K. Fluorescence lifetimes of both materials exhibit a temperature dependence which varies with dopant concentration. This work suggests the possible application of these films as pressure-temperature sensors in a planar waveguide configuration or as a coating material for optical fibers. Details of the deposition process will be reviewed and the fluorescence response of both types of films will be summarized. 15 refs., 4 figs.

  14. Detection of CXCR4 receptors on cell surface using a fluorescent metal nanoshell

    NASA Astrophysics Data System (ADS)

    Zhang, Jian; Fu, Yi; Li, Ge; Zhao, Richard Y.; Lakowicz, Joseph R.

    2011-01-01

    Fluorescence cell imaging can be used for disease diagnosis and cellular signal transduction. Using a metal nanoshell as molecular imaging agent, we develop a cellular model system to detect CXCR4 chemokine receptor on T-lymphatic cell surface. These metal nanoshells are observed to express enhanced emission intensity and shortened lifetimes due to the near-field interactions. They are covalently bound with anti-CXCR4 monoclonal antibodies for immunoreactions with the target sites of the CXCR4 receptors on the CEM-SS cells. The fluorescence intensity and lifetime cell images are recorded with a time-resolved confocal microscopy. As expected, the emission signals from the metal nanoshells are clearly isolated from the cellular autofluorescence due to strong intensities and distinctive lifetimes. The number of emission spots on the single cell image is estimated by direct count to the emission signals. Analyzing a pool of cell images, a maximal count number is obtained in a range of 200+/-50. Because there is an average of ~6000 binding sites on the cell surface, we estimate that one emission spot from the metal nanoshell may represent ~30 CXCR5 receptors. In addition, the CXCR4 receptors are estimated to distribute on ~70% area of the cell surface.

  15. Screening heavy metals levels in hair of sanitation workers by X-ray fluorescence analysis.

    PubMed

    Md Khudzari, Jauharah; Wagiran, Husin; Hossain, I; Ibrahim, Noorddin

    2013-01-01

    This work presents a study of human hair as a bio-indicator for detection of heavy metals as part of environmental health surveillance programs project to develop a subject of interest in the biomedical and environmental sciences. A total of 34 hair samples were analyzed that consisting of 29 samples from sanitation workers and five samples from students. The hair samples were prepared and treated in accordance to the International Atomic Energy Agency (IAEA) recommendations. The concentrations of heavy metals were analyzed using the energy dispersive X-ray fluorescence (EDXRF) technique by X-50 Mobile X-ray Fluorescence (XRF) at Oceanography Institute, Universiti Malaysia Terengganu. The performance of EDXRF analyzer was tested by Standard Reference Material (SRM 2711) Montana Soil which was in good agreement with certified value within 14% deviations except for Hg. While seven heavy metals: Mn, Fe, Ni, Cu, Zn, Se, and Sb were detected in both groups, three additional elements, i.e. As, Hg and Pb, were detected only in sanitation workers group. For sanitation workers group, the mean concentration of six elements, Mn, Fe, Cu, Zn, Se, and Sb, shows elevated concentration as compared to the control samples concentration. Results from both groups were compared and discussed in relation to their respective heavy metals concentrations. PMID:22846873

  16. Spermine detection via metal-mediated ethynylarene ‘turn-on’ fluorescence signaling

    PubMed Central

    Fletcher, James T.; Bruck, Brent S.

    2014-01-01

    A dicarboxylated ethynylarene was shown to behave as a fluorescent chemosensor for millimolar concentrations of polyamines when mixed with Cd(II), Pb(II) or Zn(II) ions at micromolar concentrations. A bathochromic shift and intensification of fluorescence emission was observed with increasing amounts of metal ion in the presence of aqueous polyamines buffered at pH = 7.6. Such perturbations manifested as ‘turn-on’ signals from a ratiometric comparison of emission intensities at 390 nm versus 340 nm. Using Pb(II) as the metal mediator, spermine was selectively detected as a 40-fold signal enhancement relative to spermidine, putrescine, cadaverine and several other non-biogenic diamines. Evaluation of additional triamine and tetraamine analytes showed the influence that amine group quantity and spacing had on signal generation. By increasing the ratio of Pb(II) relative to ethynylarene, the detection limit for spermine was successfully lowered to a 25 micromolar level. Noncovalent association between ethynylarene, metal ion and polyamine are believed to promote the observed spectroscopic changes. This study exploits the subtle impact that polyamine structural identity has on transition metal chelation to define a new approach towards polyamine chemosensor development. PMID:25530671

  17. A cross-reactive sensor array for the fluorescence qualitative analysis of heavy metal ions.

    PubMed

    Kang, Huaizhi; Lin, Liping; Rong, Mingcong; Chen, Xi

    2014-11-01

    A cross-reactive sensor array using mercaptopropionic acid modified cadmium telluride (CdTe), glutathione modified CdTe, poly(methacrylic acid) modified silver nanoclusters, bovine serum albumin modified gold nanoclusters, rhodamine derivative and calcein blue as fluorescent indicators has been designed for the detection of seven heavy metal ions (Ag(+), Hg(2+), Pb(2+), Cu(2+), Cr(3+), Mn(2+) and Cd(2+)). The discriminatory capacity of the sensor array to different heavy metal ions in different pH solutions has been tested and the results have been analyzed with linear discriminant analysis. Results showed that the sensor array could be used to qualitatively analyze the selected heavy metal ions. The array performance was also evaluated in the identification of known and unknown samples and the preliminary results suggested the promising practicability of the designed sensor assay. PMID:25127598

  18. Effect of hydrogen bonding and complexation with metal ions on the fluorescence of luotonin A.

    PubMed

    Miskolczy, Zsombor; Biczók, László

    2013-05-01

    Fluorescence characteristics of a biologically active natural alkaloid, luotonin A (LuA), were studied by steady-state and time-resolved spectroscopic methods. The rate constant of the radiationless deactivation from the singlet-excited state diminished by more than one order of magnitude when the solvent polarity was changed from toluene to water. Dual emission was found in polyfluorinated alcohols of large hydrogen bond donating ability due to photoinitiated proton displacement along the hydrogen bond. In CH2Cl2, LuA produced both 1 : 1 and 1 : 2 hydrogen-bonded complexes with hexafluoro-2-propanol (HFIP) in the ground state. Photoexcitation of the 1 : 2 complex led to protonated LuA, whose fluorescence appeared at a long wavelength. LuA served as a bidentate ligand forming 1 : 1 complexes with metal ions in acetonitrile. The stability of the complexes diminished in the series of Cd(2+) > Zn(2+) > Ag(+), and upon competitive binding of water to the metal cations. The effect of chelate formation on the fluorescent properties was revealed. PMID:23487318

  19. Metal-Enhanced Near-Infrared Fluorescence by Micropatterned Gold Nanocages.

    PubMed

    Camposeo, Andrea; Persano, Luana; Manco, Rita; Wang, Yi; Del Carro, Pompilio; Zhang, Chao; Li, Zhi-Yuan; Pisignano, Dario; Xia, Younan

    2015-10-27

    In metal-enhanced fluorescence (MEF), the localized surface plasmon resonances of metallic nanostructures amplify the absorption of excitation light and assist in radiating the consequent fluorescence of nearby molecules to the far-field. This effect is at the base of various technologies that have strong impact on fields such as optics, medical diagnostics, and biotechnology. Among possible emission bands, those in the near-infrared (NIR) are particularly intriguing and widely used in proteomics and genomics due to its noninvasive character for biomolecules, living cells, and tissues, which greatly motivates the development of effective and, eventually, multifunctional NIR-MEF platforms. Here, we demonstrate NIR-MEF substrates based on Au nanocages micropatterned with a tight spatial control. The dependence of the fluorescence enhancement on the distance between the nanocage and the radiating dipoles is investigated experimentally and modeled by taking into account the local electric field enhancement and the modified radiation and absorption rates of the emitting molecules. At a distance around 80 nm, a maximum enhancement up to 2-7 times with respect to the emission from pristine dyes (in the region 660-740 nm) is estimated for films and electrospun nanofibers. Due to their chemical stability, finely tunable plasmon resonances, and large light absorption cross sections, Au nanocages are ideal NIR-MEF agents. When these properties are integrated with the hollow interior and controllable surface porosity, it is feasible to develop a nanoscale system for targeted drug delivery with the diagnostic information encoded in the fluorophore. PMID:26397166

  20. Metal-Enhanced Near-Infrared Fluorescence by Micropatterned Gold Nanocages

    PubMed Central

    2015-01-01

    In metal-enhanced fluorescence (MEF), the localized surface plasmon resonances of metallic nanostructures amplify the absorption of excitation light and assist in radiating the consequent fluorescence of nearby molecules to the far-field. This effect is at the base of various technologies that have strong impact on fields such as optics, medical diagnostics, and biotechnology. Among possible emission bands, those in the near-infrared (NIR) are particularly intriguing and widely used in proteomics and genomics due to its noninvasive character for biomolecules, living cells, and tissues, which greatly motivates the development of effective and, eventually, multifunctional NIR-MEF platforms. Here, we demonstrate NIR-MEF substrates based on Au nanocages micropatterned with a tight spatial control. The dependence of the fluorescence enhancement on the distance between the nanocage and the radiating dipoles is investigated experimentally and modeled by taking into account the local electric field enhancement and the modified radiation and absorption rates of the emitting molecules. At a distance around 80 nm, a maximum enhancement up to 2–7 times with respect to the emission from pristine dyes (in the region 660–740 nm) is estimated for films and electrospun nanofibers. Due to their chemical stability, finely tunable plasmon resonances, and large light absorption cross sections, Au nanocages are ideal NIR-MEF agents. When these properties are integrated with the hollow interior and controllable surface porosity, it is feasible to develop a nanoscale system for targeted drug delivery with the diagnostic information encoded in the fluorophore. PMID:26397166

  1. Carbohydrate microarray for the detection of glycan-protein interactions using metal-enhanced fluorescence.

    PubMed

    Yang, Jie; Moraillon, Anne; Siriwardena, Aloysius; Boukherroub, Rabah; Ozanam, François; Gouget-Laemmel, Anne Chantal; Szunerits, Sabine

    2015-04-01

    Carbohydrate arrays are potentially one of the most attractive tools to study carbohydrate-based interactions. This paper describes a new analytical platform that exploits metal-enhanced fluorescence for the sensitive and selective screening of carbohydrate-lectin interactions. The chip consists of a glass slide covered with gold nanostructures, postcoated with a thin layer of amorphous silicon-carbon alloy (a-Si0.8C0.2:H). An immobilization strategy based on the formation of a covalent bond between propargyl-terminated glycans and surface-linked azide groups was used to attach various glycans at varying surface densities onto the interface and to fabricate a carbohydrate array via efficient local "click" chemistry strategy. The specific association of the new interface with fluorescently labeled lectins was assessed by fluorescence imaging and an excellent selectivity to specific proteins was achieved. Optimization of the surface architecture and the plasmonic transducer resulted in an enhancement of the fluorescence intensity by 1 order of magnitude, when compared to the corresponding substrate devoid of gold nanostructures. The limit of detection (LOD) of such microarrays is in the picomolar range, making it a promising system for development in pharmaceutical or biomedical applications. PMID:25729928

  2. Chip-scale fluorescence microscope based on a silo-filter complementary metal-oxide semiconductor image sensor.

    PubMed

    Ah Lee, Seung; Ou, Xiaoze; Lee, J Eugene; Yang, Changhuei

    2013-06-01

    We demonstrate a silo-filter (SF) complementary metal-oxide semiconductor (CMOS) image sensor for a chip-scale fluorescence microscope. The extruded pixel design with metal walls between neighboring pixels guides fluorescence emission through the thick absorptive filter to the photodiode of a pixel. Our prototype device achieves 13 μm resolution over a wide field of view (4.8 mm × 4.4 mm). We demonstrate bright-field and fluorescence longitudinal imaging of living cells in a compact, low-cost configuration. PMID:23722754

  3. PREPARATION OF HALIDES OF PLUTONIUM

    DOEpatents

    Garner, C.S.; Johns, I.B.

    1958-09-01

    A dry chemical method is described for preparing plutonium halides, which consists in contacting plutonyl nitrate with dry gaseous HCl or HF at an elevated temperature. The addition to the reaction gas of a small quantity of an oxidizing gas or a reducing gas will cause formation of the tetra- or tri-halide of plutonium as desired.

  4. Imaging metals in proteins by combining electrophoresis with rapid x-ray fluorescence mapping.

    SciTech Connect

    Finney, L.; Chishti, Y.; Khare, T.; Giometti, C.; Levina, A.; Lay, P. A.; Vogt, S.; Univ. of Sydney; Northwestern Univ.

    2010-01-01

    Growing evidence points toward a very dynamic role for metals in biology. This suggests that physiological circumstance may mandate metal ion redistribution among ligands. This work addresses a critical need for technology that detects, identifies, and measures the metal-containing components of complex biological matrixes. We describe a direct, user-friendly approach for identifying and quantifying metal?protein adducts in complex samples using native- or SDS-PAGE, blotting, and rapid synchrotron X-ray fluorescence mapping with micro-XANES (X-ray absorption near-edge structure) of entire blots. The identification and quantification of each metal bound to a protein spot has been demonstrated, and the technique has been applied in two exemplary cases. In the first, the speciation of the in vitro binding of exogenous chromium to blood serum proteins was influenced markedly by both the oxidation state of chromium exposed to the serum proteins and the treatment conditions, which is of relevance to the biochemistry of Cr dietary supplements. In the second case, in vivo changes in endogenous metal speciation were examined to probe the influence of oxygen depletion on iron speciation in Shewanella oneidensis.

  5. Imaging metals in proteins by combining electrophoresis with rapid x-ray fluorescence mapping.

    PubMed

    Finney, Lydia; Chishti, Yasmin; Khare, Tripti; Giometti, Carol; Levina, Aviva; Lay, Peter A; Vogt, Stefan

    2010-06-18

    Growing evidence points toward a very dynamic role for metals in biology. This suggests that physiological circumstance may mandate metal ion redistribution among ligands. This work addresses a critical need for technology that detects, identifies, and measures the metal-containing components of complex biological matrixes. We describe a direct, user-friendly approach for identifying and quantifying metal-protein adducts in complex samples using native- or SDS-PAGE, blotting, and rapid synchrotron X-ray fluorescence mapping with micro-XANES (X-ray absorption near-edge structure) of entire blots. The identification and quantification of each metal bound to a protein spot has been demonstrated, and the technique has been applied in two exemplary cases. In the first, the speciation of the in vitro binding of exogenous chromium to blood serum proteins was influenced markedly by both the oxidation state of chromium exposed to the serum proteins and the treatment conditions, which is of relevance to the biochemistry of Cr dietary supplements. In the second case, in vivo changes in endogenous metal speciation were examined to probe the influence of oxygen depletion on iron speciation in Shewanella oneidensis. PMID:20392082

  6. Adsorption on Alkali Halides.

    NASA Astrophysics Data System (ADS)

    Urzua Duran, Gilberto Antonio

    1995-01-01

    Using a variety of interionic potentials, I have computed the configurations of adsorbed alkali halides monomers on the (001) surface of selected alkali halides crystals. In the majority of cases studied it is found that the monomer adsorbs perpendicular to the surface with the cation sitting nearly on top of the surface anion. In about ten percent of the cases though the monomer adsorbs tilted from the vertical. In these cases the ion that is closer to the surface can be the cation or the anion. The effect of polarization forces is found to be important. In order to discuss the effects of surface retaxation with adsorbates, I have evaluated the surface relaxation of the alkali halide crystals, using a shell model for the interionic forces. It is found that surface relaxation and rumpling are generally small, especially when the van der Waals forces are included. A theory of the effect of substrate vibrations on the binding of an adsorbed atom is developed. At T = 0 the binding energy is D_0-E, where D_0 is the surface well depth (classical binding energy) and E is the quantum correction. For several simple models, it is found that E is surprisingly model-independent. We compare D _0-E with the binding energies to a rigid substrate, D_0-E_{rs}, and to a vibrationally averaged substrate, D _0-E_{va}. We prove that E_{va}>=q E>=q E_ {rs} and that similar relations hold at finite temperature for the free energy of binding. In most cases E_{rs} is better than E_{va} as an approximation to E.

  7. Fluorescence properties of riboflavin-functionalized mesoporous silica SBA-15 and riboflavin solutions in presence of different metal and organic cations

    NASA Astrophysics Data System (ADS)

    Lewandowski, Dawid; Schroeder, Grzegorz; Sawczak, Mirosław; Ossowski, Tadeusz

    2015-10-01

    Riboflavin was covalently linked to mesoporous SBA-15 silica surface via grafting technique. Then fluorescence properties of the system obtained were analyzed in the presence of several metal and organic cations. Both quenching and strengthening of fluorescence as well as significant changes in the maximum fluorescence wavelength were observed. The results were compared with absorption and fluorescence data obtained for riboflavin water solutions.

  8. Halide laser glasses

    SciTech Connect

    Weber, M.J.

    1982-01-14

    Energy storage and energy extraction are of prime importance for efficient laser action and are affected by the line strengths and linewidths of optical transitions, excited-state lifetimes, nonradiative decay processes, spectroscopic inhomogeneities, nonlinear refractive index, and damage threshold. These properties are all host dependent. To illustrate this, the spectroscopic properties of Nd/sup 3 +/ have been measured in numerous oxide, oxyhalide, and halide glasses. A table summarizes the reported ranges of stimulated emission cross sections, peak wavelengths, linewidths, and radiative lifetimes associated with the /sup 4/F/sub 3/2/ ..-->.. /sup 4/I/sub 11/2/ lasing transition.

  9. Metal-organic framework based highly selective fluorescence turn-on probe for hydrogen sulphide

    PubMed Central

    Nagarkar, Sanjog S.; Saha, Tanmoy; Desai, Aamod V.; Talukdar, Pinaki; Ghosh, Sujit K.

    2014-01-01

    Hydrogen sulphide (H2S) is known to play a vital role in human physiology and pathology which stimulated interest in understanding complex behaviour of H2S. Discerning the pathways of H2S production and its mode of action is still a challenge owing to its volatile and reactive nature. Herein we report azide functionalized metal-organic framework (MOF) as a selective turn-on fluorescent probe for H2S detection. The MOF shows highly selective and fast response towards H2S even in presence of other relevant biomolecules. Low cytotoxicity and H2S detection in live cells, demonstrate the potential of MOF towards monitoring H2S chemistry in biological system. To the best of our knowledge this is the first example of MOF that exhibit fast and highly selective fluorescence turn-on response towards H2S under physiological conditions. PMID:25394493

  10. Hybrid silver nanoparticle/conjugated polyelectrolyte nanocomposites exhibiting controllable metal-enhanced fluorescence

    NASA Astrophysics Data System (ADS)

    Wang, Xiaoyu; He, Fang; Zhu, Xi; Tang, Fu; Li, Lidong

    2014-03-01

    Metal-enhanced fluorescence of conjugated polyelectrolytes (CPs) is realized using a simple, green hybrid Ag nanocomposite film. Ag nanoparticles (Ag NPs) are pre-prepared by sodium citrate reduction and incorporated into agarose by mixing to form an Ag-containing agarose film (Ag@agarose). Through variation of the amount of Ag NPs in the Ag@agarose film as well as the thickness of the interlayer between CPs and the Ag@agarose film prepared of layer-by-layer assembly of chitosan and sodium alginate, a maximum 8.5-fold increase in the fluorescence of CPs is obtained. After introducing tyrosinase, this system also can be used to detect phenolic compounds with high sensitivity and good visualization under ultraviolet light.

  11. Chlorophyll a Fluorescence in Evaluation of the Effect of Heavy Metal Soil Contamination on Perennial Grasses

    PubMed Central

    Żurek, Grzegorz; Rybka, Krystyna; Pogrzeba, Marta; Krzyżak, Jacek; Prokopiuk, Kamil

    2014-01-01

    Chlorophyll a fluorescence gives information about the plant physiological status due to its coupling to the photosynthetic electron transfer chain and to the further biochemical processes. Environmental stresses, which acts synergistically, disturbs the photosynthesis. The OJIP test, elaborated by Strasser and co-workers, enables comparison of the physiological status of plants grown on polluted vs. control areas. The paper shows that the Chl a measurements are very useful tool in evaluating of heavy metal ions influence on perennial grasses, tested as potential phytoremediators. Among 5 cultivars tested, the highest concentration of Cd and Zn ions, not associated with the yield reduction, was detected in the biomass of tall fescue cv. Rahela. Chl a fluorescence interpreted as double normalized curves pointed out Rahela as the outstanding cultivar under the HM ions stress. PMID:24633293

  12. Two Dimensional Organometal Halide Perovskite Nanorods with Tunable Optical Properties.

    PubMed

    Aharon, Sigalit; Etgar, Lioz

    2016-05-11

    Organo-metal halide perovskite is an efficient light harvester in photovoltaic solar cells. Organometal halide perovskite is used mainly in its "bulk" form in the solar cell. Confined perovskite nanostructures could be a promising candidate for efficient optoelectronic devices, taking advantage of the superior bulk properties of organo-metal halide perovskite, as well as the nanoscale properties. In this paper, we present facile low-temperature synthesis of two-dimensional (2D) lead halide perovskite nanorods (NRs). These NRs show a shift to higher energies in the absorbance and in the photoluminescence compared to the bulk material, which supports their 2D structure. X-ray diffraction (XRD) analysis of the NRs demonstrates their 2D nature combined with the tetragonal 3D perovskite structure. In addition, by alternating the halide composition, we were able to tune the optical properties of the NRs. Fast Fourier transform, and electron diffraction show the tetragonal structure of these NRs. By varying the ligands ratio (e.g., octylammonium to oleic acid) in the synthesis, we were able to provide the formation mechanism of these novel 2D perovskite NRs. The 2D perovskite NRs are promising candidates for a variety of optoelectronic applications, such as light-emitting diodes, lasing, solar cells, and sensors. PMID:27089497

  13. Process for oxidation of hydrogen halides to elemental halogens

    DOEpatents

    Lyke, Stephen E.

    1992-01-01

    An improved process for generating an elemental halogen selected from chlorine, bromine or iodine, from a corresponding hydrogen halide by absorbing a molten salt mixture, which includes sulfur, alkali metals and oxygen with a sulfur to metal molar ratio between 0.9 and 1.1 and includes a dissolved oxygen compound capable of reacting with hydrogen halide to produce elemental halogen, into a porous, relatively inert substrate to produce a substrate-supported salt mixture. Thereafter, the substrate-supported salt mixture is contacted (stage 1) with a hydrogen halide while maintaining the substrate-supported salt mixture during the contacting at an elevated temperature sufficient to sustain a reaction between the oxygen compound and the hydrogen halide to produce a gaseous elemental halogen product. This is followed by purging the substrate-supported salt mixture with steam (stage 2) thereby recovering any unreacted hydrogen halide and additional elemental halogen for recycle to stage 1. The dissolved oxygen compound is regenerated in a high temperature (stage 3) and an optical intermediate temperature stage (stage 4) by contacting the substrate-supported salt mixture with a gas containing oxygen whereby the dissolved oxygen compound in the substrate-supported salt mixture is regenerated by being oxidized to a higher valence state.

  14. Overcoming metal-induced fluorescence quenching on plasmo-photonic metasurfaces coated by a self-assembled monolayer.

    PubMed

    Choi, Bongseok; Iwanaga, Masanobu; Miyazaki, Hideki T; Sugimoto, Yoshimasa; Ohtake, Akihiro; Sakoda, Kazuaki

    2015-07-21

    We have experimentally shown significant suppression of metal-induced fluorescence (FL) quenching on plasmo-photonic metasurfaces by incorporating a self-assembled monolayer (SAM) of sub-nm thickness. The FL signals of rhodamine dye molecules have been several-ten-fold enhanced by introducing the SAM, in comparison with the previous configuration contacting molecules and metal surfaces. PMID:26088784

  15. Investigation of metal ion accumulation in Euglena gracilis by fluorescence methods

    NASA Astrophysics Data System (ADS)

    Shen, H.; Ren, Q. G.; Mi, Y.; Shi, X. F.; Yao, H. Y.; Jin, C. Z.; Huang, Y. Y.; He, W.; Zhang, J.; Liu, B.

    2002-04-01

    Single cell synchrotron X-ray fluorescence (SXRF) microprobe measurements as well as X-ray absorption near edge structure experiments have been done at Beijing Synchrotron Radiation Facility on Euglena Gracilis cells. Concentrations of the metal ions Mn 2+, Nd 3+, Ce 3+ and other trace elements, such as Ca, Fe, Zn, etc. have been measured both by single cell SXRF and bulk PIXE technique. It was found that the content of Ca, Fe and Zn was lower after the uptake of rare earths or Mn by the cells, while the valence states of Mn 2+, Ce 3+ and Nd 3+ were unaltered. The results related to cytochemistry are also discussed.

  16. Exploring metal detoxification and accumulation potential during vermicomposting of Tea factory coal ash: sequential extraction and fluorescence probe analysis

    PubMed Central

    Goswami, Linee; Pratihar, Sanjay; Dasgupta, Suman; Bhattacharyya, Pradip; Mudoi, Pronab; Bora, Jayanta; Bhattacharya, Satya Sundar; Kim, Ki Hyun

    2016-01-01

    Metal contamination from coal ashes (CAs) is widely recognized as a significant environmental concern. To learn more about metal detoxification and accumulation potential of earthworm species, metal-rich tea factory coal ashes (TFCA) were fed to Eisenia fetida and Lampito mauritii by employing a fluorescent tag detection method. Fascinatingly, on feeding fluorescence probed Zn and Cd along with cow dung to Eisenia fetida, the detection of the gut-proteins with a molecular mass higher than 100 kDa was a distinct evidence of metal binding. Significant increases were observed in the content of humified organic C [humic acid (HAC) and fulvic acid C (FAC)] and degree of humification during vermicomposting. Concurrently, considerably large amount of toxic metals (Cr, Cd, Pb, and Zn) was transformed from exchangeable to recalcitrant (organic matter and mineral bound) fractions. Moreover, total metal concentrations were reduced with high removal efficiency upon vermicomposting. PMID:27456167

  17. Exploring metal detoxification and accumulation potential during vermicomposting of Tea factory coal ash: sequential extraction and fluorescence probe analysis

    NASA Astrophysics Data System (ADS)

    Goswami, Linee; Pratihar, Sanjay; Dasgupta, Suman; Bhattacharyya, Pradip; Mudoi, Pronab; Bora, Jayanta; Bhattacharya, Satya Sundar; Kim, Ki Hyun

    2016-07-01

    Metal contamination from coal ashes (CAs) is widely recognized as a significant environmental concern. To learn more about metal detoxification and accumulation potential of earthworm species, metal-rich tea factory coal ashes (TFCA) were fed to Eisenia fetida and Lampito mauritii by employing a fluorescent tag detection method. Fascinatingly, on feeding fluorescence probed Zn and Cd along with cow dung to Eisenia fetida, the detection of the gut-proteins with a molecular mass higher than 100 kDa was a distinct evidence of metal binding. Significant increases were observed in the content of humified organic C [humic acid (HAC) and fulvic acid C (FAC)] and degree of humification during vermicomposting. Concurrently, considerably large amount of toxic metals (Cr, Cd, Pb, and Zn) was transformed from exchangeable to recalcitrant (organic matter and mineral bound) fractions. Moreover, total metal concentrations were reduced with high removal efficiency upon vermicomposting.

  18. Exploring metal detoxification and accumulation potential during vermicomposting of Tea factory coal ash: sequential extraction and fluorescence probe analysis.

    PubMed

    Goswami, Linee; Pratihar, Sanjay; Dasgupta, Suman; Bhattacharyya, Pradip; Mudoi, Pronab; Bora, Jayanta; Bhattacharya, Satya Sundar; Kim, Ki Hyun

    2016-01-01

    Metal contamination from coal ashes (CAs) is widely recognized as a significant environmental concern. To learn more about metal detoxification and accumulation potential of earthworm species, metal-rich tea factory coal ashes (TFCA) were fed to Eisenia fetida and Lampito mauritii by employing a fluorescent tag detection method. Fascinatingly, on feeding fluorescence probed Zn and Cd along with cow dung to Eisenia fetida, the detection of the gut-proteins with a molecular mass higher than 100 kDa was a distinct evidence of metal binding. Significant increases were observed in the content of humified organic C [humic acid (HAC) and fulvic acid C (FAC)] and degree of humification during vermicomposting. Concurrently, considerably large amount of toxic metals (Cr, Cd, Pb, and Zn) was transformed from exchangeable to recalcitrant (organic matter and mineral bound) fractions. Moreover, total metal concentrations were reduced with high removal efficiency upon vermicomposting. PMID:27456167

  19. Release of the self-quenching of fluorescence near silver metallic surfaces.

    PubMed

    Lakowicz, Joseph R; Malicka, Joanna; D'Auria, Sabato; Gryczynski, Ignacy

    2003-09-01

    Fluorescein is one of the most widely used fluorescent probes in microscopy, biotechnology, and clinical assays. One difficulty with fluorescein is its self-quenching, which results in decreased intensities with increasing labeling density. In this study we examined human serum albumin (HSA), which contained one to nine covalently linked fluorescein molecules per molecule of HSA. The occurrence of homo resonance energy transfer for labeling ratios greater than 1 were confirmed by decreases in the relative quantum yields, anisotropies, and lifetimes. We found that most of the self-quenching can be partially eliminated by proximity of the labeled protein to metallic silver particles. These results suggest the use of heavily labeled proteins and metallic colloids to obtain ultrabright reagents for use in immunoassays, imaging, and other applications. PMID:12895465

  20. One-step aqueous synthesis of fluorescent copper nanoclusters by direct metal reduction

    NASA Astrophysics Data System (ADS)

    Fernández-Ujados, Mónica; Trapiella-Alfonso, Laura; Costa-Fernández, José M.; Pereiro, Rosario; Sanz-Medel, Alfredo

    2013-12-01

    A one-step aqueous synthesis of highly fluorescent water-soluble copper nanoclusters (CuNCs) is here described, based on direct reduction of the metal precursor with NaBH4 in the presence of bidentate ligands (made of lipoic acid anchoring groups, appended with a poly(ethylene glycol) short chain). A complete optical and structural characterization was carried out: the optical emission was centred at 416 nm, with a luminescence quantum yield in water of 3.6% (the highest one reported so far in water for this kind of nanocluster). The structural characterization reveals a homogeneous size distribution (of 2.5 nm diameter) with spherical shape. The CuNCs obtained offer long-term stability (the luminescence emission remained unaltered after more than two months) under a broad range of chemical conditions (e.g. stored at pH 3-12 or even in a high ionic strength medium such as 1 M NaCl) and high photostability, keeping their fluorescence emission intact after more than 2 h of daylight and UV-light exposition. All those advantageous features warrant synthesized CuNCs being promising fluorescent nanoprobes for further developments including (bio)applications.

  1. Metal enhanced fluorescence improved protein and DNA detection by zigzag Ag nanorod arrays.

    PubMed

    Ji, Xiaofan; Xiao, Chenyu; Lau, Wai-Fung; Li, Jianping; Fu, Junxue

    2016-08-15

    As metal nano-arrays show great potential on metal enhanced fluorescence (MEF) than random nanostructures, MEF of Ag zigzag nanorod (ZNR) arrays made by oblique angle deposition has been studied for biomolecule-protein interaction and DNA hybridization. By changing the folding number and the deposition substrate temperature, a 14-fold enhancement factor (EF) is obtained for biotin-neutravidin detection. The optimal folding number is decided as Z=7, owing to the high scattering intensity of Ag ZNRs. The substrate temperature T=25°C and 0°C slightly alters the morphology of Ag ZNRs but has no big difference in EF. Further, Ag ZNRs deposited on a layer of Ag film have been introduced to the DNA hybridization and a significant signal enhancement has been observed through the fluorescence microscope. Through a detailed quantitative EF analysis, which excludes the enhancing effect from the increased surface area of ZNRs and only considers the contribution of MEF, an EF of 28 is achieved for the hybridization of two single-stranded oligonucleotides with 33 bases. Furthermore, a limit of detection is determined as 0.01pM. We believe that the Ag ZNR arrays can serve as a universal and sensitive bio-detection platform. PMID:27088369

  2. Applications of Raman scattering spectroscopy to halide glasses

    NASA Astrophysics Data System (ADS)

    Bendow, B.; Banerjee, P. K.; Drexhage, M. G.

    1983-04-01

    Polarized Raman scattering spectroscopy is a useful tool for investigating fundamental vibrational properties, structure and bonding, origins of IR edge absorption, and dispersion of the IR refractive index. In this paper, the application of Raman spectroscopy to halide glasses and, in particular, heavy metal fluoride glasses, is described. The spectra of the latter differ substantially from those of simple oxide, halide or chalcogenide glasses and, moreover, display a wide range of vibrational characteristics, depending on composition. In combination with infrared spectroscopy, useful guidelines can be developed for tailoring glass compositions for specific applications.

  3. Hazardous metals in vintage plastic toys measured by a handheld X-ray fluorescence spectrometer.

    PubMed

    Miller, Gillian Zaharias; Harris, Zoe E

    2015-01-01

    Over 100 plastic toys from the 1970s and 1980s, both polyvinyl chloride ("vinyl") and nonvinyl, were analyzed in the study described here using a handheld X-ray fluorescence spectrometer to quantify hazardous metal content. A sampling of recent vinyl toys was also tested. The majority of nonvinyl samples were Fisher Price brand toys. The vinyl toys consisted largely of Barbie dolls and other dolls. Overall, lead or cadmium was found in 67% of vintage plastic toys, frequently at concentrations exceeding current U.S. and European limits. Arsenic was detected at levels of concern in 16% of the samples. In the nonvinyl toys, heavy metal content was found to correlate with certain colors of plastic. The likely sources of the detected metals are discussed. None of the contemporary vinyl toys contained detectable cadmium, lead, or arsenic. Given that vintage toys remain in widespread use by children in homes and other locations, the results illuminate a potential source of heavy metal exposure for children. PMID:25619030

  4. Photophysical characterization of fluorescent metal nanoclusters synthesized using oligonucleotides, proteins and small molecule ligands

    NASA Astrophysics Data System (ADS)

    Yeh, Hsin-Chih; Sharma, Jaswinder; Yoo, Hyojong; Martinez, Jennifer S.; Werner, James H.

    2010-02-01

    The size transition from bulk conducting metals to insulating nanoparticles and eventually to single atoms passes through the relatively unexplored few-atom nanocluster region. With dimensions close to the Fermi wavelength, these nanoclusters demonstrate molecule-like properties distinct from bulk metals or atoms, such as discrete and size-tunable electronic transitions which lead to photoluminescence. Current research aims to elucidate the fundamental photophysical properties of metal nanoclusters made by different means and based on different encapsulation agents. Here, we report the study of the photophysical properties, including quantum yields, lifetimes, extinction coefficients, blinking dynamics and sizes, of silver and gold nanoclusters synthesized using oligonucleotides, a protein (bovine serum albumin) and a Good's buffer molecule (MES, 2-(N-morpholino) ethanesulfonic acid) as encapsulation agents. We also investigate the change of photoluminescence as a function of temperature. Furthermore, we show that the fluorescent metal clusters can be used as a donor in forming a resonance energy transfer pair with a commercial organic quencher. These new fluorophores have great potential as versatile tools for a broad range of applications in biological and chemical detection.

  5. Photophysical characterization of fluorescent metal nanoclusters sythesized using oligonucleotides, proteins and small reagent moleucles

    SciTech Connect

    Yeh, Hsin-chih; Jaswinder, Sharma K; Martinez, Jennifer S; Werner, James H; Yoo, Hyojong

    2009-01-01

    The size transition from bulk metals to insulating nanoparticles and eventually to single atoms passes through the relatively unexplored few-atom nanocluster region. With climensions close to the Fermi wavelength, these nanoclusters demonstrate molecule-like properties distinct from bulk metals or atoms, such as discrete and size-tunable electronic transitions which lead to photoluminescence. Current research aims to elucidate the fundamental photophysical properties of the existing metal nanoclusters made by different means and based on different encapsulation agents. Here, we report the study of the photophysical properties, including quantum yields, lifetimes, extinction coefficients, blinking dynamics and sizes, of silver and gold nanoclusters synthesized using oligonucleotides, a protein (bovine serum albumin) and a Good's buffer molecule (MES, 2-(N-morpholino)ethanesulfonic acid) as encapsulation agents. We also investigate the change of photoluminescence under varying conditions (time, temperature and salt). Furthermore, it is demonstrated here that fluorescent metal clusters can be used as a donor in forming resonance energy transfer pairs with a commercial organic quenching dye.

  6. Significant metal enhanced fluorescence of Ag2S quantum dots in the second near-infrared window

    NASA Astrophysics Data System (ADS)

    Theodorou, I. G.; Jawad, Z. A. R.; Qin, H.; Aboagye, E. O.; Porter, A. E.; Ryan, M. P.; Xie, F.

