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Sample records for anions electronic effects

  1. Extreme electron correlation effects on the electric properties of atomic anions

    International Nuclear Information System (INIS)

    Canuto, S.

    1994-01-01

    The contribution of the electron correlation effects to the calculated dipole polarizability and hyper-polarizability of the first-row atomic anions is calculated and analyzed. It is shown that the total correlation contribution to the dipole hyperpolarizability is extremely large with the Hartree-Fock model accounting for only a small fraction of the accurate result. The linear and, more pronounced, the nonlinear response of atomic anions to the application of an electric field emphatically shows the effects of the correlated motion of the electrons

  2. Experimental evidence for interactions between anions and electron-deficient aromatic rings.

    Science.gov (United States)

    Berryman, Orion B; Johnson, Darren W

    2009-06-14

    This feature article summarizes our research aimed at using electron-deficient aromatic rings to bind anions in the context of complementary research in this active field. Particular attention is paid to the different types of interactions exhibited between anions and electron-deficient arenes in solution. The 120+ references cited in this article underscore the flurry of recent activity by numerous researchers in this field, which was relatively nascent when our efforts began in 2005. While the interaction of anions with electron-deficient aromatic rings has recently garnered much attention by supramolecular chemists, the observation of these interactions is not a recent discovery. Therefore, we begin with a historical perspective on early examples of anions interacting with electron-deficient arenes. An introduction to recent (and not so recent) computational investigations concerning anions and electron-deficient aromatic rings as well as a brief structural survey of crystalline examples of this interaction are provided. Finally, the limited solution-based observations of anions interacting with electron-deficient aromatic rings are summarized to introduce our current investigations in this area. We highlight three different systems from our lab where anion-arene interactions have been investigated. First, we show that tandem hydrogen bonds and anion-arene interactions augment halide binding in solution. Second, a crystallographic and computational study highlights the multiple types of interactions possible between anions and electron-deficient arenes. Third, we summarize the first example of a class of designed receptors that emphasize the different types of anion-arene interactions possible in solution.

  3. Benzonitrile: Electron affinity, excited states, and anion solvation

    Science.gov (United States)

    Dixon, Andrew R.; Khuseynov, Dmitry; Sanov, Andrei

    2015-10-01

    We report a negative-ion photoelectron imaging study of benzonitrile and several of its hydrated, oxygenated, and homo-molecularly solvated cluster anions. The photodetachment from the unsolvated benzonitrile anion to the X ˜ 1 A 1 state of the neutral peaks at 58 ± 5 meV. This value is assigned as the vertical detachment energy (VDE) of the valence anion and the upper bound of adiabatic electron affinity (EA) of benzonitrile. The EA of the lowest excited electronic state of benzonitrile, a ˜ 3 A 1 , is determined as 3.41 ± 0.01 eV, corresponding to a 3.35 eV lower bound for the singlet-triplet splitting. The next excited state, the open-shell singlet A ˜ 1 A 1 , is found about an electron-volt above the triplet, with a VDE of 4.45 ± 0.01 eV. These results are in good agreement with ab initio calculations for neutral benzonitrile and its valence anion but do not preclude the existence of a dipole-bound state of similar energy and geometry. The step-wise and cumulative solvation energies of benzonitrile anions by several types of species were determined, including homo-molecular solvation by benzonitrile, hydration by 1-3 waters, oxygenation by 1-3 oxygen molecules, and mixed solvation by various combinations of O2, H2O, and benzonitrile. The plausible structures of the dimer anion of benzonitrile were examined using density functional theory and compared to the experimental observations. It is predicted that the dimer anion favors a stacked geometry capitalizing on the π-π interactions between the two partially charged benzonitrile moieties.

  4. Mechanism of action of anions on the electron transport chain in thylakoid membranes of higher plants.

    Science.gov (United States)

    Singh-Rawal, Pooja; Zsiros, Ottó; Bharti, Sudhakar; Garab, Gyozo; Jajoo, Anjana

    2011-04-01

    With an aim to improve our understanding of the mechanisms behind specific anion effects in biological membranes, we have studied the effects of sodium salts of anions of varying valency in thylakoid membranes. Rates of electron transport of PS II and PS I, 77K fluorescence emission and excitation spectra, cyclic electron flow around PS I and circular dichroism (CD) spectra were measured in thylakoid membranes in order to elucidate a general mechanism of action of inorganic anions on photosynthetic electron transport chain. Re-distribution of absorbed excitation energy has been observed as a signature effect of inorganic anions. In the presence of anions, such as nitrite, sulphate and phosphate, distribution of absorbed excitation energy was found to be more in favor of Photosystem I (PS I). The amount of energy distributed towards PS I depended on the valency of the anion. In this paper, we propose for the first time that energy re-distribution and its valence dependence may not be the effect of anions per se. The entry of negative charge (anion) is accompanied by influx of positive charge (protons) to maintain a balance of charge across the thylakoid membranes. As reflected by the CD spectra, the observed energy re-distribution could be a result of structural rearrangements of the protein complexes of PS II caused by changes in the ionic environment of the thylakoid lumen.

  5. Probing Intermolecular Electron Delocalization in Dimer Radical Anions by Vibrational Spectroscopy

    International Nuclear Information System (INIS)

    Mani, Tomoyasu; Brookhaven National Laboratory; Grills, David C.

    2017-01-01

    Delocalization of charges is one of the factors controlling charge transport in conjugated molecules. It is considered to play an important role in the performance of a wide range of molecular technologies, including organic solar cells and organic electronics. Dimerization reactions are well-suited as a model to investigate intermolecular spatial delocalization of charges. And while dimerization reactions of radical cations are well investigated, studies on radical anions are still scarce. Upon dimerization of radical anions with neutral counterparts, an electron is considered to delocalize over the two molecules. By using time-resolved infrared (TRIR) detection coupled with pulse radiolysis, we show that radical anions of 4-n-hexyl-4'-cyanobiphenyl (6CB) undergo such dimerization reactions, with an electron equally delocalized over the two molecules. We have recently demonstrated that nitrile ν(C≡N) vibrations respond to the degree of electron localization of nitrile-substituted anions: we can quantify the changes in the electronic charges from the neutral to the anion states in the nitriles by monitoring the ν(C≡N) IR shifts. In the first part of this article, we show that the sensitivity of the ν(C≡N) IR shifts does not depend on solvent polarity. In the second part, we describe how probing the shifts of the nitrile IR vibrational band unambiguously confirms the formation of dimer radical anions, with K dim = 3 × 10 4 M –1 . IR findings are corroborated by electronic absorption spectroscopy and electronic structure calculations. We find that the presence of a hexyl chain and the formation of π–π interactions are both crucial for dimerization of radical anions of 6CB with neutral 6CB. Our study provides clear evidence of spatial delocalization of electrons over two molecular fragments.

  6. Probing electron density of H-bonding between cation-anion of imidazolium-based ionic liquids with different anions by vibrational spectroscopy.

    Science.gov (United States)

    Gao, Yan; Zhang, Liqun; Wang, Yong; Li, Haoran

    2010-03-04

    Attenuated total reflection infrared spectroscopy and density functional theory calculation have been employed to study the spectral properties of imidazolium-based ionic liquids (ILs) with different anions. ILs based on 1-butyl-3-methylimidazolium cation with different anions, OH(-), CF(3)CO(2)(-), HSO(4)(-), H(2)PO(4)(-), Cl(-), PF(6)(-), and BF(4)(-), are investigated in the present work. It has been shown that the C(2)-H stretching vibration of the imidazolium ring is closely related to the electron density of H-bonding between the two closest cations and anions for pure ILs. The electron density of H-bonding between cation and anion with different anions decreases in the order [OH](-) > [H(2)PO(4)](-) > [HSO(4)](-) > [CF(3)CO(2)](-) > [Cl](-) > [BF(4)](-) > [PF(6)](-). For aqueous ILs, with increasing water content, the aromatic C-H stretching vibration of the imidazolium cation showed systematic blue-shifts. Especially for BmimOH, the nu(C(2))(-H) undergoes a drastic blue-shift by 58 cm(-1), suggesting that the formation of the strong hydrogen bonds O-H...O may greatly weaken the electron density of H-bonding between the cation and anion of ILs.

  7. (100) faceted anion voids in electron irradiated fluorite

    International Nuclear Information System (INIS)

    Johnson, E.

    1979-01-01

    High fluence electron irradiation of fluorite crystals in the temperature range 150 to 320 K results in formation of a simple cubic anion void superlattice. Above 320 K the damage structure changes to a random distribution of large [001] faceted anion voids. This voidage behaviour, similar to that observed in a range of irradiated metals, is discussed in terms points defect rather than conventional colour centre terminology. (Auth.)

  8. Anion Photoelectron Spectroscopy of the Homogenous 2-Hydroxypyridine Dimer Electron Induced Proton Transfer System

    Science.gov (United States)

    Vlk, Alexandra; Stokes, Sarah; Wang, Yi; Hicks, Zachary; Zhang, Xinxing; Blando, Nicolas; Frock, Andrew; Marquez, Sara; Bowen, Kit; Bowen Lab JHU Team

    Anion photoelectron spectroscopic (PES) and density functional theory (DFT) studies on the dimer anion of (2-hydroxypyridine)2-are reported. The experimentally measured vertical detachment energy (VDE) of 1.21eV compares well with the theoretically predicted values. The 2-hydroxypyridine anionic dimer system was investigated because of its resemblance to the nitrogenous heterocyclic pyrimidine nucleobases. Experimental and theoretical results show electron induced proton transfer (EIPT) in both the lactim and lactam homogeneous dimers. Upon electron attachment, the anion can serve as the intermediate between the two neutral dimers. A possible double proton transfer process can occur from the neutral (2-hydroxypyridine)2 to (2-pyridone)2 through the dimer anion. This potentially suggests an electron catalyzed double proton transfer mechanism of tautomerization. Research supported by the NSF Grant No. CHE-1360692.

  9. Positron Spur Reactions with Excess Electrons and Anions in Liquid Organic Mixtures of Electron Acceptors

    DEFF Research Database (Denmark)

    Lévay, B.; Mogensen, O. E.

    1980-01-01

    By means of the positron lifetime technique we have measured positronium (Ps) yields in mixtures of nonpolar liquids with various electron scavengers which bind the electron fairly weakly (1–2 eV) in stable anions. The results are discussed with reference to recent excess electron works, and new...... experiments on anions and excess electrons are proposed. The minimum of the Ps yield versus CS2 concentration curves caused by partly delocalization of electrons on several scavenger molecules, which was observed previously in saturated aliphatic hydrocarbons occurred also in the saturated cyclic hydrocarbon...... cyclohexane, but did not appear in the aromatic benzene. This might be explained by the weak electron acceptor property of aromatics. In the Ps yield versus SF6 concentration curve in hexane a similar minimum appeared as in the CS2 case, probably by the same reason. By adding 0.8 M CS2 to the system...

  10. Introducing various ligands into superhalogen anions reduces their electronic stabilities

    Science.gov (United States)

    Smuczyńska, Sylwia; Skurski, Piotr

    2008-02-01

    The vertical electron detachment energies (VDE) of six NaX2- anions (where X = F, Cl, Br) were calculated at the OVGF level with the 6-311++G(3df) basis sets. In all the cases studied the VDE exceeds the electron affinity of chlorine atom and thus those species were classified as superhalogen anions. The largest vertical binding energy was found for the NaF2- system (6.644 eV). The strong VDE dependence on the ligand type, ligand-central atom distance, and the character of the highest occupied molecular orbital (HOMO) was observed and discussed.

  11. Uranium isotopic effect studies on cation and anion exchange resins

    International Nuclear Information System (INIS)

    Sarpal, S.K.; Gupta, A.R.

    1975-01-01

    Uranium isotope effects in exchange reactions involving hexavalent and tetravalent uranium, on ion exchange resins, have been re-examined. The earlier work on uranium isotope effects in electron exchange reactions involving hexavalent and tetravalent uranium, has been critically reviewed. New experimental data on these systems in hydrochloric acid medium, has been obtained, using break-through technique on anion-exchange columns. The isotope effects in these break-through experiments have been reinterpreted in a way which is consistent with the anion exchange behaviour of the various uranium species in these systems. (author)

  12. Carbonate radical anion-induced electron transfer in bovine serum albumin

    Energy Technology Data Exchange (ETDEWEB)

    Joshi, Ravi [Chemistry Group, Bhabha Atomic Research Centre, Mumbai 400 085 (India)]. E-mail: rjudrin@yahoo.com; Mukherjee, T. [Chemistry Group, Bhabha Atomic Research Centre, Mumbai 400 085 (India)

    2006-07-15

    Reaction of native and thermally denatured bovine serum albumin (BSA) with carbonate radical anion (CO{sub 3}{sup -} radical) has been studied using pulse radiolysis technique. Scavenging of CO{sub 3}{sup -} radical by native BSA and consequent electron transfer from tyrosine to tryptophan radical has been observed to occur with almost same rate constant (k{approx}1.7x10{sup 8} dm{sup 3} mol{sup -1} s{sup -1}) at pH 8.8. Effect of structural changes, due to thermal denaturation, on scavenging of CO{sub 3}{sup -} radical and the electron transfer process have been studied and discussed in this paper.

  13. Theoretical study of X⁻ · 1 · YF (1 = triazine, X = Cl, Br and I, Y = H, Cl, Br, I, PH₂ and AsH₂): noncovalently electron-withdrawing effects on anion-arene interactions.

    Science.gov (United States)

    Chen, Yishan; Yao, Lifeng

    2014-01-01

    The ternary complexes X(-) · 1 · YF (1 = triazine, X = Cl, Br and I, Y = H, Cl, Br, I, PH2 and AsH2) have been investigated by MP2 calculations to understand the noncovalently electron-withdrawing effects on anion-arene interactions. The results indicate that in binary complexes (1 · X(-)), both weak σ-type and anion-π complexes can be formed for Cl(-) and Br(-), but only anion-π complex can be formed for I(-). Moreover, the hydrogen-bonding complex is the global minimum for all three halides in binary complexes. However, in ternary complexes, anion-π complex become unstable and only σ complex can retain in many cases for Cl(-) and Br(-). Anion-π complex keeps stable only when YF = HF. In contrast with binary complexes, σ complex become the global minimum for Cl(-) and Br(-) in ternary complexes. These changes in binding mode and strength are consistent with the results of covalently electron-withdrawing effects. However, in contrast with the covalently electron-withdrawing substituents, Cl(-) and Br(-) can attack the aromatic carbon atom to form a strong σ complex when the noncovalently electron-withdrawing effect is induced by halogen bonding. The binding behavior for I(-) is different from that for Cl(-) and Br(-) in two aspects. First, the anion-π complex for I(-) can also keep stable when the noncovalent interaction is halogen bonding. Second, the anion-π complex for I(-) is the global minimum when it can retain as a stable structure.

  14. Low-energy electron-induced dissociation in condensed-phase L-cysteine I: Desorption of anions from chemisorbed films

    International Nuclear Information System (INIS)

    Alizadeh, E; Rowntree, P A; Massey, S; Sanche, L

    2015-01-01

    Among amino acids, cysteine has been widely studied, becoming a standard for molecular self-assembly experiments, because its mercapto group (-SH) allows the formation of self-assembled monolayers (SAMs) on metal surfaces. Dissociative electron attachment (DEA) on L-cysteine SAMs is investigated utilizing a time-of-flight mass spectrometer coupled with a low-energy electron gun. The results show that electrons with kinetic energies of 3 to 15 eV attach to L-cysteine producing anionic fragments of different masses (e.g., H - , O - , OH - , S - , SH - ) via dissociation of intermediate transient anions. The anion yield functions exhibited purely resonant behaviour with electron energies below 15 eV, indicating that the formation of transient anions is the predominant mechanism of production of anionic fragments from L-cysteine dissociation. (paper)

  15. Isotope effect study of κ-(BEDT-TTF)2Cu(NCS)2: Labeling in the anion

    International Nuclear Information System (INIS)

    Kini, A.M.; Wang, H.H.; Schlueter, J.A.

    1995-01-01

    Since the initial discovery of organic superconductivity in 1979, a large number of organic superconductors have now been synthesized. However, the mechanism of electron-pairing in these novel superconductors has remained largely unresolved. Isotope effect studies constitute an important experimental tool for the investigation of whether or not the electron-pairing mechanism in organic superconductors is phonon-mediated, as in conventional superconductors. Recent isotope effect studies in the authors' laboratory, involving seven different isotopically labeled BEDT-TTF (or ET) derivatives, have demonstrated the following: (1) intramolecular phonon modes involving C double-bond C and Csingle bondS stretching vibrations in the ET donor molecule are not the dominant mediators of electron-pairing, and (2) in κ-(ET) 2 Cu(NCS) 2 , there exist two competing isotope effects--a normal mass effect, i.e., lowering of T c upon isotopic labeling, when the ET molecular mass is increased by concurrent 13 C and 34 S labeling, in addition to an inverse isotope effect upon deuterium labeling in ET. It is of great interest to investigate if there is an isotope effect when the charge-compensating anions, which are also located within the non-conducting layer in the superconducting cation-radical salts, are isotopically labeled. The existence of an isotope effect when the anions are labeled would be indicative of electron-pairing with the mediation of vibrational frequencies associated with the anions. In this paper, the authors present the results of the first isotope effect study in which isotopic labeling in the anion portion of κ-(ET) 2 Cu(NCS) 2 is carried out. The authors find no isotope effect when the carbon and nitrogen atoms of the thiocyanate groups in the anion are replaced with 13 C and 15 N isotopes

  16. Photoelectron spectrum of valence anions of uracil and first-principles calculations of excess electron binding energies.

    Science.gov (United States)

    Bachorz, Rafał A; Klopper, Wim; Gutowski, Maciej; Li, Xiang; Bowen, Kit H

    2008-08-07

    The photoelectron spectrum (PES) of the uracil anion is reported and discussed from the perspective of quantum chemical calculations of the vertical detachment energies (VDEs) of the anions of various tautomers of uracil. The PES peak maximum is found at an electron binding energy of 2.4 eV, and the width of the main feature suggests that the parent anions are in a valence rather than a dipole-bound state. The canonical tautomer as well as four tautomers that result from proton transfer from an NH group to a C atom were investigated computationally. At the Hartree-Fock and second-order Moller-Plesset perturbation theory levels, the adiabatic electron affinity (AEA) and the VDE have been converged to the limit of a complete basis set to within +/-1 meV. Post-MP2 electron-correlation effects have been determined at the coupled-cluster level of theory including single, double, and noniterative triple excitations. The quantum chemical calculations suggest that the most stable valence anion of uracil is the anion of a tautomer that results from a proton transfer from N1H to C5. It is characterized by an AEA of 135 meV and a VDE of 1.38 eV. The peak maximum is as much as 1 eV larger, however, and the photoelectron intensity is only very weak at 1.38 eV. The PES does not lend support either to the valence anion of the canonical tautomer, which is the second most stable anion, and whose VDE is computed at about 0.60 eV. Agreement between the peak maximum and the computed VDE is only found for the third most stable tautomer, which shows an AEA of approximately -0.1 eV and a VDE of 2.58 eV. This tautomer results from a proton transfer from N3H to C5. The results illustrate that the characteristics of biomolecular anions are highly dependent on their tautomeric form. If indeed the third most stable anion is observed in the experiment, then it remains an open question why and how this species is formed under the given conditions.

  17. First observation of alkyne radical anions by electron spin resonance spectroscopy: Hexyne/n-hexane mixed crystals

    International Nuclear Information System (INIS)

    Matsuura, K.; Muto, H.

    1991-01-01

    The radical anions of alkynes have been first observed by electron spin resonance spectroscopy following alkene anions previously studied. Hexyne radical anions were formed in 1-, 2-, or 3-hexyne/n--hexane mixed crystals irradiated at 4.2 or 77 K. The characters of the anions were as follows; (a) the α-proton hyperfine coupling is very large (∼4.5 mT for the 1-hexyne anion), (b) the β-proton couplings are very small (∼1.0 mT for C--H β proton with the conformational angle of 0 degree), and (c) the radicals show a negative g shift (2.0014). From these observations, it was found that the anions have a nonlinear(bent) molecule structure in the anticonfiguration (trans C--C≡C--C) with the bend angle ∼60 degree, and that the unpaired electron orbital is approximately composed of the anticombination of the sp 2 hybrid orbitals of the C≡C carbon atoms. A discussion based on complete neglect of differential overlap (CNDO) molecular orbital (MO) calculations was given for the observed negative g shift, which was shown to be characteristic of the alkyne anions which have a high-lying unpaired electron orbital and an antibonding 2p--2p π carbon orbital just above it on the upper energy side

  18. Electron transfer by excited benzoquinone anions: slow rates for two-electron transitions.

    Science.gov (United States)

    Zamadar, Matibur; Cook, Andrew R; Lewandowska-Andralojc, Anna; Holroyd, Richard; Jiang, Yan; Bikalis, Jin; Miller, John R

    2013-09-05

    Electron transfer (ET) rate constants from the lowest excited state of the radical anion of benzoquinone, BQ(-•)*, were measured in THF solution. Rate constants for bimolecular electron transfer reactions typically reach the diffusion-controlled limit when the free-energy change, ΔG°, reaches -0.3 eV. The rate constants for ET from BQ(-•)* are one-to-two decades smaller at this energy and do not reach the diffusion-controlled limit until -ΔG° is 1.5-2.0 eV. The rates are so slow probably because a second electron must also undergo a transition to make use of the energy of the excited state. Similarly, ET, from solvated electrons to neutral BQ to form the lowest excited state, is slow, while fast ET is observed at a higher excited state, which can be populated in a transition involving only one electron. A simple picture based on perturbation theory can roughly account for the control of electron transfer by the need for transition of a second electron. The picture also explains how extra driving force (-ΔG°) can restore fast rates of electron transfer.

  19. Long-range intramolecular electron transfer in aromatic radical anions and binuclear transition metal complexes

    DEFF Research Database (Denmark)

    Kuznetsov, A. M.; Ulstrup, Jens

    1981-01-01

    Intramolecular electron transfer (ET) over distances up to about 10 Å between states in which the electron is localized on donor and acceptor groups by interaction with molecular or external solvent nuclear motion occurs, in particular, in two classes of systems. The excess electron in anionic ra...

  20. Cytotoxic mechanisms of hydrosulfide anion and cyanide anion in primary rat hepatocyte cultures

    International Nuclear Information System (INIS)

    Thompson, Rodney W.; Valentine, Holly L.; Valentine, William M.

    2003-01-01

    Hydrogen sulfide and hydrogen cyanide are known to compromise mitochondrial respiration through inhibition of cytochrome c oxidase and this is generally considered to be their primary mechanism of toxicity. Experimental studies and the efficiency of current treatment protocols suggest that H 2 S may exert adverse physiological effects through additional mechanisms. To evaluate the role of alternative mechanisms in H 2 S toxicity, the relative contributions of electron transport inhibition, uncoupling of mitochondrial respiration, and opening of the mitochondrial permeability transition pore (MPTP) to hydrosulfide and cyanide anion cytotoxicity in primary hepatocyte cultures were examined. Supplementation of hepatocytes with the glycolytic substrate, fructose, rescued hepatocytes from cyanide anion induced toxicity, whereas fructose supplementation increased hydrosulfide anion toxicity suggesting that hydrosulfide anion may compromise glycolysis in hepatocytes. Although inhibitors of the MPTP opening were protective for hydrosulfide anion, they had no effect on cyanide anion toxicity, consistent with an involvement of the permeability transition pore in hydrosulfide anion toxicity but not cyanide anion toxicity. Exposure of isolated rat liver mitochondria to hydrosulfide did not result in large amplitude swelling suggesting that if H 2 S induces the permeability transition it does so indirectly through a mechanism requiring other cellular components. Hydrosulfide anion did not appear to be an uncoupler of mitochondrial respiration in hepatocytes based upon the inability of oligomycin and fructose to protect hepatocytes from hydrosulfide anion toxicity. These findings support mechanisms additional to inhibition of cytochrome c oxidase in hydrogen sulfide toxicity. Further investigations are required to assess the role of the permeability transition in H 2 S toxicity, determine whether similar affects occur in other cell types or in vivo and evaluate whether this may

  1. Novel Luminescent Multilayer Films Containing π-Conjugated Anionic Polymer with Electronic Microenvironment

    Directory of Open Access Journals (Sweden)

    Tianlei Wang

    2016-09-01

    Full Text Available Layered double hydroxides (LDHs, luminescent π-conjugated anionic polymer and montmorillonite (MMT were orderly assembled into luminescent multilayer films via layer-by-layer self-assembly method. The electronic microenvironment (EME, the structure of which is like a traditional capacitor, can be constructed by exfoliated LDHs or MMT nanosheets. In addition, the rigid inorganic laminated configuration can offer stable surroundings between the interlayers. As a result, we conclude that EME can extend the luminescent lifespans of multilayer films substantially, due to affecting relaxation times of π-conjugated anionic polymer. Consequently, because of the remarkable impact on better photoemission behaviors of luminescent π-conjugated anionic polymer, EME assembled by LDHs or MMT nanosheets have had high hopes attached to them. They are expected to have the potential for designing, constructing, and investigating novel light-emitting thin films.

  2. Enhancement of encaged electron concentration by Sr(2+) doping and improvement of Gd(3+) emission through controlling encaged anions in conductive C12A7 phosphors.

    Science.gov (United States)

    Zhang, Meng; Liu, Yuxue; Zhu, Hancheng; Yan, Duanting; Yang, Jian; Zhang, Xinyang; Liu, Chunguang; Xu, Changshan

    2016-07-28

    Conductive C12A7:0.1%Gd(3+),y%Sr(2+) powders with different Sr(2+) doping concentrations have been prepared in a H2 atmosphere by a solid state method in combination with subsequent UV-irradiation. The encaged electron concentration could be modulated through tuning Sr(2+) doping and its maximum value reaches 2.3 × 10(19) cm(-3). This is attributed to the competition between enhanced uptake and the release of the encaged anions during their formation and diffusion processes and the suppression of encaged electrons generation due to the increased encaged OH(-) anions and the decreased encaged O(2-) anions. Although there exists encaged electrons and different encaged anions (O(2-), H(-) and OH(-)) in C12A7 conductive powders prepared through the hydrogen route, a dominant local environment around Gd(3+) could be observed using electron spin resonance (ESR) detection. It can be ascribed to the stronger coupling of the encaged OH(-) to the framework of C12A7 than those of the encaged electrons, O(2-) and H(-) anions. In addition, emission of Gd(3+) ions is enhanced under UV or low voltage electron beam excitation and a new local environment around Gd(3+) ions appears through the thermal annealing in air because of the decrease of the encaged OH(-) anions and the increase of the encaged O(2-) anions. Our results suggested that Sr(2+) doping in combination with thermal annealing in air is an effective strategy for increasing the conductive performance and enhancing the emission of rare earth ions doped into C12A7 conductive phosphors for low-voltage field emission displays (FEDs).

  3. Whole acute toxicity removal from industrial and domestic effluents treated by electron beam radiation: emphasis on anionic surfactants

    International Nuclear Information System (INIS)

    Moraes, M.C.F.; Romanelli, M.F; Sena, H.C.; Pasqualini da Silva, G.; Sampa, M.H.O.; Borrely, S.I.

    2004-01-01

    Electron beam radiation has been applied to improve real industrial and domestic effluents received by Suzano wastewater treatment plant. Radiation efficacy has been evaluated as toxicity reduction, using two biological assays. Three sites were sampled and submitted for toxicity assays, anionic surfactant determination and electron beam irradiation. This paper shows the reduction of acute toxicity for both test-organisms, the marine bacteria Vibrio fischeri and the crustacean Daphnia similis. The raw toxic effluents exibitted from 0.6 ppm up to 11.67 ppm for anionic surfactant before being treated by the electron beam. Radiation processing resulted in reduction of the acute toxicity as well as surfactant removal. The final biological effluent was in general less toxic than other sites but the presence of anionic surfactants was evidenced

  4. Whole acute toxicity removal from industrial and domestic effluents treated by electron beam radiation: emphasis on anionic surfactants

    Energy Technology Data Exchange (ETDEWEB)

    Moraes, M.C.F. E-mail: mariacristinafm@uol.com.br; Romanelli, M.F; Sena, H.C.; Pasqualini da Silva, G.; Sampa, M.H.O.; Borrely, S.I

    2004-10-01

    Electron beam radiation has been applied to improve real industrial and domestic effluents received by Suzano wastewater treatment plant. Radiation efficacy has been evaluated as toxicity reduction, using two biological assays. Three sites were sampled and submitted for toxicity assays, anionic surfactant determination and electron beam irradiation. This paper shows the reduction of acute toxicity for both test-organisms, the marine bacteria Vibrio fischeri and the crustacean Daphnia similis. The raw toxic effluents exibitted from 0.6 ppm up to 11.67 ppm for anionic surfactant before being treated by the electron beam. Radiation processing resulted in reduction of the acute toxicity as well as surfactant removal. The final biological effluent was in general less toxic than other sites but the presence of anionic surfactants was evidenced.

  5. REACTIVITY OF ANIONS IN INTERSTELLAR MEDIA: DETECTABILITY AND APPLICATIONS

    Energy Technology Data Exchange (ETDEWEB)

    Senent, M. L. [Departamento de Quimica y Fisica Teoricas, Instituto de Estructura de la Materia, IEM-C.S.I.C., Serrano 121, Madrid E-28006 (Spain); Hochlaf, M., E-mail: senent@iem.cfmac.csic.es, E-mail: hochlaf@univ-mlv.fr [Laboratoire de Modelisation et Simulation Multi Echelle, Universite Paris-Est, MSME UMR 8208 CNRS, 5 boulevard Descartes, F-77454 Marne-la-Vallee (France)

    2013-05-01

    We propose a general rule to distinguish between detectable and undetectable astronomical anions. We believe that only few anions live long enough in the interstellar medium and thus can be detected. Our method is based on quantum mechanical calculations capable of describing accurately the evolution of electronic states during chemical processes. The still not fully understood reactivity at low temperatures is discussed considering non-adiabatic effects. The role of excited states has usually been neglected in previous works which basically focused on the ground electronic state for interpretations of experimental observations. Here, we deal with unsaturated carbon chains (e.g., C{sub n} H{sup -}), which show a high density of electronic states close to their corresponding ground electronic states, complex molecular dynamics, and non-adiabatic phenomena. Our general rule shows that it is not sufficient that anions exist in the gas phase (in the laboratory) to be present in media such as astrophysical media, since formation and decomposition reactions of these anions may allow the population of anionic electronic states to autodetach, forming neutrals. For C{sub n} H, reactivity depends strongly on n, where long and short chains behave differently. Formation of linear chains is relevant.

  6. Effect of Structure on Charge Distribution in the Isatin Anions in Aprotic Environment: Spectral Study

    Directory of Open Access Journals (Sweden)

    Pavol Tisovský

    2017-11-01

    Full Text Available Five isatin anions were prepared by deprotonation of initial isatins in aprotic solvents using basic fluoride and acetate anions (F− and CH3COO−. The F− basicity is sufficient to deprotonate isatin NH hydrogen from all the studied compounds. This process is reversible. In the presence of proton donor solvents, the anions form the corresponding isatins. The isatin hydrogen acidity depends on the overall structure of the isatin derivatives. The anions were characterized by ultraviolet–visible (UV–Vis, Fourier transform infrared (FTIR and nuclear magnetic resonance (NMR spectroscopy. Interestingly, the anions form aggregates at concentrations above 10−3 mol·dm−3. Further, the effect of cations on the UV–Vis spectra of the studied anions was studied. Charge transfer and its distribution in the anion depends on the radius and the cation electron configuration. The alkali metal cations, tetrabutylammonium (TBA+, Mg2+ and Ag+, interact with the C-2 carbonyl oxygen of the isatin anion. The interaction has a coulombic character. On the other hand, Cd2+, Zn2+, Hg2+, Co2+, and Cu+ cations form a coordinate bond with the isatin nitrogen.

  7. Zero-point energy effects in anion solvation shells.

    Science.gov (United States)

    Habershon, Scott

    2014-05-21

    By comparing classical and quantum-mechanical (path-integral-based) molecular simulations of solvated halide anions X(-) [X = F, Cl, Br and I], we identify an ion-specific quantum contribution to anion-water hydrogen-bond dynamics; this effect has not been identified in previous simulation studies. For anions such as fluoride, which strongly bind water molecules in the first solvation shell, quantum simulations exhibit hydrogen-bond dynamics nearly 40% faster than the corresponding classical results, whereas those anions which form a weakly bound solvation shell, such as iodide, exhibit a quantum effect of around 10%. This observation can be rationalized by considering the different zero-point energy (ZPE) of the water vibrational modes in the first solvation shell; for strongly binding anions, the ZPE of bound water molecules is larger, giving rise to faster dynamics in quantum simulations. These results are consistent with experimental investigations of anion-bound water vibrational and reorientational motion.

  8. Gas-Grain Models for Interstellar Anion Chemistry

    Science.gov (United States)

    Cordiner, M. A.; Charnely, S. B.

    2012-01-01

    Long-chain hydrocarbon anions C(sub n) H(-) (n = 4, 6, 8) have recently been found to be abundant in a variety of interstellar clouds. In order to explain their large abundances in the denser (prestellar/protostellar) environments, new chemical models are constructed that include gas-grain interactions. Models including accretion of gas-phase species onto dust grains and cosmic-ray-induced desorption of atoms are able to reproduce the observed anion-to-neutral ratios, as well as the absolute abundances of anionic and neutral carbon chains, with a reasonable degree of accuracy. Due to their destructive effects, the depletion of oxygen atoms onto dust results in substantially greater polyyne and anion abundances in high-density gas (with n(sub H2) approx > / cubic cm). The large abundances of carbon-chain-bearing species observed in the envelopes of protostars such as L1527 can thus be explained without the need for warm carbon-chain chemistry. The C6H(-) anion-to-neutral ratio is found to be most sensitive to the atomic O and H abundances and the electron density. Therefore, as a core evolves, falling atomic abundances and rising electron densities are found to result in increasing anion-to-neutral ratios. Inclusion of cosmic-ray desorption of atoms in high-density models delays freeze-out, which results in a more temporally stable anion-to-neutral ratio, in better agreement with observations. Our models include reactions between oxygen atoms and carbon-chain anions to produce carbon-chain-oxide species C6O, C7O, HC6O, and HC7O, the abundances of which depend on the assumed branching ratios for associative electron detachment

  9. Hydration of a Large Anionic Charge Distribution - Naphthalene-Water Cluster Anions

    Science.gov (United States)

    Weber, J. Mathias; Adams, Christopher L.

    2010-06-01

    We report the infrared spectra of anionic clusters of naphthalene with up to three water molecules. Comparison of the experimental infrared spectra with theoretically predicted spectra from quantum chemistry calculations allow conclusions regarding the structures of the clusters under study. The first water molecule forms two hydrogen bonds with the π electron system of the naphthalene moiety. Subsequent water ligands interact with both the naphthalene and the other water ligands to form hydrogen bonded networks, similar to other hydrated anion clusters. Naphthalene-water anion clusters illustrate how water interacts with negative charge delocalized over a large π electron system. The clusters are interesting model systems that are discussed in the context of wetting of graphene surfaces and polyaromatic hydrocarbons.

  10. Electronic relaxations of radiative defects of the anion sublattice in cesium bromide crystals and exoemission of electrons

    CERN Document Server

    Galyij, P V

    2002-01-01

    The paper presents the results of investigations of thermostimulated exoelectron emission (TSEE) from CsBr crystal, excited by moderate doses (D <= 10 sup 4 Gy) of ultraviolet (h nu <= 7 eV) that selectively creates anion excitons and radiative defects in the anion sublattice. Having used the previously established connection between thermoactivated processes such as thermostimulated exoemission, electroconductivity, and luminescence in the irradiated crystal lattice, the concentrations of exoemission-active centers (EAC) and kinetics parameters of TSEE are calculated. The EAC concentration calculated on a base of the bulk, thermoactivated-recombinational, and band-gap Auger-like exoemission mechanisms, are in satisfactory agreement with the concentration of electron color centers in the irradiated crystals.

  11. Negative ion photoelectron spectroscopy of solvated electron cluster anions, (H2O)n- and (NH3)n-

    International Nuclear Information System (INIS)

    Lee, G.H.; Arnold, S.T.; Eaton, J.G; Sarkas, H.W.; Bowen, K.H.; Ludewigt, C.; Haberland, H.

    1991-01-01

    The photodetachment spectra of (H 2 O) - n=2-69 and (NH 3 ) - n=41-1100 have been recorded, and vertical detachment energies (VDEs) were obtained from the spectra. For both systems, the cluster anion VDEs increase smoothly with increasing sizes and most species plot linearly with n -1/3 , extrapolating to a VDE (n = ∞) value which is very close to the photoelectric threshold energy for the corresponding condensed phase solvated electron system. The linear extrapolation of this data to the analogous condensed phase property suggests that these cluster anions are gas phase counterparts to solvated electrons, i.e. they are embryonic forms of hydrated and ammoniated electrons which mature with increasing cluster size toward condensed phase solvated electrons. (orig.)

  12. Negative ion photoelectron spectroscopy of solvated electron cluster anions, (H2O){/n -} and (NH3){/n -}

    Science.gov (United States)

    Lee, G. H.; Arnold, S. T.; Eaton, J. G.; Sarkas, H. W.; Bowen, K. H.; Ludewigt, C.; Haberland, H.

    1991-03-01

    The photodetachment spectra of (H2O){/n =2-69/-} and (NH3){/n =41-1100/-} have been recorded, and vertical detachment energies (VDEs) were obtained from the spectra. For both systems, the cluster anion VDEs increase smoothly with increasing sizes and most species plot linearly with n -1/3, extrapolating to a VDE ( n=∞) value which is very close to the photoelectric threshold energy for the corresponding condensed phase solvated electron system. The linear extrapolation of this data to the analogous condensed phase property suggests that these cluster anions are gas phase counterparts to solvated electrons, i.e. they are embryonic forms of hydrated and ammoniated electrons which mature with increasing cluster size toward condensed phase solvated electrons.

  13. Free radicals in an adamantane matrix. XIII. Electron paramagnetic resonance study of sigma* - π* orbital crossover in fluorinated pyridine anions

    International Nuclear Information System (INIS)

    Yim, M.B.; DiGregorio, S.; Wood, D.E.

    1977-01-01

    Pentafluoropyridine,2,3,4,6-tetrafluoropyridine, 2,6-difluoropyridine, and 2-fluoropyridine anion radicals were produced by x irradiation of an adamantane matrix which was doubly doped with the aromatic precursors and Me 3 NBH 3 and their EPR spectra obtained. The large fluorine hyperfine splitting constants (hfsc) of penta- and 2,3,4,6-tetrafluoropyridine anions and the small fluorine hfsc's of 2,6-di- and 2-fluoropyridine anions suggest that the former two are sigma radicals while the latter two are π radicals. The sigma*-π* orbital crossover phenomenon observed in these fluorinated pyridine anions is explained in terms of the combined effects of stabilization of sigma* orbitals and destabilization of π* orbitals. The EPR results show that nitrogen has a negligible contribution to the unpaired electron sigma* orbitals. INDO calculations were performed for the various states and the results compared with experiment

  14. Gas-Phase Reactivity of Microsolvated Anions

    DEFF Research Database (Denmark)

    Thomsen, Ditte Linde

    the gas-phase α-effect. The experimental studies are performed by means of the flowing after glow selected ion flow tube technique, and these are supplemented by electronic structure calculations. The α-nucleophile employed is the microsolvated hydrogen peroxide anion whose reactivity is compared......Gas-phase studies of ion-molecule reactions shed light on the intrinsic factors that govern reactivity; and even solvent effects can be examined in the gasphase environment by employing microsolvated ions. An area that has received considerable attention with regard to the interplay between...... to that of a series of microsolvated oxygen centered anions. The association of the nucleophiles with a single water or methanol molecule allows the α-effect to be observed in the SN2 reaction with methyl chloride; this effect was not apparent in the reactions of the unsolvated anions. The results suggest...

  15. Zwitterion radicals and anion radicals from electron transfer and solvent condensation with the fingerprint developing agent ninhydrin.

    Science.gov (United States)

    Schertz, T D; Reiter, R C; Stevenson, C D

    2001-11-16

    Ninhydrin (the fingerprint developing agent) spontaneously dehydrates in liquid ammonia and in hexamethylphosphoramide (HMPA) to form indantrione, which has a sufficiently large solution electron affinity to extract an electron from the solvent (HMPA) to produce the indantrione anion radical. In liquid NH(3), the presence of trace amounts of amide ion causes the spontaneous formation of an anion radical condensation product, wherein the no. 2 carbon (originally a carbonyl carbon) becomes substituted with -NH(2) and -OH groups. In HMPA, the indantrione anion radical spontaneously forms condensation products with the HMPA to produce a variety of zwitterionic radicals, wherein the no. 2 carbon becomes directly attached to a nitrogen of the HMPA. The mechanisms for the formation of the zwitterionic paramagnetic condensation products are analogous to that observed in the reaction of ninhydrin with amino acids to yield Ruhemann's Purple, the contrast product in fingerprint development. The formation of anion and zwitterionic radical condensation products from ninhydrin and nitrogen-containing solvents may represent an example of a host of analogous polyketone-solvent reactions.

  16. Gas phase structures and charge localization in small aluminum oxide anions: Infrared photodissociation spectroscopy and electronic structure calculations

    Energy Technology Data Exchange (ETDEWEB)

    Song, Xiaowei; Fagiani, Matias R. [Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, D-14195 Berlin (Germany); Wilhelm-Ostwald-Institut für Physikalische und Theoretische Chemie, Universität Leipzig, Linnéstrasse 2, D-04103 Leipzig (Germany); Gewinner, Sandy; Schöllkopf, Wieland [Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, D-14195 Berlin (Germany); Asmis, Knut R., E-mail: knut.asmis@uni-leipzig.de, E-mail: js@chemie.hu-berlin.de [Wilhelm-Ostwald-Institut für Physikalische und Theoretische Chemie, Universität Leipzig, Linnéstrasse 2, D-04103 Leipzig (Germany); Bischoff, Florian A.; Berger, Fabian; Sauer, Joachim, E-mail: knut.asmis@uni-leipzig.de, E-mail: js@chemie.hu-berlin.de [Institut für Chemie, Humboldt-Universität zu Berlin, Unter den Linden 6, D-10099 Berlin (Germany)

    2016-06-28

    We use cryogenic ion trap vibrational spectroscopy in combination with quantum chemical calculations to study the structure of mono- and dialuminum oxide anions. The infrared photodissociation spectra of D{sub 2}-tagged AlO{sub 1-4}{sup −} and Al{sub 2}O{sub 3-6}{sup −} are measured in the region from 400 to 1200 cm{sup −1}. Structures are assigned based on a comparison to simulated harmonic and anharmonic IR spectra derived from electronic structure calculations. The monoaluminum anions contain an even number of electrons and exhibit an electronic closed-shell ground state. The Al{sub 2}O{sub 3-6}{sup −} anions are oxygen-centered radicals. As a result of a delicate balance between localization and delocalization of the unpaired electron, only the BHLYP functional is able to qualitatively describe the observed IR spectra of all species with the exception of AlO{sub 3}{sup −}. Terminal Al–O stretching modes are found between 1140 and 960 cm{sup −1}. Superoxo and peroxo stretching modes are found at higher (1120-1010 cm{sup −1}) and lower energies (850-570 cm{sup −1}), respectively. Four modes in-between 910 and 530 cm{sup −1} represent the IR fingerprint of the common structural motif of dialuminum oxide anions, an asymmetric four-member Al–(O){sub 2}–Al ring.

  17. Electron detachment energies in high-symmetry alkali halide solvated-electron anions

    Science.gov (United States)

    Anusiewicz, Iwona; Berdys, Joanna; Simons, Jack; Skurski, Piotr

    2003-07-01

    We decompose the vertical electron detachment energies (VDEs) in solvated-electron clusters of alkali halides in terms of (i) an electrostatic contribution that correlates with the dipole moment (μ) of the individual alkali halide molecule and (ii) a relaxation component that is related to the polarizability (α) of the alkali halide molecule. Detailed numerical ab initio results for twelve species (MX)n- (M=Li,Na; X=F,Cl,Br; n=2,3) are used to construct an interpolation model that relates the clusters' VDEs to their μ and α values as well as a cluster size parameter r that we show is closely related to the alkali cation's ionic radius. The interpolation formula is then tested by applying it to predict the VDEs of four systems [i.e., (KF)2-, (KF)3-, (KCl)2-, and (KCl)3-] that were not used in determining the parameters of the model. The average difference between the model's predicted VDEs and the ab initio calculated electron binding energies is less than 4% (for the twelve species studied). It is concluded that one can easily estimate the VDE of a given high-symmetry solvated electron system by employing the model put forth here if the α, μ and cation ionic radii are known. Alternatively, if VDEs are measured for an alkali halide cluster and the α and μ values are known, one can estimate the r parameter, which, in turn, determines the "size" of the cluster anion.

  18. Fe electron transfer and atom exchange in goethite: influence of Al-substitution and anion sorption.

    Science.gov (United States)

    Latta, Drew E; Bachman, Jonathan E; Scherer, Michelle M

    2012-10-02

    The reaction of Fe(II) with Fe(III) oxides and hydroxides is complex and includes sorption of Fe(II) to the oxide, electron transfer between sorbed Fe(II) and structural Fe(III), reductive dissolution coupled to Fe atom exchange, and, in some cases mineral phase transformation. Much of the work investigating electron transfer and atom exchange between aqueous Fe(II) and Fe(III) oxides has been done under relatively simple aqueous conditions in organic buffers to control pH and background electrolytes to control ionic strength. Here, we investigate whether electron transfer is influenced by cation substitution of Al(III) in goethite and the presence of anions such as phosphate, carbonate, silicate, and natural organic matter. Results from (57)Fe Mössbauer spectroscopy indicate that both Al-substitution (up to 9%) and the presence of common anions (PO(4)(3-), CO(3)(2-), SiO(4)(4-), and humic acid) does not inhibit electron transfer between aqueous Fe(II) and Fe(III) in goethite under the conditions we studied. In contrast, sorption of a long-chain phospholipid completely shuts down electron transfer. Using an enriched isotope tracer method, we found that Al-substitution in goethite (10%), does, however, significantly decrease the extent of atom exchange between Fe(II) and goethite (from 43 to 12%) over a month's time. Phosphate, somewhat surprisingly, appears to have little effect on the rate and extent of atom exchange between aqueous Fe(II) and goethite. Our results show that electron transfer between aqueous Fe(II) and solid Fe(III) in goethite can occur under wide range of geochemical conditions, but that the extent of redox-driven Fe atom exchange may be dependent on the presence of substituting cations such as Al.

  19. Highly Sensitive Electrochemical Sensor for the Detection of Anions in Water Based on a Redox-Active Monolayer Incorporating an Anion Receptor.

    Science.gov (United States)

    Kaur, Balwinder; Erdmann, Cristiane Andreia; Daniëls, Mathias; Dehaen, Wim; Rafiński, Zbigniew; Radecka, Hanna; Radecki, Jerzy

    2017-12-05

    In the present work, gold electrodes were modified using a redox-active layer based on dipyrromethene complexes with Cu(II) or Co(II) and a dipodal anion receptor functionalized with dipyrromethene. These modified gold electrodes were then applied for the electrochemical detection of anions (Cl - , SO 4 2- , and Br - ) in a highly diluted water solution (in the picomolar range). The results showed that both systems, incorporating Cu(II) as well as Co(II) redox centers, exhibited highest sensitivity toward Cl - . The selectivity sequence found for both systems was Cl - > SO 4 2- > Br - . The high selectivity of Cl - anions can be attributed to the higher binding constant of Cl - with the anion receptor and the stronger electronic effect between the central metal and anion in the complex. The detection limit for the determination of Cl - was found at the 1.0 pM level for both sensing systems. The electrodes based on Co(II) redox centers displayed better selectivity toward Cl - anion detection than those based on Cu(II) centers which can be attributed to the stronger electronic interaction between the receptor-target anion complex and the Co(II)/Co(III) redox centers in comparison to the Cu(II)/Cu(I) system. Applicability of gold electrodes modified with DPM-Co(II)-DPM-AR for the electrochemical determination of Cl - anions was demonstrated using the artificial matrix mimicking human serum.

  20. Perspective: Electrospray photoelectron spectroscopy: From multiply-charged anions to ultracold anions

    International Nuclear Information System (INIS)

    Wang, Lai-Sheng

    2015-01-01

    Electrospray ionization (ESI) has become an essential tool in chemical physics and physical chemistry for the production of novel molecular ions from solution samples for a variety of spectroscopic experiments. ESI was used to produce free multiply-charged anions (MCAs) for photoelectron spectroscopy (PES) in the late 1990 s, allowing many interesting properties of this class of exotic species to be investigated. Free MCAs are characterized by strong intramolecular Coulomb repulsions, which create a repulsive Coulomb barrier (RCB) for electron emission. The RCB endows many fascinating properties to MCAs, giving rise to meta-stable anions with negative electron binding energies. Recent development in the PES of MCAs includes photoelectron imaging to examine the influence of the RCB on the electron emission dynamics, pump-probe experiments to examine electron tunneling through the RCB, and isomer-specific experiments by coupling PES with ion mobility for biological MCAs. The development of a cryogenically cooled Paul trap has led to much better resolved PE spectra for MCAs by creating vibrationally cold anions from the room temperature ESI source. Recent advances in coupling the cryogenic Paul trap with PE imaging have allowed high-resolution PE spectra to be obtained for singly charged anions produced by ESI. In particular, the observation of dipole-bound excited states has made it possible to conduct vibrational autodetachment spectroscopy and resonant PES, which yield much richer vibrational spectroscopic information for dipolar free radicals than traditional PES

  1. Ab initio theoretical study of dipole-bound anions of molecular complexes: (HF)3- and (HF)4- anions

    Science.gov (United States)

    Ramaekers, Riet; Smith, Dayle M. A.; Smets, Johan; Adamowicz, Ludwik

    1997-12-01

    Ab initio calculations have been performed to determine structures and vertical electron detachment energy (VDE) of the hydrogen fluoride trimer and tetramer anions, (HF)3- and (HF)4-. In these systems the excess electron is bound by the dipole field of the complex. It was determined that, unlike the neutral complexes which prefer the cyclic structures, the equilibrium geometries of the anions have "zig-zag" shapes. For both complexes the predicted VDEs are positive [210 meV and 363 meV for (HF)3- and (HF)4-, respectively], indicating that the anions are stable systems with respect to the vertical electron detachment. These results were obtained at the coupled-cluster level of theory with single, double and triple excitations [CCSD(T) method; the triple-excitation contribution in this method is calculated approximately using the perturbation approach] with the anion geometries obtained using the second-order Møller-Plesset perturbation theory (MP2) method. The same approach was also used to determine the adiabatic electron affinities (AEA) of (HF)3 and (HF)4. In addition to the electronic contribution, we also calculated the contributions (using the harmonic approximation) resulting from different zero-point vibration energies of the neutral and anionic clusters. The calculations predicted that while the AEA of (HF)3 is positive (44 meV), the AEA for (HF)4 is marginally negative (-16 meV). This suggests that the (HF)3- anion should be a stable system, while the (HF)4- is probably metastable.

  2. Photoelectron spectroscopy of the 6-azauracil anion.

    Science.gov (United States)

    Chen, Jing; Buonaugurio, Angela; Dolgounitcheva, Olga; Zakrzewski, V G; Bowen, Kit H; Ortiz, J V

    2013-02-14

    We report the photoelectron spectrum of the 6-azauracil anion. The spectrum is dominated by a broad band exhibiting a maximum at an electron binding energy (EBE) of 1.2 eV. This spectral pattern is indicative of a valence anion. Our calculations were carried out using ab initio electron propagator and other many-body methods. Comparison of the anion and corresponding neutral of 6-azauracil with those of uracil shows that substituting a nitrogen atom for C-H at the C6 position of uracil gives rise to significant changes in the electronic structure of 6-azauracil versus that of uracil. The adiabatic electron affinity (AEA) of the canonical 6-azauracil tautomer is substantially larger than that of canonical uracil. Among the five tautomeric, 6-azauracil anions studied computationally, the canonical structure was found to be the most stable. The vertical detachment energies (VDE) of the canonical, valence-bound anion of 6-azauracil and its closest "very-rare" tautomer have been calculated. Electron propagator calculations on the canonical anion yield a VDE value that is in close agreement with the experimentally determined VDE value of 1.2 eV. The AEA value of 6-azauracil, assessed at the CCSD(T) level of theory to be 0.5 eV, corresponds with the EBE value of the onset of the experimental spectrum.

  3. Effect of carbonyl group on the lifetimes of pentafluoroacetophenone and pentafluorobenzaldehyde radical anions in aqueous solution: a pulse radiolysis study

    International Nuclear Information System (INIS)

    Shoute, L.C.T.

    1996-01-01

    Hydrated electrons react with pentafluoroacetophenone (PFA) to form radical anion. Evidence for the formation of the radical anion was obtained from observation of intermolecular electron transfer from PFA .- to p-benzoquinone (Q) and methyl viologen (MV 2+ ) to form Q .- and MV .+ . The radical anion lose fluoride with a rate constant of 5x10 4 s -1 . The radical anion has a pK a =7.5. Radical anion of pentafluorobenzaldehyde (PFB) was observed on reduction PFB with hydrated electron. It has a pK a =7.2. It loses fluoride with a rate constant of 1.2x10 5 s -1 . The studies show that substitution of a carbonyl group in the aromatic ring of a perfluorinated compound led to dramatic increase in the lifetime of the radical anion formed on electron addition due to decrease in the rate of fluoride elimination. This led to the possibility of observing their reactions with other solute present in the solution. (author). 6 refs., 1 tab

  4. Graphene-coated polymeric anion exchangers for ion chromatography

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Kai; Cao, Minyi; Lou, Chaoyan [Department of Chemistry, Xixi Campus, Zhejiang University, Hangzhou 310028 (China); Wu, Shuchao, E-mail: wushch2002@163.com [Zhejiang Institute of Geology and Mineral Resources, Hangzhou 310007 (China); Zhang, Peimin [Department of Chemistry, Xixi Campus, Zhejiang University, Hangzhou 310028 (China); Zhi, Mingyu [Hangzhou Vocational & Technical College, Hangzhou, 310018 (China); Zhu, Yan, E-mail: zhuyan@zju.edu.cn [Department of Chemistry, Xixi Campus, Zhejiang University, Hangzhou 310028 (China)

    2017-06-01

    Carbonaceous stationary phases have gained much attention for their peculiar selectivity and robustness. Herein we report the fabrication and application of a graphene-coated polymeric stationary phase for anion exchange chromatography. The graphene-coated particles were fabricated by a facile evaporation-reduction method. These hydrophilic particles were proven appropriate substrates for grafting of hyperbranched condensation polymers (HBCPs) to make pellicular anion exchangers. The new phase was characterized by zeta potentials, Fourier transform infrared spectroscopy, thermogravimetry and scanning electron microscope. Frontal displacement chromatography showed that the capacities of the anion exchangers were tuned by both graphene amount and HBCPs layer count. The chromatographic performance of graphene-coated anion exchangers was demonstrated with separation of inorganic anions, organic acids, carbohydrates and amino acids. Good reproducibility was obtained by consecutive injections, indicating high chemical stability of the coating. - Highlights: • Graphene-coated polymeric particles were fabricated by a facile method. • Hyperbranched condensation polymers (HBCPs) were grafted from graphene-coated particles to make anion exchangers. • Graphene amount and HBCPs layer count had significant effects on the anion exchange capacities. • Separation of diverse anionic analytes on the anion exchangers was demonstrated. • The prepared anion exchangers exhibited high stability.

  5. Structure Determination of Anionic Metal Clusters via Infrared Resonance Enhanced Multiple Photon Electron Detachment Spectroscopy

    NARCIS (Netherlands)

    Haertelt, M.; Lapoutre, V. J. F.; Bakker, J. M.; Redlich, B.; Harding, D. J.; Fielicke, A.; Meijer, G.

    2011-01-01

    We report vibrational spectra of anionic metal clusters, measured via electron detachment following resonant absorption of multiple infrared photons. To facilitate the sequential absorption of the required large number of photons, the cluster beam interacts with the infrared radiation inside the

  6. Study of electron transition energies between anions and cations in spinel ferrites using differential UV–vis absorption spectra

    International Nuclear Information System (INIS)

    Xue, L.C.; Wu, L.Q.; Li, S.Q.; Li, Z.Z.; Tang, G.D.; Qi, W.H.; Ge, X.S.; Ding, L.L.

    2016-01-01

    It is very important to determine electron transition energies (E_t_r) between anions and different cations in order to understand the electrical transport and magnetic properties of a material. Many authors have analyzed UV–vis absorption spectra using the curve (αhν)"2 vs E, where α is the absorption coefficient and E(=hν) is the photon energy. Such an approach can give only two band gap energies for spinel ferrites. In this paper, using differential UV–vis absorption spectra, dα/dE vs E, we have obtained electron transition energies (E_t_r) between the anions and cations, Fe"2"+ and Fe"3"+ at the (A) and [B] sites and Ni"2"+ at the [B] sites for the (A)[B]_2O_4 spinel ferrite samples Co_xNi_0_._7_−_xFe_2_._3O_4 (0.0≤x≤0.3), Cr_xNi_0_._7Fe_2_._3_−_xO_4 (0.0≤x≤0.3) and Fe_3O_4. We suggest that the differential UV–vis absorption spectra should be accepted as a general analysis method for determining electron transition energies between anions and cations.

  7. Anion effect on the retention of recoil atom of coordination crystalline compounds

    International Nuclear Information System (INIS)

    Dimotakis, P.N.; Papadopoulos, B.P.

    1980-01-01

    The anion effect of various cobaltic crystalline compounds - having the same cation and differing in anion -on the retention of neutron activated central cobalt atom has been studied. The cation was trans-dichloro(bis)ethylenediamine cobalt(III) and the anions were simple spherical anions (Cl - , Br - , I - ), planar anions (NO 3 - ), trigonal pyramidal anions (ClO 3 - , BrO 3 - ), tetrahedral anions (SO 4 2- , CrO 4 2- , MnO 4 - ) and linear anions (SCN - ). The cobalt-60 activity after reactor irradiation either in simple Co 2+ cation or in cobaltic complex cation determined the retention values. In all irradiations at ordinary temperature and at liquid nitrogen temperature the results showed an effect of the different anions, depending on the geometry, volume and charge, on the recombination of the recoil cobalt with the ligands in the coordination sphere. (author)

  8. Ultra-small and anionic starch nanospheres: formation and vitro thrombolytic behavior study.

    Science.gov (United States)

    Huang, Yinjuan; Ding, Shenglong; Liu, Mingzhu; Gao, Chunmei; Yang, Jinlong; Zhang, Xinjie; Ding, Bin

    2013-07-25

    This paper is considered as the first report on the investigation of nattokinase (NK) release from anionic starch nanospheres. The ultra-small and anionic starch nanospheres were prepared by the method of reverse micro-emulsion crosslinking in this work. Starch nanospheres were characterized through Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM) and dynamic light scattering (DLS). Effects of preparation conditions on particle size were studied. The cytotoxicity, biodegradable and vitro thrombolytic behaviors of nattokinase (NK) loaded anionic starch nanospheres were also studied. The results showed that the anionic starch nanospheres are non-toxic, biocompatible and biodegradable. Moreover, the anionic starch nanospheres can protect NK from fast biodegradation hence prolongs the circulation in vivo and can reduce the risk of acute hemorrhage complication by decreasing the thrombolysis rate. Copyright © 2013 Elsevier Ltd. All rights reserved.

  9. The gecko visual pigment: the anion hypsochromic effect.

    Science.gov (United States)

    Crescitelli, F; Karvaly, B

    1991-01-01

    The 521-pigment in the retina of the Tokay gecko (Gekko gekko) readily responds to particular physical and chemical changes in its environment. When solubilized in chloride deficient state the addition of Class I anions (Cl-, Br-) induces a bathochromic shift of the absorption spectrum. Class II anions (NO3-, IO3-, N3-, OCN-, SCN-, SeCN-, N(CN)2-), which exhibit ambidental properties, cause an hypsochromic shift. Class III anions (F-, I-, NO2-, CN-, AsO3-, SO2(4-), S2O2(3-) have no spectral effect on the 521-pigment. Cations appear to have no influence on the pigment absorption and Class I anions prevent or reverse the hypsochromic shift caused by Class II anions. It is suggested that the spectral displacements reflect specific changes in the opsin conformation, which alter the immediate (dipolar) environment of the retinal chromophore. The protein conformation seems to promote excited-state processes most in the native 521-pigment state and least in the presence of Class II anions. This in turn suggests that the photosensitivity of the 521-pigment is controlled by the excited rather than by the ground-state properties of the pigment.

  10. Specific anion effects on copper surface through electrochemical treatment: Enhanced photoelectrochemical CO2 reduction activity of derived nanostructures induced by chaotropic anions

    Science.gov (United States)

    Navaee, Aso; Salimi, Abdollah

    2018-05-01

    Copper derivatives are the most prominent CO2 reduction electrocatalyst. Herein, the metallic copper has been electrochemically treated with some of common ionic salts such as N3bar, HPO2bar, S2bar, Fbar, Clbar, Brbar and Ibar based on the dissolution of a metallic working electrode in an aqueous solution to derive the surface roughness incorporated with nanostructures. Diverse surface morphology can be obtained when the ionic radii of anions are changed. Surface study reveals various roughness shapes based on the size and polarity of the anions, where the ions with higher ionic radii have higher impact on the Cu surface. In comparison, polyatomic oxyanion such as HPO2bar even with large ionic radii do not have enough strength to create the surface roughness than that of oxygen-free anions with large ionic radii. The photoelectrochemical behavior of the modified surfaces toward CO2 reduction is studied at a wide potential window in bicarbonate aqueous solution. Based on our investigations, treated surfaces by Ibar, Clbar and S2bargive a more surface roughness, while Ibar and N3bar offer higher catalytic activity toward CO2 reduction due to possible complexing ability of these anions with Cu cations, followed by formation of the co-catalyst semiconductor and facilitate electron transfer. This methodology can be applied to investigate the effect of ions on transition metals along with obtaining different surface morphologies tailored to different applications.

  11. Effects of electrostatic interactions on electron transfer reactions

    International Nuclear Information System (INIS)

    Hickel, B.

    1987-01-01

    The fast reactions of electron transfer are studied by pulse radiolysis. This technique allows the creation in about 10 -8 second radicals and radical ions with high redox potentials. For solvated electrons electrostatic interaction on the kinetics of reactions limited by diffusion is described by Debye's equation when ion mobility is known. Deviation from theory can occur in ion pairs formation. This is evidenced experimentally for anions by cation complexation with a cryptate. Relatively slow reactions are more sensitive to electrostatic interactions than limited by diffusion. If ion pairs are not formed kinetics constant depends on dielectric constant of solvent and reaction radius. Experimentally is studied the effect of electrostatic interaction on the rate constants of solvated electrons with anions and cations in water-ethanol mixtures where the dielectric constant change from 80 to 25 at room temperature. 17 refs

  12. Low-energy electron-induced dissociation in condensed-phase L-cysteine II: a comparative study on anion desorption from chemisorbed and physisorbed films

    International Nuclear Information System (INIS)

    Alizadeh, E.; Rowntree, P.A.; Massey, S.; Sanche, L.

    2016-01-01

    In recent years it has become apparent that dissociative attachment of low energy electrons (DEA) is important for the description of radiation damage to biologically relevant molecules and living cells. Due to its multifunctional structure, cysteine is becoming an ideal model molecule for investigating the complex interactions of proteins with metallic surfaces such as gold nanoparticles. We report herein the results of low-energy electron induced degradation of L-cysteine films, chemisorbed on a gold substrate via the thiol group or physisorbed into a clean gold surface. The data were recorded under ultra-high vacuum conditions at room temperature. Anion yields desorbed from these films by the impact of 0.5 to 19 eV electrons provide clear evidence of the efficient decomposition of this amino acid via dissociative electron attachment (i.e., from dissociation of intermediate transient anions located between 5 and 14 eV). The peaks in the desorbed-anion yield functions, associated with DEA, are superimposed on a continuously rising signal attributed to dipolar dissociation. Similar to the results previously observed from physisorbed films, light anionic species, with masses lower than 35 amu, have been detected. In addition, we measured for first time fragments at 14 amu (CH_2"-) and 15 amu (CH_3"-) desorbing from physisorbed films, as well as heavier fragments of mass 45 and 46 amu desorbing from chemisorbed films

  13. Vertical detachment energies of anionic thymidine: Microhydration effects.

    Science.gov (United States)

    Kim, Sunghwan; Schaefer, Henry F

    2010-10-14

    Density functional theory has been employed to investigate microhydration effects on the vertical detachment energy (VDE) of the thymidine anion by considering the various structures of its monohydrates. Structures were located using a random searching procedure. Among 14 distinct structures of the anionic thymidine monohydrate, the low-energy structures, in general, have the water molecule bound to the thymine base unit. The negative charge developed on the thymine moiety increases the strength of the intermolecular hydrogen bonding between the water and base units. The computed VDE values of the thymidine monohydrate anions are predicted to range from 0.67 to 1.60 eV and the lowest-energy structure has a VDE of 1.32 eV. The VDEs of the monohydrates of the thymidine anion, where the N(1)[Single Bond]H hydrogen of thymine has been replaced by a 2(')-deoxyribose ring, are greater by ∼0.30 eV, compared to those of the monohydrates of the thymine anion. The results of the present study are in excellent agreement with the accompanying experimental results of Bowen and co-workers [J. Chem. Phys. 133, 144304 (2010)].

  14. Chemical Reactions Triggered Using Electrons Photodetached from "Clean" Distributions of Anions Deposited in Cryogenic Matrices via Counterion Codeposition.

    Science.gov (United States)

    Ludwig, Ryan M; Moore, David T

    2014-09-04

    Application of matrix isolation spectroscopy to ionic species is typically complicated by the presence of neutral contaminants during matrix deposition. Herein we demonstrate that simultaneous deposition of balanced currents of counterions with mass-selected ions of interest generates "clean" distributions of matrix-isolated metal carbonyl anions, where the only bands appearing in the CO-stretching region of the vibrational spectrum arise from ions. (Neutrals are initially absent.) Photodetachment by mild irradiation with visible light leads to complete conversion of the anions into their corresponding neutral species. The photodetached electrons, in turn, initiate covalent chemistry, inducing C-C bond formation following electron-capture by CO van der Waals dimers to produce trans-OCCO(-). The initial clean distribution of ions enables clear connections to be drawn between the spectral changes occurring at each experimental step, thus demonstrating the potential of the counterion codeposition technique to facilitate detailed studies of chemistry involving ions and electron transfer in cryogenic matrices.

  15. Ca2+ and Mg2+-enhanced reduction of arsenazo III to its anion free radical metabolite and generation of superoxide anion by an outer mitochondrial membrane azoreductase.

