Browsing by Subject "Negative ions"

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    Controlled optical transition rates in nanodroplets
    (IEEE, 2000) Özçelik, Serdar
    The time-resolved fluorescence measurements of 3,3′-diethyl-5,5′-dichloro-9-phenylthiacarbocyanine (DDPT) in bulk solvents and methanol-in-oil reverse micellar systems is presented which include nano-sized methanol droplets stabilized with anionic surfactant aerosol-OT (AOT) in n-heptane, at room temperature. Relative fluorescence intensities of DDPT increase with a factor of 16 in m/o reverse micelles in comparison to those in bulk methanol. The radiative and nonradiative rate constants decreases in methanol dispersions, indicating that internal motions of DDPT in the droplets is reduced due to strong electrostatic interactions between the positively charged DDPT and the negatively charged sulfonate head-groups of AOT.
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    ItemOpen Access
    Cyclodextrin functionalized poly(methyl methacrylate) (PMMA) electrospun nanofibers for organic vapors waste treatment
    (Elsevier BV, 2010) Uyar, Tamer; Havelund, R.; Nur, Y.; Balan, A.; Hacaloglu, J.; Toppare, L.; Besenbacher, F.; Kingshott, P.
    Poly(methyl methacrylate) (PMMA) nanofibers containing the inclusion complex forming betacyclodextrin (_-CD) were successfully produced by means of electrospinning in order to develop functional nanofibrous webs for organic vapor waste treatment. Electrospinning of uniform PMMA nanofibers containing different loadings of _-CD (10%, 25% and 50% (w/w)) was achieved. The surface sensitive spectroscopic techniques; X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) showed that some of the _-CD molecules are present on the surface of the PMMA nanofibers, which is essential for the trapping of organic vapors by inclusion complexation. Direct pyrolysis mass spectrometry (DP-MS) studies showed that PMMA nanowebs containing _-CD can entrap organic vapors such as aniline, styrene and toluene from the surroundings due to inclusion complexation with _-CD that is present on the fiber surface. Our study showed that electrospun nanowebs functionalized with cyclodextrinsmayhave the potential to be used as molecular filters and/or nanofilters for the treatment of organic vapor waste and air filtration purposes.
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    FTIR spectroscopic characterization of NOx species adsorbed on ZrO2 and ZrO2-SO42-
    (American Chemical Society, 2002) Kantcheva, M.; Ciftlikli, E. Z.
    The nature of the NOx species produced during the adsorption of NO at room temperature and during its coadsorption with oxygen on pure and sulfated zirconia has been investigated by means of in situ FTIR spectroscopy. The adsorption of NO on both samples occurs through disproportionation leading to the formation of nitrous acid; water molecules; nitro species; and anionic nitrosyls, NO-. A mechanism for the formation of these adsorption forms is proposed. The NO- species are stable on the surface of zirconia, whereas on the sulfated sample, they are readily oxidized by the SO42- groups. The process of NO disproportionation is favored by wet surfaces and occurs with participation of the tribridged (ZrO2) and terminal (ZrO2-SO42-) hydroxyl groups. Coadsorption of NO and O2 on pure zirconia leads to the formation of various kinds of nitrate species. The presence of sulfate ions reduces the amount of surface nitrates and decreases their thermal stability. An analysis of the combination bands of the nitrate species shows that this spectral region can be used for structural identification of bidentate and bridged nitrates.
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    Spectroscopic characterization of tungstated zirconia prepared by equilibrium adsorption from hydrogen peroxide solutions of tungsten(VI) precursors
    (2007) Kantcheva, M.; Koz, C.
    Two series of WO x /ZrO2 samples are prepared by equilibrium adsorption from H2O2 solutions at pH 1.8 containing two different precursor anions, [W2O3(O 2)4(H2O)2]2- and [H 2W12O40]6-. The starting material is amorphous zirconium oxyhydroxide. The maximum W densities obtained are larger than that reported in the literature for systems synthesized by the same method using aqueous non-peroxide solutions. In the case of the metatungstate precursor, this increase is attributed to the generation of additional anchoring sites by interaction between the amorphous support and H2O 2. The high uptake achieved when the peroxo complex is used as a precursor is a result of both the ZrO x (OH)4-2x -H 2O2 interaction and low nuclearity of the adsorbing anion. The materials are characterized by XRD, DR-UV-vis, Micro-Raman and FT-IR spectroscopy. The surface acidities of samples with identical W loading prepared by equilibrium adsorption from the [H2W12O 40]6--H2O2 system and by impregnation with aqueous solution of ammonium metatungstate are investigated by FT-IR spectroscopy of CO adsorbed at 80 K. © Springer Science+Business Media, LLC 2007.
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    Theoretical investigation of excited states of oligothiophene anions
    (2008) Alkan, F.; Salzner, U.
    Electron-hole symmetry upon p- and n-doping of conducting organic polymers is rationalized with Hückel theory by the presence of symmetrically located intragap states. Since density functional theory (DFT) predicts very different geometries and energy level diagrams for conjugated π-systems than semiempirical methods, it is an interesting question whether DFT confirms the existence of electron-hole symmetry predicted at the Hückel level. To answer this question, geometries of oligothiophene anions with 5-19 rings were optimized and their UV/vis spectra were calculated with time-dependent DFT. Although DFT does not produce symmetrically placed sub-band energy levels, spectra of cations and anions are almost identical. The similarity in transition energies and oscillator strengths of anions and cations can be explained by the fact that the single sub-band energy level of cations lies above the valence band by the same amount of energy as the single sub-band level of anions lies below the conduction band. This and the resemblance of the energy level spacings in valence bands of cations to those in conduction bands of anions give rise to peaks with equal energies and oscillator strengths. © 2008 American Chemical Society.