    2016-06-01

    The amplification of light in NIR-II from Ag2S QDs via metal enhanced fluorescence (MEF) is reported for the first time. Significant fluorescence enhancement of over 100 times for Ag2S QDs deposited on Au-nanostructured arrays, paves the way for novel sensing and imaging applications based on Ag2S QDs, with improved detection sensitivity and contrast enhancement.The amplification of light in NIR-II from Ag2S QDs via metal enhanced fluorescence (MEF) is reported for the first time. Significant fluorescence enhancement of over 100 times for Ag2S QDs deposited on Au-nanostructured arrays, paves the way for novel sensing and imaging applications based on Ag2S QDs, with improved detection sensitivity and contrast enhancement. Electronic supplementary information (ESI) available: Detailed description of experimental methods. See DOI: 10.1039/c6nr03220f

  7. Dependence of Purcell effect on fluorescence wavelength in dye molecules on metal-dielectric multilayer hyperbolic metamaterials

    NASA Astrophysics Data System (ADS)

    Tsurumachi, Noriaki; Izawa, Hayato; Tomioka, Ryo; Sakata, Tomohiro; Suzuki, Makoto; Tanaka, Yasuhiro; Shimokawa, Fusao; Nakanishi, Shunsuke

    2016-02-01

    Recently, the enhancement of spontaneous emission, i.e., broadband Purcell effect, has been achieved using hyperbolic metamaterials. Hyperbolic metamaterials, which can be realized using a metal-dielectric multilayer structure, have an extremely large optical anisotropy of permittivity in both the parallel and perpendicular directions to the propagation of light, especially when the signs of permittivities in both directions differ. In this study, we investigated the conditions for realizing the broadband Purcell effect using dye molecules with different fluorescence wavelengths. Our fabricated metal-dielectric multilayer structure exhibited hyperbolic dispersion at wavelengths beyond 500 nm. In the case of coumarin 500 whose fluorescence peak is located at 500 nm, no broadband Purcell effect was observed. However, in the case of pyridine 1 whose fluorescence peak is located at 650 nm, we observed the successfull fluorescence lifetime shortening, i.e., the broadband Purcell effect.

  8. Switch-On Fluorescence of a Perylene-Dye-Functionalized Metal-Organic Framework through Postsynthetic Modification.

    PubMed

    Dietl, Christian; Hintz, Henrik; Rühle, Bastian; Schmedt Auf der Günne, Jörn; Langhals, Heinz; Wuttke, Stefan

    2015-07-20

    A perylene dye was introduced directly as a linker into a metal-organic framework (MOF) during synthesis. Depending on the dye concentration in the MOF synthesis mixture, different fluorescent materials were generated. The successful incorporation of the dye was proven by using (13) C and (27) Al MAS NMR spectroscopy, by solution NMR spectroscopy after digestion of the MOF sample, and by synthesizing a reference dye without connecting groups, which could coordinate on the metal-oxo cluster inside the MOF. Fluorescence quenching effects of the MOF linker, 2-aminoterephthalate, were observed and overcome by postsynthetic modification with acetic anhydride. We show here for the first time that amino groups, which can be used as anchoring points for covalent attachment of other molecules, are responsible for fluorescence quenching. Thus, a very promising strategy to implement switchable fluorescence into MOFs is shown here. PMID:26037475

  9. Metal-Enhanced Fluorescence from Silver Nanowires with High Aspect Ratio on Glass Slides for Biosensing Applications

    PubMed Central

    2015-01-01

    High enhancement of fluorescence emission, improved fluorophore photostability, and significant reduction of fluorescence lifetimes have been obtained from high aspect ratio (>100) silver (Ag) nanowires. These quantities are found to depend on the surface loading of Ag nanowires on glass slides, where the enhancement of fluorescence emission increases with the density of nanowires. The surface loading dependence was attributed to the creation of intense electric fields around the network of Ag nanowires and to the coupling of fluorophore excited states that takes place efficiently at a distance of 10 nm from the surface of nanowires, which was confirmed by theoretical calculations. The enhancement of fluorescence emission of fluorescein isothiocyanate (FITC) was assessed by fluorescence spectroscopy and fluorescence-lifetime imaging microscopy (FLIM) to demonstrate the potential of high aspect ratio Ag nanowires. Fluorescence enhancement factors exceeding 14 were observed on Ag nanowires with high loading by FLIM. The photostability of FITC was the highest on nanowires with medium loading under continuous laser excitation for 10 min because of the significant reduction in the fluorescence lifetime of FITC on these surfaces. These results clearly demonstrate the potential of Ag nanowires in metal-enhanced fluorescence-based applications of biosensing on planar surfaces and cellular imaging. PMID:25598859

  10. Significant metal enhanced fluorescence of Ag2S quantum dots in the second near-infrared window.

    PubMed

    Theodorou, I G; Jawad, Z A R; Qin, H; Aboagye, E O; Porter, A E; Ryan, M P; Xie, F

    2016-07-14

    The amplification of light in NIR-II from Ag2S QDs via metal enhanced fluorescence (MEF) is reported for the first time. Significant fluorescence enhancement of over 100 times for Ag2S QDs deposited on Au-nanostructured arrays, paves the way for novel sensing and imaging applications based on Ag2S QDs, with improved detection sensitivity and contrast enhancement. PMID:27314986

  11. Vitrification of IFR and MSBR halide salt reprocessing wastes

    SciTech Connect

    Siemer, D.D.

    2013-07-01

    Both of the genuinely sustainable (breeder) nuclear fuel cycles (IFR - Integral Fast Reactor - and MSBR - Molten Salt Breeder Reactor -) studied by the USA's national laboratories would generate high level reprocessing waste (HLRW) streams consisting of a relatively small amount ( about 4 mole %) of fission product halide (chloride or fluoride) salts in a matrix comprised primarily (about 95 mole %) of non radioactive alkali metal halide salts. Because leach resistant glasses cannot accommodate much of any of the halides, most of the treatment scenarios previously envisioned for such HLRW have assumed a monolithic waste form comprised of a synthetic analog of an insoluble crystalline halide mineral. In practice, this translates to making a 'substituted' sodalite ('Ceramic Waste Form') of the IFR's chloride salt-based wastes and fluoroapatite of the MSBR's fluoride salt-based wastes. This paper discusses my experimental studies of an alternative waste management scenario for both fuel cycles that would separate/recycle the waste's halide and immobilize everything else in iron phosphate (Fe-P) glass. It will describe both how the work was done and what its results indicate about how a treatment process for both of those wastes should be implemented (fluoride and chloride behave differently). In either case, this scenario's primary advantages include much higher waste loadings, much lower overall cost, and the generation of a product (glass) that is more consistent with current waste management practices. (author)

  12. Heat capacity of molten halides.

    PubMed

    Redkin, Alexander A; Zaikov, Yurii P; Korzun, Iraida V; Reznitskikh, Olga G; Yaroslavtseva, Tatiana V; Kumkov, Sergey I

    2015-01-15

    The heat capacities of molten salts are very important for their practical use. Experimental investigation of this property is challenging because of the high temperatures involved and the corrosive nature of these materials. It is preferable to combine experimental investigations with empirical relationships, which allows for the evaluation of the heat capacity of molten salt mixtures. The isobaric molar heat capacities of all molten alkali and alkaline-earth halides were found to be constant for each group of salts. The value depends on the number of atoms in the salt, and the molar heat capacity per atom is constant for all molten halide salts with the exception of the lithium halides. The molar heat capacities of molten halides do not change when the anions are changed. PMID:25530462

  13. Correlation of photobleaching, oxidation and metal induced fluorescence quenching of DNA-templated silver nanoclusters

    NASA Astrophysics Data System (ADS)

    Morishita, Kiyoshi; Maclean, James L.; Liu, Biwu; Jiang, Hui; Liu, Juewen

    2013-03-01

    Few-atom noble metal nanoclusters have attracted a lot of interest due to their potential applications in biosensor development, imaging and catalysis. DNA-templated silver nanoclusters (AgNCs) are of particular interest as different emission colors can be obtained by changing the DNA sequence. A popular analytical application is fluorescence quenching by Hg2+, where d10-d10 metallophilic interaction has often been proposed for associating Hg2+ with nanoclusters. However, it cannot explain the lack of response to other d10 ions such as Zn2+ and Cd2+. In our effort to elucidate the quenching mechanism, we studied a total of eight AgNCs prepared by different hairpin DNA sequences; they showed different sensitivity to Hg2+, and DNA with a larger cytosine loop size produced more sensitive AgNCs. In all the cases, samples strongly quenched by Hg2+ were also more easily photobleached. Light of shorter wavelengths bleached AgNCs more potently, and photobleached samples can be recovered by NaBH4. Strong fluorescence quenching was also observed with high redox potential metal ions such as Ag+, Au3+, Cu2+ and Hg2+, but not with low redox potential ions. Such metal induced quenching cannot be recovered by NaBH4. Electronic absorption and mass spectrometry studies offered further insights into the oxidation reaction. Our results correlate many important experimental observations and will fuel the further growth of this field.Few-atom noble metal nanoclusters have attracted a lot of interest due to their potential applications in biosensor development, imaging and catalysis. DNA-templated silver nanoclusters (AgNCs) are of particular interest as different emission colors can be obtained by changing the DNA sequence. A popular analytical application is fluorescence quenching by Hg2+, where d10-d10 metallophilic interaction has often been proposed for associating Hg2+ with nanoclusters. However, it cannot explain the lack of response to other d10 ions such as Zn2+ and Cd2+. In

  14. ELECTROLYTIC PROCESS FOR PRODUCING METALS

    DOEpatents

    Kopelman, B.; Holden, R.B.

    1961-06-01

    A method is described for reducing beryllium halides to beryllium. The beryllfum halide fs placed in an eutectic mixture of alkali halides and alkaline earth halides. The constituents of this eutectic bath are so chosen that it has a melting point less than the boiling point of mercury, which acts as a cathode for the system. The beryllium metal is then deposited in the mercury upon electrolysis.

  15. The low temperature electrochemical growth of iron, nickel and other metallic single crystals from halide eutectic fluxes in a temperature gradient

    NASA Astrophysics Data System (ADS)

    Chareev, Dmitriy A.

    2015-11-01

    Single crystals of metallic Fe, Ni, Co, Cr, Al, Cu, Ag, Au, Pd, Pt and a few alloys were grown using the AlCl3/KCl and CsCl/NaCl/KCl fluxes for Men+ transport and an inert metallic wire for electron transport in a permanent temperature gradient from 350-600 °C that produced single crystalline samples with dimensions of approximately 2×2×2 mm3. Energy dispersive X-ray spectroscopy established crystal formation of pure metals.

  16. Simulated 'On-Line' Wear Metal Analysis of Lubricating Oils by X-Ray Fluorescence Spectroscopy

    NASA Technical Reports Server (NTRS)

    Kelliher, Warren C.; Partos, Richard D.; Nelson, Irina

    1996-01-01

    The objective of this project was to assess the sensitivity of X-ray Fluorescence Spectroscopy (XFS) for quantitative evaluation of metal particle content in engine oil suspensions and the feasibility of real-time, dynamic wear metal analysis. The study was focused on iron as the majority wear metal component. Variable parameters were: particle size, particle concentration and oil velocity. A commercial XFS spectrometer equipped with interchangeable static/dynamic (flow cell) sample chambers was used. XFS spectra were recorded for solutions of Fe-organometallic standard and for a series of DTE oil suspensions of high purity spherical iron particles of 2g, 4g, and 8g diameter, at concentrations from 5 ppm to 5,000 ppm. Real contaminated oil samples from Langley Air Force Base aircraft engines and NASA Langley Research Center wind tunnels were also analyzed. The experimental data conform the reliability of XFS as the analytical method of choice for this project. Intrinsic inadequacies of the instrument for precise analytic work at low metal concentrations were identified as being related to the particular x-ray beam definition, system geometry, and flow-cell materials selection. This work supports a proposal for the design, construction and testing of a conceptually new, miniature XFS spectrometer with superior performance, dedicated to on-line, real-time monitoring of lubricating oils in operating engines. Innovative design solutions include focalization of the incident x-ray beam, non-metal sample chamber, and miniaturization of the overall assembly. The instrument would contribute to prevention of catastrophic engine failures. A proposal for two-year funding has been presented to NASA Langley Research Center Internal Operation Group (IOG) Management, to continue the effort begun by this summer's project.

  17. Mapping of Heavy Metal Ion Sorption to Cell-Extracellular Polymeric Substance-Mineral Aggregates by Using Metal-Selective Fluorescent Probes and Confocal Laser Scanning Microscopy

    PubMed Central

    Li, Jianli; Kappler, Andreas; Obst, Martin

    2013-01-01

    Biofilms, organic matter, iron/aluminum oxides, and clay minerals bind toxic heavy metal ions and control their fate and bioavailability in the environment. The spatial relationship of metal ions to biomacromolecules such as extracellular polymeric substances (EPS) in biofilms with microbial cells and biogenic minerals is complex and occurs at the micro- and submicrometer scale. Here, we review the application of highly selective and sensitive metal fluorescent probes for confocal laser scanning microscopy (CLSM) that were originally developed for use in life sciences and propose their suitability as a powerful tool for mapping heavy metals in environmental biofilms and cell-EPS-mineral aggregates (CEMAs). The benefit of using metal fluorescent dyes in combination with CLSM imaging over other techniques such as electron microscopy is that environmental samples can be analyzed in their natural hydrated state, avoiding artifacts such as aggregation from drying that is necessary for analytical electron microscopy. In this minireview, we present data for a group of sensitive fluorescent probes highly specific for Fe3+, Cu2+, Zn2+, and Hg2+, illustrating the potential of their application in environmental science. We evaluate their application in combination with other fluorescent probes that label constituents of CEMAs such as DNA or polysaccharides and provide selection guidelines for potential combinations of fluorescent probes. Correlation analysis of spatially resolved heavy metal distributions with EPS and biogenic minerals in their natural, hydrated state will further our understanding of the behavior of metals in environmental systems since it allows for identifying bonding sites in complex, heterogeneous systems. PMID:23974141

  18. Highly Fluorescent Group 13 Metal Complexes with Cyclic, Aromatic Hydroxamic Acid Ligands

    SciTech Connect

    Seitz, Michael; Moore, Evan G.; Raymond, Kenneth N.

    2008-02-11

    The neutral complexes of two ligands based on the 1-oxo-2-hydroxy-isoquinoline (1,2-HOIQO) motif with group 13 metals (Al, Ga, In) show bright blue-violet luminescence in organic solvents. The corresponding transition can be attributed to ligand-centered singlet emission, characterized by a small Stokes shifts of only a few nm combined with lifetimes in the range between 1-3 ns. The fluorescence efficiency is high, with quantum yields of up to 37% in benzene solution. The crystal structure of one of the indium(III) complexes (trigonal space group R-3, a = b = 13.0384(15) {angstrom}, c = 32.870(8) {angstrom}, ? = {beta} = 90{sup o}, {gamma} = 120{sup o}, V = 4839.3(14) {angstrom}{sup 3}, Z = 6) shows a six-coordinate geometry around the indium center which is close to trigonal-prismatic, with a twist angle between the two trigonal faces of 20.7{sup o}. Time-dependent density functional theory (TD-DFT) calculations (Al and Ga: B3LYP/6-31G(d)); In: B3LYP/LANL2DZ of the fac and mer isomers with one of the two ligands indicate that there is no clear preference for either one of the isomeric forms of the metal complexes. In addition, the metal centers do not have a significant influence on the electronic structure, and as a consequence, on the predominant intraligand optical transitions.

  19. In vivo monitoring of toxic metals: assessment of neutron activation and x-ray fluorescence techniques

    SciTech Connect

    Ellis, K.J.

    1986-01-01

    To date, cadmium, lead, aluminum, and mercury have been measured in vivo in humans. The possibilities of monitoring other toxic metals have also been demonstrated, but no human studies have been performed. Neutron activation analysis appears to be most suitable for Cd and Al measurements, while x-ray fluorescence is ideally suited for measurement of lead in superficial bone. Filtered neutron beams and polarized x-ray sources are being developed which will improve in vivo detection limits. Even so, several of the current facilities are already suitable for use in epidemiological studies of selected populations with suspected long-term low-level ''environmental'' exposures. Evaluation and diagnosis of patients presenting with general clinical symptoms attributable to possible toxic metal exposure may be assisted by in vivo examination. Continued in vivo monitoring of industrial workers, especially follow-up measurements, will provide the first direct assessment of changes in body burden and a direct measure of the biological life-times of these metals in humans. 50 refs., 4 figs., 2 tabs.

  20. Microfluidic-based metal enhanced fluorescence for capillary electrophoresis by Ag nanorod arrays

    NASA Astrophysics Data System (ADS)

    Xiao, Chenyu; Cao, Zhen; Deng, Junhong; Huang, Zhifeng; Xu, Zheng; Fu, Junxue; Yobas, Levent

    2014-06-01

    As metal nanorods show much higher metal enhanced fluorescence (MEF) than metal nanospheres, microfluidic-based MEF is first explored with Ag nanorod (ND) arrays made by oblique angle deposition. By measuring the fluorescein isothiocyanate (FITC) solution sandwiched between the Ag NDs and a piece of cover slip, the enhancement factors (EFs) are found as 3.7 ± 0.64 and 6.74 ± 2.04, for a solution thickness at 20.8 μm and 10 μm, respectively. Because of the strong plasmonic coupling between the adjacent Ag NDs, only the emission of the fluorophores present in the three-dimensional NDs array gets enhanced. Thus, the corresponding effective enhancement factors (EEFs) are revealed to be relatively close, 259 ± 92 and 340 ± 102, respectively. To demonstrate the application of MEF in microfluidic systems, a multilayer of SiO2 NDs/Ag NDs is integrated with a capillary electrophoresis device. At a microchannel depth of 10 μm, an enhancement of 6.5 fold is obtained for amino acids separation detection. These results are very encouraging and open the possibility of MEF applications for the Ag ND arrays decorated microchannels. With the miniaturization of microfluidic devices, microfluidic-based MEF by Ag ND arrays will likely find more applications with further enhancement.

  1. Making and Breaking of Lead Halide Perovskites.

    PubMed

    Manser, Joseph S; Saidaminov, Makhsud I; Christians, Jeffrey A; Bakr, Osman M; Kamat, Prashant V

    2016-02-16

    A new front-runner has emerged in the field of next-generation photovoltaics. A unique class of materials, known as organic metal halide perovskites, bridges the gap between low-cost fabrication and exceptional device performance. These compounds can be processed at low temperature (typically in the range 80-150 °C) and readily self-assemble from the solution phase into high-quality semiconductor thin films. The low energetic barrier for crystal formation has mixed consequences. On one hand, it enables inexpensive processing and both optical and electronic tunability. The caveat, however, is that many as-formed lead halide perovskite thin films lack chemical and structural stability, undergoing rapid degradation in the presence of moisture or heat. To date, improvements in perovskite solar cell efficiency have resulted primarily from better control over thin film morphology, manipulation of the stoichiometry and chemistry of lead halide and alkylammonium halide precursors, and the choice of solvent treatment. Proper characterization and tuning of processing parameters can aid in rational optimization of perovskite devices. Likewise, gaining a comprehensive understanding of the degradation mechanism and identifying components of the perovskite structure that may be particularly susceptible to attack by moisture are vital to mitigate device degradation under operating conditions. This Account provides insight into the lifecycle of organic-inorganic lead halide perovskites, including (i) the nature of the precursor solution, (ii) formation of solid-state perovskite thin films and single crystals, and (iii) transformation of perovskites into hydrated phases upon exposure to moisture. In particular, spectroscopic and structural characterization techniques shed light on the thermally driven evolution of the perovskite structure. By tuning precursor stoichiometry and chemistry, and thus the lead halide charge-transfer complexes present in solution, crystallization

  2. Process for polymerizing olefins in the presence of a catalyst prepared from organomagenesium compound, epihalohydrin reducing halide source and transition metal compound

    SciTech Connect

    Lund, G.K.

    1986-08-12

    This patent describes a process for the polymerization of one or more polymerizable ethylenically unsaturated monomers containing one or more polymerizable ..cap alpha..-olefins under Ziegler polymerization conditions wherein the polymerization is conducted in the presence of a transition metal-containing catalyst. The improvement comprises employing as the transition metal-containing catalyst a catalytic product resulting from admixing in an inert hydrocarbon diluent and in an atmosphere which excludes moisture and oxygen.

  3. A fluorescent aptasensor for H5N1 influenza virus detection based-on the core-shell nanoparticles metal-enhanced fluorescence (MEF).

    PubMed

    Pang, Yuanfeng; Rong, Zhen; Wang, Junfeng; Xiao, Rui; Wang, Shengqi

    2015-04-15

    A fluorescent aptasensor system has been designed for the sensitive detection of recombinant hemagglutinin (rHA) protein of the H5N1 influenza virus in human serum. Guanine-richen anti-rHA aptamers by SELEX were immobilized on the surface of the Ag@SiO2 nanoparticles which performed as a metal-enhanced fluorescence (MEF) sensing platform. Thiazole orange (TO) was used as fluorescent tag which reported to the G-quadruplex secondary structural induced by aptamer-rHA binding event. In the absence of rHA protein, TO was free in the solution with almost no fluorescence emission. When rHA protein was added to the solution, the aptamer strand bound rHA protein to form a stable G-quadruplex complex, which can bind TO and excite the fluorescence emission of TO. Moreover, the excited-state TO captured by the G-quadruplex complex was forced to the surface of the Ag@SiO2 nanoparticles and could experience a surface plasmon resonance enhancement which can be transformed into more efficient fluorescence emission signals, therefore, the fluorescence signal of TO can be amplified largely. This system does not require covalent labeling with fluorophores to the aptamer and the background noise is very low. The detection of rHA protein of the H5N1 influenza virus could be operated both in aqueous buffer and human serum with the detection limit of 2 and 3.5ng/mL respectively. More important, the whole detection process can be finished in a PE tube within 30min, which makes it suitable as a self-contained diagnostic kit for H5N1 influenza virus point-of-care (POC) diagnostic. PMID:25506900

  4. Molecules for Fluorescence Detection of Specific Chemicals

    NASA Technical Reports Server (NTRS)

    Fedor, Steve

    2008-01-01

    A family of fluorescent dye molecules has been developed for use in on-off fluorescence detection of specific chemicals. By themselves, these molecules do not fluoresce. However, when exposed to certain chemical analytes in liquid or vapor forms, they do fluoresce (see figure). These compounds are amenable to fixation on or in a variety of substrates for use in fluorescence-based detection devices: they can be chemically modified to anchor them to porous or non-porous solid supports or can be incorporated into polymer films. Potential applications for these compounds include detection of chemical warfare agents, sensing of acidity or alkalinity, and fluorescent tagging of proteins in pharmaceutical research and development. These molecules could also be exploited for use as two-photon materials for photodynamic therapy in the treatment of certain cancers and other diseases. A molecule in this family consists of a fluorescent core (such as an anthracene or pyrene) attached to two end groups that, when the dye is excited by absorption of light, transfer an electron to the core, thereby quenching the fluorescence. The end groups can be engineered so that they react chemically with certain analytes. Upon reaction, electrons on the end groups are no longer available for transfer to the core and, consequently, the fluorescence from the core is no longer quenched. The chemoselectivity of these molecules can be changed by changing the end groups. For example, aniline end groups afford a capability for sensing acids or acid halides (including those contained in chemical warfare agents). Pyridine or bipyridyl end groups would enable sensing of metal ions. Other chemicals that can be selectively detected through suitable choice of end groups include glucose and proteins. Moreover, the fluorescent cores can be changed to alter light-absorption and -emission characteristics: anthracene cores fluoresce at wavelengths around 500 nm, whereas perylene cores absorb and emit at

  5. Effects of divalent metal ions on the fluorescence and glucose-quenching of yeast hexokinase isozymes

    SciTech Connect

    Feldman, I.; Fame, T.

    1982-01-01

    Titrations of the quenching of the tryptophan fluorescence of yeast isozymes P-I and P-II by Mg/sup 2 +/, Mn/sup 2 +/, Ca/sup 2 +/, Cd/sup 2 +/, and Zn/sup 2 +/ ions and by glucose in the presence of each of these ions (10 mM) were performed at pH 5.5 and 6.5 at 20/sup 0/C. At the higher pH there was a reversal of the type of glucose-binding cooperativity for P-II from negative to positive when either Mn/sup 2 +/ or Ca/sup 2 +/ was present in the buffered isozyme solution before the glucose titration, whereas Mg/sup 2 +/ caused the glucose binding to become noncooperative. Zn/sup 2 +/ and Cd/sup 2 +/ decreased the glucose quenching of P-II fluorescence drastically at pH 5.5, from a value of 15% in buffer to only 4%. Glucose bindings to the P-I isozyme exhibited positive cooperativity in the presence of either Ca/sup 2 +/, Mg/sup 2 +/, or Mn/sup 2 +/, as well as the buffer alone, at both pH's. At the lower pH, Ca/sup 2 +/ enhanced the efficiency of glucose quenching of P-I fluorescence several-fold, while Mn/sup 2 +/ increased it only about 40% and Mg/sup 2 +/ not at all. The biological implications of these diverse metal ion effects are discussed.

  6. Metal-Enhanced Fluorescence of Silver Island Associated with Silver Nanoparticle.

    PubMed

    Liaw, Jiunn-Woei; Wu, Hsin-Yu; Huang, Chu-Chuan; Kuo, Mao-Kuen

    2016-12-01

    The coupling plasmon of a hybrid nanostructure, silver island (SI) associated with silver nanoparticle (SNP), on metal-enhanced fluorescence (MEF) was studied theoretically. We used the multiple multipole method to analyze the plasmon-mediated enhancement factor on the fluorescence of a molecule immobilized on SNP and located in the gap zone between SI and SNP; herein, the SI was modeled as an oblate spheroid. Numerical results show that the enhancement factor of the hybrid nanostructure is higher than that of a SNP or a SI alone due to the coupled gap mode. This finding is in agreement with the previous experimental results. In addition, the plasmon band of the structure is broadband and tunable, which can be red-shifted and broadened by flattening or enlarging SI. Based on this property, the hybrid nanostructure can be tailored to obtain the optimal enhancement factor on a specific molecule according to its excitation spectrum. Moreover, we found that there is an induced optical force allowing SNP be attracted by SI. Consequently, the gap is reduced gradually to perform a stronger MEF effect. PMID:26779917

  7. Metal-Enhanced Fluorescence of Silver Island Associated with Silver Nanoparticle

    NASA Astrophysics Data System (ADS)

    Liaw, Jiunn-Woei; Wu, Hsin-Yu; Huang, Chu-Chuan; Kuo, Mao-Kuen

    2016-01-01

    The coupling plasmon of a hybrid nanostructure, silver island (SI) associated with silver nanoparticle (SNP), on metal-enhanced fluorescence (MEF) was studied theoretically. We used the multiple multipole method to analyze the plasmon-mediated enhancement factor on the fluorescence of a molecule immobilized on SNP and located in the gap zone between SI and SNP; herein, the SI was modeled as an oblate spheroid. Numerical results show that the enhancement factor of the hybrid nanostructure is higher than that of a SNP or a SI alone due to the coupled gap mode. This finding is in agreement with the previous experimental results. In addition, the plasmon band of the structure is broadband and tunable, which can be red-shifted and broadened by flattening or enlarging SI. Based on this property, the hybrid nanostructure can be tailored to obtain the optimal enhancement factor on a specific molecule according to its excitation spectrum. Moreover, we found that there is an induced optical force allowing SNP be attracted by SI. Consequently, the gap is reduced gradually to perform a stronger MEF effect.

  8. Fluorescent DNAzyme biosensors for metal ions based on catalytic molecular beacons.

    PubMed

    Liu, Juewen; Lu, Yi

    2006-01-01

    In this chapter, methods for designing metal ion sensors using fluorophore- and quencher-labeled DNAzymes are discussed. In contrast to the classical molecular beacon method based on binding, the methods described here utilize catalytic cleavage to release the fluorophore for detection and quantification, making it possible to take advantage of catalytic turnovers for signal amplification. Unlike classical molecular beacons that detect only nucleic acids, catalytic molecular beacons can be applied to different DNAzymes to detect a broad range of analytes. The methods described are based on the finding that almost all known trans-cleaving DNAzymes share a similar structure comprised of a catalytic DNAzyme core flanked by two substrate recognition arms. Using a typical DNAzyme called the "8-17" DNAzyme as an example, the design of highly sensitive and selective Pb2+ sensors is described in detail. The initial design employs a single fluorophore-quencher pair in close proximity, with the fluorophore on the 5'-end of the substrate and the quencher on the 3'-end of the enzyme. Although this sensor is highly sensitive and selective at 4 degrees C, high background fluorescence is observed at higher temperatures. Therefore a new design with an additional quencher attached to the 3'-end of the substrate is employed to suppress background fluorescence. The dual quencher method allows the sensor to perform at ambient temperatures with a high signal-to-noise ratio. PMID:16785634

  9. Use of x-ray fluorescence for in-situ detection of metals

    NASA Astrophysics Data System (ADS)

    Elam, W. T. E.; Whitlock, Robert R.; Gilfrich, John V.

    1995-01-01

    X-ray fluorescence (XRF) is a well-established, non-destructive method of determining elemental concentrations at ppm levels in complex samples. It can operate in atmosphere with no sample preparation, and provides accuracies of 1% or better under optimum conditions. This report addresses two sets of issues concerning the use of x-ray fluorescence as a sensor technology for the cone penetrometer, for shipboard waste disposal, or for other in-situ, real- time environmental applications. The first issue concerns the applicability of XRF to these applications, and includes investigation of detection limits and matrix effects. We have evaluated the detection limits and quantitative accuracy of a sensor mock-up for metals in soils under conditions expected in the field. In addition, several novel ways of improving the lower limits of detection to reach the drinking water regulatory limits have been explored. The second issue is the engineering involved with constructing a spectrometer within the 1.75 inch diameter of the penetrometer pipe, which is the most rigorous physical constraint. Only small improvements over current state-of-the-art are required. Additional advantages of XRF are that no radioactive sources or hazardous materials are used in the sensor design, and no reagents or any possible sources of ignition are involved.

  10. The Renaissance of Halide Perovskites and Their Evolution as Emerging Semiconductors.

    PubMed

    Stoumpos, Constantinos C; Kanatzidis, Mercouri G

    2015-10-20

    The recent re-emergence of the halide perovskites, of the type AMX3, derives from a sea-changing breakthrough in the field of photovoltaics that has led to a whole new generation of solar devices with remarkable power conversion efficiency. The success in the field of photovoltaics has led to intense, combined research efforts to better understand these materials both from the fundamental chemistry and physics points of view and for the improvement of applied functional device engineering. This groundswell of activity has breathed new life into this long-known but largely "forgotten" class of perovskites. The impressive achievements of halide perovskites in photovoltaics, as well as other optoelectronic applications, stem from an unusually favorable combination of optical and electronic properties, with the ability to be solution processed into films. This defines them as a brand new class of semiconductors that can rival or exceed the performance of the venerable classes of III-V and II-IV semiconductors, which presently dominate the industries of applied optoelectronics. Our aim in this Account is to highlight the basic pillars that define the chemistry of the halide perovskites and their unconventional electronic properties through the prism of structure-property relationships. We focus on the synthetic requirements under which a halide perovskite can exist and emphasize how the synthetic conditions can determine the structural integrity and the bulk properties of the perovskites. Then we proceed to discuss the origins of the optical and electronic phenomena, using the perovskite crystal structure as a guide. Some of the most remarkable features of the perovskites dealt with in this Account include the evolution of a unique type of defect, which gives rise to superlattices. These can enhance or diminish the fluorescence properties of the perovskites. For example, the exotic self-doping ability of the Sn-based perovskites allows them to adopt electrical

  11. RARE-EARTH METAL FISSION PRODUCTS FROM LIQUID U-Bi

    DOEpatents

    Wiswall, R.H.

    1960-05-10

    Fission product metals can be removed from solution in liquid bismuth without removal of an appreciable quantity of uranium by contacting the liquid metal solution with fused halides, as for example, the halides of sodium, potassium, and lithium and by adding to the contacted phases a quantity of a halide which is unstable relative to the halides of the fission products, a specific unstable halide being MgCl/sub 3/.

  12. 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

  13. Investigation of metal ions binding of humic substances using fluorescence emission and synchronous-scan spectroscopy.

    PubMed

    Piana, M J; Zahir, K O

    2000-01-01

    The binding site interactions of IHSS humic substances, Suwannee River Humic Acid, Suwannee River Fulvic Acid, Nordic Fulvic Acid, and Aldrich Humic Acid with various metals ions and a herbicide, methyl viologen were investigated using fluorescence emission and synchronous-scan spectroscopy. The metal ions used were, Fe(III), Cr(III), Cr(VI), Pb(II), Cu(II) and Ni(II). Stern-Volmer constants, Ksv for these quenchers were determined at pH 4 and 8 using an ionic strength of 0.1 M. For all four humic substances, and at both pH studied, Fe(III) was found to be the most efficient quencher. Quenching efficiency was found to be 3-10 times higher at pH 8. The bimolecular quenching rate constants were found to exceed the maximum considered for diffusion controlled interactions, and indicate that the fluorophore and quencher are in close physical association. Synchronous-scan spectra were found to change with pH and provided useful information on binding site interactions between humic substances and these quenchers. PMID:10693057

  14. Preparation of cerium halide solvate complexes

    DOEpatents

    Vasudevan, Kalyan V; Smith, Nickolaus A; Gordon, John C; McKigney, Edward A; Muenchaussen, Ross E

    2013-08-06

    Crystals of a solvated cerium(III) halide solvate complex resulted from a process of forming a paste of a cerium(III) halide in an ionic liquid, adding a solvent to the paste, removing any undissolved solid, and then cooling the liquid phase. Diffusing a solvent vapor into the liquid phase also resulted in crystals of a solvated cerium(III) halide complex.

  15. Fluorescent metal-organic polymers of zinc and cadmium from hydrothermal in situ acylation reaction.

    PubMed

    Yu, Xiao-Yang; Ye, Ling; Zhang, Xiao; Cui, Xiao-Bing; Zhang, Jian-Po; Xu, Ji-Qing; Hou, Qin; Wang, Tie-Gang

    2010-11-28

    A series of metal-organic complexes based on d(10) metals and the ligand H(4)bbh (H(4)bbh = benzene-1, 2, 4, 5-biformhydrazide), formed through hydrothermal in situ acylate reaction of H(4)bta (H(4)bta = benzene-1, 2, 4, 5-tetracarboxylic acid) with hydrazine hydrate (N(2)H(4)·H(2)O), have been prepared and structurally characterized by single-crystal X-ray diffraction. Compounds [Zn(μ(2)-H(2)bbh)(phen)(H(2)O)](2) (1) (phen = 1, 10-phenanthroline) and [Zn(μ(2)-H(2)bbh)(2, 2'-bpy)](2) (2) (2, 2'-bpy = 2, 2'-bipyridine) are both dinuclear complexes in which bridging ligands H(2)bbh(2-) display different μ(2)- coordination modes. [Zn(μ(2)-H(2)bbh)(1/2)(μ(2)-H(2)bbh)(1/2)(H(2)O)](n) (3) exhibits a two-dimensional (2-D) layer structure containing simultaneously two kinds of different coordination modes of H(2)bbh(2-): μ(2)-bidentate and μ(4)-tetradentate. [Cd(μ(3)-H(2)bbh)(phen)](n) (4) consists of one-dimensional (1-D) double-metal chains. The crystal structures of these compounds are stabilized by hydrogen bonds and π···π interactions, forming three-dimensional supramolecular networks. All of the compounds were characterized by IR, UV-vis spectra and elemental analysis and they show good fluorescence properties in the solid state at room temperature. In order to understand the emission mechanism, we carried out TDDFT calculations on the excited electronic states of compound 2. PMID:20886135

  16. Oxidation of hydrogen halides to elemental halogens with catalytic molten salt mixtures

    DOEpatents

    Rohrmann, Charles A.

    1978-01-01

    A process for oxidizing hydrogen halides by means of a catalytically active molten salt is disclosed. The subject hydrogen halide is contacted with a molten salt containing an oxygen compound of vanadium and alkali metal sulfates and pyrosulfates to produce an effluent gas stream rich in the elemental halogen. The reduced vanadium which remains after this contacting is regenerated to the active higher valence state by contacting the spent molten salt with a stream of oxygen-bearing gas.

  17. Real-time thermal imaging of microwave accelerated metal-enhanced fluorescence (MAMEF) based assays on sapphire plates.

    PubMed

    Previte, Michael J R; Zhang, Yongxia; Aslan, Kadir; Geddes, Chris D

    2007-11-01

    In this paper, we describe an optical geometry that facilitates our further characterization of the temperature changes above silver island films (SiFs) on sapphire plates, when exposed to microwave radiation. Since sapphire transmits IR, we designed an optical scheme to capture real-time temperature images of a thin water film on sapphire plates with and without SiFs during the application of a short microwave pulse. Using this optical scheme, we can accurately determine the temperature profile of solvents in proximity to metal structures when exposed to microwave irradiation. We believe that this optical scheme will provide us with a basis for further studies in designing metal structures to further improve plasmonic-fluorescence clinical sensing applications, such as those used in microwave accelerated metal-enhanced fluorescence (MAMEF). PMID:17902038

  18. Asymmetric Distribution of Metals in the Xenopus Laevis Oocyte: a Synchrotron X-Ray Fluorescence Microprobe Study

    SciTech Connect

    Popescu, B.F.Gh.; Belak, Z.R.; Ignatyev, K.; Ovsenek, N.; Nichol, H.

    2009-06-04

    The asymmetric distribution of many components of the Xenopus oocyte, including RNA, proteins, and pigment, provides a framework for cellular specialization during development. During maturation, Xenopus oocytes also acquire metals needed for development, but apart from zinc, little is known about their distribution. Synchrotron X-ray fluorescence microprobe was used to map iron, copper, and zinc and the metalloid selenium in a whole oocyte. Iron, zinc, and copper were asymmetrically distributed in the cytoplasm, while selenium and copper were more abundant in the nucleus. A zone of high copper and zinc was seen in the animal pole cytoplasm. Iron was also concentrated in the animal pole but did not colocalize with zinc, copper, or pigment accumulations. This asymmetry of metal deposition may be important for normal development. Synchrotron X-ray fluorescence microprobe will be a useful tool to examine how metals accumulate and redistribute during fertilization and embryonic development.