    Science.gov (United States)

    Moreno, S N; Mason, R P; Docampo, R

    1984-12-10

    At the concentrations usually employed as a Ca2+ indicator, arsenazo III underwent a one-electron reduction by rat liver mitochondria to produce an azo anion radical as demonstrated by electron-spin resonance spectroscopy. Either NADH or NADPH could serve as a source of reducing equivalents for the production of this free radical by intact rat liver mitochondria. Under aerobic conditions, addition of arsenazo III to rat liver mitochondria produced an increase in electron flow from NAD(P)H to molecular oxygen, generating superoxide anion. NAD(P)H generated from endogenous mitochondrial NAD(P)+ by intramitochondrial reactions could not be used for the NAD(P)H azoreductase reaction unless the mitochondria were solubilized by detergent or anaerobiosis. In addition, NAD(P)H azoreductase activity was higher in the crude outer mitochondrial membrane fraction than in mitoplasts and intact mitochondria. The steady-state concentration of the azo anion radical and the arsenazo III-stimulated cyanide-insensitive oxygen consumption were enhanced by calcium and magnesium, suggesting that, in addition to an enhanced azo anion radical-stabilization by complexation with the metal ions, enhanced reduction of arsenazo III also occurred. Accordingly, addition of cations to crude outer mitochondrial membrane preparations increased arsenazo III-stimulated cyanide-insensitive O2 consumption, H2O2 formation, and NAD(P)H oxidation. Antipyrylazo III was much less effective than arsenazo III in increasing superoxide anion formation by rat liver mitochondria and gave a much weaker electron spin resonance spectrum of an azo anion radical. These results provide direct evidence of an azoreductase activity associated with the outer mitochondrial membrane and of a stimulation of arsenazo III reduction by cations.

  16. Unusual structures of MgF5- superhalogen anion

    Science.gov (United States)

    Anusiewicz, Iwona; Skurski, Piotr

    2007-05-01

    The vertical electron detachment energies (VDE) of three MgF5- anions were calculated at the outer valence Green function level with the 6-311 + G(3df) basis sets. This species was found to form unusual geometrical structures each of which corresponds to an anionic state exhibiting superhalogen nature. The global minimum structure was described as a system in which two central magnesium atoms are linked via symmetrical triangle formed by three fluorine atoms. Extremely large electron binding energies of these anions (exceeding 8.5 eV in all cases) were predicted and discussed.

  17. Role of anion doping on electronic structure and magnetism of GdN by first principles calculations

    KAUST Repository

    Zhang, Xuejing; Mi, Wenbo; Guo, Zaibing; Cheng, Yingchun; Chen, Guifeng; Bai, Haili

    2014-01-01

    We have investigated the electronic structure and magnetism of anion doped GdN1-yXy (X = B, C, O, F, P, S and As) systems by first-principles calculations based on density functional theory. GdN 1-yXy systems doped by O, C, F, P, and S atoms are more stable than those doped by B and As atoms because of relatively high binding energies. The anion doping and the N defect states modify the density of states at the Fermi level, resulting in a decrease in spin polarization and a slight increase in the magnetic moment at the Gd and N sites. © 2014 The Royal Society of Chemistry.

  18. New borohydride anion B6H7-

    International Nuclear Information System (INIS)

    Kuznetsov, I.Yu.; Vinitskij, D.M.; Solntsev, K.A.

    1985-01-01

    The [Ni(Bipy) 3 ] (B 6 H 7 ) 2 , (Ph 4 P)B 6 H 7 , [Ni(Phen) 3 ](B 6 H 7 ) 2 crystals (where Bipy = bipyridine, Phen = phenathroline, Ph = phenyl) are obtained via the exchange reaction with a subsequent recrystallization from aqua-acetonic and acetonic solutions. The structure is studied of a new borohydride anion B 6 H 7 - possessing a four-valence bond unique for polyhedral borohydride anions. A triangular face of boride skeleton coordinating a hydrogen atom is considerably larger than other faces, and the electron density on this hydrogen atom is evidently much higher than at the end hydride hydrogen atoms. The trend of B 6 H 7 - anion to form statistically disordered structurs testifies to a rather slight effect of the seventh hydrogen atom position on the structure pattern of the ionic crystal lattice

  19. Ab initio investigation of sulfur monofluoride and its singly charged cation and anion in their ground electronic state

    International Nuclear Information System (INIS)

    Li Song; Chen Shan-Jun; Chen Yan; Chen Peng

    2016-01-01

    The SF radical and its singly charged cation and anion, SF + and SF − , have been investigated on the MRCI/aug-cc-pVXZ (X = Q, 5, 6) levels of theory with Davidson correction. Both the core–valence correlation and the relativistic effect are considered. The extrapolating to the complete basis set (CBS) limit is adopted to remove the basis set truncation error. Geometrical parameters, potential energy curves (PECs), vibrational energy levels, spectroscopic constants, ionization potentials, and electron affinities of the ground electronic state for all these species are obtained. The information with respect to molecular characteristics of the SF n (n = −1, 0, +1) systems derived in this work will help to extend our knowledge and to guide further experimental or theoretical researches. (paper)

  20. Photoinduced electron transfer between anionic fluorophores and methyl viologen in homogeneous and microheterogeneous media

    International Nuclear Information System (INIS)

    Burai, Tarak Nath; Panda, Debashis; Iyer, E Siva Subramaniam; Datta, Anindya

    2012-01-01

    The rate and extent of photoinduced electron transfer change significantly as a result of confinement in nanovolumes. Study of such processes is an active area of research in physical chemistry. The effect is most interesting when the molecules that participate in PET are charged. In the present article, the modulation of PET has been studied for two anionic fluorophores: Lucifer Yellow CH and chlorin p 6 with Methylviologen dication. PET, manifested in the quenching of fluorescence of the fluorophores, has been modulated by incorporating the molecules in organized assemblies like micelles, reverse micelles and supramolecular hosts. The dynamics of the process has been monitored in the femtosecond to nanosecond timescale. The modulation of the electron transfer has been found to be occurring mainly due to the disruption of contact ion pairs formed between the fluorophores and the quencher. - Highlights: ► Modulation of PET of biologically active fluorophores and Methyl viologen. ► Static and Dynamic Quenching present. ► PET enhanced upon encapsulation, studied through Fluorescence upconversion experiments. ► Rotational anisotropy has significant contribution in quenching.

  1. Low-energy electron-induced dissociation in condensed-phase L-cysteine II: a comparative study on anion desorption from chemisorbed and physisorbed films

    Science.gov (United States)

    Alizadeh, Elahe; Massey, Sylvain; Sanche, Léon; Rowntree, Paul A.

    2016-04-01

    Due to its multifunctional structure, cysteine is becoming an ideal model molecule for investigating the complex interactions of proteins with metallic surfaces such as gold nanoparticles. We report herein the results of low-energy electron induced degradation of L-cysteine films, chemisorbed on a gold substrate via the thiol group or physisorbed into a clean gold surface. The data were recorded under ultra-high vacuum conditions at room temperature. Anion yields desorbed from these films by the impact of 0.5 to 19 eV electrons provide clear evidence of the efficient decomposition of this amino acid via dissociative electron attachment (i.e., from dissociation of intermediate transient anions located between 5 and 14 eV). The peaks in the desorbed-anion yield functions, associated with DEA, are superimposed on a continuously rising signal attributed to dipolar dissociation. Similar to the results previously observed from physisorbed films, light anionic species, with masses lower than 35 amu, have been detected. In addition, we measured for first time fragments at 14 amu (CH2-) and 15 amu (CH3-) desorbing from physisorbed films, as well as heavier fragments of mass 45 and 46 amu desorbing from chemisorbed films. Contribution to the Topical Issue "Low-Energy Interactions related to Atmospheric and Extreme Conditions", edited by S. Ptasinska, M. Smialek-Telega, A. Milosavljevic, B. Sivaraman.

  2. In search for an optimal methodology to calculate the valence electron affinities of temporary anions.

    Science.gov (United States)

    Puiatti, Marcelo; Vera, D Mariano A; Pierini, Adriana B

    2009-10-28

    Recently, we have proposed an approach for finding the valence anion ground state, based on the stabilization exerted by a polar solvent; the methodology used standard DFT methods and relatively inexpensive basis sets and yielded correct electron affinity (EA) values by gradually decreasing the dielectric constant of the medium. In order to address the overall performance of the new methodology, to find the best conditions for stabilizing the valence state and to evaluate its scope and limitations, we gathered a pool of 60 molecules, 25 of them bearing the conventional valence state as the ground anion and 35 for which the lowest anion state found holds the extra electron in a diffuse orbital around the molecule (non valence state). The results obtained by testing this representative set suggest a very good performance for most species having an experimental EA less negative than -3.0 eV; the correlation at the B3LYP/6-311+G(2df,p) level being y = 1.01x + 0.06, with a correlation index of 0.985. As an alternative, the time dependent DFT (TD-DFT) approach was also tested with both B3LYP and PBE0 functionals. The methodology we proposed shows a comparable or better accuracy with respect to TD-DFT, although the TD-DFT approach with the PBE0 functional is suggested as a suitable estimate for species with the most negative EAs (ca.-2.5 to -3.5 eV), for which stabilization strategies can hardly reach the valence state. As an application, a pool of 8 compounds of key biological interest with EAs which remain unknown or unclear were predicted using the new methodology.

  3. Effects of microsolvation on uracil and its radical anion: Uracil.(H2O)n (n=1-5)

    Science.gov (United States)

    Kim, Sunghwan; Schaefer, Henry F.

    2006-10-01

    Microsolvation effects on the stabilities of uracil and its anion have been investigated by explicitly considering the structures of complexes of uracil with up to five water molecules at the B3LYP /DZP++ level of theory. For all five systems, the global minimum of the neutral cluster has a different equilibrium geometry from that of the radical anion. Both the vertical detachment energy (VDE) and adiabatic electron affinity (AEA) of uracil are predicted to increase gradually with the number of hydrating molecules, qualitatively consistent with experimental results from a photodetachment-photoelectron spectroscopy study [J. Schiedt et al., Chem. Phys. 239, 511 (1998)]. The trend in the AEAs implies that while the conventional valence radical anion of uracil is only marginally bound in the gas phase, it will form a stable anion in aqueous solution. The gas-phase AEA of uracil (0.24eV) was higher than that of thymine by 0.04eV and this gap was not significantly affected by microsolvation. The largest AEA is that predicted for uracil•(H2O)5, namely, 0.96eV. The VDEs range from 0.76to1.78eV.

  4. New Insights in Catalytic Sites: Characterization of Spectroscopy and Reactivity of Metal Oxide Clusters with Anion Slow Electron Velocity-Map Imaging

    Science.gov (United States)

    2016-06-08

    SEVI experiment, 16 ions were produced by expanding an appropriate gas mixture into vacuum with a pulsed solenoid valve. Anions were created from... laser ablation. They pass through an rf ion guide and are mass- selected in a quadrupole mass spectrometer. They are then injected into an rf...selected anions are dissociated by the absorption of multiple photons from a tunable infrared free electron laser . 33 This work is motivated by the

  5. Controlled Release Kinetics in Hydroxy Double Salts: Effect of Host Anion Structure

    Directory of Open Access Journals (Sweden)

    Stephen Majoni

    2014-01-01

    Full Text Available Nanodimensional layered metal hydroxides such as layered double hydroxides (LDHs and hydroxy double salts (HDSs can undergo anion exchange reactions releasing intercalated anions. Because of this, these metal hydroxides have found applications in controlled release delivery of bioactive species such as drugs and pesticides. In this work, isomers of hydroxycinnamate were used as model compounds to systematically explore the effects of anion structure on the rate and extent of anion release in HDSs. Following intercalation and subsequent release of the isomers, it has been demonstrated that the nature and position of substituent groups on intercalated anions have profound effects on the rate and extent of release. The extent of release was correlated with the magnitude of dipole moments while the rate of reaction showed strong dependence on the extent of hydrogen bonding within the layers. The orthoisomer showed a more sustained and complete release as compared to the other isomers.

  6. Importance of poly(ethylene oxide)-modification and chloride anion for the electron transfer reaction of cytochrome c in 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide

    International Nuclear Information System (INIS)

    Ohno, Hiroyuki; Suzuki, Chiiko; Fujita, Kyoko

    2006-01-01

    Horse heart cytochrome c (cyt c) was chemically modified with poly(ethylene oxide) (PEO) to dissolve it in room temperature ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([emim][TFSI]). The redox response of the modified cyt c, hereafter PEO-cyt c, was analyzed in [emim][TFSI]. PEO modification to the surface of cyt c, which exceeded 60% of the total mass of the PEO-cyt c, was an effective method to solubilize the cyt c. In spite of the high ion density and sufficient ionic conductivity of [emim][TFSI], no redox response of pure PEO-cyt c was detected. However, a reversible redox response of PEO-cyt c was observed after adding a simple electrolyte such as KCl to [emim][TFSI]. The redox response of PEO-cyt c was sensitive to the anion radius of the added salt, and the chloride anion was found to be the best anion species to produce a redox response of PEO-cyt c in [emim][TFSI]. However, above a certain salt concentration, the resulting increase in solution viscosity would suppress the redox reaction. The results strongly indicate that the chloride anions, because of their mobility in the polypeptide matrix, compensate the charge change of heme during the electron transfer reaction. Larger anions did not show such an effect due to sterical restrictions on the migration through the protein shell to the heme pocket of cyt c

  7. Photoinduced electron transfer between anionic fluorophores and methyl viologen in homogeneous and microheterogeneous media

    Energy Technology Data Exchange (ETDEWEB)

    Burai, Tarak Nath; Panda, Debashis; Iyer, E Siva Subramaniam [Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai 400 076 (India); Datta, Anindya, E-mail: anindya@chem.iitb.ac.in [Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai 400 076 (India)

    2012-11-15

    The rate and extent of photoinduced electron transfer change significantly as a result of confinement in nanovolumes. Study of such processes is an active area of research in physical chemistry. The effect is most interesting when the molecules that participate in PET are charged. In the present article, the modulation of PET has been studied for two anionic fluorophores: Lucifer Yellow CH and chlorin p{sub 6} with Methylviologen dication. PET, manifested in the quenching of fluorescence of the fluorophores, has been modulated by incorporating the molecules in organized assemblies like micelles, reverse micelles and supramolecular hosts. The dynamics of the process has been monitored in the femtosecond to nanosecond timescale. The modulation of the electron transfer has been found to be occurring mainly due to the disruption of contact ion pairs formed between the fluorophores and the quencher. - Highlights: Black-Right-Pointing-Pointer Modulation of PET of biologically active fluorophores and Methyl viologen. Black-Right-Pointing-Pointer Static and Dynamic Quenching present. Black-Right-Pointing-Pointer PET enhanced upon encapsulation, studied through Fluorescence upconversion experiments. Black-Right-Pointing-Pointer Rotational anisotropy has significant contribution in quenching.

  8. Electric field effect on the electronic structure of 2D Y2C electride

    Science.gov (United States)

    Oh, Youngtek; Lee, Junsu; Park, Jongho; Kwon, Hyeokshin; Jeon, Insu; Wng Kim, Sung; Kim, Gunn; Park, Seongjun; Hwang, Sung Woo

    2018-07-01

    Electrides are ionic compounds in which electrons confined in the interstitial spaces serve as anions and are attractive owing to their exotic physical and chemical properties in terms of their low work function and efficient charge-transfer characteristics. Depending on the topology of the anionic electrons, the surface electronic structures of electrides can be significantly altered. In particular, the electronic structures of two-dimensional (2D) electride surfaces are of interest because the localized anionic electrons at the interlayer space can be naturally exposed to cleaved surfaces. In this paper, we report the electronic structure of 2D Y2C electride surface using scanning tunneling microscopy (STM) and first-principles calculations, which reveals that anionic electrons at a cleaved surface are absorbed by the surface and subsequently resurged onto the surface due to an applied electric field. We highlight that the estranged anionic electrons caused by the electric field occupy the slightly shifted crystallographic site compared with a bulk Y2C electride. We also measure the work function of the Y2C single crystal, and it shows a slightly lower value than the calculated one, which appears to be due to the electric field from the STM junction.

  9. Intermolecular proton transfer in anionic complexes of uracil with alcohols

    International Nuclear Information System (INIS)

    Haranczyk, Maciej; Rak, Janusz; Gutowski, Maciej S.; Radisic, Dunja; Stokes, Sarah T.; Bowen, Kit H.

    2005-01-01

    A series of eighteen alcohols (ROH) has been designed with an enthalpy of deprotonation (H DP ) in a range of 13.8-16.3 eV. The effects of excess electron attachment to the binary alcohol-uracil (ROH...U) complexes have been studied at the density functional level with a B3LYP exchange-correlation functional and at the second order Moeller-Plesset perturbation theory level. The photoelectron spectra of anionic complexes of uracil with three alcohols (ethanol, 2,2,3,3,3-pentafluoroethanol and 1,1,1,3,3,3-hexafluoro-2-propanol) have been measured with 2.54 eV photons. For ROHs with deprotonation enthalpies larger than 14.8 eV only the ROH...U - minimum exists on the potential energy surface of the anionic complex. For alcohols with deprotonation enthalpies in a range of 14.3-14.8 eV two minima might exist on the anionic potential energy surface, which correspond to the RO - ...HU . and ROH...U - structures. For ROHs with deprotonation enthalpies smaller than 14.3 eV, the excess electron attachment to the ROH...U complex always induces a barrier-free proton transfer from the hydroxyl group of ROH to the O8 atom of U, with the product being RO - ...HU . . A driving force for the intermolecular proton transfer is to stabilize the excess negative charge localized on a orbital of uracil. Therefore, these complexes with proton transferred to the anionic uracil are characterized by larger values of electron vertical detachment energy (VDE). The values of VDE for anionic complexes span a range from 1.0 to 2.3 eV and roughly correlate with the acidity of alcohols. However, there is a gap of ∼0.5 eV in the values of VDE, which separates the two families, ROH...U - and RO - ...HU . , of anionic complexes. The energy of stabilization for the anionic complexes spans a range from 0.6 to 1.7 eV and roughly correlates with the acidity of alcohols. The measured photoelectron spectra are in good agreement with the theoretical predictions

  10. Surface coating of siRNA-peptidomimetic nano-self-assemblies with anionic lipid bilayers: enhanced gene silencing and reduced adverse effects in vitro

    Science.gov (United States)

    Zeng, Xianghui; de Groot, Anne Marit; Sijts, Alice J. A. M.; Broere, Femke; Oude Blenke, Erik; Colombo, Stefano; van Eden, Willem; Franzyk, Henrik; Nielsen, Hanne Mørck; Foged, Camilla

    2015-11-01

    and homoarginine residues was shown to self-assemble with small interfering RNA (siRNA). The resulting well-defined nanocomplexes were coated with anionic lipids giving rise to net anionic liposomes. These complexes and the corresponding liposomes were optimized towards efficient gene silencing and low adverse effects. The optimal anionic liposomes mediated a high silencing effect, which was comparable to that of the control (cationic Lipofectamine 2000), and did not display any noticeable cytotoxicity and immunogenicity in vitro. In contrast, the corresponding nanocomplexes mediated a reduced silencing effect with a more narrow safety window. The surface coating with anionic lipid bilayers led to partial decomplexation of the siRNA-peptidomimetic nanocomplex core of the liposomes, which facilitated siRNA release. Additionally, the optimal anionic liposomes showed efficient intracellular uptake and endosomal escape. Therefore, these findings suggest that a more efficacious and safe formulation can be achieved by surface coating of the siRNA-peptidomimetic nano-self-assemblies with anionic lipid bilayers. Electronic supplementary information (ESI) available: Non-fusogenic liposomes; cytotoxicity of naked siRNA and the empty vector; immunogenicity; low-magnification images; DOPE/DPPC liposomes. See DOI: 10.1039/c5nr04807a

  11. A photoelectron imaging and quantum chemistry study of the deprotonated indole anion.

    Science.gov (United States)

    Parkes, Michael A; Crellin, Jonathan; Henley, Alice; Fielding, Helen H

    2018-05-29

    Indole is an important molecular motif in many biological molecules and exists in its deprotonated anionic form in the cyan fluorescent protein, an analogue of green fluorescent protein. However, the electronic structure of the deprotonated indole anion has been relatively unexplored. Here, we use a combination of anion photoelectron velocity-map imaging measurements and quantum chemistry calculations to probe the electronic structure of the deprotonated indole anion. We report vertical detachment energies (VDEs) of 2.45 ± 0.05 eV and 3.20 ± 0.05 eV, respectively. The value for D0 is in agreement with recent high-resolution measurements whereas the value for D1 is a new measurement. We find that the first electronically excited singlet state of the anion, S1(ππ*), lies above the VDE and has shape resonance character with respect to the D0 detachment continuum and Feshbach resonance character with respect to the D1 continuum.

  12. AT base pair anions versus (9-methyl-A)(1-methyl-T) base pair anions.

    Science.gov (United States)

    Radisic, Dunja; Bowen, Kit H; Dabkowska, Iwona; Storoniak, Piotr; Rak, Janusz; Gutowski, Maciej

    2005-05-04

    The anionic base pairs of adenine and thymine, (AT)(-), and 9-methyladenine and 1-methylthymine, (MAMT)(-), have been investigated both theoretically and experimentally in a complementary, synergistic study. Calculations on (AT)(-) found that it had undergone a barrier-free proton transfer (BFPT) similar to that seen in other dimer anion systems and that its structural configuration was neither Watson-Crick (WC) nor Hoogsteen (HS). The vertical detachment energy (VDE) of (AT)(-) was determined by anion photoelectron spectroscopy and found to be in agreement with the VDE value predicted by theory for the BFPT mechanism. An AT pair in DNA is structurally immobilized into the WC configuration, in part, by being bonded to the sugars of the double helix. This circumstance was mimicked by methylating the sites on both A and T where these sugars would have been tied, viz., 9-methyladenine and 1-methylthymine. Calculations found no BFPT in (MAMT)(-) and a resulting (MAMT)(-) configuration that was either HS or WC, with the configurations differing in stability by ca. 2 kcal/mol. The photoelectron spectrum of (MAMT)(-) occurred at a completely different electron binding energy than had (AT)(-). Moreover, the VDE value of (MAMT)(-) was in agreement with that predicted by theory. The configuration of (MAMT)(-) and its lack of electron-induced proton transfer are inter-related. While there may be other pathways for electron-induced DNA alterations, BFPT in the WC/HS configurations of (AT)(-) is not feasible.

  13. AT Base Pair Anions vs. (9-methyl-A)(1-methyl-T) Base Pair Anions

    International Nuclear Information System (INIS)

    Radisic, Dunja; Bowen, Kit H.; Dabkowska, Iwona; Storoniak, Piotr; Rak, Janusz; Gutowski, Maciej S.

    2005-01-01

    The anionic base pairs of adenine and thymine, (AT)-, and 9-methyladenine and 1-methylthymine, (MAMT)-, have been investigated both theoretically and experimentally in a complementary, synergistic study. Calculations on (AT)- found that it had undergone a barrier-free proton transfer (BFPT) similar to that seen in other dimer anion systems and that its structural configuration that was neither Watson-Crick (WC) nor Hoogsteen (HS). The vertical detachment energy (VDE) of (AT)- was determined by anion photoelectron spectroscopy and found to be in agreement with the VDE value predicted by theory for the BFPT mechanism. An AT pair in DNA is structurally immobilized into the WC configuration, in part, by being bonded to the sugars of the double helix. This circumstance was mimicked by methylating the sites on both A and T where these sugars would have been tied, viz., 9-methyladenine and 1-methylthymine. Calculations found no BFPT in (MAMT)- and a resulting (MAMT)- configuration that wa s either HS or WC, with the configurations differing in stability by ca. 2 kcal/mol. The photoelectron spectrum of (MAMT)- occurred at a completely different electron binding energy than had (AT)-. Moreover, the VDE value of (MAMT)- was in agreement with that predicted by theory. The configuration of (MAMT)- and its lack of electron-induced proton transfer are inter-related. While there may be other pathways for electron-induced damage, BFPT in the WC/HS configurations of (AT)- is not feasible

  14. Probing structure, thermochemistry, electron affinity, and magnetic moment of thulium-doped silicon clusters TmSi n (n = 3-10) and their anions with density functional theory.

    Science.gov (United States)

    Huang, Xintao; Yang, Jucai

    2017-12-26

    The most stable structures and electronic properties of TmSi n (n = 3-10) clusters and their anions have been probed by using the ABCluster global search technique combined with the PBE, TPSSh, and B3LYP density functional methods. The results revealed that the most stable structures of neutral TmSi n and their anions can be regarded as substituting a Si atom of the ground state structure of Si n + 1 with a Tm atom. The reliable AEAs, VDEs and simulated PES of TmSi n (n = 3-10) are presented. Calculations of HOMO-LUMO gap revealed that introducing Tm atom to Si cluster can improve photochemical reactivity of the cluster. The NPA analyses indicated that the 4f electron of Tm atom in TmSi n (n = 3-10) and their anions do not participate in bonding. The total magnetic moments of TmSi n are mainly provided by the 4f electrons of Tm atom. The dissociation energy of Tm atom from the most stable structure of TmSi n and their anions has been calculated to examine relative stability.

  15. Role of Anions Associated with the Formation and Properties of Silver Clusters.

    Science.gov (United States)

    Wang, Quan-Ming; Lin, Yu-Mei; Liu, Kuan-Guan

    2015-06-16

    Metal clusters have been very attractive due to their aesthetic structures and fascinating properties. Different from nanoparticles, each cluster of a macroscopic sample has a well-defined structure with identical composition, size, and shape. As the disadvantages of polydispersity are ruled out, informative structure-property relationships of metal clusters can be established. The formation of a high-nuclearity metal cluster involves the organization of metal ions into a complex entity in an ordered way. To achieve controllable preparation of metal clusters, it is helpful to introduce a directing agent in the formation process of a cluster. To this end, anion templates have been used to direct the formation of high nuclearity clusters. In this Account, the role of anions played in the formation of a variety of silver clusters has been reviewed. Silver ions are positively charged, so anionic species could be utilized to control the formation of silver clusters on the basis of electrostatic interactions, and the size and shape of the resulted clusters can be dictated by the templating anions. In addition, since the anion is an integral component in the silver clusters described, the physical properties of the clusters can be modulated by functional anions. The templating effects of simple inorganic anions and polyoxometales are shown in silver alkynyl clusters and silver thiolate clusters. Intercluster compounds are also described regarding the importance of anions in determining the packing of the ion pairs and making contribution to electron communications between the positive and negative counterparts. The role of the anions is threefold: (a) an anion is advantageous in stabilizing a cluster via balancing local positive charges of the metal cations; (b) an anion template could help control the size and shape of a cluster product; (c) an anion can be a key factor in influencing the function of a cluster through bringing in its intrinsic properties. Properties

  16. Effect of the alkyl chain length of the ionic liquid anion on polymer electrolytes properties

    International Nuclear Information System (INIS)

    Leones, Rita; Sentanin, Franciani; Nunes, Sílvia Cristina; Esperança, José M.S.S.; Gonçalves, Maria Cristina

    2015-01-01

    New polymer electrolytes (PEs) based on chitosan and three ionic liquid (IL) families ([C 2 mim][C n SO 3 ], [C 2 mim][C n SO 4 ] and [C 2 mim][diC n PO 4 ]) were synthesized by the solvent casting method. The effect of the length of the alkyl chain of the IL anion on the thermal, morphological and electrochemical properties of the PEs was studied. The solid polymer electrolytes SPE membranes were analyzed by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray (EDX), polarized optical microscopy (POM), atomic force microscopy (AFM), complex impedance spectroscopy (ionic conductivity) and cyclic voltammetry (CV). The obtained results evidenced an influence of the alkyl chain length of the IL anion on the temperature of degradation, birefringence, surface roughness and ionic conductivity of the membranes. The DSC, XRD and CV results showed independency from the length of the IL-anion-alkyl chain. The PEs displayed an predominantly amorphous morphology, a minimum temperature of degradation of 135 °C, a room temperature (T = 25 °C) ionic conductivity of 7.78 × 10 −4 S cm −1 and a wide electrochemical window of ∼ 4.0 V.

  17. Hofmeister effect of anions on calcium translocation by sarcoplasmic reticulum Ca2+-ATPase

    Science.gov (United States)

    Tadini-Buoninsegni, Francesco; Moncelli, Maria Rosa; Peruzzi, Niccolò; Ninham, Barry W.; Dei, Luigi; Nostro, Pierandrea Lo

    2015-10-01

    The occurrence of Hofmeister (specific ion) effects in various membrane-related physiological processes is well documented. For example the effect of anions on the transport activity of the ion pump Na+, K+-ATPase has been investigated. Here we report on specific anion effects on the ATP-dependent Ca2+ translocation by the sarcoplasmic reticulum Ca2+-ATPase (SERCA). Current measurements following ATP concentration jumps on SERCA-containing vesicles adsorbed on solid supported membranes were carried out in the presence of different potassium salts. We found that monovalent anions strongly interfere with ATP-induced Ca2+ translocation by SERCA, according to their increasing chaotropicity in the Hofmeister series. On the contrary, a significant increase in Ca2+ translocation was observed in the presence of sulphate. We suggest that the anions can affect the conformational transition between the phosphorylated intermediates E1P and E2P of the SERCA cycle. In particular, the stabilization of the E1P conformation by chaotropic anions seems to be related to their adsorption at the enzyme/water and/or at the membrane/water interface, while the more kosmotropic species affect SERCA conformation and functionality by modifying the hydration layers of the enzyme.

  18. Effect of lone-electron-pair cations on the orientation of crystallographic shear planes in anion-deficient perovskites.

    Science.gov (United States)

    Batuk, Dmitry; Batuk, Maria; Abakumov, Artem M; Tsirlin, Alexander A; McCammon, Catherine; Dubrovinsky, Leonid; Hadermann, Joke

    2013-09-03

    Factors affecting the structure and orientation of the crystallographic shear (CS) planes in anion-deficient perovskites were investigated using the (Pb(1-z)Sr(z))(1-x)Fe(1+x)O(3-y) perovskites as a model system. The isovalent substitution of Sr(2+) for Pb(2+) highlights the influence of the A cation electronic structure because these cations exhibit very close ionic radii. Two compositional ranges have been identified in the system: 0.05 ≤ z ≤ 0.2, where the CS plane orientation gradually varies but stays close to (203)p, and 0.3 ≤ z ≤ 0.45 with (101)p CS planes. The incommensurately modulated structure of Pb0.792Sr0.168Fe1.040O2.529 was refined from neutron powder diffraction data using the (3 + 1)D approach (space group X2/m(α0γ), X = (1/2, 1/2, 1/2, 1/2), a = 3.9512(1) Å, b = 3.9483(1) Å, c = 3.9165(1) Å, β = 93.268(2)°, q = 0.0879(1)a* + 0.1276(1)c*, RF = 0.023, RP = 0.029, and T = 900 K). A comparison of the compounds with different CS planes indicates that the orientation of the CS planes is governed mainly by the stereochemical activity of the lone-electron-pair cations inside the perovskite blocks.

  19. Corrosion and inhibition of stainless steel pitting corrosion in alkaline medium and the effect of Cl- and Br- anions

    International Nuclear Information System (INIS)

    Refaey, S.A.M.; Taha, F.; El-Malak, A.M. Abd

    2005-01-01

    The effect of carbonate anion on the pitting corrosion and inhibition behavior of stainless steel samples (304L SS and 316L SS) has been studied using potentiodynamic and scanning electron microscope (SEM) techniques. The effect of concentration of CO 3 2- ions, pH, potential scanning rate and the composition of stainless steel are discussed. Additions of Cl - and Br - ions into the carbonate solution increase the anodic dissolution of stainless steel and decrease its pitting corrosion resistance. The effect of CO 3 2- anion on the inhibition of chloride and bromide pitting corrosion of the two stainless steel types has been studied also. Pitting corrosion decrease with the increasing of sodium carbonate concentration, i.e. increases the resistance of stainless steels towards the chloride and bromide pitting corrosion. This inhibition effect argued to formation of [Fe,Cr]CO 3 film caused by preferential adsorption of the CO 3 2- ion, leading to instantaneous repair of weak sites for pit nucleation

  20. Physicochemical treatments of anionic surfactants wastewater: Effect on aerobic biodegradability.

    Science.gov (United States)

    Aloui, Fathi; Kchaou, Sonia; Sayadi, Sami

    2009-05-15

    The effect of different physicochemical treatments on the aerobic biodegradability of an industrial wastewater resulting from a cosmetic industry has been investigated. This industrial wastewater contains 11423 and 3148mgL(-1) of chemical oxygen demand (COD) and anionic surfactants, respectively. The concentration of COD and anionic surfactants were followed throughout the diverse physicochemical treatments and biodegradation experiments. Different pretreatments of this industrial wastewater using chemical flocculation process with lime and aluminium sulphate (alum), and also advanced oxidation process (electro-coagulation (Fe and Al) and electro-Fenton) led to important COD and anionic surfactants removals. The best results were obtained using electro-Fenton process, exceeding 98 and 80% of anionic surfactants and COD removals, respectively. The biological treatment by an isolated strain Citrobacter braakii of the surfactant wastewater, as well as the pretreated wastewater by the various physicochemical processes used in this study showed that the best results were obtained with electro-Fenton pretreated wastewater. The characterization of the treated surfactant wastewater by the integrated process (electro-coagulation or electro-Fenton)-biological showed that it respects Tunisian discharge standards.

  1. Anions in Cometary Comae

    Science.gov (United States)

    Charnley, Steven B.

    2011-01-01

    The presence of negative ions (anions) in cometary comae is known from Giotto mass spectrometry of IP/Halley. The anions 0-, OH-, C-, CH- and CN- have been detected, as well as unidentified anions with masses 22-65 and 85-110 amu (Chaizy et al. 1991). Organic molecular anions are known to have a significant impact on the charge balance of interstellar clouds and circumstellar envelopes and have been shown to act as catalysts for the gas-phase synthesis of larger hydrocarbon molecules in the ISM, but their importance in cometary comae has not yet been explored. We present details of the first attempt to model the chemistry of anions in cometary comae. Based on the combined chemical and hydro dynamical model of Rodgers & Charnley (2002), we investigate the role of large carbon-chain anions in cometary coma chemistry. We calculate the effects of these anions on coma thermodynamics, charge balance and examine their impact on molecule formation.

  2. Ytterbium doped silicon clusters YbSi{sub n} (n = 4–10) and their anions: Structures, thermochemistry, and electron affinities

    Energy Technology Data Exchange (ETDEWEB)

    Xie, Xiaohong [School of Chemical Engineering, Inner Mongolia University of Technology, Hohhot 010051 (China); Hao, Dongsheng [School of Chemical Engineering, Inner Mongolia University of Technology, Hohhot 010051 (China); School of Mining and Technology, Inner Mongolia University of Technology, Hohhot 010051 (China); Yang, Jucai, E-mail: yangjc@imut.edu.cn [School of Chemical Engineering, Inner Mongolia University of Technology, Hohhot 010051 (China); School of Energy and Power Engineering, Inner Mongolia University of Technology, Hohhot 010051 (China)

    2015-11-05

    Highlights: • The ground-state structure of YbSi{sub n} and its anion is substitutional structure. • The four DFT AEAs are in excellent agreement with the experimental data. • Theoretical AEA of 2.33 eV of YbSi{sub 9} is more reasonable than the experimental 2.60 eV. • Hardness analysis reveals that doping Yb to Si{sub n} raises photochemical sensitivity. • Relative stabilities of YbSi{sub n} and their anions are examined. - Abstract: The structures, electron affinities, dissociation energies, hardness, and dipole moments of YbSi{sub n} (n = 4–10) and their anions were examined using B3LYP, TPSSh, PBE and wB97X methods. The lowest-energy structures can be regarded as replacing a Si of the ground-state structure of Si{sub n+1} with a Yb atom. The theoretical adiabatic electron affinities (AEAs) of YbSi{sub n} are in excellent agreement with experimental data. The average absolute errors from experiment are by 0.08, 0.07, 0.05 and 0.08 eV at the B3LYP, the TPSSh, the PBE and the wB97X levels, respectively. Theoretical AEAs of 2.33 ± 0.05 eV for YbSi{sub 9} are more reliable than the experimental value of 2.60 ± 0.05 eV. The hardness analysis reveals that doping Yb atom to Si{sub n} (n = 4–10) clusters raises the photochemical sensitivity. The dissociation energies of Yb atom from YbSi{sub n} and their anions were calculated to examine relative stabilities.

  3. Automated electronic tongue based on potentiometric sensors for the determination of a trinary anionic surfactant mixture.

    Science.gov (United States)

    Cortina, Montserrat; Ecker, Christina; Calvo, Daniel; del Valle, Manuel

    2008-01-22

    An automated electronic tongue consisting of an array of potentiometric sensors and an artificial neural network (ANN) has been developed to resolve mixtures of anionic surfactants. The sensor array was formed by five different flow-through sensors for anionic surfactants, based on poly(vinyl chloride) membranes having cross-sensitivity features. Feedforward multilayer neural networks were used to predict surfactant concentrations. As a great amount of information is required for the correct modelling of the sensors response, a sequential injection analysis (SIA) system was used to automatically provide it. Dodecylsulfate (DS(-)), dodecylbenzenesulfonate (DBS(-)) and alpha-alkene sulfonate (ALF(-)) formed the three-analyte study case resolved in this work. Their concentrations varied from 0.2 to 4mM for ALF(-) and DBS(-) and from 0.2 to 5mM for DS(-). Good prediction ability was obtained with correlation coefficients better than 0.933 when the obtained values were compared with those expected for a set of 16 external test samples not used for training.

  4. The chemistry of molecular anions in circumstellar sources

    Energy Technology Data Exchange (ETDEWEB)

    Agúndez, Marcelino [LUTH, Observatoire de Paris-Meudon, 5 Place Jules Janssen, 92190 Meudon (France); Cernicharo, José [Departamento de Astrofísica, CAB, CSIC-INTA, Ctra. de Torrejón a Ajalvir km 4, 28850 Madrid (Spain); Guélin, Michel [Institut de Radioastronomie Millimétrique, 300 rue de la Piscine, 38406 Saint Martin d' Héres (France)

    2015-01-22

    The detection of negatively charged molecules in the interstellar and circumstellar medium in the past four years has been one of the most impacting surprises in the area of molecular astrophysics. It has motivated the interest of astronomers, physicists, and chemists on the study of the spectroscopy, chemical kinetics, and prevalence of molecular anions in the different astronomical regions. Up to six different molecular anions have been discovered in space to date, the last one being the small ion CN{sup −}, which has been observed in the envelope of the carbon star IRC +10216 and which contrary to the other larger anions is not formed by electron attachment to CN, but through reactions of large carbon anions with nitrogen atoms. Here we briefly review the current status of our knowledge of the chemistry of molecular anions in space, with particular emphasis on the circumstellar source IRC +10216, which to date is the astronomical source harboring the largest variety of anions.

  5. Effect of superoxide anion scavenger on rat hearts with chronic intermittent hypoxia.

    Science.gov (United States)

    Pai, Peiying; Lai, Ching Jung; Lin, Ching-Yuang; Liou, Yi-Fan; Huang, Chih-Yang; Lee, Shin-Da

    2016-04-15

    Only very limited information regarding the protective effects of the superoxide anion scavenger on chronic intermittent hypoxia-induced cardiac apoptosis is available. The purpose of this study is to evaluate the effects of the superoxide anion scavenger on cardiac apoptotic and prosurvival pathways in rats with sleep apnea. Forty-two Sprague-Dawley rats were divided into three groups, rats with normoxic exposure (Control, 21% O2, 1 mo), rats with chronic intermittent hypoxia exposure (Hypoxia, 3-7% O2vs. 21% O2per 40 s cycle, 8 h per day, 1 mo), and rats with pretreatment of the superoxide anion scavenger and chronic intermittent hypoxia exposure (Hypoxia-O2 (-)-Scavenger, MnTMPyP pentachloride, 1 mg/kg ip per day; 3-7% O2vs. 21% O2per 40 s cycle, 8 h per day, 1 mo) at 5-6 mo of age. After 1 mo, the protein levels and apoptotic cells of excised hearts from three groups were measured by Western blotting and terminal deoxynucleotide transferase-mediated dUTP nick end labeling (TUNEL) assay. The superoxide anion scavenger decreased hypoxia-induced myocardial architecture abnormalities, left ventricular hypertrophy, and TUNEL-positive apoptosis. The superoxide anion scavenger decreased hypoxia-induced Fas ligand, Fas death receptors, Fas-associated death domain (FADD), activated caspase-8, and activated caspase-3 (Fas-dependent apoptotic pathway) as well as Bad, activated caspase-9 and activated caspase-3 (mitochondria-dependent apoptotic pathway), endonuclease G (EndoG), apoptosis-inducing factor (AIF), and TUNEL-positive apoptosis. The superoxide anion scavenger increased IGF-1, IGF-1R, p-PI3k, p-Akt, p-Bad, Bcl-2, and Bcl-xL (survival pathway). Our findings imply that the superoxide anion scavenger might prevent cardiac Fas-mediated and mitochondrial-mediated apoptosis and enhance the IGF-1-related survival pathway in chronic intermittent hypoxia. The superoxide anion scavenger may prevent chronic sleep apnea-enhanced cardiac apoptotic pathways and enhances

  6. Anion-based approaches to tunable functionality in oxide heterostructures

    Science.gov (United States)

    May, Steven

    2014-03-01

    The ability to control the position and composition of the anion site is emerging as a promising route to tune properties in epitaxial perovskites. This talk will focus on recent and ongoing efforts aimed at developing anion-based approaches to tailor electronic and magnetic properties in oxide films. First, I will discuss how the position of the oxygen anions can be tailored to stabilize non-bulk-like bond angles and lengths, thereby altering electronic bandwidth. Recent work on La2/3Sr1/3MnO3 will be presented in which ultrathin films under the same strain state exhibit dramatically different electronic and magnetic properties when grown on substrates with different symmetries. In the second half of the talk, I will describe efforts focused on altering the composition of the anion site. In La1/3Sr2/3FeO3-δ films, a reversible change in oxygen content leads to dramatic changes in electrical, optical, and structural properties. Finally, the synthesis of oxyfluoride ferrite and nickelate perovskite films via topotactic reactions carried out following thin film deposition will be described. This work is supported by the Office of Naval Research (N00014-11-1-0664) and the U. S. Army Research Office (W911NF-12-1-0132).

  7. An ab initio study on BeX 3- superhalogen anions (X = F, Cl, Br)

    Science.gov (United States)

    Anusiewicz, Iwona; Skurski, Piotr

    2002-06-01

    The vertical electron detachment energies (VDE) of 10 BeX 3- (X = F, Cl, Br) anions were calculated at the outer valence Green function (OVGF) level with the 6-311++G(3df) basis sets. The largest vertical electron binding energy was found for BeF 3- system (7.63 eV). All negatively charged species possess the vertical electron detachment energies that are larger than 5.5 eV and thus may be termed superhalogen anions. The strong dependence of the VDE of the BeX 3- species on the ligand-central atom (Be-X) distance and on the partial atomic charge localized on Be was observed and discussed, as well as the other factors that may influence the electronic stability of such anions. In addition, the usefulness of the various theoretical treatments for estimating the VDEs of superhalogen anions was tested and analyzed.

  8. Photochemistry and infrared spectrum of single-bridged diborane(5) anion isolated in solid argon

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Meng-Chen; Chin, Chih-Hao; Chen, Sian-Cong; Huang, Tzu-Ping [National Synchrotron Radiation Research Center (NSRRC), 101 Hsin-Ann Road, Hsinchu Science Park, Hsinchu 30076, Taiwan (China); Chen, Hui-Fen; Huang, Wei-Jie [Department of Medicinal and Applied Chemistry, Kaohsiung Medical University, 100, Shih-Chuan 1st Road, Kaohsiung 80708, Taiwan (China); Wu, Yu-Jong, E-mail: yjw@nsrrc.org.tw [National Synchrotron Radiation Research Center (NSRRC), 101 Hsin-Ann Road, Hsinchu Science Park, Hsinchu 30076, Taiwan (China); Department of Applied Chemistry, National Chiao Tung University, 1001, Ta-Hsueh Road, Hsinchu 30010, Taiwan (China)

    2016-08-21

    Three-center two-electron bonds are important for understanding electron-deficient molecules. To examine such a molecule, we produced a diborane(5) anion with a single-bridged structure upon electron bombardment during matrix deposition of Ar containing a small proportion of diborane(6). The diborane(5) anion was destroyed upon photolysis at 180, 220, 385, and 450 nm, but not at 532 nm. Moreover, the possible formation of neutral diborane(5) was observed upon photolysis at 385 and 450 nm, whereas neutral diborane(3) was observed upon photolysis at 180 and 220 nm. The observed line wavenumbers, relative intensities, and isotopic ratios of the diborane(5) anion agreed satisfactorily with those predicted by density functional theory calculations at the B3LYP/aug-cc-pVTZ level of theory. Thus, this method produced the boron hydride anion of interest with few other fragments, which enabled us to clearly identify the IR spectrum of the diborane(5) anion.

  9. Dissociative electron attachment to methyl chloride: A quasi-diatomic potential curve for the fragmentation of the metastable CH3Cl- anion

    International Nuclear Information System (INIS)

    Mach, P.; Urban, J.; Staemmler, V.

    2009-01-01

    Potential energy curves have been calculated for the dissociation of the neutral CH 3 Cl molecule and its negative ion into CH 3 + Cl and CH 3 +Cl - , respectively. The neutral molecule and the anion could be treated by means of standard wave function based quantum chemical ab initio methods for C-Cl distances larger than about 2.4 A, where CH 3 Cl - is a stable anion. In the present calculation MP3 and CCSD(T) were employed. At shorter C-Cl distances the CH 3 Cl - anion is only metastable and cannot be treated by such methods. We have applied a stabilization scheme, first proposed by Nestmann and Peyerimhoff, to stabilize the metastable anion by adding extra positive charges to the molecule. By this trick it was possible to generate the resonance energy E res and width Γ as functions of the C-Cl distance in the resonance regime between 1.5 and 2.5 A. The calculated values for the threshold energy E thresh and the exothermicity ΔE 0 of the DEA (dissociative electron attachment) process are in very good agreement with experiment; the vertical attachment energy (VAE) is smaller than its experimental counterpart

  10. Anion embedded sol-gel films on Al for corrosion protection

    International Nuclear Information System (INIS)

    Sheffer, Mari; Groysman, Alec; Starosvetsky, David; Savchenko, Natali; Mandler, Daniel

    2004-01-01

    We report here on the successful incorporation of organic anions into a sol-gel film on Al as a means of enhancing the protection against corrosion. Following our previous study where we showed that hydrophobic sol-gel films provided pronounced corrosion inhibition, we studied the corrosion inhibition that phenylphosphonic acid (PPA) has when embedded inside a thin sol-gel coating on Al. The anion of this organic anion tends to stay inside a phenyltrimethoxysilane (PTMOS) based sol-gel film due to π-interactions. Our findings, which are derived primarily from potentiodynamic polarization measurements, electrochemical noise, scanning electron microscopy measurements and Auger electron spectroscopy (AES), clearly show that the organic phosphonate adds to the protection efficiency of the sol-gel film

  11. Degenerate Perturbation Theory for Electronic g Tensors: Leading-Order Relativistic Effects.

    Science.gov (United States)

    Rinkevicius, Zilvinas; de Almeida, Katia Julia; Oprea, Cornel I; Vahtras, Olav; Ågren, Hans; Ruud, Kenneth

    2008-11-11

    A new approach for the evaluation of the leading-order relativistic corrections to the electronic g tensors of molecules with a doublet ground state is presented. The methodology is based on degenerate perturbation theory and includes all relevant contributions to the g tensor shift up to order O(α(4)) originating from the one-electron part of the Breit-Pauli Hamiltonian-that is, it allows for the treatment of scalar relativistic, spin-orbit, and mixed corrections to the spin and orbital Zeeman effects. This approach has been implemented in the framework of spin-restricted density functional theory and is in the present paper, as a first illustration of the theory, applied to study relativistic effects on electronic g tensors of dihalogen anion radicals X2(-) (X = F, Cl, Br, I). The results indicate that the spin-orbit interaction is responsible for the large parallel component of the g tensor shift of Br2(-) and I2(-), and furthermore that both the leading-order scalar relativistic and spin-orbit corrections are of minor importance for the perpendicular component of the g tensor in these molecules since they effectively cancel each other. In addition to investigating the g tensors of dihalogen anion radicals, we also critically examine the importance of various relativistic corrections to the electronic g tensor of linear molecules with Σ-type ground states and present a two-state model suitable for an approximate estimation of the g tensor in such molecules.

  12. Electronic spectra of anions intercalated in layered double hydroxides

    Indian Academy of Sciences (India)

    groups of the layers and interlayer water through the termi- nal atom symmetry ... results in a reaction with the metal hydroxide layers lead- ing to the ..... List of band positions observed for potassium salts of anion and LDH samples. Salts.

  13. Thermochemistry and electronic structure of small boron clusters (B(n), n = 5-13) and their anions.

    Science.gov (United States)

    Truong, Ba Tai; Grant, Daniel J; Nguyen, Minh Tho; Dixon, David A

    2010-01-21

    Thermochemical parameters of a set of small-sized neutral (B(n)) and anionic (B(n)(-)) boron clusters, with n = 5-13, were determined using coupled-cluster theory CCSD(T) calculations with the aug-cc-pVnZ (n = D, T, and Q) basis sets extrapolated to the complete basis set limit (CBS) plus addition corrections and/or G3B3 calculations. Enthalpies of formation, adiabatic electron affinities (EA), vertical (VDE), and adiabatic (ADE) detachment energies were evaluated. Our calculated EAs are in good agreement with recent experiments (values in eV): B(5) (CBS, 2.29; G3B3, 2.48; exptl., 2.33 +/- 0.02), B(6) (CBS, 2.59; G3B3, 3.23; exptl., 3.01 +/- 0.04), B(7) (CBS, 2.62; G3B3, 2.67; exptl., 2.55 +/- 0.05), B(8) (CBS, 3.02; G3B3, 3.11; exptl., 3.02 +/- 0.02), B(9) (G3B3, 3.03; exptl., 3.39 +/- 0.06), B(10) (G3B3, 2.85; exptl., 2.88 +/- 0.09), B(11) (G3B4, 3.48;, exptl., 3.43 +/- 0.01), B(12) (G3B3, 2.33; exptl., 2.21 +/- 0.04), and B(13) (G3B3, 3.62; exptl., 3.78 +/- 0.02). The difference between the calculated adiabatic electron affinity and the adiabatic detachment energy for B(6) is due to the fact that the geometry of the anion is not that of the ground-state neutral. The calculated adiabatic detachment energies to the (3)A(u), C(2h) and (1)A(g), D(2h) excited states of B(6), which have geometries similar to the (1)A(g), D(2h) state of B(6)(-), are 2.93 and 3.06 eV, in excellent agreement with experiment. The VDEs were also well reproduced by the calculations. Partitioning of the electron localization functions into pi and sigma components allows probing of the partial and local delocalization in global nonaromatic systems. The larger clusters appear to exhibit multiple aromaticity. The binding energies per atom vary in a parallel manner for both neutral and anionic series and approach the experimental value for the heat of atomization of B. The resonance energies and the normalized resonance energies are convenient indices to quantify the stabilization of a cluster

  14. Ab initio investigation of sulfur monofluoride and its singly charged cation and anion in their ground electronic state

    Science.gov (United States)

    Song, Li; Shan-Jun, Chen; Yan, Chen; Peng, Chen

    2016-03-01

    The SF radical and its singly charged cation and anion, SF+ and SF-, have been investigated on the MRCI/aug-cc-pVXZ (X = Q, 5, 6) levels of theory with Davidson correction. Both the core-valence correlation and the relativistic effect are considered. The extrapolating to the complete basis set (CBS) limit is adopted to remove the basis set truncation error. Geometrical parameters, potential energy curves (PECs), vibrational energy levels, spectroscopic constants, ionization potentials, and electron affinities of the ground electronic state for all these species are obtained. The information with respect to molecular characteristics of the SFn (n = -1, 0, +1) systems derived in this work will help to extend our knowledge and to guide further experimental or theoretical researches. Project supported by the National Natural Science Foundation of China (Grant Nos. 11304023 and 11447172), the Young and Middle-Aged Talent of Education Burea of Hubei Province, China (Grant No. Q20151307), and the Yangtze Youth Talents Fund of Yangtze University, China (Grant No. 2015cqr21).

  15. Induction of Apoptosis by Superoxide Anion and the Protective Effects of Selenium and Vitamin E

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    Objective The purpose of this study is to investigate the effect of superoxide anion on the apoptosis of cultured fibroblasts and the protective role of selenium and Vitamin E. Methods Cultured fibroblasts (NIH3T3), with or without selenium or vitamin E in the medium, were treated by superoxide anion produced by xanthine/xanthine oxidase reaction system and changes in cell structure and DNA were observed microscopically and electrophoretically. Results Apoptosis was observed when superoxide anion at a concentration of 5 nmol/L or 10 nmol/L had acted on the fibroblasts for 5-10 h. Selenium and Vitamin E in the medium inhibited the apoptosis significantly when their concentrations reached 1.15 mol/L and 2.3 mol/L respectively. Conclusion Selenium and vitamin E have protective effect against the apoptosis induced by superoxide anion. The effect of selenium is more remarkable than that of vitamin E.

  16. Effect of indifferent anions on reactions of cadmium ferrocyanide precipitation

    Energy Technology Data Exchange (ETDEWEB)

    Gyunner, Eh A; Mel' nichenko, L M; Vel' mozhnyj, I S [Simferopol' skij Gosudarstvennyj Univ. (Ukrainian SSR)

    1982-08-01

    To clarify the effect of indifferent anions on the processes of cadmium ferrocyanide precipitation the interaction in six systems of the type CdXsub(m)-Msub(4)R-Hsub(2)O (X-Cl/sup -/, CH/sub 3/COO/sup -/, SO/sub 4//sup 2 -/; M-K/sup +/, NH/sub 4//sup +/; R-(Fe(CN)/sub 6/)/sup 4 -/) is studied using the methods of physicochemical analysis (the method of residual concentrations, refractometry). Composition and formation regions of low-soluble interaction products are determined. Effect of anion X nature on interaction character is stated in the series Cl/sup -/, CH/sub 3/COO/sup -/, SO/sub 4//sup 2 -/ in mixtures with incomplete Cd/sup 2 +/ precipitation a tendency for the increase of Cd/sup 2 +/:R/sup 4 -/ ratios in precipitates formed is observed.

  17. Anion photoelectron spectroscopy of radicals and clusters

    Energy Technology Data Exchange (ETDEWEB)

    Travis, Taylor R. [Univ. of California, Berkeley, CA (United States)

    1999-12-01

    Anion photoelectron spectroscopy is used to study free radicals and clusters. The low-lying 2Σ and 2π states of C2nH (n = 1--4) have been studied. The anion photoelectron spectra yielded electron affinities, term values, and vibrational frequencies for these combustion and astrophysically relevant species. Photoelectron angular distributions allowed the author to correctly assign the electronic symmetry of the ground and first excited states and to assess the degree of vibronic coupling in C2H and C4H. Other radicals studied include NCN and I3. The author was able to observe the low-lying singlet and triplet states of NCN for the first time. Measurement of the electron affinity of I3 revealed that it has a bound ground state and attachment of an argon atom to this moiety enabled him to resolve the symmetric stretching progression.

  18. Synthesis and Characterization of Birnessite and Cryptomelane Nanostructures in Presence of Hoffmeister Anions

    Directory of Open Access Journals (Sweden)

    Marcos A. Cheney

    2009-01-01

    Full Text Available The effect of Hoffmeister anions Cl−, SO42−, and ClO4− on the structure and morphology of birnessite and cryptomelane-type manganese dioxide nanostructures, produced by the reduction reaction of KMnO4 and MnSO4 in aqueous acidic media, was studied. The syntheses were based on the decomposition of aqueous KMnO4 in presence of HCl for birnessite-type and acidified MnSO4 for cryptomelane-type manganese dioxide under soft hydrothermal conditions. They were characterized using X-ray diffraction (XRD, transmission electron microscopy (TEM, and high-resolution transmission electron microscopy (HRTEM techniques. XRD patterns show the formation of birnessite for the first synthesis and a mixture of cryptomelane and birnessite-types MnO2 for the second synthesis. XRD data revealed that the Hoffmeister anions have a significant effect on the nanostructures of birnessite. The sulphate ion-treated birnessite has the smallest crystals, whereas the chloride ion-treated birnessite has the largest crystals. Their TEM and HRTEM studies revealed a transformation from nanoplatelet morphology for chloride-treated samples to nanofibrous morphology for sulphate-treated birnessite. For the cryptomelane nanostructures, Hoffmeister anions also show a profound effect on their crystalline structures as determined by XRD analyses revealing a transformation of the cryptomelane phase to birnessite phase of MnO2. This transformation is also supported by TEM and HRTEM studies.

  19. Highly selective and sensitive phosphate anion sensors based on AlGaN/GaN high electron mobility transistors functionalized by ion imprinted polymer.

    Science.gov (United States)

    Jia, Xiuling; Chen, Dunjun; Bin, Liu; Lu, Hai; Zhang, Rong; Zheng, Youdou

    2016-06-09

    A novel ion-imprinted electrochemical sensor based on AlGaN/GaN high electron mobility transistors (HEMTs) was developed to detect trace amounts of phosphate anion. This sensor combined the advantages of the ion sensitivity of AlGaN/GaN HEMTs and specific recognition of ion imprinted polymers. The current response showed that the fabricated sensor is highly sensitive and selective to phosphate anions. The current change exhibited approximate linear dependence for phosphate concentration from 0.02 mg L(-1) to 2 mg L(-1), the sensitivity and detection limit of the sensor is 3.191 μA/mg L(-1) and 1.97 μg L(-1), respectively. The results indicated that this AlGaN/GaN HEMT-based electrochemical sensor has the potential applications on phosphate anion detection.

  20. Hole localization, migration, and the formation of peroxide anion in perovskite SrTiO3

    Science.gov (United States)

    Chen, Hungru; Umezawa, Naoto

    2014-07-01

    Hybrid density functional calculations are carried out to investigate the behavior of holes in SrTiO3. As in many other oxides, it is shown that a hole tend to localize on one oxygen forming an O- anion with a concomitant lattice distortion; therefore a hole polaron. The calculated emission energy from the recombination of the localized hole and a conduction-band electron is about 2.5 eV, in good agreement with experiments. Therefore the localization of the hole or self-trapping is likely to be responsible for the green photoluminescence at low temperature, which was previously attributed to an unknown defect state. Compared to an electron, the calculated hole polaron mobility is three orders of magnitude lower at room temperature. In addition, two O- anions can bind strongly to form an O22- peroxide anion. No electronic states associated with the O22- peroxide anion are located inside the band gap or close to the band edges, indicating that it is electronically inactive. We suggest that in addition to the oxygen vacancy, the formation of the O22- peroxide anion can be an alternative to compensate acceptor doping in SrTiO3.

  1. Barrier-free proton transfer in the valence anion of 2'-deoxyadenosine-5'-monophosphate. II. A computational study

    Science.gov (United States)

    Kobyłecka, Monika; Gu, Jiande; Rak, Janusz; Leszczynski, Jerzy

    2008-01-01

    The propensity of four representative conformations of 2'-deoxyadenosine-5'-monophosphate (5'-dAMPH) to bind an excess electron has been studied at the B3LYP /6-31++G(d,p) level. While isolated canonical adenine does not support stable valence anions in the gas phase, all considered neutral conformations of 5'-dAMPH form adiabatically stable anions. The type of an anionic 5'-dAMPH state, i.e., the valence, dipole bound, or mixed (valence/dipole bound), depends on the internal hydrogen bond(s) pattern exhibited by a particular tautomer. The most stable anion results from an electron attachment to the neutral syn-south conformer. The formation of this anion is associated with a barrier-free proton transfer triggered by electron attachment and the internal rotation around the C4'-C5' bond. The adiabatic electron affinity of the a&barbelow;south-syn anion is 1.19eV, while its vertical detachment energy is 1.89eV. Our results are compared with the photoelectron spectrum (PES) of 5'-dAMPH- measured recently by Stokes et al., [J. Chem. Phys. 128, 044314 (2008)]. The computational VDE obtained for the most stable anionic structure matches well with the experimental electron binding energy region of maximum intensity. A further understanding of DNA damage might require experimental and computational studies on the systems in which purine nucleotides are engaged in hydrogen bonding.

  2. Heavy atom vibrational modes and low-energy vibrational autodetachment in nitromethane anions

    International Nuclear Information System (INIS)

    Thompson, Michael C.; Weber, J. Mathias; Baraban, Joshua H.; Matthews, Devin A.; Stanton, John F.

    2015-01-01

    We report infrared spectra of nitromethane anion, CH 3 NO 2 − , in the region 700–2150 cm −1 , obtained by Ar predissociation spectroscopy and electron detachment spectroscopy. The data are interpreted in the framework of second-order vibrational perturbation theory based on coupled-cluster electronic structure calculations. The modes in the spectroscopic region studied here are mainly based on vibrations involving the heavier atoms; this work complements earlier studies on nitromethane anion that focused on the CH stretching region of the spectrum. Electron detachment begins at photon energies far below the adiabatic electron affinity due to thermal population of excited vibrational states

  3. Supramolecular Chemistry of Selective Anion Recognition for Anions of Environmental Relevance

    International Nuclear Information System (INIS)

    Sessler, Jonathan L.

    2007-01-01

    The major thrust of this project, led by the University of Kansas (Prof. Kristin Bowman-James), entails an exploration of the basic determinants of anion recognition and their application to the design, synthesis, and testing of novel sulfate extractants. A key scientific inspiration for the work comes from the need, codified in simple-to-appreciate terms by the Oak Ridge National Laboratory component of the team (viz. Dr. Bruce Moyer), for chemical entities that can help in the extractive removal of species that have low solubilities in borosilicate glass. Among such species, sulfate anion, has been identified as particularly insidious. Its presence interferes with the vitrification process, thus rendering the remediation of tank waste from, e.g., the Hanford site far more difficult and expensive. The availability of effective extractants, that would allow for the separation of separating sulfate from the major competing anions in the waste, especially nitrate, could allow for pre-vitrification removal of sulfate via liquid-liquid extraction. The efforts at The University of Texas, the subject of this report, have thus concentrated on the development of new sulfate receptors. These systems are designed to increase our basic understanding of anion recognition events and set the stage for the development of viable sulfate anion extractants. In conjunction with the Oak Ridge National Laboratory (ORNL) members of the research team, several of these new receptors were studied as putative extractants, with two of the systems being shown to act as promising synergists for anion exchange.

  4. Effect of biocides and anionic homopolymeric inhibitors on the ...

    African Journals Online (AJOL)

    This paper describes the effect of biocides and of the anionic homopolymeric inhibitors on the precipitation behavior of calcium fluoride (CaF2).The efficiency of inhibitors in the presence and absence of biocides was calculated using the half-life (t1/2) approach, where 50% of the concentration has been precipitated.

  5. Lowest auto-detachment state of the water anion

    International Nuclear Information System (INIS)

    Houfek, K.; Cizek, M.

    2016-01-01

    Because of the abundance of water in living tissue the reactive low-energy electron collisions with the water molecule represent an important step in the radiation damage of cells. In this paper, the potential energy surface of the ground state of the water anion H_2O"- is carefully mapped using multireference configuration interaction (MRCI) calculations for a large range of molecular geometries. Particular attention is paid to a consistent description of both the O"-+H_2 and OH"-+H asymptotes and to a relative position of the anion energy to the ground state energy of the neutral molecule. The auto-detachment region, where the anion state crosses to the electronic continuum is identified. The local minimum in the direction of the O"- + H_2 channel previously reported by Werner et al. [J. Chem. Phys. 87, 2913 (1987)] is found to be slightly off the linear geometry and is separated by a saddle from the auto-detachment region. The auto-detachment region is directly accessible from the OH"-+H asymptote. For the molecular geometries in the auto-detachment region and in its vicinity we also performed fixed-nuclei electron-molecule scattering calculations using the R-matrix method. Tuning of consistency of a description of the correlation energy in both the multireference CI and R-matrix calculations is discussed. Two models of the correlation energy within the R-matrix method that are consistent with the quantum chemistry calculations are found. Both models yield scattering quantities in a close agreement. The results of this work will allow a consistent formulation of the nonlocal resonance model of the water anion in a future publication

  6. Effect of anionic surfactant concentration on the variable range hopping conduction in polypyrrole nanoparticles

    International Nuclear Information System (INIS)

    Rawal, Ishpal; Kaur, Amarjeet

    2014-01-01

    The mechanism of charge transport in polypyrrole (PPy) nanoparticles prepared with different concentrations (5 to 30 mM) of anionic surfactant (sodium dodecyl sulfate) is reported. Transmission electron microscopy technique confirms the formation of PPy nanoparticles of sizes ∼52 to 28 nm under surfactant directed approach. The room temperature electrical conductivity of the prepared nanoparticles found to increase from 3 to 22 S/cm with surfactant concentration. The temperature dependent activation energy rules out the possibility of band conduction mechanism in the prepared PPy nanoparticles and thus the synthesized nanoparticles are analyzed under variable range hopping (VRH) model for conduction mechanism. The PPy nanoparticles, reduced with liquid ammonia, hold 3D VRH conduction mechanism for the charge transport. However, in the doped samples, some deviation from 3D VRH conduction behavior at higher temperatures (>150 K) has been observed. This may be attributed to the presence of anionic surfactant in these samples. The doping of anionic surfactant causes rise in conducting islands, which may lead to the change in the shape/distribution of density of states governed by Gaussian or exponential type near Fermi level

  7. Effect of anionic surfactant concentration on the variable range hopping conduction in polypyrrole nanoparticles

    Science.gov (United States)

    Rawal, Ishpal; Kaur, Amarjeet

    2014-01-01

    The mechanism of charge transport in polypyrrole (PPy) nanoparticles prepared with different concentrations (5 to 30 mM) of anionic surfactant (sodium dodecyl sulfate) is reported. Transmission electron microscopy technique confirms the formation of PPy nanoparticles of sizes ˜52 to 28 nm under surfactant directed approach. The room temperature electrical conductivity of the prepared nanoparticles found to increase from 3 to 22 S/cm with surfactant concentration. The temperature dependent activation energy rules out the possibility of band conduction mechanism in the prepared PPy nanoparticles and thus the synthesized nanoparticles are analyzed under variable range hopping (VRH) model for conduction mechanism. The PPy nanoparticles, reduced with liquid ammonia, hold 3D VRH conduction mechanism for the charge transport. However, in the doped samples, some deviation from 3D VRH conduction behavior at higher temperatures (>150 K) has been observed. This may be attributed to the presence of anionic surfactant in these samples. The doping of anionic surfactant causes rise in conducting islands, which may lead to the change in the shape/distribution of density of states governed by Gaussian or exponential type near Fermi level.

  8. On the effect of image states on resonant neutralization of hydrogen anions near metal surfaces

    International Nuclear Information System (INIS)

    Chakraborty, Himadri S.; Niederhausen, Thomas; Thumm, Uwe

    2005-01-01

    We directly assess the role of image state electronic structures on the ion-survival by comparing the resonant charge transfer dynamics of hydrogen anions near Pd(1 1 1), Pd(1 0 0), and Ag(1 1 1) surfaces. Our simulations show that image states that are degenerate with the metal conduction band favor the recapture of electrons by outgoing ions. In sharp contrast, localized image states that occur inside the band gap hinder the recapture process and thus enhance the ion-neutralization probability

  9. Effects of Anion Mobility on Electrochemical Behaviors of Lithium–Sulfur Batteries

    Energy Technology Data Exchange (ETDEWEB)

    Han, Kee Sung; Chen, Junzheng; Cao, Ruiguo; Rajput, Nav Nidhi; Murugesan, Vijayakumar; Shi, Lili; Pan, Huilin; Zhang, Jiguang; Liu, Jun; Persson, Kristin A.; Mueller, Karl T.