  19. Asymmetri Distribution of Metals in the Xenopus Laevis Oocyte: a Synchrotron X-Ray Fluorescence Microprobe Study

    SciTech Connect

    Popescu, B.F.G.; Belak, Z.R.; Ignatyev, K.; Ovsenek, N.; Nichol, H.; /Saskatchewan U. /SLAC, SSRL

    2009-04-29

    The asymmetric distribution of many components of the Xenopus oocyte, including RNA, proteins, and pigment, provides a framework for cellular specialization during development. During maturation, Xenopus oocytes also acquire metals needed for development, but apart from zinc, little is known about their distribution. Synchrotron X-ray fluorescence microprobe was used to map iron, copper, and zinc and the metalloid selenium in a whole oocyte. Iron, zinc, and copper were asymmetrically distributed in the cytoplasm, while selenium and copper were more abundant in the nucleus. A zone of high copper and zinc was seen in the animal pole cytoplasm. Iron was also concentrated in the animal pole but did not colocalize with zinc, copper, or pigment accumulations. This asymmetry of metal deposition may be important for normal development. Synchrotron X-ray fluorescence microprobe will be a useful tool to examine how metals accumulate and redistribute during fertilization and embryonic development.

  20. Performance of a cyanobacteria whole cell-based fluorescence biosensor for heavy metal and pesticide detection.

    PubMed

    Shing, Wong Ling; Heng, Lee Yook; Surif, Salmijah

    2013-01-01

    Whole cell biosensors always face the challenge of low stability of biological components and short storage life. This paper reports the effects of poly(2-hydroxyethyl methacrylate) (pHEMA) immobilization on a whole cell fluorescence biosensor for the detection of heavy metals (Cu, Pb, Cd), and pesticides (dichlorophenoxyacetic acid (2,4-D), and chlorpyrifos). The biosensor was produced by entrapping the cyanobacterium Anabaena torulosa on a cellulose membrane, followed by applying a layer of pHEMA, and attaching it to a well. The well was then fixed to an optical probe which was connected to a fluorescence spectrophotometer and an electronic reader. The optimization of the biosensor using several factors such as amount of HEMA and drying temperature were undertaken. The detection limits of biosensor without pHEMA for Cu, Cd, Pb, 2,4-D and chlorpyrifos were 1.195, 0.027, 0.0100, 0.025 and 0.025 µg/L respectively. The presence of pHEMA increased the limits of detection to 1.410, 0.250, 0.500, 0.235 and 0.117 µg/L respectively. pHEMA is known to enhance the reproducibility of the biosensor with average relative standard deviation (RSD) of ±1.76% for all the pollutants tested, 48% better than the biosensor without pHEMA (RSD = ±3.73%). In storability test with Cu 5 µg/L, the biosensor with pHEMA performed 11.5% better than the test without pHEMA on day-10 and 5.2% better on day-25. pHEMA is therefore a good candidate to be used in whole cell biosensors as it increases reproducibility and enhances biosensor storability. PMID:23673679

  1. Performance of a Cyanobacteria Whole Cell-Based Fluorescence Biosensor for Heavy Metal and Pesticide Detection

    PubMed Central

    Shing, Wong Ling; Heng, Lee Yook; Surif, Salmijah

    2013-01-01

    Whole cell biosensors always face the challenge of low stability of biological components and short storage life. This paper reports the effects of poly(2-hydroxyethyl methacrylate) (pHEMA) immobilization on a whole cell fluorescence biosensor for the detection of heavy metals (Cu, Pb, Cd), and pesticides (dichlorophenoxyacetic acid (2,4-D), and chlorpyrifos). The biosensor was produced by entrapping the cyanobacterium Anabaena torulosa on a cellulose membrane, followed by applying a layer of pHEMA, and attaching it to a well. The well was then fixed to an optical probe which was connected to a fluorescence spectrophotometer and an electronic reader. The optimization of the biosensor using several factors such as amount of HEMA and drying temperature were undertaken. The detection limits of biosensor without pHEMA for Cu, Cd, Pb, 2,4-D and chlorpyrifos were 1.195, 0.027, 0.0100, 0.025 and 0.025 μg/L respectively. The presence of pHEMA increased the limits of detection to 1.410, 0.250, 0.500, 0.235 and 0.117 μg/L respectively. pHEMA is known to enhance the reproducibility of the biosensor with average relative standard deviation (RSD) of ±1.76% for all the pollutants tested, 48% better than the biosensor without pHEMA (RSD = ±3.73%). In storability test with Cu 5 μg/L, the biosensor with pHEMA performed 11.5% better than the test without pHEMA on day-10 and 5.2% better on day-25. pHEMA is therefore a good candidate to be used in whole cell biosensors as it increases reproducibility and enhances biosensor storability. PMID:23673679

  2. Determination of oxytetracycline in salmon by liquid chromatography with metal-chelate fluorescence detection.

    PubMed

    Rupp, Heidi S; Anderson, Collin R

    2005-01-01

    A liquid chromatography (LC) method is described for the determination of oxytetracycline (OTC) in farmed Atlantic salmon muscle tissue. The method involves homogenization of salmon tissue, extraction of OTC into Mcllvaine-EDTA buffer, acid precipitation of proteins, cleanup through tandem solid-phase extraction cartridges (Strata-X and aminopropyl), elution with mobile phase containing slightly alkaline buffer and Mg2+, and LC separation with metal-chelate induced fluorescence detection. Salmon tissue was fortified with 0.10, 0.25, 0.50, 0.75, and 1.0 microg/g (ppm) oxytetracycline. Average absolute recoveries were 84, 76, 70, 76, and 85%, respectively, with relative standard deviation (RSD) values all less than 9%. The interassay average recovery was 78%, with a 4.2% RSD. Determination was based on a standard graph using peak areas with standard solutions equivalent to 0.0625, 0.125, 0.25, 0.50, and 1.0 ppm in tissue. A set of 5 matrix controls (unfortified salmon tissue) were also analyzed, in which no OTC was detected. The lowest standard was used as the limit of quantitation. PMID:15859078

  3. Micro x-ray fluorescence as a high throughput screening method for metal chelating compounds

    NASA Astrophysics Data System (ADS)

    Minogue, Edel M.; Havrilla, George J.; Taylor, Tammy P.; Burrell, Anthony K.; Warner, Benjamin P.

    2005-06-01

    Micro X-ray Fluorescence (MXRF) has proven to be a powerful tool in the rapid and quantitative means of screening oliogpeptides. MXRF is a non-destructive method of analysis, which can detect elemental composition of a sample by measuring its characteristic X-ray emission wavelengths or energies. An effective high throughput screening technique is described for the rapid screening of bead-based libraries by MXRF in order to identify suitable chelating agents that will bind metals found in radioactive dispersive devices. It is a sensitive technique which in conjunction with the wide range of chemistry inherent in peptide libraries (e.g. varying charge, length, hydrophobicity, aromaticity etc.), provides a rapid and quantitative means for screening chelator-ion binding. The method involves the selection of a suitable library of ligands; in this case it is a bead-based library of peptides. The library is exposed to the cation of interest and immobilized on to a microarray. The array is then analyzed by MXRF enabling rapid identification of chelating agents. This enables the screening of approximately 27,500 sequences per day. Initial experiments carried out successfully identified sequences that are selective for Co under certain binding conditions. This involved the screening of 8,400 sequences in adverse environmental conditions containing possible interferences (e.g. Ca, Fe, Al, Cs, Ir), which could be encountered in our application.

  4. Sensitive detection of Ochratoxin A in food and drinks using metal-enhanced fluorescence.

    PubMed

    Todescato, Francesco; Antognoli, Agnese; Meneghello, Anna; Cretaio, Erica; Signorini, Raffaella; Bozio, Renato

    2014-07-15

    Easy, sensitive, rapid and low cost ochratoxin biosensors are strongly demanded in food analysis since Ochratoxin A (OTA) is a widely diffused food contaminant, highly detrimental for human health. In this work, a novel plasmonic based optical biosensor prototype for ochratoxin A is described. It exploits the metal-enhanced fluorescence phenomenon due to the silver film over nanosphere plasmonic substrate. Since ochratoxin A could be present in different food commodities, sensor performances have been tested on three different matrices (dried milk, juices, and wheat mix). Firstly, a common OTA extraction solvent and a labeling and detection protocol were defined for the analyzed matrices. Then, the efficiency of the Ag-FON surfaces in signal amplification for the detection of low ochratoxin A concentrations was defined. Using samples spiked with OTA-AF 647 or with unlabeled OTA we were able to detect the mycotoxin at concentrations lower than E.U. specifications of 0.5 μg/kg in wheat, milk and apple juice. The test performances are comparable to those of ELISA kits but the platform presented here, once optimized, present some perspective advantages, such as: low cost and time consuming, versatility of the protocol for the investigation of different matrices, employment also in non-qualified laboratories, small dimensions that allow its integration in a compact device for OTA on-site detection. PMID:24583316

  5. 3D Imaging of Transition Metals in the Zebrafish Embryo by X-ray Fluorescence Microtomography

    PubMed Central

    Bourassa, Daisy; Gleber, Sophie-Charlotte; Vogt, Stefan; Yi, Hong; Will, Fabian; Richter, Heiko; Shin, Chong Hyun; Fahrni, Christoph J.

    2014-01-01

    Synchrotron X-ray fluorescence (SXRF) microtomography has emerged as a powerful technique for the 3D visualization of the elemental distribution in biological samples. The mechanical stability, both of the instrument and the specimen, is paramount when acquiring tomographic projection series. By combining the progressive lowering of temperature method (PLT) with femtosecond laser sectioning, we were able to embed, excise, and preserve a zebrafish embryo at 24 hours post fertilization in an X-ray compatible, transparent resin for tomographic elemental imaging. Based on a data set comprised of 60 projections, acquired with a step size of 2 μm during 100 hours of beam time, we reconstructed the 3D distribution of zinc, iron, and copper using the iterative maximum likelihood expectation maximization (MLEM) reconstruction algorithm. The volumetric elemental maps, which entail over 124 million individual voxels for each transition metal, revealed distinct elemental distributions that could be correlated with characteristic anatomical features at this stage of embryonic development. PMID:24992831

  6. A Water-Stable Metal-Organic Framework with a Double-Helical Structure for Fluorescent Sensing.

    PubMed

    Liu, Xiao-Jing; Zhang, Ying-Hui; Chang, Ze; Li, Ai-Lin; Tian, Dan; Yao, Zhao-Quan; Jia, Yan-Yuan; Bu, Xian-He

    2016-08-01

    Water instability is a crucial limiting factor in the practical application of most fluorescent metal-organic frameworks (MOFs). Here, by introducing a fascinating double-helical structure generated through dense stacking of organic ligands, a water-stable fluorescence MOF has been synthesized, namely, [Cd2(tib)2(bda)2]·(solvent)n (1) [tib =1,3,5-tris(1-imidazolyl) benzene; H2bda = 2,2'-biphenyl dicarboxylic acid]. This helical structure helps to enhance the stability of 1 against common organic solvents and water, even acid/base aqueous solutions with a pH value ranging from 3 to 11. Furthermore, this material can be a potential fluorescent sensor for ketones. PMID:27409244

  7. Detecting weak fluorescence turn-on in the presence of Pb2+ heavy metal ion using coaxial fiber optic sensor

    NASA Astrophysics Data System (ADS)

    Ma, Jianjun; Chiniforooshan, Yasser; Hao, Wenhui; Bock, Wojtek J.; Wang, Zhi Yuan

    2013-10-01

    This paper is devoted to examining the ability of a coaxial fiber-optic sensor (FOS) in detecting weak fluorescent light and weak fluorescence "turn-on" in the presence of trace heavy metal ion Pb2+. The captured fluorescent signal is detected by the Ocean Optics QE65000 spectrometer. The stock solutions include Pb2+ acetate in water (0.01 M) and a small molecule probe in water. The preliminary experiment shows that this FOS offers the Pb2+ detection limit (DL) of 1.26×10-4 mg/mL. The advantages, limitations and further improvements of this coaxial FOS are discussed in comparison with the bench-top instruments in terms of the abilities of signal light capture and stray excitation light suppression.

  8. Rapid, sensitive, and selective fluorescent DNA detection using iron-based metal-organic framework nanorods: Synergies of the metal center and organic linker.

    PubMed

    Tian, Jingqi; Liu, Qian; Shi, Jinle; Hu, Jianming; Asiri, Abdullah M; Sun, Xuping; He, Yuquan

    2015-09-15

    Considerable recent attention has been paid to homogeneous fluorescent DNA detection with the use of nanostructures as a universal "quencher", but it still remains a great challenge to develop such nanosensor with the benefits of low cost, high speed, sensitivity, and selectivity. In this work, we report the use of iron-based metal-organic framework nanorods as a high-efficient sensing platform for fluorescent DNA detection. It only takes about 4 min to complete the whole "mix-and-detect" process with a low detection limit of 10 pM and a strong discrimination of single point mutation. Control experiments reveal the remarkable sensing behavior is a consequence of the synergies of the metal center and organic linker. This work elucidates how composition control of nanostructures can significantly impact their sensing properties, enabling new opportunities for the rational design of functional materials for analytical applications. PMID:25879891

  9. Insights from the Adsorption of Halide Ions on Graphene Materials.

    PubMed

    Zhu, Chang; Yang, Gang

    2016-08-18

    Graphene has recently found applications in a wide range of fields. Density functional calculations show that halide ions can be adsorbed on pristine graphene, but only F(-) has an appreciable binding energy (-97.0 kJ mol(-1) ). Graphene materials, which are mainly electron donors, can be made strong electron acceptors by edge functionalization with F atoms. The binding strengths of halide ions are greatly enhanced by edge functionalization and show direct proportionality with the degree of functionalization Θ and increased charge transfer. In contrast, the adsorption strengths of metal ions on pristine graphene are clearly superior to those of halide ions but decline substantially with increasing degree of edge functionalization, and for Θ=100 %, the binding energies of -95.7, -44.8, and -25.9 kJ mol(-1) that are calculated for Li(+) , Na(+) , and K(+) , respectively, are obviously inferior to that of F(-) (-186.3 kJ mol(-1) ). Thus, the electronic properties of graphene are fundamentally regulated by edge functionalization, and the preferential adsorption of certain metal ions or anions can be facilely realized by choice of an appropriate degree of functionalization. Adsorbed metal ions and anions behave differently on gradual addition of water molecules, and their binding strengths remain substantial when graphene materials are in the pristine and highly edge functionalized states, respectively. PMID:27127939

  10. Atomic structure of metal-halide perovskites from first principles: The chicken-and-egg paradox of the organic-inorganic interaction

    NASA Astrophysics Data System (ADS)

    Li, Jingrui; Rinke, Patrick

    2016-07-01

    We have studied the prototype hybrid organic-inorganic perovskite CH3NH3PbI3 and its three close relatives, CH3NH3SnI3 ,CH3NH3PbCl3 , and CsPbI3, using relativistic density function theory. The long-range van der Waals (vdW) interactions were incorporated into the Perdew-Burke-Ernzerhof (PBE) exchange-correlation functional using the Tkatchenko-Scheffler pairwise scheme. Our results reveal that hydrogen bonding, which is well described by the PBE functional, plays a decisive role for the structural parameters of these systems, including the position and orientation of the organic cation as well as the deformation of the inorganic framework. The magnitude of the inorganic-framework deformation depends sensitively on the orientation of the organic cation, and directly influences the stability of the hybrid perovskites. Our results suggest that the organic and the inorganic components complement each other; the low symmetry of the organic cation is the origin of the inorganic-framework deformation, which then aids the overall stabilization of the hybrid perovskite structure. This stabilization is indirectly affected by vdW interactions, which lead to smaller unit-cell volumes than in PBE and therefore modulate the interaction between the organic cation and the inorganic framework. The vdW-induced lattice-constant corrections are system dependent and lead to PBE+vdW lattice constants in good agreement with experiment. Further insight is gained by analyzing the vdW contributions. In all iodide-based hybrid perovskites, the interaction between the organic cation and the iodide anions provides the largest lattice-constant change, followed by iodine-iodine and the organic cation—heavy-metal cation interaction. These corrections follow an almost linear dependence on the lattice constant within the range considered in our study and are therefore approximately additive.

  11. PROCESSING OF URANIUM-METAL-CONTAINING FUEL ELEMENTS

    DOEpatents

    Moore, R.H.

    1962-10-01

    A process is given for recovering uranium from neutronbombarded uranium- aluminum alloys. The alloy is dissolved in an aluminum halide--alkali metal halide mixture in which the halide is a mixture of chloride and bromide, the aluminum halide is present in about stoichiometric quantity as to uranium and fission products and the alkali metal halide in a predominant quantity; the uranium- and electropositive fission-products-containing salt phase is separated from the electronegative-containing metal phase; more aluminum halide is added to the salt phase to obtain equimolarity as to the alkali metal halide; adding an excess of aluminum metal whereby uranium metal is formed and alloyed with the excess aluminum; and separating the uranium-aluminum alloy from the fission- productscontaining salt phase. (AEC)

  12. A library-screening approach for developing a fluorescence sensing array for the detection of metal ions.

    PubMed

    Smith, David G; Sajid, Naveed; Rehn, Simone; Chandramohan, Ramya; Carney, Isaac J; Khan, Misbahul A; New, Elizabeth J

    2016-08-01

    Detection of individual metal ions is of importance across a range of fields of chemistry including environmental monitoring, and health and disease. Fluorescence is a highly sensitive technique and small fluorescent molecules are widely used for the detection and quantification of metal ions in various applications. Achieving specificity for a single metal from a single sensor is always a challenge. An alternative to selective sensing is the use of a number of non-specific sensors, in an array, which together respond in a unique pattern to each analyte. Here we show that screening a library of compounds can give a small sensor set that can be used to identify a range of metal ions following PCA and LDA. We explore a method for screening the initial compounds to identify the best performing sensors. We then present our method for reducing the size of the sensor array, resulting in a four-membered system, which is capable of identifying nine distinct metal ion species in lake water. PMID:27291513

  13. Determination of heavy metals in macrozoobenthos from the rivers Tisza and Szamos by total reflection X-ray fluorescence spectrometry

    NASA Astrophysics Data System (ADS)

    Woelfl, S.; Mages, M.; Óvári, M.; Geller, W.

    2006-11-01

    In 2000, accidents in the Romanian mining industry in key catchment areas led to heavy metal contamination of the Hungarian rivers Tisza and Szamos resulting in substantial heavy metal loads in several sediments of the upper river basins. This enhanced metal content might have been bioaccumulated in benthic organisms during the following years. Therefore, the aim of this study was to test, whether the zoobenthic fauna showed an enhanced metal content 3 years after the industrial accident. Macrozoobenthic insect larvae (chironomids) were sampled 100 m below and above the confluent site of the rivers Tisza and Szamos during summer 2003 and for comparison purpose also in the river Maros, a tributary of the Tisza river, during 2005. In order to determine their heavy metal content, single specimens were prepared and analysed by Total Reflection X-ray Fluorescence Spectrometry (TRXF) according to the modified dry method. Fe was much lower and Mn and Zn much higher concentrated in benthos from the more contaminated Szamos river compared to the Tisza and Maros rivers. In this sense, the benthic organisms reflected very well the enhanced metal concentrations in the contaminated rivers being suitable as bioindicators of metal contamination. However, the sediment bioaccumulation factor was low at all sampling sites indicating a low bioavailability of trace metals for benthic organisms.

  14. Selective extraction and recovery of rare earth metals from phosphor powders in waste fluorescent lamps using an ionic liquid system.

    PubMed

    Yang, Fan; Kubota, Fukiko; Baba, Yuzo; Kamiya, Noriho; Goto, Masahiro

    2013-06-15

    The recycling of rare earth metals from phosphor powders in waste fluorescent lamps by solvent extraction using ionic liquids was studied. Acid leaching of rare earth metals from the waste phosphor powder was examined first. Yttrium (Y) and europium (Eu) dissolved readily in the acid solution; however, the leaching of other rare earth metals required substantial energy input. Ionization of target rare earth metals from the waste phosphor powders into the leach solution was critical for their successful recovery. As a high temperature was required for the complete leaching of all rare earth metals, ionic liquids, for which vapor pressure is negligible, were used as an alternative extracting phase to the conventional organic diluent. An extractant, N, N-dioctyldiglycol amic acid (DODGAA), which was recently developed, showed a high affinity for rare earth metal ions in liquid-liquid extraction although a conventional commercial phosphonic extractant did not. An effective recovery of the rare earth metals, Y, Eu, La and Ce, from the metal impurities, Fe, Al and Zn, was achieved from the acidic leach solution of phosphor powders using an ionic liquid containing DODGAA as novel extractant system. PMID:23587931

  15. METHOD OF ALLOYING REACTIVE METALS WITH ALUMINUM OR BERYLLIUM

    DOEpatents

    Runnalls, O.J.C.

    1957-10-15

    A halide of one or more of the reactive metals, neptunium, cerium and americium, is mixed with aluminum or beryllium. The mass is heated at 700 to 1200 deg C, while maintaining a substantial vacuum of above 10/sup -3/ mm of mercury or better, until the halide of the reactive metal is reduced and the metal itself alloys with the reducing metal. The reaction proceeds efficiently due to the volatilization of the halides of the reducing metal, aluminum or beryllium.

  16. Development of Halide and Oxy-Halides for Isotopic Separations

    SciTech Connect

    Leigh R. Martin; Aaron T. Johnson; Jana Pfeiffer; Martha R. Finck

    2014-10-01

    The goal of this project was to synthesize a volatile form of Np for introduction into mass spectrometers at INL. Volatile solids of the 5f elements are typically those of the halides (e.g. UF6), however fluorine is highly corrosive to the sensitive internal components of the mass separator, and the other volatile halides exist as several different stable isotopes in nature. However, iodide is both mono-isotopic and volatile, and as such presents an avenue for creation of a form of Np suitable for introduction into the mass separator. To accomplish this goal, the technical work in the project sought to establish a novel synthetic route for the conversion NpO2+ (dissolved in nitric acid) to NpI3 and NpI4.

  17. An Optical Biosensor from Green Fluorescent Escherichia coli for the Evaluation of Single and Combined Heavy Metal Toxicities

    PubMed Central

    Futra, Dedi; Heng, Lee Yook; Ahmad, Asmat; Surif, Salmijah; Ling, Tan Ling

    2015-01-01

    A fluorescence-based fiber optic toxicity biosensor based on genetically modified Escherichia coli (E. coli) with green fluorescent protein (GFP) was developed for the evaluation of the toxicity of several hazardous heavy metal ions. The toxic metals include Cu(II), Cd(II), Pb(II), Zn(II), Cr(VI), Co(II), Ni(II), Ag(I) and Fe(III). The optimum fluorescence excitation and emission wavelengths of the optical biosensor were 400 ± 2 nm and 485 ± 2 nm, respectively. Based on the toxicity observed under optimal conditions, the detection limits of Cu(II), Cd(II), Pb(II), Zn(II), Cr(VI), Co(II), Ni(II), Ag(I) and Fe(III) that can be detected using the toxicity biosensor were at 0.04, 0.32, 0.46, 2.80, 100, 250, 400, 720 and 2600 μg/L, respectively. The repeatability and reproducibility of the proposed biosensor were 3.5%–4.8% RSD (relative standard deviation) and 3.6%–5.1% RSD (n = 8), respectively. The biosensor response was stable for at least five weeks, and demonstrated higher sensitivity towards metal toxicity evaluation when compared to a conventional Microtox assay. PMID:26029952

  18. Synthesis, characterization, DNA binding properties, fluorescence studies and antioxidant activity of transition metal complexes with hesperetin-2-hydroxy benzoyl hydrazone.

    PubMed

    Li, Yong; Yang, Zheng-Yin; Wang, Ming-Fang

    2010-07-01

    A novel Schiff-base ligand (H(5)L), hesperetin-2-hydroxy benzoyl hydrazone, and its copper (II), zinc (II) and nickel (II) complexes (M.H(3)L) [M(II) = Cu, Zn, Ni], have been synthesized and characterized. The ligand and Zn (II) complex exhibit green and blue fluorescence under UV light and the fluorescent properties of the ligand and Zn (II) complex in solid state and different solutions were investigated. In addition, DNA binding properties of the ligand and its metal complexes have been investigated by electronic absorption spectroscopy, fluorescence spectra, ethidium bromide displacement experiments, iodide quenching experiments, salt effect and viscosity measurements. Results suggest that all the compounds bind to DNA via an intercalation binding mode. Furthermore, the antioxidant activity of the ligand and its metal complexes was determined by superoxide and hydroxyl radical scavenging methods in vitro. The metal complexes were found to possess potent antioxidant activity and be better than the free ligand alone and some standard antioxidants like vitamin C and mannitol. PMID:20352308

  19. α-Regioselective Barbier Reaction of Carbonyl Compounds and Allyl Halides Mediated by Praseodymium.

    PubMed

    Wu, San; Li, Ying; Zhang, Songlin

    2016-09-01

    The first utility of praseodymium as a mediating metal in the Barbier reaction of carbonyl compounds with allyl halides was reported in this paper. In contrast to the traditional metal-mediated or catalyzed Barbier reactions, exclusive α-adducts were obtained in this one-pot reaction with a broad scope of substrates and feasible reaction conditions. PMID:27490708

  20. DEPOSITION OF METAL ON NONMETAL FILAMENT

    DOEpatents

    Magel, T.T.

    1959-02-10

    A method is described for purifying metallic uranium by passing a halogen vapor continuously over the impure uranium to form uranium halide vapor and immediately passing the halide vapor into contact with a nonmetallic refractory surface which is at a temperature above the melting point of uranium metal. The halide is decomposed at the heated surface depositing molten metal, which collects and falls into a receiver below.

  1. Laser ablation laser induced fluorescence for sensitive detection of heavy metals in water

    NASA Astrophysics Data System (ADS)

    Godwal, Yogesh

    Laser Induced Breakdown Spectroscopy LIBS is a fast non-contact technique for the analysis of the elemental composition using spectral information of the emission from a laser-induced plasma. For the LIBS studies in this thesis the focus has been in using very low energy, microjoule pulses in order to give high spatial resolution and minimize the laser system requirements. This is a regime that we refer to as microLIBS. Under such conditions it is important to maximize the signal detected to give the lowest limit of detection LOD possible. One technique to improve the signal to noise ratios is by coupling LIBS with Laser Induced Fluorescence. This is a technique where the first pulse creates a vapor plume and the second pulse tuned to a resonant absorption line of the species of interest re-excites the plume. We term this technique as Laser ablation Laser Induced Fluorescence LA-LIF. We have been investigating the performance of LA-LIF at low pulse energies (≤ 1 mJ for both pulses) for the detection of elemental contaminants in water. This technique allows reasonable performance compared to high energy single-pulse LIBS, but at a much reduced total energy expenditure. This allows LODs in the parts per billion range ppb range which typically cannot be obtained with low energy single pulse probing of the systems. This approach or exceeds the sensitivities which can be obtained with many shots using much larger energy systems. In this thesis we investigated the performance of LIBS at low pulse energies for the detection of Pb as a contaminant in water. An LOD of 70 ppb was obtained for an accumulation of 100 shots with the ablation laser pulse energy of 250 muJ and an excitation laser pulse energy of 8 muJ. A systematic study of the detector conditions was made for the system for the detection of Pb. Scaling laws for the LOD in terms of the pump and probe energies were measured and also the effect of detector gain, the gate delay and the gate width were studied. In

  2. Heavy metal stress detection and monitoring via LED-induced chlorophyll fluorescence analysis of Zea mays L. seedlings aimed at polluted soil phytoremediation

    NASA Astrophysics Data System (ADS)

    Gouveia-Neto, Artur S.; Silva, Elias A., Jr.; da Silva, Airon José; do Nascimento, Clístenes W. A.

    2012-03-01

    Chlorophyll fluorescence spectroscopy is employed to detect and study the time evolution of metal stress of Zea mays L. seedlings aiming polluted soil phytoremediation. The chlorophyll fluorescence spectra of intact leaves are analyzed using 405 nm LED excitation. Red (Fr) and far-red (FFr) emissions around 685 nm and 735 nm, respectively, are examined as a function of the heavy metal concentration. The fluorescence ratio Fr/FFr was employed to monitor the effect of heavy metal upon the physiological state of the plants before signs of visual stress became apparent. The chlorophyll fluorescence analysis permitted detection and evaluation of the damage caused by heavy metal soil contamination in the early stages of the plants growing process, which is not feasible using conventional in vitro spectral analysis.

  3. [Energy dispersive x-ray fluorescence spectrometry--a forensic chemistry method for detection of bullet metal residue in gunshot wounds].

    PubMed

    Havel, J; Zelenka, K

    2003-04-01

    The article describes using of energo-dispersive X-ray fluorescence spectrometry (EDXRF) as the forensic method as the tool for detection of metals (gunshot residues--GSR) in connection with gunshot-wounds of persons. PMID:12874887

  4. Depth profile of halide anions under highly charged biological membrane

    NASA Astrophysics Data System (ADS)

    Sung, Woongmo; Wang, Wenjie; Lee, Jonggwan; Vaknin, David; Kim, Doseok

    2015-03-01

    Halide ion (Cl- and I-) distribution under a cationic Langmuir monolayer consisting of 1,2-dipalmitoyl-3 trimethylammonium-propane (DPTAP) molecules was investigated by vibrational sum-frequency generation (VSFG) and X-ray spectroscopy. From VSFG spectra, it was observed that large halide anions (I-) screen surface charge more efficiently so that interfacial water alignment becomes more randomized. On the other hand, number density of ions directly measured by X-ray fluorescence spectroscopy at grazing incidence angle reveals that the ion densities within 6 ~ 8 nm are the same for both I- and Cl-. Since the observed ion densities in both cases are almost equal to the charge density of the DPTAP monolayer, we propose that larger halide anions are attracted closer to the surface making direct binding with the charged headgroups of the molecules in the monolayer, accomplishing charge neutrality in short distance. This direct adsorption of anions also disturbs the monolayer structure both in terms of the conformation of alkyl chains and the vertical configuration of the monolayer, with iodine having the stronger effect. Our study shows that the length scale that ions neutralize a charged interface varies significantly and specifically even between monovalent ions.

  5. 40 CFR 721.4095 - Quaternary ammonium alkyltherpropyl trialkylamine halides.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... trialkylamine halides. 721.4095 Section 721.4095 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.4095 Quaternary ammonium alkyltherpropyl trialkylamine halides. (a... generically as quaternary ammonium alkyltherpropyl trialkylamine halides (PMNs...

  6. Gaseous NH3 Confers Porous Pt Nanodendrites Assisted by Halides.

    PubMed

    Lu, Shuanglong; Eid, Kamel; Li, Weifeng; Cao, Xueqin; Pan, Yue; Guo, Jun; Wang, Liang; Wang, Hongjing; Gu, Hongwei

    2016-01-01

    Tailoring the morphology of Pt nanocrystals (NCs) is of great concern for their enhancement in catalytic activity and durability. In this article, a novel synthetic strategy is developed to selectively prepare porous dendritic Pt NCs with different structures for oxygen reduction reaction (ORR) assisted by NH3 gas and halides (F(-), Cl(-), Br(-)). The NH3 gas plays critical roles on tuning the morphology. Previously, H2 and CO gas are reported to assist the shape control of metallic nanocrystals. This is the first demonstration that NH3 gas assists the Pt anisotropic growth. The halides also play important role in the synthetic strategy to regulate the formation of Pt NCs. As-made porous dendritic Pt NCs, especially when NH4F is used as a regulating reagent, show superior catalytic activity for ORR compared with commercial Pt/C catalyst and other previously reported Pt-based NCs. PMID:27184228

  7. Gaseous NH3 Confers Porous Pt Nanodendrites Assisted by Halides

    PubMed Central

    Lu, Shuanglong; Eid, Kamel; Li, Weifeng; Cao, Xueqin; Pan, Yue; Guo, Jun; Wang, Liang; Wang, Hongjing; Gu, Hongwei

    2016-01-01

    Tailoring the morphology of Pt nanocrystals (NCs) is of great concern for their enhancement in catalytic activity and durability. In this article, a novel synthetic strategy is developed to selectively prepare porous dendritic Pt NCs with different structures for oxygen reduction reaction (ORR) assisted by NH3 gas and halides (F−, Cl−, Br−). The NH3 gas plays critical roles on tuning the morphology. Previously, H2 and CO gas are reported to assist the shape control of metallic nanocrystals. This is the first demonstration that NH3 gas assists the Pt anisotropic growth. The halides also play important role in the synthetic strategy to regulate the formation of Pt NCs. As-made porous dendritic Pt NCs, especially when NH4F is used as a regulating reagent, show superior catalytic activity for ORR compared with commercial Pt/C catalyst and other previously reported Pt-based NCs. PMID:27184228

  8. Gaseous NH3 Confers Porous Pt Nanodendrites Assisted by Halides

    NASA Astrophysics Data System (ADS)

    Lu, Shuanglong; Eid, Kamel; Li, Weifeng; Cao, Xueqin; Pan, Yue; Guo, Jun; Wang, Liang; Wang, Hongjing; Gu, Hongwei

    2016-05-01

    Tailoring the morphology of Pt nanocrystals (NCs) is of great concern for their enhancement in catalytic activity and durability. In this article, a novel synthetic strategy is developed to selectively prepare porous dendritic Pt NCs with different structures for oxygen reduction reaction (ORR) assisted by NH3 gas and halides (F‑, Cl‑, Br‑). The NH3 gas plays critical roles on tuning the morphology. Previously, H2 and CO gas are reported to assist the shape control of metallic nanocrystals. This is the first demonstration that NH3 gas assists the Pt anisotropic growth. The halides also play important role in the synthetic strategy to regulate the formation of Pt NCs. As-made porous dendritic Pt NCs, especially when NH4F is used as a regulating reagent, show superior catalytic activity for ORR compared with commercial Pt/C catalyst and other previously reported Pt-based NCs.

  9. Optical properties of lanthanide-containing halide-modified zinc tellurite glasses

    SciTech Connect

    Sidebottom, D.L.; Hruschka, M.A.; Potter, B.G.; Brow, R.K.; Hudgens, J.J.

    1996-12-31

    As part of an ongoing investigation to characterize the properties and structure of Zn halide-Te oxide glasses, we report preliminary measurements of the optical properties of several Nd- and Er-doped tellurites. Measurements include fluorescence lifetimes and estimates of the theoretical radiative lifetimes (from traditional Judd-Ofelt analysis of optical absorption spectra) as well as phonon sideband studies sensitive to vibrational characteristics near the rare earth ion. Response of these optical features to the substitution of alternative halides is examined.

  10. Synthesis and characterization of fluorescence-labelled silica core-shell and noble metal-decorated ceria nanoparticles

    PubMed Central

    Rennhak, Markus; Reller, Armin

    2014-01-01

    Summary The present review article covers work done in the cluster NPBIOMEM in the DFG priority programme SPP 1313 and focuses on synthesis and characterization of fluorescent silica and ceria nanoparticles. Synthetic methods for labelling of silica and polyorganosiloxane/silica core–shell nanoparticles with perylenediimide derivatives are described, as well as the modification of the shell with thiol groups. Photometric methods for the determination of the number of thiol groups and an estimate for the number of fluorescent molecules per nanoparticles, including a scattering correction, have been developed. Ceria nanoparticles decorated with noble metals (Pt, Pd, Rh) are models for the decomposition products of automobile catalytic converters which appear in the exhaust gases and finally interact with biological systems including humans. The control of the degree of agglomeration of small ceria nanoparticles is the basis for their synthesis. Almost monodisperse agglomerates (40 ± 4–260 ± 40 nm diameter) can be prepared and decorated with noble metal nanoparticles (2–5 nm diameter). Fluorescence labelling with ATTO 647N gave the model particles which are now under biophysical investigation. PMID:25671137

  11. Tunable Two-color Luminescence and Host-guest Energy Transfer of Fluorescent Chromophores Encapsulated in Metal-Organic Frameworks

    NASA Astrophysics Data System (ADS)

    Yan, Dongpeng; Tang, Yanqun; Lin, Heyang; Wang, Dan

    2014-03-01

    Co-assembly of chromophore guests with host matrices can afford materials which have photofunctionalities different from those of individual components. Compared with clay and zeolite materials, the use of metal-organic frameworks (MOFs) as a host structure for fabricating luminescent host-guest materials is still at an early stage. Herein, we report the incorporation of a laser dye, 4-(dicyanomethylene)-2-methyl-6-(4-dimethylaminostyryl)-4H-pyran (DCM), into stilbene-based and naphthalene-based MOF systems. The resulting materials exhibit blue/red two-color emission, and the intensity ratio of blue to red fluorescence varies in different planes within the MOF crystal as detected by 3D confocal fluorescence microscopy. The observed changes in ratiometric fluorescence suggest the occurrence of energy transfer from MOF host to DCM molecules, which can be further confirmed by periodic density functional theoretical (DFT) calculations. Moreover, selective changes in luminescence behavior are observed on treating the guest@MOF samples with volatile organic compounds (methanol, acetone and toluene), indicating that these host-guest systems have potential applications as fluorescence sensors. It can be expected that by rational selection of MOF hosts and guest chromophores with suitable emissive colors and energy levels, a wide variety of multi-color luminescent and energy-transfer systems can readily be prepared in a similar manner.