    2017-10-27

    The electrolyte is a crucial component of lithium-sulfur (Li-S) batteries, as it controls polysulfide dissolution, charge shuttling processes, and solid-electrolyte interphase (SEI) layer formation. Experimentally, the overall performance of Li-S batteries varies with choice of solvent system and Li-salt used in the electrolyte, and a lack of predictive understanding about the effects of individual electrolyte components inhibits the rational design of electrolytes for Li-S batteries. Here we analyze the role of the counter anions of common Li salts (such as TfO-, FSI-, TFSI-, and TDI-) when dissolved in DOL/DME (1:1 vol.) for use in Li-S batteries. The evolution of ion-ion and ion-solvent interactions due to vari-ous anions was analyzed using 17O NMR and pulsed-field gradient (PFG) NMR and then correlated with electrochemi-cal performance in Li-S cells. These data reveal that the for-mation of the passivation layer on the anode and the loss of active materials from the cathode (evidenced by polysulfide dissolution) are related to anion mobility and affinity with lithium polysulfide, respectively. For future electrolyte de-sign, anions with lower mobility and weaker interactions with lithium polysulfides may be superior candidates for increasing the long-term stability of Li-S batteries.

  10. Radical anion structure of β-halogen-substituted acetamides in X-ray-irradiated single crystals: an INDO and EPR study

    International Nuclear Information System (INIS)

    Samskog, P.O.; Kispert, L.D.

    1984-01-01

    The anion radicals of bromodifluoroacetamide and chlorodifluoroacetamide are investigated by using the INDO method and EPR spectroscopy. INDO calculations for the anions give a spin density distribution in agreement with that suggested from experiment. Results of the analyses show that the unpaired electron occupies the sigma* orbital composed of the rho orbitals, along the C/sub β/-X bond, on the carbon and the unique halogen atoms. The results are compared to the radical anion in trifluoroacetamide. The electronic structure of SCF 2 CONH 2 - radical anions is a π-radical anion when X = F and a sigma*-radical anion when X = Cl and Br. 2 figures, 4 tables

  11. The effect of membrane diffusion potential change on anionic drugs ...

    African Journals Online (AJOL)

    The effect of membrane potential change on anionic drugs Indomethacin and barbitone induced human erythrocyte shape change and red cell uptake of drug has been studied using microscopy and spectrophotometry techniques respectively. The membrane potential was changed by reducing the extracellular chloride ...

  12. EPR studies of the vitamin K 1 semiquinone radical anion. Comparison to the electron acceptor A 1 in green plant photosystem I

    Science.gov (United States)

    Thurnauer, Marion C.; Brown, James W.; Gast, P.; Feezel, Laura L.

    Suggestions that the electron acceptor, A 1, in Photosystem I is a quinone have come from both optical and epr experiments. Vitamin K 1 (phylloquinone) is present in the PSI complex with a stoichiometry of two molecules per reaction center. In order to determine if A 1 can be identified with vitamin K 1, X-band and Q-band epr properties of the vitamin K 1 radical anion in frozen alcohol solutions are examined. The results are compared to the epr properties that have been observed for the reduced A 1 acceptor in vivo. The g-values obtained for the vitamin K 1 radical anion are consistent with identifying A 1 with vitamin K 1.

  13. Solvation of the fluorine containing anions and their lithium salts in propylene carbonate and dimethoxyethane.

    Science.gov (United States)

    Chaban, Vitaly

    2015-07-01

    Electrolyte solutions based on the propylene carbonate (PC)-dimethoxyethane (DME) mixtures are of significant importance and urgency due to emergence of lithium-ion batteries. Solvation and coordination of the lithium cation in these systems have been recently attended in detail. However, analogous information concerning anions (tetrafluoroborate, hexafluorophosphate) is still missed. This work reports PM7-MD simulations (electronic-structure level of description) to include finite-temperature effects on the anion solvation regularities in the PC-DME mixture. The reported result evidences that the anions appear weakly solvated. This observation is linked to the absence of suitable coordination sites in the solvent molecules. In the concentrated electrolyte solutions, both BF4(-) and PF6(-) prefer to exist as neutral ion pairs (LiBF4, LiPF6).

  14. Determination of arsenate in water by anion selective membrane electrode using polyurethane–silica gel fibrous anion exchanger composite

    Energy Technology Data Exchange (ETDEWEB)

    Khan, Asif Ali, E-mail: asifkhan42003@yahoo.com; Shaheen, Shakeeba, E-mail: shakeebashaheen@ymail.com

    2014-01-15

    Highlights: • PU–Si gel is new anion exchanger material synthesized and characterized. • This material used as anion exchange membrane is applied for electroanalytical studies. • The method for detection and determination of AsO{sub 4}{sup 3−} in traces amounts discussed. • The results are also verified from arsenic analyzer. -- Abstract: Polyurethane (PU)–silica (Si gel) based fibrous anion exchanger composites were prepared by solid–gel polymerization of polyurethane in the presence of different amounts of silica gel. The formation of PU–Si gel fibrous anion exchanger composite was characterized by Fourier transform infra-red spectroscopy (FTIR), X-ray diffraction (XRD), thermogravimetric analysis (TGA-DTA), scanning electron microscopy (SEM) and elemental analysis. The membrane having a composition of 5:3 (PU:Si gel) shows best results for water content, porosity, thickness and swelling. Our studies show that the present ion selective membrane electrode is selective for arsenic, having detection limit (1 × 10{sup −8} M to 1 × 10{sup −1} M), response time (45 s) and working pH range (5–8). The selectivity coefficient values for interfering ions indicate good selectivity for arsenate (AsO{sub 4}{sup 3−}) over interfering anions. The accuracy of the detection limit results was compared by PCA-Arsenomat.

  15. Effect of electrostatic interactions on electron-transfer reactions

    International Nuclear Information System (INIS)

    Hickel, B.

    1987-01-01

    Fast reactions of electron transfer are studied by pulsed radiolysis. By this technique radicals and ionic radicals with high redox potentials are created homogeneously in the solution in about 10 -8 second. For solvated electron effect of electrostatic interaction on kinetics of reactions limited by diffusion is obtained with a good approximation by the Debye equation when ion mobility is known. Deviation from the theory occurs in ion pair formation, which is evidenced experimentally in reactions between anions when cations are complexed by a cryptate. Slow reactions k 8 M -1 s -1 are more sensitive to electrostatic interactions than reactions limited by diffusion. When there is no ion pair formation the velocity constant depends upon dielectric constant of the solvent and reaction distance. 17 refs

  16. The effect of anion on the magnetic properties of nanocrystalline NiO synthesized by homogeneous precipitation

    International Nuclear Information System (INIS)

    Ranga Rao Pulimi, V.; Jeevanandam, P.

    2009-01-01

    The effect of using different anions (nitrate, chloride, sulfate, and acetate) during the precursor synthesis, by homogeneous precipitation, on the magnetic properties of the final product (nanocrystalline NiO), has been studied. The precursors and the oxide were characterized by various analytical techniques including powder X-ray diffraction, FT-IR spectroscopy, thermal gravimetry (TGA), and magnetic measurements. The synthesized NiO samples possess crystallite size in the range, ∼2-6 nm, depending on the anion of the nickel salt. The nickel oxide nanoparticles exhibit superparamagnetic behavior. Acetate and sulfate anions lead to NiO with higher saturation magnetization (∼1.2-1.8 emu/g), while chloride and nitrate anions lead to NiO nanoparticles with lower saturation magnetization (∼0.1-0.4 emu/g) values. The observed magnetic behavior has been attributed to the size effect.

  17. The effect of anion on the magnetic properties of nanocrystalline NiO synthesized by homogeneous precipitation

    Energy Technology Data Exchange (ETDEWEB)

    Ranga Rao Pulimi, V. [Department of Chemistry, Indian Institute of Technology Roorkee, Roorkee 247667 (India); Jeevanandam, P. [Department of Chemistry, Indian Institute of Technology Roorkee, Roorkee 247667 (India)], E-mail: jeevafcy@iitr.ernet.in

    2009-09-15

    The effect of using different anions (nitrate, chloride, sulfate, and acetate) during the precursor synthesis, by homogeneous precipitation, on the magnetic properties of the final product (nanocrystalline NiO), has been studied. The precursors and the oxide were characterized by various analytical techniques including powder X-ray diffraction, FT-IR spectroscopy, thermal gravimetry (TGA), and magnetic measurements. The synthesized NiO samples possess crystallite size in the range, {approx}2-6 nm, depending on the anion of the nickel salt. The nickel oxide nanoparticles exhibit superparamagnetic behavior. Acetate and sulfate anions lead to NiO with higher saturation magnetization ({approx}1.2-1.8 emu/g), while chloride and nitrate anions lead to NiO nanoparticles with lower saturation magnetization ({approx}0.1-0.4 emu/g) values. The observed magnetic behavior has been attributed to the size effect.

  18. Design and fabrication of enhanced corrosion resistance Zn-Al layered double hydroxides films based anion-exchange mechanism on magnesium alloys

    Science.gov (United States)

    Zhou, Meng; Yan, Luchun; Ling, Hao; Diao, Yupeng; Pang, Xiaolu; Wang, Yanlin; Gao, Kewei

    2017-05-01

    Layered double hydroxides (LDHs) with brucite-like layer structure and the facile exchangeability of intercalated anions had attracted tremendous interest in many fields because of their great importance for both fundamental studies and practical applications. Herein zinc-aluminum layered double hydroxides (Zn-Al LDHs) films intercalated with nitrate anions on the magnesium alloy substrate were designed and fabricated via a facile hydrothermal crystallization method. In order to obtain better corrosion resistance, chloride and vanadate anions were intercalated into the LDHs interlayers via the anion-exchange reaction. X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy and scanning electronic microscopy (SEM) were used to examine structure, composition and morphology of the Zn-Al-NO3 LDHs, Zn-Al-Cl LDHs and Zn-Al-VOx LDHs films. The corrosion resistance of the Zn-Al LDHs with different anion films was estimated by the electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization measurement. EIS and polarization curves measurements revealed that the magnesium alloy could be effectively protected by the Zn-Al-Cl LDHs and Zn-Al-VOx LDHs films due to the blocking effect of chloride anions and the control-release ability of vanadate anions.

  19. The effect of interlayer anion on the reactivity of Mg-Al layered double hydroxides: improving and extending the customization capacity of anionic clays.

    Science.gov (United States)

    Rojas, Ricardo; Bruna, Felipe; de Pauli, Carlos P; Ulibarri, M Ángeles; Giacomelli, Carla E

    2011-07-01

    Layered double hydroxides (LDHs) reactivity and interfacial behavior are closely interconnected and control particle properties relevant to the wide range of these solids' applications. Despite their importance, their relationship has been hardly described. In this work, chloride and dodecylsulfate (DDS(-)) intercalated LDHs are studied combining experimental data (electrophoretic mobility and contact angle measurements, hydroxyl and organic compounds uptake) and a simple mathematical model that includes anion-binding and acid-base reactions. This approach evidences the anion effect on LDHs interfacial behavior, reflected in the opposite particle charge and the different surface hydrophobic/hydrophilic character. LDHs reactivity are also determined by the interlayer composition, as demonstrated by the cation uptake capability of the DDS(-) intercalated sample. Consequently, the interlayer anion modifies the LDHs interfacial properties and reactivity, which in turn extends the customization capacity of these solids. Copyright © 2011 Elsevier Inc. All rights reserved.

  20. Electronic structures and water reactivity of mixed metal sulfide cluster anions

    Energy Technology Data Exchange (ETDEWEB)

    Saha, Arjun; Raghavachari, Krishnan [Department of Chemistry, Indiana University, Bloomington, Indiana 47405 (United States)

    2014-08-21

    The electronic structures and chemical reactivity of the mixed metal sulfide cluster anion (MoWS{sub 4}{sup −}) have been investigated with density functional theory. Our study reveals the presence of two almost isoenergetic structural isomers, both containing two bridging sulfur atoms in a quartet state. However, the arrangement of the terminal sulfur atoms is different in the two isomers. In one isomer, the two metals are in the same oxidation state (each attached to one terminal S). In the second isomer, the two metals are in different oxidation states (with W in the higher oxidation state attached to both terminal S). The reactivity of water with the two lowest energy isomers has also been studied, with an emphasis on pathways leading to H{sub 2} release. The reactive behavior of the two isomers is different though the overall barriers in both systems are small. The origin of the differences are analyzed and discussed. The reaction pathways and barriers are compared with the corresponding behavior of monometallic sulfides (Mo{sub 2}S{sub 4}{sup −} and W{sub 2}S{sub 4}{sup −}) as well as mixed metal oxides (MoWO{sub 4}{sup −})

  1. Radical intermediates involved in the bleaching of the carotenoid crocin. Hydroxyl radicals, superoxide anions and hydrated electrons

    International Nuclear Information System (INIS)

    Bors, W.; Saran, M.; Michel, C.

    1982-01-01

    The participation of the primary radicals in the bleaching of aqueous solutions of the carotenoid crocin by ionizing radiation was investigated, employing both X-radiolysis and pulse radiolysis. The pulse-radiolytic data demonstrated a very rapid diffusion-controlled attack by both hydroxyl radicals (radicalsOH) and hydrated electrons (e - sub(aq)), while superoxide anions (O 2 - ) did not react at all. The site of the initial reaction of these radicals was not limited to the polyene chromophore. Slower secondary reactions involving crocin alkyl or peroxy radicals contribute mainly to the overall bleaching, in particular during steady-state irradiation. (author)

  2. Electron attachment to the phthalide molecule

    Energy Technology Data Exchange (ETDEWEB)

    Asfandiarov, N. L. [Institute of Molecule and Crystal Physics, Ufa Research Centre, Russian Academy of Sciences, Prospect Oktyabrya 151, 450075 Ufa (Russian Federation); Bashkir State Pedagogical University, Oktyabrskoy Revolutsii St., 3a, 450000 Ufa (Russian Federation); Pshenichnyuk, S. A. [Institute of Molecule and Crystal Physics, Ufa Research Centre, Russian Academy of Sciences, Prospect Oktyabrya 151, 450075 Ufa (Russian Federation); St.-Petersburg State University, Uljanovskaja, 1, 198504 St.-Petersburg (Russian Federation); Vorob’ev, A. S.; Nafikova, E. P. [Institute of Molecule and Crystal Physics, Ufa Research Centre, Russian Academy of Sciences, Prospect Oktyabrya 151, 450075 Ufa (Russian Federation); Lachinov, A. N. [Bashkir State Pedagogical University, Oktyabrskoy Revolutsii St., 3a, 450000 Ufa (Russian Federation); Kraikin, V. A. [Institute of Organic Chemistry, Ufa Research Centre, Russian Academy of Sciences, Prospect Oktyabrya 59, 450075 Ufa (Russian Federation); Modelli, A. [Dipartimento di Chimica “G. Ciamician,” Universitá di Bologna, Via Selmi 2, 40126 Bologna (Italy); Centro Interdipartimentale di Ricerca in Scienze Ambientali (CIRSA), Universitá di Bologna, Via S. Alberto 163, 48123 Ravenna (Italy)

    2015-05-07

    Phthalide, the simplest chain of conductive polymer thin film, was investigated by means of Electron Transmission Spectroscopy, Negative Ion Mass Spectrometry, and density functional theory quantum chemistry. It has been found that formation of gas-phase long-lived molecular anions of phthalide around 0.7 eV takes place through cleavage of a C–O bond of the pentacyclic ring of the parent molecular anion to give a vibrationally excited (electronically more stable) open-ring molecular anion. The energy of the transition state for ring opening of the parent negative ion is calculated to be 0.65 eV above the neutral ground state of the molecule. The energy (2.64 eV) evaluated for the corresponding transition state in the neutral molecule is much higher, so that the process of electron detachment from the anion must lead to a neutral molecule with its initial pentacyclic structure. The average lifetime of the molecular negative ions formed at an electron energy of 0.75 eV and 80 °C is measured to be about 100 μs. The known switching effect of thin phthalide films could stem from the presence of a similar open/closed transition state also in the polymer.

  3. ESR study of the anion radicals of 5-nitropyrimidines: conversion to iminoxy radicals

    International Nuclear Information System (INIS)

    Sevilla, M.D.; Clark, C.; Failor, R.

    1976-01-01

    The anion radicals of a number of 5-nitropyrimidines have been investigated by ESR spectroscopy. The anions are formed by electrolysis in dimethylformamide and by electron attachment in aqueous glasses, 12 M LiCl--D 2 O and 8 M NaOD. The electrolysis of 5-nitrouracil and 5-nitro-6-methyluracil results in relatively stable anion radicals. The results for 5-nitrouracil give evidence for two or perhaps three anions which differ only by the degree of ring nitrogen protonation. The results for 5-nitro-6-methyluracil suggest that the nitro group of the anion is twisted so that it is coupled only weakly to the ring π-electron system. The anions of 5-nitrouracil, 5-nitroorotic acid, 5-nitrobarbituric acid, and 5-nitro-6-methyluracil have been produced in the alkaline and neutral aqueous glasses. The anisotropic spectra found have been analyzed with the aid of computer simulations which assume axial symmetry. For example, the analysis of the spectrum of 5-nitrouracil anion in 12 M LiCl yields A/sub parallel//sup N/ = 33; A/sub perpendicular to//sup N/ = 5, a 6 /sup H/ = 5.5 G, g/sub parallel/ = 2.0016, and g/sub perpendicular to/ = 2.0059. A concentration dependence in the splittings is noted and discussed. Ultraviolet photolysis of the anions of 5-nitro-6-methyluracil and 5-nitrobarbituric acid results in the formation of iminoxy radicals. Mechanisms of formation of the iminoxy radicals are discussed and results found in this work are compared to results found in single crystals and aqueous solution

  4. Effect of chemical retention on anionic species diffusion in compacted clays

    International Nuclear Information System (INIS)

    Bazer-Bachi, Frederic

    2005-01-01

    Anionic radioisotopes are of particular importance within the framework of the calculated health risk associated with high-level and long-lived intermediate-level underground radioactive waste disposal. Therefore, the objective of this work is the construction of a transport model coupled with chemistry in order to quantify the behaviour of anionic solutes in the Callovo-Oxfordian (CO_x) argillite, the argillaceous host rock of the ANDRA Meuse/Haute-Marne underground laboratory. An experimental methodology was defined to characterize this migration, several experimental methods being implemented: batch experiments, laboratory columns and through-diffusion cells. The study of the diffusion of the non-sorbing anionic tracer "3"6Cl"- highlighted the fact that, due to anionic exclusion, anions only had access to a part of the porosity. The retention of "3"5SO_4"2"- and "1"2"5I- on CO_x argillite was then characterized, quantified by batch experiments and confirmed by other experimental methods. Nevertheless, their migration was less retarded than expected by a model based on batch experiments and on "3"6Cl"- diffusive data. This difference was explained by anion exclusion which reduced sorption site accessibility. Thus, the intensity of this phenomenon has to be considered to model anion migration in compacted clays. (author) [fr

  5. Superhalogen properties of hetero-binuclear anions MM‧F4- and MM″F5- (M = Li, Na, M‧ = Be, Mg, Ca; M″ = B, Al, Ga)

    Science.gov (United States)

    Yang, Hui; Li, Ying; He, Hui-Min; Tong, Jing; Wu, Di; Li, Zhi-Ru

    2017-09-01

    Hetero-binuclear superhalogen anions, namely MM‧F4- and MM″F5- (M = Li, Na; M‧ = Be, Mg, Ca; M″ = B, Al, Ga), have been theoretically characterized at the MP2(FULL)/6-311+G(3df) level. It is found that two central atoms can be linked by at most three fluorine ligands. The large vertical electron detachment energies (VDEs, 7.449-8.978 eV) verify the superhalogen identity of these anions. The VDEs of both MM‧F4- and MM″F5- decrease when the atomic size of M increases whereas increase with the size of M‧ and M″. Besides, the extra electron distribution also has effect on the VDEs of such superhalogen anions.

  6. Corrosion of conductive polypyrrole: Effects of environmental factors, electrochemical stimulation, and doping anions

    International Nuclear Information System (INIS)

    Qi Kai; Qiu Yubing; Chen Zhenyu; Guo Xingpeng

    2012-01-01

    Highlights: ► Corrosive galvanic cells form on PPy film with the electrochemical reduction of O 2. ► Suitable electrochemical stimulation can inhibit the PPy’s corrosion. ► PPy film doped with larger sized anions has better corrosion resistance performance. - Abstract: The effects of environmental factors, electrochemical stimulation, and doping anions on the corrosion behaviour of conductive polypyrrole (PPy) films in alkaline aqueous media were studied with cyclic voltammetry, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy. High concentrations of electrolyte, low dissolved oxygen and low temperatures enhance the stability of PPy. Polarising PPy at a negative potential inhibits its corrosion obviously. PPy doped with large counter anions shows better corrosion resistance than PPy doped with small counter ions. The possible mechanism involved in PPy corrosion process is discussed.

  7. Sensitization of microorganisms and enzymes by radiation-induced selective inorganic radical anions

    International Nuclear Information System (INIS)

    Schubert, J.; Stegeman, H.

    1981-01-01

    Bacterial survival and enzymatic inactivation were examined following exposure to radiolytically-generated radical anions, X - 2 , where X=Cl, Br, I or CNS - . Depending on pH, radical anions react selectively or specifically with cysteine, tryptophan, tyrosine and histidine. Consequently, when one or more of these amino acids is crucial for enzymatic activity or bacterial survival and is attacked by a radical anion, a high degree or radiosensitization may be realized. Halide radical anions can form free chlorine, bromine or iodine. However, these bactericidal halogens are destroyed by reaction with the hydrated electron, e - sub(aq), or at pHs>9, as occurs, for example, when a medium saturated with nitrous oxide, N 2 O, and e - sub(aq) scavenger, is replaced by nitrogen or oxygen. Increasing concentration of other e - sub(aq) scavengers, such as phosphate buffer, promotes formation of halogen from halides. The conditions producing formation and elimination of halogens in irradiated media must be appreciated to avoid confusing radiosensitization by X 2 to X - 2 . Radiosensitization by radical anions of several microorganisms: S. faecalis, S. typhimurium, E. coli, and M. radiodurens is described. A crucial amino acid for survival of S. faecalis appears to be tyrosine, while both tyrosine and tryptophan seem essential for recovery of S. typhimurium from effects of ionizing radiation. It is postulated that the radiosensitizing action of radical anions involves inhibition of DNA repair of strand-breaks by depriving the cells of energy. In view of the high OH scavenging power of foods, it is concluded that the radiosensitization of bacteria and enzymes in foods by radical anions, except for special cases, is not practical. Rather, radical anions serve to identify crucial amino acids to radiosensitization mechanisms in model systems, and possibly in radiotherapy. (author)

  8. Mulliken-Hush elucidation of the encounter (precursor) complex in intermolecular electron transfer via self-exchange of tetracyanoethylene anion-radical

    International Nuclear Information System (INIS)

    Rosokha, S.V.; Newton, M.D.; Head-Gordon, M.; Kochi, J.K.

    2006-01-01

    The paramagnetic [1:1] encounter complex (TCNE) 2 -dot is established as the important precursor in the kinetics and mechanism of electron-transfer for the self-exchange between tetracyanoethylene acceptor (TCNE) and its radical-anion as the donor. Spectroscopic observation of the dimeric complex (TCNE) 2 -dot by its intervalence absorption band at the solvent-dependent wavelength of λ IV ∼1500nm facilitates the application of Mulliken-Hush theory which reveals the significant electronic interaction extant between the pair of cofacial TCNE moieties with the sizable coupling of H DA =1000cm -1 . The transient existence of such an encounter complex provides the critical link in the electron-transfer kinetics by lowering the classical Marcus reorganization barrier by the amount of H DA in this strongly adiabatic system. Ab initio quantum-mechanical methods as applied to independent theoretical computations of both the reorganization energy (λ) and the electronic coupling element (H DA ) confirm the essential correctness of the Mulliken-Hush formalism for fast electron transfer via strongly coupled donor/acceptor encounter complexes

  9. Anion exchange membrane

    Science.gov (United States)

    Verkade, John G; Wadhwa, Kuldeep; Kong, Xueqian; Schmidt-Rohr, Klaus

    2013-05-07

    An anion exchange membrane and fuel cell incorporating the anion exchange membrane are detailed in which proazaphosphatrane and azaphosphatrane cations are covalently bonded to a sulfonated fluoropolymer support along with anionic counterions. A positive charge is dispersed in the aforementioned cations which are buried in the support to reduce the cation-anion interactions and increase the mobility of hydroxide ions, for example, across the membrane. The anion exchange membrane has the ability to operate at high temperatures and in highly alkaline environments with high conductivity and low resistance.

  10. Electrochemical generation of oxygen. 1: The effects of anions and cations on hydrogen chemisorption and anodic oxide film formation on platinum electrode. 2: The effects of anions and cations on oxygen generation on platinum electrode

    Science.gov (United States)

    Huang, C. J.; Yeager, E.; Ogrady, W. E.

    1975-01-01

    The effects were studied of anions and cations on hydrogen chemisorption and anodic oxide film formation on Pt by linear sweep voltammetry, and on oxygen generation on Pt by potentiostatic overpotential measurement. The hydrogen chemisorption and anodic oxide film formation regions are greatly influenced by anion adsorption. In acids, the strongly bound hydrogen occurs at more cathodic potential when chloride and sulfate are present. Sulfate affects the initial phase of oxide film formation by produced fine structure while chloride retards the oxide-film formation. In alkaline solutions, both strongly and weakly bound hydrogen are influenced by iodide, cyanide, and barium and calcium cations. These ions also influence the oxide film formation. Factors considered to explain these effects are discussed. The Tafel slope for oxygen generation was found to be independent on the oxide thickness and the presence of cations or anions. The catalytic activity indicated by the exchange current density was observed decreasing with increasing oxide layer thickness, only a minor dependence on the addition of certain cations and anions was found.

  11. Metal-Oxide Film Conversions Involving Large Anions

    Energy Technology Data Exchange (ETDEWEB)

    Pretty, S.; Zhang, X.; Shoesmith, D.W.; Wren, J.C. [The University of Western Ontario, Chemistry Department, 1151 Richmond St., N6A 5B7, London, Ontario (Canada)

    2008-07-01

    The main objective of my research is to establish the mechanism and kinetics of metal-oxide film conversions involving large anions (I{sup -}, Br{sup -}, S{sup 2-}). Within a given group, the anions will provide insight on the effect of anion size on the film conversion, while comparison of Group 6 and Group 7 anions will provide insight on the effect of anion charge. This research has a range of industrial applications, for example, hazardous radioiodine can be immobilized by reaction with Ag to yield AgI. From the perspective of public safety, radioiodine is one of the most important fission products from the uranium fuel because of its large fuel inventory, high volatility, and radiological hazard. Additionally, because of its mobility, the gaseous iodine concentration is a critical parameter for safety assessment and post-accident management. A full kinetic analysis using electrochemical techniques has been performed on the conversion of Ag{sub 2}O to (1) AgI and (2) AgBr. (authors)

  12. Metal-Oxide Film Conversions Involving Large Anions

    International Nuclear Information System (INIS)

    Pretty, S.; Zhang, X.; Shoesmith, D.W.; Wren, J.C.

    2008-01-01

    The main objective of my research is to establish the mechanism and kinetics of metal-oxide film conversions involving large anions (I - , Br - , S 2- ). Within a given group, the anions will provide insight on the effect of anion size on the film conversion, while comparison of Group 6 and Group 7 anions will provide insight on the effect of anion charge. This research has a range of industrial applications, for example, hazardous radioiodine can be immobilized by reaction with Ag to yield AgI. From the perspective of public safety, radioiodine is one of the most important fission products from the uranium fuel because of its large fuel inventory, high volatility, and radiological hazard. Additionally, because of its mobility, the gaseous iodine concentration is a critical parameter for safety assessment and post-accident management. A full kinetic analysis using electrochemical techniques has been performed on the conversion of Ag 2 O to (1) AgI and (2) AgBr. (authors)

  13. Revisiting the electrochemical formation, stability and structure of radical and biradical anionic structures in dinitrobenzenes

    International Nuclear Information System (INIS)

    Hernandez-Munoz, Lindsay S.; Gonzalez, Felipe J.; Gonzalez, Ignacio; Goulart, Marilia O.F.; Abreu, Fabiane Caxico de; Ribeiro, Adriana Santos; Ribeiro, Rogerio Tavares; Longo, Ricardo L.; Navarro, Marcelo; Frontana, Carlos

    2010-01-01

    The effects of the position of a second nitroaromatic group (orthovs.paravs.meta) during reduction of nitrobenzenes were analysed. Cyclic voltammetric experiments in acetonitrile solution revealed that ortho-, meta- and para-dinitrobenzenes show two reversible reduction processes. An Electrochemical-Electron Spin Resonance (E-ESR) study showed that the corresponding radical anions of the ortho and para derivatives, electrogenerated during the first electron transfer uptake, remain the same even after the second monoelectronic process, increasing their intensity due to the presence of a comproportionation process (A 2- + A → 2A· - ). For the case of the meta derivative, the electrogenerated radical anion at the first reduction peak is consumed at the second reduction step, forming a secondary radical species. During the electrochemical study of methyl 3,5-dinitrobenzoate, two successive and reversible electron processes were also observed; however, in this case, a very rare biradical dianion structure was found. The use of ESR-spectroelectrochemistry shed some light on controversial aspects of nitroaromatic reduction, especially concerning the second and further waves. These results were corroborated and interpreted with quantum chemical calculations of the molecular and electronic structures, electron affinities and spin densities. As a result, electrochemical mechanisms are presented and discussed.

  14. Design and fabrication of enhanced corrosion resistance Zn-Al layered double hydroxides films based anion-exchange mechanism on magnesium alloys

    International Nuclear Information System (INIS)

    Zhou, Meng; Yan, Luchun; Ling, Hao; Diao, Yupeng; Pang, Xiaolu; Wang, Yanlin; Gao, Kewei

    2017-01-01

    Highlights: • Zn-Al LDHs film loaded nitrate anions has been fabricated on a magnesium alloy substrate via a facile hydrothermal crystallization method. • The Zn-Al-Cl LDHs and Zn-Al-VO_x LDHs film were obtained based on anion-exchange mechanism. • The Zn-Al-Cl LDHs and Zn-Al-VO_x LDHs film could effectively protect magnesium alloy. - Abstract: Layered double hydroxides (LDHs) with brucite-like layer structure and the facile exchangeability of intercalated anions had attracted tremendous interest in many fields because of their great importance for both fundamental studies and practical applications. Herein zinc-aluminum layered double hydroxides (Zn-Al LDHs) films intercalated with nitrate anions on the magnesium alloy substrate were designed and fabricated via a facile hydrothermal crystallization method. In order to obtain better corrosion resistance, chloride and vanadate anions were intercalated into the LDHs interlayers via the anion-exchange reaction. X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy and scanning electronic microscopy (SEM) were used to examine structure, composition and morphology of the Zn-Al-NO_3 LDHs, Zn-Al-Cl LDHs and Zn-Al-VO_x LDHs films. The corrosion resistance of the Zn-Al LDHs with different anion films was estimated by the electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization measurement. EIS and polarization curves measurements revealed that the magnesium alloy could be effectively protected by the Zn-Al-Cl LDHs and Zn-Al-VO_x LDHs films due to the blocking effect of chloride anions and the control-release ability of vanadate anions.

  15. Design and fabrication of enhanced corrosion resistance Zn-Al layered double hydroxides films based anion-exchange mechanism on magnesium alloys

    Energy Technology Data Exchange (ETDEWEB)

    Zhou, Meng; Yan, Luchun; Ling, Hao; Diao, Yupeng; Pang, Xiaolu; Wang, Yanlin; Gao, Kewei, E-mail: kwgao@yahoo.com

    2017-05-15

    Highlights: • Zn-Al LDHs film loaded nitrate anions has been fabricated on a magnesium alloy substrate via a facile hydrothermal crystallization method. • The Zn-Al-Cl LDHs and Zn-Al-VO{sub x} LDHs film were obtained based on anion-exchange mechanism. • The Zn-Al-Cl LDHs and Zn-Al-VO{sub x} LDHs film could effectively protect magnesium alloy. - Abstract: Layered double hydroxides (LDHs) with brucite-like layer structure and the facile exchangeability of intercalated anions had attracted tremendous interest in many fields because of their great importance for both fundamental studies and practical applications. Herein zinc-aluminum layered double hydroxides (Zn-Al LDHs) films intercalated with nitrate anions on the magnesium alloy substrate were designed and fabricated via a facile hydrothermal crystallization method. In order to obtain better corrosion resistance, chloride and vanadate anions were intercalated into the LDHs interlayers via the anion-exchange reaction. X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy and scanning electronic microscopy (SEM) were used to examine structure, composition and morphology of the Zn-Al-NO{sub 3} LDHs, Zn-Al-Cl LDHs and Zn-Al-VO{sub x} LDHs films. The corrosion resistance of the Zn-Al LDHs with different anion films was estimated by the electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization measurement. EIS and polarization curves measurements revealed that the magnesium alloy could be effectively protected by the Zn-Al-Cl LDHs and Zn-Al-VO{sub x} LDHs films due to the blocking effect of chloride anions and the control-release ability of vanadate anions.

  16. New magnetic organic-inorganic composites based on hydrotalcite-like anionic clays for drug delivery

    Energy Technology Data Exchange (ETDEWEB)

    Carja, Gabriela [Department of Physical Chemistry, Faculty of Industrial Chemistry, Technical University of Iasi, 71 Mangeron Boulevard, 700050 Iasi (Romania); Chiriac, Horia [National Institute of Research and Development for Technical Physics, 47 Mangeron Boulevard, 700050 Iasi (Romania)]. E-mail: hchiriac@phys-iasi.ro; Lupu, Nicoleta [National Institute of Research and Development for Technical Physics, 47 Mangeron Boulevard, 700050 Iasi (Romania)

    2007-04-15

    The structural 'memory effect' of anionic clays was used to obtain layered double hydroxides (LDHs) with tailored magnetic properties, by loading iron oxides and/or spinel structures on iron partially substituted hydrotalcite-like materials. The obtained magnetic layered structures were further used as precursors for new hybrid nanostructures, such as aspirin-hydrotalcite-like anionic clays. Transmission electron microscopy (TEM) analysis shows that small iron oxide or spinel nanoparticles coexist with the fibrous drug particles on the surface of partially aggregated typical clay-like particles. The specific saturation magnetization of the loaded LDHs can be increased up to 70 emu/g by using specific post-synthesis treatments.

  17. New magnetic organic-inorganic composites based on hydrotalcite-like anionic clays for drug delivery

    International Nuclear Information System (INIS)

    Carja, Gabriela; Chiriac, Horia; Lupu, Nicoleta

    2007-01-01

    The structural 'memory effect' of anionic clays was used to obtain layered double hydroxides (LDHs) with tailored magnetic properties, by loading iron oxides and/or spinel structures on iron partially substituted hydrotalcite-like materials. The obtained magnetic layered structures were further used as precursors for new hybrid nanostructures, such as aspirin-hydrotalcite-like anionic clays. Transmission electron microscopy (TEM) analysis shows that small iron oxide or spinel nanoparticles coexist with the fibrous drug particles on the surface of partially aggregated typical clay-like particles. The specific saturation magnetization of the loaded LDHs can be increased up to 70 emu/g by using specific post-synthesis treatments

  18. Colorless to purple-red switching electrochromic anthraquinone imides with broad visible/near-IR absorptions in the radical anion state: simulation-aided molecular design.

    Science.gov (United States)

    Chen, Fengkun; Zhang, Jie; Jiang, Hong; Wan, Xinhua

    2013-07-01

    The large redshift of near-infrared (NIR) absorptions of nitro-substituted anthraquinone imide (Nitro-AQI) radical anions, relative to other AQI derivatives, is rationalized based on quantum chemical calculations. Calculations reveal that the delocalization effects of electronegative substitution in the radical anion states is dramatically enhanced, thus leading to a significant decrease in the HOMO-LUMO band gap in the radical anion states. Based on this understanding, an AQI derivative with an even stronger electron-withdrawing dicyanovinyl (di-CN) substituent was designed and prepared. The resulting molecule, di-CN-AQI, displays no absorption in the Vis/NIR region in the neutral state, but absorbs intensively in the range of λ=700-1000 (λmax ≈860 nm) and λ=1100-1800 nm (λmax ≈1400 nm) upon one-electron reduction; this is accompanied by a transition from a highly transmissive colorless solution to one that is purple-red. The relationship between calculated radical anionic HOMO-LUMO gaps and the electron-withdrawing capacity of the substituents is also determined by employing Hammett parameter, which could serve as a theoretical tool for further molecular design. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. a Moessbauer Effect and Fenske-Hall Molecular Orbital Study of the Electronic Properties of Organoiron Clusters.

    Science.gov (United States)

    Buhl, Margaret Linn

    The electronic properties of trinuclear iron, tetranuclear iron butterfly, iron-cobalt, and iron-copper clusters have been studied experimentally at 78K by the Mossbauer effect and theoretically by Fenske-Hall molecular orbital calculations. The Mossbauer effect isomer shift is very sensitive to the differences in the iron s-electron densities in these clusters and, as expected, decreases as the sum of the iron 4s Mulliken population and the Clementi and Raimondi effective nuclear charge increases. The molecular orbital wave functions and the Mulliken atomic charges are used to calculate the electric field gradient at the metal nuclei and the iron Mossbauer effect quadrupole splittings. The valence contribution was found to be the major component of the electric field gradient in all the clusters studied. In general the calculated value of Delta E_ {Q} is larger than the observed value, as a result of neglect of the valence Sternheimer factor, R. The metal charge depends upon its electronegativity and upon the nature of its Lewis base ligands. The carbonyl ligand carbon charge becomes more positive as the metal electronegativity increases. The oxygen charge becomes more negative as the anionic cluster charge increases, and in so doing, yields the maximum anionic charge separation. The electronic properties of the terminal carbonyl ligands are similar to those of carbon monoxide, whereas the electronic properties of the bridging carbonyl ligands are similar to those of the carbonyl group found in aldehydes and ketones.

  20. Electron spin resonance and optical studies on the radiolysis of carbon tetrachloride. II. Structure and reaction of CClṡ-4 radical anion in tetramethylsilane low-temperature solids

    Science.gov (United States)

    Muto, Hachizo; Nunome, Keichi

    1991-04-01

    An electron spin resonance (ESR) and optical study of carbon tetrachloride radical anion has been made to provide for a better understanding of the radiolysis of CCl4, following CClṡ+4 cation previously studied. It was found that the anion was metastably trapped in tetramethylsilane (TMS) matrices γ irradiated at 4 or 77 K. The g tensor and the hyperfine coupling tensors of all atoms of the radical were determined from ESR spectral simulation by using 12 CCl4 and the 13C enriched compound: g∥=2.004-5, g1=2.015,(A∥,A⊥) =(24.3,18.3) mT for 13C, (0.9, 0.2) mT for one 35Cl atom, and (A1,A2=A3)=(1.98,0.45) mT for the other three equivalent 35Cl atoms. From these parameters and a consideration on the g anisotropy combined with the optical data, the anion was found to have a predissociating molecular structure (CCl3ṡṡṡCl) ˙- with C3v symmetry, where the unpaired electron occupies A*1γ antibonding orbital. The carbon atom has a large spin density and near sp3 hybridization: ρp=0.62, ρs=0.18, ρp/ρs=3.4, and three Cl atoms and the other Cl atom have the spin densities ρp=0.10 and ρp=0.05, respectively. The species had two optical absorptions at λmax=265 and 370 nm which were assigned to the Eγ-A*1γ and A1γ-A*1γ electronic transitions, respectively. The anion converted to CCl ṡ3 radical by warming to ˜150 K in the TMS matrix. The present results have given unequivocal ESR and optical spectroscopic evidence and support for the assignment of the 370 nm band reported in the radiolyses of organic solutions containing CCl4.

  1. Probing microhydration effect on the electronic structure of the GFP chromophore anion: Photoelectron spectroscopy and theoretical investigations

    Energy Technology Data Exchange (ETDEWEB)

    Bhaskaran-Nair, Kiran; Shelton, William A. [Cain Department of Chemical Engineering, Louisiana State University, Baton Rouge, Louisiana 70803 (United States); Center for Computation and Technology, Louisiana State University, Baton Rouge, Louisiana 70803 (United States); Valiev, Marat; Kowalski, Karol, E-mail: karol.kowalski@pnnl.gov [William R. Wiley Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, K8-91, P.O. Box 999, Richland, Washington 99352 (United States); Deng, S. H. M.; Wang, Xue-Bin, E-mail: xuebin.wang@pnnl.gov [Physical Sciences Division, Pacific Northwest National Laboratory, K8-88, P.O. Box 999, Richland, Washington 99352 (United States)

    2015-12-14

    The photophysics of the Green Fluorescent Protein (GFP) chromophore is critically dependent on its local structure and on its environment. Despite extensive experimental and computational studies, there remain many open questions regarding the key fundamental variables that govern this process. One outstanding problem is the role of autoionization as a possible relaxation pathway of the excited state under different environmental conditions. This issue is considered in our work through combined experimental and theoretical studies of microsolvated clusters of the deprotonated p-hydroxybenzylidene-2,3-dimethylimidazolinone anion (HBDI{sup −}), an analog of the GFP chromophore. Through selective generation of microsolvated structures of predetermined size and subsequent analysis of experimental photoelectron spectra by high level ab initio methods, we are able to precisely identify the structure of the system, establish the accuracy of theoretical data, and provide reliable description of auto-ionization process as a function of hydrogen-bonding environment. Our study clearly illustrates the first few water molecules progressively stabilize the excited state of the chromophore anion against the autodetached neutral state, which should be an important trait for crystallographic water molecules in GFPs that has not been fully explored to date.

  2. Ionic liquid based on α-amino acid anion and N7,N9-dimethylguaninium cation ([dMG][AA]): theoretical study on the structure and electronic properties.

    Science.gov (United States)

    Shakourian-Fard, Mehdi; Fattahi, Alireza; Bayat, Ahmad

    2012-06-07

    The interactions between five amino acid based anions ([AA](-) (AA = Gly, Phe, His, Try, and Tyr)) and N7,N9-dimethylguaninium cation ([dMG](+)) have been investigated by the hybrid density functional theory method B3LYP together with the basis set 6-311++G(d,p). The calculated interaction energy was found to decrease in magnitude with increasing side-chain length in the amino acid anion. The interaction between the [dMG](+) cation and [AA](-) anion in the most stable configurations of ion pairs is a hydrogen bonding interaction. These hydrogen bonds (H bonds) were analyzed by the quantum theory of atoms in molecules (QTAIM) and natural bond orbital (NBO) analysis. Finally, several correlations between electron densities in bond critical points of hydrogen bonds and interaction energy as well as vibrational frequencies in the most stable configurations of ion pairs have been checked.

  3. Molecules for materials: germanium hydride neutrals and anions. Molecular structures, electron affinities, and thermochemistry of GeHn/GeHn- (n = 0-4) and Ge2Hn/Ge2Hn(-) (n = 0-6).

    Science.gov (United States)

    Li, Qian-Shu; Lü, Rui-Hua; Xie, Yaoming; Schaefer, Henry F

    2002-12-01

    The GeH(n) (n = 0-4) and Ge(2)H(n) (n = 0-6) systems have been studied systematically by five different density functional methods. The basis sets employed are of double-zeta plus polarization quality with additional s- and p-type diffuse functions, labeled DZP++. For each compound plausible energetically low-lying structures were optimized. The methods used have been calibrated against a comprehensive tabulation of experimental electron affinities (Chemical Reviews 102, 231, 2002). The geometries predicted in this work include yet unknown anionic species, such as Ge(2)H(-), Ge(2)H(2)(-), Ge(2)H(3)(-), Ge(2)H(4)(-), and Ge(2)H(5)(-). In general, the BHLYP method predicts the geometries closest to the few available experimental structures. A number of structures rather different from the analogous well-characterized hydrocarbon radicals and anions are predicted. For example, a vinylidene-like GeGeH(2) (-) structure is the global minimum of Ge(2)H(2) (-). For neutral Ge(2)H(4), a methylcarbene-like HGë-GeH(3) is neally degenerate with the trans-bent H(2)Ge=GeH(2) structure. For the Ge(2)H(4) (-) anion, the methylcarbene-like system is the global minimum. The three different neutral-anion energy differences reported in this research are: the adiabatic electron affinity (EA(ad)), the vertical electron affinity (EA(vert)), and the vertical detachment energy (VDE). For this family of molecules the B3LYP method appears to predict the most reliable electron affinities. The adiabatic electron affinities after the ZPVE correction are predicted to be 2.02 (Ge(2)), 2.05 (Ge(2)H), 1.25 (Ge(2)H(2)), 2.09 (Ge(2)H(3)), 1.71 (Ge(2)H(4)), 2.17 (Ge(2)H(5)), and -0.02 (Ge(2)H(6)) eV. We also reported the dissociation energies for the GeH(n) (n = 1-4) and Ge(2)H(n) (n = 1-6) systems, as well as those for their anionic counterparts. Our theoretical predictions provide strong motivation for the further experimental study of these important germanium hydrides. Copyright 2002 Wiley

  4. Band-gap-confinement and image-state-recapture effects in the survival of anions scattered from metal surfaces

    International Nuclear Information System (INIS)

    Schmitz, Andrew; Shaw, John; Chakraborty, Himadri S.; Thumm, Uwe

    2010-01-01

    The resonant charge transfer process in the collision of hydrogen anions with metal surfaces is described within a single-active-electron wave-packet propagation method. The ion-survival probability is found to be strongly enhanced at two different surface-specific perpendicular velocities of the ion. It is shown that, while the low-velocity enhancement is induced from a dynamical confinement of the ion level inside the band gap, the high-velocity enhancement is due to electron recapture from transiently populated image states. Results are presented for Li(110), Cu(111), and Pd(111) surfaces.

  5. Expanding frontiers in materials chemistry and physics with multiple anions.

    Science.gov (United States)

    Kageyama, Hiroshi; Hayashi, Katsuro; Maeda, Kazuhiko; Attfield, J Paul; Hiroi, Zenji; Rondinelli, James M; Poeppelmeier, Kenneth R

    2018-02-22

    During the last century, inorganic oxide compounds laid foundations for materials synthesis, characterization, and technology translation by adding new functions into devices previously dominated by main-group element semiconductor compounds. Today, compounds with multiple anions beyond the single-oxide ion, such as oxyhalides and oxyhydrides, offer a new materials platform from which superior functionality may arise. Here we review the recent progress, status, and future prospects and challenges facing the development and deployment of mixed-anion compounds, focusing mainly on oxide-derived materials. We devote attention to the crucial roles that multiple anions play during synthesis, characterization, and in the physical properties of these materials. We discuss the opportunities enabled by recent advances in synthetic approaches for design of both local and overall structure, state-of-the-art characterization techniques to distinguish unique structural and chemical states, and chemical/physical properties emerging from the synergy of multiple anions for catalysis, energy conversion, and electronic materials.

  6. Characterization of an anion antisite defect as a deep double donor in InP

    International Nuclear Information System (INIS)

    Ando, K.; Katsui, A.; Jeon, D.Y.; Watkins, G.D.; Gislason, H.P.

    1989-01-01

    A study of optically detected magnetic resonance (ODMR) on the anion antisite defect in electron irradiated InP has been made by monitoring the magnetic circular dichroism (MCD), combined with DLTS experiment. Comparison of the ODMR and DLTS results reveals that the intrinsic anion antisite defect acts as a deep double-donor in the gap. The first ionization (D o /D 1+ ) process occurs both in thermal and optical excitation as a mid-gap electron trap, detected by DLTS and DLOS experiment. (author) 12 refs., 6 figs

  7. The serum anion gap in the evaluation of acid-base disorders: what are its limitations and can its effectiveness be improved?

    Science.gov (United States)

    Kraut, Jeffrey A; Nagami, Glenn T

    2013-11-01

    The serum anion gap has been utilized to identify errors in the measurement of electrolytes, to detect paraproteins, and, most relevant to the nephrologist, to evaluate patients with suspected acid-base disorders. In regard to the latter purpose, traditionally an increased anion gap is identified when it exceeds the upper limit of normal for a particular clinical laboratory measurement. However, because there is a wide range of normal values (often 8-10 mEq/L), an increase in anion concentration can be present in the absence of an increased anion gap. In addition, the type of retained anion can affect the magnitude of the increase in anion gap relative to change in serum [HCO3(-)] being greater with lactic acidosis compared with ketoacidosis. This review examines the methods of calculation of the serum anion gap in textbooks and published literature, the effect of perturbations other than changes in acid-base balance, and its effectiveness in identifying mild and more severe disturbances in acid-base balance. Limitations of the present methods of determining the normal anion gap and change in the anion gap are highlighted. The possibility of identifying the baseline value for individuals to optimize the use of the calculation in the detection of metabolic acidosis is suggested.

  8. Effects of anion size and concentration on electrolyte invasion into molecular-sized nanopores

    International Nuclear Information System (INIS)

    Liu Ling; Chen Xi; Kim, Taewan; Han Aijie; Qiao Yu

    2010-01-01

    When an electrolyte solution is pressurized into a molecular-sized nanopore, oppositely charged ions are strongly inclined to aggregate, which effectively reduces the ion solubility to zero. Inside the restrictive confinement, a unique quasi-periodic structure is formed where the paired ion couples are periodically separated by a number of water molecules. As the anion size or ion concentration varies, the geometrical characteristics of the confined ion structure would change considerably, leading to a significant variation in the transport pressure. Both experimental and simulation results indicate that, contradictory to the prediction of conventional theory, infiltration pressure decreases as the anions become larger.

  9. Revisiting the electrochemical formation, stability and structure of radical and biradical anionic structures in dinitrobenzenes

    Energy Technology Data Exchange (ETDEWEB)

    Hernandez-Munoz, Lindsay S.; Gonzalez, Felipe J. [Departamento de Quimica, Centro de Investigacion y Estudios Avanzados, Av. I.P.N. 2508. Col. San Pedro Zacatenco, 07360, D.F. (Mexico); Gonzalez, Ignacio [Departamento de Quimica, Universidad Autonoma Metropolitana-Iztapalapa, Area de Electroquimica, Apartado Postal 55-534, 09340, D.F. (Mexico); Goulart, Marilia O.F.; Abreu, Fabiane Caxico de; Ribeiro, Adriana Santos [Instituto de Quimica e Biotecnologia, Universidade Federal de Alagoas, Tabuleiro do Martins, Maceio, AL, 57072-970 (Brazil); Ribeiro, Rogerio Tavares; Longo, Ricardo L. [Departamento de Quimica Fundamental, Universidade Federal de Pernambuco, Av. Prof. Luiz Freire, s/n, Cid. Universitaria, Recife, PE, 50740-540 (Brazil); Navarro, Marcelo, E-mail: navarro@ufpe.b [Departamento de Quimica Fundamental, Universidade Federal de Pernambuco, Av. Prof. Luiz Freire, s/n, Cid. Universitaria, Recife, PE, 50740-540 (Brazil); Frontana, Carlos, E-mail: ultrabuho@yahoo.com.m [Departamento de Quimica, Centro de Investigacion y Estudios Avanzados, Av. I.P.N. 2508. Col. San Pedro Zacatenco, 07360, D.F. (Mexico)

    2010-11-30

    The effects of the position of a second nitroaromatic group (orthovs.paravs.meta) during reduction of nitrobenzenes were analysed. Cyclic voltammetric experiments in acetonitrile solution revealed that ortho-, meta- and para-dinitrobenzenes show two reversible reduction processes. An Electrochemical-Electron Spin Resonance (E-ESR) study showed that the corresponding radical anions of the ortho and para derivatives, electrogenerated during the first electron transfer uptake, remain the same even after the second monoelectronic process, increasing their intensity due to the presence of a comproportionation process (A{sup 2-} + A {yields} 2A{center_dot}{sup -}). For the case of the meta derivative, the electrogenerated radical anion at the first reduction peak is consumed at the second reduction step, forming a secondary radical species. During the electrochemical study of methyl 3,5-dinitrobenzoate, two successive and reversible electron processes were also observed; however, in this case, a very rare biradical dianion structure was found. The use of ESR-spectroelectrochemistry shed some light on controversial aspects of nitroaromatic reduction, especially concerning the second and further waves. These results were corroborated and interpreted with quantum chemical calculations of the molecular and electronic structures, electron affinities and spin densities. As a result, electrochemical mechanisms are presented and discussed.

  10. Theoretical study on effects of curvature of graphene in conjunction with simultaneous anion- and - stacking interactions

    Directory of Open Access Journals (Sweden)

    Pouya Karimi

    2015-12-01

    Full Text Available A graphene sheet (C102H30 has been rolled up by computational quantum chemistry methods to construct single-walled carbon nanotube fragments (SWCNTFs. The anion-π interactions of F- anion together with π-π stacking interactions of benzene on inner face and outer face of the central rings of SWCNTFs have been concurrently investigated. Structural parameters and energy data of the ternary benzene-SWCNTF-F- complexes were considered. Also, effects of charge transfer and aromaticity were estimated to determine how curvature of graphene influences on simultaneous anion-π and π-π stacking interactions.  Results indicate that curvature of graphene leads to structural changes in SWCNTFs which effects on simultaneous interactions of F- anion and benzene with SWCNTFs. Also, results show that although p-p stacking is a weak interaction, but it can impact on order of binding energies in complexes involved both p-p stacking and anion-p interactions. 

  11. A computational study of anion-modulated cation-π interactions.

    Science.gov (United States)

    Carrazana-García, Jorge A; Rodríguez-Otero, Jesús; Cabaleiro-Lago, Enrique M

    2012-05-24

    The interaction of anions with cation-π complexes formed by the guanidinium cation and benzene was thoroughly studied by means of computational methods. Potential energy surface scans were performed in order to evaluate the effect of the anion coming closer to the cation-π pair. Several structures of guanidinium-benzene complexes and anion approaching directions were examined. Supermolecule calculations were performed on ternary complexes formed by guanidinium, benzene, and one anion and the interaction energy was decomposed into its different two- and three-body contributions. The interaction energies were further dissected into their electrostatic, exchange, repulsion, polarization and dispersion contributions by means of local molecular orbital energy decomposition analysis. The results confirm that, besides the electrostatic cation-anion attraction, the effect of the anion over the cation-π interaction is mainly due to polarization and can be rationalized following the changes in the anion-π and the nonadditive (three-body) terms of the interaction. When the cation and the anion are on the same side of the π system, the three-body interaction is anticooperative, but when the anion and the cation are on opposite sides of the π system, the three-body interaction is cooperative. As far as we know, this is the first study where this kind of analysis is carried out with a structured cation as guanidinium with a significant biological interest.

  12. Study of the effect of anions and mixed solvents on the kinetics of reduction of Eu(III)

    International Nuclear Information System (INIS)

    Chandrasekaran, V.R.; Sundaram, A.K.

    1983-01-01

    The kinetics of reduction of Eu(III) to Eu(II) in aqueous solutions of perchlorate, chloride, sulphate, acetate and lactate anions and water-methanol and water-acetone mixtures containing potassium chloride as the inert electrolyte is reported and the effect of anions and solvent on the kinetics is studied. (author)

  13. Properties of solvated electrons, alkali anions and other species in metal solutions and kinetics of cation and electron exchange reactions. Final report

    International Nuclear Information System (INIS)

    Dye, J.L.

    1979-01-01

    The properties of solutions of alkali metals in amine solvents were studied by optical, ETR, NMR and electrochemical methods. Complexation of the alkali cations by crown ethers and cryptands permitted the preparation of concentrated solutions of alkali metals in amine and ether solvents. Extensive alkali metal NMR studies of the exchange of M + with crown-ethers and cryptands and of the alkali metal anion, M - , were made. The first crystalline salt of an alkali metal anion, Na + Cryptand [2.2.2]Na - was synthesized and characterized and led to the preparation of other alkali metal anion salts. This research provided the foundation for continuing studies of crystalline alkalide salts

  14. Solution and gas phase evidence of anion binding through the secondary bonding interactions of a bidentate bis-antimony(iii) anion receptor.

    Science.gov (United States)

    Qiu, J; Song, B; Li, X; Cozzolino, A F

    2017-12-20

    The solution and gas phase halide binding to a bis-antimony(iii) anion receptor was studied. This new class of anion receptors utilizes the strong Sb-centered secondary bonding interactions (SBIs) that are formed opposite to the polar Sb-O primary bond. 1 H NMR titration data were fitted statistically to binding models and solution-phase binding energetics were extracted, while the formation of anion-to-receptor complexes was observed using ESI-MS. Density functional theory calculations suggest that their affinity towards binding halide anions is mitigated by the strong explicit solvation effect in DMSO, which gives insights into future designs that circumvent direct solvent binding and are anticipated to yield tighter and perhaps more selectivity in anion binding.

  15. An ab initio study on MgX3- and CaX3- superhalogen anions (X=F, Cl, Br)

    International Nuclear Information System (INIS)

    Anusiewicz, Iwona; Sobczyk, Monika; Dabkowska, Iwona; Skurski, Piotr

    2003-01-01

    The vertical electron detachment energies (VDEs) of twenty MX 3 - (M=Mg, Ca; X=F, Cl, Br) anions were calculated at the OVGF level with the 6-311++G(3df) basis sets. The largest vertical electron binding energy was found for MgF 3 - system (8.793 eV). All negatively charged species possess the VDEs that are larger than 5.9 eV and thus may be termed superhalogen anions. The strong dependence of the VDE of the MX 3 - species on the ligand-central atom (M-X) distance and on the partial atomic charge localized on Mg or Ca was observed and discussed, as well as the other factors that may influence the electronic stability of such anions

  16. An ab initio study on MgX 3- and CaX 3- superhalogen anions (X=F, Cl, Br)

    Science.gov (United States)

    Anusiewicz, Iwona; Sobczyk, Monika; Dąbkowska, Iwona; Skurski, Piotr

    2003-06-01

    The vertical electron detachment energies (VDEs) of twenty MX 3- (M=Mg, Ca; X=F, Cl, Br) anions were calculated at the OVGF level with the 6-311++G(3df) basis sets. The largest vertical electron binding energy was found for MgF 3- system (8.793 eV). All negatively charged species possess the VDEs that are larger than 5.9 eV and thus may be termed superhalogen anions. The strong dependence of the VDE of the MX 3- species on the ligand-central atom (M-X) distance and on the partial atomic charge localized on Mg or Ca was observed and discussed, as well as the other factors that may influence the electronic stability of such anions.

  17. Super-pnicogen bonding in the radical anion of the fluorophosphine dimer

    Science.gov (United States)

    Setiawan, Dani; Cremer, Dieter

    2016-10-01

    The LUMO of the pnicogen-bonded fluoro-phosphine dimer has PP bonding character. Radical anion and dianion form relatively strong pnicogen bonds with some covalent character where however the dianion turns out to be a second order transition state. The binding energy of (FPH 2)2- is 30.4 kcal/mol (CCSD(T)/aug-cc-pVTZ; CASPT2(5,8): 30.7 kcal/mol) and the bond strength order measured with the local PP bond stretching force constant increases from 0.055 for the neutral dimer to 0.187 thus revealing that the stabilization of the radical anion is to a large extend a result of one-electron six-center delocalization. Pnicogen-bonded complexes have a stabilizing electron affinity.

  18. Review on anionic redox for high-capacity lithium- and sodium-ion batteries

    International Nuclear Information System (INIS)

    Zhao, Chenglong; Lu, Yaxiang; Hu, Yong-Sheng; Chen, Liquan; Wang, Qidi; Li, Baohua

    2017-01-01

    Rechargeable batteries, especially lithium-ion batteries, are now widely used as power sources for portable electronics and electric vehicles, but material innovations are still needed to satisfy the increasing demand for larger energy density. Recently, lithium- and sodium-rich electrode materials, including the A 2 MO 3 -family layered compounds (A  =  Li, Na; M  =  Mn 4+ , Ru 4+ , etc), have been extensively studied as potential high-capacity electrode materials for a cumulative cationic and anionic redox activity. Negatively charged oxide ions can potentially donate electrons to compensate for the absence of oxidable transition metals as a redox center to further increase the reversible capacity. Understanding and controlling the state-of-the-art anionic redox processes is pivotal for the design of advanced energy materials, highlighted in rechargeable batteries. Hence, experimental and theoretical approaches have been developed to consecutively study the diverting processes, states, and structures involved. In this review, we attempt to present a literature overview and provide insight into the reaction mechanism with respect to the anionic redox processes, proposing some opinions as target oriented. It is hoped that, through this discussion, the search for anionic redox electrode materials with high-capacity rechargeable batteries can be advanced, and practical applications realized as soon as possible. (topical review)

  19. New insights in low-energy electron-fullerene interactions

    Science.gov (United States)

    Msezane, Alfred Z.; Felfli, Zineb

    2018-03-01

    The robust Regge-pole methodology has been used to probe for long-lived metastable anionic formation in Cn (n = 20, 24, 26, 28, 44, 70, 92 and 112) through the calculated electron elastic scattering total cross sections (TCSs). All the TCSs are found to be characterized by Ramsauer-Townsend minima, shape resonances and dramatically sharp resonances manifesting metastable anionic formation during the collisions. The energy positions of the anionic ground states resonances are found to match the measured electron affinities (EAs). We also investigated the size-effect through the correlation and polarization induced metastable resonances as the fullerene size varied from C20 through C112. The C20 TCSs exhibit atomic behavior while the C112 TCSs demonstrate strong departure from atomic behavior attributed to the size effect. Surprisingly C24 is found to have the largest EA among the investigated fullerenes making it suitable for use in organic solar cells and nanocatalysis.

  20. Anion dynamics in the first 10 milliseconds of an argon-acetylene radio-frequency plasma

    International Nuclear Information System (INIS)

    Van de Wetering, F M J H; Beckers, J; Kroesen, G M W

    2012-01-01

    The time evolution of the smallest anions (C 2 H - and H 2 CC - ), just after plasma ignition, is studied by means of microwave cavity resonance spectroscopy (MCRS) in concert with laser-induced photodetachment under varying gas pressure and temperature in an argon-acetylene radio-frequency (13.56 MHz) plasma. These anions act as an initiator for spontaneous dust particle formation in these plasmas. With an intense 355 nm Nd:YAG laser pulse directed through the discharge, electrons are detached only from these anions present in the laser path. This results in a sudden increase in the electron density in the plasma, which can accurately and with sub-microsecond time resolution be measured with MCRS. By adjusting the time after plasma ignition at which the laser is fired through the discharge, the time evolution of the anion density can be studied. We have operated in the linear regime: the photodetachment signal is proportional to the laser intensity. This allowed us to study the trends of the photodetachment signal as a function of the operational parameters of the plasma. The density of the smallest anions steadily increases in the first few milliseconds after plasma ignition, after which it reaches a steady state. While keeping the gas density constant, increasing the gas temperature in the range 30-120 °C limits the number of smallest anions and saturates at a temperature of about 90 °C. A reaction pathway is proposed to explain the observed trends.

  1. Photophysics and Photochemistry of 2-Aminobenzoic Acid Anion in Aqueous Solution

    Science.gov (United States)

    Pozdnyakov, Ivan P.; Plyusnin, Victor F.; Grivin, Vjacheslav P.

    2009-11-01

    Nanosecond laser flash photolysis and absorption and fluorescence spectroscopy were used to study photochemical processes of 2-aminobenzoic acid anion (ABA-) in aqueous solutions. Excitation of this species gives rise to the ABA- triplet state to the ABA• radical and to the hydrated electron (eaq-). The last two species result from two-photon processes. In a neutral medium, the main decay channels of ABA- triplet state, the ABA• radical, and eaq- are T-T annihilation, recombination, and capture by the ABA- anion, respectively.

  2. Phospatidylserine or ganglioside--which of anionic lipids determines the effect of cationic dextran on lipid membrane?

    Science.gov (United States)

    Hąc-Wydro, Katarzyna; Wydro, Paweł; Cetnar, Andrzej; Włodarczyk, Grzegorz

    2015-02-01

    In this work the influence of cationic polymer, namely diethylaminoethyl DEAE-dextran on model lipid membranes was investigated. This polymer is of a wide application as a biomaterial and a drug carrier and its cytotoxicity toward various cancer cells was also confirmed. It was suggested that anticancer effect of cationic dextran is connected with the binding of the polymer to the negatively charged sialic acid residues overexpressed in cancer membrane. This fact encouraged us to perform the studies aimed at verifying whether the effect of cationic DEAE-dextran on membrane is determined only by the presence of the negatively charged lipid in the system or the kind of anionic lipid is also important. To reach this goal systematic investigations on the effect of dextran on various one-component lipid monolayers and multicomponent hepatoma cell model membranes differing in the level and the kind of anionic lipids (phosphatidylserine, sialic acid-containing ganglioside GM3 or their mixture) were done. As evidenced the results the effect of DEAE-dextran on the model system is determined by anionic lipid-polymer electrostatic interactions. However, the magnitude of the effect of cationic polymer is strongly dependent on the kind of anionic lipid in the model system. Namely, the packing and ordering of the mixtures containing ganglioside GM3 were more affected by DEAE-dextran than phosphatidylserine-containing monolayers. Although the experiments were done on model systems and therefore further studies are highly needed, the collected data may indicate that ganglioside may be important in the differentiation of the effect of cationic dextran on membranes. Copyright © 2014 Elsevier B.V. All rights reserved.

  3. Supramolecular Chemistry of Selective Anion Recognition for Anions of Environmental Relevance

    International Nuclear Information System (INIS)

    Moyer, Bruce a.; Bostick, Debra A.; Fowler, Christopher J.; Kang, Hyun-Ah; Ruas, Alexandre; Delmau, Laetitia H.; Haverlock, Tamara J.; Llinares, Jose M.; Hossain, Alamgir; Kang, S. O.; Bowman-James, Kristin; Shriver, James A.; Marquez, Manuel; Sessler, Jonathan L.

    2005-01-01

    The major thrust of this project led by the University of Kansas (Prof. Kristin Bowman-Jones) entails the exploration of the principles of recognition and separation of sulfate by the design, synthesis, and testing of novel sulfate extractants. A key science need for the cleanup of tank wastes at Hanford has been identified in developing methods to separate those bulk waste components that have low solubilities in borosilicate glass. Sulfate has been identified as a particularly difficult and expensive problem in that its concentration in the waste is relatively high, its solubility in glass is especially low, and it interferes with the performance of both vitrification equipment and the glass waste form. The new extractants will be synthesized by the University of Kansas and the University of Texas, Austin. Oak Ridge National Laboratory (ORNL) is subjecting the new extractants to experiments that will determine their properties and effectiveness in separating sulfate from the major competing anions in the waste, especially nitrate. Such experiments will entail primarily liquid-liquid extraction. Current efforts focus on exciting new systems in which the anion receptors act as synergists for anion exchange

  4. Ultracold Anions for High-Precision Antihydrogen Experiments.

    Science.gov (United States)

    Cerchiari, G; Kellerbauer, A; Safronova, M S; Safronova, U I; Yzombard, P

    2018-03-30

    Experiments with antihydrogen (H[over ¯]) for a study of matter-antimatter symmetry and antimatter gravity require ultracold H[over ¯] to reach ultimate precision. A promising path towards antiatoms much colder than a few kelvin involves the precooling of antiprotons by laser-cooled anions. Because of the weak binding of the valence electron in anions-dominated by polarization and correlation effects-only few candidate systems with suitable transitions exist. We report on a combination of experimental and theoretical studies to fully determine the relevant binding energies, transition rates, and branching ratios of the most promising candidate La^{-}. Using combined transverse and collinear laser spectroscopy, we determined the resonant frequency of the laser cooling transition to be ν=96.592 713(91)  THz and its transition rate to be A=4.90(50)×10^{4}  s^{-1}. Using a novel high-precision theoretical treatment of La^{-} we calculated yet unmeasured energy levels, transition rates, branching ratios, and lifetimes to complement experimental information on the laser cooling cycle of La^{-}. The new data establish the suitability of La^{-} for laser cooling and show that the cooling transition is significantly stronger than suggested by a previous theoretical study.