  12. Analysis of trace metals in thin silicon nitride films by total-reflection X-ray fluorescence

    NASA Astrophysics Data System (ADS)

    Vereecke, G.; Arnauts, S.; Van Doorne, P.; Kenis, K.; Onsia, B.; Verstraeten, K.; Schaekers, M.; Van Hoeymissen, J. A. B.; Heyns, M. M.

    2001-11-01

    The validity of a matrix withdrawal method for the analysis of trace metals in silicon nitride films on silicon wafers by total-reflection X-ray fluorescence has been evaluated with samples contaminated with diluted standard solutions of eight metals (Ca, V, Cr, Fe, Ni, Cu, Ta, W). The nitride matrix was removed by a decomposition step with HF vapor at ambient conditions followed by the vaporization of the product at a temperature higher than 240°C. The recovery of added metals was determined first directly after vaporization and secondly after preconcentration by the droplet collection (DC) method. The recovery of metals after vaporization at a temperature of 300±50°C was generally close to 100%, except for Cu whose recovery was approximately 40%. The efficiency of the DC step was approximately 50% for most metals but only 10-20% for Cu and Cr. Thus for most metals the total recovery was close to 50%, which is acceptable for analytical purpose. The recovery of Cu and Cr was studied in more detail considering the influence of the thickness of the nitride film, the vaporization temperature, and the composition of the DC solution. The total recovery of Cu increased from approximately 10 to 40% by lowering the temperature of the vaporization step and using a more concentrated DC solution. The recovery of Cr by DC was markedly influenced by the thickness of the nitride film with no great benefit of using a more concentrated DC solution.

  13. Efficient stray-light suppression for resonance fluorescence in quantum dot micropillars using self-aligned metal apertures

    NASA Astrophysics Data System (ADS)

    Hopfmann, Caspar; Musiał, Anna; Maier, Sebastian; Emmerling, Monika; Schneider, Christian; Höfling, Sven; Kamp, Martin; Reitzenstein, Stephan

    2016-09-01

    Within this work we propose and demonstrate a technological approach to efficiently suppress excitation laser stray-light in resonance fluorescence experiments on quantum dot micropillars. To ensure efficient stray-light suppression, their fabrication process includes a planarization step and subsequent covering with a titanium mask to fabricate self-aligned apertures at the micropillar positions. These apertures aim to limit laser stray-light in the side-excitation vertical-detection configuration, while enabling detection of the optical signal through the top facet of the micropillars. The beneficial effects of these apertures are proven and quantitatively evaluated within a statistical study in which we determine and compare the stray-light suppression of 48 micropillars with and without metal apertures. Actual resonance fluorescence experiments on single quantum dots coupled to the cavity mode prove the relevance of the proposed approach and demonstrate that it will foster further studies on cavity quantum electrodynamics phenomena under coherent optical excitation.

  14. Synthesis, crystal structures, biological activities and fluorescence studies of transition metal complexes with 3-carbaldehyde chromone thiosemicarbazone.

    PubMed

    Li, Yong; Yang, Zheng-Yin; Wu, Jin-Cai

    2010-12-01

    3-carbaldehyde chromone thiosemicarbazone (L) and its transition metal complexes were synthesized and characterized systematically. Crystal structures of Zn(II) and Ni(II) complexes were determined by single crystal X-ray diffraction analysis. Zn(II) complex exhibits blue fluorescence under UV light and its fluorescent property in solid state was investigated. Interactions of ligand and Cu(II), Zn(II) and Ni(II) complexes with DNA were investigated by spectral and viscosity studies, indicating the compounds bind to DNA via intercalation and Zn(II) complex binds to DNA most strongly. Antioxidant tests in vitro show the compounds possess significant antioxidant activity against superoxide and hydroxyl radicals, and the scavenging effects of Cu(II) complex are stronger than Zn(II), Ni(II) complexes and some standard antioxidants, such as mannitol and vitamin C. PMID:20884087

  15. Combined synchrotron X-ray tomography and X-ray powder diffraction using a fluorescing metal foil

    SciTech Connect

    Kappen, P.; Arhatari, B. D.; Luu, M. B.; Balaur, E.; Caradoc-Davies, T.

    2013-06-15

    This study realizes the concept of simultaneous micro-X-ray computed tomography and X-ray powder diffraction using a synchrotron beamline. A thin zinc metal foil was placed in the primary, monochromatic synchrotron beam to generate a divergent wave to propagate through the samples of interest onto a CCD detector for tomographic imaging, thus removing the need for large beam illumination and high spatial resolution detection. Both low density materials (kapton tubing and a piece of plant) and higher density materials (Egyptian faience) were investigated, and elemental contrast was explored for the example of Cu and Ni meshes. The viability of parallel powder diffraction using the direct beam transmitted through the foil was demonstrated. The outcomes of this study enable further development of the technique towards in situ tomography/diffraction studies combining micrometer and crystallographic length scales, and towards elemental contrast imaging and reconstruction methods using well defined fluorescence outputs from combinations of known fluorescence targets (elements).

  16. Cohesive Energy-Lattice Constant and Bulk Modulus-Lattice Constant Relationships: Alkali Halides, Ag Halides, Tl Halides

    NASA Technical Reports Server (NTRS)

    Schlosser, Herbert

    1992-01-01

    In this note we present two expressions relating the cohesive energy, E(sub coh), and the zero pressure isothermal bulk modulus, B(sub 0), of the alkali halides. Ag halides and TI halides, with the nearest neighbor distances, d(sub nn). First, we show that the product E(sub coh)d(sub 0) within families of halide crystals with common crystal structure is to a good approximation constant, with maximum rms deviation of plus or minus 2%. Secondly, we demonstrate that within families of halide crystals with a common cation and common crystal structure the product B(sub 0)d(sup 3.5)(sub nn) is a good approximation constant, with maximum rms deviation of plus or minus 1.36%.

  17. [Derivative fluorescence probe recognition results of the light physical mechanism of metal ions].

    PubMed

    Dai, Yu-mei; Hu, Xiao-jun; Li, Fu-jun; Xie, Yu-meng; Zhao, Yang-yang; Zhou, Qiao

    2015-02-01

    As people deeply study the electronic spectra of fluorescent compounds and photophysical behavior, enormous progress has been made in the aspect of changes and states of different systems in the use of fluorescent molecules as probes. PTC-DA is a kind of typical fluorescent molecular probe that is highly sensitive and selective in water environment. This paper makes a research on the physical mechanism of light of PTCDA by TDF (Density Functional Theory), calculates the optimal configuration the charge population and excitation spectra of PTCDA molecules under ideal condition and acquires PTCDA fluorescence emission spectra then analyses that PTCDA is a kind of quenching and dual colorimetric signal probe response. Its optical signal response mechanism belongs to ICT (Intramolecular Charge Transfer) mechanism. According to the results, this perylene derivatives is fitted with Cu2+ excited state absorption spectra. Before and after the combination with Cu2+, the peak shape of absorption spectrum is similar. When copper is added, the overall absorption peak position occurred redshift, quenching discoloration happens. By comparing with experimental values, the calculated molecular configuration is reasonable and effective and the peak of excitation spectra is realistic. Analysis shows that: PTCDA molecules divalent copper ions have better fluorescence detection activity, the optical signal response mechanisms are intramolecular charge transfer (ICT) mechanisms. When a molecule receives divalent copper ions, the absorption spectrum peak position redshifts, intramolecular charge transfer direction and intensity changes. There occur both quenching signal and discoloration signal. It is a kind of fluorescent probe material with double quenching and discoloration fluorescent signal, which has great potential for development. This paper makes an early-stage exploration of the physical mechanism of light response mechanism analysis in molecular fluorescent probe field and

  18. Meditating metal coenhanced fluorescence and SERS around gold nanoaggregates in nanosphere as bifunctional biosensor for multiple DNA targets.

    PubMed

    Liu, Yong; Wu, Peiyi

    2013-06-26

    Gold nanoparticles (Au NPs) are very attractive candidate nanoparticles in biological assay because of their high chemical stabilities, high homogeneities, good biocompatibilities, and low toxicities. However, molecular beacon assays via encapsulating the combined fluorescence or surface-enhanced Raman scattering (SERS) signals of reporters and Au NPs in nanobarcodes particles usually suffer from fluorescence quenching or weak Raman enhancement when Au NPs are employed (especially with size smaller than 15 nm). Herein, we present a new design of simultaneously realizing metal-enhanced fluorescence and coenhanced surface-enhanced Raman scattering by facilely embedding Ag nanoparticle into the shell of two kinds of Au nanoaggregate (5 and 10 nm), meanwhile, fluorophore is located between the silver core and gold nanoparticle layers and the distance among them is adjusted by SiO2 spacer (Ag@first SiO2 spacer@FiTC+SiO2@second SiO2 spacer@Au nanoaggregate). In this architecture, Ag nanoparticle not only is utilized as an efficient fluorescence enhancer to overcome the common fluorescence quenching around Au nanoaggregates but also behaves like a mirror. Thus, incident light that passes through the SERS-active Au nanoaggregate and the intervening dielectric layer of SiO2 could be reflected multiply from the surface of Ag nanoparticle and coupled with the light at the nanogap between the Au nanoaggregates to further amplify Raman intensity. This results in enhancement factors for fluorescence and SERS ~1.6-fold and more than 300-fold higher than the control samples without silver core under identical experimental conditions, respectively. Moreover, fluorophore and SERS reporters are assembled onto different layers of the concentric hybrid microsphere, resulting in a feasible fabrication protocol when a large number of agents need to be involved into the dual-mode nanobarcodes. A proof-of-concept chip-based DNA sandwich hybridization assay using genetically modified

  19. Hygroscopicity Evaluation of Halide Scintillators

    SciTech Connect

    Zhuravleva, M; Stand, L; Wei, H; Hobbs, C. L.; Boatner, Lynn A; Ramey, Joanne Oxendine; Burger, Arnold; Rowe, E; Bhattacharya, P.; Tupitsyn, E; Melcher, Charles L

    2014-01-01

    A collaborative study of relative hygroscopicity of anhydrous halide scintillators grown at various laboratories is presented. We have developed a technique to evaluate moisture sensitivity of both raw materials and grown crystals, in which the moisture absorption rate is measured using a gravimetric analysis. Degradation of the scintillation performance was investigated by recording gamma-ray spectra and monitoring the photopeak position, count rate and energy resolution. The accompanying physical degradation of the samples exposed to ambient atmosphere was photographically recorded as well. The results were compared with ben

  20. Permeation of halide anions through phospholipid bilayers occurs by the solubility-diffusion mechanism

    NASA Technical Reports Server (NTRS)

    Paula, S.; Volkov, A. G.; Deamer, D. W.

    1998-01-01

    Two alternative mechanisms are frequently used to describe ionic permeation of lipid bilayers. In the first, ions partition into the hydrophobic phase and then diffuse across (the solubility-diffusion mechanism). The second mechanism assumes that ions traverse the bilayer through transient hydrophilic defects caused by thermal fluctuations (the pore mechanism). The theoretical predictions made by both models were tested for halide anions by measuring the permeability coefficients for chloride, bromide, and iodide as a function of bilayer thickness, ionic radius, and sign of charge. To vary the bilayer thickness systematically, liposomes were prepared from monounsaturated phosphatidylcholines (PC) with chain lengths between 16 and 24 carbon atoms. The fluorescent dye MQAE (N-(ethoxycarbonylmethyl)-6-methoxyquinolinium bromide) served as an indicator for halide concentration inside the liposomes and was used to follow the kinetics of halide flux across the bilayer membranes. The observed permeability coefficients ranged from 10(-9) to 10(-7) cm/s and increased as the bilayer thickness was reduced. Bromide was found to permeate approximately six times faster than chloride through bilayers of identical thickness, and iodide permeated three to four times faster than bromide. The dependence of the halide permeability coefficients on bilayer thickness and on ionic size were consistent with permeation of hydrated ions by a solubility-diffusion mechanism rather than through transient pores. Halide permeation therefore differs from that of a monovalent cation such as potassium, which has been accounted for by a combination of the two mechanisms depending on bilayer thickness.

  1. A novel fluorescence-quenching immunochromatographic sensor for detection of the heavy metal chromium.

    PubMed

    Fu, QiangQiang; Tang, Yong; Shi, CongYing; Zhang, XiaoLi; Xiang, JunJian; Liu, Xi

    2013-11-15

    A novel fluorescence quenching immunochromatographic sensor (ICS) was developed for detecting chromium (Cr(3+)) within 15 min utilizing the fluorescence quenching function of gold nanoparticles (Au-NPs). The sensor performed with a positive readout. When the low concentrations of Cr(3+) samples were applied, detection signals of the test line (T line) were quenched, whereas when higher concentration Cr(3+) samples (1.56 ng/mL) were applied, the detection signal of the T line appeared. The detection signal intensity of the T line increased with increasing concentrations of Cr(3+). The low detection limit of developed fluorescence quenching ICS was 1.56 ng/mL. The fluorescence quenching ICS has a linear range of detection of Cr(3+) comprising between 6.25 ng/mL to 800 ng/mL. The recoveries of the fluorescence quenching ICS to detect Cr(3+) in tap water ranged from 94.7% to 101.7%. This result indicated that the developed sensor gave higher sensitivity and reliable reproducibility. It could provide a general detection method for small analyte in water samples. PMID:23800612

  2. APPARATUS FOR HIGH PURITY METAL RECOVERY

    DOEpatents

    Magel, T.T.

    1959-02-10

    An apparatus is described for preparing high purity metal such as uranium, plutonium and the like from an impure mass of the same metal. The apparatus is arranged so that the impure metal is heated and swept by a stream of hydrogen gas bearing a halogen such as iodine. The volatiie metal halide formed is carried on to a hot filament where the metal halide is decomposed and the molten high purity metal is collected in a rceeiver below

  3. Electronic excitation in bulk and nanocrystalline alkali halides.

    PubMed

    Bichoutskaia, Elena; Pyper, Nicholas C

    2012-11-14

    The lowest energy excitations in bulk alkali halides are investigated by considering five different excited state descriptions. It is concluded that excitation transfers one outermost halide electron in the fully ionic ground state to the lowest energy vacant s orbital of one closest cation neighbour to produce the excited state termed dipolar. The excitation energies of seven salts were computed using shell model description of the lattice polarization produced by the effective dipole moment of the excited state neutral halogen-neutral metal pair. Ab initio uncorrelated short-range inter-ionic interactions computed from anion wavefunctions adapted to the in-crystal environment were augmented by short-range electron correlation contributions derived from uniform electron-gas density functional theory. Dispersive attractions including wavefunction overlap damping were introduced using reliable semi-empirical dispersion coefficients. The good agreement between the predicted excitation energies and experiment provides strong evidence that the excited state is dipolar. In alkali halide nanocrystals in which each ionic plane contains only four ions, the Madelung energies are significantly reduced compared with the bulk. This predicts that the corresponding intra-crystal excitation energies in the nanocrystals, where there are two excited states depending on whether the halide electron is transferred to a cation in the same or in the neighbouring plane, will be reduced by almost 2 eV. For such an encapsulated KI crystal, it has been shown that the greater polarization in the excited state of the bulk crystal causes these reductions to be lowered to a 1.1 eV-1.5 eV range for the case of charge transfer to a neighbouring plane. For intra-plane charge transfer the magnitude of the polarization energy is further reduced thus causing the excitation in these encapsulated materials to be only 0.2 eV less than in the bulk crystal. PMID:23163361

  4. Photocrystallographic Observation of Halide-Bridged Intermediates in Halogen Photoeliminations

    PubMed Central

    2015-01-01

    Polynuclear transition metal complexes, which frequently constitute the active sites of both biological and chemical catalysts, provide access to unique chemical transformations that are derived from metal–metal cooperation. Reductive elimination via ligand-bridged binuclear intermediates from bimetallic cores is one mechanism by which metals may cooperate during catalysis. We have established families of Rh2 complexes that participate in HX-splitting photocatalysis in which metal–metal cooperation is credited with the ability to achieve multielectron photochemical reactions in preference to single-electron transformations. Nanosecond-resolved transient absorption spectroscopy, steady-state photocrystallography, and computational modeling have allowed direct observation and characterization of Cl-bridged intermediates (intramolecular analogues of classical ligand-bridged intermediates in binuclear eliminations) in halogen elimination reactions. On the basis of these observations, a new class of Rh2 complexes, supported by CO ligands, has been prepared, allowing for the isolation and independent characterization of the proposed halide-bridged intermediates. Direct observation of halide-bridged structures establishes binuclear reductive elimination as a viable mechanism for photogenerating energetic bonds. PMID:25264809

  5. Triplet state magnetic resonance and fluorescence spectroscopy of metal-substituted hemoglobins.

    PubMed

    Polm, M W; Schaafsma, T J

    1997-01-01

    Fluorescence detected magnetic resonance (FDMR) spectra detected at 596 nm of zinc-substituted hemoglobins at 4.2 K show a split D-E transition, which is not observed for zinc protoporphyrins ligated by methylimidazole in glasses. Incorporation of the zinc heme into the globin pocket is also accompanied by a blue shift of the fluorescence of 20 nm at 4.2 K. FDMR spectra recorded at 576 nm do not show the D-E splitting. The D-E splitting and the huge blue shift are not observed for the magnesium-substituted hemoglobins. Fluorescence measurements at 4.2 K and 77 K, and EPR measurements at 110 K, were carried out to obtain information about the ligation states of the zinc and magnesium protoporphyrins in glasses and in hemoglobin. The results are explained by considering ligation effects and distortion of the porphyrin plane. PMID:8994622

  6. Optimization of metal-enhanced fluorescence by different concentrations of gold-silica core-shell nanoparticles

    NASA Astrophysics Data System (ADS)

    Chen, Jiawei; Wang, Kai; Wu, Ke; Qian, Lihua; Long, Hua; Wang, Bing; Lu, Peixiang

    2015-08-01

    Colloidal solutions of Au/SiO2 core-shell nanoparticles (NPs) are synthesized. The diameters of Au core are 40 nm, 60 nm, 80 nm and 110 nm and the thickness of SiO2 shell is 20 nm. The metal-enhanced fluorescence of CdTe quantum dots (QDs) in aqueous solutions is studied by mixing the Au/SiO2 NPs colloidal solutions with different concentrations. As the molar ratio of the Au/SiO2 NPs and the CdTe QDs increases, the fluorescence enhancement factor grows rapidly because of the plasmonic enhancement, and then a reduction of the enhancement factor is observed because of the absorption of Au/SiO2 NPs. The largest fluorescence enhancement factor of 8 is obtained at the optimal molar ratio, when the surface plasmon resonance of the Au/SiO2 NPs (60 nm) matches the emission peak of the CdTe QDs. The results of our theoretical analysis support the experimental results.

  7. 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.

  8. Competitive DNA-Binding Studies between Metal Complexes and GelRed as a New and Safe Fluorescent DNA Dye.

    PubMed

    Anjomshoa, Marzieh; Torkzadeh-Mahani, Masoud

    2016-07-01

    The focus of this work is introduction of GelRed (GR) as a stable, sensitive and environmentally safe fluorescent DNA dye instead of the highly toxic ethidium bromide (EB). Competitive DNA-binding studies between metal complexes, [Cu(phen-dion)(phen)Cl]Cl (1), [Cu(phen-dione)(bpy)Cl]Cl (2), [Cu(dppt)2(H2O)]PF6 (3), [Ni(dppt)2Cl2] (4), [Zn(dppt)2Cl2] (5), and K3[Fe(CN)6] (6) (where phen-dione is 1,10-phenanthroline-5,6-dione, phen is 1,10- phenanthroline, bpy is 2,2'-bipyridine, and dppt is 5,6-diphenyl-3-(2-pyridyl)-1,2,4-triazine), and GelRed have been investigated under physiological conditions by fluorescence spectroscopy. This simple method can reveal the binding affinity and mode of metal complexes with DNA. The method is based on the decrease of fluorescence derived from the displacement of GelRed from DNA by metal complexes. The % fluorescence decrease is directly related to the extent of DNA binding. Results indicate the DNA binding affinities of complexes follow the order 3 > 4 > 1 > 2 > 5 > 6. The significant quenching of the emission band of the GR-DNA with the addition of complexes 1, 3, and 4 suggests that complexes compete for DNA-binding sites with GR and displace GR from the GR-DNA, which is usually characteristic of the intercalative interaction of compounds with DNA. A small quenching of the emission band of the GR-DNA with the addition of the complex 2 was observed that show the complex weaker competes for DNA-binding sites with GR than complexes 1, 3, and 4. Results show complexes 5 and 6 cannot compete for DNA-binding sites with GR and their interaction with DNA is external binding (groove or electrostatic bindig). PMID:27324950

  9. Halide anion dependence of ionic surfactant adsorption in air/water interface

    NASA Astrophysics Data System (ADS)

    Kim, Doseok; Wang, Wenjie; Sung, Woongmo; Ao, Mingqi; Vaknin, David

    2014-03-01

    It was recently proposed that there is surface excess of halide anions at the air/water interface, and more surface excess of I- than Br- or Cl-, which cannot be explained by Debye-Huckel theory. In case of charged surfaces such as Gibbs monolayer consisting of cationic surfactant molecules, surface excess of anions can also be expected. In this study, by using surface-sensitive grazing angle X-ray fluorescence in conjunction with surface tension measurement, we investigated adsorption behavior of [C12mim]Cl, [C12mim]Br, [C12mim]I aqueous solutions, in which the surface is first covered by [C12mim]+ cations at low concentrations, and the adsorption of the halide anions to this charged interface would follow with the increase in the concentration of solutes. From the surface tension measurements, it was observed that critical micelle concentration of [C12mim]I solution was 4.6 mM, much smaller than that of [C12mim]Cl (16.7 mM) indicating surface activity of surfactant increases with size of halide anions. From X-ray fluorescence, surface excess of halide anion was measured quantitatively from the interface of these solutions. By putting NaCl and NaI in [C12mim]I and [C12mim]Cl solutions, respectively, competition between Cl- and I- adsorption was investigated, to find that I- has stronger adsorption on the charged surface than Cl-.

  10. Shallow halogen vacancies in halide optoelectronic materials

    DOE PAGESBeta

    Shi, Hongliang; Du, Mao -Hua

    2014-11-05

    Halogen vacancies (VH) are usually deep color centers (F centers) in halides and can act as major electron traps or recombination centers. The deep VH contributes to the typically poor carrier transport properties in halides. However, several halides have recently emerged as excellent optoelectronic materials, e.g., CH3NH3PbI3 and TlBr. Both CH3NH3PbI3 and TlBr have been found to have shallow VH, in contrast to commonly seen deep VH in halides. In this paper, several halide optoelectronic materials, i.e., CH3NH3PbI3, CH3NH3SnI3 (photovoltaic materials), TlBr, and CsPbBr3, (gamma-ray detection materials) are studied to understand the material chemistry and structure that determine whether VHmore » is a shallow or deep defect in a halide material. It is found that crystal structure and chemistry of ns2 ions both play important roles in creating shallow VH in halides such as CH3NH3PbI3, CH3NH3SnI3, and TlBr. The key to identifying halides with shallow VH is to find the right crystal structures and compounds that suppress cation orbital hybridization at VH, such as those with long cation-cation distances and low anion coordination numbers, and those with crystal symmetry that prevents strong hybridization of cation dangling bond orbitals at VH. Furthermore, the results of this paper provide insight and guidance to identifying halides with shallow VH as good electronic and optoelectronic materials.« less

  11. Shallow halogen vacancies in halide optoelectronic materials

    NASA Astrophysics Data System (ADS)

    Shi, Hongliang; Du, Mao-Hua

    2014-11-01

    Halogen vacancies (VH ) are usually deep color centers (F centers) in halides and can act as major electron traps or recombination centers. The deep VH contributes to the typically poor carrier transport properties in halides. However, several halides have recently emerged as excellent optoelectronic materials, e.g., C H3N H3Pb I3 and TlBr. Both C H3N H3Pb I3 and TlBr have been found to have shallow VH , in contrast to commonly seen deep VH in halides. In this paper, several halide optoelectronic materials, i.e., C H3N H3Pb I3 , C H3N H3Sn I3 (photovoltaic materials), TlBr, and CsPbB r3 (gamma-ray detection materials) are studied to understand the material chemistry and structure that determine whether VH is a shallow or deep defect in a halide material. It is found that crystal structure and chemistry of n s2 ions both play important roles in creating shallow VH in halides such as C H3N H3Pb I3 , C H3N H3Sn I3 , and TlBr. The key to identifying halides with shallow VH is to find the right crystal structures and compounds that suppress cation orbital hybridization at VH , such as those with large cation-cation distances and low anion coordination numbers and those with crystal symmetry that prevents strong hybridization of cation dangling bond orbitals at VH . The results of this paper provide insight and guidance to identifying halides with shallow VH as good electronic and optoelectronic materials.

  12. Cross-Electrophile Coupling of Vinyl Halides with Alkyl Halides.

    PubMed

    Johnson, Keywan A; Biswas, Soumik; Weix, Daniel J

    2016-05-23

    An improved method for the reductive coupling of aryl and vinyl bromides with alkyl halides that gave high yields for a variety of substrates at room temperature with a low (2.5 to 0.5 mol %) catalyst loading is presented. Under the optimized conditions, difficult substrates, such as unhindered alkenyl bromides, can be coupled to give the desired olefins with minimal diene formation and good stereoretention. These improved conditions also worked well for aryl bromides. For example, a gram-scale reaction was demonstrated with 0.5 mol % catalyst loading, whereas reactions at 10 mol % catalyst loading completed in as little as 20 minutes. Finally, a low-cost single-component pre-catalyst, (bpy)NiI2 (bpy=2,2'-bipyridine) that is both air- and moisture-stable over a period of months was introduced. PMID:27017436

  13. A new mechanism for radiation damage processes in alkali halides

    NASA Astrophysics Data System (ADS)

    Dubinko, V. I.; Turkin, A. A.; Vainshtein, D. I.; den Hartog, H. W.

    1999-12-01

    We present a theory of radiation damage formation in alkali halides based on a new mechanism of dislocation climb, which involves the production of VF centers (self-trapped hole neighboring a cation vacancy) as a result of the absorption of H centers of dislocation lines. We consider the evolution of all experimentally observed extended defects: metal colloids, gas bubbles, and vacancy voids. Voids are shown to arise and grow large due to the reaction between F and VF centers at the surface of halogen bubbles. Voids can ignite a back reaction between the radiolytic products resulting in decomposition of the irradiated material.

  14. Plasmonic characterization of photo-induced silver nanoparticles extracted from silver halide based TEM film

    NASA Astrophysics Data System (ADS)

    Sudheer, Tiwari, P.; Varshney, G. K.; Rai, V. N.; Srivastava, A. K.

    2016-05-01

    The plasmonic responses of silver nanoparticles extracted from silver halide based electron microscope film are investigated. Photo-reduction process is carried out to convert the silver halide grains into the metallic silver. The centrifuge technique is used for separating the silver nanoparticles from the residual solution. Morphological study performed by field emission scanning electron microscope (FESEM) shows that all the nanoparticles have an average diameter of ~120 nm with a high degree of mono dispersion in size. The localized surface plasmon resonance (LSPR) absorption peak at ~537 nm confirms the presence of large size silver nanoparticles.

  15. Determining analyte concentrations in plutonium metal by x-ray fluorescence using a dried residue method

    NASA Astrophysics Data System (ADS)

    Worley, Christopher G.; Havrilla, George J.

    2000-07-01

    Accurately determining the concentration of certain elements in plutonium is of vital importance in manufacturing nuclear weapons. X-ray fluorescence (XRF) provides a means of obtaining this type of elemental information accurately, quickly, with high precision, and often with little sample preparation. In the present work, a novel method was developed to analyze the gallium concentration in plutonium samples using wavelength-dispersive XRF. A description of the analytical method will be discussed.

  16. Synthesis of Cesium Lead Halide Perovskite Nanocrystals in a Droplet-Based Microfluidic Platform: Fast Parametric Space Mapping.

    PubMed

    Lignos, Ioannis; Stavrakis, Stavros; Nedelcu, Georgian; Protesescu, Loredana; deMello, Andrew J; Kovalenko, Maksym V

    2016-03-01

    Prior to this work, fully inorganic nanocrystals of cesium lead halide perovskite (CsPbX3, X = Br, I, Cl and Cl/Br and Br/I mixed halide systems), exhibiting bright and tunable photoluminescence, have been synthesized using conventional batch (flask-based) reactions. Unfortunately, our understanding of the parameters governing the formation of these nanocrystals is still very limited due to extremely fast reaction kinetics and multiple variables involved in ion-metathesis-based synthesis of such multinary halide systems. Herein, we report the use of a droplet-based microfluidic platform for the synthesis of CsPbX3 nanocrystals. The combination of online photoluminescence and absorption measurements and the fast mixing of reagents within such a platform allows the rigorous and rapid mapping of the reaction parameters, including molar ratios of Cs, Pb, and halide precursors, reaction temperatures, and reaction times. This translates into enormous savings in reagent usage and screening times when compared to analogous batch synthetic approaches. The early-stage insight into the mechanism of nucleation of metal halide nanocrystals suggests similarities with multinary metal chalcogenide systems, albeit with much faster reaction kinetics in the case of halides. Furthermore, we show that microfluidics-optimized synthesis parameters are also directly transferrable to the conventional flask-based reaction. PMID:26836149

  17. Hybrid magnetic nanoparticle/nanogold clusters and their distance-dependent metal-enhanced fluorescence effect via DNA hybridization

    NASA Astrophysics Data System (ADS)

    GuThese Authors Contributed Equally To This Study., Xuefan; Wu, Youshen; Zhang, Lingze; Liu, Yongchun; Li, Yan; Yan, Yongli; Wu, Daocheng

    2014-07-01

    To improve the metal-enhanced fluorescence (MEF) effect of nanogolds (AuNPs) and accurately detect specific DNA sequences via DNA hybridization, novel hybrid magnetic nanoparticles/nanogold clusters (HMNCs) were designed based on finite-difference time-domain simulation results and prepared by using Fe3O4 and nanogolds. The nanogolds outside the HMNC were then conjugated with thiol-terminated DNA molecules, thus DNA modified-HMNCs (DNA-HMNCs) were obtained. The size distributions of these nanostructures were measured by a Malvern size analyzer, and their morphology was observed via transmission electron microscopy (TEM). The ultraviolet (UV)-visible (vis) absorption spectra of the samples were recorded with a UV-2600 spectrophotometer. Fluorescence spectra and the MEF effect were recorded using a spectrophotofluorometer, and lifetimes were determined using a time-correlated single photon counting apparatus. The prepared HMNCs were stable in aqueous solutions and had an average diameter of 87 +/- 3.2 nm, with six to eight AuNPs around a single Fe3O4 nanoparticle. Fluorescein isothiocyanate (FITC) tagged DNA-HMNC conjugates exhibited a significant MEF effect and could accurately detect specific DNA sequences after DNA hybridization. This result indicates their various potential applications in sensors and biomedical fields.To improve the metal-enhanced fluorescence (MEF) effect of nanogolds (AuNPs) and accurately detect specific DNA sequences via DNA hybridization, novel hybrid magnetic nanoparticles/nanogold clusters (HMNCs) were designed based on finite-difference time-domain simulation results and prepared by using Fe3O4 and nanogolds. The nanogolds outside the HMNC were then conjugated with thiol-terminated DNA molecules, thus DNA modified-HMNCs (DNA-HMNCs) were obtained. The size distributions of these nanostructures were measured by a Malvern size analyzer, and their morphology was observed via transmission electron microscopy (TEM). The ultraviolet (UV

  18. Soil Heavy Metal Pollution along Subin River in Kumasi, Ghana; Using X-Ray Fluorescence (XRF) Analysis

    NASA Astrophysics Data System (ADS)

    Kodom, K.; Wiafe-Akenten, J.; Boamah, D.

    2010-04-01

    This study is aimed to analyze and assess the existence of heavy metal pollution in the surface soils along Subin River in the Kumasi metropolis using X-Ray Fluorescence (XRF) analysis. Twenty (20) soil samples were collected along the River at regular interval of 5 m (covering entire area of about 100 m2), with the aid of a core sampler. The samples were suitably packaged and conveyed into the laboratory for sample preparation and analysis. The concentration of heavy metals (Cr, Cu, Pb, Hg, Ni, Zn, Tl, V and Cd) were measured and quantified (mgkg-1) after the elemental analysis using XRF spectrometry, and their respective average concentrations (121.89 mgkg-1, 49.24 mgkg-1, 80.84 mgkg-1, 2.52 mgkg-1, 17.01 mgkg-1, 148.08 mgkg-1, 3.21 mgkg-1, 84.40 mgkg-1, and 4.05 mgkg-1) were attained. According to these results, the presence of heavy metals such as (Pb, Cd and Hg) present in the soil, were highly recorded above their threshold limit values (TLVs) by an amount of 60.84 mgkg-1, 3.05 mgkg-1 and 1.52 mgkg-1 respectively. These metals are highly toxic even in very low concentrations and their toxicity and poisoning in living organisms often occur through exchange and co-ordination mechanisms in the soft tissues. These high excess concentration values alarmingly depict that, the study site is highly polluted with those metals, and the Subin river-body and the inhabitants who reside closely to the polluted river, are at serious risk. The extent to which the study area is polluted, was successfully and statistically analyzed from the standard deviation (σ) and difference between the average concentration values recorded, and the TLVs.

  19. Spatially resolved synchrotron-induced X-ray fluorescence analyses of metal point drawings and their mysterious inscriptions

    NASA Astrophysics Data System (ADS)

    Reiche, Ina; Radtke, Martin; Berger, Achim; Görner, Wolf; Ketelsen, Thomas; Merchel, Silke; Riederer, Josef; Riesemeier, Heinrich; Roth, Michael

    2004-10-01

    Synchrotron-induced X-ray fluorescence (Sy-XRF) analysis was used to study the chemical composition of precious Renaissance silverpoint drawings. Drawings by famous artists such as Albrecht Dürer (1471-1528) and Jan van Eyck (approximately 1395-1441) must be investigated non-destructively. Moreover, extremely sensitive synchrotron- or accelerator-based techniques are needed since only small quantities of silver are deposited on the paper. New criteria for attributing these works to a particular artist could be established based on the analysis of the chemical composition of the metal points used. We illustrate how analysis can give new art historical information by means of two case studies. Two particular drawings, one of Albrecht Dürer, showing a profile portrait of his closest friend, "Willibald Pirckheimer" (1503), and a second one attributed to Jan van Eyck, showing a "Portrait of an elderly man", often named "Niccolò Albergati", are the object of intense art historical controversy. Both drawings show inscriptions next to the figures. Analyses by Sy-XRF could reveal the same kind of silverpoint for the Pirckheimer portrait and its mysterious Greek inscription, contrary to the drawing by Van Eyck where at least three different metal points were applied. Two different types of silver marks were found in this portrait. Silver containing gold marks were detected in the inscriptions and over-subscriptions. This is the first evidence of the use of gold points for metal point drawings in the Middle Ages.

  20. Enhancement of Exciton Emission in Lead Halide-Based Layered Perovskites by Cation Mixing.

    PubMed

    Era, Masanao; Komatsu, Yumeko; Sakamoto, Naotaka

    2016-04-01

    Spin-coated films of a lead halide, PbX: X = I and Br, layered perovskites having cyclohexenylethyl ammonium molecule as an organic layer, which were mixed with other metal halide-based layered perovskites consisting of various divalent metal halides (for example, Ca2, Cdl2, FeI2, SnBr2 and so on), were prepared. The results of X-ray diffraction measurements exhibited that solid solution formation between PbX-based layered perovskite and other divalent metal halide-based layered perovskites was observed up to very high molar concentration of 50 molar% in the mixed film samples when divalent cations having ionic radius close to that of Pb2+ were employed. In the solid solution films, the exciton emission was much enhanced at room temperature. Exciton emission intensity of Pbl-based layered perovskite mixed with Cal-based layered perovskite (20 molar%) is about 5 times large that of the pristine Pbl-based layered perovskite, and that of PbBr-based layered perovskite mixed with SnBr-based layered perovskite (20 molar%) was also about 5 times large that of the pristine PbBr-based layered perovskite at room temperature. PMID:27451628

  1. Low-threshold amplified spontaneous emission and lasing from colloidal nanocrystals of caesium lead halide perovskites

    PubMed Central

    Yakunin, Sergii; Protesescu, Loredana; Krieg, Franziska; Bodnarchuk, Maryna I.; Nedelcu, Georgian; Humer, Markus; De Luca, Gabriele; Fiebig, Manfred; Heiss, Wolfgang; Kovalenko, Maksym V.

    2015-01-01

    Metal halide semiconductors with perovskite crystal structures have recently emerged as highly promising optoelectronic materials. Despite the recent surge of reports on microcrystalline, thin-film and bulk single-crystalline metal halides, very little is known about the photophysics of metal halides in the form of uniform, size-tunable nanocrystals. Here we report low-threshold amplified spontaneous emission and lasing from ∼10 nm monodisperse colloidal nanocrystals of caesium lead halide perovskites CsPbX3 (X=Cl, Br or I, or mixed Cl/Br and Br/I systems). We find that room-temperature optical amplification can be obtained in the entire visible spectral range (440–700 nm) with low pump thresholds down to 5±1 μJ cm−2 and high values of modal net gain of at least 450±30 cm−1. Two kinds of lasing modes are successfully observed: whispering-gallery-mode lasing using silica microspheres as high-finesse resonators, conformally coated with CsPbX3 nanocrystals and random lasing in films of CsPbX3 nanocrystals. PMID:26290056

  2. Low-threshold amplified spontaneous emission and lasing from colloidal nanocrystals of caesium lead halide perovskites

    NASA Astrophysics Data System (ADS)

    Yakunin, Sergii; Protesescu, Loredana; Krieg, Franziska; Bodnarchuk, Maryna I.; Nedelcu, Georgian; Humer, Markus; de Luca, Gabriele; Fiebig, Manfred; Heiss, Wolfgang; Kovalenko, Maksym V.