  5. Effect of dietary cation-anion balance on milk production and blood ...

    African Journals Online (AJOL)

    This study was conducted to evaluate the effects of three diets with different cation-anion differences ((DCAD: mEq[(Na + K) − (Cl + S)]/100 g of dry matter)) in far-off and close-up period, on milk production and blood mineral of Holstein cows. Eighteen pregnant cows (220 - 225 d) were fed a base diet with three DCAD (+13 ...

  6. Communication: Remarkable electrophilicity of the oxalic acid monomer: An anion photoelectron spectroscopy and theoretical study

    International Nuclear Information System (INIS)

    Buonaugurio, Angela; Graham, Jacob; Buytendyk, Allyson; Bowen, Kit H.; Ryder, Matthew R.; Gutowski, Maciej; Keolopile, Zibo G.; Haranczyk, Maciej

    2014-01-01

    Our experimental and computational results demonstrate an unusual electrophilicity of oxalic acid, the simplest dicarboxylic acid. The monomer is characterized by an adiabatic electron affinity and electron vertical detachment energy of 0.72 and 1.08 eV (±0.05 eV), respectively. The electrophilicity results primarily from the bonding carbon-carbon interaction in the singly occupied molecular orbital of the anion, but it is further enhanced by intramolecular hydrogen bonds. The well-resolved structure in the photoelectron spectrum is reproduced theoretically, based on Franck-Condon factors for the vibronic anion → neutral transitions

  7. Low-energy electron-induced dissociation in gas-phase nicotine, pyridine, and methyl-pyrrolidine

    Science.gov (United States)

    Ryszka, Michal; Alizadeh, Elahe; Li, Zhou; Ptasińska, Sylwia

    2017-09-01

    Dissociative electron attachment to nicotine, pyridine, and N-methyl-pyrrolidine was studied in the gas phase in order to assess their stability with respect to low-energy electron interactions. Anion yield curves for different products at electron energies ranging from zero to 15 eV were measured, and the molecular fragmentation pathways were proposed. Nicotine does not form a stable parent anion or a dehydrogenated anion, contrary to other biological systems. However, we have observed complex dissociation pathways involving fragmentation at the pyrrolidine side accompanied by isomerization mechanisms. Combining structure optimization and enthalpy calculations, performed with the Gaussian09 package, with the comparison with a deuterium-labeled N-methyl-d3-pyrrolidine allowed for the determination of the fragmentation pathways. In contrast to nicotine and N-methylpyrrolidine, the dominant pathway in dissociative electron attachment to pyridine is the loss of hydrogen, leading to the formation of an [M—H]- anion. The presented results provide important new information about the stability of nicotine and its constituent parts and contribute to a better understanding of the fragmentation mechanisms and their effects on the biological environment.

  8. Anion Effects on the Ion Exchange Process and the Deformation Property of Ionic Polymer Metal Composite Actuators

    Directory of Open Access Journals (Sweden)

    Wataru Aoyagi

    2016-06-01

    Full Text Available An ionic polymer-metal composite (IPMC actuator composed of a thin perfluorinated ionomer membrane with electrodes plated on both surfaces undergoes a large bending motion when a low electric field is applied across its thickness. Such actuators are soft, lightweight, and able to operate in solutions and thus show promise with regard to a wide range of applications, including MEMS sensors, artificial muscles, biomimetic systems, and medical devices. However, the variations induced by changing the type of anion on the device deformation properties are not well understood; therefore, the present study investigated the effects of different anions on the ion exchange process and the deformation behavior of IPMC actuators with palladium electrodes. Ion exchange was carried out in solutions incorporating various anions and the actuator tip displacement in deionized water was subsequently measured while applying a step voltage. In the step voltage response measurements, larger anions such as nitrate or sulfate led to a more pronounced tip displacement compared to that obtained with smaller anions such as hydroxide or chloride. In AC impedance measurements, larger anions generated greater ion conductivity and a larger double-layer capacitance at the cathode. Based on these mechanical and electrochemical measurements, it is concluded that the presence of larger anions in the ion exchange solution induces a greater degree of double-layer capacitance at the cathode and results in enhanced tip deformation of the IPMC actuators.

  9. Electron attachment and electron ionization of acetic acid clusters embedded in helium nanodroplets

    NARCIS (Netherlands)

    da Silva, F. Ferreira; Jaksch, S.; Martins, G.; Dang, H. M.; Dampc, M.; Denifl, S.; Maerk, T. D.; Limao-Vieira, P.; Liu, J.; Yang, S.; Ellis, A. M.; Scheier, P.

    2009-01-01

    The effect of incident electrons on acetic acid clusters is explored for the first time. The acetic acid clusters are formed inside liquid helium nanodroplets and both cationic and anionic products ejected into the gas phase are detected by mass spectrometry. The cation chemistry (induced by

  10. Interstellar dehydrogenated PAH anions: vibrational spectra

    Science.gov (United States)

    Buragohain, Mridusmita; Pathak, Amit; Sarre, Peter; Gour, Nand Kishor

    2018-03-01

    Interstellar polycyclic aromatic hydrocarbon (PAH) molecules exist in diverse forms depending on the local physical environment. Formation of ionized PAHs (anions and cations) is favourable in the extreme conditions of the interstellar medium (ISM). Besides in their pure form, PAHs are also likely to exist in substituted forms; for example, PAHs with functional groups, dehydrogenated PAHs etc. A dehydrogenated PAH molecule might subsequently form fullerenes in the ISM as a result of ongoing chemical processes. This work presents a density functional theory (DFT) calculation on dehydrogenated PAH anions to explore the infrared emission spectra of these molecules and discuss any possible contribution towards observed IR features in the ISM. The results suggest that dehydrogenated PAH anions might be significantly contributing to the 3.3 μm region. Spectroscopic features unique to dehydrogenated PAH anions are highlighted that may be used for their possible identification in the ISM. A comparison has also been made to see the size effect on spectra of these PAHs.

  11. Gas-phase infrared spectrum of the anionic GFP-chromophore

    NARCIS (Netherlands)

    Almasian, M.; Grzetic, J.; G. Berden,; Bakker, B.; Buma, W. J.; Oomens, J.

    2012-01-01

    The gas-phase IR spectrum of the anionic chromophore of the green fluorescent protein (p-hydroxy-benzylidene-2,3-dimethylimidazolidinone, HBDI) is recorded in the 800–1800 cm−1 frequency range using the free electron laser FELIX in combination with an electrospray ionization (ESI) Fourier

  12. Effect of the electrolyte cations and anions on the photocurrent of dodecylsulphate doped polypyrrole films

    Energy Technology Data Exchange (ETDEWEB)

    Martini, Milena; De Paoli, Marco-A. [Laboratorio de Poliimeros Condutores, Instituto de Quimica-UNICAMP, Universidade de Campinas, Cx Postal 6154, 13081-970 , SP Campinas (Brazil)

    2002-07-01

    Photoelectrochemical and UV-Vis spectroelectrochemical measurements were performed in a three-electrode cell containing dodecylsulphate-doped polypyrrole films as active layers in contact with different aqueous electrolytes. The effect of both cations and anions of the electrolyte on the photocurrent generation and on the absorption spectra of the system was studied. Dynamic photocurrent and absorption spectra measurements performed during the redox cycles of the films show that both cation and anion insertion and deinsertion occurs during the cycles. These results are in agreement with the previously reported redox mechanism proposed for amphiphilic anion doped polypyrrole. Reduced films show cathodic photocurrent at -0.4>E>-0.8V vs. Ag|AgCl. Photocurrent voltammograms are reproducible after the conditioning of the films and the higher cathodic currents were observed in films with thickness of =0.05-0.5{mu}m.

  13. Low energy electron attachment to the uracil molecule

    International Nuclear Information System (INIS)

    Hanel, G.; Gstir, B.; Denifl, S.; Scheier, P.; Maerk, T.D.; Farizon, B.; Farizon, M.

    2002-01-01

    Using a recently constructed high resolution crossed beam apparatus involving a hemispherical electron monochromator, electron attachment to the uracil molecule C 4 H 4 N 2 O 2 was studied. The electron energy range investigated was in the region between 0 and 12 eV. What will happen when slow electrons are colliding with the cellular RNA compound uracil was the objective of this investigation. The following anion fragments were detected: (C 4 H 3 N 2 O 2 ) - , OCN - , (H 2 C 3 NO) - , CN - , O - . The most important result was that within the detection efficiency any traces of the parent anion were observed. The most intense fragment anion appeared on a mass to charge ratio 111 amu., it corresponds to a uracil molecule missing one hydrogen. Another observation was whereas the parent minus H anion is observed at zero electron energy, all other fragments appear in other range. (nevyjel)

  14. Modelling the transport of carbonic acid anions through anion-exchange membranes

    International Nuclear Information System (INIS)

    Nikonenko, V.; Lebedev, K.; Manzanares, J.A.; Pourcelly, G.

    2003-01-01

    Electrodiffusion of carbonate and bicarbonate anions through anion-exchange membranes (AEM) is described on the basis of the Nernst-Planck equations taking into account coupled hydrolysis reactions in the external diffusion boundary layers (DBLs) and internal pore solution. The model supposes local electroneutrality as well as chemical and thermodynamic equilibrium. The transport is considered in three layers being an anion exchange membrane and two adjoining diffusion layers. A mechanism of competitive transport of HCO 3 - and CO 3 2- anions through the membrane which takes into account Donnan exclusion of H + ions is proposed. It is predicted that the pH of the depleting solution decreases and that of the concentrating solution increases during electrodialysis (ED). Eventual deviations from local electroneutrality and local chemical equilibrium are discussed

  15. Anion capture and sensing with cationic boranes: on the synergy of Coulombic effects and onium ion-centred Lewis acidity.

    Science.gov (United States)

    Zhao, Haiyan; Leamer, Lauren A; Gabbaï, François P

    2013-06-21

    Stimulated by the growing importance and recognized toxicity of anions such as fluoride, cyanide and azides, we have, in the past few years, developed a family of Lewis acidic triarylboranes that can be used for the complexation of these anions in organic and protic solvents, including water. A central aspect of our approach lies in the decoration of the boranes with peripheral ammonium, phosphonium, sulfonium stibonium or telluronium groups. The presence of these cationic groups provides a Coulombic drive for the capture of the anion, leading to boranes that can be used in aqueous solutions where anion hydration and/or protonation are usually competitive. The anion affinity of these boranes can be markedly enhanced by narrowing the separation between the anion binding site (i.e. the boron atom) and the onium ion. In such systems, the latent Lewis acidity of the onium ion also plays a role as manifested by the formation of B-X→E (E = P, S, Sb, or Te; X = F, CN or N3) chelate motifs that provide additional stability to the resulting complexes. These effects, which are maximum in stibonium and telluronium boranes, show that the Lewis acidity of heavy onium ions can be exploited for anion coordination and capture. The significance of these advances is illustrated by the development of applications in anion sensing, fluorination chemistry and (18)F radiolabeling for positron emission tomography.

  16. The existence and stability of the anions matching the MFk+2- formula (M = Li, Na, K, Be, Mg, Ca, B, Al, Ga)

    Science.gov (United States)

    Marchaj, Marzena; Freza, Sylwia; Skurski, Piotr

    2013-02-01

    The electronic stabilities of the MFk+2- anions (where M = Li, Na, K, Be, Mg, Ca, B, Al, Ga; and k is the maximal formal valence of atom M) were investigated at the OVGF/6-311 + G(3df) level. The vertical electron detachment energies (VDE) of the anions examined were found to be large (7.1-10.1 eV) albeit not significantly exceeding those for the corresponding MFk+1- superhalogen anions. Even though all the MFk+2- species studied were predicted to be both geometrically and electronically stable, some of them turned out to be thermodynamically unstable (i.e., susceptible to the F atom loss).

  17. Dissociative electron attachment and charge transfer in condensed matter

    International Nuclear Information System (INIS)

    Bass, A.D.; Sanche, L.

    2003-01-01

    Experiments using energy-selected beams of electrons incident from vacuum upon thin vapour deposited solids show that, as in the gas-phase, scattering cross sections at low energies are dominated by the formation of temporary negative ions (or resonances) and that molecular damage may be effected via dissociative electron attachment (DEA). Recent results also show that charge transfer between anionic states of target molecules and their environment is often crucial in determining cross sections for electron driven processes. Here, we review recent work from our laboratory, in which charge transfer is observed. For rare gas solids, electron exchange between the electron-exciton complex and either a metal substrate or co-adsorbed molecule enhances the desorption of metastable atoms and/or molecular dissociation. We discuss how transient electron capture by surface electron states of a substrate and subsequent electron transfer to a molecular adsorbate enhances the effective cross sections for DEA. We also consider the case of DEA to CF 2 Cl 2 condensed on water and ammonia ices, where electron exchange between pre-solvated electron states of ice and transient molecular anions can also increase DEA cross sections. Electron transfer from molecular resonances into pre-solvated electron states of ice is also discussed

  18. Formation of interstellar anions

    Science.gov (United States)

    Senent, Maria Luisa

    2012-05-01

    Formation of interstellar anions: M.L. Senent. The recent detection of negative charged species in the ISM1 has instigated enthusiasm for anions in the astrophysical community2. Many of these species are new and entail characterization. How they are formed in astrophysical sources is a question of major relevance. The anion presence in ISM was first predicted theoretically on the basis of electron affinities and on the negative linear chain molecular stabilities. Although very early, they were considered in astrochemical models3-4, their discovery is so recent because their abundances seem to be relatively low. These have to be understood in terms of molecular stabilities, reaction probabilities and radiative and collisional excitations. Then, we present our theoretical work on even carbon chains type Cn and CnH (n=2,4,6) focused to the understanding of anion abundances. We use highly correlated ab initio methods. We performed spectroscopic studies of various isomers that can play important roles as intermediates5-8. In previous papers9-10, we compared C2H and C2H- collisional rates responsible for observed line intensities. Actually, we study hydrogen attachment (Cn +H → CnH and Cn- +H → CnH-) and associative detachment processes (Cn- +H → CnH +e-) for 2, 4 and 6 carbon atom chains11. [1] M.C.McCarthy, C.A.Gottlieb, H.Gupta, P.Thaddeus, Astrophys.J, 652, L141 (2006) [2] V.M.Bierbaum, J.Cernicharo, R.Bachiller, eds., 2011, pp 383-389. [3] A. Dalgarno, R.A. Mc Cray, Astrophys.J,, 181, 95 (1973) [4] E. Herbst E., Nature, 289, 656 (1981); [5] H.Massó, M.L.Senent, P.Rosmus, M.Hochlaf, J.Chem.Phys., 124, 234304 (2006) [6] M.L.Senent, M.Hochlaf, Astrophys. J. , 708, 1452(2010) [7] H.Massó, M.L.Senent, J.Phys.Chem.A, 113, 12404 (2009) [8] D. Hammoutene, M.Hochlaf, M.L.Senent, submitted. [9] A. Spielfiedel, N. Feautrier, F. Najar, D. ben Abdallah, F. Dayou, M.L. Senent, F. Lique, Mon.Not.R.Astron.Soc., 421, 1891 (2012) [10] F.Dumouchel, A, Spielfieldel , M

  19. Anion effect controlling the selectivity in the zinc-catalysed copolymerisation of CO2 and cyclohexene oxide

    Directory of Open Access Journals (Sweden)

    Sait Elmas

    2015-01-01

    Full Text Available The choice of the anion has a surprisingly strong effect on the incorporation of CO2 into the polymer obtained during the zinc-catalysed copolymerisation of CO2 and cyclohexene oxide. The product span ranges from polyethercarbonates, where short polyether sequences alternate with carbonate linkages, to polycarbonates with a strictly alternating sequence of the repeating units. Herein, we report on the influence of the coordination ability of the anion on the selectivity and kinetics of the copolymerisation reaction.

  20. Making the invisible visible: improved electrospray ion formation of metalloporphyrins/-phthalocyanines by attachment of the formate anion (HCOO(-)).

    Science.gov (United States)

    Hitzenberger, Jakob Felix; Dammann, Claudia; Lang, Nina; Lungerich, Dominik; García-Iglesias, Miguel; Bottari, Giovanni; Torres, Tomás; Jux, Norbert; Drewello, Thomas

    2016-02-21

    A protocol is developed for the coordination of the formate anion (HCOO(-)) to neutral metalloporphyrins (Pors) and -phthalocyanines (Pcs) containing divalent metals as a means to improve their ion formation in electrospray ionization (ESI). This method is particularly useful when the oxidation of the neutral metallomacrocycle fails. While focusing on Zn(II)Pors and Zn(II)Pcs, we show that formate is also readily attached to Mn(II), Mg(II) and Co(II)Pcs. However, for the Co(II)Pc secondary reactions can be observed. Upon collision-induced dissociation (CID), Zn(II)Por/Pc·formate supramolecular complexes can undergo the loss of CO2 in combination with transfer of a hydride anion (H(-)) to the zinc metal center. Further dissociation leads to electron transfer and hydrogen atom loss, generating a route to the radical anion of the Zn(II)Por/Pc without the need for electrochemical reduction, although the Zn(II)Por/Pc may have a too low electron affinity to allow electron transfer directly from the formate anion. In addition to single Por molecules, multi Por arrays were successfully analyzed by this method. In this case, multiple addition of formate occurs, giving rise to multiply charged species. In these multi Por arrays, complexation of the formate anion occurs by two surrounding Por units (sandwich). Therefore, the maximum attainment of formate anions in these arrays corresponds to the number of such sandwich complexes rather than the number of porphyrin moieties. The same bonding motif leads to dimers of the composition [(Zn(II)Por/Pc)2·HCOO](-). In these, the formate anion can act as a structural probe, allowing the distinction of isomeric ions with the formate bridging two macrocycles or being attached to a dimer of directly connected macrocycles.

  1. The Thermodynamics of Anion Complexation to Nonpolar Pockets.

    Science.gov (United States)

    Sullivan, Matthew R; Yao, Wei; Tang, Du; Ashbaugh, Henry S; Gibb, Bruce C

    2018-02-08

    The interactions between nonpolar surfaces and polarizable anions lie in a gray area between the hydrophobic and Hofmeister effects. To assess the affinity of these interactions, NMR and ITC were used to probe the thermodynamics of eight anions binding to four different hosts whose pockets each consist primarily of hydrocarbon. Two classes of host were examined: cavitands and cyclodextrins. For all hosts, anion affinity was found to follow the Hofmeister series, with associations ranging from 1.6-5.7 kcal mol -1 . Despite the fact that cavitand hosts 1 and 2 possess intrinsic negative electrostatic fields, it was determined that these more enveloping hosts generally bound anions more strongly. The observation that the four hosts each possess specific anion affinities that cannot be readily explained by their structures, points to the importance of counter cations and the solvation of the "empty" hosts, free guests, and host-guest complexes, in defining the affinity.

  2. Effect of the pore water composition on the diffusive anion transport in argillaceous, low permeability sedimentary rocks.

    Science.gov (United States)

    Wigger, Cornelia; Van Loon, Luc R

    2018-06-01

    The effect of the pore water composition on the diffusive anion transport was studied for two different argillaceous, low permeability sedimentary rocks, Opalinus Clay (OPA) and Helvetic Marl (HM). The samples were saturated with different solutions with varying molar concentration and different main cations in the solution: NaCl based pore solutions and CaCl 2 based pore solutions. The total porosity was measured by through-diffusion experiments with the neutral tracer HTO. Experiments performed in NaCl solutions resulted in a porosity of 0.12 for OPA and 0.03 for HM, and are consistent with results of the experiments in CaCl 2 solutions. The total porosity was independent of the molar concentration, in contrast to the measured anion porosity, which increased with increasing molar concentration. It could further be observed that the pore solution based on the bivalent cation calcium shielded the negative surface charge stronger than the monovalent cation sodium, resulting in a larger measureable anion-accessible porosity in the case of CaCl 2 solutions. The data was modelled based on an adapted Donnan approach of Birgersson and Karnland (2009). The model had to be adjusted with a permanent free, uncharged porosity, as well as with structural information on the permanent anion exclusion because of so-called bottleneck pores. Both parameters can only be evaluated from experiments. Nevertheless, taking these two adaptions into account, the effect of varying pore water compositions on the anion-accessible porosity of the investigated argillaceous rocks could be satisfactorily described. Copyright © 2018 Elsevier B.V. All rights reserved.

  3. Effect of the pore water composition on the diffusive anion transport in argillaceous, low permeability sedimentary rocks

    Science.gov (United States)

    Wigger, Cornelia; Van Loon, Luc R.

    2018-06-01

    The effect of the pore water composition on the diffusive anion transport was studied for two different argillaceous, low permeability sedimentary rocks, Opalinus Clay (OPA) and Helvetic Marl (HM). The samples were saturated with different solutions with varying molar concentration and different main cations in the solution: NaCl based pore solutions and CaCl2 based pore solutions. The total porosity was measured by through-diffusion experiments with the neutral tracer HTO. Experiments performed in NaCl solutions resulted in a porosity of 0.12 for OPA and 0.03 for HM, and are consistent with results of the experiments in CaCl2 solutions. The total porosity was independent of the molar concentration, in contrast to the measured anion porosity, which increased with increasing molar concentration. It could further be observed that the pore solution based on the bivalent cation calcium shielded the negative surface charge stronger than the monovalent cation sodium, resulting in a larger measureable anion-accessible porosity in the case of CaCl2 solutions. The data was modelled based on an adapted Donnan approach of Birgersson and Karnland (2009). The model had to be adjusted with a permanent free, uncharged porosity, as well as with structural information on the permanent anion exclusion because of so-called bottleneck pores. Both parameters can only be evaluated from experiments. Nevertheless, taking these two adaptions into account, the effect of varying pore water compositions on the anion-accessible porosity of the investigated argillaceous rocks could be satisfactorily described.

  4. Electron attachment to the guanine-cytosine nucleic acid base pair and the effects of monohydration and proton transfer.

    Science.gov (United States)

    Gupta, Ashutosh; Jaeger, Heather M; Compaan, Katherine R; Schaefer, Henry F

    2012-05-17

    The guanine-cytosine (GC) radical anion and its interaction with a single water molecule is studied using ab initio and density functional methods. Z-averaged second-order perturbation theory (ZAPT2) was applied to GC radical anion for the first time. Predicted spin densities show that the radical character is localized on cytosine. The Watson-Crick monohydrated GC anion is compared to neutral GC·H2O, as well as to the proton-transferred analogue on the basis of structural and energetic properties. In all three systems, local minima are identified that correspond to water positioned in the major and minor grooves of macromolecular DNA. On the anionic surface, two novel structures have water positioned above or below the GC plane. On the neutral and anionic surfaces, the global minimum can be described as water interacting with the minor groove. These structures are predicted to have hydration energies of 9.7 and 11.8 kcal mol(-1), respectively. Upon interbase proton-transfer (PT), the anionic global minimum has water positioned in the major groove, and the hydration energy increases to 13.4 kcal mol(-1). PT GC·H2O(•-) has distonic character; the radical character resides on cytosine, while the negative charge is localized on guanine. The effects of proton transfer are further investigated through the computed adiabatic electron affinities (AEA) of GC and monohydrated GC, and the vertical detachment energies (VDE) of the corresponding anions. Monohydration increases the AEAs and VDEs by only 0.1 eV, while proton-transfer increases the VDEs substantially (0.8 eV). The molecular charge distribution of monohydrated guanine-cytosine radical anion depends heavily on interbase proton transfer.

  5. Microhydration of cytosine and its radical anion: Cytosine.(H2O)n (n=1-5)

    Science.gov (United States)

    Kim, Sunghwan; Schaefer, Henry F.

    2007-02-01

    Microhydration effects on cytosine and its radical anion have been investigated theoretically, by explicitly considering various structures of cytosine complexes with up to five water molecules. Each successive water molecule (through n =5) is bound by 7-10kcalmol-1 to the relevant cytosine complex. The hydration energies are uniformly higher for the analogous anion systems. While the predicted vertical detachment energy (VDE) of the isolated cytosine is only 0.48eV, it is predicted to increase to 1.27eV for the lowest-lying pentahydrate of cytosine. The adiabatic electron affinity (AEA) of cytosine was also found to increase from 0.03to0.61eV for the pentahydrate, implying that the cytosine anion, while questionable in the gas phase, is bound in aqueous solution. Both the VDE and AEA values for cytosine are smaller than those of uracil and thymine for a given hydration number. These results are in qualitative agreement with available experimental results from photodetachment-photoelectron spectroscopy studies of Schiedt et al. [Chem. Phys. 239, 511 (1998)].

  6. Radiation-induced decomposition of anion exchange resins

    International Nuclear Information System (INIS)

    Baidak, Aliaksandr; LaVerne, Jay A.

    2010-01-01

    Radiation-induced degradation of the strongly basic anion exchange resin Amberlite TM IRA400 in NO 3 - , Cl - and OH - forms has been studied. The research focused on the formation of molecular hydrogen in the gamma-radiolysis of water slurries of these quaternary ammonium resins with varying water content. Extended studies with various electron scavengers (NO 3 - , N 2 O and O 2 ) prove an important role of e solv - in the formation of H 2 from these resins. An excess production of H 2 in these systems at about 85% water weight fraction was found to be due to trimethylamine, dimethylamine and other compounds that leach from the resin to the aqueous phase. Irradiations with 5 MeV 4 He ions were performed to simulate the effects of α-particles.

  7. Mimicking the cell membrane: bio-inspired simultaneous functions with monovalent anion selectivity and antifouling properties of anion exchange membrane

    Science.gov (United States)

    Zhao, Yan; Liu, Huimin; Tang, Kaini; Jin, Yali; Pan, Jiefeng; der Bruggen, Bart Van; Shen, Jiangnan; Gao, Congjie

    2016-01-01

    A new bio-inspired method was applied in this study to simultaneously improve the monovalent anion selectivity and antifouling properties of anion exchange membranes (AEMs). Three-layer architecture was developed by deposition of polydopamine (PDA) and electro-deposition of N-O-sulfonic acid benzyl chitosan (NSBC). The innermost and outermost layers were PDA with different deposition time. The middle layer was prepared by NSBC. Fourier transform infrared spectroscopy and scanning electron microscopy confirmed that PDA and NSBC were successfully modified on the surfaces of AEMs. The contact angle of the membranes indicated an improved hydrophilicity of the modified membranes. A series of electrodialysis experiments in which Cl−/SO42− separation was studied, demonstrating the monovalent anion selectivity of the samples. The Cl−/SO42− permselectivity of the modified membranes can reach up to 2.20, higher than that of the commercial membrane (only 0.78) during 90 minutes in electrodialysis (ED). The increase value of the resistance of the membranes was also measured to evaluate the antifouling properties. Sodium dodecyl benzene sulfonate (SDBS) was used as the fouling material in the ED process and the membrane area resistance of modified membrane increase value of was only 0.08 Ωcm2 30 minutes later. PMID:27853255

  8. Mimicking the cell membrane: bio-inspired simultaneous functions with monovalent anion selectivity and antifouling properties of anion exchange membrane

    Science.gov (United States)

    Zhao, Yan; Liu, Huimin; Tang, Kaini; Jin, Yali; Pan, Jiefeng; der Bruggen, Bart Van; Shen, Jiangnan; Gao, Congjie

    2016-11-01

    A new bio-inspired method was applied in this study to simultaneously improve the monovalent anion selectivity and antifouling properties of anion exchange membranes (AEMs). Three-layer architecture was developed by deposition of polydopamine (PDA) and electro-deposition of N-O-sulfonic acid benzyl chitosan (NSBC). The innermost and outermost layers were PDA with different deposition time. The middle layer was prepared by NSBC. Fourier transform infrared spectroscopy and scanning electron microscopy confirmed that PDA and NSBC were successfully modified on the surfaces of AEMs. The contact angle of the membranes indicated an improved hydrophilicity of the modified membranes. A series of electrodialysis experiments in which Cl-/SO42- separation was studied, demonstrating the monovalent anion selectivity of the samples. The Cl-/SO42- permselectivity of the modified membranes can reach up to 2.20, higher than that of the commercial membrane (only 0.78) during 90 minutes in electrodialysis (ED). The increase value of the resistance of the membranes was also measured to evaluate the antifouling properties. Sodium dodecyl benzene sulfonate (SDBS) was used as the fouling material in the ED process and the membrane area resistance of modified membrane increase value of was only 0.08 Ωcm2 30 minutes later.

  9. Inhibition of nuclear waste solutions containing multiple aggressive anions

    International Nuclear Information System (INIS)

    Congdon, J.W.

    1987-01-01

    The inhibition of localized corrosion of carbon steel in caustic, high-level radioactive waste solutions was studied using cyclic potentiodynamic polarization scans, supplemented by partially immersed coupon tests. The electrochemical tests provided a rapid and accurate means of determining the relationship between the minimum inhibitor requirements and the concentration of the aggressive anions in this system. Nitrate, sulfate, chloride, and fluoride were identified as aggressive anions, however, no synergistic effects were observed between these anions. This observation may have important theoretical implications because it tends to contradict the behavior of aggressive anions as predicted by existing theories for localized corrosion. 10 refs., 5 figs., 2 tabs

  10. Study of organic radicals through anion photoelectron velocity-map imaging spectroscopy

    Science.gov (United States)

    Dixon, Andrew Robert

    We report preliminary results on the photoelectron imaging of phenylcarbene, cyanophenylcarbene, and chlorophenylcarbene anions. Triplet phenylcarbene is observed to have an EA of ≤ 0.83 eV, considerably lower than the previously indirectly-determined value. Transitions to the singlet and triplet ground state of both cyanophenylcarbene and chlorophenylcarbene are observable, though unidentified bands make full assignment difficult. Cyanophenylcarbene is found to have a triplet ground-state, with a tentative EA of 2.04 eV. Chlorophenylcarbene is found to have a singlet ground-state. The phenyl-group is found to favor the singlet state slightly. The cyanofluoromethyl radical, FC(H)CN, was estimated to have an EA of 1.53 +/- 0.08 eV, by a combination of experimental and theoretical results.. With similar methodology, we report the adiabatic electron affinity of the cyanobenzyl radical, EA(PhCHCN) = 1.90 +/- 0.01 eV, and assign an upper limit of the EA for the chlorobenzyl radical, EA(PhCHCl) ≤ 1.12 eV. These values were used to estimate the C-H bond dissociation energy (BDE)s for these substituted methanes. Fluoroacetonitrile was found to have a BDE of D H198 = 90.7 +/- 2.8 kcal mol□1. The C-H bond dissociation energies at the benzyl-alpha sites of the phenylmethanes are determined as 80.9 +/- 2.3 kcal mol-1 for benzyl nitrile and an upper limit of 84.2 kcal mol-1 for benzyl chloride. These results are discussed in terms of substituent interactions in a simple MO framework and in relation to other similar molecules, including recently reported results for chloroacetonitrile. The 532 nm photoelectron spectrum of glyoxal provides the first direct spectroscopic determination of the adiabatic electron affinity, EA = 1.10(2) eV. This assignment is supported by a Franck-Condon simulation of the experimental spectrum that successfully reproduces the observed spectral features. The vertical detachment energy (VDE) of the glyoxal radical anion is determined as VDE = 1

  11. Hydrothermal carbon nanosphere-based agglomerated anion exchanger for ion chromatography.

    Science.gov (United States)

    Zhao, Qiming; Wu, Shuchao; Zhang, Kai; Lou, Chaoyan; Zhang, Peiming; Zhu, Yan

    2016-10-14

    This work reports the application of hydrothermal carbon nanospheres (HCNSs) as stationary phases in ion chromatography. HCNSs were facilely quaternized through polycondensation of methylamine and 1,4-butanediol diglycidyl ether. The quaternization was confirmed by Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. Owing to the electrostatic interaction, quaternized HCNSs were equably attached onto the surface of sulfonated polystyrene-divinylbenzene (PS-DVB) beads to construct the anion exchangers. The aggregation was verified by scanning electron microscopy and elemental analysis. Common anions, aliphatic monocarboxylic acids, polarizable anions, and aromatic acids were well separated on the stationary phases with good stability and symmetry. The prepared column was further applied to detect phosphate content in Cola drink samples. The limit of detection (S/N=3) was 0.09mg/L, and the relative standard deviation (n=10) of retention time was 0.31%. The average recovery was 99.58%. Copyright © 2016 Elsevier B.V. All rights reserved.

  12. The Production of Polycyclic Aromatic Hydrocarbon Anions in Inert Gas Matrices Doped with Alkali Metals. Electronic Absorption Spectra of the Pentacene Anion (C22H14(-))

    Science.gov (United States)

    Halasinski, Thomas M.; Hudgins, Douglas M.; Salama, Farid; Allamandola, Louis J.; Mead, Susan (Technical Monitor)

    1999-01-01

    The absorption spectra of pentacene (C22H14) and its radical cation (C22H14(+)) and anion (C22H14(-)) isolated in inert-gas matrices of Ne, Ar, and Kr are reported from the ultraviolet to the near-infrared. The associated vibronic band systems and their spectroscopic assignments are discussed together with the physical and chemical conditions governing ion (and counterion) production in the solid matrix. In particular, the formation of isolated pentacene anions is found to be optimized in matrices doped with alkali metal (Na and K).

  13. Study of the surface-enhanced Raman spectroscopy of residual impurities in hydroxylamine-reduced silver colloid and the effects of anions on the colloid activity.

    Science.gov (United States)

    Dong, Xiao; Gu, Huaimin; Liu, Fangfang

    2012-03-01

    The paper investigated the residual ions in hydroxylamine-reduced silver colloid (HRSC) and the relationship between the condition of HRSC and the enhanced mechanisms of this colloid. We also detected the SERS of MB and studied the effects of anions on the Raman signal. In the case of HRSC, the bands of residual ions diminish while the bands of Ag-anions increase gradually with increasing the concentrations of Cl(-) and NO(3)(-). It means the affinity of residual ions on the silver surface is weaker than that of Cl(-) and NO(3)(-) and the residual ions are replaced gradually by the added Cl(-) or NO(3)(-). The Raman signal of residual ions can be detected by treatment with anions that do not bind strongly to the silver surface, such as SO(4)(2-). The most intense band of Ag-anions bonds can be also observed when adding weakly binding anions to the colloid. However, the anions which make up the Ag-anions bonds are residual Cl(-) and the effect of weakly binding anions is only to aggregate the silver particles. Residual Cl(-) can be replaced by I(-) which has the highest affinity. From the detection of methylene blue (MB), the effects of anions on the enhancement of Raman signal are discussed in detail, and these findings could make the conditions suitable for detecting analytes in high efficiency. This study will have a profound implication to SERS users about their interpretation of SERS spectra when obtaining these anomalous bands. Copyright © 2011 Elsevier B.V. All rights reserved.

  14. Effect of an inefficient electron scavenger on infrared- and visible-absorbing electrons in an ethanol matrix

    International Nuclear Information System (INIS)

    Noda, S.; Yoshida, K.; Ogasawara, M.; Yoshida, H.

    1980-01-01

    In order to obtain a deeper insight into the initial localization and the subsequent stabilization of electrons and to unravel the detailed mechanism of the electron scavenging reaction in a glassy ethanol matrix, spectrophotometric studies have been made on this matrix with toluene, an inefficient electron scavenger, γ irradiated at 4.2 0 K. Inhomogeneous depletion of the trapped electron spectrum by toluene indicates that IR-absorbing (lambda/sub max/ = 1500 nm) and visible-absorbing (lambda/sub max/ = 640 nm) electrons are initially generated, but that the former are unstable at higher temperature. Toluene scavenges the IR-absorbing electrons more efficiently by a factor of 10 than the visible-absorbing electrons. This selectivity is much higher than that of an efficient scavenger, such as benzyl chloride, as previously reported. The electron scavenging reaction results in the formation of the transient radical anion of toluene, which is readily protonated to yield the methylcyclohexadienyl radical at 77 0 K. 3 figures

  15. Mitochondrial respiration scavenges extramitochondrial superoxide anion via a nonenzymatic mechanism.

    OpenAIRE

    Guidot, D M; Repine, J E; Kitlowski, A D; Flores, S C; Nelson, S K; Wright, R M; McCord, J M

    1995-01-01

    We determined that mitochondrial respiration reduced cytosolic oxidant stress in vivo and scavenged extramitochondrial superoxide anion (O2-.) in vitro. First, Saccharomyces cerevisiae deficient in both the cytosolic antioxidant cupro-zinc superoxide dismutase (Cu,Zn-SOD) and electron transport (Rho0 state) grew poorly (P 0.05) in all yeast. Seco...

  16. Dowex anion exchanger-loaded-baker's yeast as bi-functionalized biosorbents for selective extraction of anionic and cationic mercury(II) species

    International Nuclear Information System (INIS)

    Mahmoud, Mohamed E.; Yakout, Amr A.; Osman, Maher M.

    2009-01-01

    Dowex anion exchanger-immobilized-baker's yeast [Dae-yeast] were synthesized and potentially applied as environmental friendly biosorbents to evaluate the up-take process of anionic and cationic mercury(II) species as well as other metal ions. Optimization of mass ratio of Dowex anion exchanger versus yeast (1:1-1:10) in presence of various interacting buffer solutions (pH 4.0-9.0) was performed and evaluated. Surface modification of [Dae-yeast] was characterized by scanning electron microscopy (SEM) and infrared spectroscopy. The maximum metal biosorption capacity values of [Dae-yeast] towards mercury(II) were found in the range of 0.800-0.960, 0.840-0.950 and 0.730-0.900 mmol g -1 in presence of buffer solutions pH 2.0, 4.0 and 7.0, respectively. Three possible and different mechanisms are proposed to account for the biosorption of mercury and mercuric species under these three buffering conditions based on ion exchange, ion pair and chelation interaction processes. Factors affecting biosorption of mercury from aqueous medium including the pH effect of aqueous solutions (1.0-7.0), shaking time (1-30 min) and interfering ions were searched. The potential applications of modified biosorbents for selective biosorption and extraction of mercury from different real matrices including dental filling waste materials, industrial waste water samples and mercury lamp waste materials were also explored. The results denote to excellent percentage extraction values, from nitric acid as the dissolution solvent with a pH 2.0, as determined in the range of 90.77-97.91 ± 3.00-5.00%, 90.00-93.40 ± 4.00-5.00% and 92.31-100.00 ± 3.00-4.00% for the three tested samples, respectively.

  17. Effects of temperature and isotopic substitution on electron attachment dynamics of guanine–cytosine base pair: Ring-polymer and classical molecular dynamics simulations

    International Nuclear Information System (INIS)

    Minoshima, Yusuke; Seki, Yusuke; Takayanagi, Toshiyuki; Shiga, Motoyuki

    2016-01-01

    Highlights: • Dynamics of excess electron attachment to guanine–cytosine base pair. • Ring-polymer and classical molecular dynamics simulations are performed. • Temperature and isotope substitution effects are investigated. - Abstract: The dynamical process of electron attachment to a guanine–cytosine pair in the normal (h-GC) and deuterated (d-GC) forms has been studied theoretically by semiclassical ring-polymer molecular dynamics (RPMD) simulations using the empirical valence bond model. The initially formed dipole-bound anion is converted rapidly to the valence-bound anion within about 0.1 ps in both h-GC and d-GC. However, the subsequent proton transfer in h-GC occurs with a rate five times greater than the deuteron transfer in d-GC. The change of rates with isotopic substitution and temperature variation in the RPMD simulations are quantitatively and qualitatively different from those in the classical molecular dynamics (MD) simulations, demonstrating the importance of nuclear quantum effects on the dynamics of this system.

  18. Effects of temperature and isotopic substitution on electron attachment dynamics of guanine–cytosine base pair: Ring-polymer and classical molecular dynamics simulations

    Energy Technology Data Exchange (ETDEWEB)

    Minoshima, Yusuke; Seki, Yusuke [Department of Chemistry, Saitama University, 255 Shimo-Okubo, Sakura-ku, Saitama City, Saitama 338-8570 (Japan); Takayanagi, Toshiyuki, E-mail: tako@mail.saitama-u.ac.jp [Department of Chemistry, Saitama University, 255 Shimo-Okubo, Sakura-ku, Saitama City, Saitama 338-8570 (Japan); Shiga, Motoyuki [Center for Computational Science and E-Systems, Japan Atomic Energy Agency, 148-4, Kashiwanoha Campus, 178-4 Wakashiba, Kashiwa, Chiba 277-0871 (Japan)

    2016-06-15

    Highlights: • Dynamics of excess electron attachment to guanine–cytosine base pair. • Ring-polymer and classical molecular dynamics simulations are performed. • Temperature and isotope substitution effects are investigated. - Abstract: The dynamical process of electron attachment to a guanine–cytosine pair in the normal (h-GC) and deuterated (d-GC) forms has been studied theoretically by semiclassical ring-polymer molecular dynamics (RPMD) simulations using the empirical valence bond model. The initially formed dipole-bound anion is converted rapidly to the valence-bound anion within about 0.1 ps in both h-GC and d-GC. However, the subsequent proton transfer in h-GC occurs with a rate five times greater than the deuteron transfer in d-GC. The change of rates with isotopic substitution and temperature variation in the RPMD simulations are quantitatively and qualitatively different from those in the classical molecular dynamics (MD) simulations, demonstrating the importance of nuclear quantum effects on the dynamics of this system.

  19. Anion binding in biological systems

    Energy Technology Data Exchange (ETDEWEB)

    Feiters, Martin C [Department of Organic Chemistry, Institute for Molecules and Materials, Faculty of Science, Radboud University Nijmegen, Heyendaalseweg 135, 6525 AJ Nijmegen (Netherlands); Meyer-Klaucke, Wolfram [EMBL Hamburg Outstation at DESY, Notkestrasse 85, D-22607 Hamburg (Germany); Kostenko, Alexander V; Soldatov, Alexander V [Faculty of Physics, Southern Federal University, Sorge 5, Rostov-na-Donu, 344090 (Russian Federation); Leblanc, Catherine; Michel, Gurvan; Potin, Philippe [Centre National de la Recherche Scientifique and Universite Pierre et Marie Curie Paris-VI, Station Biologique de Roscoff, Place Georges Teissier, BP 74, F-29682 Roscoff cedex, Bretagne (France); Kuepper, Frithjof C [Scottish Association for Marine Science, Dunstaffnage Marine Laboratory, Oban, Argyll PA37 1QA, Scotland (United Kingdom); Hollenstein, Kaspar; Locher, Kaspar P [Institute of Molecular Biology and Biophysics, ETH Zuerich, Schafmattstrasse 20, Zuerich, 8093 (Switzerland); Bevers, Loes E; Hagedoorn, Peter-Leon; Hagen, Wilfred R, E-mail: m.feiters@science.ru.n [Department of Biotechnology, Delft University of Technology, Julianalaan 67, 2628 BC Delft (Netherlands)

    2009-11-15

    We compare aspects of biological X-ray absorption spectroscopy (XAS) studies of cations and anions, and report on some examples of anion binding in biological systems. Brown algae such as Laminaria digitata (oarweed) are effective accumulators of I from seawater, with tissue concentrations exceeding 50 mM, and the vanadate-containing enzyme haloperoxidase is implicated in halide accumulation. We have studied the chemical state of iodine and its biological role in Laminaria at the I K edge, and bromoperoxidase from Ascophyllum nodosum (knotted wrack) at the Br K edge. Mo is essential for many forms of life; W only for certain archaea, such as Archaeoglobus fulgidus and the hyperthermophilic archaeon Pyrococcus furiosus, and some bacteria. The metals are bound and transported as their oxo-anions, molybdate and tungstate, which are similar in size. The transport protein WtpA from P. furiosus binds tungstate more strongly than molybdate, and is related in sequence to Archaeoglobus fulgidus ModA, of which a crystal structure is known. We have measured A. fulgidus ModA with tungstate at the W L{sub 3} (2p{sub 3/2}) edge, and compared the results with the refined crystal structure. XAS studies of anion binding are feasible even if only weak interactions are present, are biologically relevant, and give new insights in the spectroscopy.

  20. Anion binding in biological systems

    International Nuclear Information System (INIS)

    Feiters, Martin C; Meyer-Klaucke, Wolfram; Kostenko, Alexander V; Soldatov, Alexander V; Leblanc, Catherine; Michel, Gurvan; Potin, Philippe; Kuepper, Frithjof C; Hollenstein, Kaspar; Locher, Kaspar P; Bevers, Loes E; Hagedoorn, Peter-Leon; Hagen, Wilfred R

    2009-01-01

    We compare aspects of biological X-ray absorption spectroscopy (XAS) studies of cations and anions, and report on some examples of anion binding in biological systems. Brown algae such as Laminaria digitata (oarweed) are effective accumulators of I from seawater, with tissue concentrations exceeding 50 mM, and the vanadate-containing enzyme haloperoxidase is implicated in halide accumulation. We have studied the chemical state of iodine and its biological role in Laminaria at the I K edge, and bromoperoxidase from Ascophyllum nodosum (knotted wrack) at the Br K edge. Mo is essential for many forms of life; W only for certain archaea, such as Archaeoglobus fulgidus and the hyperthermophilic archaeon Pyrococcus furiosus, and some bacteria. The metals are bound and transported as their oxo-anions, molybdate and tungstate, which are similar in size. The transport protein WtpA from P. furiosus binds tungstate more strongly than molybdate, and is related in sequence to Archaeoglobus fulgidus ModA, of which a crystal structure is known. We have measured A. fulgidus ModA with tungstate at the W L 3 (2p 3/2 ) edge, and compared the results with the refined crystal structure. XAS studies of anion binding are feasible even if only weak interactions are present, are biologically relevant, and give new insights in the spectroscopy.

  1. Anion binding in biological systems

    Science.gov (United States)

    Feiters, Martin C.; Meyer-Klaucke, Wolfram; Kostenko, Alexander V.; Soldatov, Alexander V.; Leblanc, Catherine; Michel, Gurvan; Potin, Philippe; Küpper, Frithjof C.; Hollenstein, Kaspar; Locher, Kaspar P.; Bevers, Loes E.; Hagedoorn, Peter-Leon; Hagen, Wilfred R.

    2009-11-01

    We compare aspects of biological X-ray absorption spectroscopy (XAS) studies of cations and anions, and report on some examples of anion binding in biological systems. Brown algae such as Laminaria digitata (oarweed) are effective accumulators of I from seawater, with tissue concentrations exceeding 50 mM, and the vanadate-containing enzyme haloperoxidase is implicated in halide accumulation. We have studied the chemical state of iodine and its biological role in Laminaria at the I K edge, and bromoperoxidase from Ascophyllum nodosum (knotted wrack) at the Br K edge. Mo is essential for many forms of life; W only for certain archaea, such as Archaeoglobus fulgidus and the hyperthermophilic archaeon Pyrococcus furiosus, and some bacteria. The metals are bound and transported as their oxo-anions, molybdate and tungstate, which are similar in size. The transport protein WtpA from P. furiosus binds tungstate more strongly than molybdate, and is related in sequence to Archaeoglobus fulgidus ModA, of which a crystal structure is known. We have measured A. fulgidus ModA with tungstate at the W L3 (2p3/2) edge, and compared the results with the refined crystal structure. XAS studies of anion binding are feasible even if only weak interactions are present, are biologically relevant, and give new insights in the spectroscopy.

  2. Effect of isolated hepatic ischemia on organic anion clearance and oxidative metabolism.

    Science.gov (United States)

    Minard, G; Bynoe, R; Wood, G C; Fabian, T C; Croce, M; Kudsk, K A

    1992-04-01

    Hepatic failure is frequently seen following severe hemorrhagic shock, sepsis, and trauma. Clearance of various drugs has been used to evaluate hepatocellular dysfunction, including indocyanine green (ICG), an organic anionic dye that is transported similarly to bilirubin, and antipyrine (AP), a marker of oxidative phosphorylation. Previous investigators have noted a decrease in ICG excretion following systemic hemorrhage. The effect of isolated hepatic ischemia on the clearances of ICG and AP was studied in 16 pigs after 90 minutes of vascular occlusion to the liver. Antipyrine clearance decreased almost 50% from baseline values at 24 and 72 hours after the ischemia procedure, indicating a significant depression in the cytochrome P-450 system. On the other hand, ICG clearance did not change significantly. In conclusion, ICG clearance is not depressed after isolated hepatic ischemia in pigs. Changes in organic anion clearance after systemic hemorrhage may be because of release of toxic products from ischemic peripheral tissue.

  3. The anionic basis of fluid secretion by the rabbit mandibular salivary gland

    DEFF Research Database (Denmark)

    Case, R M; Hunter, M; Novak, I

    1984-01-01

    The role played by anions in salivary secretion has been studied in experiments on the isolated, perfused mandibular gland of the rabbit, in which perfusate Cl- and/or HCO3- were replaced by other anions. Replacement of Cl- with Br- had no significant effect on salivary secretion rate, but replac......The role played by anions in salivary secretion has been studied in experiments on the isolated, perfused mandibular gland of the rabbit, in which perfusate Cl- and/or HCO3- were replaced by other anions. Replacement of Cl- with Br- had no significant effect on salivary secretion rate...

  4. Femtosecond photoelectron spectroscopy: a new tool for the study of anion dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Greenblatt, Benjamin J. [Univ. of California, Berkeley, CA (United States)

    1999-02-01

    A new experimental technique for the time-resolved study of anion reactions is presented. Using femtosecond laser pulses, which provide extremely fast (~100 fs) time resolution, in conjunction with photoelectron spectroscopy, which reveals differences between anion and neutral potential energy surfaces, a complex anion reaction can be followed from its inception through the formation of asymptotic products. Experimental data can be modeled quantitatively using established theoretical approaches, allowing for the refinement of potential energy surfaces as well as dynamical models. After a brief overview, a detailed account of the construction of the experimental apparatus is presented. Documentation of the data acquisition program is contained in the Appendix. The first experimental demonstration of the technique is then presented for I2- photodissociation, modeled using a simulation program which is also detailed in the Appendix. The investigation of I2- photodissociation in several size-selected I2-(Ar)n (n = 6-20) and I2-(CO2)n (n = 4-16) clusters forms the heart of the dissertation. In a series of chapters, the numerous effects of solvation on this fundamental bond-breaking reaction are explored, the most notable of which is the recombination of I2- on the ground $\\tilde{X}$(2Σu+) state in sufficiently large clusters. Recombination and trapping of I2- on the excited $\\tilde{A}$(2π3/2,g) state is also observed in both types of clusters. The studies have revealed electronic state transitions, the first step in recombination, on a ~500 fs to ~10 ps timescale. Accompanying the changes in electronic state is solvent reorganization, which occurs on a similar timescale. Over longer periods (~1 ps to >200 ps), energy is transferred from vibrationally

  5. Fluorescence anisotropy of tyrosinate anion using one-, two- and three-photon excitation: tyrosinate anion fluorescence.

    Science.gov (United States)

    Kierdaszuk, Borys

    2013-03-01

    We examined the emission spectra and steady-state anisotropy of tyrosinate anion fluorescence with one-photon (250-310 nm), two-photon (570-620 nm) and three-photon (750-930 nm) excitation. Similar emission spectra of the neutral (pH 7.2) and anionic (pH 13) forms of N-acetyl-L-tyrosinamide (NATyrA) (pKa 10.6) were observed for all modes of excitation, with the maxima at 302 and 352 nm, respectively. Two-photon excitation (2PE) and three-photon excitation (3PE) spectra of the anionic form were the same as that for one-photon excitation (1PE). In contrast, 2PE spectrum from the neutral form showed ~30-nm shift to shorter wavelengths relative to 1PE spectrum (λmax 275 nm) at two-photon energy (550 nm), the latter being overlapped with 3PE spectrum, both at two-photon energy (550 nm). Two-photon cross-sections for NATyrA anion at 565-580 nm were 10 % of that for N-acetyl-L-tryptophanamide (NATrpA), and increased to 90 % at 610 nm, while for the neutral form of NATyrA decreased from 2 % of that for NATrpA at 570 nm to near zero at 585 nm. Surprisingly, the fundamental anisotropy of NATyrA anion in vitrified solution at -60 °C was ~0.05 for 2PE at 610 nm as compared to near 0.3 for 1PE at 305 nm, and wavelength-dependence appears to be a basic feature of its anisotropy. In contrast, the 3PE anisotropy at 900 nm was about 0.5, and 3PE and 1PE anisotropy values appear to be related by the cos(6) θ to cos(2) θ photoselection factor (approx. 10/6) independently of excitation wavelength. Attention is drawn to the possible effect of tyrosinate anions in proteins on their multi-photon induced fluorescence emission and excitation spectra as well as excitation anisotropy spectra.

  6. The many ways of making anionic clays

    Indian Academy of Sciences (India)

    Together with hydrotalcite-like layered double hydroxides, bivalent and trivalent metal hydroxides and their hydroxy salts are actually anionic clays consisting of positively charged hydroxide layers with anions intercalated in the interlayer region. The anionic clays exhibit anion sorption, anion diffusion and exchange ...

  7. Communication: State mixing by spin-orbit coupling in the anionic chloroiodine dissociations

    Energy Technology Data Exchange (ETDEWEB)

    Xia, L.; Wang, X.-D.; Xuan, C.-J.; Zeng, X.-J.; Li, H.-K.; Tian, S. X., E-mail: sxtian@ustc.edu.cn, E-mail: kaichung@cityu.edu.hk [Hefei National Laboratory for Physical Sciences at the Microscale, Department of Chemical Physics, University of Science and Technology of China, 96 Jinzhai Road, Hefei, Anhui 230026 (China); Pan, Y.; Lau, K.-C., E-mail: sxtian@ustc.edu.cn, E-mail: kaichung@cityu.edu.hk [Department of Biology and Chemistry, City University of Hong Kong, 83 Tat Chee Avenue, Kowloon, Hong Kong (China)

    2014-01-28

    Three spin-orbit states, 1{sup 2}Π{sub 1/2}, 2{sup 2}Π{sub 3/2}, and 2{sup 2}Π{sub 1/2}, of chloroiodine anion (ICl{sup −}) formed by low-energy electron attachment in the Franck-Condon region are associated with the dissociative limits of I{sup −} ({sup 1}S{sub 0}) and Cl ({sup 2}P{sub 3/2}) or Cl{sup *} ({sup 2}P{sub 1/2}) fragments. Within the adiabatic scheme, the presumptive Π-symmetry of the fragment angular distributions is dramatically changed to be the Π-Σ mixing symmetry, due to the significant spin-orbit interaction effect on the electronic state couplings of ICl{sup −}. The present experimental approach also enables us to separate the contributions of different electronic states from the mixed states, providing a crucial method for quantitatively evaluating the configuration-interaction wavefunctions.

  8. Carbon Chain Anions and the Growth of Complex Organic Molecules in Titan’s Ionosphere

    Science.gov (United States)

    Desai, R. T.; Coates, A. J.; Wellbrock, A.; Vuitton, V.; Crary, F. J.; González-Caniulef, D.; Shebanits, O.; Jones, G. H.; Lewis, G. R.; Waite, J. H.; Cordiner, M.; Taylor, S. A.; Kataria, D. O.; Wahlund, J.-E.; Edberg, N. J. T.; Sittler, E. C.

    2017-08-01

    Cassini discovered a plethora of neutral and ionized molecules in Titan’s ionosphere including, surprisingly, anions and negatively charged molecules extending up to 13,800 u q-1. In this Letter, we forward model the Cassini electron spectrometer response function to this unexpected ionospheric component to achieve an increased mass resolving capability for negatively charged species observed at Titan altitudes of 950-1300 km. We report on detections consistently centered between 25.8 and 26.0 u q-1 and between 49.0-50.1 u q-1 which are identified as belonging to the carbon chain anions, CN-/C3N- and/or C2H-/C4H-, in agreement with chemical model predictions. At higher ionospheric altitudes, detections at 73-74 u q-1 could be attributed to the further carbon chain anions C5N-/C6H- but at lower altitudes and during further encounters extend over a higher mass/charge range. This, as well as further intermediary anions detected at >100 u, provide the first evidence for efficient anion chemistry in space involving structures other than linear chains. Furthermore, at altitudes below environments where chain anions have been observed and shows that anion chemistry plays a role in the formation of complex organics within a planetary atmosphere as well as in the interstellar medium.

  9. The effect of varying the anion of an ionic liquid on the solvent effects on a nucleophilic aromatic substitution reaction.

    Science.gov (United States)

    Hawker, Rebecca R; Haines, Ronald S; Harper, Jason B

    2018-05-09

    A variety of ionic liquids, each containing the same cation but a different anion, were examined as solvents for a nucleophilic aromatic substitution reaction. Varying the proportion of ionic liquid was found to increase the rate constant as the mole fraction of ionic liquid increased demonstrating that the reaction outcome could be controlled through varying the ionic liquid. The solvent effects were correlated with the hydrogen bond accepting ability (β) of the ionic liquid anion allowing for qualitative prediction of the effect of changing this component of the solute. To determine the microscopic origins of the solvent effects, activation parameters were determined through temperature-dependent kinetic analyses and shown to be consistent with previous studies. With the knowledge of the microscopic interactions in solution, an ionic liquid was rationally chosen to maximise rate enhancement demonstrating that an ionic solvent can be selected to control reaction outcome for this reaction type.

  10. Solution and solid-state studies on the halide binding affinity of perfluorophenyl-armed uranyl-salophen receptors enhanced by anion-π interactions

    Energy Technology Data Exchange (ETDEWEB)

    Leoni, Luca; Mele, Andrea; Giannicchi, Ilaria; Mihan, Francesco Yafteh; Dalla Cort, Antonella [Dipartimento di Chimica and IMC-CNR, Universita di Roma La Sapienza (Italy); Puttreddy, Rakesh; Jurcek, Ondrej; Rissanen, Kari [University of Jyvaeskylae, Department of Chemistry, Nanoscience Center (Finland)

    2016-12-23

    The enhancement of the binding between halide anions and a Lewis acidic uranyl-salophen receptor has been achieved by the introduction of pendant electron-deficient arene units into the receptor skeleton. The association and the occurrence of the elusive anion-π interaction with halide anions (as tetrabutylammonium salts) have been demonstrated in solution and in the solid state, providing unambiguous evidence on the interplay of the concerted interactions responsible for the anion binding. (copyright 2016 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  11. Supramolecular Chemistry of Environmentally Relevant Anions

    International Nuclear Information System (INIS)

    Bowman-James, Kristin; Moyer, B.A.; Sessler, Jonathan L.

    2003-01-01

    The goal of this project is the development of highly selective extractants for anions targeting important and timely problems of critical interest to the EMSP mission. In particular, sulfate poses a special problem in cleaning up the Hanford waste tanks in that it interferes with vitrification, but available technologies for sulfate removal are limited. The basic chemical aspects of anion receptor design of functional pH independent systems as well as design of separations strategies for selective and efficient removal of targeted anions have been probed. Key findings include: (1) some of the first synthetic sulfate-selective anion-binding agents; (2) simple, structure-based methods for modifying the intrinsic anion selectivity of a given class of anion receptors; and (3) the first system capable of extracting sulfate from acidic, nitrate-containing aqueous media. Receptor design, structural influences on anion binding affinities, and findings from liquid-liquid extraction studies will be discussed

  12. NMR studies of Na+-anion association effects in polymer electrolytes

    International Nuclear Information System (INIS)

    Greenbaum, S.G.; Pak, Y.S.; Wintergill, M.C.; Fontanella, J.J.

    1988-01-01

    23 Na nuclear magnetic resonance (NMR) measurements on poly (propylene oxide) (PPO) and siloxane based polymer electrolytes containing various sodium salts at a single nominal concentration are reported. In addition, differential scanning calorimetry (DSC) and electrical conductivity studies were carried out on the PPO materials. The NMR-determined mobile Na + concentrations and DSC results provide evidence for ionic aggregation effects which, for some samples, result in salt precipitation at elevated temperatures. 23 Na chemical shifts observed in solid state NMR due to mobile Na + -anion interactions influence ionic transport as well as the number of available carriers. (author). 19 refs.; 7 figs

  13. Low energy electron attachment to cyanamide (NH{sub 2}CN)

    Energy Technology Data Exchange (ETDEWEB)

    Tanzer, Katrin; Denifl, Stephan, E-mail: Andrzej.Pelc@poczta.umcs.lublin.pl, E-mail: Stephan.Denifl@uibk.ac.at [Institut für Ionenphysik und Angewandte Physik, Leopold Franzens Universität Innsbruck, Technikerstr. 25, 6020 Innsbruck (Austria); Pelc, Andrzej, E-mail: Andrzej.Pelc@poczta.umcs.lublin.pl, E-mail: Stephan.Denifl@uibk.ac.at [Mass Spectrometry Department, Institute of Physics, Marie Curie-Sklodowska University, Pl. M. C.-Sklodowskiej 1, 20-031 Lublin (Poland); Huber, Stefan E. [Institut für Ionenphysik und Angewandte Physik, Leopold Franzens Universität Innsbruck, Technikerstr. 25, 6020 Innsbruck (Austria); Lehrstuhl für Theoretische Chemie, Technische Universität München, Lichtenbergstr. 4, 85747 Garching (Germany); Czupyt, Z. [Ion Microprobe Facility Micro-area Analysis Laboratory, Polish Geological Institute–National Research Institute, Rakowiecka 4, 00-975 Warszawa (Poland)

    2015-01-21

    Cyanamide (NH{sub 2}CN) is a molecule relevant for interstellar chemistry and the chemical evolution of life. In the present investigation, dissociative electron attachment to NH{sub 2}CN has been studied in a crossed electron–molecular beams experiment in the electron energy range from about 0 eV to 14 eV. The following anionic species were detected: NHCN{sup −}, NCN{sup −}, CN{sup −}, NH{sub 2}{sup −}, NH{sup −}, and CH{sub 2}{sup −}. The anion formation proceeds within two broad electron energy regions, one between about 0.5 and 4.5 eV and a second between 4.5 and 12 eV. A discussion of possible reaction channels for all measured negative ions is provided. The experimental results are compared with calculations of the thermochemical thresholds of the anions observed. For the dehydrogenated parent anion, we explain the deviation between the experimental appearance energy of the anion with the calculated corresponding reaction threshold by electron attachment to the isomeric form of NH{sub 2}CN—carbodiimide.

  14. Supramolecular Chemistry of Selective Anion Recognition for Anions of Environmental Relevance

    International Nuclear Information System (INIS)

    Bowman-James, K.; Wilson, G.; Moyer, B. A.

    2004-01-01

    This project involves the design and synthesis of receptors for oxoanions of environmental importance, including emphasis on high level and low activity waste. Target anions have included primarily oxoanions and a study of the basic concepts behind selective binding of target anions. A primary target has been sulfate because of its deleterious influence on the vitrification of tank wastes

  15. Sorption of vanillin on highly basic anion exchanger under static conditions

    Science.gov (United States)

    Sholokhova, A. Yu.; Eliseeva, T. V.; Voronyuk, I. V.

    2017-11-01

    The kinetics of the sorption of vanillin by a granulated anion exchanger is studied under static conditions. A comparison of the kinetic curves of the uptake of hydroxybenzaldehyde by gel and macroporous anion exchanger shows that macroporous sorbent has better kinetic characteristics. The effect temperature has on the capacity of an anion exchanger and the time needed to establish sorption equilibrium is found, and the activation energy of vanillin uptake is determined. Studying the effect experimental factors have on the rate of sorption and using the formal kinetics approach, it is established that in the investigated range of concentrations, the limiting stage of the uptake of vanillin by an anion exchanger with the functional groups of a quaternary ammonium base is that of external diffusion. Vanillin sorption by a highly basic anion exchanger in hydroxyl form is characterized by polymolecular uptake best described by a BET isotherm; at the same time, the uptake of sorbate by a chloride form is of a monomolecular character and can be described by a Freindlich isotherm. Structural changes in the anion exchanger sorbed hydroxybenzaldehyde are identified via FTIR spectroscopy.

  16. Non-iterative triple excitations in equation-of-motion coupled-cluster theory for electron attachment with applications to bound and temporary anions

    Science.gov (United States)

    Jagau, Thomas-C.

    2018-01-01

    The impact of residual electron correlation beyond the equation-of-motion coupled-cluster singles and doubles (EOM-CCSD) approximation on positions and widths of electronic resonances is investigated. To establish a method that accomplishes this task in an economical manner, several approaches proposed for the approximate treatment of triple excitations are reviewed with respect to their performance in the electron attachment (EA) variant of EOM-CC theory. The recently introduced EOM-CCSD(T)(a)* method [D. A. Matthews and J. F. Stanton, J. Chem. Phys. 145, 124102 (2016)], which includes non-iterative corrections to the reference and the target states, reliably reproduces vertical attachment energies from EOM-EA-CC calculations with single, double, and full triple excitations in contrast to schemes in which non-iterative corrections are applied only to the target states. Applications of EOM-EA-CCSD(T)(a)* augmented by a complex absorbing potential (CAP) to several temporary anions illustrate that shape resonances are well described by EOM-EA-CCSD, but that residual electron correlation often makes a non-negligible impact on their positions and widths. The positions of Feshbach resonances, on the other hand, are significantly improved when going from CAP-EOM-EA-CCSD to CAP-EOM-EA-CCSD(T)(a)*, but the correct energetic order of the relevant electronic states is still not achieved.

  17. Stabilization of very rare tautomers of uracil by an excess electron.

    Science.gov (United States)

    Bachorz, Rafał A; Rak, Janusz; Gutowski, Maciej

    2005-05-21

    We characterized valence-type and dipole-bound anionic states of uracil using various electronic structure methods. We found that the most stable anion is related to neither the canonical 2,4-dioxo nor a rare imino-hydroxy tautomer. Instead, it is related to an imino-oxo tautomer, in which the N1H proton is transferred to the C5 atom. This valence anion is characterized by an electron vertical detachment energy (VDE) of 1267 meV and it is adiabatically stable with respect to the canonical neutral by 3.93 kcal mol(-1). It is also more stable by 2.32 and 5.10 kcal mol(-1) than the dipole-bound and valence anion, respectively, of the canonical tautomer. The VDE values for the former and the latter are 73 and 506 meV, respectively. Another, anionic, low-lying imino-oxo tautomer with a VDE of 2499 meV has a proton transferred from N3H to C5. It is less stable than the neutral canonical tautomer by 1.38 kcal mol(-1). The mechanism of formation of anionic tautomers with the carbon C5 protonated may involve intermolecular proton transfer or dissociative electron attachment to the canonical neutral tautomer followed by a barrier-free attachment of a hydrogen atom to C5. The six-member ring structure of anionic tautomers with carbon atoms protonated might be unstable upon an excess electron detachment. Indeed, the neutral systems resulting from electron detachment from anionic tautomers with carbon atoms protonated evolve along barrier-free decomposition pathways to a linear or a bicyclo structure, which might be viewed as lesions to RNA. Within the PCM hydration model, the low-lying valence anions become adiabatically bound with respect to the canonical neutral and the two most stable tautomers have carbon atoms protonated.

  18. Optimum conditions for intercalation of lacunary tungstophosphate(V) anions into layered Ni(II)-Zn(II) hydroxyacetate

    International Nuclear Information System (INIS)

    Ballesteros, M. Angeles; Ulibarri, M. Angeles; Rives, Vicente; Barriga, Cristobalina

    2008-01-01

    Acetate containing nickel-zinc hydroxysalts (LHS-Ni-Zn) have been synthesized by coprecipitation and hydrothermal treatment. The acetate anions were exchanged with PW 12 O 40 3- anions, and optimum conditions to attain the maximum level of W in the compound have been identified. The W intercalated compound was characterized by powder X-ray diffraction, FT-IR spectroscopy, thermogravimetric and differential thermal analyses, scanning electron microscopy and transmission electron microscopy. The exchange of LHS-Ni-Zn with PW 12 O 40 3- at pH=3 for 72 h leads to a solid with a basal spacing of 9.62 A and a W content (weight) of 37%. The hydrothermal treatment at 90 deg. C for 24 h increases this value to 48% with a W/Zn molar ratio of 1.38, which corresponds to a layered compound with lacunary tungstophosphate anions in the interlayer space. The intercalated solid is stable up to 250 deg. C, the layer structure collapses on dehydroxylation and amorphous compounds were identified at 500 deg. C. Two crystalline phases, NiO (rock salt) and a solid solution (Zn 1-x Ni x )WO 4 , were identified by powder X-ray diffraction at high temperature (ca. 1000 deg. C). - Graphical abstract: Optimum conditions for intercalation of Keggin-type anions in Ni, Zn hydroxysalts have been identified. Lacunary species are formed via partial depolymerization of the starting anion. The thermal decomposition of the intercalated phases has been also studied

  19. The Anion Paradox in Sodium Taste Reception: Resolution by Voltage-Clamp Studies

    Science.gov (United States)

    Ye, Qing; Heck, Gerard L.; Desimone, John A.

    1991-11-01

    Sodium salts are potent taste stimuli, but their effectiveness is markedly dependent on the anion, with chloride yielding the greatest response. The cellular mechanisms that mediate this phenomenon are not known. This "anion paradox" has been resolved by considering the field potential that is generated by restricted electrodiffusion of the anion through paracellular shunts between taste-bud cells. Neural responses to sodium chloride, sodium acetate, and sodium gluconate were studied while the field potential was voltage-clamped. Clamping at electronegative values eliminated the anion effect, whereas clamping at electropositive potentials exaggerated it. Thus, field potentials across the lingual epithelium modulate taste reception, indicating that the functional unit of taste reception includes the taste cell and its paracellular microenvironment.

  20. Low energy electron-driven damage in biomolecules

    International Nuclear Information System (INIS)

    Sanche, L.

    2005-01-01

    The damage induced by the impact of low energy electrons (LEE) on biomolecules is reviewed from a radiobiological perspective with emphasis on transient anion formation. The major type of experiments, which measure the yields of fragments produced as a function of incident electron energy (0.1 - 30 eV), are briefly described. Theoretical advances are also summarized. Several examples are presented from the results of recent experiments performed in the gas-phase and on bio-molecular films bombarded with LEE under ultra-high vacuum conditions. These include the results obtained from DNA films and those obtained from the fragmentation of elementary components of the DNA molecule (i.e., the bases, sugar and phosphate group analogs and oligonucleotides) and of proteins (e.g. amino acids). By comparing the results from different experiments and theory, it is possible to determine fundamental mechanisms that are involved in the dissociation of the biomolecules and the production of single- and double-strand breaks in DNA. Below 15 eV, electron resonances (i.e., the formation of transient anions) play a dominant role in the fragmentation of all biomolecules investigated. These transient anions fragment molecules by decaying into dissociative electronically excited states or by dissociating into a stable anion and a neutral radical. These fragments can initiate further reactions within large biomolecules or with nearby molecules and thus cause more complex chemical damage. Dissociation of a transient anion within DNA may occur by direct electron attachment at the location of dissociation or by electron transfer from another subunit. Damage to DNA is dependent on the molecular environment, topology, type of counter ion, sequence context and chemical modifications. (author)

  1. Role of phosphate and other proton-donating anions in respiration-coupled transport of Ca2+ by mitochondria.

    Science.gov (United States)

    Lehninger, A L

    1974-04-01

    Measurements of extra oxygen consumption, (45)Ca(2+) uptake, and the osmotic expansion of the matrix compartment show that not all permeant anions are capable of supporting and accompanying the energy-dependent transport of Ca(2+) from the medium into the matrix in respiring rat-liver mitochondria. Phosphate, arsenate, acetate, butyrate, beta-hydroxybutyrate, lactate, and bicarbonate + CO(2) supported Ca(2+) uptake, whereas the permeant anions, nitrate, thiocyanate, chlorate, and perchlorate, did not. The active anions share a common denominator, the potential ability to donate a proton to the mitochondrial matrix; the inactive anions lack this capacity. Phosphate and the other active permeant anions move into the matrix in response to the alkaline-inside electrochemical gradient of protons generated across the mitochondrial membrane by electron transport, thus forming a negative-inside anion gradient. It is postulated that the latter gradient is the immediate "pulling" force for the influx of Ca(2+) on the electrogenic Ca(2+) carrier in respiring mitochondria under intracellular conditions. Since mitochondria in the cell are normally exposed to an excess of phosphate (and the bicarbonate-CO(2) system), particularly in state 4, inward transport of these proton-yielding anions probably precedes and is necessary for inward transport of Ca(2+) and other cations under biological conditions. These observations indicate that a negative-inside gradient of phosphate generated by electron transport is a common step and provides the immediate motive power not only for (a) the inward transport of dicarboxylates and tricarboxylates and (b) the energy-dependent exchange of external ADP(3-) for internal ATP(4-) during oxidative phosphorylation, as has already been established, but also for (c) the inward transport of Ca(2+), K(+), and other cations.

  2. Self-assembled arene-ruthenium-based rectangles for the selective sensing of multi-carboxylate anions.

    Science.gov (United States)

    Vajpayee, Vaishali; Song, Young Ho; Lee, Min Hyung; Kim, Hyunuk; Wang, Ming; Stang, Peter J; Chi, Ki-Whan

    2011-07-04

    Novel arene-ruthenium [2+2] metalla-rectangles 4 and 5 have been synthesized by self-assembly using dipyridyl amide ligand 3 and arene-ruthenium acceptors (arene: benzoquinone (1), naphthacenedione (2)) and characterized by NMR spectroscopy and ESI-MS. The solid-state structure of 5 was determined by X-ray diffraction and shows encapsulated diethyl ether molecule in the rectangular cavity of 5. The luminescent 5 was further used for anion sensing with the amidic linkage serving as a hydrogen-bond donor site for anions and the ruthenium moiety serving as a signaling unit. A UV/Vis titration study demonstrated that although 5 interacts very weakly with common monoanions as well as with flexible dicarboxylate anions such as malonate and succinate, it displays significant binding affinity (K>10(3) in MeOH) for rigid multi-carboxylate anions such as oxalate, citrate, and tartrate, exhibiting a 1:1 stoichiometry. It has been suggested that 1:1 bidentate hydrogen bonding assisted by appropriate geometrical complementarity is mainly responsible for the increased affinity of 5 towards such anions. A fluorescence titration study revealed a large fluorescence enhancement of 5 upon binding to multi-carboxylate anions, which can be attributed to the blocking of the photoinduced electron-transfer process from the arene-Ru moiety to the amidic donor in 5 as a result of hydrogen bonding between the donor and the anion. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. The effects of anionic and cationic surfactants on the ion flotation of Cd2+

    International Nuclear Information System (INIS)

    Kobayashi, Koichi

    1975-01-01

    The ion flotation of Cd 2+ ions has been investigated from the surface chemical point of view in comparison with the case of Cu 2+ ions reported previously. The effects of the change in the pH, the anionic and cationic surfactants, and bentonite on the flotation rate have also been studied. Sodium α-sulfolaurate proved to be one of the best surfactants among the anionic surfactants used for removing Cd 2+ ions, showing as high as a 97% removal. About 97% of the Cd 2+ ions could be floated in the region of pH 11.3 when a cationic surfactant was used with bentonite, regardless of the exact surfactant used. The addition of bentonite reduced the foam formation and liquid hold-up, resulting in effective bubble flotation. This behavior was as a whole similar to that of Cu 2+ ions. However, in all the flotation systems tested, the flotation rate increased sharply at about pH 8, and the flotation rate vs. pH curve for Cd 2+ shifted towards a more alkaline region than that for Cu 2+ , because of the stronger basic nature of the former. Also, the flotation rate of Cd 2+ ions for the Cd 2+ -anionic surfactant systems attained a steady value after about 7 min, longer than the 2-min gas flow required in the case of Cu 2+ ion flotation. The adjustment of the pH using ammonia gave a lower rate of flotation than in the case of flotation using sodium hydroxide. (auth.)

  4. Anodization of Zr-Nb-Cu alloy in mandelic acid - effect of solvent and anionic impurities

    International Nuclear Information System (INIS)

    Lavanya, A.; Raghunath Reddy, G.; Ch Anjaneyulu

    2004-01-01

    Anodization of zirconium-niobium-copper (ZNC) alloy in 0.1 M mandelic acid has been carried out. The effect of solvent (ethylene glycol) and added anionic impurities (sulphates, phosphates and carbonates) showed better kinetic results (formation rate, current efficiency and differential field of formation). (author)

  5. Methods and systems for measuring anions

    KAUST Repository

    Masih, Dilshad; Mohammed, Omar F.; Aly, Shawkat M.; Alarousu, Erkki

    2016-01-01

    Embodiments of the present disclosure provide for methods for detecting the presence and/or concentration of anions in a solution, systems for detecting the presence and/or concentration of anions in a solution, anion sensor systems, and the like.

  6. Methods and systems for measuring anions

    KAUST Repository

    Masih, Dilshad

    2016-08-18

    Embodiments of the present disclosure provide for methods for detecting the presence and/or concentration of anions in a solution, systems for detecting the presence and/or concentration of anions in a solution, anion sensor systems, and the like.

  7. Reactions induced by low energy electrons in cryogenic films

    International Nuclear Information System (INIS)

    Bass, A.D.; Sanche, L.

    2003-01-01

    We review recent research on reactions (including dissociation) initiated by low-energy electron bombardment of monolayer and multilayer molecular solids at cryogenic temperatures. With incident electrons of energies below 20 eV, dissociation is observed by the electron stimulated desorption (ESD) of anions from target films and is attributed to the processes of dissociative electron attachment (DEA) and to dipolar dissociation. It is shown that DEA to condensed molecules is sensitive to environmental factors such as the identity of co-adsorbed species and film morphology. The effects of image-charge induced polarization on cross-sections for DEA to CH3Cl are also discussed. Taking as examples, the electron-induced production of CO within multilayer films of methanol and acetone, it is shown that the detection of electronic excited states by high resolution electron energy loss spectroscopy can be used to monitor electron beam damage. In particular, the incident energy dependence of the CO indicates that below 19 eV, dissociation proceeds via the decay of transient negative ions (TNI) into electronically excited dissociative states. The electron induced dissociation of biomolecular targets is also considered, taking as examples the ribose analog tetrahydrofuran and DNA bases adenine and thymine, cytosine and guanine. The ESD of anions from such films also show dissociation via the formation of TNI. In multilayer molecular solids, fragment species resulting from dissociation, may react with neighboring molecules, as is demonstrated in anion ESD measurements from films containing O 2 and various hydrocarbon molecules. X-ray photoelectron spectroscopy measurements reported for electron irradiated monolayers of H 2 O and CF 4 on a Si - H passivated surface further show that DEA is an important initial step in the electron-induced chemisorption of fragment species

  8. Phosphazene-promoted anionic polymerization

    KAUST Repository

    Zhao, Junpeng

    2014-01-01

    In the recent surge of metal-free polymerization techniques, phosphazene bases have shown their remarkable potential as organic promoters/catalysts for the anionic polymerization of various types of monomers. By complexation with the counterion (e.g. proton or lithium cation), phosphazene base significantly improve the nucleophilicity of the initiator/chain-end resulting in rapid and usually controlled anionic/quasi-anionic polymerization. In this review, we will introduce the general mechanism, i.e. in situ activation (of initiating sites) and polymerization, and summarize the applications of such a mechanism on macromolecular engineering toward functionalized polymers, block copolymers and complex macromolecular architectures.

  9. Preparation of Two-Layer Anion-Exchange Poly(ethersulfone Based Membrane: Effect of Surface Modification

    Directory of Open Access Journals (Sweden)

    Lucie Zarybnicka

    2016-01-01

    Full Text Available The present work deals with the surface modification of a commercial microfiltration poly(ethersulfone membrane by graft polymerization technique. Poly(styrene-co-divinylbenzene-co-4-vinylbenzylchloride surface layer was covalently attached onto the poly(ethersulfone support layer to improve the membrane electrochemical properties. Followed by amination, a two-layer anion-exchange membrane was prepared. The effect of surface layer treatment using the extraction in various solvents on membrane morphological and electrochemical characteristics was studied. The membranes were tested from the point of view of water content, ion-exchange capacity, specific resistance, permselectivity, FT-IR spectroscopy, and SEM analysis. It was found that the two-layer anion-exchange membranes after the extraction using tetrahydrofuran or toluene exhibited smooth and porous surface layer, which resulted in improved ion-exchange capacity, electrical resistance, and permselectivity of the membranes.

  10. Carbon Chain Anions and the Growth of Complex Organic Molecules in Titan’s Ionosphere

    Energy Technology Data Exchange (ETDEWEB)

    Desai, R. T.; Coates, A. J.; Wellbrock, A.; González-Caniulef, D.; Jones, G. H.; Lewis, G. R.; Taylor, S. A.; Kataria, D. O. [Mullard Space Science Laboratory, University College London, Holmbury St. Mary, Surrey RH5 6NT (United Kingdom); Vuitton, V. [Université Grenoble Alpes, CNRS, IPAG, F-38000 Grenoble (France); Crary, F. J. [Laboratory for Atmospheric and Space Physics, University of Colorado, Innovation Drive, Boulder, CO 80303 (United States); Shebanits, O.; Wahlund, J.-E. [Department of Physics and Astronomy, Uppsala University, Box 516, SE-751 20 Uppsala (Sweden); Waite, J. H. [Space Science and Engineering Division, Southwest Research Institute (SWRI), 6220 Culebra Road, San Antonio, TX 78238 (United States); Cordiner, M.; Sittler, E. C. [NASA Goddard Space Flight Center, 8800 Greenbelt Road, Greenbelt, MD 20771 (United States); Edberg, N. J. T., E-mail: r.t.desai@ucl.ac.uk [Swedish Institute of Space Physics, Box 537, SE-751 21 Uppsala (Sweden)

    2017-08-01

    Cassini discovered a plethora of neutral and ionized molecules in Titan’s ionosphere including, surprisingly, anions and negatively charged molecules extending up to 13,800 u q{sup −1}. In this Letter, we forward model the Cassini electron spectrometer response function to this unexpected ionospheric component to achieve an increased mass resolving capability for negatively charged species observed at Titan altitudes of 950–1300 km. We report on detections consistently centered between 25.8 and 26.0 u q{sup −1} and between 49.0–50.1 u q{sup −1} which are identified as belonging to the carbon chain anions, CN{sup −}/C{sub 3}N{sup −} and/or C{sub 2}H{sup −}/C{sub 4}H{sup −}, in agreement with chemical model predictions. At higher ionospheric altitudes, detections at 73–74 u q{sup −1} could be attributed to the further carbon chain anions C{sub 5}N{sup −}/C{sub 6}H{sup −} but at lower altitudes and during further encounters extend over a higher mass/charge range. This, as well as further intermediary anions detected at >100 u, provide the first evidence for efficient anion chemistry in space involving structures other than linear chains. Furthermore, at altitudes below <1100 km, the low-mass anions (<150 u q{sup −1}) were found to deplete at a rate proportional to the growth of the larger molecules, a correlation that indicates the anions are tightly coupled to the growth process. This study adds Titan to an increasing list of astrophysical environments where chain anions have been observed and shows that anion chemistry plays a role in the formation of complex organics within a planetary atmosphere as well as in the interstellar medium.

  11. Carbon Chain Anions and the Growth of Complex Organic Molecules in Titan’s Ionosphere

    International Nuclear Information System (INIS)

    Desai, R. T.; Coates, A. J.; Wellbrock, A.; González-Caniulef, D.; Jones, G. H.; Lewis, G. R.; Taylor, S. A.; Kataria, D. O.; Vuitton, V.; Crary, F. J.; Shebanits, O.; Wahlund, J.-E.; Waite, J. H.; Cordiner, M.; Sittler, E. C.; Edberg, N. J. T.

    2017-01-01

    Cassini discovered a plethora of neutral and ionized molecules in Titan’s ionosphere including, surprisingly, anions and negatively charged molecules extending up to 13,800 u q"−"1. In this Letter, we forward model the Cassini electron spectrometer response function to this unexpected ionospheric component to achieve an increased mass resolving capability for negatively charged species observed at Titan altitudes of 950–1300 km. We report on detections consistently centered between 25.8 and 26.0 u q"−"1 and between 49.0–50.1 u q"−"1 which are identified as belonging to the carbon chain anions, CN"−/C_3N"− and/or C_2H"−/C_4H"−, in agreement with chemical model predictions. At higher ionospheric altitudes, detections at 73–74 u q"−"1 could be attributed to the further carbon chain anions C_5N"−/C_6H"− but at lower altitudes and during further encounters extend over a higher mass/charge range. This, as well as further intermediary anions detected at >100 u, provide the first evidence for efficient anion chemistry in space involving structures other than linear chains. Furthermore, at altitudes below <1100 km, the low-mass anions (<150 u q"−"1) were found to deplete at a rate proportional to the growth of the larger molecules, a correlation that indicates the anions are tightly coupled to the growth process. This study adds Titan to an increasing list of astrophysical environments where chain anions have been observed and shows that anion chemistry plays a role in the formation of complex organics within a planetary atmosphere as well as in the interstellar medium.

  12. o-Iminobenzosemiquinonate and o-imino-p-methylbenzosemiquinonate anion radicals coupled VO2+ stabilization.

    Science.gov (United States)

    Roy, Amit Saha; Saha, Pinaki; Adhikary, Nirmal Das; Ghosh, Prasanta

    2011-03-21

    complexes are unstable with respect to triplet perturbations. But BS (1,1) M(s) = 0 (VO(2+)-iminobenzosemiquinonate anion radical (L(R)(IS)(•-)) coordination) solutions of these species are stable and reproduce the experimental bond parameters well. Spin density distributions of one electron oxidized cations are consistent with the [(L(-))(VO(2+))(L(R)(IQ))](+) descriptions [VO(2+)-o-iminobenzoquinone (L(R)(IQ)) coordination], and one electron reduced anions are consistent with the [(L(•2-))(VO(3+))(L(R)(AP)(2-))](-) descriptions [VO(3+)-amidophenolato (L(R)(AP)(2-)) coordination], incorporating the diimine anion radical (L(1)(•2-)) or azo anion radical (L(2)(3-)). Although, cations and anions are not isolable, but electro-and spectro-electrochemical experiments have shown that 3(+) and 3(-) ions are more stable than 1(+), 2(+) and 1(-), 2(-) ions. In all cases, the reductions occur with simultaneous two electron transfer, may be due to formation of coupled diimine/azo anion radical-VO(2+) species as in [(L(•2-))(VO(2+))(L(R)(AP)(2-))](2-).

  13. Organic anion and cation transport in vitro by dog choroid plexus: Effects of neuroleptics and tricyclic antidepressants

    Energy Technology Data Exchange (ETDEWEB)

    Barany, E H [Uppsala Univ. (Sweden)

    1979-01-01

    Dog lateral choroid plexus accumulates the cation /sup 14/C-emepronium and the divalent anion /sup 125/I-iodipamide in vitro. At 10 ..mu..M, high potency neuroleptics with a substituted piperazine side chain and also haloperidol depress only the uptake of the cation and even stimulate the uptake of the anion. In contrast, at 1-10..mu..M, the accumulation of both test substances is inhibited by neuroleptics and tricyclic antidepresssants with an aliphatic side chain. Such unspecific effects on seemingly unrelated transport systems at concentrations reached clinically in the CSF might explain some side actions of low potency neuroleptics and antidepressants.

  14. In Situ formation of pentafluorophosphate benzimidazole anion stabilizes high-temperature performance of lithium-ion batteries

    International Nuclear Information System (INIS)

    Pradanawati, Sylvia Ayu; Wang, Fu-Ming; Rick, John

    2014-01-01

    Highlights: • A new pentafluorophosphate benzimidazole anion was formed by Lewis acid-base reaction. • This pentafluorophosphate benzimidazole anion is fabricated with the benzimidazole anion and PF 5 . • This pentafluorophosphate benzimidazole anion avoids the ominous side reactions that PF 5 reacts SEI to form LiF and HF at high temperature. • The additional pentafluorophosphate benzimidazole anion formation well maintains the battery performance at 60 °C measurement compares to the electrolyte only with contains the salt, LiPF 6 . - Abstract: Lithium salts play a critical role in initiating electrochemical reactions in Li-ion batteries. Single Li ions dissociate from bulk-salt and associate with carbonates to form a solid electrolyte interface (SEI) during the first charge-discharge of the battery. SEI formation and the chemical stability of salt must both be controlled and optimized to minimize irreversible reactions in SEI formation and to suppress the decomposition of the salt at high temperatures. This study synthesizes a new benzimidazole-based anion in the electrolyte. This anion, pentafluorophosphate benzimidazole, results from a Lewis acid-base reaction between the benzimidazole anion and PF 5 . The new pentafluorophosphate benzimidazole anion inhibits the decomposition of LiPF 6 by inhibiting PF 5 side reactions, which degrade the SEI, and lead to the formation of LiF and HF at high temperatures. In addition, the use of the pentafluorophosphate benzimidazole anion results in the formation of a modified SEI that is able to modify the battery's performance. Cyclic voltammetry, scanning electron microscopy, differential scanning calorimetry, electrochemical impedance spectroscopy, as well as charge-discharge and X-ray photoelectron spectroscopy measurements have been used to characterize the materials in this study. The formation of the pentafluorophosphate benzimidazole anion in the electrolyte caused a 14% decrease in the activation energy

  15. Anion-π Catalysts with Axial Chirality.

    Science.gov (United States)

    Wang, Chao; Matile, Stefan

    2017-09-04

    The idea of anion-π catalysis is to stabilize anionic transition states by anion-π interactions on aromatic surfaces. For asymmetric anion-π catalysis, π-acidic surfaces have been surrounded with stereogenic centers. This manuscript introduces the first anion-π catalysts that operate with axial chirality. Bifunctional catalysts with tertiary amine bases next to π-acidic naphthalenediimide planes are equipped with a bulky aromatic substituent in the imide position to produce separable atropisomers. The addition of malonic acid half thioesters to enolate acceptors is used for evaluation. In the presence of a chiral axis, the selective acceleration of the disfavored but relevant enolate addition was much better than with point chirality, and enantioselectivity could be observed for the first time for this reaction with small-molecule anion-π catalysts. Enantioselectivity increased with the π acidity of the π surface, whereas the addition of stereogenic centers around the aromatic plane did not cause further improvements. These results identify axial chirality of the active aromatic plane generated by atropisomerism as an attractive strategy for asymmetric anion-π catalysis. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Electron transfer reactions of ruthenium(II) complexes with polyphenolic acids in micelles

    Energy Technology Data Exchange (ETDEWEB)

    Rajeswari, Angusamy [School of Chemistry, Madurai Kamaraj University, Madurai 625 021 (India); Department of Chemistry, Fatima College, Madurai 625 018 (India); Ramdass, Arumugam [School of Chemistry, Madurai Kamaraj University, Madurai 625 021 (India); Research Department of Chemistry, Aditanar College of Arts and Science, Tiruchendur 628 216 (India); Muthu Mareeswaran, Paulpandian [School of Chemistry, Madurai Kamaraj University, Madurai 625 021 (India); Department of Industrial Chemistry, Alagappa University, Karaikudi 630 003 (India); Rajagopal, Seenivasan, E-mail: rajagopalseenivasan@yahoo.com [School of Chemistry, Madurai Kamaraj University, Madurai 625 021 (India)

    2016-02-15

    The electron transfer in a microhetrogeneous system is a perfect mimic of biological electron transfer. The electron transfer between biologically important phenolic acids and ruthenium (II) complexes is systematically studied in the presence of anionic and cationic micelles. The photophysical properties of these ruthenium (II) complexes with anionic and cationic micelles and their binding abilities with these two type of micelles are also studies using absorption, emission and excited state lifetime spectral techniques. Pseudophase Ion Exchange (PIE) Model is applied to derive mechanism of electron transfer in two types of micelles. - Highlights: • Effect of microhetrogeneous system is studied using ruthenium (II) complexes and gallic acid is studied. • Pseudophase Ion exchange model is applied to derive the mechanism. • Binding constants are in the range of 10{sup 2}–10{sup 4} M{sup −1}.

  17. Creating molecular macrocycles for anion recognition

    Directory of Open Access Journals (Sweden)

    Amar H. Flood

    2016-03-01

    Full Text Available The creation and functionality of new classes of macrocycles that are shape persistent and can bind anions is described. The genesis of triazolophane macrocycles emerges out of activity surrounding 1,2,3-triazoles made using click chemistry; and the same triazoles are responsible for anion capture. Mistakes made and lessons learnt in anion recognition provide deeper understanding that, together with theory, now provides for computer-aided receptor design. The lessons are acted upon in the creation of two new macrocycles. First, cyanostars are larger and like to capture large anions. Second is tricarb, which also favors large anions but shows a propensity to self-assemble in an orderly and stable manner, laying a foundation for future designs of hierarchical nanostructures.

  18. Anion-π aromatic neutral tweezers complexes: are they stable in polar solvents?

    Science.gov (United States)

    Sánchez-Lozano, Marta; Otero, Nicolás; Hermida-Ramón, Jose M; Estévez, Carlos M; Mandado, Marcos

    2011-03-17

    The impact of the solvent environment on the stabilization of the complexes formed by fluorine (T-F) and cyanide (T-CN) substituted tweezers with halide anions has been investigated theoretically. The study was carried out using computational methodologies based on density functional theory (DFT) and symmetry adapted perturbation theory (SAPT). Interaction energies were obtained at the M05-2X/6-31+G* level. The obtained results show a large stability of the complexes in solvents with large dielectric constant and prove the suitability of these molecular tweezers as potential hosts for anion recognition in solution. A detailed analysis of the effects of the solvent on the electron withdrawing ability of the substituents and its influence on the complex stability has been performed. In particular, the interaction energy in solution was split up into intermonomer and solvent-complex terms. In turn, the intermonomer interaction energy was partitioned into electrostatic, exchange, and polarization terms. Polar resonance structures in T-CN complexes are favored by polar solvents, giving rise to a stabilization of the intermonomer interaction, the opposite is found for T-F complexes. The solvent-complex energy increases with the polarity of the solvent in T-CN complexes, nonetheless the energy reaches a maximum and then decreases slowly in T-F complexes. An electron density analysis was also performed before and after complexation, providing an explanation to the trends followed by the interaction energies and their different components in solution.

  19. The influence of channel anion identity on the high-pressure crystal structure, compressibility, and stability of apatite

    Science.gov (United States)

    Skelton, Richard; Walker, Andrew M.

    2018-03-01

    The material properties of the common phosphate mineral apatite are influenced by the identity of the channel anion, which is usually F-, Cl-, or (OH)-. Density functional theory calculations have been used to determine the effect of channel anion identity on the compressibility and structure of apatite. Hydroxyapatite and fluorapatite are found to have similar zero pressure bulk moduli, of 79.2 and 82.1 GPa, respectively, while chlorapatite is considerably more compressible, with K 0 = 55.0 GPa. While the space groups of hydroxyapatite and fluorapatite do not change between 0 and 25 GPa, symmetrization of the Cl- site in chlorapatite at 7.5 GPa causes the space group to change from P2 1 /b to P6 3 /m. Examination of the valence electron density distribution in chlorapatite reveals that this symmetry change is associated with a change in the coordination of the Cl- anion from threefold to sixfold coordinated by Ca. We also calculate the pressure at which apatite decomposes to form tuite, a calcium orthophosphate mineral, and find that the transition pressure is sensitive to the identity of the channel anion, being lowest for fluorapatite (13.8 GPa) and highest for chlorapatite (26.9 GPa). Calculations are also performed within the DFT-D2 framework to investigate the influence of dispersion forces on the compressibility of apatite minerals.

  20. Thermoluminescent and dosimetric properties of anion-defective a-Al2O3 single crystals with filled deep traps

    International Nuclear Information System (INIS)

    Kortov, V.S.; Milman, I.I.; Nikiforov, S.V.

    2002-01-01

    Some new experimental results illustrating the effect of deep traps on luminescent and dosimetric properties of anion-defective single crystals of a-Al 2 O 3 have been described. It was found that deep traps had an electronic origin. They were filled thanks to the photoionisation of F-centres and their filling was accompanied by the conversion of FF+ centres. The experiments revealed an interactive interaction of deep trapping centres. A model taking into account the thermal ionisation of excited states of F-centres was proposed. This model describes the trap filling process and mechanisms of the radio-, photo- and thermoluminescence, TSC and TSEE of the crystals under study. The sensitivity of TLD-500 detectors based on anion-defective a-Al 2 O 3 equalised when deep trapping centres were filled. (author)

  1. Zeolite-like Metal–Organic Framework (MOF) Encaged Pt(II)-Porphyrin for Anion-Selective Sensing

    KAUST Repository

    Masih, Dilshad

    2018-03-26

    The selectivity and sensitivity of sensors are of great interest to the materials chemistry community, and a lot of effort is now devoted to improving these characteristics. More specifically, the selective sensing of anions is one of the largest challenges impeding the sensing-research area due to their similar physical and chemical behaviors. In this work, platinum–metalated porphyrin (Pt(II)TMPyP) was successfully encapsulated in a rho-type zeolite-like metal–organic framework (rho-ZMOF) and applied for anion-selective sensing. The sensing activity and selectivity of the MOF-encaged Pt(II)TMPyP for various anions in aqueous and methanolic media were compared to that of the free (nonencapsulated) Pt(II)TMPyP. While the photoinduced triplet-state electron transfer of Pt(II)TMPyP showed a very low detection limit for anions with no selectivity, the Pt(II)TMPyP encapsulated in the rho-ZMOF framework possessed a unique chemical structure to overcome such limitations. This new approach has the potential for use in other complex sensing applications, including biosensors, which require ion selectivity.

  2. Stabilization of very rare tautomers of 1-methylcytosine by an excess electron.

    Science.gov (United States)

    Harańczyk, Maciej; Rak, Janusz; Gutowski, Maciej

    2005-12-22

    We characterized valence anionic states of 1-methylcytosine using various electronic structure methods. We found that the most stable valence anion is related to neither the canonical amino-oxo nor a rare imino-oxo tautomer, in which a proton is transferred from the N4 to N3 atom. Instead, it is related to an imino-oxo tautomer, in which the C5 atom is protonated. This anion is characterized by an electron vertical detachment energy (VDE) of 2.12 eV and it is more stable than the anion based on the canonical tautomer by 1.0 kcal/mol. The latter is characterized by a VDE of 0.31 eV. Another unusual low-lying imino-oxo tautomer with a VDE of 3.60 eV has the C6 atom protonated and is 3.6 kcal/mol less stable than the anion of the canonical tautomer. All these anionic states are adiabatically unbound with respect to the canonical amino-oxo neutral, with the instability of 5.8 kcal/mol for the most stable valence anion. The mechanism of formation of anionic tautomers with carbon atoms protonated may involve intermolecular proton transfer or dissociative electron attachment to the canonical neutral tautomer followed by a barrier-free attachment of a hydrogen atom to the C5 or C6 atom. The six-member ring structure of anionic tautomers with carbon atoms protonated is unstable upon an excess electron detachment. Indeed the neutral systems collapse without a barrier to a linear or a bicyclo structure, which might be viewed as lesions to DNA or RNA. Within the PCM hydration model, the anions become adiabatically bound with respect to the corresponding neutrals, and the two most stable tautomers have a carbon atom protonated.

  3. Cell wall bound anionic peroxidases from asparagus byproducts.

    Science.gov (United States)

    Jaramillo-Carmona, Sara; López, Sergio; Vazquez-Castilla, Sara; Jimenez-Araujo, Ana; Rodriguez-Arcos, Rocio; Guillen-Bejarano, Rafael

    2014-10-08

    Asparagus byproducts are a good source of cationic soluble peroxidases (CAP) useful for the bioremediation of phenol-contaminated wastewaters. In this study, cell wall bound peroxidases (POD) from the same byproducts have been purified and characterized. The covalent forms of POD represent >90% of the total cell wall bound POD. Isoelectric focusing showed that whereas the covalent fraction is constituted primarily by anionic isoenzymes, the ionic fraction is a mixture of anionic, neutral, and cationic isoenzymes. Covalently bound peroxidases were purified by means of ion exchange chromatography and affinity chromatography. In vitro detoxification studies showed that although CAP are more effective for the removal of 4-CP and 2,4-DCP, anionic asparagus peroxidase (AAP) is a better option for the removal of hydroxytyrosol (HT), the main phenol present in olive mill wastewaters.

  4. Anion concurrence and anion selectivity in the sorption of radionuclides by organotones

    International Nuclear Information System (INIS)

    Behnsen, Julia G.

    2007-01-01

    Some long-lived and radiologically important nuclear fission products, such as I-129 (half-life t 1/2 = 1,6 . 10 7 a), Tc-99 (t 1/2 = 2,1 . 10 5 a), and Se-79 (t 1/2 = 6,5 . 10 4 a) are anionic in aqueous environments. This study focuses on the adsorption of such anions to organoclays and the understanding of the selectivity of the process. The organoclays used in this study were prepared from a bentonite (MX-80) and a vermiculite clay, and the cationic surfactants hexadcylpyridium, hexadecyltrimethylammonium, and benzethonium. Surfactant adsorption to the bentonite exceeds the cation exchange capacity of the clay, with the surplus positive charge being balanced by the co-adsorption of chloride. The interlayer distance of the bentonites is increased sufficiently to contain bi- and pseudotrimolecular structures of the surfactants. Adsorption experiments were carried out using the batch technique. Anion adsorption of iodide, perrhenate, selenite, nitrate, and sulphate is mainly due to ion exchange with chloride. As an additional adsorption mechanism, the incorporation of inorganic ion pairs into the interlayer space of the clay is proposed as a result of experiments showing differences in the adsorption levels of sodium and potassium iodide. Anion adsorption results show a clear selectivity of the organoclays, with the affinity sequence being: ReO - 4 > I - > NO - 3 > Cl - > SO 2- 4 > SeO 2- 3 . This sequence corresponds to the sequence of increasing hydration energies of the anions, thus selectivity could be due to the process of minimization of free energy of the system. (orig.)

  5. Dynamics of anion exchange of lanthanides in aqueous-organic complexing media

    International Nuclear Information System (INIS)

    Sheveleva, I.V.; Bogatyrev, I.O.

    1987-01-01

    Effect of organic solvents (ethanol, acetone, acetonitrile) on change in kinetic parameters of the anion exchange process (anion-exchange column chromatography) of r.e.e. (europium and gadolinium) in complexing nitric acid media has been studied. It is established that complex LnA 4 anion is the only sorbing form of europium and gadolinium on anionite. When the organic component content of the solution being the same, the dynamic parameters of lanthanide exchange have higher values in aqueous-acetonitrile and aqueous-acetone media in comparison with aqueous-enthanol solutions of nitric acid. Lesser mobility of complex lanthanide anions in aqueous-alcoholic solutions can be explained by stronger solvation in the presence of solvents with higher acceptor properties

  6. Water permeation through anion exchange membranes

    Science.gov (United States)

    Luo, Xiaoyan; Wright, Andrew; Weissbach, Thomas; Holdcroft, Steven

    2018-01-01

    An understanding of water permeation through solid polymer electrolyte (SPE) membranes is crucial to offset the unbalanced water activity within SPE fuel cells. We examine water permeation through an emerging class of anion exchange membranes, hexamethyl-p-terphenyl poly (dimethylbenzimidazolium) (HMT-PMBI), and compare it against series of membrane thickness for a commercial anion exchange membrane (AEM), Fumapem® FAA-3, and a series of proton exchange membranes, Nafion®. The HMT-PMBI membrane is found to possess higher water permeabilities than Fumapem® FAA-3 and comparable permeability than Nafion (H+). By measuring water permeation through membranes of different thicknesses, we are able to decouple, for the first time, internal and interfacial water permeation resistances through anion exchange membranes. Permeation resistances on liquid/membrane interface is found to be negligible compared to that for vapor/membrane for both series of AEMs. Correspondingly, the resistance of liquid water permeation is found to be one order of magnitude smaller compared to that of vapor water permeation. HMT-PMBI possesses larger effective internal water permeation coefficient than both Fumapem® FAA-3 and Nafion® membranes (60 and 18% larger, respectively). In contrast, the effective interfacial permeation coefficient of HMT-PMBI is found to be similar to Fumapem® (±5%) but smaller than Nafion®(H+) (by 14%).

  7. Synthesis and prospective study of the use of thiophene thiosemicarbazones as signalling scaffolding for the recognition of anions

    OpenAIRE

    Raposo, M. Manuela M.; García-Acosta, Beatriz; Ábalos, Tatiana; Calero, P.; Martínez-Máñez, Ramón; Ros-Lis, José Vicente; Soto, Juan

    2010-01-01

    A family of phenyl-thiosemicarbazone dyes have been prepared and their interactions with anions monitorized via UV-Vis, fluorescence and 1H NMR titrations. Additionally quantum chemical calculations and electrochemical studies completed the studies carried out. The phenyl-thiosemicarbazone dyes show a modulation of their hydrogen-bonding and electron-donating capabilities as a function of the chemical groups attached and display two different chromo-fluorogenic responses towards anions in ace...

  8. Simultaneous anion and cation mobility in polypyrrole

    DEFF Research Database (Denmark)

    Skaarup, Steen; Bay, Lasse; Vidanapathirana, K.

    2003-01-01

    and the expulsion of anions; a broad anodic peak centered at ca. - 0.5 V representing the expulsion of cations; and a second broad peak at +0.2 to +0.5 V corresponding to anions being inserted. Although the motion of cations is the most important, as expected, there is a significant anion contribution, thereby...... complicating reproducibility when employing PPy(DBS) polymers as actuators. When the cation is doubly charged, it enters the film less readily, and anions dominate the mobility. Using a large and bulky cation switches the mechanism to apparently total anion motion. The changes in area of the three peaks...

  9. Substrate dependence of electron-stimulated O - yields from dissociative electron attachment to physisorbed O2

    Science.gov (United States)

    Huels, M. A.; Parenteau, L.; Sanche, L.

    1994-03-01

    We present measurements of O- electron stimulated desorption yields obtained under identical experimental conditions from 0.15 monolayers (ML) of O2 deposited onto disordered substrates consisting of 4 ML of either Kr, Xe, C2H6, C2H4, N2O, CH3Cl, or H2O, all condensed on Pt (polycrystalline). The resulting O- yield functions, for incident electron energies below 20 eV, are compared to that obtained from the O2/Kr solid; this allows us to assess the order of magnitude effects of the local substrate environment on dissociative electron attachment (DEA) via the 2Πu and gas phase forbidden 2Σ+g,u resonances of O-2. We note that, in addition to electron energy losses in the substrate prior to DEA to O2 and post-dissociation interactions of the O- with the substrate molecules, charge or energy transfer from the O-2 transient anion to a substrate molecule, and capture of the incident electron into a dissociative anion resonance of the substrate molecule may contribute to a reduced O- yield from the physisorbed O2. In the case of O2 deposited on amorphous ice, we find that the O- signal from DEA to O2 is completely absent for electron energies below 14 eV; we attribute this to a complete quenching of the dissociative O-2(2Πu, 2Σ+) resonances by the adjacent water molecules.

  10. A Study of Picosecond Dehalogenation of Chlorobenzene Anions in Liquids of Positronium Inhibition Measurements

    DEFF Research Database (Denmark)

    Wikander, G.; Mogensen, O. E.

    1982-01-01

    on intramolecular electron transfer with subsequent dehalogenation of the molecular anion on a picosecond timescale. The divergence in inhibitor efficiency obtained for the chlorobenzenes when dissolved in aromatic solvents compared to the same solutes when dissolved in a saturated alkane appears most probably...

  11. A highly sensitive and selective fluorescent sensor for detection of sulfide anion based on the steric hindrance effect

    Science.gov (United States)

    Chen, Guanfan; Tang, Mengzhuo; Fu, Xiufang; Cheng, Fenmin; Zou, Xianghua; Wang, Jingpei; Zeng, Rongjin

    2018-01-01

    Sulfide anions are not only generated as a byproduct from industrial processes but also as a crucial kind of element in biological systems. Therefore, fluorescent probes for detecting sulfide anion with sensitive and selective characters are highly popular. In this study, we report a highly sensitive and selective fluorescent sensor M1 for detection of sulfide anion based on the steric hindrance effect, where the recognition unit, dinitrobenzenesulfonate ester group is linked to aromatic ortho-position in the porphyrin, and correspondingly the fluorescence of fluorescein is efficiently quenched. Compared with the sensors with recognition unit linked to the other aromatic positions, the fluorescent sensor M1 has a lower fluorescence background. Furthermore, the corresponding fluorescence responses (F/F0) of M1 for mercapto amino-acid GSH, Hcy and Cys, were all far lower than the relative fluorescence ratio F/F0 values for S2-. It means that M1 is sensitive and selective to detection of S2-, and has an anti-disturbance ability to the biologically-relevant thiols, GSH, Hcy and Cys, and has the prospect of application in the exact detection of sulfide anions in living organisms. This approach offers some useful insights for realizing sensitive and selective fluorescent turn-on sensing in the detection assays for other analytes.

  12. Electron attachment to indole and related molecules

    Energy Technology Data Exchange (ETDEWEB)

    Modelli, Alberto, E-mail: alberto.modelli@unibo.it [Dipartimento di Chimica “G. Ciamician”, Universitá di Bologna, via Selmi 2, 40126 Bologna (Italy); Centro Interdipartimentale di Ricerca in Scienze Ambientali (CIRSA), Universitá di Bologna, via S. Alberto 163, 48123 Ravenna (Italy); Jones, Derek, E-mail: d.jones@isof.cnr.it [ISOF, Istituto per la Sintesi Organica e la Fotoreattività, C.N.R., via Gobetti 101, 40129 Bologna (Italy); Pshenichnyuk, Stanislav A., E-mail: sapsh@anrb.ru [Institute of Molecule and Crystal Physics, Ufa Research Centre, Russian Academy of Sciences, Prospekt Oktyabrya 151, 450075 Ufa (Russian Federation)

    2013-11-14

    Gas-phase formation of temporary negative ion states via resonance attachment of low-energy (0–6 eV) electrons into vacant molecular orbitals of indoline (I), indene (II), indole (III), 2-methylen-1,3,3-trimethylindoline (IV), and 2,3,3-trimethyl-indolenine (V) was investigated for the first time by electron transmission spectroscopy (ETS). The description of their empty-level structures was supported by density functional theory and Hartree-Fock calculations, using empirically calibrated linear equations to scale the calculated virtual orbital energies. Dissociative electron attachment spectroscopy (DEAS) was used to measure the fragment anion yields generated through dissociative decay channels of the parent molecular anions of compounds I-V, detected with a mass filter as a function of the incident electron energy in the 0–14 eV energy range. The vertical and adiabatic electron affinities were evaluated at the B3LYP/6-31+G(d) level as the anion/neutral total energy difference. The same theoretical method is also used for evaluation of the thermodynamic energy thresholds for production of the negative fragments observed in the DEA spectra. The loss of a hydrogen atom from the parent molecular anion ([M-H]{sup −}) provides the most intense signal in compounds I-IV. The gas-phase DEAS data can provide support for biochemical reaction mechanisms in vivo involving initial hydrogen abstraction from the nitrogen atom of the indole moiety, present in a variety of biologically important molecules.

  13. Preparation of high-capacity, weak anion-exchange membranes by surface-initiated atom transfer radical polymerization of poly(glycidyl methacrylate) and subsequent derivatization with diethylamine

    International Nuclear Information System (INIS)

    Qian, Xiaolei; Fan, Hua; Wang, Chaozhan; Wei, Yinmao

    2013-01-01

    Ion-exchange membrane is of importance for the development of membrane chromatography. In this work, a high-capacity anion-exchange membrane was prepared by grafting of glycidyl methacrylate (GMA) onto the surface of regenerated cellulose (RC) membranes via surface-initiated atom transfer radical polymerization (SI-ATRP) and subsequent derivatization with diethylamine. Attenuated total reflectance Fourier-transform infrared (ATR-FTIR), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) were used to characterize changes in the chemical functionality, surface topography and pore morphology of the modified membranes. The static capacity of the prepared anion-exchange membrane was evaluated with bovine serum albumin (BSA) as a model protein. The results indicated that the anion-exchange membrane which could reach a maximum capacity of 96 mg/mL for static adsorption possesses a higher adsorption capacity, and the adsorption capacity increases with the polymerization time. The effect of pH and salt concentration confirmed that the adsorption of BSA followed ion-exchange mechanism. The established method would have potential application in the preparation of anion-exchange membrane.

  14. [Effect of simulated inorganic anion leaching solution of electroplating sludge on the bioactivity of Acidithiobacillus ferrooxidans].

    Science.gov (United States)

    Chen, Yan; Huang, Fang; Xie, Xin-Yuan

    2014-04-01

    An Acidithiobacillus ferrooxidans strain WZ-1 (GenBank sequence number: JQ968461) was used as the research object. The effects of Cl-, NO3-, F- and 4 kinds of simulated inorganic anions leaching solutions of electroplating sludge on the bioactivity of Fe2+ oxidation and apparent respiratory rate of WZ-1 were investigated. The results showed that Cl-, NO3(-)- didn't have any influence on the bioactivity of WZ-1 at concentrations of 5.0 g x L(-1), 1.0 g x L(-1), respectively. WZ-1 showed tolerance to high levels of Cl- and NO3- (about 10.0 g x L(-1), 5.0 g x L(-1), respectively), but it had lower tolerance to F- (25 mg x L(-1)). Different kinds of simulated inorganic anions leaching solutions of electroplating sludge had significant differences in terms of their effects on bioactivity of WZ-1 with a sequence of Cl-/NO3(-)/F(-) > or = NO3(-)/F(-) > Cl-/F(-) > Cl(-)/NO3(-).

  15. Theoretical study of structure and electronic properties of cyano-substituted pyrroles

    International Nuclear Information System (INIS)

    Rimarcik, Jan; Lukes, Vladimir; Klein, Erik; Griesser, Markus; Kelterer, Anne-Marie

    2008-01-01

    DFT and ab initio MP2 calculations of optimal geometries, dipole moments, polarizabilities, excitation energies and enthalpies of hydrogen or proton transfer from N-H group for cyano derivatives of pyrrole are presented. CN groups in α and β positions have distinct effects on electron spectra absorption bands. CN in α position causes larger bathochromic shift in comparison to β position. N-H bond dissociation enthalpies (BDE) of substituted pyrroles are higher by 7 kJ mol -1 than pyrrole BDE. Number and position of CN groups do not affect BDEs. Proton affinities of pyrrolyl anions and enthalpies of electron transfer from these anions are proportional to the number of CN groups in molecule. Each CN group causes decrease in proton affinity by 72 kJ mol -1 and 73 kJ mol -1 rise in electron transfer enthalpy. For several studied pyrroles, BDEs, proton affinities and electron transfer enthalpies in water and benzene were computed

  16. Negative atomic halogens incident on argon and molecular nitrogen: electron detachment studies

    International Nuclear Information System (INIS)

    Jalbert, G; Medina, A; Magalhaes, S D; Wolff, W; Barros, A L F de; Carrilho, P; Rocha, A B; Faria, N V de Castro

    2007-01-01

    During the last years we have measured total detachment cross sections of atomic and cluster anions colliding with gases in the velocity range of 0.2 to 1.8 a.u. In particular, we measured negative atomic halogens incident on argon and molecular nitrogen. These last data are for the first time analyzed using the simple semi-classical model that we have developed. For that purpose, the values of elastic plus inelastic cross sections for impact of free electrons on Ar and N 2 , the latter showing a shape resonance, convoluted with the anion's outermost electron momentum distribution yielded the overall shape of the anion cross sections. Inclusion of a velocity independent additive term, interpreted as an effective area of the collision region, led to accurate absolute cross section values. The high affinity of the halogens and the existence of a not well described resonance in the e-N 2 collision, are characteristics that may be used to delimit the scope and validity of the model

  17. The assessment of pellicular anion-exchange resins for the determination of anions by ion chromatography

    International Nuclear Information System (INIS)

    Pohlandt, C.

    1981-01-01

    Because pellicular anion-exchange resins suitable for the determination, by ion chromatography, of anions with alkaline eluents were unavailable in South Africa at the inception of this work, an attempt was made to prepare such resins. In this study it is shown that the pellicular resins produced are more efficient than the surface-aminated resins used previously. The simultaneous separation and determination of five common anions is demonstrated. The method was applied to the analysis of uranium leach liquors, effluent samples, and a solid sample of ferric oxide (goethite)

  18. Importance of Vibronic Effects in the UV-Vis Spectrum of the 7,7,8,8-Tetracyanoquinodimethane Anion.

    Science.gov (United States)

    Tapavicza, Enrico; Furche, Filipp; Sundholm, Dage

    2016-10-11

    We present a computational method for simulating vibronic absorption spectra in the ultraviolet-visible (UV-vis) range and apply it to the 7,7,8,8-tetracyanoquinodimethane anion (TCNQ - ), which has been used as a ligand in black absorbers. Gaussian broadening of vertical electronic excitation energies of TCNQ - from linear-response time-dependent density functional theory produces only one band, which is qualitatively incorrect. Thus, the harmonic vibrational modes of the two lowest doublet states were computed, and the vibronic UV-vis spectrum was simulated using the displaced harmonic oscillator approximation, the frequency-shifted harmonic oscillator approximation, and the full Duschinsky formalism. An efficient real-time generating function method was implemented to avoid the exponential complexity of conventional Franck-Condon approaches to vibronic spectra. The obtained UV-vis spectra for TCNQ - agree well with experiment; the Duschinsky rotation is found to have only a minor effect on the spectrum. Born-Oppenheimer molecular dynamics simulations combined with calculations of the electronic excitation energies for a large number of molecular structures were also used for simulating the UV-vis spectrum. The Born-Oppenheimer molecular dynamics simulations yield a broadening of the energetically lowest peak in the absorption spectrum, but additional vibrational bands present in the experimental and simulated quantum harmonic oscillator spectra are not observed in the molecular dynamics simulations. Our results underline the importance of vibronic effects for the UV-vis spectrum of TCNQ - , and they establish an efficient method for obtaining vibronic spectra using a combination of linear-response time-dependent density functional theory and a real-time generating function approach.

  19. Hofmeister Effect on PNIPAM in Bulk and at an Interface: Surface Partitioning of Weakly Hydrated Anions

    DEFF Research Database (Denmark)

    Moghaddam, Saeed Zajforoushan; Thormann, Esben

    2017-01-01

    The effect of sodium fluoride, sodium trichloroacetate, and sodium thiocyanate on the stability and conformation of poly(N-isopropylacrylamide), in bulk solution and at the gold-aqueous interface, is investigated by differential scanning calorimetry, dynamic light scattering, quartz crystal...... for thiocyanate and trichloroacetate, a salting-out effect is found for sodium trichloroacetate. This apparent contradiction is explained by a combination of previously suggested mechanisms for the salting-out effect by weakly hydrated anions....

  20. Dissecting Hofmeister Effects: Direct Anion-Amide Interactions Are Weaker than Cation-Amide Binding.

    Science.gov (United States)

    Balos, Vasileios; Kim, Heejae; Bonn, Mischa; Hunger, Johannes

    2016-07-04

    Whereas there is increasing evidence for ion-induced protein destabilization through direct ion-protein interactions, the strength of the binding of anions to proteins relative to cation-protein binding has remained elusive. In this work, the rotational mobility of a model amide in aqueous solution was used as a reporter for the interactions of different anions with the amide group. Protein-stabilizing salts such as KCl and KNO3 do not affect the rotational mobility of the amide. Conversely, protein denaturants such as KSCN and KI markedly reduce the orientational freedom of the amide group. Thus these results provide evidence for a direct denaturation mechanism through ion-protein interactions. Comparing the present findings with results for cations shows that in contrast to common belief, anion-amide binding is weaker than cation-amide binding. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Infrared Spectroscopy of Discrete Uranyl Anion Complexes

    International Nuclear Information System (INIS)

    Groenewold, G. S.; Gianotto, Anita K.; McIIwain, Michael E.; Van Stipdonk, Michael J.; Kullman, Michael; Moore, David T.; Polfer, Nick; Oomens, Jos; Infante, Ivan A.; Visscher, Lucas; Siboulet, Bertrand; De Jong, Wibe A.

    2008-01-01

    The Free-Electron Laser for Infrared Experiments (FELIX) w 1 as used to study the wavelength-resolved multiple photon photodissociation of discrete, gas phase uranyl (UO2 2 2+) complexes containing a single anionic ligand (A), with or without ligated solvent molecules (S). The uranyl antisymmetric and symmetric stretching frequencies were measured for complexes with general formula [UO2A(S)n]+, where A was either hydroxide, methoxide, or acetate; S was water, ammonia, acetone, or acetonitrile; and n = 0-3. The values for the antisymmetric stretching frequency for uranyl ligated with only an anion ([UO2A]+) were as low or lower than measurements for [UO2]2+ ligated with as many as five strong neutral donor ligands, and are comparable to solution phase values. This result was surprising because initial DFT calculations predicted values that were 30-40 cm-1 higher, consistent with intuition but not with the data. Modification of the basis sets and use of alternative functionals improved computational accuracy for the methoxide and acetate complexes, but calculated values for the hydroxide were greater than the measurement regardless of the computational method used. Attachment of a neutral donor ligand S to [UO2A]+ produced [UO2AS]+, which produced only very modest changes to the uranyl antisymmetric stretch frequency, and did not universally shift the frequency to lower values. DFT calculations for [UO2AS]+ were in accord with trends in the data, and showed that attachment of the solvent was accommodated by weakening of the U-anion bond as well as the uranyl. When uranyl frequencies were compared for [UO2AS]+ species having different solvent neutrals, values decreased with increasing neutral nucleophilicity

  2. Anionic Palladium(0) and Palladium(II) Ate Complexes.

    Science.gov (United States)

    Kolter, Marlene; Böck, Katharina; Karaghiosoff, Konstantin; Koszinowski, Konrad

    2017-10-16

    Palladium ate complexes are frequently invoked as important intermediates in Heck and cross-coupling reactions, but so far have largely eluded characterization at the molecular level. Here, we use electrospray-ionization mass spectrometry, electrical conductivity measurements, and NMR spectroscopy to show that the electron-poor catalyst [L 3 Pd] (L=tris[3,5-bis(trifluoromethyl)phenyl]phosphine) readily reacts with Br - ions to afford the anionic, zero-valent ate complex [L 3 PdBr] - . In contrast, more-electron-rich Pd catalysts display lower tendencies toward the formation of ate complexes. Combining [L 3 Pd] with LiI and an aryl iodide substrate (ArI) results in the observation of the Pd II ate complex [L 2 Pd(Ar)I 2 ] - . © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. The effects of fouled anion resin on condensate polishing plant performance at Dungeness B power station

    International Nuclear Information System (INIS)

    Bates, Chris

    2008-01-01

    The return to power, after an outage, at Dungeness B Power Station was delayed because of problems in achieving an in-specification feedwater acid conductivity. Dungeness B has a full flow cation/mixed bed condensate polishing plant (CPP). Investigations showed that the acid conductivity was produced by carbon dioxide and organic impurities both by-passing the CPP and slipping through it. Resin analysis showed that the anion resin had severely impaired sulfate removal kinetics. The paper covers the work done to try and identify the nature and source of the organics and their effect on the anion resin. One significant finding was that the carbonate removal kinetics were as impaired as those for sulfate removal; this had not been previously experienced in the CPP at any British Energy plant. (orig.)

  4. Effects of pH and Competing Anions on the Solution Speciation of Arsenic by Ion Exchange Resins

    Energy Technology Data Exchange (ETDEWEB)

    Impellitteri, Christopher A.; Ryan, JAmes A.; Al-Abed, Souhail R.; Scheckel, Kirk G.; Randall, Paul M.; Richardson, Collin A.

    2003-03-26

    Anion-exchange resins (AER) are used to differentiate As(V) and As(III) by retaining As(V) and allowing As(III) to pass through. AERs allow rapid speciation of As in the field which precludes the effects of sample preservation on As speciation. Aqueous environmental samples contain anions that may interfere with the speciation of As. This study compares the speciation of As by two commercially available AERs. A silica-based AER was selected for further study. As(V) and As(III) were passed through the AER in the presence of NO3 -, SO4 2-, HPO4 2-, Cl- and HCO3 - at pH 4, 6 and 8. Recoveries of As species in mixed systems range between 90 to 100%. Breakthrough curves for As(V) are presented which allow calculation of loading rates. HPO4 2- has the greatest effect on the speciation of As by AER.

  5. 4fn-15d centroid shift in lanthanides and relation with anion polarizability, covalency, and cation electronegativity

    International Nuclear Information System (INIS)

    Dorenbos, P.; Andriessen, J.; Eijk, C.W.E. van

    2003-01-01

    Data collected on the centroid shift of the 5d-configuration of Ce 3+ in oxide and fluoride compounds were recently analyzed with a model involving the correlated motion between 5d-electron and ligand electrons. The correlation effects are proportional to the polarizability of the anion ligands and it leads, like covalency, to lowering of the 5d-orbital energies. By means of ab initio Hartree-Fock-LCAO calculations including configuration interaction the contribution from covalency and correlated motion to the centroid shift are determined separately for Ce 3+ in various compounds. It will be shown that in fluoride compounds, covalency provides an insignificant contribution. In oxides, polarizability appears to be of comparable importance as covalency

  6. Efficiency of superoxide anions in the inactivation of selected dehydrogenases

    International Nuclear Information System (INIS)

    Rodacka, Aleksandra; Serafin, Eligiusz; Puchala, Mieczyslaw

    2010-01-01

    The most ubiquitous of the primary reactive oxygen species, formed in all aerobes, is the superoxide free radical. It is believed that the superoxide anion radical shows low reactivity and in oxidative stress it is regarded mainly as an initiator of more reactive species such as · OH and ONOO - . In this paper, the effectiveness of inactivation of selected enzymes by radiation-generated superoxide radicals in comparison with the effectiveness of the other products of water radiolysis is examined. We investigate three enzymes: glyceraldehyde-3-phosphate dehydrogenase (GAPDH), alcohol dehydrogenase (ADH) and lactate dehydrogenase (LDH). We show that the direct contribution of the superoxide anion radical to GAPDH and ADH inactivation is significant. The effectiveness of the superoxide anion in the inactivation of GAPDH and ADG was only 2.4 and 2.8 times smaller, respectively, in comparison with hydroxyl radical. LDH was practically not inactivated by the superoxide anion. Despite the fact that the studied dehydrogenases belong to the same class of enzymes (oxidoreductases), all have a similar molecular weight and are tetramers, their susceptibility to free-radical damage varies. The differences in the radiosensitivity of the enzymes are not determined by the basic structural parameters analyzed. A significant role in inactivation susceptibility is played by the type of amino acid residues and their localization within enzyme molecules.

  7. Efficiency of superoxide anions in the inactivation of selected dehydrogenases

    Energy Technology Data Exchange (ETDEWEB)

    Rodacka, Aleksandra, E-mail: olakow@biol.uni.lodz.p [Department of Molecular Biophysics, University of Lodz, Banacha 12/16, 90-237 Lodz (Poland); Serafin, Eligiusz, E-mail: serafin@biol.uni.lodz.p [Laboratory of Computer and Analytical Techniques, University of Lodz, Banacha 12/16, 90-237 Lodz (Poland); Puchala, Mieczyslaw, E-mail: puchala@biol.uni.lodz.p [Department of Molecular Biophysics, University of Lodz, Banacha 12/16, 90-237 Lodz (Poland)

    2010-09-15

    The most ubiquitous of the primary reactive oxygen species, formed in all aerobes, is the superoxide free radical. It is believed that the superoxide anion radical shows low reactivity and in oxidative stress it is regarded mainly as an initiator of more reactive species such as {sup {center_dot}}OH and ONOO{sup -}. In this paper, the effectiveness of inactivation of selected enzymes by radiation-generated superoxide radicals in comparison with the effectiveness of the other products of water radiolysis is examined. We investigate three enzymes: glyceraldehyde-3-phosphate dehydrogenase (GAPDH), alcohol dehydrogenase (ADH) and lactate dehydrogenase (LDH). We show that the direct contribution of the superoxide anion radical to GAPDH and ADH inactivation is significant. The effectiveness of the superoxide anion in the inactivation of GAPDH and ADG was only 2.4 and 2.8 times smaller, respectively, in comparison with hydroxyl radical. LDH was practically not inactivated by the superoxide anion. Despite the fact that the studied dehydrogenases belong to the same class of enzymes (oxidoreductases), all have a similar molecular weight and are tetramers, their susceptibility to free-radical damage varies. The differences in the radiosensitivity of the enzymes are not determined by the basic structural parameters analyzed. A significant role in inactivation susceptibility is played by the type of amino acid residues and their localization within enzyme molecules.

  8. Dissociative electron attachment to the gas-phase nucleobase hypoxanthine

    Energy Technology Data Exchange (ETDEWEB)

    Dawley, M. Michele [Radiation Laboratory, University of Notre Dame, Notre Dame, Indiana 46556 (United States); Tanzer, Katrin; Denifl, Stephan, E-mail: Stephan.Denifl@uibk.ac.at, E-mail: Sylwia.Ptasinska.1@nd.edu [Institut für Ionenphysik und Angewandte Physik, and Center for Molecular Biosciences Innsbruck (CMBI), Leopold-Franzens Universität Innsbruck, Technikerstr. 25, A-6020 Innsbruck (Austria); Carmichael, Ian [Radiation Laboratory, University of Notre Dame, Notre Dame, Indiana 46556 (United States); Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556 (United States); Ptasińska, Sylwia, E-mail: Stephan.Denifl@uibk.ac.at, E-mail: Sylwia.Ptasinska.1@nd.edu [Radiation Laboratory, University of Notre Dame, Notre Dame, Indiana 46556 (United States); Department of Physics, University of Notre Dame, Notre Dame, Indiana 46556 (United States)

    2015-06-07

    We present high-resolution measurements of the dissociative electron attachment (DEA) to isolated gas-phase hypoxanthine (C{sub 5}H{sub 4}N{sub 4}O, Hyp), a tRNA purine base. The anion mass spectra and individual ion efficiency curves from Hyp were measured as a function of electron energy below 9 eV. The mass spectra at 1 and 6 eV exhibit the highest anion yields, indicating possible common precursor ions that decay into the detectable anionic fragments. The (Hyp − H) anion (C{sub 5}H{sub 3}N{sub 4}O{sup −}) exhibits a sharp resonant peak at 1 eV, which we tentatively assign to a dipole-bound state of the keto-N1H,N9H tautomer in which dehydrogenation occurs at either the N1 or N9 position based upon our quantum chemical computations (B3LYP/6-311+G(d,p) and U(MP2-aug-cc-pVDZ+)) and prior studies with adenine. This closed-shell dehydrogenated anion is the dominant fragment formed upon electron attachment, as with other nucleobases. Seven other anions were also observed including (Hyp − NH){sup −}, C{sub 4}H{sub 3}N{sub 4}{sup −}/C{sub 4}HN{sub 3}O{sup −}, C{sub 4}H{sub 2}N{sub 3}{sup −}, C{sub 3}NO{sup −}/HC(HCN)CN{sup −}, OCN{sup −}, CN{sup −}, and O{sup −}. Most of these anions exhibit broad but weak resonances between 4 and 8 eV similar to many analogous anions from adenine. The DEA to Hyp involves significant fragmentation, which is relevant to understanding radiation damage of biomolecules.

  9. Process for removing sulfate anions from waste water

    Science.gov (United States)

    Nilsen, David N.; Galvan, Gloria J.; Hundley, Gary L.; Wright, John B.

    1997-01-01

    A liquid emulsion membrane process for removing sulfate anions from waste water is disclosed. The liquid emulsion membrane process includes the steps of: (a) providing a liquid emulsion formed from an aqueous strip solution and an organic phase that contains an extractant capable of removing sulfate anions from waste water; (b) dispersing the liquid emulsion in globule form into a quantity of waste water containing sulfate anions to allow the organic phase in each globule of the emulsion to extract and absorb sulfate anions from the waste water and (c) separating the emulsion including its organic phase and absorbed sulfate anions from the waste water to provide waste water containing substantially no sulfate anions.

  10. Photoelectron spectroscopy and density functional theory studies of (FeS)mH- (m = 2-4) cluster anions: effects of the single hydrogen.

    Science.gov (United States)

    Yin, Shi; Bernstein, Elliot R

    2017-12-20

    Single hydrogen containing iron hydrosulfide cluster anions (FeS) m H - (m = 2-4) are studied by photoelectron spectroscopy (PES) at 3.492 eV (355 nm) and 4.661 eV (266 nm) photon energies, and by Density Functional Theory (DFT) calculations. The structural properties, relative energies of different spin states and isomers, and the first calculated vertical detachment energies (VDEs) of different spin states for these (FeS) m H - (m = 2-4) cluster anions are investigated at various reasonable theory levels. Two types of structural isomers are found for these (FeS) m H - (m = 2-4) clusters: (1) the single hydrogen atom bonds to a sulfur site (SH-type); and (2) the single hydrogen atom bonds to an iron site (FeH-type). Experimental and theoretical results suggest such available different SH- and FeH-type structural isomers should be considered when evaluating the properties and behavior of these single hydrogen containing iron sulfide clusters in real chemical and biological systems. Compared to their related, respective pure iron sulfur (FeS) m - clusters, the first VDE trend of the diverse type (FeS) m H 0,1 - (m = 1-4) clusters can be understood through (1) the different electron distribution properties of their highest singly occupied molecular orbital employing natural bond orbital analysis (NBO/HSOMO), and (2) the partial charge distribution on the NBO/HSOMO localized sites of each cluster anion. Generally, the properties of the NBO/HSOMOs play the principal role with regard to the physical and chemical properties of all the anions. The change of cluster VDE from low to high is associated with the change in nature of their NBO/HSOMO from a dipole bound and valence electron mixed character, to a valence p orbital on S, to a valence d orbital on Fe, and to a valence p orbital on Fe or an Fe-Fe delocalized valence bonding orbital. For clusters having the same properties for NBO/HSOMOs, the partial charge distributions at the NBO/HSOMO localized sites additionally

  11. Hybrid capacitive deionization with anion-exchange membranes for lithium extraction

    Directory of Open Access Journals (Sweden)

    Siekierka Anna

    2017-01-01

    Full Text Available Lithium is considered to be a critical material for various industrial fields. We present our studies on extraction lithium from diluted aqueous solution by novel hybrid system based on a membrane capacitive deionization and batteries desalination. Hybrid CDI is comprised by a lithium selective adsorbent, activated carbon electrode and anion-exchange membranes. Here, we demonstrated implication of various type of anion-exchange membranes and influence their properties on effective capacity and energy requirements in charge/discharge steps. We described a configuration with anion-exchange membrane characterized by adsorption capacity of 35 mg/g of Li+ with 0.08Wh/g and removal efficiency of 60 % of lithium ions, using novel selective desalination technique.