    2015-08-01

    Metal halide semiconductors with perovskite crystal structures have recently emerged as highly promising optoelectronic materials. Despite the recent surge of reports on microcrystalline, thin-film and bulk single-crystalline metal halides, very little is known about the photophysics of metal halides in the form of uniform, size-tunable nanocrystals. Here we report low-threshold amplified spontaneous emission and lasing from ~10 nm monodisperse colloidal nanocrystals of caesium lead halide perovskites CsPbX3 (X=Cl, Br or I, or mixed Cl/Br and Br/I systems). We find that room-temperature optical amplification can be obtained in the entire visible spectral range (440-700 nm) with low pump thresholds down to 5+/-1 μJ cm-2 and high values of modal net gain of at least 450+/-30 cm-1. Two kinds of lasing modes are successfully observed: whispering-gallery-mode lasing using silica microspheres as high-finesse resonators, conformally coated with CsPbX3 nanocrystals and random lasing in films of CsPbX3 nanocrystals.

  3. Hydrogen Halides on Jupiter and Saturn

    NASA Astrophysics Data System (ADS)

    Showman, Adam P.

    2001-07-01

    The quest to detect gaseous HCl, HBr, and HF in the atmospheres of Jupiter and Saturn has led to a tentative detection of 1 ppb HCl near Saturn's cloud deck. The detection is puzzling because, while these hydrogen halides may be present several scale heights below the clouds, they are expected to react with ammonia to form solid ammonium halide salts in the upper troposphere. I show that the loss timescale for condensation of gaseous hydrogen halides onto particles is ˜10 3-10 5 s for realistic cloud densities and particle sizes, which is much less than the ˜10 8 s residence time of upper tropospheric air. The hydrogen halides can only survive transport up to the cloud layer if less than 1 in 10 6 of their collisions with particle surfaces leads to condensation, which is unlikely. Even in the absence of foreign particles, homogeneous nucleation would probably prevent supersaturations in excess of a few hundred, which is ˜10 20-10 40 times too low to explain the observation. These calculations therefore suggest that hydrogen halides cannot exist at part-per-billion levels in the upper troposphere. The interplanetary source of halogens is also too low to produce detectable quantities of hydrogen halides except perhaps at pressures less than 1 mbar. A possible detection of chlorine by the Galileo probe at pressures exceeding 9 bars on Jupiter may be consistent with the equilibrium abundance of gaseous HCl or NH 4Cl.

  4. Simultaneous SERS and surface-enhanced fluorescence from dye-embedded metal core-shell nanoparticles.

    PubMed

    Zhou, Yan; Zhang, Peng

    2014-05-21

    We demonstrate a methodology to prepare Au-core-Ag-shell nanoparticles displaying both SERS and surface-enhanced fluorescence (SEF) activities simultaneously by embedding dye molecules between the core and the shell. Polyelectrolytes are used to adjust the spacing and the dye position between the core and the shell. Layer-by-layer polyelectrolyte deposition can serve as an effective and flexible way to introduce various types of dye molecules into the nanostructures. Results from the spectral measurements shed light on the intricacy between SERS and SEF. PMID:24695881

  5. Immobilized metal ion affinity-based fluorescence polarization (IMAP): advances in kinase screening.

    PubMed

    Sportsman, J Richard; Gaudet, Elizabeth A; Boge, Annegret

    2004-04-01

    The IMAP Fluorescence Polarization technology is a homogeneous antibody-free method for analysis of kinases, phosphatases, and phosphodiesterases. Recent developments to the technology include an enhancement of the reagent system (the Progressive Binding System) that significantly expands the range of useable concentrations of ATP, choices of substrates, and assay configurations. With the new Progressive System, we are able to design multiplexed assays that allow the simultaneous determination of multiple kinase activities. In addition, coupled assays are now possible, allowing the assay of kinases through natural or artificial coupling through kinase cascades. PMID:15165516

  6. Synthesis of fluorescent metal nanoparticles in aqueous solution by photochemical reduction

    NASA Astrophysics Data System (ADS)

    Kshirsagar, Prakash; Shankar Sangaru, Shiv; Brunetti, Virgilio; Malvindi, Maria Ada; Pompa, Pier Paolo

    2014-01-01

    A facile green chemistry approach for the synthesis of sub-5 nm silver and gold nanoparticles is reported. The synthesis was achieved by a photochemical method using tyrosine as the photoreducing agent. The size of the gold and silver nanoparticles was about 3 and 4 nm, respectively. The nanoparticles were characterized using x-ray diffraction, transmission electron microscopy, Fourier transform infrared spectroscopy and photoluminescence spectroscopy. Both silver and gold nanoparticles synthesized by this method exhibited fluorescence properties and their use for cell imaging applications has been demonstrated.

  7. One-Pot Ketone Synthesis with Alkylzinc Halides Prepared from Alkyl Halides via a Single Electron Transfer (SET) Process: New Extension of Fukuyama Ketone Synthesis.

    PubMed

    Lee, Jung Hwa; Kishi, Yoshito

    2016-06-01

    One-pot ketone synthesis has been developed with in situ activation of alkyl halides to alkylzinc halides in the presence of thioesters and Pd-catalyst. The new method provides us with a reliable option for a coupling at a late stage in a convergent synthesis of complex molecules, with use of a near 1:1 molar ratio of coupling partners. First, two facile, orthogonal methods have been developed for preparation of alkylzinc halides: (1) direct insertion of zinc dust to 1°- and 2°-alkyl halides in the presence of LiI in DMI and (2) early transition-metal assisted activation of alkyl halides via a single electron transfer (SET) process. CrCl2 has been found as an unprecedented, inevitable mediator for preparation of alkylzinc halides from alkyl halides, where CrCl2 likely functions to trap R·, generated via a SET process, and transfer it to Zn(II) to form RZnX. In addition to a commonly used CoPc, a new radical initiator NbCpCl4 has been discovered through the study. Second, with use of the two orthogonal methods, three sets of coupling conditions have been developed to complete one-pot ketone synthesis, with Condition A (Pd2dba3, PR3, Zn, LiI, TESCl, DMI), Condition B (A + CrCl2), and Condition C (B + NbCpCl4 or CoPc) being useful for simple linear and α-substituted substrates, simple linear and β-substituted substrates, and complex substrates, respectively. Condition C is applicable to the broadest range of substrates. Overall, one-pot ketone synthesis gives excellent yields, with good functional group tolerance. Controlled formation of alkylzinc halides by a combination of CrCl2 and NbCpCl4 or CoPc is crucial for its application to complex substrates. Interestingly, one-pot ketone synthesis does not suffer from the chemical instability due to the inevitable radical pathway(s), for example a 1,5-H shift. Notably, even with the increase in molecular size, no significant decrease in coupling efficiency has been noticed. To illustrate the synthetic value at a late

  8. Assessment of Occupational Exposure to Manganese and Other Metals in Welding Fumes by Portable X-ray Fluorescence Spectrometer

    PubMed Central

    Laohaudomchok, Wisanti; Cavallari, Jennifer M.; Fang, Shona C.; Lin, Xihong; Herrick, Robert F.; Christiani, David C.; Weisskopf, Marc G.

    2011-01-01

    Elemental analysis of welding fume samples can be done using several laboratory-based techniques. However, portable measurement techniques could offer several advantages. In this study, we sought to determine whether the portable X-ray fluorescence spectrometer (XRF) is suitable for analysis of five metals (manganese, iron, zinc, copper, and chromium) on 37-mm polytetrafluoroethylene filters. Using this filter fitted on a cyclone in line with a personal pump, gravimetric samples were collected from a group of boilermakers exposed to welding fumes. We assessed the assumption of uniform deposition of these metals on the filters, and the relationships between measurement results of each metal obtained from traditional laboratory-based XRF and the portable XRF. For all five metals of interest, repeated measurements with the portable XRF at the same filter area showed good consistency (reliability ratios are equal or close to 1.0 for almost all metals). The portable XRF readings taken from three different areas of each filter were not significantly different (p-values = 0.77 to 0.98). This suggested that the metal rich PM2.5 deposits uniformly on the samples collected using this gravimetric method. For comparison of the two XRFs, the results from the portable XRF were well correlated and highly predictive of those from the laboratory XRF. The Spearman correlation coefficients were from 0.325 for chromium, to 0.995 for manganese and 0.998 for iron. The mean differences as a percent of the mean laboratory XRF readings were also small (<5%) for manganese, iron, and copper. The differences were greater for zinc and chromium, which were present at very low amounts in our samples and below the limits of detection of the portable XRF for many of the samples. These five metals were moderately to strongly correlated with the total fine particle fraction on filters (Spearman ρ = 0.41 for zinc to 0.97 for iron). Such strong correlations and comparable results suggested that the

  9. Using Nondestructive Portable X-ray Fluorescence Spectrometers on Stone, Ceramics, Metals, and Other Materials in Museums: Advantages and Limitations.

    PubMed

    Tykot, Robert H

    2016-01-01

    Elemental analysis is a fundamental method of analysis on archaeological materials to address their overall composition or identify the source of their geological components, yet having access to instrumentation, its often destructive nature, and the time and cost of analyses have limited the number and/or size of archaeological artifacts tested. The development of portable X-ray fluorescence (pXRF) instruments over the past decade, however, has allowed nondestructive analyses to be conducted in museums around the world, on virtually any size artifact, producing data for up to several hundred samples per day. Major issues have been raised, however, about the sensitivity, precision, and accuracy of these devices, and the limitation of performing surface analysis on potentially heterogeneous objects. The advantages and limitations of pXRF are discussed here regarding archaeological studies of obsidian, ceramics, metals, bone, and painted materials. PMID:26767632

  10. Use of Synchrotron X-ray Fluorescence to Measure Trace Metal Distribution in the Brain

    NASA Astrophysics Data System (ADS)

    Linkous, D.; Flinn, J. M.; Lanzirotti, A.; Frederickson, C.; Jones, B. F.; Bertsch, P. M.

    2002-12-01

    X26A, National Synchrotron Light Source, was used to quantitatively evaluate the spatial distribution of trace metals, such as Zn and Cu, in brain tissue. X-ray microprobe techniques offer distinct advantages over other analytical methods by allowing analyses to be done in-situ with little or no chemical pretreatment and low detection limits (about 1 ppm). In the context of neuroscience, SXRF can provide non-destructive measurements of specific metal concentrations and distribution within nerve (brain) tissue. Neuronal tissue from organisms having undergone different normal or experimental conditions may be compared, with analytical capacities not limited by binding states of the metal (i.e., vesicular or enzymatic), as is the case with staining techniques.. Whole regions of tissue may be scanned for detectable trace metals at spatial resolutions of 10um or less using focused monochromatic x-ray beams. Here special attention has been given to zinc because it is the most common trace metal in the brain, and levels have been increasing in the environment. In this investigation, zinc concentrations present within the hilus of a rat hippocampus, and to a lesser extent in the cortex, have been shown to increase following long-term ingestion of zinc-enhanced drinking water that was associated with deficits in spatial memory. Concomitantly, copper concentrations in the internal capsule were comparatively lower. Other first order transition metals, Cr, V, Mn, and Co were not detected. In contrast, elevated levels of Zn, Cu, and Fe have been seen in amyloid plaques associated with Alzheimer's disease.

  11. X-ray Fluorescence Tomography of Aged Fluid-Catalytic-Cracking Catalyst Particles Reveals Insight into Metal Deposition Processes

    PubMed Central

    Kalirai, Sam; Boesenberg, Ulrike; Falkenberg, Gerald; Meirer, Florian; Weckhuysen, Bert M

    2015-01-01

    Microprobe X-ray fluorescence tomography was used to investigate metal poison deposition in individual, intact and industrially deactivated fluid catalytic cracking (FCC) particles at two differing catalytic life-stages. 3 D multi-element imaging, at submicron resolution was achieved by using a large-array Maia fluorescence detector. Our results show that Fe, Ni and Ca have significant concentration at the exterior of the FCC catalyst particle and are highly co-localized. As concentrations increase as a function of catalytic life-stage, the deposition profiles of Fe, Ni, and Ca do not change significantly. V has been shown to penetrate deeper into the particle with increasing catalytic age. Although it has been previously suggested that V is responsible for damaging the zeolite components of FCC particles, no spatial correlation was found for V and La, which was used as a marker for the embedded zeolite domains. This suggests that although V is known to be detrimental to zeolites in FCC particles, a preferential interaction does not exist between the two. PMID:26613011

  12. Blue fluorescence of three metal-organic zinc polymers containing tetrazinc units and asymmetric ligand of btc{sup 3-}

    SciTech Connect

    Xu Ling; Liu Bing; Zheng Fakun; Guo Guocong . E-mail: gcguo@ms.fjirsm.ac.cn; Huang Jinshun

    2005-11-15

    Three new zinc coordination polymers [Zn{sub 2}(btc){sub 2}(H{sub 2}O){sub 2}] {sub n} .n[Zn(H{sub 2}O){sub 6}] (1), [Zn{sub 3}(btc){sub 2}(2,2'-bipy){sub 2}(H{sub 2}O){sub 3}] {sub n} .2nH{sub 2}O (2) and [Zn{sub 3}(btc){sub 2}(H{sub 2}O){sub 6}] {sub n} .nH{sub 2}O (3) (H{sub 3}btc=1,2,4-benzenetricarboxylic acid, 2,2'-bipy=2,2'-bipyridine) were obtained by the diffusion method and their crystal structures were determined by single-crystal X-ray diffraction. Compounds 1-3 have the similar tetrametallic unit [Zn{sub 4}(btc){sub 2}] SBUs and these SBUs are further connected into stair-like structure, 2-D layer and 3-D framework for 1, 2 and 3, in which the btc{sup 3-} ligands adopt {mu} {sub 3}, {mu} {sub 4} and {mu} {sub 5} coordination modes, respectively. The title compounds show strong blue fluorescence, which may be assigned as {pi}*{sup {yields}}n transition of the ligand mixed with the ligand-to-metal change transfer (LMCT), indicating the fluorescence, indicates the title compounds may be good candidates for blue-light photoactive materials.

  13. Online X-ray Fluorescence (XRF) Analysis of Heavy Metals in Pulverized Coal on a Conveyor Belt.

    PubMed

    Yan, Zhang; XinLei, Zhang; WenBao, Jia; Qing, Shan; YongSheng, Ling; DaQian, Hei; Da, Chen

    2016-02-01

    Heavy metals in haze episode will continue to threaten the quality of public health around the world. In order to decrease the emission of heavy metals produced from coal burning, an online X-ray fluorescence (XRF) analyzer system, consisting of an XRF analyzer with data acquisition software and a laser rangefinder, was developed to carry out the measurement of heavy metals in pulverized coal. The XRF analyzer was mounted on a sled, which can effectively smooth the surface of pulverized coal and reduce the impact of surface roughness during online measurement. The laser rangefinder was mounted over the sled for measuring the distance between a pulverized coal sample and the analyzer. Several heavy metals and other elements in pulverized coal were online measured by the XRF analyzer directly above a conveyor belt. The limits of detection for Hg, Pb, Cr, Ti, Fe, and Ca by the analyzer were 44 ± 2, 34 ± 2, 17 ± 3, 41 ± 4, 19 ± 3, and 65 ± 2 mg·kg(-1), respectively. The relative standard deviation (%RSD) for the elements mentioned was less than 7.74%. By comparison with the results by inductively-coupled plasma mass spectrometry (ICP-MS), relative deviation (%D) of the online XRF analyzer was less than 10% for Cr, Ti, and Ca, in the range of 0.8-24.26% for Fe, and greater than 20% for Hg and Pb. PMID:26787706

  14. Trace metal determinations by total-reflection X-ray fluorescence analysis in the open Atlantic Ocean

    NASA Astrophysics Data System (ADS)

    Schmidt, Diether; Gerwinski, Wolfgang; Radke, Ina

    1993-02-01

    The Intergovernmental Oceanographic Commission (IOC), as a major component of its programme "Global Investigation of Pollution in the Marine Environment" (GIPME), maintains a long-standing project on "Open Ocean Baseline Studies of Trace Contaminants". Initially, the Atlantic Ocean and trace metals were selected. A first cruise with the RVMeteor to the eastern parts of the south and north Atlantic Ocean was successfully organized, in March and April 1990, from Cape Town (South Africa) to Funchal (Madeira, Portugal). Thirteen scientists from laboratories in Europe and North America participated with the first author as coordinator. Four deep-water stations in the Cape Basin, Angola Basin, Cape Verde Abyssal Plain and Seine Abyssal Plain were regularly sampled for at least 36 depths. Additional samples were taken between stations. Samples were distributed to participants and a similar number of additional laboratories. As a central part of our own contribution to the project, we determined the trace heavy metals manganese, nickel, copper, zinc and lead and the lighter selenium by total-reflection X-ray fluorescence analysis. Additional methods applied, interalia, were anodic stripping voltammetry for lead and cadmium and graphite furnace atomic absorption spectrometry (GFAAS) for cadmium, using two different extraction procedures. For the TXRF, the pre-enrichment of the trace metals and the separation from the salt matrix were performed by complexation with sodium dibenzyldithiocarbamate and reverse-phase chromatography. Generally, very low levels of trace elements were found in filtered and unaltered water samples from these remote areas of the open Atlantic Ocean. Typical examples of the distributions of trace metal concentrations on depth profiles from the four deep-water stations as well as intercomparisons between the stations are presented.

  15. "Turn on" and label-free core-shell Ag@SiO2 nanoparticles-based metal-enhanced fluorescent (MEF) aptasensor for Hg2+

    NASA Astrophysics Data System (ADS)

    Pang, Yuanfeng; Rong, Zhen; Xiao, Rui; Wang, Shengqi

    2015-03-01

    A turn on and label-free fluorescent apasensor for Hg2+ with high sensitivity and selectivity has been demonstrated in this report. Firstly, core-shell Ag@SiO2 nanoparticles (NPs) were synthetized as a Metal-Enhanced Fluorescent (MEF) substrate, T-rich DNA aptamers were immobilized on the surface of Ag@SiO2 NPs and thiazole orange (TO) was selected as fluorescent reporter. After Hg2+ was added to the aptamer-Ag@SiO2 NPs and TO mixture buffer solution, the aptamer strand can bind Hg2+ to form T-Hg2+-T complex with a hairpin structure which TO can insert into. When clamped by the nucleic acid bases, the fluorescence quanta yield of TO will be increased under laser excitation and emitted a fluorescence emission. Furthermore, the fluorescence emission can be amplified largely by the MEF effect of the Ag@SiO2 NPs. The whole experiment can be finished within 30 min and the limit of detection is 0.33 nM even with interference by high concentrations of other metal ions. Finally, the sensor was applied for detecting Hg2+ in different real water samples with satisfying recoveries over 94%.

  16. "Turn on" and label-free core−shell Ag@SiO2 nanoparticles-based metal-enhanced fluorescent (MEF) aptasensor for Hg2+

    PubMed Central

    Pang, Yuanfeng; Rong, Zhen; Xiao, Rui; Wang, Shengqi

    2015-01-01

    A turn on and label-free fluorescent apasensor for Hg2+ with high sensitivity and selectivity has been demonstrated in this report. Firstly, core−shell Ag@SiO2 nanoparticles (NPs) were synthetized as a Metal-Enhanced Fluorescent (MEF) substrate, T-rich DNA aptamers were immobilized on the surface of Ag@SiO2 NPs and thiazole orange (TO) was selected as fluorescent reporter. After Hg2+ was added to the aptamer-Ag@SiO2 NPs and TO mixture buffer solution, the aptamer strand can bind Hg2+ to form T-Hg2+-T complex with a hairpin structure which TO can insert into. When clamped by the nucleic acid bases, the fluorescence quanta yield of TO will be increased under laser excitation and emitted a fluorescence emission. Furthermore, the fluorescence emission can be amplified largely by the MEF effect of the Ag@SiO2 NPs. The whole experiment can be finished within 30 min and the limit of detection is 0.33 nM even with interference by high concentrations of other metal ions. Finally, the sensor was applied for detecting Hg2+ in different real water samples with satisfying recoveries over 94%. PMID:25819733

  17. Fabrication of freestanding silk fibroin films containing Ag nanowires/NaYF4:Yb,Er nanocomposites with metal-enhanced fluorescence behavior.

    PubMed

    Zhao, Bing; Qi, Ning; Zhang, Ke-Qin; Gong, Xiao

    2016-06-01

    Solar cells containing upconversion nanoparticles (UCNPs) used as a power source in biomedical nanosystems have attracted great interest. However, such solar cells further need to be developed because their substrate materials should be biocompatible, flexible and highly luminescent. Here, we report that freestanding silk fibroin (SF) films containing a mesh of silver nanowires (AgNWs) and β-NaYF4:Yb,Er nanocrystals with metal-enhanced fluorescence behavior can be fabricated. The freestanding composite films exhibit properties such as good optical transparency, conductivity and flexibility. Furthermore, they show significantly enhanced upconversion fluorescence due to surface plasmon polaritons (SPPs) of AgNWs compared to the SF-UCNP films without AgNWs. The freestanding composite films with metal-enhanced fluorescence behavior show great promise for future applications in self-powered nanodevices such as cardiac pacemakers, biosensors and nanorobots. PMID:27210511

  18. Method and apparatus for convection control of metallic halide vapor density in a metallic halide laser

    NASA Technical Reports Server (NTRS)

    Pivirotto, T. J. (Inventor)

    1982-01-01

    An apparatus is disclosed in which a reservoir containing copper chloride is heated so that the copper chloride is maintained in a liquid form. The apparatus includes a means for flowing a buffer gas (which in the exemplary embodiment is neon) over the liquid copper chloride to provide a mixture of copper chloride vapor and neon above the liquid copper chloride. A conduit provides fluid communication between the reservoir containing the copper chloride vapor/neon mixture and the laser. The copper chloride vapor density in the laser is related to the liquid copper chloride temperature and the neon flow rate through the reservoir. In accordance with a further feature of the exemplary embodiment, neon is also provided directly to the laser in order to provide a further means of controlling the copper chloride vapor density in the laser.

  19. X-ray fluorescence analysis of wear metals in used lubricating oils

    NASA Technical Reports Server (NTRS)

    Maddox, W. E.; Kelliher, W. C.

    1986-01-01

    Used oils from several aircraft at NASA's Langley Research Center were analyzed over a three year period using X-ray fluorescence (XRF) and atomic emission spectrometry. The results of both analyses are presented and comparisons are made. Fe and Cu data for oil from four internal combustion engines are provided and XRF and atomic emission spectrometry measurements were found to be in perfect agreement. However, distributions were found in the case of oil from a jet aircraft engine whereby the latter method gave values for total iron concentration in the oil and did not distinguish between suspended particles and oil additives. XRF does not have these particle-size limitations; moreover, it is a faster process. It is concluded that XRF is the preferred method in the construction of a man-portable oil wear analysis instrument.

  20. Quantitation and localization of intracellular redox active metals by X-ray fluorescence microscopy in cortical neurons derived from APP and APLP2 knockout tissue

    DOE PAGESBeta

    Ciccotosto, Giuseppe D.; James, Simon A.; Altissimo, Matteo; Paterson, David; Vogt, Stefan; Lai, Barry; de Jonge, Martin D.; Howard, Daryl L.; Bush, Ashley I.; Cappai, Roberto

    2014-10-01

    The amyloid precursor protein (APP) gene family includes APP and the amyloid precursor-like proteins, APLP1 and APLP2. These proteins contain metal binding sites for copper, zinc and iron and are known to have physiological roles in modulating the metal homeostasis in brain cells. Here we report the application of X-ray fluorescence microscopy (XFM) to investigate the subcellular distribution patterns of the metal ions Cu, Zn, Fe, and Ca in individual neurons derived from APP and APLP2 knockout mice brains to further define their role in metal homeostasis. These studies add to the growing body of data that the APP familymore » of proteins are metalloproteins that have shared as well as distinct effects on metals. As we continue to delineate the cellular effects of the APP family of proteins it is important to consider how metals are involved in their actions.« less

  1. Quantitation and localization of intracellular redox active metals by X-ray fluorescence microscopy in cortical neurons derived from APP and APLP2 knockout tissue

    SciTech Connect

    Ciccotosto, Giuseppe D.; James, Simon A.; Altissimo, Matteo; Paterson, David; Vogt, Stefan; Lai, Barry; de Jonge, Martin D.; Howard, Daryl L.; Bush, Ashley I.; Cappai, Roberto

    2014-10-01

    The amyloid precursor protein (APP) gene family includes APP and the amyloid precursor-like proteins, APLP1 and APLP2. These proteins contain metal binding sites for copper, zinc and iron and are known to have physiological roles in modulating the metal homeostasis in brain cells. Here we report the application of X-ray fluorescence microscopy (XFM) to investigate the subcellular distribution patterns of the metal ions Cu, Zn, Fe, and Ca in individual neurons derived from APP and APLP2 knockout mice brains to further define their role in metal homeostasis. These studies add to the growing body of data that the APP family of proteins are metalloproteins that have shared as well as distinct effects on metals. As we continue to delineate the cellular effects of the APP family of proteins it is important to consider how metals are involved in their actions.

  2. Intelligent Simultaneous Quantitative Online Analysis of Environmental Trace Heavy Metals with Total-Reflection X-Ray Fluorescence

    PubMed Central

    Ma, Junjie; Wang, Yeyao; Yang, Qi; Liu, Yubing; Shi, Ping

    2015-01-01

    Total-reflection X-ray fluorescence (TXRF) has achieved remarkable success with the advantages of simultaneous multi-element analysis capability, decreased background noise, no matrix effects, wide dynamic range, ease of operation, and potential of trace analysis. Simultaneous quantitative online analysis of trace heavy metals is urgently required by dynamic environmental monitoring and management, and TXRF has potential in this application domain. However, it calls for an online analysis scheme based on TXRF as well as a robust and rapid quantification method, which have not been well explored yet. Besides, spectral overlapping and background effects may lead to loss of accuracy or even faulty results during practical quantitative TXRF analysis. This paper proposes an intelligent, multi-element quantification method according to the established online TXRF analysis platform. In the intelligent quantification method, collected characteristic curves of all existing elements and a pre-estimated background curve in the whole spectrum scope are used to approximate the measured spectrum. A novel hybrid algorithm, PSO-RBFN-SA, is designed to solve the curve-fitting problem, with offline global optimization and fast online computing. Experimental results verify that simultaneous quantification of trace heavy metals, including Cr, Mn, Fe, Co, Ni, Cu and Zn, is realized on the online TXRF analysis platform, and both high measurement precision and computational efficiency are obtained. PMID:25954949

  3. Ligand-centred fluorescence and electronic relaxation cascade at vibrational time scales in transition-metal complexes.

    PubMed

    Messina, Fabrizio; Pomarico, Enrico; Silatani, Mahsa; Baranoff, Etienne; Chergui, Majed

    2015-11-19

    Using femtosecond-resolved photoluminescence up-conversion, we report the observation of the fluorescence of the high-lying ligand-centered (LC) electronic state upon 266 nm excitation of an iridium complex, Ir(ppy)3, with a lifetime of 70 ± 10 fs. It is accompanied by a simultaneous emission of all lower-lying electronic states, except the lowest triplet metal-to-ligand charge-transfer ((3)MLCT) state that shows a rise on the same time scale. Thus, we observe the departure, the intermediate steps, and the arrival of the relaxation cascade spanning ∼1.6 eV from the (1)LC state to the lowest (3)MLCT state, which then yields the long-lived luminescence of the molecule. This represents the first measurement of the total relaxation time over an entire cascade of electronic states in a polyatomic molecule. We find that the relaxation cascade proceeds in ≤10 fs, which is faster than some of the highest-frequency modes of the system. We invoke the participation of the latter modes in conical intersections and their overdamping to low-frequency intramolecular modes. On the basis of literature, we also conclude that this behavior is not specific to transition-metal complexes but also applies to organic molecules. PMID:26509329

  4. Intelligent simultaneous quantitative online analysis of environmental trace heavy metals with total-reflection X-ray fluorescence.

    PubMed

    Ma, Junjie; Wang, Yeyao; Yang, Qi; Liu, Yubing; Shi, Ping

    2015-01-01

    Total-reflection X-ray fluorescence (TXRF) has achieved remarkable success with the advantages of simultaneous multi-element analysis capability, decreased background noise, no matrix effects, wide dynamic range, ease of operation, and potential of trace analysis. Simultaneous quantitative online analysis of trace heavy metals is urgently required by dynamic environmental monitoring and management, and TXRF has potential in this application domain. However, it calls for an online analysis scheme based on TXRF as well as a robust and rapid quantification method, which have not been well explored yet. Besides, spectral overlapping and background effects may lead to loss of accuracy or even faulty results during practical quantitative TXRF analysis. This paper proposes an intelligent, multi-element quantification method according to the established online TXRF analysis platform. In the intelligent quantification method, collected characteristic curves of all existing elements and a pre-estimated background curve in the whole spectrum scope are used to approximate the measured spectrum. A novel hybrid algorithm, PSO-RBFN-SA, is designed to solve the curve-fitting problem, with offline global optimization and fast online computing. Experimental results verify that simultaneous quantification of trace heavy metals, including Cr, Mn, Fe, Co, Ni, Cu and Zn, is realized on the online TXRF analysis platform, and both high measurement precision and computational efficiency are obtained. PMID:25954949

  5. Correlative super-resolution fluorescence and metal replica transmission electron microscopy

    PubMed Central

    Sochacki, Kem A.; Shtengel, Gleb; van Engelenburg, Schuyler B.; Hess, Harald F.; Taraska, Justin W.

    2014-01-01

    Super-resolution localization microscopy is combined with a complementary imaging technique, transmission electron microscopy of metal replicas, to locate proteins on the landscape of the cellular plasma membrane at the nanoscale. Robust correlation on the scale of 20 nm is validated by imaging endogenous clathrin (with 2D and 3D PALM/TEM) and the method is further used to find the previously unknown 3D position of epsin on clathrin coated structures. PMID:24464288

  6. Determining heavy metals in spent compact fluorescent lamps (CFLs) and their waste management challenges: Some strategies for improving current conditions

    SciTech Connect

    Taghipour, Hassan; Amjad, Zahra; Jafarabadi, Mohamad Asghari; Gholampour, Akbar; Norouz, Prviz

    2014-07-15

    Highlights: • Heavy metals in spent compact fluorescent lamps (CFLs) determined. • Current waste management condition of CFLs in Iran assessed. • Currently, waste of CFLs is disposed by municipal waste stream in waste landfills. • We propose extended producer responsibility (EPR) for CFLs waste management. - Abstract: From environmental viewpoint, the most important advantage of compact fluorescent lamps (CFLs) is reduction of green house gas emissions. But their significant disadvantage is disposal of spent lamps because of containing a few milligrams of toxic metals, especially mercury and lead. For a successful implementation of any waste management plan, availability of sufficient and accurate information on quantities and compositions of the generated waste and current management conditions is a fundamental prerequisite. In this study, CFLs were selected among 20 different brands in Iran. Content of heavy metals including mercury, lead, nickel, arsenic and chromium was determined by inductive coupled plasma (ICP). Two cities, Tehran and Tabriz, were selected for assessing the current waste management condition of CFLs. The study found that waste generation amount of CFLs in the country was about 159.80, 183.82 and 153.75 million per year in 2010, 2011 and 2012, respectively. Waste generation rate of CFLs in Iran was determined to be 2.05 per person in 2012. The average amount of mercury, lead, nickel, arsenic and chromium was 0.417, 2.33, 0.064, 0.056 and 0.012 mg per lamp, respectively. Currently, waste of CFLs is disposed by municipal waste stream in waste landfills. For improving the current conditions, we propose by considering the successful experience of extended producer responsibility (EPR) in other electronic waste management. The EPR program with advanced recycling fee (ARF) is implemented for collecting and then recycling CFLs. For encouraging consumers to take the spent CFLs back at the end of the products’ useful life, a proportion of

  7. Seed-mediated growth of palladium nanocrystals: the effect of pseudo-halide thiocyanate ions.

    PubMed

    Zhang, Ling; Niu, Wenxin; Xu, Guobao

    2011-02-01

    In synthesis in a solution phase, adsorbates such as halides can interact selectively with different metal crystal facets and affect the final morphology of nanocrystals. Pseudo-halide thiocyanate ions (SCN-) can also adsorb on the metal surface, but they have never been used for the synthesis of shape-controlled colloidal metal nanocrystals. In this study, we first investigated the effect of SCN- on the morphology of palladium nanocrystals through a seed-mediated growth method. The presence of 1 µM SCN- in the growth solutions could lead to the formation of palladium polyhedra: truncated rhombic dodecahedra enclosed by twelve {110}, eight {111} and six {100} facets. The products were nanocubes enclosed with six {100} facets if cetyltrimethylammonium bromide (CTAB) was the only capping agent. Meanwhile, the mechanism of the effect of SCN- on the morphology of Pd nanocrystals is discussed. PMID:21170425

  8. The Remarkable Reactivity of Aryl Halides with Nucleophiles

    ERIC Educational Resources Information Center

    Bunnett, Joseph F.

    1974-01-01

    Discusses the reactivity of aryl halides with nucleophilic or basic reagents, including nucleophilic attacks on carbon, hydrogen, halogen, and arynes. Suggestions are made concerning revisions of the sections on aryl halide chemistry courses and the corresponding chapters in textbooks. (CC)

  9. Shallow halogen vacancies in halide optoelectronic materials

    SciTech Connect

    Shi, Hongliang; Du, Mao -Hua

    2014-11-05

    Halogen vacancies (VH) are usually deep color centers (F centers) in halides and can act as major electron traps or recombination centers. The deep VH contributes to the typically poor carrier transport properties in halides. However, several halides have recently emerged as excellent optoelectronic materials, e.g., CH3NH3PbI3 and TlBr. Both CH3NH3PbI3 and TlBr have been found to have shallow VH, in contrast to commonly seen deep VH in halides. In this paper, several halide optoelectronic materials, i.e., CH3NH3PbI3, CH3NH3SnI3 (photovoltaic materials), TlBr, and CsPbBr3, (gamma-ray detection materials) are studied to understand the material chemistry and structure that determine whether VH is a shallow or deep defect in a halide material. It is found that crystal structure and chemistry of ns2 ions both play important roles in creating shallow VH in halides such as CH3NH3PbI3, CH3NH3SnI3, and TlBr. The key to identifying halides with shallow VH is to find the right crystal structures and compounds that suppress cation orbital hybridization at VH, such as those with long cation-cation distances and low anion coordination numbers, and those with crystal symmetry that prevents strong hybridization of cation dangling bond orbitals at VH. Furthermore, the results of this paper provide insight and guidance to identifying halides with shallow VH as good electronic and optoelectronic materials.

  10. Treatability study for removal of leachable mercury in crushed fluorescent lamps

    SciTech Connect

    Bostick, W.D.; Beck, D.E.; Bowser, K.T.

    1996-02-01

    Nonserviceable fluorescent lamps removed from radiological control areas at the Oak Ridge Department of Energy facilities have been crushed and are currently managed as mixed waste (hazardous and radiologically contaminated). We present proposed treatment flowsheets and supporting treatability study data for conditioning this solid waste residue so that it can qualify for disposal in a sanitary landfill. Mercury in spent fluorescent lamps occurs primarily as condensate on high-surface-area phosphor material. It can be solubilized with excess oxidants (e.g., hypochlorite solution) and stabilized by complexation with halide ions. Soluble mercury in dechlorinated saline solution is effectively removed by cementation with zero-valent iron in the form of steel wool. In packed column dynamic flow testing, soluble mercury was reduced to mercury metal and insoluble calomel, loading > 1.2 g of mercury per grain of steel wool before an appreciable breakthrough of soluble mercury in the effluent.

  11. Interactions between fluorescence of atomically layered graphene oxide and metallic nanoparticles

    NASA Astrophysics Data System (ADS)

    Wang, Yu; Li, Shao-Sian; Yeh, Yun-Chieh; Yu, Chen-Chieh; Chen, Hsuen-Li; Li, Feng-Chieh; Chang, Yu-Ming; Chen, Chun-Wei

    2013-01-01

    Graphene oxide (GO) demonstrates interesting photoluminescence (PL) because of its unique heterogeneous atomic structure, which consists of variable sp2- and sp3-bonded carbons. In this study, we report the interaction between the luminescence of GO ranging from a single atomic layer to few-layered thin films and localized surface plasmon resonance (LSPR) from silver nanoparticles (Ag NPs). The photoluminescence of GO in the vicinity of the Ag NPs is enhanced significantly due to the near-field plasmonic effect by coupling electron-hole pairs of GO with oscillating electrons in Ag NPs, leading to an increased PL intensity and a decreased PL decay lifetime. The maxima 30-fold enhancement in PL intensity is obtained with an optimized film thickness of GO, and the luminescence image from a single atomic layer GO sheet is successfully observed with the assistance of the LSPR effect. The results provide an ideal platform for exploring the interactions between the fluorescence of two-dimensional layered materials and the LSPR effect.Graphene oxide (GO) demonstrates interesting photoluminescence (PL) because of its unique heterogeneous atomic structure, which consists of variable sp2- and sp3-bonded carbons. In this study, we report the interaction between the luminescence of GO ranging from a single atomic layer to few-layered thin films and localized surface plasmon resonance (LSPR) from silver nanoparticles (Ag NPs). The photoluminescence of GO in the vicinity of the Ag NPs is enhanced significantly due to the near-field plasmonic effect by coupling electron-hole pairs of GO with oscillating electrons in Ag NPs, leading to an increased PL intensity and a decreased PL decay lifetime. The maxima 30-fold enhancement in PL intensity is obtained with an optimized film thickness of GO, and the luminescence image from a single atomic layer GO sheet is successfully observed with the assistance of the LSPR effect. The results provide an ideal platform for exploring the

  12. Characterization of quaternary metal oxide films by synchrotron x-ray fluorescence microprobe

    SciTech Connect

    Perry, D.L.; Thompson, A.C.; Russo, R.E.

    1997-04-01

    A high demand for thin films in industrial technology has been responsible for the creation of new techniques for the fabrication of such films. One highly effective method for the syntheses of variable composition thin films is pulsed-laser deposition (PLD). The technique has a large number of characteristics which make it an attractive approach for making films. It offers rapid deposition rates, congruent material transfer, simple target requirements from which to make the films, in situ multilayer deposition, and no gas composition or pressure requirements. Additionally, the technique can also afford crystalline films and films with novel structures. Pulsed-laser deposition can be used to make films of semiconductors, insulators, high-temperature superconductors, diamond-like films, and piezoelectric materials. Quaternary metal oxides involving calcium, nickel, and potassium have been shown to be quite effective in the catalysis of coal gasification and methane coupling. One approach to incorporating all three of the metal oxides into one phase is the use of laser ablation to prepare films of the catalysts so that they may be used for coatings, smooth surfaces on which to conduct detailed studies of gas-solid interface reactions that are involved in catalytic processes, and other applications. The problem of dissimilar boiling points of the three metal oxides system is overcome, since the laser ablation process effects the volatilization of all three components from the laser target essentially simultaneously. There is strong interest in gaining an understanding of the chemical and morphological aspects of the films that are deposited. Phenomena such as lattice defects and chemical heterogeneity are of interest. The experimental data discussed here are restricted to the matrix homogeneity of the films themselves for films which were void of microparticles.

  13. X-ray fluorescence analysis of low concentrations metals in geological samples and technological products

    NASA Astrophysics Data System (ADS)

    Lagoida, I. A.; Trushin, A. V.

    2016-02-01

    For the past several years many nuclear physics methods of quantitative elemental analysis have been designed. Many of these methods have applied in different devices which have become useful and effective instrument in many industrial laboratories. Methods of a matter structure analysis are based on the intensity detection of the X-ray radiation from the nuclei of elements which are excited by external X-ray source. The production of characteristic X-rays involves transitions of the orbital electrons of atoms in the target material between allowed orbits, or energy states, associated with ionization of the inner atomic shells. One of these methods is X-ray fluorescence analysis, which is widespread in metallurgical and processing industries and is used to identify and measure the concentration of the elements in ores and minerals on a conveyor belt. Samples of copper ore with known concentrations of elements, were taken from the Ural deposit. To excite the characteristic X-rays radionuclide sources 109Cd, with half-life 461.4 days were used. After finding the calibration coefficients, control measurements of samples and averaging of overall samples were made. The measurement error did not exceed 3%.

  14. Interactions between fluorescence of atomically layered graphene oxide and metallic nanoparticles.

    PubMed

    Wang, Yu; Li, Shao-Sian; Yeh, Yun-Chieh; Yu, Chen-Chieh; Chen, Hsuen-Li; Li, Feng-Chieh; Chang, Yu-Ming; Chen, Chun-Wei

    2013-02-21

    Graphene oxide (GO) demonstrates interesting photoluminescence (PL) because of its unique heterogeneous atomic structure, which consists of variable sp(2)- and sp(3)-bonded carbons. In this study, we report the interaction between the luminescence of GO ranging from a single atomic layer to few-layered thin films and localized surface plasmon resonance (LSPR) from silver nanoparticles (Ag NPs). The photoluminescence of GO in the vicinity of the Ag NPs is enhanced significantly due to the near-field plasmonic effect by coupling electron-hole pairs of GO with oscillating electrons in Ag NPs, leading to an increased PL intensity and a decreased PL decay lifetime. The maxima 30-fold enhancement in PL intensity is obtained with an optimized film thickness of GO, and the luminescence image from a single atomic layer GO sheet is successfully observed with the assistance of the LSPR effect. The results provide an ideal platform for exploring the interactions between the fluorescence of two-dimensional layered materials and the LSPR effect. PMID:23340692

  15. X-ray Fluorescence Spectroscopy Study of Coating Thickness and Base Metal Composition

    NASA Technical Reports Server (NTRS)

    Rolin, T. D.; Leszczuk, Y.

    2008-01-01

    For electrical, electronic, and electromechanical (EEE) parts to be approved for space use, they must be able to meet safety standards approved by NASA. A fast, reliable, and precise method is needed to make sure these standards are met. Many EEE parts are coated in gold (Au) and nickel (Ni), and the thickness coating is crucial to a part s performance. A nondestructive method that is efficient in measuring coating thickness is x-ray fluorescence (XRF) spectroscopy. The XRF spectrometer is a machine designed to measure layer thickness and composition of single or multilayered samples. By understanding the limitations in the collection of the data by this method, accurate composition and thickness measurements can be obtained for samples with Au and Ni coatings. To understand the limitations of data found, measurements were taken with the XRF spectrometer and compared to true values of standard reference materials (SRM) that were National Institute of Standards and Technology (NIST) traceable. For every sample, six different parameters were varied to understand measurement error: coating/substrate combination, number of layers, counting interval, collimator size, coating thickness, and test area location. Each measurement was taken in accordance with standards set by the American Society for Testing and Materials (ASTM) International Standard B 568.

  16. Seed-mediated growth of palladium nanocrystals: The effect of pseudo-halide thiocyanate ions

    NASA Astrophysics Data System (ADS)

    Zhang, Ling; Niu, Wenxin; Xu, Guobao

    2011-02-01

    In synthesis in a solution phase, adsorbates such as halides can interact selectively with different metal crystal facets and affect the final morphology of nanocrystals. Pseudo-halide thiocyanate ions (SCN-) can also adsorb on the metal surface, but they have never been used for the synthesis of shape-controlled colloidal metal nanocrystals. In this study, we first investigated the effect of SCN- on the morphology of palladium nanocrystals through a seed-mediated growth method. The presence of 1 µM SCN- in the growth solutions could lead to the formation of palladium polyhedra: truncated rhombic dodecahedra enclosed by twelve {110}, eight {111} and six {100} facets. The products were nanocubes enclosed with six {100} facets if cetyltrimethylammonium bromide (CTAB) was the only capping agent. Meanwhile, the mechanism of the effect of SCN- on the morphology of Pd nanocrystals is discussed.In synthesis in a solution phase, adsorbates such as halides can interact selectively with different metal crystal facets and affect the final morphology of nanocrystals. Pseudo-halide thiocyanate ions (SCN-) can also adsorb on the metal surface, but they have never been used for the synthesis of shape-controlled colloidal metal nanocrystals. In this study, we first investigated the effect of SCN- on the morphology of palladium nanocrystals through a seed-mediated growth method. The presence of 1 µM SCN- in the growth solutions could lead to the formation of palladium polyhedra: truncated rhombic dodecahedra enclosed by twelve {110}, eight {111} and six {100} facets. The products were nanocubes enclosed with six {100} facets if cetyltrimethylammonium bromide (CTAB) was the only capping agent. Meanwhile, the mechanism of the effect of SCN- on the morphology of Pd nanocrystals is discussed. Electronic supplementary information (ESI) available: Additional SEM, TEM and XRD data. See DOI: 10.1039/c0nr00622j

  17. Fluorescent probes for tracking the transfer of iron-sulfur cluster and other metal cofactors in biosynthetic reaction pathways.

    PubMed

    Vranish, James N; Russell, William K; Yu, Lusa E; Cox, Rachael M; Russell, David H; Barondeau, David P

    2015-01-14

    Iron-sulfur (Fe-S) clusters are protein cofactors that are constructed and delivered to target proteins by elaborate biosynthetic machinery. Mechanistic insights into these processes have been limited by the lack of sensitive probes for tracking Fe-S cluster synthesis and transfer reactions. Here we present fusion protein- and intein-based fluorescent labeling strategies that can probe Fe-S cluster binding. The fluorescence is sensitive to different cluster types ([2Fe-2S] and [4Fe-4S] clusters), ligand environments ([2Fe-2S] clusters on Rieske, ferredoxin (Fdx), and glutaredoxin), and cluster oxidation states. The power of this approach is highlighted with an extreme example in which the kinetics of Fe-S cluster transfer reactions are monitored between two Fdx molecules that have identical Fe-S spectroscopic properties. This exchange reaction between labeled and unlabeled Fdx is catalyzed by dithiothreitol (DTT), a result that was confirmed by mass spectrometry. DTT likely functions in a ligand substitution reaction that generates a [2Fe-2S]-DTT species, which can transfer the cluster to either labeled or unlabeled Fdx. The ability to monitor this challenging cluster exchange reaction indicates that real-time Fe-S cluster incorporation can be tracked for a specific labeled protein in multicomponent assays that include several unlabeled Fe-S binding proteins or other chromophores. Such advanced kinetic experiments are required to untangle the intricate networks of transfer pathways and the factors affecting flux through branch points. High sensitivity and suitability with high-throughput methodology are additional benefits of this approach. We anticipate that this cluster detection methodology will transform the study of Fe-S cluster pathways and potentially other metal cofactor biosynthetic pathways. PMID:25478817

  18. Green light-emitting polyepinephrine-based fluorescent organic dots and its application in intracellular metal ions sensing.

    PubMed

    Gao, Zhong Feng; Li, Ting Ting; Xu, Xiao Lei; Liu, Yi Yao; Luo, Hong Qun; Li, Nian Bing

    2016-09-15

    In this paper, we present a class of bio-dots, polyepinephrine (PEP)-based fluorescent organic dots (PEP-FODs) for selective and sensitive detection of Fe(2+), Fe(3+), and Cu(2+). The PEP-FODs were derived from epinephrine via self-polymerization at relatively low temperature down to 60°C with low cytotoxicity and relative long lifetime (7.24ns). The surface morphology and optical properties of the synthesized PEP-FODs were characterized. We found that the diameters of PEP-FODs were mainly distributed in the narrow range of 2-4nm with an average diameter of 2.9nm. An optimal emission peak located at 490nm was observed when the green light-emitting PEP-FODs were excited at 400nm. It is discovered that Fe(2+), Fe(3+), and Cu(2+)can strongly quench the fluorescence of PEP-FODs through the nonradiative electron-transfer. The detection limit of 0.16, 0.67, and 0.15μM was obtained for Fe(2+), Fe(3+), and Cu(2+), respectively. The independent sensing platform of Fe(2+), Fe(3+), and Cu(2+)could be established by using NaF as a complexing agent and by regulating the reaction time between NaF and metal ions. Cell viability studies reveal that the as-prepared PEP-FODs possess good solubility and biocompatibility, making it as excellent imaging nanoprobes for intracellular Fe(2+), Fe(3+), and Cu(2+)sensing. The developed PEP-FODs might hold great promise to broaden applications in nanotechnology and bioanalysis. PMID:27108256

  19. 40 CFR 721.575 - Substituted alkyl halide.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Substituted alkyl halide. 721.575... Substances § 721.575 Substituted alkyl halide. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as substituted alkyl halide (PMN P-83-1222)...

  20. Tetrazine chromophore-based metal-organic frameworks with unusual configurations: synthetic, structural, theoretical, fluorescent, and nonlinear optical studies.

    PubMed

    Li, Jianghua; Jia, Ding; Meng, Suci; Zhang, Jinfang; Cifuentes, Marie P; Humphrey, Mark G; Zhang, Chi

    2015-05-18

    Three unusual three-dimensional (3D) tetrazine chromophore-based metal-organic frameworks (MOFs) {(Et4 N)[WS4 Cu3 (CN)2 (4,4'-pytz)0.5 ]}n (1), {[MoS4 Cu4 (CN)2 (4,4'-pytz)2 ]⋅CH2 Cl2 }n (2), and {[WS4 Cu3 (4,4'-pytz)3 ]⋅[N(CN)2 ]}n (3; 4,4'-pytz=3,6-bis(4-pyridyl)tetrazine) have been synthesized and characterized by using FTIR and UV/Vis spectroscopy, elemental analysis, powder X-ray diffraction, gel permeation chromatography, steady-state fluorescence, and thermogravimetric analysis; their identities were confirmed by single-crystal X-ray diffraction studies. MOF 1 possesses the first five-connected M/S/Cu (M=Mo, W) framework with an unusual 3D (4(4) ⋅6(6) ) topology constructed from T-shaped [WS4 Cu3 ](+) clusters as nodes and single CN(-) /4,4'-pytz bridges as linkers. MOF 2 features a novel 3D MOF structure with (4(20) ⋅6(8) ) topology, in which the bridging 4,4'-pytz ligands exhibit unique distorted arch structures. MOF 3 displays the first 3D MOF structure based on flywheel-shaped [WS4 Cu3 ](+) clusters with a non-interpenetrating honeycomb-like framework and a heavily distorted "ACS" topology. Steady-state fluorescence studies of 1-3 reveal significant fluorescence emissions. The nonlinear optical (NLO) properties of 1-3 were investigated by using a Z-scan technique with 5 ns pulses at λ=532 nm. The Z-scan experimental results show that the π-delocalizable tetrazine-based 4,4'-pytz ligands contribute to the strong third-order NLO properties exhibited by 1-3. Time-dependent density functional theory studies afforded insight into the electronic transitions and spectral characterization of these functionalized NLO molecular materials. PMID:25877804

  1. Development of a flow injection analysis (FIA) system for the measurement of heavy metals using a fiber optic chemical sensor based on laser-induced fluorescence

    NASA Astrophysics Data System (ADS)

    Zhang, Jingdong; Prestel, Harald; Gahr, Achim; Niessner, Reinhard

    2000-05-01

    The development of a fiber optic sensor system is described, for the on-line detection of heavy metal ions in water. This is based on laser-induced fluorescence spectroscopy of suitable metal-ligand complexes. The sensor system is designed to measure heavy metal ions in the field. Flow injection analysis (FIA) is coupled with the sensor system, to overcome problems of a slow diffusion rate of heavy metals through the membrane of an in situ sensor head. Preliminary experiments show the new FIA system has good reproducibility, a high sample analysis rate and it can measure heavy metal ions (Cu(II), Ni(II), Cd(II) and Zn(II)) at the ppb level, when using the appropriate ligands.

  2. Synthesis, characterization and in vitro antimicrobial activity of a new blue fluorescent Cu(II) metal complex of bis-1,8-naphthalimide

    NASA Astrophysics Data System (ADS)

    Yordanova, Stanislava; Temiz, Havva Tümay; Boyaci, Ismail Hakki; Stoyanov, Stanimir; Vasileva-Tonkova, Evgenia; Asiri, Abdullah; Grabchev, Ivo

    2015-12-01

    A new blue fluorescent copper complex of bis-(4-N,N-dimetylaminoethoxy-N-ethyl-1,8- naphthalimidyl) amine has been synthesized and characterized by FT-IR, Raman and Surface enhanced Raman spectroscopy (SERS). Absorption and fluorescence spectral characteristics have been also used for the characterization of the copper complex. The antibacterial and antifungal activities of the new complex have been investigated and the minimum inhibitory concentrations have been determined. The metal complex has a good antibacterial and antifungal potential suggesting its prospective application in biomedicine for designing new effective antimicrobial preparations.

  3. Two-Dimensional Halide Perovskites: Tuning Electronic Activities of Defects.

    PubMed

    Liu, Yuanyue; Xiao, Hai; Goddard, William A

    2016-05-11

    Two-dimensional (2D) halide perovskites are emerging as promising candidates for nanoelectronics and optoelectronics. To realize their full potential, it is important to understand the role of those defects that can strongly impact material properties. In contrast to other popular 2D semiconductors (e.g., transition metal dichalcogenides MX2) for which defects typically induce harmful traps, we show that the electronic activities of defects in 2D perovskites are significantly tunable. For example, even with a fixed lattice orientation one can change the synthesis conditions to convert a line defect (edge or grain boundary) from electron acceptor to inactive site without deep gap states. We show that this difference originates from the enhanced ionic bonding in these perovskites compared with MX2. The donors tend to have high formation energies and the harmful defects are difficult to form at a low halide chemical potential. Thus, we unveil unique properties of defects in 2D perovskites and suggest practical routes to improve them. PMID:27100910

  4. Two-Dimensional Halide Perovskites: Tuning Electronic Activities of Defects

    NASA Astrophysics Data System (ADS)

    Liu, Yuanyue; Xiao, Hai; Goddard, William A., III

    2016-05-01

    Two-dimensional (2D) halide perovskites are emerging as promising candidates for nano-electronics and optoelectronics. To realize their full potential, it is important to understand the role of those defects that can strongly impact material properties. In contrast to other popular 2D semiconductors (e.g. transition metal dichalcogenides MX2) for which defects typically induce harmful traps, we show that the electronic activities of defects in 2D perovskites are significantly tunable. For example, even with a fixed lattice orientation, one can change the synthesis conditions to convert a line defect (edge or grain boundary) from electron acceptor to inactive site without deep gap states. We show that this difference originates from the enhanced ionic bonding in these perovskites compared with MX2. The donors tend to have high formation energies, and the harmful defects are difficult to form at a low halide chemical potential. Thus we unveil unique properties of defects in 2D perovskites and suggest practical routes to improve them.

  5. PROCESS OF PRODUCING ACTINIDE METALS

    DOEpatents

    Magel, T.T.

    1959-07-14

    The preparation of actinide metals in workable, coherent form is described. In general, the objects of the invention are achieved by heating a mixture of an oxide and a halide of an actinide metal such as uranium with an alkali metal on alkaline earth metal reducing agent in the presence of iodine.

  6. Graphene oxide and metal-mediated base pairs based "molecular beacon" integrating with exonuclease I for fluorescence turn-on detection of biothiols.

    PubMed

    Xing, Xiaojing; Zhou, Ying; Liu, Xueguo; Pang, Daiwen; Tang, Hongwu

    2014-08-27

    A novel fluorescence turn-on strategy, based on the resistance of metal-mediated molecular-beacons (MBs) toward nuclease digestion and the remarkable difference in the affinity of graphene oxide (GO) with MBs and the mononucleotides, is designed for the biothiols assay. Specifically, the metal-mediated base pairs facilitate the dye labeled MBs to fold into a hairpin structure preventing the digestion by exonuclease I, and thus allow the fluorescence quenching. The competition binding by biothiols removes metal ions from the base pairs, causing the nuclease reaction, and less decrease in the fluorescence is obtained after incubating with GO due to the weak affinity of the product-mononucleotides to GO. Hg(2+)-mediated MBs were firstly designed for the biothiols detection, and glutathione (GSH) was applied as the model target. Under the optimal conditions, the approach exhibits high sensitivity to GSH with a detection limit of 1.53 nM. Ag(+)-mediated MBs based sensor was also constructed to demonstrate its versatility, and cysteine was studied as the model target. The satisfactory results in the determination of biothiols in serum demonstrate that the method possesses great potential for detecting thiols in biological fluids. This new approach is expected to promote the exploitation of metal-mediated base pairs-based biosensors in biochemical and biomedical studies. PMID:24788855

  7. A fluorescent paramagnetic Mn metal-organic framework based on semi-rigid pyrene tetra-carboxylic acid: sensing of solvent polarity and explosive nitroaromatics.

    PubMed

    Bajpai, Alankriti; Mukhopadhyay, Arindam; Krishna, Manchugondanahalli Shivakumar; Govardhan, Savitha; Moorthy, Jarugu Narasimha

    2015-09-01

    An Mn metal-organic framework (Mn-MOF), Mn-L, based on a pyrene-tetraacid linker (H4 L), displays a respectable fluorescence quantum yield of 8.3% in spite of the presence of the paramagnetic metal ions, due presumably to fixation of the metal ions in geometries that do not allow complete energy/charge-transfer quenching. Remarkably, the porous Mn-L MOF with ∼25% solvent-accessible volume exhibits a heretofore unprecedented solvent-dependent fluorescence emission maximum, permitting its use as a probe of solvent polarity; the emission maxima in different solvents correlate excellently with Reichardt's solvent polarity parameter (E T (N)). Further, the applicability of Mn-L to the sensing of nitroaromatics via fluorescence quenching is demonstrated; the detection limit for TNT is shown to be 125 p.p.m. The results bring out the fact that MOFs based on paramagnetic metal ions can indeed find application when the quenching mechanisms are attenuated by certain geometries of the organic linkers of the MOF. PMID:26306197

  8. Determining heavy metals in spent compact fluorescent lamps (CFLs) and their waste management challenges: some strategies for improving current conditions.

    PubMed

    Taghipour, Hassan; Amjad, Zahra; Jafarabadi, Mohamad Asghari; Gholampour, Akbar; Norouz, Prviz

    2014-07-01

    From environmental viewpoint, the most important advantage of compact fluorescent lamps (CFLs) is reduction of green house gas emissions. But their significant disadvantage is disposal of spent lamps because of containing a few milligrams of toxic metals, especially mercury and lead. For a successful implementation of any waste management plan, availability of sufficient and accurate information on quantities and compositions of the generated waste and current management conditions is a fundamental prerequisite. In this study, CFLs were selected among 20 different brands in Iran. Content of heavy metals including mercury, lead, nickel, arsenic and chromium was determined by inductive coupled plasma (ICP). Two cities, Tehran and Tabriz, were selected for assessing the current waste management condition of CFLs. The study found that waste generation amount of CFLs in the country was about 159.80, 183.82 and 153.75 million per year in 2010, 2011 and 2012, respectively. Waste generation rate of CFLs in Iran was determined to be 2.05 per person in 2012. The average amount of mercury, lead, nickel, arsenic and chromium was 0.417, 2.33, 0.064, 0.056 and 0.012 mg per lamp, respectively. Currently, waste of CFLs is disposed by municipal waste stream in waste landfills. For improving the current conditions, we propose by considering the successful experience of extended producer responsibility (EPR) in other electronic waste management. The EPR program with advanced recycling fee (ARF) is implemented for collecting and then recycling CFLs. For encouraging consumers to take the spent CFLs back at the end of the products' useful life, a proportion of ARF (for example, 50%) can be refunded. On the other hand, the government and Environmental Protection Agency should support and encourage recycling companies of CFLs both technically and financially in the first place. PMID:24726659

  9. Multielemental analysis of dried residue from metal-bearing waters by wavelength dispersive X-ray fluorescence spectrometry

    NASA Astrophysics Data System (ADS)

    Gonzalez-Fernandez, Oscar; Margui, Eva; Queralt, Ignacio

    2009-02-01

    The purpose of this work was evaluation of instrumental sensitivity and detection limits for determination of elemental composition (20 different elements ranging from Na to Pb) of liquid mining samples by using conventional Wavelength Dispersive X-Ray Fluorescence (WDXRF) instrumentation. Preconcentration of elements from liquid samples was performed by means of a simple dried residue process, and spectral evaluation was carried out by integration of the peak area (using WinQXAS/AXIL package software, International Atomic Energy Agency (IAEA)) instead of the common net peak line intensity traditionally used in conventional WDXRF systems. With the proposed methodology, the calculated detection limits were in the µg L - 1 range (from 0.005 to 0.1 mg L - 1 level depending on the element) in all cases, which is suitable for element determination in most liquid samples involved in environmental studies such as metal mining liquid effluents. The detection limits are also below the established limits of the TCLP 1311 (United States Environmental Protection Agency (US-EPA)) and DIN 38414-S4 (German Standard legislation) procedures, which are commonly used to evaluate the leaching of metals from landfill disposal. Accuracy of the procedure was confirmed by analysis, based on the German Standard Method DIN 3814-S4, of water lixiviates from three overbank sediment samples collected in two abandoned mining areas. The attained results were compared with those obtained by inductively coupled plasma (ICP) techniques, and acceptable agreement for elements with Z > 20 was found. This study highlights the possibility of using a simple methodology for analysis of liquid mining samples using the WDXRF technique, commonly employed for geochemical exploration of solid samples in environmental studies.

  10. Combined use of hard X-ray phase contrast imaging and X-ray fluorescence microscopy for sub-cellular metal quantification.

    PubMed

    Kosior, Ewelina; Bohic, Sylvain; Suhonen, Heikki; Ortega, Richard; Devès, Guillaume; Carmona, Asuncion; Marchi, Florence; Guillet, Jean Francois; Cloetens, Peter

    2012-02-01

    Hard X-ray fluorescence microscopy and magnified phase contrast imaging are combined to obtain quantitative maps of the projected metal concentration in whole cells. The experiments were performed on freeze dried cells at the nano-imaging station ID22NI of the European Synchrotron Radiation Facility (ESRF). X-ray fluorescence analysis gives the areal mass of most major, minor and trace elements; it is validated using a biological standard of known composition. Quantitative phase contrast imaging provides maps of the projected mass and is validated using calibration samples and through comparison with Atomic Force Microscopy and Scanning Transmission Ion Microscopy. Up to now, absolute quantification at the sub-cellular level was impossible using X-ray fluorescence microscopy but can be reached with the use of the proposed approach. PMID:22182730

  11. Potential environmental impacts from the metals in incandescent, compact fluorescent lamp (CFL), and light-emitting diode (LED) bulbs.

    PubMed

    Lim, Seong-Rin; Kang, Daniel; Ogunseitan, Oladele A; Schoenung, Julie M

    2013-01-15

    Artificial lighting systems are transitioning from incandescent to compact fluorescent lamp (CFL) and light-emitting diode (LED) bulbs in response to the U.S. Energy Independence and Security Act and the EU Ecodesign Directive, which leads to energy savings and reduced greenhouse gas emissions. Although CFLs and LEDs are more energy-efficient than incandescent bulbs, they require more metal-containing components. There is uncertainty about the potential environmental impacts of these components and whether special provisions must be made for their disposal at the end of useful life. Therefore, the objective of this study is to analyze the resource depletion and toxicity potentials from the metals in incandescent, CFL, and LED bulbs to complement the development of sustainable energy policy. We assessed the potentials by examining whether the lighting products are to be categorized as hazardous waste under existing U.S. federal and California state regulations and by applying life cycle impact-based and hazard-based assessment methods (note that "life cycle impact-based method" does not mean a general life cycle assessment (LCA) but rather the elements in LCA used to quantify toxicity potentials). We discovered that both CFL and LED bulbs are categorized as hazardous, due to excessive levels of lead (Pb) leachability (132 and 44 mg/L, respectively; regulatory limit: 5) and the high contents of copper (111,000 and 31,600 mg/kg, respectively; limit: 2500), lead (3860 mg/kg for the CFL bulb; limit: 1000), and zinc (34,500 mg/kg for the CFL bulb; limit: 5000), while the incandescent bulb is not hazardous (note that the results for CFL bulbs excluded mercury vapor not captured during sample preparation). The CFLs and LEDs have higher resource depletion and toxicity potentials than the incandescent bulb due primarily to their high aluminum, copper, gold, lead, silver, and zinc. Comparing the bulbs on an equivalent quantity basis with respect to the expected lifetimes of

  12. Energetics and dynamics in organic-inorganic halide perovskite photovoltaics and light emitters.

    PubMed

    Sum, Tze Chien; Chen, Shi; Xing, Guichuan; Liu, Xinfeng; Wu, Bo

    2015-08-28

    The rapid transcendence of organic-inorganic metal halide perovskite solar cells to above the 20% efficiency mark has captivated the broad photovoltaic community. As the efficiency race continues unabated, it is essential that fundamental studies keep pace with these developments. Further gains in device efficiencies are expected to be increasingly arduous and harder to come by. The key to driving the perovskite solar cell efficiencies towards their Shockley-Queisser limit is through a clear understanding of the interfacial energetics and dynamics between perovskites and other functional materials in nanostructured- and heterojunction-type devices. In this review, we focus on the current progress in basic characterization studies to elucidate the interfacial energetics (energy-level alignment and band bending) and dynamical processes (from the ultrafast to the ultraslow) in organic-inorganic metal halide perovskite photovoltaics and light emitters. Major findings from these studies will be distilled. Open questions and scientific challenges will also be highlighted. PMID:26234397

  13. Energetics and dynamics in organic-inorganic halide perovskite photovoltaics and light emitters

    NASA Astrophysics Data System (ADS)

    Chien Sum, Tze; Chen, Shi; Xing, Guichuan; Liu, Xinfeng; Wu, Bo

    2015-08-01

    The rapid transcendence of organic-inorganic metal halide perovskite solar cells to above the 20% efficiency mark has captivated the broad photovoltaic community. As the efficiency race continues unabated, it is essential that fundamental studies keep pace with these developments. Further gains in device efficiencies are expected to be increasingly arduous and harder to come by. The key to driving the perovskite solar cell efficiencies towards their Shockley-Queisser limit is through a clear understanding of the interfacial energetics and dynamics between perovskites and other functional materials in nanostructured- and heterojunction-type devices. In this review, we focus on the current progress in basic characterization studies to elucidate the interfacial energetics (energy-level alignment and band bending) and dynamical processes (from the ultrafast to the ultraslow) in organic-inorganic metal halide perovskite photovoltaics and light emitters. Major findings from these studies will be distilled. Open questions and scientific challenges will also be highlighted.

  14. Vibration-Resistant Support for Halide Lamps

    NASA Technical Reports Server (NTRS)

    Kiss, J.

    1987-01-01

    Lamp envelope protected against breakage. Old and new mounts for halide arc lamp sealed in housing with parabolic refector and quartz window. New version supports lamp with compliant garters instead of rigid brazed joint at top and dimensionally unstable finger stock at bottom.

  15. The Additive Coloration of Alkali Halides

    ERIC Educational Resources Information Center

    Jirgal, G. H.; and others

    1969-01-01

    Describes the construction and use of an inexpensive, vacuum furnace designed to produce F-centers in alkali halide crystals by additive coloration. The method described avoids corrosion or contamination during the coloration process. Examination of the resultant crystals is discussed and several experiments using additively colored crystals are…

  16. Fluorescence quenching study of 2,6-bis(5-(4-methylphenyl)-1-H-pyrazol-3-yl)pyridine with metal ions

    NASA Astrophysics Data System (ADS)

    Liu, Hua; Li, Fang-Xiong; Pi, Yan; Wang, Dun-Jia; Hu, Yan-Jun; Zheng, Jing

    2015-06-01

    A novel bispyrazole derivative 2,6-bis(5-(4-methylphenyl)-1-H-pyrazol-3-yl)pyridine was synthesized and its structure was confirmed by 1H NMR, FTIR, MS techniques and elemental analysis. The binding interactions of BMPP with Cd2+, Co2+, Pb2+ and Cu2+ ions were investigated in MeOH-H2O solution by fluorescence quenching technique at two temperatures (25 and 35 °C). Their quenching constants KSV, binding constants K, binding sites n and thermodynamic parameters (ΔH, ΔG and ΔS) were determined. The results indicated that the metal ions quenched the intrinsic fluorescence of the bispyrazole by forming the bispyrazole-metal complexes and their quenching process was a static quenching mechanism. In addition, the process of interaction was spontaneous and mainly ΔS-driven.

  17. A microscale multi-functional metal-organic framework as a fluorescence chemosensor for Fe(III), Al(III) and 2-hydroxy-1-naphthaldehyde.

    PubMed

    Kang, Yang; Zheng, Xiang-Jun; Jin, Lin-Pei

    2016-06-01

    A microscale metal-organic framework [Eu(atpt)1.5(phen)(H2O)]n (H2atpt=2-aminoterephthalic acid, phen=1,10-phenanthroline) (Eu-MOF) was synthesized and characterized by elemental analysis, luminescence spectrum, powder X-ray diffraction, dynamic light scattering and scanning electron microscope. The fluorescence response of Eu-MOF to metal ions and aldehydes showed that Eu-MOF is highly selective to Fe(III), Al(III) and 2-hydroxy-1-naphthaldehyde (2-OH-NA). Eu-MOF could be utilized as a multi-functional fluorescence chemosensor for Fe(III), Al(III) and 2-hydroxy-1-naphthaldehyde (2-OH-NA). The detection limit of Fe(III), Al(III) and 2-OH-NA was 45, 10 and 36μM, respectively. The corresponding sensing mechanisms were explored. PMID:26967663

  18. Confocal Fluorescence Microscopy Studies of a Fluorophore-Labeled Dirhodium Compound: Visualizing Metal–Metal Bonded Molecules in Lung Cancer (A549) Cells

    PubMed Central

    2015-01-01

    The new dirhodium compound [Rh2(μ-O2CCH3)2(η1-O2CCH3)(phenbodipy)(H2O)3][O2CCH3] (1), which incorporates a bodipy fluorescent tag, was prepared and studied by confocal fluorescence microscopy in human lung adenocarcinoma (A549) cells. It was determined that 1 localizes mainly in lysosomes and mitochondria with no apparent nuclear localization in the 1–100 μM range. These results support the conclusion that cellular organelles rather than the nucleus can be targeted by modification of the ligands bound to the Rh24+ core. This is the first study of a fluorophore-labeled metal–metal bonded compound, work that opens up new venues for the study of intracellular distribution of dinuclear transition metal anticancer complexes. PMID:24854400

  19. Dimensional diversity in transition metal trihalides

    SciTech Connect

    Jianhua Lin; Miller, G.J. )

    1993-04-14

    Structural variations of the second- and third-row transition metal trihalides are rationalized via tight-binding band calculations and evaluation of Madelung energetic factors. The observed structure for a given metal halide is controlled by both the coordination geometry at the anion and the d electron configuration at the metal. As the polarizability of the halide increases, the M-X-M angle, in general, decreases so that three-dimensional frameworks occur for the fluorides, while layer and chain structures are found for the chlorides, bromides, and iodides. Within a particular halide system, systematic structural trends also occur as the d electron configuration changes. 56 refs., 23 figs., 4 tabs.

  20. Halide anion effect on surface enhanced Raman scattering of 2-amino,5-nitropyridine adsorbed on silver sols

    NASA Astrophysics Data System (ADS)

    Muniz-Miranda, Maurizio; Neto, Natale; Sbrana, Giuseppe

    1995-03-01

    2-Amino,5-nitropiridine (ANP) can be adsorbed on silver sols as neutral molecule or ANP- anion, as detected by SERS. The adsorption of the ANP- is related to the presence of hydroxide ions on the metal surface. Strongly adsorbed halide anions are able to remove hydroxide ions from the silver surface, inducing the adsorption of ANP as neutral molecule.

  1. Mapping the Microstructural Location of Salts and Metals in Sea Ice with X-Ray Micro-Fluorescence Spectroscopy

    NASA Astrophysics Data System (ADS)

    Lieb-Lappen, R.; Leonard, J.; Obbard, R. W.

    2015-12-01

    Sea ice forms a permeable boundary between the ocean and the atmosphere, mediating chemical, physical, and transport processes that can have large impacts on a changing climate. It is a complex media composed of ice, brine, air pockets, and salt precipitates whose fine microstructure is constantly evolving with time and temperature. To gain insight of the processes occurring within the sea ice, it is key to have an understanding of how the different phases interact. Using synchrotron x-ray micro-fluorescence (XRF) at Argonne National Laboratory's Advanced Photon Source (APS), we examined the microstructural location of different salts and metals in Antarctic sea ice. In particular, we sought to determine whether these elements are found solely in brine channels and at grain boundaries or exist ubiquitously throughout the crystal lattice of ice. Further, we also investigated the spatial distribution of each impurity to determine how microstructure may vary within the sea ice column. Although it is well known that salts are expelled from the ice matrix during the freezing process and the bulk of impurities lies in brine inclusions and channels, providing quantitative and visual evidence with high resolution remains an ongoing process. XRF enables us to detect and map the precise microstructural and stratigraphic location of the constituent salts in sea ice. Cores were cut into 0.5 cm-thick slices every ten cm along the length of the core. At APS, a 2 mm x 2 mm region of each sample was scanned by an 18 kV X-ray beam and the resulting fluorescence signal detected using a silicon drift detector. By integrating the detected signal for the respective characteristic energy, we were able to obtain two-dimensional elemental maps with ten micron resolution for bromide, chloride, potassium, calcium, strontium, iron, copper, and zinc. Maps were compared to thin sections obtained under cross-polarizing lenses to identify particular features. We were able to show that salts

  2. Enhanced quantum efficiency from hybrid cesium halide/copper photocathodes

    NASA Astrophysics Data System (ADS)

    Kong, Lingmei; Joly, Alan G.; Droubay, Timothy C.; Gong, Yu; Hess, Wayne P.

    2014-04-01

    The quantum efficiency (QE) of Cu is found to increase dramatically when coated by a CsI film and then irradiated by a UV laser. Over three orders of magnitude quantum efficiency enhancement at 266 nm is observed in CsI/Cu(100), indicating potential application in future photocathode devices. Upon laser irradiation, a large work function reduction to a value less than 2 eV is also observed, significantly greater than for similarly treated CsBr/Cu(100). The initial QE enhancement, prior to laser irradiation, is attributed to interface interaction and the intrinsic properties of the Cs halide film. Further QE enhancement following activation is attributed to formation of inter-band states and Cs metal accumulation at the interface induced by laser irradiation.

  3. Enhanced Quantum Efficiency From Hybrid Cesium Halide/Copper Photocathode

    SciTech Connect

    Kong, Lingmei; Joly, Alan G.; Droubay, Timothy C.; Gong, Yu; Hess, Wayne P.