  12. Hybrid capacitive deionization with anion-exchange membranes for lithium extraction

    Science.gov (United States)

    Siekierka, Anna; Bryjak, Marek

    2017-11-01

    Lithium is considered to be a critical material for various industrial fields. We present our studies on extraction lithium from diluted aqueous solution by novel hybrid system based on a membrane capacitive deionization and batteries desalination. Hybrid CDI is comprised by a lithium selective adsorbent, activated carbon electrode and anion-exchange membranes. Here, we demonstrated implication of various type of anion-exchange membranes and influence their properties on effective capacity and energy requirements in charge/discharge steps. We described a configuration with anion-exchange membrane characterized by adsorption capacity of 35 mg/g of Li+ with 0.08Wh/g and removal efficiency of 60 % of lithium ions, using novel selective desalination technique.

  13. Hybrid capacitive deionization with anion-exchange membranes for lithium extraction

    OpenAIRE

    Siekierka Anna; Bryjak Marek

    2017-01-01

    Lithium is considered to be a critical material for various industrial fields. We present our studies on extraction lithium from diluted aqueous solution by novel hybrid system based on a membrane capacitive deionization and batteries desalination. Hybrid CDI is comprised by a lithium selective adsorbent, activated carbon electrode and anion-exchange membranes. Here, we demonstrated implication of various type of anion-exchange membranes and influence their properties on effective capacity an...

  14. Understanding the effects of electronic polarization and delocalization on charge-transport levels in oligoacene systems

    KAUST Repository

    Sutton, Christopher; Tummala, Naga Rajesh; Kemper, Travis; Aziz, Saadullah G.; Sears, John; Coropceanu, Veaceslav; Bredas, Jean-Luc

    2017-01-01

    Electronic polarization and charge delocalization are important aspects that affect the charge-transport levels in organic materials. Here, using a quantum mechanical/ embedded-charge (QM/EC) approach based on a combination of the long-range corrected omega B97X-D exchange-correlation functional (QM) and charge model 5 (CM5) point-charge model (EC), we evaluate the vertical detachment energies and polarization energies of various sizes of crystalline and amorphous anionic oligoacene clusters. Our results indicate that QM/EC calculations yield vertical detachment energies and polarization energies that compare well with the experimental values obtained from ultraviolet photoemission spectroscopy measurements. In order to understand the effect of charge delocalization on the transport levels, we considered crystalline naphthalene systems with QM regions including one or five-molecules. The results for these systems show that the delocalization and polarization effects are additive; therefore, allowing for electron delocalization by increasing the size of the QM region leads to the additional stabilization of the transport levels. Published by AIP Publishing.

  15. Understanding the effects of electronic polarization and delocalization on charge-transport levels in oligoacene systems

    KAUST Repository

    Sutton, Christopher

    2017-06-13

    Electronic polarization and charge delocalization are important aspects that affect the charge-transport levels in organic materials. Here, using a quantum mechanical/ embedded-charge (QM/EC) approach based on a combination of the long-range corrected omega B97X-D exchange-correlation functional (QM) and charge model 5 (CM5) point-charge model (EC), we evaluate the vertical detachment energies and polarization energies of various sizes of crystalline and amorphous anionic oligoacene clusters. Our results indicate that QM/EC calculations yield vertical detachment energies and polarization energies that compare well with the experimental values obtained from ultraviolet photoemission spectroscopy measurements. In order to understand the effect of charge delocalization on the transport levels, we considered crystalline naphthalene systems with QM regions including one or five-molecules. The results for these systems show that the delocalization and polarization effects are additive; therefore, allowing for electron delocalization by increasing the size of the QM region leads to the additional stabilization of the transport levels. Published by AIP Publishing.

  16. Infrared spectroscopy of anionic hydrated fluorobenzenes

    International Nuclear Information System (INIS)

    Schneider, Holger; Vogelhuber, Kristen M.; Weber, J. Mathias

    2007-01-01

    We investigate the structural motifs of anionic hydrated fluorobenzenes by infrared photodissociation spectroscopy and density functional theory. Our calculations show that all fluorobenzene anions under investigation are strongly distorted from the neutral planar molecular geometries. In the anions, different F atoms are no longer equivalent, providing structurally different binding sites for water molecules and giving rise to a multitude of low-lying isomers. The absorption bands for hexa- and pentafluorobenzene show that only one isomer for the respective monohydrate complexes is populated in our experiment. For C 6 F 6 - ·H 2 O, we can assign these bands to an isomer where water forms a weak double ionic hydrogen bond with two F atoms in the ion, in accord with the results of Bowen et al. [J. Chem. Phys. 127, 014312 (2007), following paper.] The spectroscopic motif of the binary complexes changes slightly with decreasing fluorination of the aromatic anion. For dihydrated hexafluorobenzene anions, several isomers are populated in our experiments, some of which may be due to hydrogen bonding between water molecules

  17. Anion channels: master switches of stress responses.

    Science.gov (United States)

    Roelfsema, M Rob G; Hedrich, Rainer; Geiger, Dietmar

    2012-04-01

    During stress, plant cells activate anion channels and trigger the release of anions across the plasma membrane. Recently, two new gene families have been identified that encode major groups of anion channels. The SLAC/SLAH channels are characterized by slow voltage-dependent activation (S-type), whereas ALMT genes encode rapid-activating channels (R-type). Both S- and R-type channels are stimulated in guard cells by the stress hormone ABA, which leads to stomatal closure. Besides their role in ABA-dependent stomatal movement, anion channels are also activated by biotic stress factors such as microbe-associated molecular patterns (MAMPs). Given that anion channels occur throughout the plant kingdom, they are likely to serve a general function as master switches of stress responses. Copyright © 2012 Elsevier Ltd. All rights reserved.

  18. Partitioning of hydrophobic pesticides within a soil-water-anionic surfactant system.

    Science.gov (United States)

    Wang, Peng; Keller, Arturo A

    2009-02-01

    Surfactants can be added to pesticide-contaminated soils to enhance the treatment efficiency of soil washing. Our results showed that pesticide (atrazine and diuron) partitioning and desorbability within a soil-water-anionic surfactant system is soil particle-size dependent and is significantly influenced by the presence of anionic surfactant. Anionic surfactant (linear alkylbenzene sulphonate, LAS) sorption was influenced by its complexation with both the soluble and exchangeable divalent cations in soils (e.g. Ca2+, Mg2+). In this study, we propose a new concept: soil system hardness which defines the total amount of soluble and exchangeable divalent cations associated with a soil. Our results showed that anionic surfactant works better with soils having lower soil system hardness. It was also found that the hydrophobic organic compounds (HOCs) sorbed onto the LAS-divalent cation precipitate, resulting in a significant decrease in the aqueous concentration of HOC. Our results showed that the effect of exchangeable cations and sorption of HOC onto the surfactant precipitates needs to be considered to accurately predict HOC behavior within soil-water-anionic surfactant systems.

  19. Electrokinetic remediation of anionic contaminants from unsaturated soils

    International Nuclear Information System (INIS)

    Lindgren, E.R.; Kozak, M.W.; Mattson, E.D.

    1992-01-01

    Heavy-metal contamination of soil and groundwater is a widespread problem in the DOE weapons complex, and for the nation as a whole. Electrokinetic remediation is one possible technique for in situ removal of such contaminants from unsaturated soils. In previous studies at Sandia National Laboratories, the electromigration of chromate ions and anionic dye ions have been demonstrated. This paper reports on a series of experiments that were conducted to study the effect of moisture content on the electromigration rate of anionic contaminants in unsaturated soil and determine the limiting moisture content for which electromigration occurs

  20. Effects of arginine on multimodal anion exchange chromatography.

    Science.gov (United States)

    Hirano, Atsushi; Arakawa, Tsutomu; Kameda, Tomoshi

    2015-12-01

    The effects of arginine on binding and elution properties of a multimodal anion exchanger, Capto adhere, were examined using bovine serum albumin (BSA) and a monoclonal antibody against interleukin-8 (mAb-IL8). Negatively charged BSA was bound to the positively charged Capto adhere and was readily eluted from the column with a stepwise or gradient elution using 1M NaCl at pH 7.0. For heat-treated BSA, small oligomers and remaining monomers were also eluted using a NaCl gradient, whereas larger oligomers required arginine for effective elution. The positively charged mAb-IL8 was bound to Capto adhere at pH 7.0. Arginine was also more effective for elution of the bound mAb-IL8 than was NaCl. The results imply that arginine interacts with the positively charged Capto adhere. The mechanism underlying the interactions of arginine with Capto adhere was examined by calculating the binding free energy between an arginine molecule and a Capto adhere ligand in water through molecular dynamics simulations. The overall affinity of arginine for Capto adhere is attributed to the hydrophobic and π-π interactions between an arginine side chain and the aromatic moiety of the ligand as well as hydrogen bonding between arginine and the ligand hydroxyl group, which may account for the characteristics of protein elution using arginine. Copyright © 2015 Elsevier Inc. All rights reserved.

  1. Effects of Hofmeister Anions on the LCST of PNIPAM as a Function of Molecular Weight

    Science.gov (United States)

    Zhang, Yanjie; Furyk, Steven; Sagle, Laura B.; Cho, Younhee; Bergbreiter, David E.; Cremer, Paul S.

    2008-01-01

    The effect of a series of sodium salts on the lower critical solution temperature (LCST) of poly(N-isopropylacrylamide), PNIPAM, was investigated as a function of molecular weight and polymer concentration with a temperature gradient microfluidic device under a dark-field microscope. In solutions containing sufficient concentrations of kosmotropic anions, the phase transition of PNIPAM was resolved into two separate steps for higher molecular weight samples. The first step of this two step transition was found to be sensitive to the polymer’s molecular weight and solution concentration, while the second step was not. Moreover, the binding of chaotropic anions to the polymer was also influenced by molecular weight. Both sets of results could be explained by the formation of intramolecular and intermolecular hydrogen-bonding between polymer chains. By contrast, the hydrophobic hydration of the isopropyl moieties and polymer backbone was found to be unaffected by either the polymer’s molecular weight or solution concentration. PMID:18820735

  2. N-acetylglyoxylic amide bearing a nitrophenyl group as anion receptors: NMR and X-ray investigations on anion binding and selectivity

    Science.gov (United States)

    Suryanti, Venty; Bhadbhade, Mohan; Black, David StC; Kumar, Naresh

    2017-10-01

    N-Nitrophenylglyoxylic amides 1 and 2 in presence of tetrabutylammonium cation (TBA) act as receptors for anions HSO4-, Cl-, Br- and NO3- as investigated by NMR studies. The receptors formed 1:1 host-guest complexes in solution. X-ray structure of 1 along with TBA that bind a chloride anion is reported. Molecule 1 showed the highest selectivity for HSO4- anion over others measured. X-ray structure of the bound Cl- revealed a pocket containing the anion making strong (Nsbnd H⋯Cl) and weak hydrogen bonds (Csbnd H⋯Cl) that contribute to the recognition of the chloride anion. Nsbnd H and Csbnd H hydrogen bonds resulted in a relatively strong binding for chloride ions.

  3. Synthesis, structure, and electronic structure calculation of a new centrosymmetric borate Pb{sub 2}O[BO{sub 2}(OH)] based on anion-centered OPb{sub 4} tetrahedra

    Energy Technology Data Exchange (ETDEWEB)

    Sun, Feng [College of Chemistry and Chemical Engineering, Xinjiang Normal University, Urumqi 830054 (China); Wang, Li, E-mail: wangliresearch@163.com [College of Chemistry and Chemical Engineering, Xinjiang Normal University, Urumqi 830054 (China); Stoumpos, Constantinos C. [Department of Chemistry, Northwestern University, Evanston, IL 60208 (United States)

    2016-08-15

    The synthesis, structure, and characterization of a new centrosymmetric borate Pb{sub 2}O[BO{sub 2}(OH)] based on anion-centered OPb{sub 4} tetrahedra are reported. Pb{sub 2}O[BO{sub 2}(OH)] crystallizes in monoclinic space group C2/m with a=12.725(7) Å, b=5.698(3) Å, c=7.344(4) Å, β=116.277(6)°. The electronic band structure and density of states of Pb{sub 2}O[BO{sub 2}(OH)] have been calculated via the density functional theory (DFT). Electron density difference calculation indicates that lone-pair electrons of Pb{sup 2+} cation should be stereoactive. - Graphical abstract: An indirect gap compound of Pb{sub 2}O[BO{sub 2}(OH)] with 2D inorganic layers motif based on OPb{sub 4} tetrahedra has been synthesized and full characterized by crystallographic, IR, TG, UV–vis-NIR Diffuse Reflectance, and theoretical calculations. Display Omitted - Highlights: • A centrosymmetric borate Pb{sub 2}O[BO{sub 2}(OH)] was synthesized and characterized. • The crystalstructure, electronic band and density states was analyzed. • The lone-pair electrons of Pb{sup 2+} were proved to be stereoactive.

  4. Partial-depth modulation study of anions and neutrals in low pressure silane plasmas

    International Nuclear Information System (INIS)

    Cozurteille, C.; Dorier, J.L.; Hollenstein, C.; Sansonnens; Howling, A.A.

    1995-10-01

    Partial-depth modulation of the rf power in a capacitive discharge is used to investigate the relative importance of negative ions and neutral radicals for particle formation in low power, low pressure silane plasmas. For less than 85% modulation depth, anions are trapped indefinitely in the plasma and particle formation ensues, whereas the polymerised neutral flux magnitudes and dynamics are independent of the modulation depth and the powder formation. These observations suggest that negative ions could be the particle precursors in plasma conditions where powder appears many seconds after plasma ignition. Microwave interferometry and mass spectrometry were combined to infer an anion density of ≅7.10 9 cm -3 which is approximately twice the free electron density in these modulated plasmas. (author) 6 figs., tabs., refs

  5. Electronic structure of incident carbon ions on a graphite surface

    International Nuclear Information System (INIS)

    Kiuchi, Masato; Takeuchi, Takae; Yamamoto, Masao.

    1997-01-01

    The electronic structure of an incident carbon ion on a graphite surface is discussed on the basis of ab initio molecular orbital calculations. A carbon cation forms a covalent bond with the graphite, and a carbon nonion is attracted to the graphite surface through van der Waals interaction. A carbon anion has no stable state on a graphite surface. The charge effects of incident ions become clear upon detailed examination of the electronic structure. (author)

  6. Anion-Controlled Architecture and Photochromism of Naphthalene Diimide-Based Coordination Polymers

    Directory of Open Access Journals (Sweden)

    Jian-Jun Liu

    2018-02-01

    Full Text Available Three new cadmium coordination polymers, namely [Cd(NO32(DPNDI(CH3OH]·CH3OH (1, [Cd(SCN2(DPNDI] (2, and [Cd(DPNDI2(DMF2]·2ClO4 (3 (DPNDI = N,N-di(4-pyridyl-1,4,5,8-naphthalene diimide, DMF = N,N-dimethylformamide have been synthesized by reactions of DPNDI with Cd(NO32, Cd(SCN2, and Cd(ClO42, respectively. Compound 1 is a one-dimensional coordination polymer with strong lone pair-π interactions between the coordinated NO3− anions and the imide ring of DPNDI; while 2 is a two-dimensional network with a (4, 4 net topology. In the case of 3, due to the presence of uncoordinated perchlorate counter ions, it exhibits a non-interpenetrated square-grid coordination polymer containing one-dimensional rhomboid channels. The structural diversity in these compounds is attributed to different coordination abilities and geometries of counter anions. Due to the presence of electron-deficient NDI moiety, the photochromic behavior of these compounds was studied. Interestingly, only compounds 1 and 3 exhibit color changes under light irradiation. The influence of the anions on the photochromism process of the NDI-based materials has been discussed.

  7. Freezing-Enhanced Dissolution of Iron Oxides: Effects of Inorganic Acid Anions.

    Science.gov (United States)

    Jeong, Daun; Kim, Kitae; Min, Dae Wi; Choi, Wonyong

    2015-11-03

    Dissolution of iron from mineral dust particles greatly depends upon the type and amount of copresent inorganic anions. In this study, we investigated the roles of sulfate, chloride, nitrate, and perchlorate on the dissolution of maghemite and lepidocrocite in ice under both dark and UV irradiation and compared the results with those of their aqueous counterparts. After 96 h of reaction, the total dissolved iron in ice (pH 3 before freezing) was higher than that in the aqueous phase (pH 3) by 6-28 times and 10-20 times under dark and UV irradiation, respectively. Sulfuric acid was the most efficient in producing labile iron under dark condition, whereas hydrochloric acid induced the most dissolution of the total and ferrous iron in the presence of light. This ice-induced dissolution result was also confirmed with Arizona Test Dust (AZTD). In the freeze-thaw cycling test, the iron oxide samples containing chloride, nitrate, or perchlorate showed a similar extent of total dissolved iron after each cycling while the sulfate-containing sample rapidly lost its dissolution activity with repeating the cycle. This unique phenomenon observed in ice might be related to the freeze concentration of protons, iron oxides, and inorganic anions in the liquid-like ice grain boundary region. These results suggest that the ice-enhanced dissolution of iron oxides can be a potential source of bioavailable iron, and the acid anions critically influence this process.

  8. Cationic and Anionic Disorder in CZTSSe Kesterite Compounds: A Chemical Crystallography Study.

    Science.gov (United States)

    Bais, Pierre; Caldes, Maria Teresa; Paris, Michaël; Guillot-Deudon, Catherine; Fertey, Pierre; Domengès, Bernadette; Lafond, Alain

    2017-10-02

    The cationic and anionic disorder in the Cu 2 ZnSnSe 4 -Cu 2 ZnSnS 4 (CZTSe-CZTS) system has been investigated through a chemical crystallography approach including X-ray diffraction (in conventional and resonant setup), 119 Sn and 77 Se NMR spectroscopy, and high-resolution transmission electron microscopy (HRTEM) techniques. Single-crystal XRD analysis demonstrates that the studied compounds behave as a solid solution with the kesterite crystal structure in the whole S/(S + Se) composition range. As previously reported for pure sulfide and pure selenide compounds, the 119 Sn NMR spectroscopy study gives clear evidence that the level of Cu/Zn disorder in mixed S/Se compounds depends on the thermal history of the samples (slow cooled or quenched). This conclusion is also supported by the investigation of the 77 Se NMR spectra. The resonant single-crystal XRD technique shows that regardless of the duration of annealing step below the order-disorder critical temperature the ordering is not a long-range phenomenon. Finally, for the very first time, HREM images of pure selenide and mixed S/Se crystals clearly show that these compounds have different microstructures. Indeed, only the mixed S/Se compound exhibits a mosaic-type contrast which could be the sign of short-range anionic order. Calculated images corroborate that HRTEM contrast is highly dependent on the nature of the anion as well as on the local anionic order.

  9. Confinement and electron correlation effects in photoionization of atoms in endohedral anions: Ne-Cz-60

    International Nuclear Information System (INIS)

    Dolmatov, V K; Craven, G T; Keating, D

    2010-01-01

    Trends in resonances, termed confinement resonances, in photoionization of atoms A in endohedral fullerene anions A-C z- 60 are theoretically studied and exemplified by the photoionization of Ne in Ne-C z- 60 . Remarkably, above a particular nl ionization threshold of Ne in neutral Ne-C 60 (I z=0 nl ), confinement resonances in corresponding partial photoionization cross sections σ nl of Ne in any charged Ne-C z- 60 are not affected by a variation in the charge z of the carbon cage, as a general phenomenon. At lower photon energies, ω z=0 nl , the corresponding photoionization cross sections of charged Ne-C z- 60 (i.e., those with z ≠ 0) develop additional, strong, z-dependent resonances, termed Coulomb confinement resonances, as a general occurrence. Furthermore, near the innermost 1s ionization threshold, the 2p photoionization cross section σ 2p of the outermost 2p subshell of thus confined Ne is found to inherit the confinement resonance structure of the 1s photoionization spectrum, via interchannel coupling. As a result, new confinement resonances emerge in the 2p photoionization cross section of the confined Ne atom at photoelectron energies which exceed the 2p threshold by about a thousand eV, i.e., far above where conventional wisdom said they would exist. Thus, the general possibility for confinement resonances to resurrect in photoionization spectra of encapsulated atoms far above thresholds is revealed, as an interesting novel general phenomenon.

  10. The strong influence of the solvent on the electron spin resonance spectra of semiquinone radical anions

    DEFF Research Database (Denmark)

    Spanget-Larsen, Jens

    2013-01-01

    ). The proton hyperfine constants predicted for the chrysazin semiquinone radical anion were highly sensitive to the assumed dielectric constant ε of the solvent continuum, inverting the relative magnitudes of the hyperfine constants and thereby leading to agreement with the observed data published by Stegmann...

  11. Acetate and phosphate anion adsorption linear sweep voltammograms simulated using density functional theory

    KAUST Repository

    Savizi, Iman Shahidi Pour

    2011-04-01

    Specific adsorption of anions to electrode surfaces may alter the rates of electrocatalytic reactions. Density functional theory (DFT) methods are used to predict the adsorption free energy of acetate and phosphate anions as a function of Pt(1 1 1) electrode potential. Four models of the electrode potential are used including a simple vacuum slab model, an applied electric field model with and without the inclusion of a solvating water bi-layer, and the double reference model. The linear sweep voltammogram (LSV) due to anion adsorption is simulated using the DFT results. The inclusion of solvation at the electrochemical interface is necessary for accurately predicting the adsorption peak position. The Langmuir model is sufficient for predicting the adsorption peak shape, indicating coverage effects are minor in altering the LSV for acetate and phosphate adsorption. Anion adsorption peak positions are determined for solution phase anion concentrations present in microbial fuel cells and microbial electrolysis cells and discussion is provided as to the impact of anion adsorption on oxygen reduction and hydrogen evolution reaction rates in these devices. © 2011 Elsevier Ltd. All rights reserved.

  12. The effect of electron irradiation on the structure and iron speciation in sodium aluminum (iron) phosphate glasses

    Energy Technology Data Exchange (ETDEWEB)

    Stefanovsky, S.V., E-mail: serge.stefanovsky@yandex.ru [Frumkin Institute of Physical Chemistry and Electrochemistry RAS (Russian Federation); Presniakov, I.A.; Sobolev, A.V.; Glazkova, I.S. [Lomonosov Moscow State University, Department of Chemistry (Russian Federation); Kadyko, M.I.; Stefanovsky, O.I. [Frumkin Institute of Physical Chemistry and Electrochemistry RAS (Russian Federation)

    2016-08-01

    The effect of 8 MeV electron irradiation on the structure of glasses in the series 40 Na{sub 2}O, (20-x) Al{sub 2}O{sub 3}, x Fe{sub 2}O{sub 3}, 40 P{sub 2}O{sub 5} (mol.%) and on the iron speciation in these samples was studied by FTIR and Mössbauer spectroscopic techniques. Irradiation up to a dose of 1.0 MGy has no appreciable effects on the character of the bonds within anionic motif of the glass network. Electron irradiation increases the fraction of aluminum in octahedral coordination. Iron in both unirradiated and irradiated glasses is present mainly as Fe(III) (60–75% of the total amount) in the glasses and partly as Fe(II) and the ratio of two forms remains constant up to a dose of 1.0 MGy.

  13. Observations on small anionic clusters in an electrostatic ion beam trap

    International Nuclear Information System (INIS)

    Eritt, Markus

    2008-01-01

    The term atomic cluster relates to compounds of at least two or three atoms. Thereby the physical properties are size dependent and the property transitions between single atoms and bulk material are not always smooth. Ion traps allow it to observe internal cluster properties independent from the influence of external forces. In this work the electron induced decay of singly negatively charged atomic clusters was observed. The dissociation cross section of the clusters is dominated by detachment of the only weakly bound outer electrons. For simple atoms at low electron energies a simple scaling law can be obtained that includes only the binding energies of the valence electrons. Nevertheless for larger sizes theoretical calculations predict so called ''giant resonances'' as dominant decay process in metal clusters. Due to mass limitations in storage rings exist so far only cross section measurements for simple anions and small negative molecules. In this work the electron detachment cross sections of small negatively charged carbon (C n - n=2-12), aluminium (Al n - n=2-7) and silver clusters (Ag n - n=1-11) were measured in an electrostatic ion beam trap. The classical scaling law, including only the binding energies of the valence electrons, turned out to be not sufficient, especially for larger clusters. In order to improve the correlation between measured and predicted values it was proposed to involve the influence of the cluster volume and the specific polarisability induced by long range coulomb interaction. For silver clusters the best agreement was obtained using a combination of the projected area reduced by the polarisability. The existence of ''giant resonances'' could not be confirmed. According to theory for clusters with a broad internal energy distribution, a power-law decay close to 1/time is expected. For some clusters the lifetime behaviour would be strongly quenched by photon emission. The thermionic evaporative decay of anionic aluminium and

  14. Electron-detachment cross sections of halogen negative-ion projectiles for inertial confinement fusion

    Science.gov (United States)

    Sant'Anna, M. M.; Zappa, F.; Santos, A. C. F.; de Barros, A. L. F.; Wolff, W.; Coelho, L. F. S.; de Castro Faria, N. V.

    2004-07-01

    Negative-ion beams have recently been suggested as sources of high-energy heavy atoms to be used as drivers for inertial confinement fusion (ICF). Owing to their electron affinities limited to a few eV, anions can be efficiently photo-detached in the vicinity of the fusion chamber, with the resulting high-velocity neutral projectiles following ballistic trajectories towards the hydrogen pellet target. Electron-detachment cross sections are needed as parameters to estimate the beam attenuation in the path from the ion source to the hydrogen pellet. Halogen anions are possible projectile choices. In this paper we present experimental data for total electron-detachment cross sections for F-, Cl-, Br- and I- ions incident on N2, in the 0.94-74 keV u-1 energy range. Our measurements can benchmark theory on anion electron detachment at intermediate to high velocities. Comparison between different projectiles shows very similar collision velocity dependencies. A simple geometrical scaling is presented, providing an estimate for electron-detachment cross sections at the MeV u-1 energy range. The presented scaling indicates that the vacuum requirements due to the use of halogen anions for ICF are less critical than previously suggested.

  15. Electron-detachment cross sections of halogen negative-ion projectiles for inertial confinement fusion

    International Nuclear Information System (INIS)

    Sant'Anna, M M; Zappa, F; Santos, A C F; Barros, A L F de; Wolff, W; Coelho, L F S; Faria, N V de Castro

    2004-01-01

    Negative-ion beams have recently been suggested as sources of high-energy heavy atoms to be used as drivers for inertial confinement fusion (ICF). Owing to their electron affinities limited to a few eV, anions can be efficiently photo-detached in the vicinity of the fusion chamber, with the resulting high-velocity neutral projectiles following ballistic trajectories towards the hydrogen pellet target. Electron-detachment cross sections are needed as parameters to estimate the beam attenuation in the path from the ion source to the hydrogen pellet. Halogen anions are possible projectile choices. In this paper we present experimental data for total electron-detachment cross sections for F - , Cl - , Br - and I - ions incident on N 2 , in the 0.94-74 keV u -1 energy range. Our measurements can benchmark theory on anion electron detachment at intermediate to high velocities. Comparison between different projectiles shows very similar collision velocity dependencies. A simple geometrical scaling is presented, providing an estimate for electron-detachment cross sections at the MeV u -1 energy range. The presented scaling indicates that the vacuum requirements due to the use of halogen anions for ICF are less critical than previously suggested

  16. Effects of anions on the zwitterion stability of Glu, His and Arg investigated by IRMPD spectroscopy and theory

    NARCIS (Netherlands)

    O'Brien, J.T.; Prell, J.S.; Berden, G.; Oomens, J.; Williams, E.R.

    2010-01-01

    Interactions of halide anions (Cl-, Br-, and I-) with glutamic acid (Glu), histidine (His), and arginine (Arg) and their effects on stabilizing the zwitterionic form of these amino acids were investigated using infrared multiple photon dissociation (IRMPD) spectroscopy between 850 and 1900 cm(-1)

  17. Specificity of anion-binding in the substrate-pocket ofbacteriorhodopsin

    Energy Technology Data Exchange (ETDEWEB)

    Facciotti, Marc T.; Cheung, Vincent S.; Lunde, Christopher S.; Rouhani, Shahab; Baliga, Nitin S.; Glaeser, Robert M.

    2003-08-30

    The structure of the D85S mutant of bacteriorhodopsin with a nitrate anion bound in the Schiff-base binding site, and the structure of the anion-free protein have been obtained in the same crystal form. Together with the previously solved structures of this anion pump, in both the anion-free state and bromide-bound state, these new structures provide insight into how this mutant of bacteriorhodopsin is able to bind a variety of different anions in the same binding pocket. The structural analysis reveals that the main structural change that accommodates different anions is the repositioning of the polar side-chain of S85. On the basis of these x-ray crystal structures, the prediction is then made that the D85S/D212N double mutant might bind similar anions and do so over a broader pH range than does the single mutant. Experimental comparison of the dissociation constants, K{sub d}, for a variety of anions confirms this prediction and demonstrates, in addition, that the binding affinity is dramatically improved by the D212N substitution.

  18. Evaluating of arsenic(V) removal from water by weak-base anion exchange adsorbents.

    Science.gov (United States)

    Awual, M Rabiul; Hossain, M Amran; Shenashen, M A; Yaita, Tsuyoshi; Suzuki, Shinichi; Jyo, Akinori

    2013-01-01

    Arsenic contamination of groundwater has been called the largest mass poisoning calamity in human history and creates severe health problems. The effective adsorbents are imperative in response to the widespread removal of toxic arsenic exposure through drinking water. Evaluation of arsenic(V) removal from water by weak-base anion exchange adsorbents was studied in this paper, aiming at the determination of the effects of pH, competing anions, and feed flow rates to improvement on remediation. Two types of weak-base adsorbents were used to evaluate arsenic(V) removal efficiency both in batch and column approaches. Anion selectivity was determined by both adsorbents in batch method as equilibrium As(V) adsorption capacities. Column studies were performed in fixed-bed experiments using both adsorbent packed columns, and kinetic performance was dependent on the feed flow rate and competing anions. The weak-base adsorbents clarified that these are selective to arsenic(V) over competition of chloride, nitrate, and sulfate anions. The solution pH played an important role in arsenic(V) removal, and a higher pH can cause lower adsorption capacities. A low concentration level of arsenic(V) was also removed by these adsorbents even at a high flow rate of 250-350 h(-1). Adsorbed arsenic(V) was quantitatively eluted with 1 M HCl acid and regenerated into hydrochloride form simultaneously for the next adsorption operation after rinsing with water. The weak-base anion exchange adsorbents are to be an effective means to remove arsenic(V) from drinking water. The fast adsorption rate and the excellent adsorption capacity in the neutral pH range will render this removal technique attractive in practical use in chemical industry.

  19. Fundamental characteristics study of anion-exchange PVDF-SiO(2) membranes.

    Science.gov (United States)

    Zuo, Xingtao; Shi, Wenxin; Yu, Shuili; He, Jiajie

    2012-01-01

    A new type of poly(vinylidene fluoride)(PVDF)-SiO(2) hybrid anion-exchange membrane was prepared by blending method. The anion-exchange groups were introduced by the reaction of epoxy groups with trimethylamine (TMA). Contact angle between water and the membrane surface was measured to characterize the hydrophilicity change of the membrane surface. The effects of nano-sized SiO(2) particles in the membrane-forming materials on the membrane mechanical properties and conductivity were also investigated. The experimental results indicated that PVDF-SiO(2) anion-exchange membranes exhibited better water content, ion-exchange capacity, conductivity and mechanic properties, and so may find potential applications in alkaline membrane fuel cells and water treatment processes.

  20. Electron transfer in organic glass. Distance and energy dependence

    International Nuclear Information System (INIS)

    Krongauz, V.V.

    1992-01-01

    The authors have investigated the distance and energy dependence of electron transfer in rigid organic glasses containing randomly dispersed electron donor and electron acceptor molecules. Pulsed radiolysis by an electron beam from a linear accelerator was used for ionization resulting in charge deposition on donor molecules. The disappearance kinetics of donor radical anions due to electron transfer to acceptor was monitored spectroscopically by the change in optical density at the wavelength corresponding to that of donor radical anion absorbance. It was found that the rate of the electron transfer observed experimentally was higher than that computed using the Marcus-Levich theory assuming that the electron-transfer activation barrier is equal to the binding energy of electron on the donor molecule. This discrepancy between the experimental and computed results suggests that the open-quotes inertclose quotes media in which electron-transfer reaction takes place may be participating in the process, resulting in experimentally observed higher electron-transfer rates. 32 refs., 3 figs., 2 tabs

  1. Quantum chemical study of the geometrical and electronic structures of ScSi{sub 3}{sup −/0} clusters and assignment of the anion photoelectron spectra

    Energy Technology Data Exchange (ETDEWEB)

    Tran, Quoc Tri; Tran, Van Tan, E-mail: tvtan@dthu.edu.vn [Theoretical and Physical Chemistry Division, Dong Thap University, 783-Pham Huu Lau, Cao Lanh City, Ward 6, Dong Thap (Viet Nam)

    2016-06-07

    The geometrical and electronic structures of ScSi{sub 3}{sup −/0} clusters have been studied with the B3LYP, CCSD(T), and CASPT2 methods. The ground state of the anionic cluster was evaluated to be the {sup 1}A{sub 1} of rhombic η{sup 2}-(Si{sub 3})Sc{sup −} isomer, whereas that of the neutral cluster was computed to be the {sup 2}A{sub 1} of the same isomer. All features in the 266 and 193 nm photoelectron spectra of ScSi{sub 3}{sup −} cluster were interpreted by the one- and two-electron detachments from the {sup 1}A{sub 1} of rhombic η{sup 2}-(Si{sub 3})Sc{sup −} isomer. The Franck-Condon factor simulation results show that the first broad band starting at 1.78 eV in the spectra comprises several vibrational progression peaks of two totally symmetric modes with the corresponding frequencies of 296 and 354 cm{sup −1}.

  2. Neutral anion receptors: design and application

    NARCIS (Netherlands)

    Antonisse, M.M.G.; Reinhoudt, David

    1998-01-01

    After the development of synthetic cation receptors in the late 1960s, only in the past decade has work started on the development of synthetic neutral anion receptors. Combination and preorganization of different anion binding groups, like amides, urea moieties, or Lewis acidic metal centers lead

  3. Electron inductive effects in the radiolysis of substituted phenylboronic acid solutions

    International Nuclear Information System (INIS)

    Brown, B.J.; Fitch, P.G.; Sangster, D.F.

    1976-01-01

    The pulse radiolysis of aqueous solutions of phenylboronic acid PhB(OH) 2 and its m-nitro and m-amino derivatives has been investigated. The transient optical absorption spectra indicate the presence of three intermediate species absorbing with independent maxima at 297, 317 and 400 nm. The 297-nm band has been assigned to the anion formed in an electron capture reaction, i.e. PhB(OH) 2 +epsilonsub(aq) - → PhB(OH) 2 - and the 317-nm band to cyclohexadienyl radicals formed from OH and H attack on OhB(OH) 2 . Hydroxyphenylboronic acid has been identified as the major stable radiation product. For each of the systems studied the respective yield and reactivity of observed intermediate species can be interpreted relative to the inductive effects of substituent groups in agreement with the Hammett relationship. (author)

  4. Effects of inorganic anions on carbon isotope fractionation during Fenton-like degradation of trichloroethene

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Yunde [State Key Laboratory of Biogeology and Environmental Geology, China University of Geosciences, Wuhan 430074 (China); School of Environmental Studies, China University of Geosciences, Wuhan 430074 (China); Laboratory of Basin Hydrology and Wetland Eco-restoration, China University of Geosciences, Wuhan 430074 (China); Zhou, Aiguo, E-mail: aiguozhou@cug.edu.cn [State Key Laboratory of Biogeology and Environmental Geology, China University of Geosciences, Wuhan 430074 (China); School of Environmental Studies, China University of Geosciences, Wuhan 430074 (China); Gan, Yiqun; Li, Xiaoqian [State Key Laboratory of Biogeology and Environmental Geology, China University of Geosciences, Wuhan 430074 (China); School of Environmental Studies, China University of Geosciences, Wuhan 430074 (China)

    2016-05-05

    Highlights: • The effect of inorganic anions on carbon isotope fractionation was evaluated. • The enrichment factors was independent concentration of NO{sub 3}{sup −}, or SO{sub 4}{sup 2−}. • Cl{sup −} significantly influenced the carbon isotope fractionation. - Abstract: Understanding the magnitude and variability in isotope fractionation with respect to specific processes is crucial to the application of stable isotopic analysis as a tool to infer and quantify transformation processes. The variability of carbon isotope fractionation during Fenton-like degradation of trichloroethene (TCE) in the presence of different inorganic ions (nitrate, sulfate, and chloride), was investigated to evaluate the potential effects of inorganic anions on carbon isotope enrichment factor (ε value). A comparison of ε values obtained in deionized water, nitrate solution, and sulfate solution demonstrated that the ε values were identical and not affected by the presence of nitrate and sulfate. In the presence of chloride, however, the ε values (ranging from −6.3 ± 0.8 to 10 ± 1.3‰) were variable and depended on the chloride concentration, indicating that chloride could significantly affect carbon isotope fractionation during Fenton-like degradation of TCE. Thus, caution should be exercised in selecting appropriate ε values for the field application of stable isotope analysis, as various chloride concentrations may be present due to naturally present or introduced with pH adjustment and iron salts during Fenton-like remediation. Furthermore, the effects of chloride on carbon isotope fractionation may be able to provide new insights about reaction mechanisms of Fenton-like processes.

  5. Effects of inorganic anions on carbon isotope fractionation during Fenton-like degradation of trichloroethene

    International Nuclear Information System (INIS)

    Liu, Yunde; Zhou, Aiguo; Gan, Yiqun; Li, Xiaoqian

    2016-01-01

    Highlights: • The effect of inorganic anions on carbon isotope fractionation was evaluated. • The enrichment factors was independent concentration of NO_3"−, or SO_4"2"−. • Cl"− significantly influenced the carbon isotope fractionation. - Abstract: Understanding the magnitude and variability in isotope fractionation with respect to specific processes is crucial to the application of stable isotopic analysis as a tool to infer and quantify transformation processes. The variability of carbon isotope fractionation during Fenton-like degradation of trichloroethene (TCE) in the presence of different inorganic ions (nitrate, sulfate, and chloride), was investigated to evaluate the potential effects of inorganic anions on carbon isotope enrichment factor (ε value). A comparison of ε values obtained in deionized water, nitrate solution, and sulfate solution demonstrated that the ε values were identical and not affected by the presence of nitrate and sulfate. In the presence of chloride, however, the ε values (ranging from −6.3 ± 0.8 to 10 ± 1.3‰) were variable and depended on the chloride concentration, indicating that chloride could significantly affect carbon isotope fractionation during Fenton-like degradation of TCE. Thus, caution should be exercised in selecting appropriate ε values for the field application of stable isotope analysis, as various chloride concentrations may be present due to naturally present or introduced with pH adjustment and iron salts during Fenton-like remediation. Furthermore, the effects of chloride on carbon isotope fractionation may be able to provide new insights about reaction mechanisms of Fenton-like processes.

  6. Synergistic effect of dicarbollide anions in liquid-liquid extraction: a molecular dynamics study at the octanol-water interface.

    Science.gov (United States)

    Chevrot, G; Schurhammer, R; Wipff, G

    2007-04-28

    We report a molecular dynamics study of chlorinated cobalt bis(dicarbollide) anions [(B(9)C(2)H(8)Cl(3))(2)Co](-)"CCD(-)" in octanol and at the octanol-water interface, with the main aim to understand why these hydrophobic species act as strong synergists in assisted liquid-liquid cation extraction. Neat octanol is quite heterogeneous and is found to display dual solvation properties, allowing to well solubilize CCD(-), Cs(+) salts in the form of diluted pairs or oligomers, without displaying aggregation. At the aqueous interface, octanol behaves as an amphiphile, forming either monolayers or bilayers, depending on the initial state and confinement conditions. In biphasic octanol-water systems, CCD(-) anions are found to mainly partition to the organic phase, thus attracting Cs(+) or even more hydrophilic counterions like Eu(3+) into that phase. The remaining CCD(-) anions adsorb at the interface, but are less surface active than at the chloroform interface. Finally, we compare the interfacial behavior of the Eu(BTP)(3)(3+) complex in the absence and in the presence of CCD(-) anions and extractant molecules. It is found that when the CCD(-)'s are concentrated enough, the complex is extracted to the octanol phase. Otherwise, it is trapped at the interface, attracted by water. These results are compared to those obtained with chloroform as organic phase and discussed in the context of synergistic effect of CCD(-) in liquid-liquid extraction, pointing to the importance of dual solvation properties of octanol and of the hydrophobic character of CCD(-) for synergistic extraction of cations.

  7. Reactions of the hydrated electron with pyrene in lipid bilayer vesicles

    International Nuclear Information System (INIS)

    Schnecke, W.; Graetzel, M.; Henglein, A.

    1977-01-01

    Pyrene and some pyrene derivatives were solubilized in bilayer vesicles of lecithin and the rates of lecithin and the rates of reaction with the hydrated electron investigated. The concentration of the vesicles was 1.3 x 10 -7 M, that of pyrene 10 -6 - 10 -4 M. The rate constant decreases with increasing pyrene concentration. The effect is explained by the highly inhomogeneous distribution of pyrene molecules in the solutions. Only those pyrene molicules are reactive that reside close to the outer surface of the vesicles. The anions of pyrene formed disappear in a second order process. It is concluded that the anions are rapidly detached from their vesicular carriers and react with each other in the aqueous phase. Fluorescence, light scattering and electron microscopic investigations were also carried out to obtain information about the properties of the vesicles used. (orig.) [de

  8. Energy density functionals from the strong-coupling limit applied to the anions of the He isoelectronic series

    International Nuclear Information System (INIS)

    Mirtschink, André; Gori-Giorgi, Paola; Umrigar, C. J.; Morgan, John D.

    2014-01-01

    Anions and radicals are important for many applications including environmental chemistry, semiconductors, and charge transfer, but are poorly described by the available approximate energy density functionals. Here we test an approximate exchange-correlation functional based on the exact strong-coupling limit of the Hohenberg-Kohn functional on the prototypical case of the He isoelectronic series with varying nuclear charge Z − and to capture in general the physics of loosely bound anions, with a tendency to strongly overbind that can be proven mathematically. We also include corrections based on the uniform electron gas which improve the results

  9. New anion-exchange polymers for improved separations

    International Nuclear Information System (INIS)

    Jarvinen, G.D.; Barr, M.E.; Marsh, S.F.

    1997-01-01

    Objective is to improve the understanding of how the structure of a new class of anion-exchange polymers controls the binding of anionic actinide complexes from solution. This is needed to develop practical separation systems that will reduce the cost of actinide processing operations within the DOE complex. In addition anion exchange is widely used in industry. Several new series of bifunctional anion- exchange polymers have been designed, synthesized, and tested for removing Pu(IV), Am(III), and U(VI) from nitric acid. The polymers contain a pyridinium site derived from the host poly(4-vinylpyridine) and a second cationic site attached through a chain of 2 to 6 methylene groups. The new polymers removed Pu four to ten times more efficiently than the best commercial materials

  10. The adsorption-desorption transition of double-stranded DNA interacting with an oppositely charged dendrimer induced by multivalent anions.

    Science.gov (United States)

    Jiang, Yangwei; Zhang, Dong; Zhang, Yaoyang; Deng, Zhenyu; Zhang, Linxi

    2014-05-28

    The adsorption-desorption transition of DNA in DNA-dendrimer solutions is observed when high-valence anions, such as hexavalent anions, are added to the DNA-dendrimer solutions. In the DNA-dendrimer solutions with low-valence anions, dendrimers bind tightly with the V-shaped double-stranded DNA. When high-valence anions, such as pentavalent or hexavalent anions, are added to the DNA-dendrimer solutions, the double-stranded DNA chains can be stretched straightly and the dendrimers are released from the double-stranded DNA chains. In fact, adding high-valence anions to the solutions can change the charge spatial distribution in the DNA-dendrimer solutions, and weaken the electrostatic interactions between the positively charged dendrimers and the oppositely charged DNA chains. Adsorption-desorption transition of DNA is induced by the overcharging of dendrimers. This investigation is capable of helping us understand how to control effectively the release of DNA in gene/drug delivery because an effective gene delivery for dendrimers includes non-covalent DNA-dendrimer binding and the effective release of DNA in gene therapy.

  11. Dehydroacetic Acid Derivatives Bearing Amide or Urea Moieties as Effective Anion Receptors.

    Science.gov (United States)

    Bregović, Nikola; Cindro, Nikola; Bertoša, Branimir; Barišić, Dajana; Frkanec, Leo; Užarević, Krunoslav; Tomišić, Vladislav

    2017-08-01

    Derivatives of dehydroacetic acid comprising amide or urea subunits have been synthesized and their anion-binding properties investigated. Among a series of halides and oxyanions, the studied compounds selectively bind acetate and dihydrogen phosphate in acetonitrile and dimethyl sulfoxide. The corresponding complexation processes were characterized by means of 1 H NMR titrations, which revealed a 1:1 complex stoichiometry in most cases, with the exception of dihydrogen phosphate, which formed 2:1 (anion/ligand) complexes in acetonitrile. The complex stability constants were determined and are discussed with respect to the structural properties of the receptors, the hydrogen-bond-forming potential of the anions, and the characteristics of the solvents used. Based on the spectroscopic data and results of Monte Carlo simulations, the amide or urea groups were affirmed as the primary binding sites in all cases. The results of the computational methods indicate that an array of both inter- and intramolecular hydrogen bonds can form in the studied systems, and these were shown to play an important role in defining the overall stability of the complexes. Solubility measurements were carried out in both solvents and the thermodynamics of transfer from acetonitrile to dimethyl sulfoxide were characterized on a quantitative level. This has afforded a detailed insight into the impact of the medium on the complexation reactions. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Effect of anionic dopants on thickness, morphology and electrical properties of polypyrrole ultra-thin films prepared by in situ chemical polymerization

    Energy Technology Data Exchange (ETDEWEB)

    Mahmoodian, Mehrnoosh [Dep. of Polymer Engineering, Nanostructured Materials Research Center, Sahand University of Technology, Tabriz 51335-1996 (Iran, Islamic Republic of); Pourabbas, Behzad, E-mail: pourabas@sut.ac.ir [Dep. of Polymer Engineering, Nanostructured Materials Research Center, Sahand University of Technology, Tabriz 51335-1996 (Iran, Islamic Republic of); Mohajerzadeh, Shams [Nano-Electronics and Thin Film Lab, School of Electrical and Computer Engineering, University of Tehran, P.O. Box 14395/515, Tehran (Iran, Islamic Republic of)

    2015-05-29

    The effect of different dopant anions on deposition and characteristics of polypyrrole (PPy) thin film has been studied in this work. Ultra-thin films of conducting PPy were deposited on insulating surfaces of glass and oxidized silicon wafer by in situ chemical polymerization in the presence of different anionic dopants including sodium dodecylbenzenesulfonate, sodium dodecyl sulfate, α-naphthalene sulfonic acid, anthraquinone-2-sulfonic acid sodium salt monohydrate/5-sulfosalicylic acid dehydrate, and camphor sulfonic acid. Hydrophilic/hydrophobic properties and morphology of the self-assembled monolayer of N-(3-trimethoxysilylpropyl)pyrrole, the surface modifying agent in this work, and PPy thin films were characterized before and after deposition by contact angle measurements, field emission scanning electron microscopy, and atomic force microscopy. Chemical structure, thickness, and conductivity of the thin films were also studied by attenuated total reflectance Fourier transform infrared spectrometer, ellipsometry, and four-point probe measurements. The results showed deposition of thin films of conducting PPy with comparable thickness in the range of 6-31 nm and different morphologies, uniformity, and smoothness with average roughness in the range of 0.3-6 nm and relatively high range of conductivity on the modified surfaces. - Highlights: • Conducting thin films of polypyrrole were deposited on glass and SiO{sub 2} substrates. • Surface modification using pyrrole-silane was employed prior to polymerization. • Films as thin as ≈ 7 nm were deposited using different surfactant/counter ions. • Chemistry of the counter ion affects thickness, conductivity and morphology. • Lower thickness/higher conductivity were obtained by structurally flexible dopants.

  13. Proton Affinities of Anionic Bases:  Trends Across the Periodic Table, Structural Effects, and DFT Validation.

    Science.gov (United States)

    Swart, Marcel; Bickelhaupt, F Matthias

    2006-03-01

    We have carried out an extensive exploration of the gas-phase basicity of archetypal anionic bases across the periodic system using the generalized gradient approximation of density functional theory (DFT) at BP86/QZ4P//BP86/TZ2P. First, we validate DFT as a reliable tool for computing proton affinities and related thermochemical quantities:  BP86/QZ4P//BP86/TZ2P is shown to yield a mean absolute deviation of 1.6 kcal/mol for the proton affinity at 0 K with respect to high-level ab initio benchmark data. The main purpose of this work is to provide the proton affinities (and corresponding entropies) at 298 K of the anionic conjugate bases of all main-group-element hydrides of groups 14-17 and periods 2-6. We have also studied the effect of stepwise methylation of the protophilic center of the second- and third-period bases.

  14. Evaluation of the presence of major anionic surfactants in marine sediments.

    Science.gov (United States)

    Cantarero, S; Camino-Sánchez, F J; Zafra-Gómez, A; Ballesteros, O; Navalón, A; Vílchez, J L; Verge, C; Reis, M S; Saraiva, P M

    2012-03-01

    The contamination of aquatic environments has become the focus of increasing regulation and public concern due to their potential and unknown negative effects on the ecosystems. The present work develops a monitoring and statistical study, based on the analysis of variance test (ANOVA) and the multivariable analysis, both for insoluble soap and LAS in order to compare the behavior of different anionic surfactants in this environmental compartment. First, a novel and successfully validated methodology to analyze insoluble soap in these samples is developed. The matrix effect and the comparison of different extraction techniques were also performed. The optimized analytical methodologies were applied to 48 representative samples collected from the Almeria Coast (Spain) and then a statistical analysis to correlate anionic surfactant concentration and several variables associated with marine sediment samples was also developed. The results obtained showed relevant conclusions related to the environmental behavior of anionic surfactants in marine sediments. Copyright © 2011 Elsevier Ltd. All rights reserved.

  15. A practical approach to temperature effects in dissociative electron attachment cross sections using local complex potential theory

    International Nuclear Information System (INIS)

    Sugioka, Yuji; Takayanagi, Toshiyuki

    2012-01-01

    Highlights: ► Dissociative electron attachment cross sections for polyatomic molecules are calculated by a simple theoretical approach. ► Temperature effects can be reasonably reproduced with the present model. ► All the degrees-of-freedom are taken into account in the present dynamics approach. -- Abstract: We propose a practical computational scheme to obtain temperature dependence of dissociative electron attachment cross sections to polyatomic molecules within a local complex potential theory formalism. First we perform quantum path-integral molecular dynamics simulations on the potential energy surface for the neutral molecule in order to sample initial nuclear configurations as well as momenta. Classical trajectories are subsequently integrated on the potential energy surface for the anionic state and survival probabilities are simultaneously calculated along the obtained trajectories. We have applied this simple scheme to dissociative electron attachment processes to H 2 O and CF 3 Cl, for which several previous studies are available from both the experimental and theoretical sides.

  16. A practical approach to temperature effects in dissociative electron attachment cross sections using local complex potential theory

    Energy Technology Data Exchange (ETDEWEB)

    Sugioka, Yuji [Department of Chemistry, Saitama University, 255 Shimo-Okubo, Sakura-ku, Saitama City, Saitama 338-8570 (Japan); Takayanagi, Toshiyuki, E-mail: tako@mail.saitama-u.ac.jp [Department of Chemistry, Saitama University, 255 Shimo-Okubo, Sakura-ku, Saitama City, Saitama 338-8570 (Japan)

    2012-09-11

    Highlights: Black-Right-Pointing-Pointer Dissociative electron attachment cross sections for polyatomic molecules are calculated by a simple theoretical approach. Black-Right-Pointing-Pointer Temperature effects can be reasonably reproduced with the present model. Black-Right-Pointing-Pointer All the degrees-of-freedom are taken into account in the present dynamics approach. -- Abstract: We propose a practical computational scheme to obtain temperature dependence of dissociative electron attachment cross sections to polyatomic molecules within a local complex potential theory formalism. First we perform quantum path-integral molecular dynamics simulations on the potential energy surface for the neutral molecule in order to sample initial nuclear configurations as well as momenta. Classical trajectories are subsequently integrated on the potential energy surface for the anionic state and survival probabilities are simultaneously calculated along the obtained trajectories. We have applied this simple scheme to dissociative electron attachment processes to H{sub 2}O and CF{sub 3}Cl, for which several previous studies are available from both the experimental and theoretical sides.

  17. Cation–Anion Interactions within the Nucleic Acid Ion Atmosphere Revealed by Ion Counting

    Science.gov (United States)

    Gebala, Magdalena; Giambasu, George M.; Lipfert, Jan; Bisaria, Namita; Bonilla, Steve; Li, Guangchao; York, Darrin M.; Herschlag, Daniel

    2016-01-01

    The ion atmosphere is a critical structural, dynamic, and energetic component of nucleic acids that profoundly affects their interactions with proteins and ligands. Experimental methods that “count” the number of ions thermodynamically associated with the ion atmosphere allow dissection of energetic properties of the ion atmosphere, and thus provide direct comparison to theoretical results. Previous experiments have focused primarily on the cations that are attracted to nucleic acid polyanions, but have also showed that anions are excluded from the ion atmosphere. Herein, we have systematically explored the properties of anion exclusion, testing the zeroth-order model that anions of different identity are equally excluded due to electrostatic repulsion. Using a series of monovalent salts, we find, surprisingly, that the extent of anion exclusion and cation inclusion significantly depends on salt identity. The differences are prominent at higher concentrations and mirror trends in mean activity coefficients of the electrolyte solutions. Salts with lower activity coefficients exhibit greater accumulation of both cations and anions within the ion atmosphere, strongly suggesting that cation–anion correlation effects are present in the ion atmosphere and need to be accounted for to understand electrostatic interactions of nucleic acids. To test whether the effects of cation–anion correlations extend to nucleic acid kinetics and thermodynamics, we followed the folding of P4–P6, a domain of the Tetrahymena group I ribozyme, via single-molecule fluorescence resonance energy transfer in solutions with different salts. Solutions of identical concentration but lower activity gave slower and less favorable folding. Our results reveal hitherto unknown properties of the ion atmosphere and suggest possible roles of oriented ion pairs or anion-bridged cations in the ion atmosphere for electrolyte solutions of salts with reduced activity. Consideration of these new

  18. In-situ anion exchange fabrication of porous ZnO/ZnSe heterostructural microspheres with enhanced visible light photocatalytic activity

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Hairui, E-mail: liuhairui1@126.com [College of Physics & Electrics Engineering, Henan Normal University, Henan Key Laboratory of Photovoltaic Materials, Xinxiang 453007 (China); Key Laboratory of Interface Science and Engineering in Advanced Materials (Taiyuan University of Technology), Ministry of Education, Taiyuan, Shanxi, 030024 (China); College of Materials Science and Engineering, Taiyuan University of Technology, Taiyuan, Shanxi 030024 (China); Hu, Yanchun [College of Physics & Electrics Engineering, Henan Normal University, Henan Key Laboratory of Photovoltaic Materials, Xinxiang 453007 (China); He, Xia [Key Laboratory of Interface Science and Engineering in Advanced Materials (Taiyuan University of Technology), Ministry of Education, Taiyuan, Shanxi, 030024 (China); Jia, Husheng, E-mail: jia_husheng@126.com [Key Laboratory of Interface Science and Engineering in Advanced Materials (Taiyuan University of Technology), Ministry of Education, Taiyuan, Shanxi, 030024 (China); College of Materials Science and Engineering, Taiyuan University of Technology, Taiyuan, Shanxi 030024 (China); Liu, Xuguang; Xu, Bingshe [Key Laboratory of Interface Science and Engineering in Advanced Materials (Taiyuan University of Technology), Ministry of Education, Taiyuan, Shanxi, 030024 (China)

    2015-11-25

    Porous ZnO microspheres were fabricated by an ultrasonic irradiation technique. Subsequently, through a facile in-situ anion exchange reaction between the ZnO microsphere and sodium selenite, spherical ZnO/ZnSe heterostructures with different ratios of the two components were fabricated. The as-obtained products were characterized by field emission scanning electron microscopy (FE-SEM), energy-dispersive X-ray (EDX) spectroscopy, transmission electron microscopy (TEM), X-ray diffraction (XRD), and UV–vis spectrometry. The results reveal that the secondary ZnSe nanoparticles are grown on the surface of pre-grown ZnO microspheres. Compared with pure ZnO microspheres, the ZnO/ZnSe hetero-microspheres show enhance visible-light photocatalytic activity for degradation of methylene blue (MB) and 4-nitrophenol (4-NP). The enhanced photocatalytic performance is attributed to fast separation and transport of photogenerated electrons and holes derived from the coupling effect of ZnSe and ZnO heterostructure. Photoluminescent spectra further indicate that the ZnO/ZnSe heterostructures greatly suppress the charge recombination of photogenerated electron–hole pairs, which would be beneficial to improve their photocatalytic activity. Finally, the photocatalytic mechanism of the ZnO/ZnSe heterostructures is proposed. - Graphical abstract: Porous ZnO/ZnSe heterostructures with different ratios of the two components were fabricated and present enhance visible-light photocatalytic activity for degradation of methylene blue (MB) and 4-nitrophenol (4-NP). The enhanced photocatalytic performance is attributed to fast separation and transport of photogenerated electrons and holes derived from the coupling effect of ZnSe and ZnO heterostructure. - Highlights: • Spherical ZnO/ZnSe porous composites were fabricated by in-situ anion exchange. • ZnO/ZnSe composites exhibited enhanced visible-light photocatalytic activity. • The matching band gap improves the separation of

  19. Amino-functionalized mesoporous MCM-41 silica as an efficient adsorbent for water treatment: batch and fixed-bed column adsorption of the nitrate anion

    Science.gov (United States)

    Ebrahimi-Gatkash, Mehdi; Younesi, Habibollah; Shahbazi, Afsaneh; Heidari, Ava

    2017-07-01

    In the present study, amino-functionalized Mobil Composite Material No. 41 (MCM-41) was used as an adsorbent to remove nitrate anions from aqueous solutions. Mono-, di- and tri-amino functioned silicas (N-MCM-41, NN-MCM-41 and NNN-MCM-41) were prepared by post-synthesis grafting method. The samples were characterized by means of X-ray powder diffraction, FTIR spectroscopy, thermogravimetric analysis, scanning electron microscopy and nitrogen adsorption-desorption. The effects of pH, initial concentration of anions, and adsorbent loading were examined in batch adsorption system. Results of adsorption experiments showed that the adsorption capacity increased with increasing adsorbent loading and initial anion concentration. It was found that the Langmuir mathematical model indicated better fit to the experimental data than the Freundlich. According to the constants of the Langmuir equation, the maximum adsorption capacity for nitrate anion by N-MCM-41, NN-MCM-41 and NNN-MCM-41 was found to be 31.68, 38.58 and 36.81 mg/g, respectively. The adsorption kinetics were investigated with pseudo-first-order and pseudo-second-order model. Adsorption followed the pseudo-second-order rate kinetics. The coefficients of determination for pseudo-second-order kinetic model are >0.99. For continuous adsorption experiments, NNN-MCM-41 adsorbent was used for the removal of nitrate anion from solutions. Breakthrough curves were investigated at different bed heights, flow rates and initial nitrate anion concentrations. The Thomas and Yan models were utilized to calculate the kinetic parameters and to predict the breakthrough curves of different bed height. Results from this study illustrated the potential utility of these adsorbents for nitrate removal from water solution.

  20. Effective electron-electron and electron-phonon interactions in the Hubbard-Holstein model

    International Nuclear Information System (INIS)

    Aprea, G.; Di Castro, C.; Grilli, M. . E-mail marco.grilli@roma1.infn.it; Lorenzana, J.

    2006-01-01

    We investigate the interplay between the electron-electron and the electron-phonon interaction in the Hubbard-Holstein model. We implement the flow-equation method to investigate within this model the effect of correlation on the electron-phonon effective coupling and, conversely, the effect of phonons in the effective electron-electron interaction. Using this technique we obtain analytical momentum-dependent expressions for the effective couplings and we study their behavior for different physical regimes. In agreement with other works on this subject, we find that the electron-electron attraction mediated by phonons in the presence of Hubbard repulsion is peaked at low transferred momenta. The role of the characteristic energies involved is also analyzed

  1. Influence of cations and anions on the formation of β-FeOOH

    International Nuclear Information System (INIS)

    Kamimura, T.; Nasu, S.; Segi, T.; Tazaki, T.; Miyuki, H.; Morimoto, S.; Kudo, T.

    2005-01-01

    In the presence of cations such as Cr 3+ , Cu 2+ and Ni 2+ , and anions such as SO 4 2- and NO 3 - , precipitation of β-FeOOH from Fe 3+ -solution containing Cl - by hydrolysis have been investigated by means of X-ray diffraction technique (XRD), Mossbauer spectroscopy (MS) and transmission electron microscopy (TEM). XRD peaks of β-FeOOH were broadened when the cations were added as sulfates, and this tendency for Cr 3+ was significantly observed. When the cations were added as nitrates, there was no significant change in XRD peaks. Inductively coupled plasma (ICP) analysis showed that only Cr added as sulfate was contained in β-FeOOH. Ni and Cu added as sulfates, and any cations added as nitrates were not contained in it. When β-FeOOH was synthesized with Na 2 SO 4 , the XRD peaks were broadened. XRD-peak broadening was mainly caused by the coexistence of SO 4 2- ion. The incorporation of cations in β-FeOOH is affected by coexistent anions, and the XRD-peak broadening is caused by not only cations but also anions. This behavior has been discussed in association with the stability of Fe 3+ -complexes in the solution

  2. Studies of the ionizing radiation effects on the effluents acute toxicity due to anionic surfactants

    International Nuclear Information System (INIS)

    Moraes, Maria Cristina Franco de

    2004-01-01

    Several studies have shown the negative effects of surfactants, as detergents active substance, when discharged on biological sewage wastewater treatment plants. High toxicity may represent a lower efficiency for biological treatment. When surfactants are in aquatic environment they may induce a loss of grease revetment on birds (feather). Depending on the surfactant concentration, several damages to all biotic systems can happen. Looking for an alternative technology for wastewater treatment, efficient for surfactant removal, the present work applied ionizing radiation as an advanced oxidation process for affluents and effluents from Suzano Treatment Station. Such wastewater samples were submitted to radiation using an electron beam from a Dynamic Electron Beam Accelerator from Instituto de Pesquisas Energeticas e Nucleares. In order to assess this proposed treatment efficacy, it was performed acute toxicity evaluation with two test-organisms, the crustacean Daphnia similis and the luminescent bacteria Vibrio fischeri. The studied effluents were: one from a chemical industry (IND), three from sewage plant (affluents - GG, GM and Guaio) and the last biologically treated secondary effluent (EfF), discharged at Tiete river. The applied radiation doses varied from 3 kGy to 50 kGy, being 50 kGy enough for surfactant degradation contained at industrial effluent. For GG, GM and Guaio samples, doses of 6 kGy and 10 kGy were efficient for surfactant and toxicity reduction, representing an average removal that varied from 71.80% to 82.76% and toxicity from 30% to 91% for most the effluents. The final effluent was less toxic than the others and the radiation induced an average 11% removal for anionic surfactant. The industrial effluents were also submitted to an aeration process in order to quantify the contribution of surfactant to the whole sample toxicity, once it was partially removed as foam and several fractions were evaluated for toxicity. (author)

  3. Electron Beam Mediated Simple Synthetic Route to Preparing Layered Zinc Hydroxide

    International Nuclear Information System (INIS)

    Bae, Hyo Sun; Jung, Hyun

    2012-01-01

    We have developed a novel and eco-friendly synthetic route for the preparation of a two-dimensional layered zinc hydroxide with intercalated nitrate anions. The layered zinc hydroxide nitrate, called 'zinc basic salt', was, in general, successfully synthesized, using an electron beam irradiation technique. The 2-propanol solutions containing hydrated zinc nitrate were directly irradiated with an electron-beam at room temperature, under atmospheric conditions, without stabilizers or base molecules. Under electron beam irradiation, the reactive OH· radicals were generated by radiolysis of water molecules in precursor metal salts. After further radiolytic processes, the hydroxyl anions might be formed by the reaction of solvated electrons and the OH· radical. Finally, the Zn 5 (OH) 8 (NO 3 ) 2 ·2H 2 O was precipitated by the reaction of zinc cation and hydroxyl anions. Structure and morphology of obtained compounds were characterized by powder X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), and high resolution transmission electron microscopy (HR-TEM). The chemical components of the products were determined by Fourier transform infrared spectroscopy (FT-IR) and elemental analysis (EA). The thermal behavior of products was studied by thermogravimetric (TG) and differential thermal analysis (DTA)

  4. Anion Gap Blood Test: MedlinePlus Lab Test Information

    Science.gov (United States)

    ... https://medlineplus.gov/labtests/aniongapbloodtest.html Anion Gap Blood Test To use the sharing features on this page, please enable JavaScript. What is an Anion Gap Blood Test? An anion gap blood test is a way ...

  5. Antibacterial effect of cationic porphyrazines and anionic phthalocyanine and their interaction with plasmid DNA

    Science.gov (United States)

    Hassani, Leila; Hakimian, Fatemeh; Safaei, Elham; Fazeli, Zahra

    2013-11-01

    Resistance to antibiotics is a public health issue and identification of new antibacterial agents is one of the most important goals of pharmacological research. Among the novel developed antibacterial agents, porphyrin complexes and their derivatives are ideal candidates for use in medical applications. Phthalocyanines differ from porphyrins by having nitrogen atoms link the individual pyrrol units. The aza analogues of the phthalocyanines (azaPcs) such as tetramethylmetalloporphyrazines are heterocyclic Pc analogues. In this investigation, interaction of an anionic phthalocyanine (Cu(PcTs)) and two cationic tetrapyridinoporphyrazines including [Cu(2,3-tmtppa)]4+ and [Cu(3,4-tmtppa)]4+ complexes with plasmid DNA was studied using spectroscopic and gel electrophoresis methods. In addition, antibacterial effect of the complexes against Gram-positive (Staphylococcus aureus) and Gram-negative (Escherichia coli) bacteria was investigated using dilution test method. The results indicated that both porphyrazines have significant antibacterial properties, but Cu(PcTs) has weak antibacterial effect. Compairing the binding of the phthalocyanine and the porphyrazines to DNA demonstrated that the interaction of cationic porphyrazines is stronger than the anionic phthalocyanine remarkably. The extent of hypochromicity and red shift of absorption spectra indicated preferential intercalation of the two porphyrazine into the base pairs of DNA helix. Gel electrophoresis result implied Cu(2,3-tmtppa) and Cu(3,4-tmtppa) are able to perform cleavage of the plasmid DNA. Consequently, DNA binding and cleavage might be one of the antibacterial mechanisms of the complexes.