    2014-04-28

    The quantum efficiency of Cu is found to increase dramatically when coated by a CsI film and then irradiated by a UV laser. Over three orders of magnitude quantum efficiency enhancement at 266 nm is observed in CsI/Cu(100), indicating potential application in future photocathode devices. Upon laser irradiation, a large work function reduction to a value less than 2 eV is also observed, significantly greater than for similarly treated CsBr/Cu(100). The initial QE enhancement, prior to laser irradiation, is attributed to interface interaction, surface cleanliness and the intrinsic properties of the Cs halide film. Further QE enhancement following activation is attributed to formation of inter-band states and Cs metal accumulation at the interface induced by laser irradiation.

  4. Large Magnetoresistance Effects in Novel Layered Rare Earth Halides

    NASA Astrophysics Data System (ADS)

    Kremer, R. K.; Ryazanov, M.; Simon, A.

    We give a survey of the structures, electric, magnetic and magnetoresistance properties of the two novel low dimensional rare-earth halide systems, GdI2 and GdIHy (2/3 < y ≤ 1). The large magnetoresistance e.ect observed for GdI2 can be understood on the basis of a conventional spin disorder scattering mechanism, however, strongly magni.ed by the structural anisotropy and the special topology of the Fermi surface. Bound magnetic polarons are formed in GdIHy leading to a metal insulator transition below ~ 30 K. The mobility of the magnetic polarons can be e.ectively modi.ed by external magnetic .fields resulting in the large experimentally found magnetoresistance.

  5. Enhanced quantum efficiency from hybrid cesium halide/copper photocathodes

    SciTech Connect

    Kong, Lingmei; Joly, Alan G.; Droubay, Timothy C.; Gong, Yu; Hess, Wayne P.

    2014-04-28

    The quantum efficiency (QE) of Cu is found to increase dramatically when coated by a CsI film and then irradiated by a UV laser. Over three orders of magnitude quantum efficiency enhancement at 266 nm is observed in CsI/Cu(100), indicating potential application in future photocathode devices. Upon laser irradiation, a large work function reduction to a value less than 2 eV is also observed, significantly greater than for similarly treated CsBr/Cu(100). The initial QE enhancement, prior to laser irradiation, is attributed to interface interaction and the intrinsic properties of the Cs halide film. Further QE enhancement following activation is attributed to formation of inter-band states and Cs metal accumulation at the interface induced by laser irradiation.

  6. Ionic alkali halide XUV laser feasibility study

    SciTech Connect

    Yang, T.T.; Gylys, V.T.; Bower, R.D.; Harris, D.G.; Blauer, J.A.; Turner, C.E.; Hindy, R.N.

    1989-11-10

    The objective of this work is to assess the feasibility of a select set of ionic alkali halide XUV laser concepts by obtaining the relevant kinetic and spectroscopic parameters required for a proof-of-principle and conceptual design. The proposed lasers operate in the 80--200 nm spectral region and do not require input from outside radiation sources for their operation. Frequency up-conversion and frequency mixing techniques and therefore not considered in the work to be described. An experimental and theoretical study of a new type of laser operating in the extreme ultraviolet wavelength region has been conducted. The lasing species are singly ionized alkali halide molecules such as Rb{sup 2+}F{sub {minus}}, Rb{sup 2+}Br{sup {minus}} and Cs{sup 2+}F{sup {minus}}. These species are similar in electronic structure to the rare gas halide excimers, such as XeF and Krf, except that the ionic molecules emit at wavelengths of 80--200 nm, much shorter than the conventional rare-gas halide excimer laser. The radiative lifetime of these molecules are typically near 1 ns, which is about an order of magnitude shorter than that for rare-gas halide systems. The values of the cross section for stimulated emission are on the order of 1 {times} 10{sup {minus}16}cm{sup 2}. Because of the fundamental similarity to existing UV lasers, these systems show promise as a high power, efficient XUV lasers. 55 refs., 50 figs., 5 tabs.

  7. A label-free aptasensor for highly sensitive detection of ATP and thrombin based on metal-enhanced PicoGreen fluorescence.

    PubMed

    Wang, Kaiyu; Liao, Jian; Yang, Xiangyue; Zhao, Meng; Chen, Min; Yao, Weirong; Tan, Weihong; Lan, Xiaopeng

    2015-01-15

    A label-free fluorescence aptasensor for highly selective and sensitive detection of ATP and thrombin was developed by using PicoGreen (PG) as signal molecule and surface-bound metal-enhanced fluorescence (MEF) substrates (silver island films, SIFs) as signal enhancers. On binding with ATP or thrombin, aptamers undergo structure switching, leading to a reduction of fluorescence intensity of PG. Chang of fluorescence intensity can be magnified by SIFs. The limit of detection for ATP and thrombin is 1.3 nM and 0.073 nM, respectively. The fluorescence quenching efficiency is linear in the logarithmic scale with ATP concentration range from 10 nM to 100 μM (R(2)=0.995) and thrombin concentration range from 0.1 nM to 100 nM (R(2)=0.997). The coefficients of variation of the intra-assay reproducibility and inter-assay reproducibility for ATP (10 μM) assay are 3.8% and 5.2%, respectively. In addition, the aptasensor is stable and can be reliably used for ATP measurement in biological samples. Overall, the aptasensor can be a useful and cost effective tool for the specific detection of ATP, thrombin and potentially other biomolecules in biological samples. PMID:25086329

  8. Structural Characterization of Methanol Substituted Lanthanum Halides

    PubMed Central

    Boyle, Timothy J.; Ottley, Leigh Anna M.; Alam, Todd M.; Rodriguez, Mark A.; Yang, Pin; Mcintyre, Sarah K.

    2010-01-01

    The first study into the alcohol solvation of lanthanum halide [LaX3] derivatives as a means to lower the processing temperature for the production of the LaBr3 scintillators was undertaken using methanol (MeOH). Initially the de-hydration of {[La(µ-Br)(H2O)7](Br)2}2 (1) was investigated through the simple room temperature dissolution of 1 in MeOH. The mixed solvate monomeric [La(H2O)7(MeOH)2](Br)3 (2) compound was isolated where the La metal center retains its original 9-coordination through the binding of two additional MeOH solvents but necessitates the transfer of the innersphere Br to the outersphere. In an attempt to in situ dry the reaction mixture of 1 in MeOH over CaH2, crystals of [Ca(MeOH)6](Br)2 (3) were isolated. Compound 1 dissolved in MeOH at reflux temperatures led to the isolation of an unusual arrangement identified as the salt derivative {[LaBr2.75•5.25(MeOH)]+0.25 [LaBr3.25•4.75(MeOH)]−0.25} (4). The fully substituted species was ultimately isolated through the dissolution of dried LaBr3 in MeOH forming the 8-coordinated [LaBr3(MeOH)5] (5) complex. It was determined that the concentration of the crystallization solution directed the structure isolated (4 concentrated; 5 dilute) The other LaX3 derivatives were isolated as [(MeOH)4(Cl)2La(µ-Cl)]2 (6) and [La(MeOH)9](I)3•MeOH (7). Beryllium Dome XRD analysis indicated that the bulk material for 5 appear to have multiple solvated species, 6 is consistent with the single crystal, and 7 was too broad to elucidate structural aspects. Multinuclear NMR (139La) indicated that these compounds do not retain their structure in MeOD. TGA/DTA data revealed that the de-solvation temperatures of the MeOH derivatives 4 – 6 were slightly higher in comparison to their hydrated counterparts. PMID:20514349

  9. METAL SURFACE TREATMENT

    DOEpatents

    Eubank, L.D.

    1958-08-12

    Improved flux baths are described for use in conjunction with hot dipped coatings for uranium. The flux bath consists of molten alkali metal, or alkaline earth metal halides. One preferred embodiment comprises a bath containing molten KCl, NaCl, and LiCl in proportions approximating the triple eutectic.

  10. Welding, bonding, and sealing of refractory metals by vapor deposition

    NASA Technical Reports Server (NTRS)

    1967-01-01

    Plating process welds, bonds, and seals refractory metals without weakening or changing the structure of the base metals. A metal halide compound in the vapor phase is decomposed to deposit filler metal on the base metal. The resulting bond is a true metal-to-metal bond.

  11. Shedding new light on historical metal samples using micro-focused synchrotron X-ray fluorescence and spectroscopy

    NASA Astrophysics Data System (ADS)

    Grolimund, D.; Senn, M.; Trottmann, M.; Janousch, M.; Bonhoure, I.; Scheidegger, A. M.; Marcus, M.

    2004-10-01

    Synchrotron-based micro-X-ray fluorescence (micro-XRF) and micro-X-ray absorption spectroscopy (micro-XAS) were used in the present study to obtain spatially resolved micro-scale information on elemental composition, trace element distribution, chemical speciation and oxidation state and/or mineral phase distribution within historical iron artefacts dating from the Iron Age to early Medieval Times. Large area two-dimensional trace element distribution maps and oxidation state maps with micrometer spatial resolution were required to answer open archaeological questions in the context of ancient metal processing. The first set of examples was focusing on historical weapons and included two ancient iron sword blades. The micro-XRF maps revealed a distinct, highly correlated distribution pattern of trace elements such as As, Ni, Cu and Zn. Accordingly, the number of used raw materials could be determined unambiguously and key information concerning the used ancient smithing technique were gained. Further, the ability to record—in a fast manner—large area maps with high spatial resolution ('elemental screening') led to the discovery of a hitherto unknown enhanced occurrence of selected trace elements (Cu, Zn, and Au) at the blade surface. Complementary investigations by high resolution scanning electron microscopy were able to localize these trace metals within a carbon-rich matrix may be pointing towards an artifact induced during preservation. A second set of investigated artefacts is dealing with smithing waste products and related historical processing techniques and conditions. Synchrotron-based micro-XRF and micro-XAS were used to determine the structural composition as well as the spatial variation of the predominant Fe oxidation state and corresponding crystallographic phases. The study revealed the presence of distinct domains of Fe 0, Fe IIO (wustite), and α-Fe IIIOOH (goethite), separated by sharp domain boundaries. These findings help to gain new

  12. Monte Carlo simulation of source-excited in vivo x-ray fluorescence measurements of heavy metals.

    PubMed

    O'Meara, J M; Chettle, D R; McNeill, F E; Prestwich, W V; Svensson, C E

    1998-06-01

    This paper reports on the Monte Carlo simulation of in vivo x-ray fluorescence (XRF) measurements. Our model is an improvement on previously reported simulations in that it relies on a theoretical basis for modelling Compton momentum broadening as well as detector efficiency. Furthermore, this model is an accurate simulation of experimentally detected spectra when comparisons are made in absolute counts; preceding models have generally only achieved agreement with spectra normalized to unit area. Our code is sufficiently flexible to be applied to the investigation of numerous source-excited in vivo XRF systems. Thus far the simulation has been applied to the modelling of two different systems. The first application was the investigation of various aspects of a new in vivo XRF system, the measurement of uranium in bone with 57Co in a backscatter (approximately 180 degrees) geometry. The Monte Carlo simulation was critical in assessing the potential of applying XRF to the measurement of uranium in bone. Currently the Monte Carlo code is being used to evaluate a potential means of simplifying an established in vivo XRF system, the measurement of lead in bone with 57Co in a 90 degrees geometry. The results from these simulations may demonstrate that calibration procedures can be significantly simplified and subject dose may be reduced. As well as providing an excellent tool for optimizing designs of new systems and improving existing techniques, this model can be used in the investigation of the dosimetry of various XRF systems. Our simulation allows a detailed understanding of the numerous processes involved when heavy metal concentrations are measured in vivo with XRF. PMID:9651014

  13. Analyses of Heavy Metal Contents in the Bulk Atmospheric Aerosols Simultaneously Collected at Okinawa Archipelago, Japan by Using X-ray fluorescence spectrometric method (XRF)

    NASA Astrophysics Data System (ADS)

    Oshiro, Y.; ITOH, A.; Azechi, S.; Somada, Y.; Handa, D.; Miyagi, Y.; Arakaki, T.; Tanahara, A.

    2012-12-01

    We studied heavy metal contents of bulk atmospheric aerosols using an X-ray fluorescence spectrometric method (XRF). The XRF method enables us to analyze heavy metal contents in the bulk aerosols rapidly without any chemical pretreatments. We used an energy dispersive X-ray fluorescence spectrometer that is compact and portable. We prepared several different amounts of standard reference materials (referred to "SRM", NIES No.28 of Japanese National Institute of Environmental Studies) on quartz filters for calibration curves in two different methods; 1) water-insoluble materials were collected after dispersing SRM in pure water and filtered with the quartz filters ("wet method"), and 2) SRM was dispersed in air in the plastic container and the aerosols were collected by using the low-volume air sampler ("dry method"). Good linear relationships between X-ray intensity and amount of aerosols on the filter were seen in the following 9 metals; Al, K, Ti, V, Fe, Ni, Rb, Ba, and Pb (with wet method) and 12 metals; K, Ti, Fe, Ni, Rb, Ba, Pb, Sr, Ca, Mn, Zn, and Cu (with dry method). Furthermore, we evaluated quantitative responses of XRF method by comparing with the metal contents determined by inductively coupled plasma mass spectrometry (ICP-MS) and atomic absorption spectrometry (AAS) after acid-digestion. We then used XRF method to determine heavy metal contents in authentic atmospheric aerosols collected in Okinawa islands, Japan. We simultaneously collected bulk aerosol samples by using identical high-volume air samplers at 3 islands; Cape Hedo Atmospheric Aerosol Monitoring Station (CHAAMS, Okinawa island), Kume island (ca. 160 km south-west of CHAAMS), and Minami-Daitou island (ca. 320 km south-east of CHAAMS). We report and discuss spatial and temporal distribution of heavy metals determined by the XRF method in the bulk atmospheric aerosols collected at the three islands during June 2008 to June 2010, and for CHAAMS during June 2008 to October 2012.

  14. Inferring the Geometry of Fourth-Period Metallic Elements in Arabidopsis thaliana Seeds using Synchrotron-Based Multi-Angle X-ray Fluorescence Mapping

    SciTech Connect

    Young, Lester; Westcott, Neil; Christensen, Colleen; Terry, Jeff; Lydiate, Derek; Reaney, Martin

    2008-06-16

    Improving our knowledge of plant metal metabolism is facilitated by the use of analytical techniques to map the distribution of elements in tissues. One such technique is X-ray fluorescence (XRF), which has been used previously to map metal distribution in both two and three dimensions. One of the difficulties of mapping metal distribution in two dimensions is that it can be difficult to normalize for tissue thickness. When mapping metal distribution in three dimensions, the time required to collect the data can become a major constraint. In this article a compromise is suggested between two- and three-dimensional mapping using multi-angle XRF imaging. A synchrotron-based XRF microprobe was used to map the distribution of K, Ca, Mn, Fe, Ni, Cu and Zn in whole Arabidopsis thaliana seeds. Relative concentrations of each element were determined by measuring fluorescence emitted from a 10 {micro}m excitation beam at 13 keV. XRF spectra were collected from an array of points with 25 or 30 {micro}m steps. Maps were recorded at 0 and 90{sup o}, or at 0, 60 and 120{sup o} for each seed. Using these data, circular or ellipsoidal cross-sections were modelled, and from these an apparent pathlength for the excitation beam was calculated to normalize the data. Elemental distribution was mapped in seeds from ecotype Columbia-4 plants, as well as the metal accumulation mutants manganese accumulator 1 (man1) and nicotianamine synthetase (nasx). Multi-angle XRF imaging will be useful for mapping elemental distribution in plant tissues. It offers a compromise between two- and three-dimensional XRF mapping, as far as collection times, image resolution and ease of visualization. It is also complementary to other metal-mapping techniques. Mn, Fe and Cu had tissue-specific accumulation patterns. Metal accumulation patterns were different between seeds of the Col-4, man1 and nasx genotypes.

  15. Enhanced 2-5 μm emission in Ho3+/Yb3+ codoped halide modified transparent tellurite glasses

    NASA Astrophysics Data System (ADS)

    Zhang, Wenjun; Lin, Jian; Jia, Yujie; Zhang, Shuo; Zhao, Junhong; Sun, Guangyao; Ye, Song; Ren, Junjiang; Rong, Liang

    2015-01-01

    Ho3+/Yb3+ codoped TeO2-WO3-ZnO-ZnX2(X = F, Cl) glasses were prepared by melt-quenching method. The absorption spectra, transmittance spectra, X-ray diffraction (XRD) curves, Raman spectra and mid-infrared fluorescence spectra were measured, along with the Judd-Ofelt intensity parameters, stimulated emission and absorption cross-sections were calculated to evaluate the effects of halide amount of the spectroscopic properties. It is shown that the introduction of an appropriate amount of halide can further improve the mid-infrared fluorescence intensity through an enhanced phonon-assisted energy transfer between Ho3+/Yb3+ ions and the energy transfer mechanisms are investigated quantitatively in detail by calculating energy transfer microparameters and phonon contribution ratios. The results indicate that this kind of glasses is a promising material for mid-infrared optical fiber.

  16. Rapid and non-destructive analysis of metallic dental restorations using X-ray fluorescence spectra and light-element sampling tools

    NASA Astrophysics Data System (ADS)

    Furuhashi, K.; Uo, M.; Kitagawa, Y.; Watari, F.

    2012-12-01

    IntroductionRecently, allergic diseases caused by dental metals have been increasing. Therefore, rapid and accurate analytical methods for the metal restorations in the oral cavities of patients are required. The purpose of this study was to develop a non-destructive extraction method for dental alloys, along with a subsequent, rapid and accurate elemental analysis. Materials and methodSamples were obtained by polishing the surfaces of metal restorations using a dental rotating tool with disposable buffs and polishing pastes. As materials for the analysis, three dental alloys were used. To compare the sampling and analysis efficiencies, two buffs and seven pastes were used. After polishing the surface of a metal restoration, the buff was analyzed using X-ray scanning analytical microscopy (XSAM). ResultsThe efficiency of the analysis was judged based on the sampling rate achieved and the absence of disturbing elements in the background in fluorescence X-ray spectra. The best results were obtained for the combination of TexMet as a buff with diamond as a paste. This combination produced a good collection efficiency and a plain background in the fluorescence X-ray spectra, resulting in a high precision of the analysis.

  17. Transport of Soil Halides through Rice Paddies: A Viable Mechanism for Rapid Dispersion of the Soil Halide Reservoir

    NASA Astrophysics Data System (ADS)

    Redeker, K. R.; Manley, S.; Wang, N.; Cicerone, R.

    2002-05-01

    On short time scales (1-10 years) soil halide concentrations have been assumed to be primarily driven by leaching and deposition processes. Recent results however, have shown that terrestrial plants volatilize soil halides in the form of methyl halides. Emissions of methyl chloride, methyl bromide and methyl iodide represent major pathways for delivery of inorganic halogen radicals to the atmosphere. Inorganic halogen radicals destroy ozone in the stratosphere and modify the oxidative capacity of the lower atmosphere. We have previously shown that rice paddies emit methyl halides and that emissions depend on growth stage of the rice plant as well as field water management. We show here that rice grown in a greenhouse at UCI is capable of volatilizing and/or storing up to 30%, 5%, and 10% of the available chloride, bromide and iodide within the top meter of soil. The percent of plant tissue halide volatilized as methyl halide over the course of the season is calculated to be 0.05%, 0.25% and 85.0% for chloride, bromide and iodide. We compare our greenhouse soil halide concentrations to other commercial rice fields around the world and estimate the e-folding time for soil halides within each region. We suggest that rice agriculture is the driving removal mechanism for halides within rice paddies and that terrestrial plants play a larger role in global cycling of halides than previously estimated.

  18. Controlling the Fluorescence Response of PET Sensors via the Metal-Ion π-Contacting Ability of the Fluorophore: Coumarin, a Weaker π Contacter.

    PubMed

    Nugent, Joseph W; Reibenspies, Joseph H; Hancock, Robert D

    2015-10-19

    The π-contact hypothesis, that quenching of the fluorescence of complexes of photoinduced electron transfer sensors with heavy diamagnetic metal ions may be caused by π contacts between the metal ion and the fluorophore of the sensor, is examined with a study of the fluorescent properties of the sensor 4-[[bis(2-pyridinylmethyl)amino]methyl]-6,7-dimethoxy-1-benzopyran-2-one (cdpa) and the structures of its complexes with some metal ions. The coumarin-type fluorophore of cdpa is a weaker π-contact former than the anthracenyl fluorophore of the analogue adpa (Inorg. Chem. 2014, 53, 9014): only Ag(I), the strongest π contact former, quenches the fluorescence of cdpa, apart from paramagnetic Cu(II) and Ni(II), which quench fluorescence by a redox mechanism not requiring π contacts. The structures of [Ag(cdpa)NO3] (1), [Pb(cdpa)(NO3)2] (2), [Zn(cdpa)(NO3)2] (3), [Cd(cdpa)Cl2]2 (4), [Cd(cdpa)2H2O](NO3)2 (5), and [Hg(cdpa)2H2O](NO3)2 (6) are reported. Structure 1 shows that Ag(I) is the only metal ion studied that forms π contacts with the fluorophore of cdpa in the solid state: Ag···C η(2) π contacts of 3.083 and 3.095 Å, in line with quenching of the fluorescence of the Ag(I)(cdpa) complex. In contrast, Pb(II), Zn(II), and Cd(II) show chelation-enhanced fluorescence in their cdpa complexes, and the structures of 2-4 show that the fluorophore of cdpa in each case forms no π contacts. By contrast, the adpa complexes of Pb(II) and Cd(II) show π contacts with its more strongly π-contacting fluorophore (Inorg. Chem. 2014, 53, 9014). The structures of 5 and 6 show bis-complexes of cdpa: the coordination geometries of Cd(II) and Hg(II) are discussed in relation to the number of covalently bound donor atoms present. The preferred hapticity of π-contacted metal ions is evaluated from the literature structures, suggesting that d(10) metal ions such as Ag(I) and Hg(II), and tetragonally distorted Cu(II) and Pd(II), prefer η(1) and η(2) π contacts, while more

  19. A sensitive and selective sensor for biothiols based on the turn-on fluorescence of the Fe-MIL-88 metal-organic frameworks-hydrogen peroxide system.

    PubMed

    Sun, Zheng Juan; Jiang, Jun Ze; Li, Yuan Fang

    2015-12-21

    Herein, we present a novel strategy based on a "turn-on" fluorescence system made up of metal-organic frameworks Fe-MIL-88 and H2O2 for detecting biothiols in human serum. The nonfluorescent Fe-MIL-88 gives weak fluorescence in the presence of H2O2. Interestingly, it was found that biothiols such as glutathione (GSH), cysteine (Cys) or homocysteine (Hcy) could induce fluorescence turn-on of the Fe-MIL-88/H2O2 system. Under optimal conditions, the relative fluorescence intensity exhibited a good linear relationship in the range from 50 nM-10 μM for GSH (r = 0.994), 50 nM-10 μM for Cys (r = 0.990), and 50 nM-10 μM (r = 0.992) for Hcy; the detection limits of GSH, Cys and Hcy were 30 nM, 40 nM, and 40 nM respectively. Mechanism investigation reveals that biothiols could associate with Fe-MIL-88 via hydrogen bonding and electrostatic interaction followed by redox reaction between biothiols and Fe(3+) present in the Fe-MIL-88, Fe(3+) was thus reduced to Fe(2+), and then Fe(2+) could efficiently catalyze the decomposition of H2O2 to yield ˙OH radicals through the Fenton reaction. Besides, biothiols were able to reduce H2O2 to produce ˙OH radicals directly. Thus the Fe-MIL-88 as well as biothiols could cooperatively contribute to the activation of H2O2 to generate higher amounts of ˙OH radicals, which in turn oxidize the free ligand terephthalic acid (BDC) outside or within the Fe-MIL-88 structure to strongly fluorescent hydroxylated terephthalic acid (OHBDC), thereby turning on the fluorescence. PMID:26568205

  20. Flame inhibition by hydrogen halides - Some spectroscopic measurements

    NASA Technical Reports Server (NTRS)

    Lerner, N. R.; Cagliostro, D. E.

    1973-01-01

    The far-ultraviolet absorption spectrum of an air-propane diffusion flame inhibited with hydrogen halides has been studied. Plots of the absorption of light by hydrogen halides as a function of position in the flame and also as a function of the amount of hydrogen halide added to the flame have been obtained. The hydrogen halides are shown to be more stable on the fuel side of the reaction zone than they are on the air side. Thermal diffusion is seen to be important in determining the concentration distribution of the heavier hydrogen halides in diffusion flames. The relationship between the concentration distribution of the hydrogen halides in the flame and the flame inhibition mechanism is discussed.

  1. Morphology-Controlled Synthesis of Organometal Halide Perovskite Inverse Opals.

    PubMed

    Chen, Kun; Tüysüz, Harun

    2015-11-01

    The booming development of organometal halide perovskites in recent years has prompted the exploration of morphology-control strategies to improve their performance in photovoltaic, photonic, and optoelectronic applications. However, the preparation of organometal halide perovskites with high hierarchical architecture is still highly challenging and a general morphology-control method for various organometal halide perovskites has not been achieved. A mild and scalable method to prepare organometal halide perovskites in inverse opal morphology is presented that uses a polystyrene-based artificial opal as hard template. Our method is flexible and compatible with different halides and organic ammonium compositions. Thus, the perovskite inverse opal maintains the advantage of straightforward structure and band gap engineering. Furthermore, optoelectronic investigations reveal that morphology exerted influence on the conducting nature of organometal halide perovskites. PMID:26376773

  2. Lanthanide-halide based humidity indicators

    DOEpatents

    Beitz, James V.; Williams, Clayton W.

    2008-01-01

    The present invention discloses a lanthanide-halide based humidity indicator and method of producing such indicator. The color of the present invention indicates the humidity of an atmosphere to which it is exposed. For example, impregnating an adsorbent support such as silica gel with an aqueous solution of the europium-containing reagent solution described herein, and dehydrating the support to dryness forms a substance with a yellow color. When this substance is exposed to a humid atmosphere the water vapor from the air is adsorbed into the coating on the pore surface of the silica gel. As the water content of the coating increases, the visual color of the coated silica gel changes from yellow to white. The color change is due to the water combining with the lanthanide-halide complex on the pores of the gel.

  3. Lead halide perovskite nanowire lasers with low lasing thresholds and high quality factors.

    PubMed

    Zhu, Haiming; Fu, Yongping; Meng, Fei; Wu, Xiaoxi; Gong, Zizhou; Ding, Qi; Gustafsson, Martin V; Trinh, M Tuan; Jin, Song; Zhu, X-Y

    2015-06-01

    The remarkable performance of lead halide perovskites in solar cells can be attributed to the long carrier lifetimes and low non-radiative recombination rates, the same physical properties that are ideal for semiconductor lasers. Here, we show room-temperature and wavelength-tunable lasing from single-crystal lead halide perovskite nanowires with very low lasing thresholds (220 nJ cm(-2)) and high quality factors (Q ∼ 3,600). The lasing threshold corresponds to a charge carrier density as low as 1.5 × 10(16) cm(-3). Kinetic analysis based on time-resolved fluorescence reveals little charge carrier trapping in these single-crystal nanowires and gives estimated lasing quantum yields approaching 100%. Such lasing performance, coupled with the facile solution growth of single-crystal nanowires and the broad stoichiometry-dependent tunability of emission colour, makes lead halide perovskites ideal materials for the development of nanophotonics, in parallel with the rapid development in photovoltaics from the same materials. PMID:25849532

  4. EVALUATION OF METHODS FOR THE DETERMINATION OF TOTAL ORGANIC HALIDE IN WATER AND WASTE

    EPA Science Inventory

    Various methods for the determination of total organic halides (TOX) in groundwater and in waste oil samples have been evaluated. Of three inorganic halide species generation approaches and three inorganic halide determinative techniques evaluated for groundwater analyses, one co...

  5. Comparison of Synchrotron X-Ray Fluorescence Mapping and Micro-XANES to Bulk X-Ray Absorption Spectra in Metal-Contaminated Sediments

    SciTech Connect

    O'Day, P; Carroll, S A; Bajt, S

    2003-01-16

    Synchrotron X-ray absorption spectroscopy (XAS) is one of the few techniques that can supply molecular-scale information for a variety of elements at concentrations relevant to natural systems in non-vacuum conditions. Bulk XAS analysis supplies the dominant chemical bonding mode(s) for a specific element. In complex materials such as natural soils and sediments, however, the dominant mode may not necessarily be the most reactive because changes in speciation at surfaces may results in changes in reactivity. Our previous work at Naval Air Station (NAS) Alameda (CA) focused on in situ metal chemistry in surface and deep sediments, and the impact of metal mobility by sediment oxidation. Estuary sediments at the Alameda Naval Station Air in California have elevated metal concentrations that increase with increasing depth. The metal concentrations in these sediments are: Cd (10-350 ppm), Cr (200-1000 ppm), Cu (100-230 ppm), Pb (200-1200 ppm) and Zn (250-600 ppm). We have extensively characterized these sediments using bulk XAS and other non-synchrotron supporting methods [ 1]. In this experiment, we collected fluorescence element maps using synchrotron X-ray microprobe of unreacted and seawater-oxidized sediment samples from Alameda NAS to determine the spatial distribution and correlation of lead, zinc, and iron. We then compared micro-XANES spectra for lead and zinc collected with the X-ray microprobe to previously collected bulk XANES spectra. The results from our bulk XAS characterization of the sediments showed both oxide and sulfide components for the trace metals. However, the bulk XAS data were not able to identify the composition of the oxide component (i.e. carbonate or hydroxide), nor could absorbed species or solid solutions be definitively identified. Our objective in using micro-XANES and fluorescence element maps was to attempt a more precise identification of metal speciation in or on individual particles.

  6. [Design and synthesis of imine compound for metal cation logical gates recognition and setup of double-control fluorescent molecule switch].

    PubMed

    Huang, Tao; Zhu, Yu-lian; Dai, Xue-qin; Zhang, Qi; Huang, Yan

    2011-07-01

    The Schiff base's reduced product N,N-bis(4-methoxybenzyl) ethane-1,2-diamine, which was used as a receptor L, was designed and synthesized for the first time in the present article. It was found that Cu2+ and Fe3+ could quench L in fluorescence observably and Zn2+ and Cd2+ could enhance L remarkably. So the two pair metal cation could set up "OR" logical gate relation with the receptor molecule L, then a logical recognition system be formed. The data of resolved ZnL's single crystal indicated that ZnL belonged to monoclinic (CCDC No. 747994). Integrated spectrum instrument was used to characterize the structure of its alike series of complex compound. According to ZnL's excellent fluorescence character and the ability to exchange with contiguous metal cation, ZnZ+/ZnL/Co2+, Zn2+/ZnL/Nit+ fluorescent molecule switch was designed. It is hoped that the work above could be positive for the development of molecule computer, bio-intellectualized inspection technology (therapy) and instrument. PMID:21942034

  7. Spectral Features and Charge Dynamics of Lead Halide Perovskites: Origins and Interpretations.

    PubMed

    Sum, Tze Chien; Mathews, Nripan; Xing, Guichuan; Lim, Swee Sien; Chong, Wee Kiang; Giovanni, David; Dewi, Herlina Arianita

    2016-02-16

    Lead halide perovskite solar cells are presently the forerunner among the third generation solution-processed photovoltaic technologies. With efficiencies exceeding 20% and low production costs, they are prime candidates for commercialization. Critical insights into their light harvesting, charge transport, and loss mechanisms have been gained through time-resolved optical probes such as femtosecond transient absorption spectroscopy (fs-TAS), transient photoluminescence spectroscopy, and time-resolved terahertz spectroscopy. Specifically, the discoveries of long balanced electron-hole diffusion lengths and gain properties in halide perovskites underpin their significant roles in uncovering structure-function relations and providing essential feedback for materials development and device optimization. In particular, fs-TAS is becoming increasingly popular in perovskite characterization studies, with commercial one-box pump-probe systems readily available as part of a researcher's toolkit. Although TAS is a powerful probe in the study of charge dynamics and recombination mechanisms, its instrumentation and data interpretation can be daunting even for experienced researchers. This issue is exacerbated by the sensitive nature of halide perovskites where the kinetics are especially susceptible to pump fluence, sample preparation and handling and even degradation effects that could lead to disparate conclusions. Nonetheless, with end-users having a clear understanding of TAS's capabilities, subtleties, and limitations, cutting-edge work with deep insights can still be performed using commercial setups as has been the trend for ubiquitous spectroscopy instruments like absorption, fluorescence, and transient photoluminescence spectrometers. Herein, we will first briefly examine the photophysical processes in lead halide perovskites, highlighting their novel properties. Next, we proceed to give a succinct overview of the fundamentals of pump-probe spectroscopy in relation

  8. Reflectivities of Four Shock-Compressed Alkali Halides

    NASA Astrophysics Data System (ADS)

    Diamond, M. R.; McWilliams, R. S.; Eggert, J.; Jeanloz, R.; Ali, S. J.; Collins, G. W.

    2015-12-01

    Laser-shock compression on four alkali halides has been used to probe the transition from insulating to metallic states, a high-pressure transition in chemical bonding that has fundamental implications for planetary formation and structure. Collectively, pressures up to 450 GPa and densities up to three-fold compression were explored across a total of fourteen single-crystal samples of CsI, CsBr, KBr and NaCl. Velocity interferometry was used to record shock velocities and reflectivities at 532 nm during decaying shock compression. The data show up to 40% (or higher) reflectivity, corresponding to notable electrical conductivities, in response to high pressures and temperatures. Furthermore, band-gap closure, dependent on density, can be examined from the reflectivity data. Ionic salts are simple model systems amenable to first-principles theory and serve as analog materials for predicting whether specific chemical constituents can reside in the rocky mantles or metallic cores of planets. A key objective is to disentangle the complementary roles of temperature and compression in transforming ionic into metallic bonding. Furthermore, at high pressures CsI becomes analogous to Xe: they are isoelectronic and follow matching equations of state. Therefore, studies on CsI could inform understanding of noble-gas geochemistry at conditions deep inside planets.

  9. Anthropogenic signature of sediment organic matter probed by UV-Visible and fluorescence spectroscopy and the association with heavy metal enrichment.

    PubMed

    He, Wei; Lee, Jong-Hyun; Hur, Jin

    2016-05-01

    Sediment organic matter (SOM) was extracted in an alkaline solution from 43 stream sediments in order to explore the anthropogenic signatures. The SOM spectroscopic characteristics including excitation-emission matrix (EEM)-parallel factor analysis (PARAFAC) were compared for five sampling site groups classified by the anthropogenic variables of land use, population density, the loadings of organics and nutrients, and metal enrichment. The conventional spectroscopic characteristics including specific UV absorbance, absorbance ratio, and humification index did not properly discriminate among the different cluster groups except in the case of metal enrichment. Of the four decomposed PARAFAC components, humic-like and tryptophan-like fluorescence responded negatively and positively, respectively, to increasing degrees of the anthropogenic variables except for land use. The anthropogenic enrichment of heavy metals was positively associated with the abundance of tryptophan-like component. In contrast, humic-like component, known to be mostly responsible for metal binding, exhibited a decreasing trend corresponding with metal enrichment. These conflicting trends can be attributed to the overwhelmed effects of the coupled discharges of heavy metals and organic pollutants into sediments. Our study suggests that the PARAFAC components can be used as functional signatures to probe the anthropogenic influences on sediments. PMID:26901475

  10. Comparative Study of Metal Quantification in Neurological Tissue Using Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry Imaging and X-ray Fluorescence Microscopy.

    PubMed

    Davies, Katherine M; Hare, Dominic J; Bohic, Sylvain; James, Simon A; Billings, Jessica L; Finkelstein, David I; Doble, Philip A; Double, Kay L

    2015-07-01

    Redox-active metals in the brain mediate numerous biochemical processes and are also implicated in a number of neurodegenerative diseases. A number of different approaches are available for quantitatively measuring the spatial distribution of biometals at an image resolution approaching the subcellular level. Measured biometal levels obtained using laser ablation-inductively coupled plasma mass spectrometry (LA-ICPMS; spatial resolution 15 μm × 15 μm) were within the range of those obtained using X-ray fluorescence microscopy (XFM; spatial resolution 2 μm × 7 μm) and regional changes in metal concentration across discrete brain regions were replicated to the same degree. Both techniques are well suited to profiling changes in regional biometal distribution between healthy and diseased brain tissues, but absolute quantitation of metal levels varied significantly between methods, depending on the metal of interest. Where all possible variables affect metal levels, independent of a treatment/phenotype are controlled, either method is suitable for examining differences between experimental groups, though, as with any method for imaging post mortem brain tissue, care should be taken when interpreting the total metal levels with regard to physiological concentrations. PMID:26020362

  11. The Electrolytic Production of Metallic Uranium

    DOEpatents

    Rosen, R.

    1950-08-22

    This patent covers a process for producing metallic uranium by electrolyzing uranium tetrafluoride at an elevated temperature in a fused bath consisting essentially of mixed alkali and alkaline earth halides.

  12. Lanthanide doped strontium-barium cesium halide scintillators

    SciTech Connect

    Bizarri, Gregory; Bourret-Courchesne, Edith; Derenzo, Stephen E.; Borade, Ramesh B.; Gundiah, Gautam; Yan, Zewu; Hanrahan, Stephen M.; Chaudhry, Anurag; Canning, Andrew

    2015-06-09

    The present invention provides for a composition comprising an inorganic scintillator comprising an optionally lanthanide-doped strontium-barium, optionally cesium, halide, useful for detecting nuclear material.

  13. Monte Carlo simulation of source-excited in vivo x-ray fluorescence measurements of heavy metals

    NASA Astrophysics Data System (ADS)

    O'Meara, J. M.; Chettle, D. R.; McNeill, F. E.; Prestwich, W. V.; Svensson, C. E.

    1998-06-01

    This paper reports on the Monte Carlo simulation of in vivo x-ray fluorescence (XRF) measurements. Our model is an improvement on previously reported simulations in that it relies on a theoretical basis for modelling Compton momentum broadening as well as detector efficiency. Furthermore, this model is an accurate simulation of experimentally detected spectra when comparisons are made in absolute counts; preceding models have generally only achieved agreement with spectra normalized to unit area. Our code is sufficiently flexible to be applied to the investigation of numerous source-excited in vivo XRF systems. Thus far the simulation has been applied to the modelling of two different systems. The first application was the investigation of various aspects of a new in vivo XRF system, the measurement of uranium in bone with in a backscatter geometry. The Monte Carlo simulation was critical in assessing the potential of applying XRF to the measurement of uranium in bone. Currently the Monte Carlo code is being used to evaluate a potential means of simplifying an established in vivo XRF system, the measurement of lead in bone with in a geometry. The results from these simulations may demonstrate that calibration procedures can be significantly simplified and subject dose may be reduced. As well as providing an excellent tool for optimizing designs of new systems and improving existing techniques, this model can be used in the investigation of the dosimetry of various XRF systems. Our simulation allows a detailed understanding of the numerous processes involved when heavy metal concentrations are measured in vivo with XRF.

  14. EPR study of electron bombarded alkali- and alkaline-earth halide crystal surfaces

    NASA Technical Reports Server (NTRS)

    Fryburg, G. C.; Lad, R. A.

    1975-01-01

    An EPR study of electron bombarded LiF, NaCl, KCl, CaF2 and BaF2 polycrystalline surfaces has shown that small metal particles are formed on the surfaces of the crystals. Identification was made from CESR signals. The symmetric line-shape of the signals, even at 77 K, indicated that the particles were less than 0.5 micron in diameter. Signals due to F centers were observed in LiF but not in the other halides. Implications to metal deposition are considered.

  15. Exploration geochemical technique for the determination of preconcentrated organometallic halides by ICP-AES

    USGS Publications Warehouse

    Motooka, J.M.

    1988-01-01

    An atomic absorption extraction technique which is widely used in geochemical exploration for the determination of Ag, As, Au, Bi, Cd, Cu, Mo, Pb, Sb, and Zn has been modified and adapted to a simultaneous inductively coupled plasma-atomic emission instrument. the experimental and operating parameters are described for the preconcentration of the metals into their organometallic halides and for the determination of the metals. Lower limits of determination are equal to or improved over those for flame atomic absorption (except Au) and ICP results are very similar to the accepted AA values, with precision for the ICP data in excess of that necessary for exploration purposes.

  16. Selective and Sensitive Detection of Heavy Metal Ions in 100% Aqueous Solution and Cells with a Fluorescence Chemosensor Based on Peptide Using Aggregation-Induced Emission.

    PubMed

    Neupane, Lok Nath; Oh, Eun-Taex; Park, Heon Joo; Lee, Keun-Hyeung

    2016-03-15

    A fluorescent peptidyl chemosensor for the detection of heavy metal ions in aqueous solution as well as in cells was synthesized on the basis of the peptide receptor for the metal ions using an aggregation-induced emission fluorophore. The peptidyl chemosensor (1) bearing tetraphenylethylene fluorophore showed an exclusively selective turn-on response to Hg(2+) among 16 metal ions in aqueous buffered solution containing NaCl. The peptidyl chemosensor complexed Hg(2+) ions and then aggregated in aqueous buffered solution, resulting in the significant enhancement (OFF-On) of emissions at around 470 nm. The fluorescent sensor showed a highly sensitive response to Hg(2+), and about 1.0 equiv of Hg(2+) was enough for the saturation of the emission intensity change. The detection limit (5.3 nM, R(2) = 0.99) of 1 for Hg(2+) ions was lower than the maximum allowable level of Hg(2+) in drinking water by EPA. Moreover, the peptidyl chemosensor penetrated live cells and detected intracellular Hg(2+) ions by the turn-on response. PMID:26872241

  17. Mechanism and Selectivity in Nickel-Catalyzed Cross-Electrophile Coupling of Aryl Halides with Alkyl Halides

    PubMed Central

    Biswas, Soumik; Weix, Daniel J.

    2013-01-01

    The direct cross-coupling of two different electrophiles, such as an aryl halide with an alkyl halide, offers many advantages over conventional cross-coupling methods that require a carbon nucleophile. Despite its promise as a versatile synthetic strategy, a limited understanding of the mechanism and origin of cross selectivity has hindered progress in reaction development and design. Herein, we shed light on the mechanism for the nickel-catalyzed cross-electrophile coupling of aryl halides with alkyl halides and demonstrate that the selectivity arises from an unusual catalytic cycle that combines both polar and radical steps to form the new C-C bond. PMID:23952217

  18. Dual channel sensor for detection and discrimination of heavy metal ions based on colorimetric and fluorescence response of the AuNPs-DNA conjugates.

    PubMed

    Tan, Lulu; Chen, Zhengbo; Zhao, Yan; Wei, Xiangcong; Li, Yonghui; Zhang, Chi; Wei, Xinling; Hu, Xiaochen

    2016-11-15

    We have presented an extensible, facile and sensitive multidimensional sensor based on DNA-gold nanoparticle (DNA-AuNP) conjugates for heavy metal ions (Ag(+), Hg(2+), Cr(3+), Sn(4+), Cd(2+), Cu(2+), Pb(2+), Zn(2+), and Mn(2+)) discrimination. In the presence of metal ions, the excluded effect of DNA and AuNPs with the same negative charges is disrupted, and the amount of FAM-labeled DNA adsorbed on AuNP surfaces increases, resulting in a more obvious fluorescence quenching effect. With the addition of NH2OH and HAuCl4, AuNPs grow into morphologically varied nanostructures (spherical to branched) depending on the resulting aptamer coverage, which gives rise to different colored solutions (reddish blush, purple and blue) observed by naked eyes. By simply changing the DNA sequences, three sensing elements can be easily obtained and added into this dual-channel multidimensional sensor. 9 heavy metal ions are distinguished by linear discriminant analysis (LDA) and primary component analysis (PCA). A highly sensitive discrimination of metal ion targets with the detection limit as low as 50nM with 100% identification accuracy is obtained. Remarkably, Cu(2+) and Hg(2+) ions with similar catalytic performance at various concentrations (300nM, 400nM, 500nM, respectively) and the mixture of the two metal ions with different volume ratios (total metal ion concentration: 500nM) can be successfully discriminated. In addition, nine heavy metal ions are also well-distinguished in river samples, and the accuracy of discrimination of these metal ions samples reaches 100%. Therefore, it will broaden the application field of DNA-AuNP conjugates-based multidimensional sensors. PMID:27208473

  19. Fluorescence-suppressed time-resolved Raman spectroscopy of pharmaceuticals using complementary metal-oxide semiconductor (CMOS) single-photon avalanche diode (SPAD) detector.

    PubMed

    Rojalin, Tatu; Kurki, Lauri; Laaksonen, Timo; Viitala, Tapani; Kostamovaara, Juha; Gordon, Keith C; Galvis, Leonardo; Wachsmann-Hogiu, Sebastian; Strachan, Clare J; Yliperttula, Marjo

    2016-01-01

    In this work, we utilize a short-wavelength, 532-nm picosecond pulsed laser coupled with a time-gated complementary metal-oxide semiconductor (CMOS) single-photon avalanche diode (SPAD) detector to acquire Raman spectra of several drugs of interest. With this approach, we are able to reveal previously unseen Raman features and suppress the fluorescence background of these drugs. Compared to traditional Raman setups, the present time-resolved technique has two major improvements. First, it is possible to overcome the strong fluorescence background that usually interferes with the much weaker Raman spectra. Second, using the high photon energy excitation light source, we are able to generate a stronger Raman signal compared to traditional instruments. In addition, observations in the time domain can be performed, thus enabling new capabilities in the field of Raman and fluorescence spectroscopy. With this system, we demonstrate for the first time the possibility of recording fluorescence-suppressed Raman spectra of solid, amorphous and crystalline, and non-photoluminescent and photoluminescent drugs such as caffeine, ranitidine hydrochloride, and indomethacin (amorphous and crystalline forms). The raw data acquired by utilizing only the picosecond pulsed laser and a CMOS SPAD detector could be used for identifying the compounds directly without any data processing. Moreover, to validate the accuracy of this time-resolved technique, we present density functional theory (DFT) calculations for a widely used gastric acid inhibitor, ranitidine hydrochloride. The obtained time-resolved Raman peaks were identified based on the calculations and existing literature. Raman spectra using non-time-resolved setups with continuous-wave 785- and 532-nm excitation lasers were used as reference data. Overall, this demonstration of time-resolved Raman and fluorescence measurements with a CMOS SPAD detector shows promise in diverse areas, including fundamental chemical research, the

  20. The Oxidation State of Europium in Halide Glasses

    PubMed Central

    Weber, J.K.R.; Vu, M.; Paßlick, C.; Schweizer, S.; Brown, D.E.; Johnson, C.E.; Johnson, J.A.

    2012-01-01

    The luminescent properties of divalent europium ions can be exploited to produce storage phosphors for x-ray imaging applications. The relatively high cost and limited availability of divalent europium halides makes it desirable to synthesize them from the readily available trivalent salts. In this work, samples of pure EuCl3 and fluoride glass melts doped with EuCl3 were processed at 700-800 °C in an inert atmosphere furnace. The Eu oxidation state in the resulting materials was determined using fluorescence and Mössbauer spectroscopy. Heat treatment of pure EuCl3 for 10 minutes at 710 °C resulted in a material comprising approximately equal amounts of Eu2+ and Eu3+. Glasses made using mixtures of EuCl2 and EuCl3 in the starting material contained both oxidation states. This paper describes the sample preparation and analysis and discusses the results in the context of chemical equilibria in the melts. PMID:22101252

  1. [Emissions of methyl halides from coastal salt marshes: A review].

    PubMed

    Xie, Wen-xia; Zhao, Quan-sheng; Cui, Yu-qian; Du, Hui-na; Ye, Si-yuan

    2015-11-01

    Methyl halides are the major carrier of halogens in the atmosphere, and they play an important role in tropospheric and stratospheric ozone depletion. Meanwhile, methyl halides can act as greenhouse gases in the atmosphere, and they are also environmentally significant because of their toxicity. Coastal salt marshes, the important intertidal ecosystems at the land-ocean interface, have been considered to be a large potential natural source of methyl halides. In this paper, the research status of the natural source or sink of methyl halides, the mechanisms of their emission from coastal salt marshes and affecting factors were summarized. In view of this, the following research fields need to be strengthened in the future: 1) Long time-scale and large region-range researches about the emission of methyl halides and the evaluation of their source and sink function, 2) Accurate quantification of contribution rates of different plant species and various biological types to fluxes of methyl halides, 3) Further researches on effects of the tidal fluctuation process and flooding duration on methyl halides emission, 4) Effects of the global change and human activities on methyl halides emission. PMID:26915215

  2. A dual amplification strategy for DNA detection combining bio-barcode assay and metal-enhanced fluorescence modality.

    PubMed

    Zhou, Zhenpeng; Li, Tian; Huang, Hongduan; Chen, Yang; Liu, Feng; Huang, Chengzhi; Li, Na

    2014-11-11

    Silver-enhanced fluorescence was coupled with a bio-barcode assay to facilitate a dual amplification assay to demonstrate a non-enzymatic approach for simple and sensitive detection of DNA. In the assay design, magnetic nanoparticles seeded with silver nanoparticles were modified with the capture DNA, and silver nanoparticles were modified with the binding of ssDNA and the fluorescently labeled barcode dsDNA. Upon introduction of the target DNA, a sandwich structure was formed because of the hybridization reaction. By simple magnetic separation, silver-enhanced fluorescence of barcode DNAs could be readily measured without the need of a further step to liberate barcode DNAs from silver nanoparticles, endowing the method with simplicity and high sensitivity with a detection limit of 1 pM. PMID:25233044

  3. A Metal-Organic Framework/DNA Hybrid System as a Novel Fluorescent Biosensor for Mercury(II) Ion Detection.

    PubMed

    Wu, Lan-Lan; Wang, Zhuo; Zhao, Shu-Na; Meng, Xing; Song, Xue-Zhi; Feng, Jing; Song, Shu-Yan; Zhang, Hong-Jie

    2016-01-11

    Mercury(II) ions have emerged as a widespread environmental hazard in recent decades. Despite different kinds of detection methods reported to sense Hg(2+) , it still remains a challenging task to develop new sensing molecules to replenish the fluorescence-based apparatus for Hg(2+) detection. This communication demonstrates a novel fluorescent sensor using UiO-66-NH2 and a T-rich FAM-labeled ssDNA as a hybrid system to detect Hg(2+) sensitively and selectively. To the best of our knowledge, it has rarely been reported that a MOF is utilized as the biosensing platform for Hg(2+) assay. PMID:26555340

  4. How specific halide adsorption varies hydrophobic interactions.

    PubMed

    Stock, Philipp; Müller, Melanie; Utzig, Thomas; Valtiner, Markus

    2016-03-01

    Hydrophobic interactions (HI) are driven by the water structure around hydrophobes in aqueous electrolytes. How water structures at hydrophobic interfaces and how this influences the HI was subject to numerous studies. However, the effect of specific ion adsorption on HI and hydrophobic interfaces remains largely unexplored or controversial. Here, the authors utilized atomic force microscopy force spectroscopy at well-defined nanoscopic hydrophobic interfaces to experimentally address how specific ion adsorption of halide ions as well as NH4 (+), Cs(+), and Na(+) cations alters interaction forces across hydrophobic interfaces. Our data demonstrate that iodide adsorption at hydrophobic interfaces profoundly varies the hydrophobic interaction potential. A long-range and strong hydration repulsion at distances D > 3 nm, is followed by an instability which could be explained by a subsequent rapid ejection of adsorbed iodides from approaching hydrophobic interfaces. In addition, the authors find only a weakly pronounced influence of bromide, and as expected no influence of chloride. Also, all tested cations do not have any significant influence on HI. Complementary, x-ray photoelectron spectroscopy and quartz-crystal-microbalance with dissipation monitoring showed a clear adsorption of large halide ions (Br(-)/I(-)) onto hydrophobic self-assembled monolayers (SAMs). Interestingly, iodide can even lead to a full disintegration of SAMs due to specific and strong interactions of iodide with gold. Our data suggest that hydrophobic surfaces are not intrinsically charged negatively by hydroxide adsorption, as it was generally believed. Hydrophobic surfaces rather interact strongly with negatively charged large halide ions, leading to a surface charging and significant variation of interaction forces. PMID:26753786

  5. Ultraviolet absorption spectra of mercuric halides.

    NASA Technical Reports Server (NTRS)

    Templet, P.; Mcdonald, J. R.; Mcglynn, S. P.; Kendrow, C. H.; Roebber, J. L.; Weiss, K.

    1972-01-01

    The gas phase transitions of the mercuric halides were observed in the UV region by operating at temperatures above 400 K and at vapor pressures on the order of 0.5 mm. Spectral features exhibited by the chloride, bromide, and iodide of mercury correlate energetically with bands previously designated as intermolecular charge transfer transitions. The solution spectra of mercuric iodide and deep color of the crystals (if not due to some solid state interactions) indicate that this molecule may also have longer wavelength transitions.

  6. Raman spectra of hydroxide-halide melts

    NASA Astrophysics Data System (ADS)

    Zakiriyanova, I. D.; Khokhlov, V. A.

    2012-08-01

    The Raman spectra of molten binary mixtures based on sodium hydroxide and containing (mol %) 35 NaCl, 30 NaBr, and 30 NaI have been recorded at various temperatures. An increase in the vibrational frequency and the force constant of the O-H bond is detected under isothermal conditions upon a variation of the anionic composition of a melt in the series I → Br → Cl. Based on the experimental data, the viscosity of the hydroxide-halide melts is estimated.

  7. Detection of halide ions with AlGaN /GaN high electron mobility transistors

    NASA Astrophysics Data System (ADS)

    Kang, B. S.; Ren, F.; Kang, M. C.; Lofton, C.; Tan, Weihong; Pearton, S. J.; Dabiran, A.; Osinsky, A.; Chow, P. P.

    2005-04-01

    AlGaN /GaN high electron mobility transistors (HEMTs) both with and without a Au gate are found to exhibit significant changes in channel conductance upon exposing the gate region to various halide ions. The polar nature of the halide ions leads to a change of surface charge in the gate region on the HEMT, producing a change in the surface potential at the semiconductor/liquid interface. HEMTs with a Au-gate electrode not only doubled the sensitivity of changing the channel conductance as compared to gateless HEMT, but also showed the opposite conductance behavior. When anions adsorbed on the Au, they produced a counter charge for electrovalence. These anions drag some counter ions from the bulk solution or create an image positive charge on the metal for the required neutrality. The gateless HEMTs can be used as sensors for a range of chemicals through appropriate modification with covalently bonded halide functional groups on the Au surface. This creates many possibilities to functionalize the surface for a wide range of integrated biological, chemical, and fluid monitoring sensors.

  8. Resonance-Raman-scattering spectroscopy for the halogen-molecular-ion centers in alkali halides

    NASA Astrophysics Data System (ADS)

    Suzuki, T.; Tanimura, K.; Itoh, N.

    1993-10-01

    We have measured the Raman scattering in resonance with the bonding-to-antibonding transitions of two types of dihalogen-molecular-ion centers in alkali halides, the VK and H centers; the molecular ion occupies two adjacent halogen sites in the former and a single halogen site in the latter. It is found that the stretching-vibration frequency of the molecular ion is higher by more than 30% for the H center than for the VK center. The hardening is ascribed to the bond tightening due to the Madelung potential. Although the Raman line due to the stretching vibration consists of a single line in most alkali halides, two closely lying lines are observed for the H centers in alkali halides with small alkali-metal to halogen radius ratio and also for the VK center in NaCl. The paired-line structure is ascribed to the coupling of the stretching vibration of the halogen molecular ion with the lattice.

  9. Discrimination of fluorescence light-up effects induced by pH and metal ion chelation on a spirocyclic derivative of rhodamine B.

    PubMed

    Leite, Andreia; Silva, Ana M G; Cunha-Silva, Luís; de Castro, Baltazar; Gameiro, Paula; Rangel, Maria

    2013-05-01

    In the present work we describe the structure and the spectroscopic characterization of a spirocyclic derivative of a rhodamine B ligand whose properties allow discrimination of light-up effects induced by metal ion chelation and variation of pH. Distinction of the two effects is important for the use of this type of ligand to detect and monitor metal ions in aqueous solutions. The synthesis of the ligand was performed in two steps, which involve the reaction of rhodamine B with hydrazine hydrate to form rhodamine B hydrazide followed by condensation with 2-pyridinecarboxaldehyde and was successfully optimized using a solvent free approach under microwave irradiation. The ligand was obtained in the expected spirolactam form and was characterized in the solid state by EA, MS and single-crystal X-ray diffraction. The ligand was characterized in solution by NMR and absorption and fluorescence spectroscopies and its properties were found to be sensitive to pH and concentration of iron(III). The study of the fluorescence properties at variable pH shows that the compound is fluorescent in the range 2 < pH < 4 with maximum intensity at pH 3 and allowed the determination of two pK(a) values (pK(a1) = 2.98, pK(a2) = 2.89) and establishment of the corresponding distribution diagram. The very low pK(a) values guarantee that above pH equal to 4 the ligand is mostly present in the fully non-protonated and non-fluorescent form L. The study of the interaction of the ligand with iron(iii) was performed in DMSO and DMSO-H(2)O to exclude the influence of pH and due to the low solubility of the compound. The results indicate that the presence of iron(III) triggers the opening of the spirolactam form of the ligand and the maximum intensity obtained at a metal : ligand ratio of 1 : 2 is consistent with the formation of an iron(III) complex with the tridentate ligand. PMID:23299402

  10. Highly selective detection of 2,4,6-trinitrophenol and Cu(2+) ions based on a fluorescent cadmium-pamoate metal-organic framework.

    PubMed

    Ye, Junwei; Zhao, Limei; Bogale, Raji Feyisa; Gao, Yuan; Wang, Xiaoxiao; Qian, Xiaomin; Guo, Song; Zhao, Jianzhang; Ning, Guiling

    2015-01-26

    A luminescent cadmium-pamoate metal-organic framework, [Cd2 (PAM)2 (dpe)2 (H2 O)2 ]⋅0.5(dpe) (1), has been synthesized under hydrothermal conditions by using π-electron-rich ligands 4,4'-methylenebis(3-hydroxy-2-naphthalenecarboxylic acid) (H2 PAM) and 1,2-di(4-pyridyl)ethylene (dpe). Its structure is composed of both mononuclear and dinuclear Cd(II) building units, which are linked by the PAM and dpe ligands, resulting in a (4,8)-connected 3D framework. The π-conjugated dpe guests are located in a 1D channel of 1. The strong emission of 1 could be quenched efficiently by trace amounts of 2,4,6-trinitrophenol (TNP), even in the presence of other competing analogues such as 4-nitrophenol, 2,6-dinitrotoluene, 2,4-dinitrotoluene, nitrobenzene, 1,3-dinitrobenzene, hydroquinone, dimethylbenzene, and bromobenzene. The high sensitivity and selectivity of the fluorescence response of 1 to TNP shows that this framework could be used as an excellent sensor for identifying and quantifying TNP. In the same manner, 1 also exhibits superior selectivity and sensitivity towards Cu(2+) compared with other metal ions such as Zn(2+) , Mn(2+) , Mg(2+) , K(+) , Na(+) , Ni(2+) , Co(2+) , and Ca(2+) . This is the first MOF that can serve as a dual functional fluorescent sensor for selectively detecting trace amounts of TNP and Cu(2+) . PMID:25431256

  11. Analytical capabilities of laboratory, benchtop and handheld X-ray fluorescence systems for detection of metals in aqueous samples pre-concentrated with solid-phase extraction disks

    NASA Astrophysics Data System (ADS)

    Marguí, E.; Hidalgo, M.; Queralt, I.; Van Meel, K.; Fontàs, C.

    2012-01-01

    We aimed to achieve improved instrumental sensitivity and detection limits for the analysis of several elements (Cu, Ni, Zn, Pb and Cd) in aqueous samples with energy dispersive X-ray fluorescence spectrometry (EDXRF). The metals were pre-concentrated from aqueous solutions using commercially available organic-based solid-phase extraction (SPE) disks functionalized with iminodiacetate groups. These thin-layer organic materials provide an ideal support for XRF analysis. The elements were collected on the SPE extraction disks using a simple filtration procedure (starting with 1 L of aqueous sample) that allows direct XRF measurements to be performed in the field (in situ). We evaluated the analytical possibilities and drawbacks of using this pre-concentration procedure in combination with the following XRF configurations: a handheld unit, a benchtop EDXRF system and a high-energy polarized-beam EDXRF instrument (HE-P-EDXRF). Using the HE-P-EDXRF system, the detection limits for all metals were more than one order of magnitude lower than those attained using handheld and benchtop EDXRF instrumentation. For the detection of metal concentrations higher than ~ 20 μg/L, however, handheld or benchtop systems remain a very good option due to their extreme simplicity of operation and low-cost, compact design. We demonstrate the application of these methodologies, using the three equipment systems, to the analysis of trace concentrations of metals in different types of aqueous samples, including tap water and waste water.

  12. Employing a portable X-Ray fluorescence (P-XRF) analyser and GIS to identify and map heavy metal pollution in soils of a traditional bonfire site

    NASA Astrophysics Data System (ADS)

    Dao, Ligang; Zhang, Chaosheng; Morrison, Liam

    2010-05-01

    Soils in the vicinity of bonfires are recipients of metal contaminants from burning of metal-containing materials. In order to better understand the impacts of bonfires on soils, a total of 218 surface soil samples were collected from a traditional bonfire site in Galway City, Ireland. Concentrations of Cu, Pb and Zn were determined using a portable X-ray Fluorescence (P-XRF) analyser. Strong variations were observed for these metals, and several samples contained elevated Zn concentrations which exceeded the intervention threshold of the Dutch criteria (720 mg kg-1). Spatial clusters and spatial outliers were detected using the local Moran's I index and were mapped using GIS. Two clear high value spatial clusters could be observed on the upper left side and centre part of the study area for Cu, Pb and Zn. Results of variogram analyses showed high nugget-sill-ratios for Cu, Pb and Zn, indicating strong spatial variation over short distances which could be resulted from anthropogenic activities. The spatial interpolation method of ordinary kriging was applied to produce the spatial interpolation maps for Cu, Pb and Zn, and the areas with elevated concentrations were in line with historical locations of the bonfires. The hazard maps showed small parts of the study area with Zn concentrations exceeding the Dutch intervention values. In order to prevent further contamination from bonfires, it is advised that tyres and other metal-containing wastes should not be burnt. The results in this study provide useful information for management of bonfires.

  13. Tunable Two-color Luminescence and Host–guest Energy Transfer of Fluorescent Chromophores Encapsulated in Metal-Organic Frameworks

    PubMed Central

    Yan, Dongpeng; Tang, Yanqun; Lin, Heyang; Wang, Dan

    2014-01-01

    Co-assembly of chromophore guests with host matrices can afford materials which have photofunctionalities different from those of individual components. Compared with clay and zeolite materials, the use of metal–organic frameworks (MOFs) as a host structure for fabricating luminescent host–guest materials is still at an early stage. Herein, we report the incorporation of a laser dye, 4-(dicyanomethylene)-2-methyl-6-(4-dimethylaminostyryl)-4H-pyran (DCM), into stilbene-based and naphthalene-based MOF systems. The resulting materials exhibit blue/red two-color emission, and the intensity ratio of blue to red fluorescence varies in different planes within the MOF crystal as detected by 3D confocal fluorescence microscopy. The observed changes in ratiometric fluorescence suggest the occurrence of energy transfer from MOF host to DCM molecules, which can be further confirmed by periodic density functional theoretical (DFT) calculations. Moreover, selective changes in luminescence behavior are observed on treating the guest@MOF samples with volatile organic compounds (methanol, acetone and toluene), indicating that these host–guest systems have potential applications as fluorescence sensors. It can be expected that by rational selection of MOF hosts and guest chromophores with suitable emissive colors and energy levels, a wide variety of multi-color luminescent and energy-transfer systems can readily be prepared in a similar manner. PMID:24614015

  14. Metal-enhanced fluorescence-based core-shell Ag@SiO₂ nanoflares for affinity biosensing via target-induced structure switching of aptamer.

    PubMed

    Lu, Lu; Qian, Yunxia; Wang, Lihui; Ma, Keke; Zhang, Yaodong

    2014-02-12

    One of the great challenges in metal-enhanced fluorescence (MEF) technology is the achievement of distance modulation with nanometer accuracy between the fluorophore and metal surface to obtain maximum enhancement. We propose an MEF-based core-shell Ag@SiO2 nanoflare for distance control via the thickness of silica shell with cooperation of DNA hybridization. The nanoflare contains a 50 nm spherical silver nanoparticle (Ag NP) core, a 8 nm silica shell, and cyanine (Cy5)-labeled aptamer hybridized with a complementary DNA (cDNA) immobilized onto the shell surface. The formation of the Cy5-labeled aptamer/cDNA duplex on the Ag@SiO2 NP surface results in the confinement of Cy5 to the shell surface and an increase in the fluorescence of Cy5 with a 32-fold enhancement factor in bulk solution (signal-on). In the presence of affinity-binding targets, the Cy5-labeled aptamers confined onto the Ag@SiO2 NP surface dissociate from their cDNA into the solution because of structure switching. The target-induced release of aptamer leads to a reduction in the enhanced fluorescence signal of the labeled Cy5 moiety (signal-off). Thus, the nanoflare can be used as a sensor for target recognition. Using adenosine-5'-triphosphate (ATP) aptamer, detection of ATP has a linear response from 0 to 0.5 mM and a detection limit of 8 μM. With various types of DNA probes immobilized onto the core-shell Ag@SiO2 NPs, the MEF-based nanoflare has provided an effective platform for the detection and quantification of a broad range of analytes, such as mRNA regulation and detection, cell sorting, and gene profiling. PMID:24480015

  15. Ag@SiO2-entrapped hydrogel microarray: a new platform for a metal-enhanced fluorescence-based protein assay.

    PubMed

    Jang, Eunji; Kim, Minsu; Koh, Won-Gun

    2015-05-21

    We developed a novel protein-based bioassay platform utilizing metal-enhanced fluorescence (MEF), which is a hydrogel microarray entrapping silica-coated silver nanoparticles (Ag@SiO2). As a model system, different concentrations of glucose were detected using a fluorescence method by sequential bienzymatic reaction of hydrogel-entrapped glucose oxidase (GOX) and peroxidase (POD) inside a hydrogel microarray. Microarrays based on poly(ethylene glycol)(PEG) hydrogels were prepared by photopatterning a solution containing PEG diacrylate (PEG-DA), photoinitiator, enzymes, and Ag@SiO2. The resulting hydrogel microarrays were able to entrap both enzymes and Ag@SiO2 without leaching and deactivation problems. The presence of Ag@SiO2 within the hydrogel microarray enhanced the fluorescence signal, and the extent of the enhancement was dependent on the thickness of silica shells and the amount of Ag@SiO2. Optimal MEF effects were achieved when the thickness of the silica shell was 17.5 nm, and 0.5 mg mL(-1) of Ag@SiO2 was incorporated into the assay systems. Compared with the standard hydrogel microarray-based assay performed without Ag@SiO2, more than a 4-fold fluorescence enhancement was observed in a glucose concentration range between 10(-3) mM and 10.0 mM using hydrogel microarray entrapping Ag@SiO2, which led to significant improvements in the sensitivity and the limit of detection (LOD). The hydrogel microarray system presented in this study could be successfully combined with a microfluidic device as an initial step to create an MEF-based micro-total-analysis-system (μ-TAS). PMID:25837891

  16. In situ induced metal-enhanced fluorescence: a new strategy for biosensing the total acetylcholinesterase activity in sub-microliter human whole blood.

    PubMed

    Ma, KeKe; Lu, Lu; Qi, Zongli; Feng, Jingjing; Zhuo, Caixia; Zhang, Yaodong

    2015-06-15

    Acetylcholinesterase (AChE) and butyrylcholinesterase (BChE) activities (i.e., total AChE) in human blood are biomarkers for theranostic monitoring of organophosphate neurotoxin-poisoned patients. We developed an ultra-sensitive method to detect the total AChE activity in sub-microliter human whole blood based on in situ induced metal-enhanced fluorescence (MEF). Both AChE and BChE can catalyze the hydrolysis of the acetylthiocholine (ATCh) substrate and produce positively-charged thiocholine (TCh). TCh can reverse the negatively-charged surface of core-shell Ag@SiO2 nanoparticles (NPs). The negatively-charged fluorescent dye (8-hydroxypyrene-1,3,6-trisulfonic acid, HPTS) is then confined to the surface of Ag@SiO2 NPs and generates an enhanced fluorescence signal in situ. Changes in the surface charge of Ag@SiO2 NPs are monitored by Zeta potential, and the MEF effect is confirmed by the measurements of fluorescence time decay. AChE activity has a dynamic range of 0 U/mL to 0.005 U/mL and a detection limit of 0.05 mU/mL. The total AChE activity in the sub-microliter human whole blood could be determined; the results were further validated. Therefore, combining the AChE catalytic reaction with MEF provides a simple, ultra-sensitive, and cost-effective "in situ MEF" approach to determine the total AChE activity in human whole blood sample down to sub-microliters without matrix interferences. The strategy also allows potential usage in other tissues and other fields. PMID:25660508

  17. Detection of Early Stage Apoptotic Cells Based on Label-Free Cytochrome c Assay Using Bioconjugated Metal Nanoclusters as Fluorescent Probes.

    PubMed

    Shamsipur, Mojtaba; Molaabasi, Fatemeh; Hosseinkhani, Saman; Rahmati, Fereshteh

    2016-02-16

    Cytochrome c (Cyt c) is an important biomarker in cell lysates for the early stage of apoptosis or anticancer agents. Here, two novel label-free fluorescence assays based on hemoglobin-stabilized gold nanoclusters (Hb/AuNCs) and aptamer-stabilized silver nanoclusters (DNA/AgNCs) for analysis of Cyt c are presented. The heme group of the protein induces sensitive sensing platforms accompanied by the decreased fluorescence of both metal nanoclusters. The quenching processes observed found to be based on the fluorescence resonance energy transfer mechanism from Hb/AuNCs to Cyt c and photoinduced electron transfer from DNA/AgNCs to the aptamer-Cyt c complex. The linear range for Cyt c was found to be 0-10 μM for Hb/AuNCs and from 0 to 1 μM for DNA/AgNCs, with limits of detection of ∼15 nM. On the basis of strong binding affinity of DNA aptamers for their target proteins, the DNA/AgNCs probe was successfully applied to the quantitative determination of Cyt c in cell lysates, which opens a new avenue to early diagnostics and drug screening with high sensitivity. Compared to the conventional Western blot method, the presented assays are low cost, easy to prepare the fluorescent probes, and sensitive, while overall time for the detection and quantitation of Cyt c from isolated mitochondria is only 20 min. The proposed method for Cyt c detection may also be useful for the study of those materials that cause mitochondrial dysfunction and apoptotic cell death. PMID:26812937

  18. Interionic Force Model for Pentahalide Molecules and Higher Niobium-Based Halide Clusters

    NASA Astrophysics Data System (ADS)

    Önem, Z. Çiçek; Akdeniz, Z.; Tosi, M. P.

    2002-12-01

    Molecular bound states tend to become progressively more stable in the melts of polyvalent metal halides as the nominal valence of the metal increases. We examine in this work the case of pentavalent metal halides. First we propose a simple ionic model for the binding in several pentahalide clusters: the chlorides of Nb, Ta, Sb, and Mo and the bromides of Nb and Ta. The molecular monomers of these compounds have a D3h trigonal-bipyramidal structure in the ground state, and we make use of data on equatorial bond lengths and breathing mode frequencies in the vapour to determine the main force-law parameters of the metal ion. We also find that the C4v square-pyramidal structure is mechanically unstable against transformation into the D3h shape.We then consider higher molecular clusters, i. e. the dimers of Nb pentahalides and the bound states formed by NbCl5 with the chlorides of Cs, Al, Ga, and Sb. We propose structural models for all these stable clusters and compare their calculated vibrational frequencies with the available data from vibrational spectroscopy of mixed melts.

  19. Characterization of Heavy Metal Contents in the Bulk Atmospheric Aerosols Simultaneously Collected at Three Islands in Okinawa, Japan by X-ray fluorescence spectrometric method (XRF)

    NASA Astrophysics Data System (ADS)

    Oshiro, Y.; ITOH, A.; Azechi, S.; Somada, Y.; Handa, D.; Miyagi, Y.; Arakaki, T.; Tanahara, A.

    2011-12-01

    We studied heavy metal contents of atmospheric aerosols using an X-ray fluorescence spectrometric method (XRF). The XRF method enables us to analyze heavy metal contents of bulk aerosols rapidly without any chemical pretreatments. We used an energy dispersive X-ray fluorescence spectrometer that is compact and portable. We prepared several different amounts of standard reference materials (NIES No.28) of Japanese National Institute of Environmental Studies on quartz filters for calibration curves. Then, we evaluated quantitative responses of XRF method by comparing with the metal contents determined by inductively coupled plasma mass spectrometry (ICP-MS) and atomic absorption spectrometry (AAS) after acid-digestion. Good linear relationships between X-ray intensity and amount of aerosol on filter were seen in the following 10 metals; Al, K, Ti, V, Fe, Ni, Rb, Ba, Pb and As. We then used XRF method to determine heavy metal contents in authentic atmospheric aerosols collected in Okinawa islands, Japan. Okinawa islands, consisting of many small islands, are situated east of Asian continent, and its location in Asian is well suited for studying long-range transport of air pollutants. Also, in Okinawa islands, maritime air mass prevails during summer, while Asian continental air mass dominates during fall, winter, and spring. The maritime air mass data can be seen as background clean air and can be compared with continental air mass which has been affected by anthropogenic activities such as industries and automobiles. Therefore, Okinawa region is suitable area for studying impacts of air pollutants from East Asia. We simultaneously collected bulk aerosol samples by using identical high-volume air samplers at 3 islands; Cape Hedo Atmospheric Aerosol Monitoring Station (CHAAMS, Okinawa island), Kume island (ca. 160 km south-west of CHAAMS), and Minami-Daitou island (ca. 320 km south-east of CHAAMS). We report and discuss spatial and temporal distribution of heavy metals

  20. Methyl halide production associated with kelp

    NASA Technical Reports Server (NTRS)

    Dastoor, Minoo N.; Manley, Steven L.

    1985-01-01

    Methyl halides (MeX) are important trace constituents of the atmosphere because they, mostly MeCl, have a major impact on the atmospheric ozone layer. Also, MeCl may account for 5 pct. of the total Cl budget and MeI may have a central role in the biogeochemical cycling of iodine. High MeI concentrations were found in seawater from kelp beds and it has been suggested that MeI is produced by kelps and that MeI and MeBr along with numerous other halocarbons were released by non-kelp marine macroalgae. The objective was to determine if kelps (and other seaweeds) are sources of MeX and to assess their contribution to the estimated global source strength (EGSS) of MeX. Although the production of MeX appears to be associated with kelp, microbes involved with kelp degradation also produce MeX. Microbial MeX production may be of global significance. The microbial MeX production potential, assuming annual kelp production equals kelp degradation and 100 pct. conversion of kelp halides to MeX, is approx. 2 x the EGSS. This is not achieved but indicates that microbial production of MeX may be of global significance.