  6. Surface modification of polystyrene with atomic oxygen radical anions-dissolved solution

    International Nuclear Information System (INIS)

    Wang Lian; Yan Lifeng; Zhao Peitao; Torimoto, Yoshifumi; Sadakata, Masayoshi; Li Quanxin

    2008-01-01

    A novel approach to surface modification of polystyrene (PS) polymer with atomic oxygen radical anions-dissolved solution (named as O - water) has been investigated. The O - water, generated by bubbling of the O - (atomic oxygen radical anion) flux into the deionized water, was characterized by UV-absorption spectroscopy and electron paramagnetic resonance (EPR) spectroscopy. The O - water treatments caused an obvious increase of the surface hydrophilicity, surface energy, surface roughness and also caused an alteration of the surface chemical composition for PS surfaces, which were indicated by the variety of contact angle and material characterization by atomic force microscope (AFM) imaging, field emission scanning electron microscopy (FESEM), X-ray photoelectron spectroscopy (XPS), and attenuated total-reflection Fourier transform infrared (ATR-FTIR) measurements. Particularly, it was found that some hydrophilic groups such as hydroxyl (OH) and carbonyl (C=O) groups were introduced onto the polystyrene surfaces via the O - water treatment, leading to the increases of surface hydrophilicity and surface energy. The active oxygen species would react with the aromatic ring molecules on the PS surfaces and decompose the aromatic compounds to produce hydrophilic hydroxyl and carbonyl compounds. In addition, the O - water is also considered as a 'clean solution' without adding any toxic chemicals and it is easy to be handled at room temperature. Present method may suit to the surface modification of polymers and other heat-sensitive materials potentially

  7. Resonance electron attachment to plant hormones and its likely connection with biochemical processes

    Energy Technology Data Exchange (ETDEWEB)

    Pshenichnyuk, Stanislav A., E-mail: sapsh@anrb.ru [Institute of Molecule and Crystal Physics, Ufa Research Centre, Russian Academy of Sciences, Prospekt Oktyabrya 151, 450075 Ufa (Russian Federation); Modelli, Alberto [Dipartimento di Chimica “G. Ciamician”, Università di Bologna, via Selmi 2, 40126 Bologna, Italy and Centro Interdipartimentale di Ricerca in Scienze Ambientali, via S. Alberto 163, 48123 Ravenna (Italy)

    2014-01-21

    Gas-phase formation of temporary negative ion states via resonance attachment of low-energy (0–6 eV) electrons into vacant molecular orbitals of salicylic acid (I) and its derivatives 3-hydroxy- (II) and 4-hydroxybenzoic acid (III), 5-cloro salicylic acid (IV) and methyl salicylate (V) was investigated for the first time by electron transmission spectroscopy. The description of their empty-level structures was supported by density functional theory and Hartree-Fock calculations, using empirically calibrated linear equations to scale the calculated virtual orbital energies. Dissociative electron attachment spectroscopy (DEAS) was used to measure the fragment anion yields generated through dissociative decay channels of the parent molecular anions of compounds I–V, detected with a mass filter as a function of the incident electron energy in the 0–14 eV energy range. The most intense negative fragment produced by DEA to isomers I–III is the dehydrogenated molecular anion [M–H]{sup −}, mainly formed at incident electron energies around 1 eV. The vertical and adiabatic electron affinities were evaluated at the B3LYP/6-31+G(d) level as the anion/neutral total energy difference. The same theoretical method was also used for evaluation of the thermodynamic energy thresholds for production of the negative fragments observed in the DEA spectra. The gas-phase DEAS data can provide support for biochemical reaction mechanisms in vivo.

  8. Resonance electron attachment to plant hormones and its likely connection with biochemical processes

    International Nuclear Information System (INIS)

    Pshenichnyuk, Stanislav A.; Modelli, Alberto

    2014-01-01

    Gas-phase formation of temporary negative ion states via resonance attachment of low-energy (0–6 eV) electrons into vacant molecular orbitals of salicylic acid (I) and its derivatives 3-hydroxy- (II) and 4-hydroxybenzoic acid (III), 5-cloro salicylic acid (IV) and methyl salicylate (V) was investigated for the first time by electron transmission spectroscopy. The description of their empty-level structures was supported by density functional theory and Hartree-Fock calculations, using empirically calibrated linear equations to scale the calculated virtual orbital energies. Dissociative electron attachment spectroscopy (DEAS) was used to measure the fragment anion yields generated through dissociative decay channels of the parent molecular anions of compounds I–V, detected with a mass filter as a function of the incident electron energy in the 0–14 eV energy range. The most intense negative fragment produced by DEA to isomers I–III is the dehydrogenated molecular anion [M–H] − , mainly formed at incident electron energies around 1 eV. The vertical and adiabatic electron affinities were evaluated at the B3LYP/6-31+G(d) level as the anion/neutral total energy difference. The same theoretical method was also used for evaluation of the thermodynamic energy thresholds for production of the negative fragments observed in the DEA spectra. The gas-phase DEAS data can provide support for biochemical reaction mechanisms in vivo

  9. Electrolyte control of photosynthetic electron transport in cyanobacteria

    International Nuclear Information System (INIS)

    Papageorgiou, G.C.

    1986-01-01

    Ion-permeable cells (permeaplasts) of the cyanobacterium Anacystis nidulans were prepared enzymatically and were characterized with respect to several structural and functional indices. The permeaplasts contain intact, ion-impermeable thylakoids and are photosynthetically active. The authors discuss how, employing these cells, they investigated the effects of cations, acting either on the outer, or on the inner thylakoid membrane surface, on photoinduced electron exchanges with anionic donors (Cyt c-550, plastocyanin, innersurface), or anionic acceptors (FeCN 3- ; outer surface). Cations accelerate such exchanges by accumulating near the solution-membrane interfaces and screening the negative surface charge of membranes. Electrostatic screening, however, is not the only contributing factor, and other electrolyte-linked influences must be invoked in order to interpret the experimental observations

  10. Effect of sodium aromatic sulfonate group in anionic polymer dispersant on the viscosity of coal-water mixtures

    Energy Technology Data Exchange (ETDEWEB)

    Toshio Kakui; Hidehiro Kamiya [Lion Corporation, Tokyo (Japan). Chemicals Research Laboratories, Chemicals Division

    2004-06-01

    This paper focused on the effect of sodium aromatic sulfonate in anionic polymer dispersants on the viscosity of coal-water mixtures (CWMs) with a Tatung coal powder. To determine the optimum molecular structure of a polymer dispersant for the minimum viscosity of a CWM, various anionic co-polymers with different hydrophilic and hydrophobic groups or different molecular weights were prepared, using various types of monomers. Anionic co-polymers with sodium aromatic sulfonate, such as sodium styrene-sulfonate and sodium naphthalene-sulfonate, reduced the viscosity of dense CWMs. In particular, a co-polymer of sodium styrene-sulfonate and sodium acrylate with a molar ratio of 70:30 and a molecular weight of {approximately} 10 000 gave the minimum viscosity of a 70 wt % CWM. To obtain a low viscosity for a CWM, a large electrostatic repulsive force with an absolute value of the zeta potential of the coal particles of {gt} 70 mV and {gt} 6.5 mg/g of adsorbed polymer on the coal surface were needed. The mixture of sodium polystyrene-sulfonate and sodium polyacrylate with a weight ratio of 50:50 also gave a low viscosity of 70 wt % CWM. On the basis of the results, the adsorption behavior of polymer dispersants on the coal surface is examined by measuring the wettability of coal powder pellets. 27 refs., 8 figs., 3 tabs.

  11. Radio-iodide uptake by modified poly (glycidyl methacrylate) as anion exchange resin

    Energy Technology Data Exchange (ETDEWEB)

    Othman, Sameh H. [Atomic Energy Authority, Cairo (Egypt). Nuclear Research Center; Atomic Energy Authority, Cairo (Egypt). Second Research Reactor; Elbarbary, Ahmed M. [Atomic Energy Authority, Cairo (Egypt). Radiation Research of Polymer Chemistry Dept.; Rashad, Ghada; Fasih, T.W. [Atomic Energy Authority, Cairo (Egypt). Hot Laboratories Center

    2017-03-01

    Poly(glycidyl methacrylate) (PGMA) microspheres were prepared by radiation induced polymerization of glycidyl methacrylate (GMA) monomer. The factors affecting the degree of polymerization and yield (%) of PGMA such as type of solvent, monomer concentration, and irradiation dose were investigated. It was found that the PGMA yield (%) increases with increasing monomer concentration up to 50% and absorbed dose of 5 kGy. The resulting PGMA containing the epoxy group was chemically modified by hydroxyl amine to act as anion-exchange resin for uptake of {sup 131}I{sup -} ions. The modified PGMA (MPGMA) was characterized by Fourier transform infrared (FT-IR) spectrophotometer, thermal gravimetric analysis (TGA) and scanning electron microscopy (SEM). I-131 is produced from the fission of U-235 with low-enrichment uranium (LEU) targets in the Egyptian Second Research Reactor (ETRR-2). Separation of iodide from the radioactive solution by batchwise and column techniques was employed to determine the adsorption capacity of the MPGMA. Quality control of {sup 131}I product solution and radiochemical purity was examined by using the ascending paper chromatography method. The uptake behavior of MPGMA towards {sup 131}I{sup -} ions were studied at different experimental conditions and achieved by X-ray fluorescence (XRF). The synthesized MPGMA showed good results as anion-exchange and an effective adsorbent for uptaking {sup 131}I{sup -} ions.

  12. Diffusion and retention of organic anions in Callovian-Oxfordian clay rock

    International Nuclear Information System (INIS)

    Rasamimanana, Sabrina

    2016-01-01

    The Callovo-Oxfordian mud-stone (CO_x) is studied as a possible host rock for a deep disposal of radioactive waste (Cigeo project). Indeed, besides being very weakly permeable, it presents a high content of clayey minerals, capable of retaining radionuclides under cationic form and to delay strongly their transport. Nevertheless, some waste packages may release a significant amount of organic molecules, capable of complexing these radionuclides and drastically increase their mobility. So, the objective of this work was to better understand the diffusive behavior of several organic molecules of interest in this mudstone, by investigating at first their affinity with the host rock. The retention of organic molecules under anionic form (acetate, phthalate, adipate, benzoate, and citrate) was quantified on to the dispersed CO_x mudstone using adsorption/desorption batch experiments. Experiments on de-carbonated rock and clay fraction only (≤ 2μm) were also performed to identify solid phases and chemical functions responsible for the retention. a correlation of the intensity of retention, R_d, was pointed out whit the dipole moment μ(Orga.), providing a qualitative estimate of retention capacity for polar hydrophilic organic molecules. So, phthalate, slightly polar, displays a reversible retention (R_d ≅1,6 L.kg"-"1), mainly on clayey phases. Citrate, very polar and strongly adsorbed (R_d ≅ 40 L.kg"-"1), displays a persistent desorption hysteresis and an affinity to different solid phases (clayey minerals and minor oxides). Lastly, acetate, adipate and benzoate, weakly polar, display a lower affinity with rock (R_d ≤ 0,2 L.kg"-"1). The diffusive behavior in compact rock of these organic anions was then studied. The effective diffusion coefficient and retardation factor values were quantified. The low diffusivity, [D_e/D_0](Organic Anions) ≅ 0,1 a0,25 * [D_e/D_0](Water) evidences an effect of anionic exclusion, with a same intensity as that observed for

  13. Acute and chronic influence of temperature on red blood cell anion exchange.

    Science.gov (United States)

    Jensen, F B; Wang, T; Brahm, J

    2001-01-01

    Unidirectional (36)Cl(-) efflux via the red blood cell anion exchanger was measured under Cl(-) self-exchange conditions (i.e. no net flow of anions) in rainbow trout Oncorhynchus mykiss and red-eared freshwater turtle Trachemys scripta to examine the effects of acute temperature changes and acclimation temperature on this process. We also evaluated the possible adaptation of anion exchange to different temperature regimes by including our previously published data on other animals. An acute temperature increase caused a significant increase in the rate constant (k) for unidirectional Cl(-) efflux in rainbow trout and freshwater turtle. After 3 weeks of temperature acclimation, 5 degrees C-acclimated rainbow trout showed only marginally higher Cl(-) transport rates than 15 degrees C-acclimated trout when compared at the same temperature. Apparent activation energies for red blood cell Cl(-) exchange in trout and turtle were lower than values reported in endothermic animals. The Q(10) for red blood cell anion exchange was 2.0 in trout and 2.3 in turtle, values close to those for CO(2) excretion, suggesting that, in ectothermic animals, the temperature sensitivity of band-3-mediated anion exchange matches the temperature sensitivity of CO(2) transport (where red blood cell Cl(-)/HCO(3)(-) exchange is a rate-limiting step). In endotherms, such as man and chicken, Q(10) values for red blood cell anion exchange are considerably higher but are no obstacle to CO(2) transport, because body temperature is normally kept constant at values at which anion exchange rates are high. When compared at constant temperature, red blood cell Cl(-) permeability shows large differences among species (trout, carp, eel, cod, turtle, alligator, chicken and man). Cl(-) permeabilities are, however, remarkable similar when compared at preferred body temperatures, suggesting an appropriate evolutionary adaptation of red blood cell anion exchange function to the different thermal niches occupied

  14. Tripodal receptors for cation and anion sensors

    NARCIS (Netherlands)

    Kuswandi, Bambang; Nuriman, [Unknown; Verboom, Willem; Reinhoudt, David

    2006-01-01

    This review discusses different types of artificial tripodal receptors for the selectiverecognition and sensing of cations and anions. Examples on the relationship between structure andselectivity towards cations and anions are described. Furthermore, their applications as potentiometricion sensing

  15. On the applicability of one- and many-electron quantum chemistry models for hydrated electron clusters

    Science.gov (United States)

    Turi, László

    2016-04-01

    We evaluate the applicability of a hierarchy of quantum models in characterizing the binding energy of excess electrons to water clusters. In particular, we calculate the vertical detachment energy of an excess electron from water cluster anions with methods that include one-electron pseudopotential calculations, density functional theory (DFT) based calculations, and ab initio quantum chemistry using MP2 and eom-EA-CCSD levels of theory. The examined clusters range from the smallest cluster size (n = 2) up to nearly nanosize clusters with n = 1000 molecules. The examined cluster configurations are extracted from mixed quantum-classical molecular dynamics trajectories of cluster anions with n = 1000 water molecules using two different one-electron pseudopotenial models. We find that while MP2 calculations with large diffuse basis set provide a reasonable description for the hydrated electron system, DFT methods should be used with precaution and only after careful benchmarking. Strictly tested one-electron psudopotentials can still be considered as reasonable alternatives to DFT methods, especially in large systems. The results of quantum chemistry calculations performed on configurations, that represent possible excess electron binding motifs in the clusters, appear to be consistent with the results using a cavity structure preferring one-electron pseudopotential for the hydrated electron, while they are in sharp disagreement with the structural predictions of a non-cavity model.

  16. On the applicability of one- and many-electron quantum chemistry models for hydrated electron clusters

    Energy Technology Data Exchange (ETDEWEB)

    Turi, László, E-mail: turi@chem.elte.hu [Department of Physical Chemistry, Eötvös Loránd University, P.O. Box 32, H-1518 Budapest 112 (Hungary)

    2016-04-21

    We evaluate the applicability of a hierarchy of quantum models in characterizing the binding energy of excess electrons to water clusters. In particular, we calculate the vertical detachment energy of an excess electron from water cluster anions with methods that include one-electron pseudopotential calculations, density functional theory (DFT) based calculations, and ab initio quantum chemistry using MP2 and eom-EA-CCSD levels of theory. The examined clusters range from the smallest cluster size (n = 2) up to nearly nanosize clusters with n = 1000 molecules. The examined cluster configurations are extracted from mixed quantum-classical molecular dynamics trajectories of cluster anions with n = 1000 water molecules using two different one-electron pseudopotenial models. We find that while MP2 calculations with large diffuse basis set provide a reasonable description for the hydrated electron system, DFT methods should be used with precaution and only after careful benchmarking. Strictly tested one-electron psudopotentials can still be considered as reasonable alternatives to DFT methods, especially in large systems. The results of quantum chemistry calculations performed on configurations, that represent possible excess electron binding motifs in the clusters, appear to be consistent with the results using a cavity structure preferring one-electron pseudopotential for the hydrated electron, while they are in sharp disagreement with the structural predictions of a non-cavity model.

  17. Ion-exchange concentration of inorganic anions from aqueous solution

    Directory of Open Access Journals (Sweden)

    L. P. Bondareva

    2016-01-01

    Full Text Available Monitoring of natural waters in the present time - consuming process, the accuracy of which is influenced by many factors: the composition of water, the presence of impurities and "interfering" components. The water sample preparation process includes the step of concentration and separation of ions determined. The most versatile, efficient, and frequently used method is the concentration of inorganic anions from aqueous solutions by ion exchanger, which can optimize the composition of water to the optimal for identification and quantitative determination of anions. The characteristics of sorption chloride, nitrate and sulfate ions of basic anion exchange resin AВ-17 and Purolite A430 were compared in the article. The constants of protolysis of ion exchangers both AB 17 and Purolite A430 are the same and equal 0.037 ± 0,002. The value of total capacity (POE Purolite A430 was 4.3 mmol/g, AB 17 – 3.4 mmol/g. The studied ion exchangers have the same type of ionic groups – quaternary ammonium, but their number and denotes differ. The number of quaternary ammonium groups is higher in Purolite A430, respectively the number of absorbed anions of these ion exchanger is higher. The values of dynamic exchange capacity (DOE of ion exchanger Purolite A430 is higher than these values of AB-17 and equal to 1.48 ± 0.03 mmol / dm3 for chloride ion, 1.50 ± 0.03 mmol / dm3 for nitrate ion, 1.62 ± 0.03 mmol / dm3 for sulfate ion. The values of the POE and DOE of anion-exchange resins Purolite A430 and AV-17 and the characteristics of the individual sorption of chloride, nitrate, sulfate ions showed an advantage of the Purolite for the concentrationing of anions. It is found that times of anions sorption from triple-anion solutions by Purolite A430 are significantly different for different anions, and these times are close for anion-exchanger AV-17. It proves the possibility of quantitative separation and concentration by anion-exchanger Purolite A430.

  18. Theoretical and Experimental: The Synthetic and Anion-Binding Properties of Tripodal Salicylaldehyde Derivatives

    Directory of Open Access Journals (Sweden)

    Zhong-Jie Xu

    2016-05-01

    Full Text Available A series of colorimetric anion probes 1–6 containing OH and NO2 groups were synthesized, and their recognition properties toward various anions were investigated by visual observation, ultraviolet–visible spectroscopy, fluorescence, 1H nuclear magnetic resonance titration spectra and theoretical investigation. Nanomaterials of three compounds 2–4 were prepared successfully. Four compounds 3–6 that contain electron-withdrawing substituents showed a high binding ability for AcO−. The host–guest complex formed through a 1:1 binding ratio, and color changes were detectable during the recognition process. Theoretical investigation analysis revealed that an intramolecular hydrogen bond existed in the structures of compounds and the roles of molecular frontier orbitals in molecular interplay. These studies suggested that this series of compounds could be used as colorimetric probes to detect of AcO−.

  19. Photo-driven electron transfer from the highly reducing excited state of naphthalene diimide radical anion to a CO 2 reduction catalyst within a molecular triad

    Energy Technology Data Exchange (ETDEWEB)

    Martinez, Jose F. [Department of Chemistry and Argonne-Northwestern Solar Energy Research (ANSER) Center; Northwestern University; Evanston; USA; La Porte, Nathan T. [Department of Chemistry and Argonne-Northwestern Solar Energy Research (ANSER) Center; Northwestern University; Evanston; USA; Mauck, Catherine M. [Department of Chemistry and Argonne-Northwestern Solar Energy Research (ANSER) Center; Northwestern University; Evanston; USA; Wasielewski, Michael R. [Department of Chemistry and Argonne-Northwestern Solar Energy Research (ANSER) Center; Northwestern University; Evanston; USA

    2017-01-01

    The naphthalene-1,4:5,8-bis(dicarboximide) radical anion (NDI-˙), which is easily produced by mild chemical or electrochemical reduction (-0.5 Vvs.SCE), can be photoexcited at wavelengths as long as 785 nm, and has an excited state (NDI-˙*) oxidation potential of -2.1 Vvs.SCE, making it a very attractive choice for artificial photosynthetic systems that require powerful photoreductants, such as CO2 reduction catalysts. However, once an electron is transferred from NDI-˙* to an acceptor directly bound to it, a combination of strong electronic coupling and favorable free energy change frequently make the back electron transfer rapid. To mitigate this effect, we have designed a molecular triad system comprising an NDI-˙ chromophoric donor, a 9,10-diphenylanthracene (DPA) intermediate acceptor, and a Re(dmb)(CO)3carbon dioxide reduction catalyst, where dmb is 4,4'-dimethyl-2,2'-bipyridine, as the terminal acceptor. Photoexcitation of NDI-˙ to NDI-˙* is followed by ultrafast reduction of DPA to DPA-˙, which then rapidly reduces the metal complex. The overall time constant for the forward electron transfer to reduce the metal complex is τ = 20.8 ps, while the time constant for back-electron transfer is six orders of magnitude longer, τ = 43.4 μs. Achieving long-lived, highly reduced states of these metal complexes is a necessary condition for their use as catalysts. The extremely long lifetime of the reduced metal complex is attributed to careful tuning of the redox potentials of the chromophore and intermediate acceptor. The NDI-˙–DPA fragment presents many attractive features for incorporation into other photoinduced electron transfer assemblies directed at the long-lived photosensitization of difficult-to-reduce catalytic centers.

  20. Influence of the type of oxidant on anion exchange properties of fibrous Cladophora cellulose/polypyrrole composites.

    Science.gov (United States)

    Razaq, Aamir; Mihranyan, Albert; Welch, Ken; Nyholm, Leif; Strømme, Maria

    2009-01-15

    The electrochemically controlled anion absorption properties of a novel large surface area composite paper material composed of polypyrrole (PPy) and cellulose derived from Cladophora sp. algae, synthesized with two oxidizing agents, iron(III) chloride and phosphomolybdic acid (PMo), were analyzed in four different electrolytes containing anions (i.e., chloride, aspartate, glutamate, and p-toluenesulfonate) of varying size.The composites were characterized with scanning and transmission electron microscopy, N2 gas adsorption,and conductivity measurements. The potential-controlled ion exchange properties of the materials were studied by cyclic voltammetry and chronoamperometry at varying potentials. The surface area and conductivity of the iron(III) chloride synthesized sample were 58.8 m2/g and 0.65 S/cm, respectively, while the corresponding values for the PMo synthesized sample were 31.3 m2/g and 0.12 S/cm. The number of absorbed ions per sample mass was found to be larger for the iron(III) chloride synthesized sample than for the PMo synthesized one in all four electrolytes. Although the largest extraction yields were obtained in the presence of the smallest anion (i.e., chloride) for both samples, the relative degree of extraction for the largest ions (i.e., glutamate and p-toluenesulfonate) was higher for the PMo sample. This clearly shows that it is possible to increase the extraction yield of large anions by carrying out the PPy polymerization in the presence of large anions. The results likewise show that high ion exchange capacities, as well as extraction and desorption rates, can be obtained for large anions with high surface area composites coated with relatively thin layers of PPy.

  1. Dehydroabiethylamine acetate as metal-containing anion precipitant

    International Nuclear Information System (INIS)

    Skrylev, L.D.; Borisov, V.A.

    1979-01-01

    The precipitation is studied of vanadate, tungstate-, molybdate- and chromate-ions by dehydroabiethylamine acetate. The degree of precipitation of metal-bearing anions is a function of the anion and of pH of the treated solutions. There exists a predetermined value of pH for each anion, at which the content of metal-bearing anion in the ultra-filtrate is at a minimum. For vanadate-ions, this pH is 5.0; for tungstate-ions, 3.0; for molybdate-ions, 4.0; for chrommate-ions, 8.0. The heats of solution of methavanadate, paratungstate, paramolybdate and dehydroabiethylamine chromate, calculated in accordance with the Vant-Hoff equation, range between 3.5 and 8.3 kJ/mole; free energy varies between 45.8 and 137.5 kJ/mole; and entropy varies between 110 and 371 J/degree mole

  2. Are polynuclear superhalogens without halogen atoms probable? A high-level ab initio case study on triple-bridged binuclear anions with cyanide ligands

    Science.gov (United States)

    Yin, Bing; Li, Teng; Li, Jin-Feng; Yu, Yang; Li, Jian-Li; Wen, Zhen-Yi; Jiang, Zhen-Yi

    2014-03-01

    The first theoretical exploration of superhalogen properties of polynuclear structures based on pseudohalogen ligand is reported here via a case study on eight triply-bridged [Mg2(CN)5]- clusters. From our high-level ab initio results, all these clusters are superhalogens due to their high vertical electron detachment energies (VDE), of which the largest value is 8.67 eV at coupled-cluster single double triple (CCSD(T)) level. Although outer valence Green's function results are consistent with CCSD(T) in most cases, it overestimates the VDEs of three anions dramatically by more than 1 eV. Therefore, the combined usage of several theoretical methods is important for the accuracy of purely theoretical prediction of superhalogen properties of new structures. Spatial distribution of the extra electron of high-VDE anions here indicates two features: remarkable aggregation on bridging CN units and non-negligible distribution on every CN unit. These two features lower the potential and kinetic energies of the extra electron respectively and thus lead to high VDE. Besides superhalogen properties, the structures, relative stabilities and thermodynamic stabilities with respect to detachment of CN-1 were also investigated for these anions. The collection of these results indicates that polynuclear structures based on pseudohalogen ligand are promising candidates for new superhalogens with enhanced properties.

  3. The influence of plutonium concentration and solution flow rate on the effective capacity of macroporous anion exchange resin

    International Nuclear Information System (INIS)

    Marsh, S.F.; Gallegos, T.D.

    1987-07-01

    The principal aqueous process used to recover and purify plutonium at the Los Alamos Plutonium Facility is anion exchange in nitric acid. Previous studies with gel-type anion exchange resin have shown an inverse relationship between plutonium concentration in the feed solution and the optimum flow rate for this process. Because gel-type resin has been replaced with macroporous resin at Los Alamos, the relationship between plutonium concentration and solution flow rate was reexamined with the selected Lewatit MP-500-FK resin using solutions of plutonium in nitric acid and in nitric acid with high levels of added nitrate salts. Our results with this resin differ significantly from previous data obtained with gel-type resin. Flow-rate variation from 10 to 80 liters per hour had essentially no effect on the measured quantities of plutonium sorbed by the macroporous resin. However, the effect of plutonium concentration in the feed solutions was pronounced, as feed solutions that contained the highest concentrations of plutonium also produced the highest resin loadings. The most notable effect of high concentrations of dissolved nitrate salts in these solutions was an increased resin capacity for plutonium at low flow rates. 16 refs., 7 figs., 2 tabs

  4. Effect of alterations in glomerular charge on deposition of cationic and anionic antibodies to fixed glomerular antigens in the rat.

    Science.gov (United States)

    Adler, S; Baker, P; Pritzl, P; Couser, W G

    1985-07-01

    Reduction of the negative charge of the glomerular capillary wall alters its charge- and size-selective properties. To investigate the effect of alteration in glomerular charge properties on antibody localization, we prepared cationic and anionic fractions of antibodies to subepithelial and glomerular basement membrane (GBM) antigens, and compared their deposition in normal rats and rats treated with protamine sulfate or aminonucleoside of puromycin to reduce capillary wall charge. IgG antibodies were eluted from kidneys of rats with active Heymann's nephritis (AICN), passive Heymann's nephritis (PHN), or anti-GBM nephritis (NTN), separated into cationic and anionic fractions, and radiolabeled with iodine 125 or iodine 131. Relative antibody content of each fraction was determined by incubation with an excess of glomerular antigen. Varying amounts of cationic and anionic IgG eluted from kidneys of rats with AICN or PHN were injected into 24 normal or protamine sulfate-treated rats. Glomerular binding of all antibodies was highly correlated with IgG delivery to the kidney. The ratio of cationic to anionic antibody deposited in the glomeruli of normal rats after 4 hours was 1.08 +/- 0.07 for AICN eluate and 0.37 +/- 0.04 for PHN eluate. The ratios were not significantly different in animals pretreated with protamine sulfate (1.15 +/- 0.06 and 0.44 +/- 0.06, respectively; P greater than 0.05). Varying amounts of cationic and anionic IgG eluted from kidneys of rats with NTN were injected into 10 normal rats and four rats treated with aminonucleoside of puromycin. Glomerular binding of antibody was again highly correlated with IgG delivery to the kidney. The ratio of cationic to anionic antibody deposited in the glomeruli of normal rats after 1 hour was 1.03 +/- 0.06, and was not significantly altered in rats treated with aminonucleoside of puromycin (1.05 +/- 0.03, P greater than 0.5). Proteinuria in PHN rats was also unaffected by treatment with protamine sulfate for

  5. Electrochemical Sensing of Neurotoxic Agents Based on Their Electron Transfer Promotion Effect on an Au Electrode.

    Science.gov (United States)

    Shimada, Hiroshi; Noguchi, Shiori; Yamamoto, Masahiro; Nishiyama, Katsuhiko; Kitamura, Yusuke; Ihara, Toshihiro

    2017-06-06

    An electrochemical molecular sensor based on a new principle is reported. Nereistoxin (NRT, 4-N,N-dimethylamino-1,2-dithiolane), a naturally occurring neurotoxin (nicotinic acetylcholine receptor agonist), was adsorbed on an Au electrode via Au-S covalent bonding and accelerated the electron transfer between the electrode and the marker, ferricyanide anion. The contrast between the electrochemical responses obtained with the bare and NRT-modified Au electrodes was more pronounced at a low ionic strength of the supporting electrolyte, KCl. In the presence of 1 mM KCl, almost a 0/1 contrast between the signals was obtained through electrostatic interaction between the protonated tertiary amino group of NRT and the anionic ferricyanide ion. No current was observed with an electrode modified with mercaptopropionic acid. An unusually low ionic strength thickened the electric double layer to the degree where current was not observed with the bare electrode. The effect of the electrostatic concentration of the marker ion becomes obvious under such conditions. Commercially available NRT-related pesticides such as Cartap and Bensultap were also detected using the same format after pretreatments by hydrolysis/reduction. The present sensing method was successfully applied to human serum with satisfactory sensitivity.

  6. Ultrathin self-assembled anionic polymer membranes for superfast size-selective separation

    Science.gov (United States)

    Deng, Chao; Zhang, Qiu Gen; Han, Guang Lu; Gong, Yi; Zhu, Ai Mei; Liu, Qing Lin

    2013-10-01

    commercial membranes, and can highly efficiently separate 5 and 15 nm gold nanoparticles from their mixtures. The newly developed nanoporous membranes have a wide application in separation and purification of biomacromolecules and nanoparticles. Electronic supplementary information (ESI) available: Synthesis and characterization of SPEK-C; effect of the sulfonation degree on membrane formation; structure and properties of the self-assembled membranes; separation of cyt.c by the self-assembled membranes; size-selective separation of gold nanoparticles by the self-assembled membranes; comparison with commercial flat sheet ultrafiltration membranes. See DOI: 10.1039/c3nr03362g

  7. Study of radicals, clusters and transition state species by anion photoelectron spectroscopy

    International Nuclear Information System (INIS)

    Arnold, D.W.

    1994-08-01

    Free radicals, elemental and van der Waals clusters and transition state species for bimolecular chemical reactions are investigated using anion photoelectron spectroscopy. Several low-lying electronic states of ozone have been identified via photoelectron spectroscopy of O 3 - . A characterization of these states is important to models for atmospheric ozone reaction kinetics. The fluoroformyloxyl radical, FCO 2 , has been investigated, providing vibrational frequencies and energies for two electronic states. The technique has also been employed to make the first direct observation and characterization of the NNO 2 molecule. Several electronic states are observed for this species which is believed to play a role as a reactive intermediate in the N + NO 2 reaction. The experimental results for all three of these radicals are supplemented by ab initio investigations of their molecular properties. The clusters investigations include studies of elemental carbon clusters (C 2 - - C 11 - ), and van der Waals clusters (X - (CO 2 ) n , X = I, Br, Cl; n ≤ 13 and I - (N 2 O) n=1--11 ). Primarily linear clusters are observed for the smaller carbon clusters, while the spectra of the larger clusters contain contribution from cyclic anion photodetachment. Very interesting ion-solvent interactions are observed in the X - (CO 2 )n clusters. The transition state regions for several bimolecular chemical reactions have also been investigated by photodetachment of a negative ion precursor possessing a geometry similar to that of the transition state species. These spectra show features which are assigned to motions of the unstable neutral complex existing between reactants and products

  8. Observations on small anionic clusters in an electrostatic ion beam trap

    Energy Technology Data Exchange (ETDEWEB)

    Eritt, Markus

    2008-10-02

    The term atomic cluster relates to compounds of at least two or three atoms. Thereby the physical properties are size dependent and the property transitions between single atoms and bulk material are not always smooth. Ion traps allow it to observe internal cluster properties independent from the influence of external forces. In this work the electron induced decay of singly negatively charged atomic clusters was observed. The dissociation cross section of the clusters is dominated by detachment of the only weakly bound outer electrons. For simple atoms at low electron energies a simple scaling law can be obtained that includes only the binding energies of the valence electrons. Nevertheless for larger sizes theoretical calculations predict so called ''giant resonances'' as dominant decay process in metal clusters. Due to mass limitations in storage rings exist so far only cross section measurements for simple anions and small negative molecules. In this work the electron detachment cross sections of small negatively charged carbon (C{sub n}{sup -} n=2-12), aluminium (Al{sub n}{sup -} n=2-7) and silver clusters (Ag{sub n}{sup -} n=1-11) were measured in an electrostatic ion beam trap. The classical scaling law, including only the binding energies of the valence electrons, turned out to be not sufficient, especially for larger clusters. In order to improve the correlation between measured and predicted values it was proposed to involve the influence of the cluster volume and the specific polarisability induced by long range coulomb interaction. For silver clusters the best agreement was obtained using a combination of the projected area reduced by the polarisability. The existence of ''giant resonances'' could not be confirmed. According to theory for clusters with a broad internal energy distribution, a power-law decay close to 1/time is expected. For some clusters the lifetime behaviour would be strongly quenched by photon

  9. Test procedure for anion exchange chromatography

    International Nuclear Information System (INIS)

    Cooper, T.D.

    1994-01-01

    Plutonium from stored nitrate solutions will be sorbed onto anion exchange resins and converted to storable plutonium dioxide. Useful information will be simultaneously gained on the thermal stability and ion exchange capacity of four commercially available anion exchange resins over several years and under severe degradative conditions. This information will prove useful in predicting the safe and efficient lifetimes of these resins

  10. Electron accommodation dynamics in the DNA base thymine

    Science.gov (United States)

    King, Sarah B.; Stephansen, Anne B.; Yokoi, Yuki; Yandell, Margaret A.; Kunin, Alice; Takayanagi, Toshiyuki; Neumark, Daniel M.

    2015-07-01

    The dynamics of electron attachment to the DNA base thymine are investigated using femtosecond time-resolved photoelectron imaging of the gas phase iodide-thymine (I-T) complex. An ultraviolet pump pulse ejects an electron from the iodide and prepares an iodine-thymine temporary negative ion that is photodetached with a near-IR probe pulse. The resulting photoelectrons are analyzed with velocity-map imaging. At excitation energies ranging from -120 meV to +90 meV with respect to the vertical detachment energy (VDE) of 4.05 eV for I-T, both the dipole-bound and valence-bound negative ions of thymine are observed. A slightly longer rise time for the valence-bound state than the dipole-bound state suggests that some of the dipole-bound anions convert to valence-bound species. No evidence is seen for a dipole-bound anion of thymine at higher excitation energies, in the range of 0.6 eV above the I-T VDE, which suggests that if the dipole-bound anion acts as a "doorway" to the valence-bound anion, it only does so at excitation energies near the VDE of the complex.

  11. Electron accommodation dynamics in the DNA base thymine

    Energy Technology Data Exchange (ETDEWEB)

    King, Sarah B.; Yandell, Margaret A.; Kunin, Alice [Department of Chemistry, University of California, Berkeley, California 94720 (United States); Stephansen, Anne B. [Department of Chemistry, University of Copenhagen, Universitetsparken 5, DK-2100 København Ø (Denmark); Yokoi, Yuki; Takayanagi, Toshiyuki [Department of Chemistry, Saitama University, 255 Shimo-Okubo, Sakura-ku, Saitama City, Saitama 338-8570 (Japan); Neumark, Daniel M., E-mail: dneumark@berkeley.edu [Department of Chemistry, University of California, Berkeley, California 94720 (United States); Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States)

    2015-07-14

    The dynamics of electron attachment to the DNA base thymine are investigated using femtosecond time-resolved photoelectron imaging of the gas phase iodide-thymine (I{sup −}T) complex. An ultraviolet pump pulse ejects an electron from the iodide and prepares an iodine-thymine temporary negative ion that is photodetached with a near-IR probe pulse. The resulting photoelectrons are analyzed with velocity-map imaging. At excitation energies ranging from −120 meV to +90 meV with respect to the vertical detachment energy (VDE) of 4.05 eV for I{sup −}T, both the dipole-bound and valence-bound negative ions of thymine are observed. A slightly longer rise time for the valence-bound state than the dipole-bound state suggests that some of the dipole-bound anions convert to valence-bound species. No evidence is seen for a dipole-bound anion of thymine at higher excitation energies, in the range of 0.6 eV above the I{sup −}T VDE, which suggests that if the dipole-bound anion acts as a “doorway” to the valence-bound anion, it only does so at excitation energies near the VDE of the complex.

  12. Can an Excess Electron Localise on a Purine Moiety in the Adenine-thymine Watson-Crick Base Pair? A Computational Study

    International Nuclear Information System (INIS)

    Mazurkiewicz, Kamil; Haranczyk, Maciej; Gutowski, Maciej S.; Rak, Janusz

    2007-01-01

    The electron affinity and the propensity to electron-induced proton transfer (PT) of hydrogen-bonded complexes between the Watson-Crick adenine-thymine pair (AT) and simple organic acid (HX), attached to adenine in the Hoogsteen-type configuration, were studied at the B3LYP/6-31+G** level. Although the carboxyl group is deprotonated at physiological pH, its neutral form, COOH, resembles the peptide bond or the amide fragment in the side chain of asparagine (Asn) or glutamine (Gln). Thus, these complexes mimic the interaction between the DNA environment (e.g., proteins) and nucleobase pairs incorporated in the biopolymer. Electron attachment is thermodynamically feasible and adiabatic electron affinities range from 0.41 to 1.28 eV, while the vertical detachment energies of the resulting anions span the range of 0.39-2.88 eV. Low-energy activation barriers separate the anionic minima: aHX(AT) from the more stable single-PT anionic geometry, aHX(AT)-SPT, and aHX(AT)-SPT from the double-PT anionic geometry, aHX(AT)-DPT. Interaction between the adenine of the Watson-Crick AT base pair with an acidic proton donor probably counterbalances the larger EA of isolated thymine, as SOMO is almost evenly delocalized over both types of nucleic bases in the aHX(AT) anions. Moreover, as a result of PT the excess electron localizes entirely on adenine. Thus, in DNA interacting with its physiological environment, damage induced by low-energy electrons could begin, contrary to the current view, with the formation of purine anions, which are not formed in isolated DNA because of the greater stability of anionic pyrimidines.

  13. Organic anion transporter (Slc22a) family members as mediators of toxicity

    International Nuclear Information System (INIS)

    Sweet, Douglas H.

    2005-01-01

    Exposure of the body to toxic organic anions is unavoidable and occurs from both intentional and unintentional sources. Many hormones, neurotransmitters, and waste products of cellular metabolism, or their metabolites, are organic anions. The same is true for a wide variety of medications, herbicides, pesticides, plant and animal toxins, and industrial chemicals and solvents. Rapid and efficient elimination of these substances is often the body's best defense for limiting both systemic exposure and the duration of their pharmacological or toxicological effects. For organic anions, active transepithelial transport across the renal proximal tubule followed by elimination via the urine is a major pathway in this detoxification process. Accordingly, a large number of organic anion transport proteins belonging to several different gene families have been identified and found to be expressed in the proximal nephron. The function of these transporters, in combination with the high volume of renal blood flow, predisposes the kidney to increased toxic susceptibility. Understanding how the kidney mediates the transport of organic anions is integral to achieving desired therapeutic outcomes in response to drug interactions and chemical exposures, to understanding the progression of some disease states, and to predicting the influence of genetic variation upon these processes. This review will focus on the organic anion transporter (OAT) family and discuss the known members, their mechanisms of action, subcellular localization, and current evidence implicating their function as a determinant of the toxicity of certain endogenous and xenobiotic agents

  14. Rejuvenation processes applied to 'poisoned' anion exchangers in uranium processing

    International Nuclear Information System (INIS)

    Gilmore, A.J.

    1979-11-01

    The removal of 'poisons' from anion exchangers in uranium processing of Canadian radioactive ores is commonly called rejuvenation or regeneration. The cost of the ion exchange recovery of uranium is adversely affected by a decrease in the capacity and efficiency of the anion exchangers, due to their being 'poisoned' by silica, elemental sulphur, molybdenum and tetrathionates. These 'poisons' have a high affinity for the anion exchangers, are adsorbed in preference to the uranyl complex, and do not desorb with the reagents used normally in the uranyl desorption phase. The frequency of rejuvenation and the reagents required for rejuvenation are determined by the severity of the 'poisoning' accumulated by the exchanger in contact with the uranium leach liquor. Caustic soda (NaOH) at approximately equal to 18 cents/lb is commonly used to remove uranium anion exchangers of tetrathionate ((S 4 0 6 )/-/-) 'poisons'. A potential saving in operating cost would be of consequence if other reagents, e.g. sodium carbonate (Na 2 CO 3 ) at approximately equal to 3.6 cents/lb or calcium hydroxide (Ca(OH) 2 ) at approximately equal to 1.9 cents/lb, were effective in removing (S 4 0 6 )/-/-) from a 'poisoned' exchanger. A rejuvenation process for a test program was adopted after a perusal of the literature

  15. Assessing the reactivation efficacy of hydroxylamine anion towards VX-inhibited AChE: a computational study.

    Science.gov (United States)

    Khan, Md Abdul Shafeeuulla; Ganguly, Bishwajit

    2012-05-01

    Oximate anions are used as potential reactivating agents for OP-inhibited AChE because of they possess enhanced nucleophilic reactivity due to the α-effect. We have demonstrated the process of reactivating the VX-AChE adduct with formoximate and hydroxylamine anions by applying the DFT approach at the B3LYP/6-311 G(d,p) level of theory. The calculated results suggest that the hydroxylamine anion is more efficient than the formoximate anion at reactivating VX-inhibited AChE. The reaction of formoximate anion and the VX-AChE adduct is a three-step process, while the reaction of hydroxylamine anion with the VX-AChE adduct seems to be a two-step process. The rate-determining step in the process is the initial attack on the VX of the VX-AChE adduct by the nucleophile. The subsequent steps are exergonic in nature. The potential energy surface (PES) for the reaction of the VX-AChE adduct with hydroxylamine anion reveals that the reactivation process is facilitated by the lower free energy of activation (by a factor of 1.7 kcal mol(-1)) than that of the formoximate anion at the B3LYP/6-311 G(d,p) level of theory. The higher free energy of activation for the reverse reactivation reaction between hydroxylamine anion and the VX-serine adduct further suggests that the hydroxylamine anion is a very good antidote agent for the reactivation process. The activation barriers calculated in solvent using the polarizable continuum model (PCM) for the reactivation of the VX-AChE adduct with hydroxylamine anion were also found to be low. The calculated results suggest that V-series compounds can be more toxic than G-series compounds, which is in accord with earlier experimental observations.

  16. Preparation of methacrylate-based anion-exchange monolithic microbore column for chromatographic separation of DNA fragments and oligonucleotides

    Energy Technology Data Exchange (ETDEWEB)

    Sabarudin, Akhmad, E-mail: sabarjpn@ub.ac.id [Division of Nano-materials Science, EcoTopia Science Institute, Nagoya University, Furu-Cho, Chikusa-Ku, Nagoya 464-8603 (Japan); Department of Chemistry, Faculty of Science, Brawijaya University, Jl Veteran Malang 65145 (Indonesia); Huang, Junchao; Shu, Shin; Sakagawa, Shinnosuke [Division of Nano-materials Science, EcoTopia Science Institute, Nagoya University, Furu-Cho, Chikusa-Ku, Nagoya 464-8603 (Japan); Umemura, Tomonari, E-mail: umemura@apchem.nagoya-u.ac.jp [Division of Nano-materials Science, EcoTopia Science Institute, Nagoya University, Furu-Cho, Chikusa-Ku, Nagoya 464-8603 (Japan)

    2012-07-29

    Highlights: Black-Right-Pointing-Pointer Microbore-scale (1 mm i.d.) anion-exchange monolithic column. Black-Right-Pointing-Pointer Potentially preparative applications. Black-Right-Pointing-Pointer Separation of oligodeoxythymidylic acids and DNA fragments. - Abstract: In this paper, we report on the preparation of a microbore-scale (1 mm i.d.) anion-exchange monolithic column suitable not only for analytical purposes but also for potentially preparative applications. In order to meet the conflicting requirements of high permeability and good mechanical strength, the following two-step procedure was applied. First, an epoxy-containing monolith was synthesized by in situ copolymerization of glycidyl methacrylate (GMA) and ethylene dimethacrylate (EDMA) within the confines of a silicosteel tubing of 1.02 mm i.d. and 1/16 Double-Prime o.d. in the presence of a ternary porogenic mixture of 1-propanol, 1,4-butanediol, and water. The monolithic matrix was subsequently converted into weak anion-exchanger via the ring-opening reaction of epoxy group with diethyl amine. The dynamic binding capacity was 21.4 mg mL{sup -1} for bovine serum albumin (BSA) at 10% breakthrough. The morphology and porous structure of this monolith were assessed by scanning electron microscope (SEM) and inverse size exclusion chromatography (ISEC). To optimize the separation efficiency, the effects of various chromatographic parameters upon the separation of DNA fragments were investigated. The resulting monolithic anion exchanger demonstrated good potential for the separation of both single- and double-stranded DNA molecules using a gradient elution with NaCl in Tris-HCl buffer (20 mM). Oligodeoxythymidylic acids (dT{sub 12}-dT{sub 18}) were successfully resolved at pH 8, while the fragments of 20 bp DNA ladder, 100 bp DNA ladder, and pBR322-HaeIII digest were efficiently separated at pH 9.

  17. A series of poly(butylimidazolium) ionic liquid functionalized copolymers for anion exchange membranes

    Science.gov (United States)

    Ouadah, Amina; Xu, Hulin; Luo, Tianwei; Gao, Shuitao; Wang, Xing; Fang, Zhou; Jing, Chaojun; Zhu, Changjin

    2017-12-01

    A new series of ionic liquid functionalized copolymers for anion exchange membranes (AEM) is prepared. Poly(butylvinylimidazolium)(b-VIB) is copolymerized with para-methyl styrene (p-MS) by the radical polymerization formed block copolymers b-VIB/p-MS, which is crosslinked with poly(diphenylether bibenzimidazole) (DPEBI) providing the desired materials b-VIB/p-MS/DPEBI. Structures are characterized via H1NMR, FTIR spectra and elemental analysis. The b-VIB blocks offer the anion conduction function while DPEBI moieties contribute to enhancing other properties. The prepared membranes display chloride conductivity as high as 19.5 mS/cm at 25 °C and 69.2 mS/cm at 100 °C-higher than that of the commercial membrane tokuyuama A201-. Their hydroxide conductivity reaches 35.7 Scm-1 at 25 °C and 73.1 Scm-1 at 100 °C. The membranes showed a linear Arrhenius behavior in the anion conduction, low activation energies and distinguished nanophase separation of hydrophilic/hydrophobic regions by the transmission electron microscopy (TEM) studies. Thermal investigations using TGA and DSC confirm that the membranes are stable up to 250 °C. Particularly, drastically alkaline stability due to no decrease in the hydroxide conductivity after 168 h of treatment with 2M KOH.

  18. A study of sorption of pertechnetate anion on chitosan

    International Nuclear Information System (INIS)

    Pivarciova, L.; Rosskopfova, O.; Rajec, P.; Galambos, M.

    2015-01-01

    Chitosan is one of the natural materials of biological origin. The sorption of pertechnetate anions from aqueous solutions on chitosan was studied in a batch system. This work was aimed to study influence of the contact time, effect of pH and effect of different ions on sorption of pertechnetate anions on chitosan. This sorbent was characterized by BET-surface area and potentiometric titration. The point of zero charge (pH pzc ) was at pH=7.15. The highest percentage of technetium sorption on chitosan was near pH 3. The adsorption capacity of chitosan decreased with increase in pH value above 3. In the initial pH range of 4-10, final pHs are the same. The selectivity of chitosan for these cations with concentration above 1·10 -3 mol·dm -3 was in the order Na + > Ca 2+ > Fe 3+ > Fe 2+ . The competition effect of (SO 4 ) 2- towards TcO 4 - sorption was stronger than the competition effect (ClO 4 ) - of ions. (authors)

  19. Effect of ionic liquids with different cations and anions on photosystem and cell structure of Scenedesmus obliquus.

    Science.gov (United States)

    Xia, Yilu; Liu, Dingdong; Dong, Ying; Chen, Jiazheng; Liu, Huijun

    2018-03-01

    The rapid increase in the production and practical application of ionic liquids (ILs) could pose potential threats to aquatic systems. In this study, we investigated the effects of four ILs with different cations and anions, including 1-hexyl-3-methylimidazolium nitrate ([HMIM]NO 3 ), 1-hexyl-3-methylimidazolium chloride ([HMIM]Cl), N-hexyl-3-metylpyridinium chloride ([HMPy]Cl), and N-hexyl-3-metylpyridinium bromide ([HMPy]Br), on photosystem and cellular structure of Scenedesmus obliquus. The results indicated that ILs are phytotoxic to S. obliquus. The contents of chlorophyll a, chlorophyll b and total chlorophyll decreased with increasing ILs concentrations. The chlorophyll fluorescence parameters of photosynthetic system II (PSII), including minimal fluorescence yield (F 0 ), potential efficiency of PSII (F v /F o ), maximum quantum efficiency of PSII photochemistry (F v /F m ), yield of photochemical quantum [Y(II)], and non-photochemical quenching coefficient without measuring F 0 ' (NPQ), were all affected. This indicates that ILs could damage PSII, inhibit the primary reaction of photosynthesis, interdict the process of electron-transfer and lead to loss of heat-dissipating ability. ILs also increased cell membrane permeability of S. obliquus, influenced the cellular ultrastructure, changed the morphology of algae cells and destroyed the cell wall, cell membrane and organelles. The results indicated that imidazolium ILs had greater effect than pyridinium ILs, NO 3 - -IL and Br - -IL had greater effect than Cl - -IL. To minimize threats to the environment, the structure of ILs should be taken into consideration. Copyright © 2017 Elsevier Ltd. All rights reserved.

  20. Preparation and performance evaluation of novel alkaline stable anion exchange membranes

    Science.gov (United States)

    Irfan, Muhammad; Bakangura, Erigene; Afsar, Noor Ul; Hossain, Md. Masem; Ran, Jin; Xu, Tongwen

    2017-07-01

    Novel alkaline stable anion exchange membranes are prepared from various amounts of N-methyl dipicolylamine (MDPA) and brominated poly (2,6-dimethyl-1,4-phenylene oxide) (BPPO). The dipicolylamine and MDPA are synthesized through condensation reaction and confirmed by 1H NMR spectroscopy. The morphologies of prepared membranes are investigated by atomic force microscopy (AFM), fourier transform infrared spectroscopy (FTIR), 1H NMR spectroscopy and scanning electron microscopy (SEM). The electrochemical and physical properties of AEMs are tested comprising water uptake (WU), ion exchange capacity (IEC), alkaline stability, linear expansion ratio (LER), thermal stability and mechanical stability. The obtained hydroxide conductivity of MDPA-4 is 66.5 mS/cm at 80 °C. The MDPA-4 membrane shows good alkaline stability, high hydroxide conductivity, low methanol permeability (3.43 × 10-7 cm2/s), higher selectivity (8.26 × 107 mS s/cm3), less water uptake (41.1%) and lower linear expansion (11.1%) despite of high IEC value (1.62 mmol/g). The results prove that MDPA membranes have great potential application in anion exchange membrane fuel cell.

  1. Cytosolic nucleotides block and regulate the Arabidopsis vacuolar anion channel AtALMT9.

    Science.gov (United States)

    Zhang, Jingbo; Martinoia, Enrico; De Angeli, Alexis

    2014-09-12

    The aluminum-activated malate transporters (ALMTs) form a membrane protein family exhibiting different physiological roles in plants, varying from conferring tolerance to environmental Al(3+) to the regulation of stomatal movement. The regulation of the anion channels of the ALMT family is largely unknown. Identifying intracellular modulators of the activity of anion channels is fundamental to understanding their physiological functions. In this study we investigated the role of cytosolic nucleotides in regulating the activity of the vacuolar anion channel AtALMT9. We found that cytosolic nucleotides modulate the transport activity of AtALMT9. This modulation was based on a direct block of the pore of the channel at negative membrane potentials (open channel block) by the nucleotide and not by a phosphorylation mechanism. The block by nucleotides of AtALMT9-mediated currents was voltage dependent. The blocking efficiency of intracellular nucleotides increased with the number of phosphate groups and ATP was the most effective cellular blocker. Interestingly, the ATP block induced a marked modification of the current-voltage characteristic of AtALMT9. In addition, increased concentrations of vacuolar anions were able to shift the ATP block threshold to a more negative membrane potential. The block of AtALMT9-mediated anion currents by ATP at negative membrane potentials acts as a gate of the channel and vacuolar anion tune this gating mechanism. Our results suggest that anion transport across the vacuolar membrane in plant cells is controlled by cytosolic nucleotides and the energetic status of the cell. © 2014 by The American Society for Biochemistry and Molecular Biology, Inc.

  2. Cytosolic Nucleotides Block and Regulate the Arabidopsis Vacuolar Anion Channel AtALMT9*

    Science.gov (United States)

    Zhang, Jingbo; Martinoia, Enrico; De Angeli, Alexis

    2014-01-01

    The aluminum-activated malate transporters (ALMTs) form a membrane protein family exhibiting different physiological roles in plants, varying from conferring tolerance to environmental Al3+ to the regulation of stomatal movement. The regulation of the anion channels of the ALMT family is largely unknown. Identifying intracellular modulators of the activity of anion channels is fundamental to understanding their physiological functions. In this study we investigated the role of cytosolic nucleotides in regulating the activity of the vacuolar anion channel AtALMT9. We found that cytosolic nucleotides modulate the transport activity of AtALMT9. This modulation was based on a direct block of the pore of the channel at negative membrane potentials (open channel block) by the nucleotide and not by a phosphorylation mechanism. The block by nucleotides of AtALMT9-mediated currents was voltage dependent. The blocking efficiency of intracellular nucleotides increased with the number of phosphate groups and ATP was the most effective cellular blocker. Interestingly, the ATP block induced a marked modification of the current-voltage characteristic of AtALMT9. In addition, increased concentrations of vacuolar anions were able to shift the ATP block threshold to a more negative membrane potential. The block of AtALMT9-mediated anion currents by ATP at negative membrane potentials acts as a gate of the channel and vacuolar anion tune this gating mechanism. Our results suggest that anion transport across the vacuolar membrane in plant cells is controlled by cytosolic nucleotides and the energetic status of the cell. PMID:25028514

  3. Rational design of organic superconductors through the use of the large, discrete molecular anions M(CF3)4-(M = Cu, Ag, Au) and SO3CF2CH2SF5-

    International Nuclear Information System (INIS)

    Schlueter, J.A.; Geiser, U.; Williams, J.M.

    1996-01-01

    A new approach to synthesis of organic superconductors has recently been pioneered which involves the use of large discrete molecular anions as the charge-compensating entities in these charge transfer salts. The organic electron-donor molecule bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF or ET) has been electrocrystallized with the novel organometallic M(CF 3 ) 4 - (M=Cu, Ag, Au) anions in a variety of 1,1,2-trihaloethane solvents. Over 20 organic superconductors have been synthesized which can be described by (ET) 2 M(CF 3 ) 4 (1,1,2- trihaloethane). These solvated salts are shown to have highly anisotropic physical properties which can be tuned via modifications of each of their three molecular components: ET electron donor molecule, M(CF 3 ) 4 - anion, and neutral 1,1,2- trihaloethane solvent molecule. Superconductivity has also been observed in an ET salt containing the discrete SF 5 CH 2 CF 2 SO 3 - anion with onset temperature near 5.2 K

  4. Coumarin amide derivatives as fluorescence chemosensors for cyanide anions

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Qianqian [School of Material Science and Engineering, Shandong Provincial Key Laboratory of Preparation and Measurement of Building Materials, University of Jinan, Jinan 250022, Shandong (China); Liu, Zhiqiang [State Key Laboratory of Crystal Materials, Shandong University, Jinan 250100, Shandong (China); Cao, Duxia, E-mail: duxiacao@ujn.edu.cn [School of Material Science and Engineering, Shandong Provincial Key Laboratory of Preparation and Measurement of Building Materials, University of Jinan, Jinan 250022, Shandong (China); Guan, Ruifang, E-mail: mse_guanrf@ujn.edu.cn [School of Material Science and Engineering, Shandong Provincial Key Laboratory of Preparation and Measurement of Building Materials, University of Jinan, Jinan 250022, Shandong (China); Wang, Kangnan; Shan, Yanyan; Xu, Yongxiao; Ma, Lin [School of Material Science and Engineering, Shandong Provincial Key Laboratory of Preparation and Measurement of Building Materials, University of Jinan, Jinan 250022, Shandong (China)

    2015-07-01

    Four coumarin amide derivatives with 4-methyl coumarin or pyrene as terminal group have been synthesized. Their photophysical properties and recognition properties for cyanide anions have been examined. The results indicate that the compounds can recognize cyanide anions with obvious absorption and fluorescence spectra change, at the same time, obvious color and fluorescence change can be observed by naked eye. The in situ hydrogen nuclear magnetic resonance spectra and photophysical properties change confirm that Michael additions between the chemosensors and cyanide anions take place at the 4-position of coumarin. - Highlights: • Four coumarin amide derivatives with 4-methyl coumarin or pyrene as terminal group were synthesized. • The compounds can recognize cyanide anions with obvious absorption and fluorescence spectra change. • Michael additions between the chemosensors and cyanide anions take place at the 4-position of coumarin.

  5. Electrocatalytic analysis of superoxide anion radical using nitrogen-doped graphene supported Prussian Blue as a biomimetic superoxide dismutase

    International Nuclear Information System (INIS)

    Liu, Tingting; Niu, Xiangheng; Shi, Libo; Zhu, Xiang; Zhao, Hongli; Lana, Minbo

    2015-01-01

    Graphical abstract: Prussian Blue (PB) cubes supported on nitrogen-doped graphene sheets (NGS) were synthesized using a simple and scalable method, and the utilization of the PB-NGS hybrid as an efficient superoxide dismutase mimic in the electrochemical sensing of O 2 ·− was demonstrated. - Highlights: • Facile and scalable synthesis of Prussian Blue cubes supported on nitrogen-doped graphene; • Nitrogen-doped graphene supported Prussian Blue as an efficient biomimetic superoxide dismutase for the electrocatalytic sensing of superoxide anion; • Good sensitivity, excellent selectivity and attractive long-term stability for superoxide anion sensing. - Abstract: Considering the double-sided roles of superoxide anion radical, monitoring of its track in living systems is attracting increasing academic and practical interest. Here we synthesized Prussian Blue (PB) cubes that were supported on nitrogen-doped graphene sheets (NGS) using a facile and scalable method, and explored their potential utilization in the electrochemical sensing of superoxide anion. As an efficient superoxide dismutase mimic, direct electron transfer of the prepared PB-NGS hybrid immobilized on a screen-printed gold electrode was harvested in physiological media. With the bifunctional activities, the synthetic mimic could catalyze the dismutation of superoxide anion via the redox cycle of active iron. By capturing the electro-reduction amperometric responses of superoxide anion radical to hydrogen peroxide in the cathodic polarization, highly sensitive determination (a sensitivity of as high as 0.32 μA cm −2 μM −1 ) of the target was achieved, with no interference from common coexisting species including ascorbic acid, dopamine, and uric acid observed. Compared to natural superoxide dismutases, the artificial enzyme mimic exhibited favorable activity stability, indicating its promising applications in the in vivo long-term monitoring of superoxide anion

  6. Transformation of methano[60]fullerenes in dihydrofullerofuranes induced by electron transfer

    International Nuclear Information System (INIS)

    Yanilkin, V.V.; Toropchina, A.V.; Morozov, V.I.; Nastapova, N.V.; Gubskaya, V.P.; Sibgatullina, F.G.; Azancheev, N.M.; Efremov, Yu.Ya.; Nuretdinov, I.A.

    2004-01-01

    The electrochemical reduction of methano[60]fullerenes (61-acetyl-61-(diethoxyphosphoryl)methano-60-fullerene 1, 61-acetyl-61-(diisopropoxyphosphoryl)methano-60-fullerene 2, 61-(2,2-diethoxyacetyl)-61-(diethoxy-phosphoryl)methano-60-fullerene 3, 61-phenyl-61-(1,2-dioxo-3,3-dimethyl-buthyl)methano-60-fullerene 4) in o-dichlorobenzene-DMF (3:1 v/v)/0.1 M Bu 4 NBF 4 on a glass-carbon electrode proceeds in a few steps. The reversible transfer of the first electron results in the formation of radical anions registered by ESR method. The subsequent reduction proceeds differently because of the various stability of anionic intermediates. The radical anions of the methanofullerenes 3 and 4 are less stable than the radical anions of compounds 1 and 2 and less stable than the radical anions of methanofullerenes, which contain an ester and/or a phosphonate group. The opening of a cyclopropane ring occurs during the stage of the formation of radical trianions of methanofullerenes 1, 2. The same process for compounds 3, 4 proceeds slowly in radical anions and fast in dianions. The opening of cyclopropane ring for all compounds is not accompanied by the elimination of methanogroup and results in the formation of dihydrofullerenofurane derivatives. The transformation of methanofullerene 3 induced by single electron transfer proceeds via a chain reaction mechanism

  7. Pentafluorobenzyl bromide-A versatile derivatization agent in chromatography and mass spectrometry: I. Analysis of inorganic anions and organophosphates.

    Science.gov (United States)

    Tsikas, Dimitrios

    2017-02-01

    Pentafluorobenzyl bromide (PFB-Br) is a versatile derivatization agent. It is widely used in chromatography and mass spectrometry since several decades. The bromide atom is largely the single leaving group of PFB-Br. It is substituted by wide a spectrum of nucleophiles in aqueous and non-aqueous systems to form electrically neutral, in most organic solvents soluble, generally thermally stable, volatile, strongly electron-capturing and ultraviolet light-absorbing derivatives. Because of these greatly favoured physicochemical properties, PFB-Br emerged an ideal derivatization agent for highly sensitive analysis of endogenous and exogenous substances including various inorganic and organic anions by electron capture detection or after electron-capture negative-ion chemical ionization in GC-MS. The present article attempts an appraisal of the utility of PFB-Br in analytical chemistry. It reviews and discusses papers dealing with the use of PFB-Br as the derivatization reagent in the qualitative and quantitative analysis of endogenous and exogenous inorganic anions in various biological samples, notably plasma, urine and saliva. These analytes include nitrite, nitrate, cyanide and dialkyl organophosphates. Special emphasis is given to mass spectrometry-based approaches and stable-isotope dilution techniques. Copyright © 2016 Elsevier B.V. All rights reserved.

  8. Are polynuclear superhalogens without halogen atoms probable? A high-level ab initio case study on triple-bridged binuclear anions with cyanide ligands

    International Nuclear Information System (INIS)

    Yin, Bing; Wen, Zhen-Yi; Li, Teng; Li, Jin-Feng; Yu, Yang; Li, Jian-Li; Jiang, Zhen-Yi

    2014-01-01

    The first theoretical exploration of superhalogen properties of polynuclear structures based on pseudohalogen ligand is reported here via a case study on eight triply-bridged [Mg 2 (CN) 5 ] − clusters. From our high-level ab initio results, all these clusters are superhalogens due to their high vertical electron detachment energies (VDE), of which the largest value is 8.67 eV at coupled-cluster single double triple (CCSD(T)) level. Although outer valence Green's function results are consistent with CCSD(T) in most cases, it overestimates the VDEs of three anions dramatically by more than 1 eV. Therefore, the combined usage of several theoretical methods is important for the accuracy of purely theoretical prediction of superhalogen properties of new structures. Spatial distribution of the extra electron of high-VDE anions here indicates two features: remarkable aggregation on bridging CN units and non-negligible distribution on every CN unit. These two features lower the potential and kinetic energies of the extra electron respectively and thus lead to high VDE. Besides superhalogen properties, the structures, relative stabilities and thermodynamic stabilities with respect to detachment of CN −1 were also investigated for these anions. The collection of these results indicates that polynuclear structures based on pseudohalogen ligand are promising candidates for new superhalogens with enhanced properties

  9. Are polynuclear superhalogens without halogen atoms probable? A high-level ab initio case study on triple-bridged binuclear anions with cyanide ligands

    Energy Technology Data Exchange (ETDEWEB)

    Yin, Bing, E-mail: rayinyin@gmail.com; Wen, Zhen-Yi [MOE Key Laboratory of Synthetic and Natural Functional Molecule Chemistry, Shaanxi Key Laboratory of Physico-Inorganic Chemistry, College of Chemistry and Materials Science, Northwest University, Xi' an 710069 (China); Institute of Modern Physics, Northwest University, Xi' an 710069 (China); Li, Teng; Li, Jin-Feng; Yu, Yang; Li, Jian-Li [MOE Key Laboratory of Synthetic and Natural Functional Molecule Chemistry, Shaanxi Key Laboratory of Physico-Inorganic Chemistry, College of Chemistry and Materials Science, Northwest University, Xi' an 710069 (China); Jiang, Zhen-Yi [Institute of Modern Physics, Northwest University, Xi' an 710069 (China)

    2014-03-07

    The first theoretical exploration of superhalogen properties of polynuclear structures based on pseudohalogen ligand is reported here via a case study on eight triply-bridged [Mg{sub 2}(CN){sub 5}]{sup −} clusters. From our high-level ab initio results, all these clusters are superhalogens due to their high vertical electron detachment energies (VDE), of which the largest value is 8.67 eV at coupled-cluster single double triple (CCSD(T)) level. Although outer valence Green's function results are consistent with CCSD(T) in most cases, it overestimates the VDEs of three anions dramatically by more than 1 eV. Therefore, the combined usage of several theoretical methods is important for the accuracy of purely theoretical prediction of superhalogen properties of new structures. Spatial distribution of the extra electron of high-VDE anions here indicates two features: remarkable aggregation on bridging CN units and non-negligible distribution on every CN unit. These two features lower the potential and kinetic energies of the extra electron respectively and thus lead to high VDE. Besides superhalogen properties, the structures, relative stabilities and thermodynamic stabilities with respect to detachment of CN{sup −1} were also investigated for these anions. The collection of these results indicates that polynuclear structures based on pseudohalogen ligand are promising candidates for new superhalogens with enhanced properties.

  10. Anionic salts in the prepartum diet and addition of sodium bicarbonate to colostrum replacer, and their effects on immunoglobulin G absorption in the neonate.

    Science.gov (United States)

    Morrill, K M; Marston, S P; Whitehouse, N L; Van Amburgh, M E; Schwab, C G; Haines, D M; Erickson, P S

    2010-05-01

    for an interaction with calves born from dams fed anionic salts having a greater area under the curve when fed supplemental sodium bicarbonate. Of the 40 calves in the study, 90% obtained adequate passive transfer (serum IgG > or = 10g/L). This study indicates that feeding anionic salts to the dam has no effect on passive transfer, whereas adding sodium bicarbonate to the CR increased IgG uptake in calves. Copyright 2010 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

  11. Mercury monohalides: suitability for electron electric dipole moment searches.

    Science.gov (United States)

    Prasannaa, V S; Vutha, A C; Abe, M; Das, B P

    2015-05-08

    Heavy polar diatomic molecules are the primary tools for searching for the T-violating permanent electric dipole moment of the electron (eEDM). Valence electrons in some molecules experience extremely large effective electric fields due to relativistic interactions. These large effective electric fields are crucial to the success of polar-molecule-based eEDM search experiments. Here we report on the results of relativistic ab initio calculations of the effective electric fields in a series of molecules that are highly sensitive to an eEDM, the mercury monohalides (HgF, HgCl, HgBr, and HgI). We study the influence of the halide anions on E_{eff}, and identify HgBr and HgI as attractive candidates for future electric dipole moment search experiments.

  12. Tripodal Receptors for Cation and Anion Sensors

    Directory of Open Access Journals (Sweden)

    David N. Reinhoudt

    2006-08-01

    Full Text Available This review discusses different types of artificial tripodal receptors for the selectiverecognition and sensing of cations and anions. Examples on the relationship between structure andselectivity towards cations and anions are described. Furthermore, their applications as potentiometricion sensing are emphasised, along with their potential applications in optical sensors or optodes.

  13. Interaction of a potyviral VPg with anionic phospholipid vesicles

    International Nuclear Information System (INIS)

    Rantalainen, Kimmo I.; Christensen, Peter A.; Hafren, Anders; Otzen, Daniel E.; Kalkkinen, Nisse; Maekinen, Kristiina

    2009-01-01

    The viral genome-linked protein (VPg) of Potato virus A (PVA) is a multifunctional protein that belongs to a class of intrinsically disordered proteins. Typically, this type of protein gains a more stable structure upon interactions or posttranslational modifications. In a membrane lipid strip overlay binding assay, PVA VPg was found to bind phosphatidylserine (PS), but not phosphatidylcholine (PC). According to circular dichroism spectroscopy, the secondary structure of PVA VPg was stabilized upon interactions with PS and phosphatidylglycerol (PG), but not with PC vesicles. It is possible that this stabilization favored the formation of α-helical structures. Limited tryptic digestion showed that the interaction with anionic vesicles protected certain, otherwise accessible, trypsin cleavage sites. An electron microscopy study revealed that interaction with VPg substantially increased the vesicle diameter and caused the formation of pore or plaque-like electron dense spots on the vesicle surface, which gradually led to disruption of the vesicles.

  14. Zn-Al LAYERED DOUBLE HYDROXIDE PILLARED BY DIFFERENT DICARBOXYLATE ANIONS

    Directory of Open Access Journals (Sweden)

    S. Gago

    2004-12-01

    Full Text Available Zn-Al layered double hydroxides (LDHs intercalated by terephthalate (TPH and biphenyl-4,4'-dicarboxylate (BPH anions have been synthesized by direct co-precipitation from aqueous solution. The Zn/Al ratio in the final materials was 1.8. The products were characterized by powder X-ray diffraction, thermogravimetric analysis, FTIR and FT Raman spectroscopy, and MAS NMR spectroscopy. The basal spacing for the TPH-LDH intercalate was 14.62 Å, indicating that the guest anions stack to form a monolayer with the aromatic rings perpendicular to the host layers. For the LDH intercalate containing BPH anions, a basal spacing of at least 19.2 Å would be expected if the anions adopted an arrangement similar to that for the TPH anions. The observed spacing was 18.24 Å, suggesting that the anions are tilted slightly with respect to the host layers.

  15. Pu Anion Exchange Process Intensification

    International Nuclear Information System (INIS)

    Taylor-Pashow, Kathryn M. L.

    2017-01-01

    This research is focused on improving the efficiency of the anion exchange process for purifying plutonium. While initially focused on plutonium, the technology could also be applied to other ion-exchange processes. Work in FY17 focused on the improvement and optimization of porous foam columns that were initially developed in FY16. These foam columns were surface functionalized with poly(4-vinylpyridine) (PVP) to provide the Pu specific anion-exchange sites. Two different polymerization methods were explored for maximizing the surface functionalization with the PVP. The open-celled polymeric foams have large open pores and large surface areas available for sorption. The fluid passes through the large open pores of this material, allowing convection to be the dominant mechanism by which mass transport takes place. These materials generally have very low densities, open-celled structures with high cell interconnectivity, small cell sizes, uniform cell size distributions, and high structural integrity. These porous foam columns provide advantages over the typical porous resin beads by eliminating the slow diffusion through resin beads, making the anion-exchange sites easily accessible on the foam surfaces. The best performing samples exceeded the Pu capacity of the commercially available resin, and also offered the advantage of sharper elution profiles, resulting in a more concentrated product, with less loss of material to the dilute heads and tails cuts. An alternate approach to improving the efficiency of this process was also explored through the development of a microchannel array system for performing the anion exchange.

  16. Pu Anion Exchange Process Intensification

    Energy Technology Data Exchange (ETDEWEB)

    Taylor-Pashow, Kathryn M. L. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)

    2017-10-06

    This research is focused on improving the efficiency of the anion exchange process for purifying plutonium. While initially focused on plutonium, the technology could also be applied to other ion-exchange processes. Work in FY17 focused on the improvement and optimization of porous foam columns that were initially developed in FY16. These foam columns were surface functionalized with poly(4-vinylpyridine) (PVP) to provide the Pu specific anion-exchange sites. Two different polymerization methods were explored for maximizing the surface functionalization with the PVP. The open-celled polymeric foams have large open pores and large surface areas available for sorption. The fluid passes through the large open pores of this material, allowing convection to be the dominant mechanism by which mass transport takes place. These materials generally have very low densities, open-celled structures with high cell interconnectivity, small cell sizes, uniform cell size distributions, and high structural integrity. These porous foam columns provide advantages over the typical porous resin beads by eliminating the slow diffusion through resin beads, making the anion-exchange sites easily accessible on the foam surfaces. The best performing samples exceeded the Pu capacity of the commercially available resin, and also offered the advantage of sharper elution profiles, resulting in a more concentrated product, with less loss of material to the dilute heads and tails cuts. An alternate approach to improving the efficiency of this process was also explored through the development of a microchannel array system for performing the anion exchange.

  17. Copper(I) coordination compounds with closododecaborate anion

    International Nuclear Information System (INIS)

    Malinina, E.A.; Drozdova, V.V.; Mustyatsa, V.N.; Goeva, L.V.; Polyakova, I.N.; Votinova, N.A.; Zhizhin, K.Yu.; Kuznetsov, N.T.

    2006-01-01

    Cu(I) Complexes with closo-dodecaborate anion Cat[CuB 12 H 12 ], where Cat= Cs + , Ph 4 P + , Ph 4 As + , R x NH 4-x + (R=Me, Et, Pr, Bu, X=3-4) are synthesized. Synthesis of complexes was conducted in the copper(II) salt-salt of dodecaborate anion-sulfur dioxide (sodium sulfite) system. Structure of the complex [Cu 2 (NCCH 3 ) 4 B 12 H 12 ] assigned by X-ray structural analysis discloses that B 12 H 12 2- anion enters into the inner sphere of metal-complexing agent, and connection of closo-borate ligand with the metal is caused by the formation of three-centric metal-hydrogen-boron bonds [ru

  18. Evidence for radical anion formation during liquid secondary ion mass spectrometry analysis of oligonucleotides and synthetic oligomeric analogues: a deconvolution algorithm for molecular ion region clusters.

    Science.gov (United States)

    Laramée, J A; Arbogast, B; Deinzer, M L

    1989-10-01

    It is shown that one-electron reduction is a common process that occurs in negative ion liquid secondary ion mass spectrometry (LSIMS) of oligonucleotides and synthetic oligonucleosides and that this process is in competition with proton loss. Deconvolution of the molecular anion cluster reveals contributions from (M-2H).-, (M-H)-, M.-, and (M + H)-. A model based on these ionic species gives excellent agreement with the experimental data. A correlation between the concentration of species arising via one-electron reduction [M.- and (M + H)-] and the electron affinity of the matrix has been demonstrated. The relative intensity of M.- is mass-dependent; this is rationalized on the basis of base-stacking. Base sequence ion formation is theorized to arise from M.- radical anion among other possible pathways.

  19. Effect of Codoping Cl Anion and 5-AVA Cation on Performance of Large-Area Perovskite Solar Cells with Double-Mesoporous Layers

    Directory of Open Access Journals (Sweden)

    Yaxian Pei

    2016-01-01

    Full Text Available For the perovskite solar cells (PSCs, the performance of the PSCs has become the focus of the research by improving the quality of the perovskite absorption layer. So far, the performance of the large-area PSCs is lower than that of small-area PSCs. In the paper, the experiments were designed to improve the photovoltaic performance of the large-area PSCs by improved processing technique. Here we investigated the optoelectronic properties of the prototypical CH3NH3PbI3 (MAPbI3 further modulated by introducing other extrinsic ions (specifically codoped Cl− and 5-AVA+. Moreover, we used inorganic electron extraction layer to achieve very rapid photogenerated carrier extraction eliminating local structural defects over large areas. Ultimately, we fabricated a best-performing perovskite solar cell based on codoping Cl anion and 5-AVA cation which uses a double layer of mesoporous TiO2 and ZrO2 as a scaffold infiltrated with perovskite and does not require a hole-conducting layer. The experiment results indicated that an average efficiency of double-mesoporous layer-based devices with codoping Cl anion and 5-AVA cation was obtained with exceeding 50% enhancement, compared to that of pure single-mesoporous layer-based device.

  20. Regulation of organic anion transport in the liver

    NARCIS (Netherlands)

    Roelofsen, H; Jansen, PLM

    1997-01-01

    In several liver diseases the biliary transport is disturbed, resulting in, for example, jaundice and cholestasis. Many of these symptoms can be attributed to altered regulation of hepatic transporters. Organic anion transport, mediated by the canalicular multispecific organic anion transporter

  1. Electron transfer to sulfides:

    International Nuclear Information System (INIS)

    Meneses, Ana Belen; Antonello, Sabrina; Arevalo, Maria Carmen; Maran, Flavio

    2005-01-01

    The problem of characterizing the steps associated with the dissociative reduction of sulfides has been addressed. The electrochemical reduction of diphenylmethyl para-methoxyphenyl sulfide in N,N-dimethylformamide, on both glassy carbon and mercury electrodes, was chosen as a test system. The electrode process involves the slow heterogeneous outer-sphere electron transfer to the sulfide, the fast cleavage of the C-S bond, the reduction of the ensuing carbon radical, and the self-protonation triggered by the generation of the strong base Ph 2 CH - . The latter reaction is rather slow, in agreement with the large intrinsic barriers characterizing proton transfers between CH-acids and carbon bases. The dissociative reduction was studied in the presence of an exogenous acid. The results, obtained by convolution analysis, point to a stepwise DET mechanism in which the ET step is accompanied by rather large reorganization energy. Similar results were obtained on both electrode materials. Analysis of the heterogeneous electron transfer and associated C-S bond cleavage indicate that the reduction of this and other sulfides lies between the stepwise dissociative electron transfers leading to the formation of stiff π* radical anions and those going through the intermediacy of loose σ* radical anions

  2. Effects of the anion salt nature on the rate constants of the aqueous proton exchange reactions.

    Science.gov (United States)

    Paredes, Jose M; Garzon, Andres; Crovetto, Luis; Orte, Angel; Lopez, Sergio G; Alvarez-Pez, Jose M

    2012-04-28

    The proton-transfer ground-state rate constants of the xanthenic dye 9-[1-(2-methyl-4-methoxyphenyl)]-6-hydroxy-3H-xanthen-3-one (TG-II), recovered by Fluorescence Lifetime Correlation Spectroscopy (FLCS), have proven to be useful to quantitatively reflect specific cation effects in aqueous solutions (J. M. Paredes, L. Crovetto, A. Orte, J. M. Alvarez-Pez and E. M. Talavera, Phys. Chem. Chem. Phys., 2011, 13, 1685-1694). Since these phenomena are more sensitive to anions than to cations, in this paper we have accounted for the influence of salts with the sodium cation in common, and the anion classified according to the empirical Hofmeister series, on the proton transfer rate constants of TG-II. We demonstrate that the presence of ions accelerates the rate of the ground-state proton-exchange reaction in the same order than ions that affect ion solvation in water. The combination of FLCS with a fluorophore undergoing proton transfer reactions in the ground state, along with the desirable feature of a pseudo-dark state when the dye is protonated, allows one unique direct determination of kinetic rate constants of the proton exchange chemical reaction. This journal is © the Owner Societies 2012

  3. Effect of the chemical structure of anion exchange resin on the adsorption of humic acid: behavior and mechanism.

    Science.gov (United States)

    Shuang, Chendong; Wang, Jun; Li, Haibo; Li, Aimin; Zhou, Qing

    2015-01-01

    Polystyrenic (PS) anion-exchange resin and polyacrylic (PA) anion-exchange resin were used to investigate the effect of resin chemical structure on the adsorption of humic acid (HA). Due to the rearrangement of HA to form layers that function as barricades to further HA diffusion, PS resin exhibited 12.4 times slower kinetics for the initial adsorption rate and 8.4 times for the diffusion constant in comparison to that of the PA resin. An HA layer and a spherical cluster of HA can be observed on the surface of the PS and PA resins after adsorption, respectively. The considerable difference in HA adsorption between the PS and PA resins was due to the difference in molecule shape for interaction with different resin structures, which can essentially be explained by the hydrophobicity and various interactions of the PS resin. A given amount of HA occupies more positively charged sites and hydrophobic sites on the PS resin than were occupied by the same amount of HA on the PA resin. Increased pH resulted in an increase of HA adsorption onto the PA resin but a decrease in adsorption onto PS resin, as the non-electrostatic adsorption led to electrostatic repulsion between the HA attached to the resin and the HA dissolved in solution. These results suggest higher rates of adsorption and higher regeneration efficiency for interaction of HA with more hydrophilic anion exchange materials. Copyright © 2014 Elsevier Inc. All rights reserved.

  4. Nanoparticles of nickel oxide: growth and organization on zinc-substituted anionic clay matrix by one-pot route at room temperature

    International Nuclear Information System (INIS)

    Carja, Gabriela; Nakajima, Akira; Dranca, Cristian; Okada, Kiyoshi

    2010-01-01

    A room temperature nanocarving strategy is developed for the fabrication of nanoparticles of nickel oxide on zinc-substituted anionic clay matrix (Ni/ZnLDH). It is based on the growth and organization of nanoparticles of nickel oxide which occur during the structural reconstruction of the layered structure of the anionic clay in NiSO 4 aqueous solution. No organic compounds are used during the fabrication. The described material was characterized by X-ray diffraction (XRD), IR spectroscopy (FTIR), transmission electron microscopy (TEM), field-emission scanning electron microscopy (FESEM), energy dispersive X-ray (EDX) spectroscopy, and X-ray photoelectron spectroscopy (XPS). Results show that the nickel-clay nanoarchitecture consists of small nanoparticles of nickel oxide (average size 7 nm) deposited on the larger nanoparticles (average size 90 nm) of zinc-substituted clay. The optical properties of the new nickel-zinc formulation are studied by UV-Vis.

  5. Nanoparticles of nickel oxide: growth and organization on zinc-substituted anionic clay matrix by one-pot route at room temperature

    Science.gov (United States)

    Carja, Gabriela; Nakajima, Akira; Dranca, Cristian; Okada, Kiyoshi

    2010-10-01

    A room temperature nanocarving strategy is developed for the fabrication of nanoparticles of nickel oxide on zinc-substituted anionic clay matrix (Ni/ZnLDH). It is based on the growth and organization of nanoparticles of nickel oxide which occur during the structural reconstruction of the layered structure of the anionic clay in NiSO4 aqueous solution. No organic compounds are used during the fabrication. The described material was characterized by X-ray diffraction (XRD), IR spectroscopy (FTIR), transmission electron microscopy (TEM), field-emission scanning electron microscopy (FESEM), energy dispersive X-ray (EDX) spectroscopy, and X-ray photoelectron spectroscopy (XPS). Results show that the nickel-clay nanoarchitecture consists of small nanoparticles of nickel oxide (average size 7 nm) deposited on the larger nanoparticles (average size 90 nm) of zinc-substituted clay. The optical properties of the new nickel-zinc formulation are studied by UV-Vis.

  6. Use of inorganic materials for the uptake of anions from simulated nuclear wastes

    International Nuclear Information System (INIS)

    Usman, J.N.

    1991-01-01

    Investigations on some commercially available hydrous oxides (Ferrox, Zirox, Alumina, Oxti and Oxtain) have been carried out with a view to understanding their sorption properties for anions (such as 36 C1 - , 51 Cr 2 O 4 2- , 99 MoO 4 - and 106 Ru complexes) and to assess their suitability in specific applications in the nuclear fuel cycle. All the materials exhibited sorption for the anions with oxtain showing the lowest of sorption in various media solutions. Sorption was most effective at solution pH 2-9 following the amphotericism of these materials. The presence of competing anions had a marked effect on the sorption properties of the exchangers for all the anions investigated. TG and DTG results revealed a general weight loss presumably due to loss of moisture. The selectivity for NO 3 - and 36 C1 - was studied by plotting ion-exchange isotherms for each exchanger. All isotherms displayed large hysteresis. The fixed-bed column experiments revealed a high affinity for 36 C1 - on Ferrox, Zirox and Alumina than was observed in the K d measurements. In-vivo γ-radiation effects on the materials and their sorption properties were investigated. Prolonged chemical treatment had little or no effect on the sorption properties of the exchangers, and revealed that none of the materials withstood long term exposure to acid or alkaline conditions. The leachability of isotopically labelled exchangers contained in cement (OPC) composites was studied along deionised water, synthetic sea-water and synthetic ground water as leachants. The effect of cement additives (BFS) on the leachability of the composites was also studied. The diffusion coefficients for the leaching process were evaluated by using the Carman-Haul equation. Results clearly showed that BFS had little or no effect on the leachability of 36 C1 - . (author)

  7. Strapped Calix[4]pyrroles Bearing an 1,3-Indanedione at a β-Pyrrolic Position: Chemodosimeters for the Cyanide Anion

    Science.gov (United States)

    Kim, Sook-Hee; Hong, Seong-Jin; Yoo, Jaeduk; Kim, Sung Kuk; Sessler, Janathan L.; Lee, Chang-Hee

    2014-01-01

    A strapped calix[4]pyrrole bearing an 1,3-indanedione group at a β-pyrrolic position has been synthesized and studied as a ratiometric cyanide selective chemosensor. A concentration-dependent bleaching of the initial yellow color was observed upon addition of the cyanide anion. The bleaching, which was observed exclusively with the cyanide anion, occurred even in the presence of other anions. Spectroscopic studies provides support for a mechanistic interpretation wherein the cyanide anion forms a complex with the receptor (K = 2.78 × 104 M-1) through a fast equilibrium, which is followed by slow nucleophilic addition to the β-position of the 1,3-indanedione group. A minimum inhibitory effect from other anions was observed, a feature that could be beneficial in the selective sensing of the cyanide anion. PMID:19639968

  8. High resolution electron attachment to molecules of atmospheric relevance

    International Nuclear Information System (INIS)

    Senn, G.

    2000-10-01

    This Ph.D. thesis is divided into three parts. The first is an introduction into the field of electron attachment. In the second part the experimental apparatus is described, and in the third part the results are presented. In the present thesis molecules were chosen for our investigations that are not only of academic interest but that also play an important role for applications or even the life on this planet. All the molecules studied in this work are of atmospheric relevance. NO, and OClO, are involved in the ozone depletion of the stratosphere. The D-layer of the ionosphere is an upper boundary of the ozone layer, therefore the interaction of the electrons from the D-layer with O 3 might play an important role for the chemistry in that part of the atmosphere. Especially the interaction of slow electrons (that will be present in the D-layer in large numbers) with ozone was emphasized in the present study. The production of O - and O 2 - by dissociative electron attachment to ozone was measured for incident electron energies between 0 and 10eV. A previously unobserved sharp structure was discovered in the formation of O - ions for electrons with zero kinetic energy. This additional cross section peak has important consequences for the role of ozone in the anion formation process in the ionosphere. Since OClO is a night time reservoir for chlorine atoms (Cl) and chlorine monoxide (ClO) both of which play a critical role in the depletion of the stratospheric ozone, we have studied negative ion formation following electron impact (0-10eV) to OClO. Despite its atmospheric relevance the mechanism of dissociative electron attachment (DEA) to NO is still a matter of controversy. DEA was studied at high energy resolution and with a kinetic-energy analysis of the O - fragment in two independent crossed electron-molecular-beam experiments. The DEA cross section exhibits a vertical onset near 7.45eV that corresponds to the energy threshold of the DEA channel O - ( 2 P

  9. Preparation of Cationic MOFs with Mobile Anions by Anion Stripping to Remove 2,4-D from Water

    Directory of Open Access Journals (Sweden)

    Tao Chen

    2017-07-01

    Full Text Available A cationic porous framework with mobile anions (MIL-101(Cr-Cl was easily and successfully synthesized by utilizing the stronger affinity of F− to Al3+ than Cr3+ in the charge-balanced framework of MIL-101(Cr. The structure, morphology and porosity of MIL-101(Cr-Cl were characterized. The obtained new materials retain the high surface area, good thermostability, and structure topology of MIL-101(Cr. With the mobile Cl− anion, MIL-101(Cr-Cl can be used as an ion-exchange material for anionic organic pollutions. In this work, 2,4-dichlorophenoxyacetic acid (2,4-D was used as a model to test the absorption performance of this new material. This new material exhibited improved adsorbability compared to that of the original metal-organic frameworks (MOFs. At the same time, this material also shows high anti-interference performance with changing solution pH.

  10. Effect of cation-anion interactions on the structural and vibrational properties of 1-buthyl-3-methyl imidazolium nitrate ionic liquid

    Science.gov (United States)

    Kausteklis, Jonas; Aleksa, Valdemaras; Iramain, Maximiliano A.; Brandán, Silvia Antonia

    2018-07-01

    The cation-anion interactions present in the 1-butyl-3-methylimidazolium nitrate ionic liquid [BMIm][NO3] were studied by using density functional theory (DFT) calculations and the experimental FT-Raman spectrum in liquid phase and its available FT-IR spectrum. For the three most stable conformers found in the potential energy surface and their 1-butyl-3-methylimidazolium [BMIm] cation, the atomic charges, molecular electrostatic potentials, stabilization energies, bond orders and topological properties were computed by using NBO and AIM calculations and the hybrid B3LYP level of theory with the 6-31G* and 6-311++G** basis sets. The force fields, force constants and complete vibrational assignments were also reported for those species by using their internal coordinates and the scaled quantum mechanical force field (SQMFF) approach. The dimeric species of [BMIm][NO3] were also considered because their presence could probably explain the most intense bands observed at 1344 and 1042 cm-1 in both experimental FT-IR and FT-Raman spectra, respectively. The geometrical parameters suggest monodentate cation-anion coordination while the studies by charges, NBO and AIM calculations support bidentate coordinations between those two species. Additionally several quantum chemical descriptors were also calculated in order to interpret various molecular properties such as electronic structure, reactivity of those species and predict their gas phase behaviours.

  11. Isotopic enrichments via altered first and second solution electron affinities

    International Nuclear Information System (INIS)

    Stevenson, G.R.; Espe, M.P.; Reiter, R.C.

    1986-01-01

    Electron spin resonance experiments have been utilized to show that the solution electron affinity of benzene- 13 C 6 is less than that of benzene by 0.24 kcal/mol and that the solution EA of benzene-d 6 is less than that of benzene by 0.44 kcal/mol. Perdeuteration of naphthalene, anthracene, or perylene results in a very similar lowering of the solution EA of the hydrocarbon as evidenced by the fact that the equilibrium constant for the electron transfer between the hydrocarbon anion radical, X/sup .-/, and the perdeuterated hydrocarbon, Xd (X/sup .-/ + Xd = Xd/sup .-/ + X), is less than unity. Likewise the second EAs of perdeuterated perylene and anthracene are lower than those of the unsubstituted hydrocarbons (K/sub eq/ for X 2- + Xd/sup .-/ = X/sup .-/ + Xd 2- is less than unity). The free energy and enthalpy of electron transfer from the anthracene anion radical to perdeuterated anthracene is 0.41 kcal/mol and that from the anthracene dianion to the perdeuterated anion radical is 0.10 kcal/mol. The fact that these equilibrium constants are not equal to 1 enables one to use the difference in the chemical reactivity of the ions and neutral molecules to selectively isotopically enrich the hydrocarbons involved

  12. Superconductivity at 2.8 K and 1.5 kbar in κ-(BEDT-TTF)2Cu2(CN)3: The first organic superconductor containing a polymeric copper cyanide anion

    International Nuclear Information System (INIS)

    Geiser, Urs; Wang Hau, H.; Carlson, K.D.; Williams, J.M.; Charlier, H.A. Jr.; Heindl, J.E.; Yaconi, G.A.; Love, B.J.; Lathrop, M.W.; Schirber, J.E.; Overmyer, D.L.; Ren, Jingquing; Whangbo, Myung-Hwan

    1991-01-01

    Attempts to synthesize new k-phase superconductors have concentrated on ET salts with complex anions composed of Cu(I) or Ag(I) metal ions and pseudohalide anions. The 'targeted anion approach', by use of a preformed anion found in KCu 2 (CN) 3 .H 2 O and the presence of trace amounts of water, led to the discovery of the first copper-cyanide containing superconductor, K-(ET) 2 Cu 2 (CN) 3 . The crystal structure, superconducting properties, and band electronic structure are described in this article. The complex k-(ET) 2 Cu 2 (CN) 3 is in many ways similar to the superconductor K-(ET) 2 Cu[N(CN) 2 ]Cl, the superconductor with the highest T c reported to date. 28 refs., 3 figs

  13. Spectrally resolved thermally stimulated luminescence of irradiated anion-defective alumina single crystals

    Energy Technology Data Exchange (ETDEWEB)

    Kortov, V., E-mail: vskortov@mail.ru [Ural Federal University, Mira Str. 19, 620002 Ekaterinburg (Russian Federation); Lushchik, A.; Nagirnyi, V. [Institute of Physics, University of Tartu, W. Ostwald Str. 1, 50411 Tartu (Estonia); Ananchenko, D. [Ural Federal University, Mira Str. 19, 620002 Ekaterinburg (Russian Federation); Romet, I. [Institute of Physics, University of Tartu, W. Ostwald Str. 1, 50411 Tartu (Estonia)

    2017-06-15

    Thermally stimulated luminescence (TSL) spectra in the 313–580 K temperature range have been studied in anion-defective alumina crystals (named in literature as Al{sub 2}O{sub 3}:C) exposed to different irradiation doses. The TSL curve features two peaks with the maxima at T{sub m1}=437 K and T{sub m2}=565 K. The TSL spectrum of the first peak contains the emission of F centers and the R line of Cr{sup 3+} impurity ions. The absence of the emission of F{sup +} centers indicates that electron traps are responsible for the first dosimetric TSL peak. The TSL spectrum of the second peak features emission bands of F, F{sup +} centers, R line as well as a wide band centered at 550 nm and associated with the formation of aggregate centers (F{sub 2} and F{sub 2}{sup 2+}) under irradiation. Possible excitation mechanisms of the TSL emission bands that involve both electron and hole traps related to anion vacancies and impurities are discussed. - Highlights: •TSL curve of alumina crystals features peaks at 437 and 565 K. •There are emission bands of 410 and 695 nm in the TSL spectrum of the first peak. •TSL spectrum of the second peak features bands of F, F{sub 2}-type centers and the R line of trivalent chromium. •Excitation mechanisms of the emission bands in TSL spectra are discussed.

  14. Electron beam effects in auger electron spectroscopy and scanning electron microscopy

    International Nuclear Information System (INIS)

    Fontaine, J.M.; Duraud, J.P.; Le Gressus, C.

    1979-01-01

    Electron beam effects on Si(100) and 5% Fe/Cr alloy samples have been studied by measurements of the secondary electron yield delta, determination of the surface composition by Auger electron spectroscopy and imaging with scanning electron microscopy. Variations of delta as a function of the accelerating voltage Esub(p) (0.5 -9 Torr has no effect on technological samples covered with their reaction layers; the sensitivities to the beam depend rather on the earlier mechanical, thermal and chemical treatment of the surfaces. (author)

  15. Fluorescence quenching of derivatives of anthracene by organic electron donors and acceptors in acetonitrile. Electron and proton transfer mechanism

    Science.gov (United States)

    Mac, Marek; Najbar, Jan; Wirz, Jakob

    1995-03-01

    Fluorescence quenching of anthracene derivatives by organic electron donors (amines) and acceptors was investigated using stationary fluorescence measurements. The dependence of log( kq) on Δ Get shows Rehm-Weller-type behavior. The formation of anion radicals of anthracene, bianthryl, and 9-cyanoanthracene was detected by flash photolysis in systems containing aromatic amines (aniline, 2-bromoaniline, 4-bromoaniline, N,N-dimethylaniline, 4-bromo-N,N-dimethylaniline, N,N-diethylaniline, and 1,4-diazabicyclo[2.2.2]octane). The radical yields decreased and triplet yields increased when bromo derivatives of amines were used as donor quenchers, indicating the heavy-atom effect on spin conversion within radical pairs. The importance of the heavy-atom effect decreased when the energy gap between the charge transfer and molecular triplet states was small. The formation of separated radicals decreased when primary amines were used as quenchers which indicated the existence of an additional path of deactivation of the radical pair. The behavior of amines as quenchers of bianthryl and anthracene is compared with that of inorganic anion quenchers.

  16. Studing electronic structure of water molecules in aquocomplexes by the method of pions minus capture by hydrogen

    International Nuclear Information System (INIS)

    Dezhi, I.; Krumshtejn, Z.V.; Molnar, B.; Petrukhin, V.I.; Rybakov, V.N.; Suvorov, V.M.; Khorvat, D.; Tsisek, Z.; Yutlandov, I.A.

    1980-01-01

    Using the effect of electron shell state on π-meson capture by chemically bound hydrogen studied has been change of electron density in hydrogen atoms of water molecules bound into aquocomplexes. The fact of depression of π-meson capture probability by hydrogen of water in aquocomplexes has been established. The magnitudes of depression indicate essential decrease of electron density in a hydrogen atom of coordinated water. Interaction of ligands with oxygen-containing anions also essentially contributes to a magnitude of depression

  17. Novel Fragmentation Pathways of Anionic Adducts of Steroids Formed by Electrospray Anion Attachment Involving Regioselective Attachment, Regiospecific Decompositions, Charge-Induced Pathways, and Ion-Dipole Complex Intermediates

    Science.gov (United States)

    Rannulu, Nalaka S.; Cole, Richard B.

    2012-09-01

    The analysis of several bifunctional neutral steroids, 5-α-pregnane diol (5-α-pregnane-3α-20βdiol), estradiol (3,17α-dihydroxy-1,3,5(10)-estratriene), progesterone (4-pregnene-3,20-dione), lupeol (3β-hydroxy-20(29)-lupene), pregnenolone (5-pregnen-3β-ol-20-one), and pregnenolone acetate (5-pregnen-3β-ol-20-one acetate) was accomplished by negative ion electrospray mass spectrometry (ESI-MS) employing adduct formation with various anions: fluoride, bicarbonate, acetate, and chloride. Fluoride yielded higher abundances of anionic adducts and more substantial abundances of deprotonated molecules compared with other investigated anions. Collision-induced dissociation (CID) of precursor [M + anion]- adducts of these steroids revealed that fluoride adduct [M + F]- precursors first lose HF to produce [M - H]- and then undergo consecutive decompositions to yield higher abundances of structurally-informative product ions than the other tested anions. In addition to charge-remote fragmentations, the majority of CID pathways of estradiol are deduced to occur via charge-induced fragmentation. Most interestingly, certain anions exhibit preferential attachment to a specific site on these bifunctional steroid molecules, which we are calling "regioselective anion attachment." Regioselective anion attachment is evidenced by subsequent regiospecific decomposition. Regioselective attachment of fluoride (and acetate) anions to low (and moderate) acidity functional groups of pregnenolone, respectively, is demonstrated using deuterated compounds. Moreover, the formation of unique intermediate ion-dipole complexes leading to novel fragmentation pathways of fluoride adducts of pregnenolone acetate, and bicarbonate adducts of d4-pregnenolone, are also discussed.

  18. Effect of CO2 absorption on ion and water mobility in an anion exchange membrane

    Science.gov (United States)

    Peng, Jing; Roy, Asa L.; Greenbaum, Steve G.; Zawodzinski, Thomas A.

    2018-03-01

    We report the measured water uptake, density, ionic conductivity and water transport properties in Tokuyama A201 membrane in OH-, HCO3- and Cl- forms. The water uptake of the AEM varies with anion type in the order λ(OH-) > λ(HCO3-) > λ(Cl-) for samples equilibrated with the same water vapor activity (aw). The conductivity of the AEM is reduced by absorption of CO2. Pulsed-field gradient nuclear magnetic resonance (PFG-NMR) measurements were utilized to characterize the diffusivity of water and HCO3- ion. The anion diffusion coefficient and membrane conductivity are used to probe the applicability of the Nernst-Einstein equation in these AEMs.

  19. Effect of Anionic Salt and Highly Fermentable Carbohydrate Supplementations on Urine pH and on Experimentally Induced Hypocalcaemia in Cows

    Directory of Open Access Journals (Sweden)

    Enemark JMD

    2004-09-01

    Full Text Available The objective of this experiment was to determine the effect of dietary grain on calcium homeostasis. Six rumen-fistulated dairy cows with 3 or more previous lactations and no history of parturient paresis were randomly assigned to a sequence of diets in a crossover study with 4 periods of 10 days each. Dietary treatments were: A control ration consisting of wrap grass silage alone (1, the control ration supplemented with ammonium chloride and ammonium sulphate salt solution (2, control ration following a period with supplementation (3 and control ration supplemented with increasing amounts of barley from 4 to 10 kg/cow per day, expected to produce subclinical rumen acidosis (4. Daily intake of the diets was adjusted to 14 kg DM/cow per day. On day 11, the calcium-regulating mechanisms in cows were challenged until recumbency by a standardized intravenous EDTA infusion and cows were left to recover spontaneously. Anion supplementation and the feeding of highly fermentable carbohydrate lowered urine pH below 7.0 due to subclinical acidosis. During spontaneous recovery from EDTA induced hypocalcaemia, the cows more quickly regained a whole blood free calcium concentration of 1.00 mmol/L if they had most recently been supplemented with either anionic salts or with increasing amounts of barley, as compared to the basic ration. It is concluded that so-called slug-feeding or 'steaming up' with highly fermentable carbohydrates before parturition in milk fever susceptible cows enhanced calcium homeostasis similar to the effect seen in cows on anionic diets.

  20. Anion exchange of 58 elements in hydrobromic acid and in hydriodic acid

    International Nuclear Information System (INIS)

    Marsh, S.F.; Alarid, J.E.; Hammond, C.F.; McLeod, M.J.; Roensch, F.R.; Rein, J.E.

    1978-02-01

    Anion exchange distributions of 58 elements have been measured from 0.1-8.7M HBr and from 0.1-7.4M HI onto three strong-base resins, 8 and 4% cross-linked and macroporous. Data were obtained by 16- to 18-h dynamic batch contacts. Anion exchange in these media is compared to that in HCl. The effect of resin cross-linkage is considerably greater in HI media than in HBr and HCl media. Examples are presented of potentially useful separations using HBr and HI media alone and in combination with HCl

  1. Effect of proquinazid and copper hydroxide on homeostasis of anions in winter wheat plants in generative phase of development

    Directory of Open Access Journals (Sweden)

    M. E. Riazanova

    2015-03-01

    Full Text Available The study deals with the effect of proquinazid and copper oxide application on structural characteristics and resistance of wheat to powdery mildew, as well as remobilisation and redistribution of anions pools at generative stage of development. The trial series was conducted in the experimental agricultural production of the Institute of Plant Physiology and Genetics, National Academy of Sciences of Ukraine. Field experiments were carried out with Smuglyanka variety of winter wheat. The trial series included the application of fungicides such as Talius (proquinazid, 200 g/L 0,25 L/ha and Kocide 2000 (copper hydroxide, 350 g/kg 150 and 300 g/ha, and combination of both fungicides. Sprays were applied at tillering stage in autumn in the first trial series and at tillering-booting stage in spring in the second one. Assessment of affected plants by powdery mildew was carried out visually in points. Anion concentration was determined with the use of ion chromatography. Application of fungicides at tillering stage increases the amount of productive stems in wheat plants. The highest effect was recorded for application of copper hydroxide at dose of 300 g/ha in autumn. Analysis of plants affected by powdery mildew shows that application of proquinazid and its composition with copper hydroxide provides sustained protection against Blumeria graminis (DC Speer. Application of fungicides at tillering stage contributes to increase of the pool of free nitrogen, phosphorus and sulfur anions in leaf tissues compared to control. These changes in anion composition may be caused by fungicide effect on activity of N, P, S transporters, as well as internal regulatory mechanisms of elements’ uptake by plants. Comparing the results of the autumn and spring application of fungicides should note the increase in concentration of free phosphates in wheat leaves in the 2nd trial with proquinazid and its composition with copper hydroxide. Accumulation of nitrogen in the

  2. Anion size and isotope effects in (EDO-TTF)2XF6

    International Nuclear Information System (INIS)

    Nakano, Yoshiaki; Yamochi, Hideki; Saito, Gunzi; Uruichi, Mikio; Yakushi, Kyuya

    2009-01-01

    (EDO-TTF) 2 PF 6 is a quasi one-dimensional molecular conductor and undergoes a peculiar metal-insulator (MI) transition. The phase transition mechanism is cooperative among Peierls, charge ordering, and anion ordering transitions, which is accompanied with a distinct molecular deformation. (EDO-TTF) 2 XF 6 (X = P (1h), As (2h), Sb (3h)) showed that the transition temperature (T MI ) and the width of thermal hysteresis (ΔT MI ) were systematically changed depending on the anion size, i.e., the T MI decreased in order of 279.0 K (1h), 270.8 K (2h), and 242 K (3h) and the ΔT MI increased in order of 1.0 K (1h), 5.5 K (2h), and 14 K (3h). The deuterated salts, (EDO-TTF-d 2 ) 2 XF 6 (X = P (1d) and As (2d)), showed higher T MI of 282.0 (1d) and 274.0 K (2d) and narrower ΔT MI of 0.0 (1d) and 5.0 K (2d) than the undeuterated 1h and 2h, respectively. X-ray analysis revealed the anisotropic thermal expansion of unit cell. The linear relationship between ΔT MI and volume change at T MI was found.

  3. Effect of pore structure on the removal of clofibric acid by magnetic anion exchange resin.

    Science.gov (United States)

    Tan, Liang; Shuang, Chendong; Wang, Yunshu; Wang, Jun; Su, Yihong; Li, Aimin

    2018-01-01

    The effect of pore structure of resin on clofibric acid (CA) adsorption behavior was investigated by using magnetic anion exchange resins (ND-1, ND-2, ND-3) with increasing pore diameter by 11.68, 15.37, 24.94 nm. Resin with larger pores showed faster adsorption rates and a higher adsorption capacity because the more opened tunnels provided by larger pores benefit the CA diffusion into the resin matrix. The ion exchange by the electrostatic interactions between Cl-type resin and CA resulted in chloride releasing to the solution, and the ratio of released chloride to CA adsorption amount decreased from 0.90 to 0.65 for ND-1, ND-2 and ND-3, indicating that non-electrostatic interactions obtain a larger proportional part of the adsorption into the pores. Co-existing inorganic anions and organic acids reduced the CA adsorption amounts by the competition effect of electrostatic interaction, whereas resins with more opened pore structures weakened the negative influence on CA adsorption because of the existence of non-electrostatic interactions. 85.2% and 65.1% adsorption amounts decrease are calculated for resin ND-1 and ND-3 by the negative influence of 1 mmol L -1 NaCl. This weaken effect of organic acid is generally depends on its hydrophobicity (Log Kow) for carboxylic acid and its ionization degree (pKb) for sulfonic acid. The resins could be reused with the slightly decreases by 1.9%, 3.2% and 5.4% after 7 cycles of regeneration, respectively for ND-1, ND-2 and ND-3, suggesting the ion exchange resin with larger pores are against its reuse by the brine solution regeneration. Copyright © 2017 Elsevier Ltd. All rights reserved.

  4. Laboratory Anion Chemistry: Implications for the DIBs, and a Potential Formation Mechanism for a Known Interstellar Molecule

    Science.gov (United States)

    Eichelberger, B.; Barckholtz, C.; Stepanovic, M.; Bierbaum, V.; Snow, T.

    2002-01-01

    Due to recent interest in molecular anions as possible interstellar species, we have carried out several laboratory studies of anion chemistry. The reactions of the series C(sub n)(sup -); and C(sub n)H(sup -) with H and H2 were studied to address the viability of such species in the diffuse interstellar medium and to address their ability to be carriers of the diffuse interstellar bands (DIBs). These same molecules were also reacted with N and O to show possible heteroatomic products. C(sub m)N(sup - was a particularly stable product from the reaction of C(sub n)(sup -) + N. C3N(sup -) was further reacted with H to study chemistry that could produce HC3N, a known interstellar species. The reactions were done in a flowing afterglow selected ion flow tube apparatus (FA-SIFT). The anions were generated in an electron impact or cold cathode discharge source and the anion of interest was then selected by a quadrupole mass filter. The selected ion was then reacted with the atomic or molecular species in the flow tube and products were detected by another quadrupole. While the C(sub n)(sup -) species do not appear to be viable DIB carriers, their possible presence could provide a mechanism for the formation of known heteroatomic neutral molecules detected in the interstellar medium (ISM).

  5. Diffuse neutron scattering from anion-excess strontium chloride

    DEFF Research Database (Denmark)

    Goff, J.P.; Clausen, K.N.; Fåk, B.

    1992-01-01

    The defect structure and diffusional processes have been studied in the anion-excess fluorite (Sr, Y)Cl2.03 by diffuse neutron scattering techniques. Static cuboctahedral clusters found at ambient temperature break up at temperatures below 1050 K, where the anion disorder is highly dynamic. The a...

  6. Anion binding by biotin[6]uril in water

    DEFF Research Database (Denmark)

    Lisbjerg, Micke; Nielsen, Bjarne Enrico; Milhøj, Birgitte Olai

    2015-01-01

    In this contribution we show that the newly discovered 6 + 6 biotin-formaldehyde macrocycle Biotin[6]uril binds a variety of anionic guest molecules in water. We discuss how and why the anions are bound based on data obtained using NMR spectroscopy, mass spectrometry, isothermal titration...

  7. EFFECTIVE ELECTRONIC TUTORIAL

    Directory of Open Access Journals (Sweden)

    Andrei A. Fedoseev

    2014-01-01

    Full Text Available The article analyzes effective electronic tutorials creation and application based on the theory of pedagogy. Herewith the issues of necessary electronic tutorial functional, ways of the educational process organization with the use of information and communication technologies and the logistics of electronic educational resources are touched upon. 

  8. Construction of a Nano Biosensor for Cyanide Anion Detection and Its Application in Environmental and Biological Systems.

    Science.gov (United States)

    Dong, Zhen-Zhen; Yang, Chao; Vellaisamy, Kasipandi; Li, Guodong; Leung, Chung-Hang; Ma, Dik-Lung

    2017-10-27

    We have developed a Ag@Au core-shell nanoparticle (NP)/iridium(III) complex-based sensing platform for the sensitive luminescence "turn-on" sensing of cyanide ions, an acutely toxic pollutant. The assay is based on the quenching effect of Ag@Au NPs on the emission of complex 1, but luminescence is restored after the addition of cyanide anions due to their ability to dissolve the Au shell. Our sensing platform exhibited a high sensitivity toward cyanide anions with a detection limit of 0.036 μM, and also showed high selectivity for cyanide over 10-fold excess amounts of other anions. The sensing platform was also successfully applied to monitor cyanide anions in drinking water and in living cells.

  9. Indirect photometric detection of boron cluster anions electrophoretically separated in methanol.

    Science.gov (United States)

    Vítová, Lada; Fojt, Lukáš; Vespalec, Radim

    2014-04-18

    3,5-Dinitrobenzoate and picrate are light absorbing anions pertinent to indirect photometric detection of boron cluster anions in buffered methanolic background electrolytes (BGEs). Tris(hydroxymethyl)aminomethane and morpholine have been used as buffering bases, which eliminated baseline steps, and minimized the baseline noise. In methanolic BGEs, mobilities of boron cluster anions depend on both ionic constituents of the BGE buffer. This dependence can be explained by ion pair interaction of detected anions with BGE cations, which are not bonded into ion pairs with the BGE anions. The former ion pair interaction decreases sensitivity of the indirect photometric detection. Copyright © 2014 Elsevier B.V. All rights reserved.

  10. Anion analysis in uranium more concentrates by ion chromatography

    International Nuclear Information System (INIS)

    Badaut, V.

    2009-01-01

    In the present exploratory study, the applicability of anionic impurities or attributing nuclear material to a certain chemical process or origin has been investigated. Anions (e.g., nitrate, sulphate, fluoride, chloride) originate from acids or salt solutions that are used for processing of solutions containing uranium or plutonium. The study focuses on uranium ore concentrates ('yellow cakes') originating from different mines. Uranium is mined from different types of ore body and depending on the type of rock, different chemical processes for leaching, dissolving and precipitating the uranium need to be applied. Consequently, the anionic patterns observed in he products of these processes (the 'ore concentrates') are different. The concentrations of different anionic species were measured by ion chromatography using conductivity detection. The results show clear differences of anion concentrations and patterns between samples from different uranium mines. Besides this, differences between sampling campaigns n a same mine were also observed indicating that the uranium ore is not homogeneous in a mine. These within-mine variations, however, were smaller than the between-mine variations. (author)

  11. Separation of transfer ribonucleic acids on polystyrene anion exchangers

    Energy Technology Data Exchange (ETDEWEB)

    Singhal, R.P.; Griffin, G.D.; Novelli, G.D.

    1976-11-16

    The transfer RNA separation by chromatography on strong-base-polystyrene exchange materials is examined and compared with the widely used reversed-phase chromatography. Results indicate important differences in some transfer RNA (tRNA) elution patterns by the anion-exchange chromatography, as compared with the reversed-phase chromatography. Transfer RNAs containing hydrophobic groups are adsorbed more strongly. The anion exchanger has twice the number of theoretical plates. Single peaks of tRNA/sub 2//sup Glu/ and tRNA/sub 1//sup Phe/ obtained from the reversed-phase column give multiple peaks on polystyrene anion-exchange chromatography. All six leucine tRNAs (Escherichia coli) and differences in tRNA populations synthesized during early and late stages of the dividing lymphocytes from normal human blood can be characterized by the anion-exchange chromatography. Different separation profiles are obtained by two separation systems for tyrosine tRNAs from mouse liver and mouse-plasma-cell tumor. The results indicate that, in contrast to the reversed-phase chromatography, strong-base-polystyrene anion-exchange chromatography is capable of separating tRNAs with minor structural differences.

  12. Study of radicals, clusters and transition state species by anion photoelectron spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Arnold, Don Wesley [Univ. of California, Berkeley, CA (United States)

    1994-08-01

    Free radicals, elemental and van der Waals clusters and transition state species for bimolecular chemical reactions are investigated using anion photoelectron spectroscopy. Several low-lying electronic states of ozone have been identified via photoelectron spectroscopy of O3-. A characterization of these states is important to models for atmospheric ozone reaction kinetics. The fluoroformyloxyl radical, FCO2, has been investigated, providing vibrational frequencies and energies for two electronic states. The technique has also been employed to make the first direct observation and characterization of the NNO2 molecule. Several electronic states are observed for this species which is believed to play a role as a reactive intermediate in the N + NO2 reaction. The experimental results for all three of these radicals are supplemented by ab initio investigations of their molecular properties. The clusters investigations include studies of elemental carbon clusters (C2- - C11-), and van der Waals clusters (X-(CO2)n, X = I, Br, Cl; n {le} 13 and I- (N2O)n=1--11). Primarily linear clusters are observed for the smaller carbon clusters, while the spectra of the larger clusters contain contribution from cyclic anion photodetachment. Very interesting ion-solvent interactions are observed in the X-(CO2)n clusters. The transition state regions for several bimolecular chemical reactions have also been investigated by photodetachment of a negative ion precursor possessing a geometry similar to that of the transition state species. These spectra show features which are assigned to motions of the unstable neutral complex existing between reactants and products.

  13. Solution Phase Measurement of Both Weak Sigma and C-H---X- Hydrogen Bonding Interactions in Synthetic Anion Receptors

    Energy Technology Data Exchange (ETDEWEB)

    Berryman, Mr. Orion B. [University of Oregon; Sather, Mr. Aaron C [University of Oregon; Hay, Benjamin [ORNL; Meisner, Mr. Jeffrey S. [University of Oregon; Johnson, Prof. Darren W. [University of Oregon

    2008-01-01

    A series of tripodal receptors preorganize electron-deficient aromatic rings to bind halides in organic solvents using weak sigma anion-to-arene interactions or C-H---X- hydrogen bonds. 1H NMR spectroscopy proves to be a powerful technique for quantifying binding in solution, and determining the interaction motifs, even in cases of weak binding.

  14. REMOVAL OF ANIONIC SURFACTANTS FROM WASTEWATER BY MAGNETIC MINERAL SORBENTS

    Directory of Open Access Journals (Sweden)

    Oksana Vladimirova Makarchuk

    2016-07-01

    Full Text Available The simplest and most effective method of removing low concentrations of anionic surfactants such as sodium dodecyl benzenesulfonate (SDBS and sodium lauryl sulfate (SLS is adsorption. Among adsorbents the natural clays are cheap and promising for these purposes. However, there are significant difficulties in removal of spent sorbent after the adsorption process. So, the creation of magnetic sorbents that can be effectively removed from water after sorption by magnetic separation will be a successful decision. The aim of this investigation is the creation of cheap and efficient magnetic sorbents based on natural clays and magnetite for anionic surfactant removal from wastewater. We have synthesized a series of magnetic sorbents from different natural clays with a content of magnetite from 2 to 10 wt%. The ability of magnetic sorbents to remove SDBS and SLS from aqueous solutions has been studied for different adsorbate concentrations by varying the amount of adsorbent, temperature and shaking time. Thermodynamic parameters were calculated from the slope and intercept of the linear plots of ln K against 1/T. Analysis of adsorption results obtained at different temperatures showed that the adsorption pattern on magnetic sorbents correspond to the Langmuir isotherm. It is shown that with increasing the content of magnetite in the magnetic sorbents improves not only their separation from water by magnetic separation, but adsorption capacity to SDBS and SLS. Thus, we obtained of cheap magnetic sorbents based on natural clays and magnetite by the easy way, which not only quickly separated from the solution by magnetic separation, but effectively remove anionic surfactants.

  15. BF2 complex of fluorinated dipyrrolyldiketone: a new class of efficient receptor for acetate anions.

    Science.gov (United States)

    Maeda, Hiromitsu; Ito, Yoshihiro

    2006-10-02

    The beta-fluorinated derivative (2b) of the 1,3-dipyrrolyl-1,3-propanedione BF2 complex has been prepared from 3,4-difluoropyrrole and malonyl chloride, followed by treatment with BF3.OEt2. Despite the simple, acyclic, and neutral structure, 2b exhibits efficient 1:1 binding for anions in CH2Cl2 using the bridging CH and pyrrole NH as interaction sites. The binding constant (Ka) of 2b for acetate (CH3CO(2-)), associating more effectively than anions such as F-, Cl-, Br-, H2PO(4-), and HSO(4-), is estimated to be 9.6 x 10(5) M(-1), approximately 9 times larger than that of the beta-H derivative 2a (1.1 x 10(5) M(-1)). The UV-vis and fluorescence spectral changes of 2b elucidate the effective recognition of an amino acid, such as phenylalanine, in the anionic form; this is also supported by CD spectral changes with mirror images by L- and D-isomers. Furthermore, in the solid state, BF2 complex 2b provides Cl- -bridged supramolecular networks and, in sharp contrast, deprotonated "anionic" self-assembled structures by F- binding.

  16. Dissociation dynamics of anionic and excited neutral fragments of gaseous SiCl4 following Cl 2p and Si 2p core-level excitations

    International Nuclear Information System (INIS)

    Chen, J M; Lu, K T; Lee, J M; Chou, T L; Chen, H C; Chen, S A; Haw, S C; Chen, T H

    2008-01-01

    The state-selective dissociation dynamics for anionic and excited neutral fragments of gaseous SiCl 4 following Cl 2p and Si 2p core-level excitations were characterized by combining measurements of the photon-induced anionic dissociation, x-ray absorption and UV/visible dispersed fluorescence. The transitions of core electrons to high Rydberg states/doubly excited states in the vicinity of both Si 2p and Cl 2p ionization thresholds of gaseous SiCl 4 lead to a remarkably enhanced production of anionic, Si - and Cl - , fragments and excited neutral atomic, Si*, fragments. This enhancement via core-level excitation near the ionization threshold of gaseous SiCl 4 is explained in terms of the contributions from the Auger decay of doubly excited states, shake-modified resonant Auger decay, or/and post-collision interaction. These complementary results provide insight into the state-selective anionic and excited neutral fragmentation of gaseous molecules via core-level excitation.

  17. Effect of adsorbed/intercalated anionic dyes into the mechanical properties of PVA: layered zinc hydroxide nitrate nanocomposites.

    Science.gov (United States)

    Marangoni, Rafael; Mikowski, Alexandre; Wypych, Fernando

    2010-11-15

    Zinc hydroxide nitrate (ZHN) was adsorbed with anions of blue dyes (Chicago sky blue, CSB; Evans blue, EB; and Niagara blue, NB) and intercalated with anions of orange dyes (Orange G, OG; Orange II, OII; methyl orange, MO). Transparent, homogeneous and colored nanocomposite films were obtained by casting after dispersing the pigments (dye-intercalated/adsorbed into LHSs) into commercial poly(vinyl alcohol) (PVA). The films were characterized by XRD, UV-Vis spectroscopy, and mechanical testing. The mechanical properties of the PVA compounded with the dye-intercalated/adsorbed ZHN were evaluated, and reasonable increases in Young's modulus and ultimate tensile strength were observed, depending on the amount and choice of layered filler. These results demonstrate the possibility of using a new class of layered hydroxide salts intercalated and adsorbed with anionic dyes to prepare multifunctional polymer nanocomposite materials. Copyright © 2010 Elsevier Inc. All rights reserved.

  18. Study of the ion-channel behavior on glassy carbon electrode supported bilayer lipid membranes stimulated by perchlorate anion

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Zhiquan; Shi, Jun; Huang, Weimin, E-mail: huangwm@jlu.edu.cn

    2015-10-01

    In this paper, a kind of didodecyldimethylammonium bromide (DDAB) layer membranes was supported on a glassy carbon electrode (GCE). We studied the ion channel behavior of the supported bilayer lipid membrane by scanning electrochemical microscopy (SCEM) in tris(2,2′-bipyridine) ruthenium(II) solution. Perchlorate anion was used as a presence of stimulus and ruthenium(II) complex cations as the probing ions for the measurement of SECM, the lipid membrane channel was opened and exhibited the behavior of distinct SECM positive feedback curve. The channel was in a closed state in the absence of perchlorate anions while reflected the behavior of SECM negative feedback curve. The rates of electron transfer reaction in the lipid membranes surface were detected and it was dependant on the potential of SECM. - Highlights: • The rates of electron transfer reaction in the lipid membranes surface were detected. • Dynamic investigations of ion-channel behavior of supported bilayer lipid membranes by scanning electrochemical microscopy • A novel way to explore the interaction between molecules and supported bilayer lipid membranes.

  19. Full-dimensional characterization of photoelectron spectra of HOCO− and DOCO− and tunneling facilitated decay of HOCO prepared by anion photodetachment

    International Nuclear Information System (INIS)

    Wang, Jun; Li, Jun; Guo, Hua; Ma, Jianyi

    2014-01-01

    The photodetachment of both the HOCO − and DOCO − anions is investigated using full-dimensional quantum wave packets on new ab initio based global potential energy surfaces for both the neutral and anionic species. The calculated electron affinities and neutral fundamental vibrational frequencies of both isotopomers are in good agreement with available experimental data. The measured photoelectron spectra are also accurately reproduced, further validating the accuracy of the potential energy surfaces. In addition, strong mode specificity is found in the lifetimes of the HOCO vibrational features and the tunneling facilitated predissociation rates to H + CO 2 are rationalized using the recently proposed sudden vector projection model

  20. Electron transfer from nucleobase electron adducts to 5-bromouracil. Is guanine an ultimate sink for the electron in irradiated DNA?

    International Nuclear Information System (INIS)

    Nese, C.; Yuan, Z.; Schuchmann, M.N.; Sonntag, C. von

    1992-01-01

    Electron transfer to 5-bromouracil (5-BrU) from nucleobase (N) electron adducts (and their protonated forms) has been studied by product analysis and pulse radiolysis. When an electron is transferred to 5-BrU, the ensuing 5-BrU radical anion rapidly loses a bromide ion; the uracilyl radical thus formed reacts with added t-butanol, yielding uracil. From the uracil yields measured as the function of [N]/[5-BrU] after γ-radiolysis of Ar-saturated solutions it is concluded that thymine and adenine electron adducts and their heteroatom-protonated forms transfer electrons quantitatively to 5-BrU. The data raise the question whether in DNA the guanine moiety may act as the ultimate sink of the electron in competition with other processes such as protonation at C(6) of the thymine electron adduct. (Author)

  1. Electron-electron collision effects on the bremsstrahlung emission in Lorentzian plasmas

    International Nuclear Information System (INIS)

    Jung, Young-Dae; Kato, Daiji

    2009-01-01

    Electron-electron collision effects on the electron-ion bremsstrahlung process are investigated in Lorentzian plasmas. The effective electron-ion interaction potential is obtained by including the far-field terms caused by electron-electron collisions with an effective Debye length in Lorentzian plasmas. The bremsstrahlung radiation cross section is obtained as a function of the electron energy, photon energy, collision frequency, spectral index and Debye length using the Born approximation for the initial and final states of the projectile electron. It is shown that the non-Maxwellian character suppresses the bremsstrahlung radiation cross section. It is also shown that the electron-electron collision effect enhances the bremsstrahlung emission spectrum. In addition, the bremsstrahlung radiation cross section decreases with an increase in the plasma temperature.

  2. Electron detachment of the hydrogen-bonded amino acid side-chain guanine complexes

    Science.gov (United States)

    Wang, Jing; Gu, Jiande; Leszczynski, Jerzy

    2007-07-01

    The photoelectron spectra of the hydrogen-bonded amino acid side-chain-guanine complexes has been studied at the partial third order (P3) self-energy approximation of the electron propagator theory. The correlation between the vertical electron detachment energy and the charge distributions on the guanine moiety reveals that the vertical electron detachment energy (VDE) increases as the positive charge distribution on the guanine increases. The low VDE values determined for the negatively charged complexes of the guanine-side-chain-group of Asp/Glu suggest that the influence of the H-bonded anionic groups on the VDE of guanine could be more important than that of the anionic backbone structure. The even lower vertical electron detachment energy for guanine is thus can be expected in the H-bonded protein-DNA systems.

  3. The triel bond: a potential force for tuning anion-π interactions

    Science.gov (United States)

    Esrafili, Mehdi D.; Mousavian, Parisasadat

    2018-02-01

    Using ab-initio calculations, the mutual influence between anion-π and B···N or B···C triel bond interactions is investigated in some model complexes. The properties of these complexes are studied by molecular electrostatic potential, noncovalent interaction index, quantum theory of atoms in molecules (QTAIM) and natural bond orbital (NBO) analyses. According to the results, the formation of B···N or B···C triel bond interactions in the multi-component systems makes a significant shortening of anion-π distance. Such remarkable variation in the anion-π distances has not been reported previously. The strengthening of the anion-π bonding in the multi-component systems depend significantly on the nature of the anion, and it becomes larger in the order Br- > Cl- > F-. The parameters derived from the QTAIM and NBO methodologies are used to study the mechanism of the cooperativity between the anion-π and triel bond interactions in the multi-component complexes.

  4. One electron reduction and absorption characteristics of Cresyl violet in micellar medium

    International Nuclear Information System (INIS)

    Gawandi, Vijay B.; Guha, S.N.; Hari Mohan

    2000-01-01

    Effect of surfactant micelles on absorption characteristics of Cresyl violet (CV) and on its redox reactions have been studied. Among the various surfactants investigated anionic surfactants particularly sodium lauryl sulfate (SLS) and sodium dodecyl benzene sulfonate (SDDBS) showed marked effect on these properties. Reactions of hydrated electron in these micellar media were studied using the technique of nanosecond pulse radiolysis. Results of other surfactants, viz.BSS, CTAB and TritonX-100 have also been presented. (author)

  5. Patchy proteins, anions and the Hofmeister series

    Energy Technology Data Exchange (ETDEWEB)

    Lund, Mikael; Jungwirth, Pavel [Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic, Flemingovo namesti 2, 16610 Prague 6 (Czech Republic); Center for Complex Molecular Systems and Biomolecules, Flemingovo namesti 2, 16610 Prague 6 (Czech Republic)], E-mail: mikael.lund@uochb.cas.cz

    2008-12-10

    We investigate specific anion binding to a range of patchy protein models and use our results to probe protein-protein interactions for aqueous lysozyme solutions. Our molecular simulation studies show that the ion-protein interaction mechanism and strength largely depend on the nature of the interfacial amino acid residues. Via direct ion pairing, small anions interact with charged side-chains while larger anions are attracted to non-polar residues due to several solvent assisted mechanisms. Incorporating ion and surface specificity into a mesoscopic model for protein-protein interactions we calculate the free energy of interaction between lysozyme molecules in aqueous solutions of sodium chloride and sodium iodide. In agreement with experiment, our finding is that 'salting out' follows the reverse Hofmeister series for pH below the iso-electric point and the direct series for pH above pI.

  6. Reducing nitrogen crossover in microbial reverse-electrodialysis cells by using adjacent anion exchange membranes and anion exchange resin

    KAUST Repository

    Wallack, Maxwell J.; Geise, Geoffrey M.; Hatzell, Marta C.; Hickner, Michael A.; Logan, Bruce E.

    2015-01-01

    Microbial reverse electrodialysis cells (MRECs) combine power generation from salinity gradient energy using reverse electrodialysis (RED), with power generation from organic matter using a microbial fuel cell. Waste heat can be used to distill ammonium bicarbonate into high (HC) and low salt concentration (LC) solutions for use in the RED stack, but nitrogen crossover into the anode chamber must be minimized to avoid ammonia loses, and foster a healthy microbial community. To reduce nitrogen crossover, an additional low concentration (LC) chamber was inserted before the anode using an additional anion exchange membrane (AEM) next to another AEM, and filled with different amounts of anion or cation ion exchange resins. Addition of the extra AEM increased the ohmic resistance of the test RED stack from 103 Ω cm2 (1 AEM) to 295 Ω cm2 (2 AEMs). However, the use of the anion exchange resin decreased the solution resistance of the LC chamber by 74% (637 Ω cm2, no resin; 166 Ω cm2 with resin). Nitrogen crossover into the anode chamber was reduced by up to 97% using 50% of the chamber filled with an anion exchange resin compared to the control (no additional chamber). The added resistance contributed by the use of the additional LC chamber could be compensated for by using additional LC and HC membrane pairs in the RED stack.

  7. One-electron reduction reactions with enzymes in solution

    International Nuclear Information System (INIS)

    Bisby, R.H.; Cundall, R.B.; Redpath, J.L.; Adams, G.E.

    1976-01-01

    At pH 8 and above, hydrated electrons react with ribonuclease lysozyme and α-chymotrypsin to form transient products whose spectra resemble, but are not identical to, those for the RSSR - radical anion already known for simple disulphides. Assuming a value for the extinction coefficient similar to that for RSSR - in simple disulphides, only a fraction of the hydrated electrons are shown to react with the disulphide bridges: the remainder react at other sites in the protein molecule, such as histidine, tyrosine and, in lysozyme, tryptophan residues, giving rise to comparatively weak optical absorptions between 300 and 400 nm. This has been substantiated by studying the reaction of e - sub(aq) with subtilisin Novo (an enzyme which does not contain disulphide bridges), with enzymes in which the sulphur bridges have been oxidised and with some amino acid derivatives. On lowering the pH of the solution the intensity of the RSSR - absorption diminishes as the protonated histidine residues become the favoured reaction sites. In acid solutions (pH 2 to 3) the transient optical absoptions observed are due to reactions of hydrogen atoms with the aromatic amino acids tyrosine, tryptophan and phenylalanine. The CO - 2 radical anion is only observed to transfer an electron to disulphide groups in ribonuclease, although the effect of repeated pulsing shows that some reaction must occur elsewhere in the protein molecule. In acid solutions, protonation of the electron adduct appears to produce the RSSRH. radical, whose spectrum has a maximum at 340 nm. (author)

  8. Anion induced conformational preference of Cα NN motif residues in functional proteins.

    Science.gov (United States)

    Patra, Piya; Ghosh, Mahua; Banerjee, Raja; Chakrabarti, Jaydeb

    2017-12-01

    Among different ligand binding motifs, anion binding C α NN motif consisting of peptide backbone atoms of three consecutive residues are observed to be important for recognition of free anions, like sulphate or biphosphate and participate in different key functions. Here we study the interaction of sulphate and biphosphate with C α NN motif present in different proteins. Instead of total protein, a peptide fragment has been studied keeping C α NN motif flanked in between other residues. We use classical force field based molecular dynamics simulations to understand the stability of this motif. Our data indicate fluctuations in conformational preferences of the motif residues in absence of the anion. The anion gives stability to one of these conformations. However, the anion induced conformational preferences are highly sequence dependent and specific to the type of anion. In particular, the polar residues are more favourable compared to the other residues for recognising the anion. © 2017 Wiley Periodicals, Inc.

  9. A colorimetric tetrathiafulvalene-calix 4 pyrrole anion sensor

    DEFF Research Database (Denmark)

    Nielsen, K. A.

    2012-01-01

    The interaction and colorimetric sensing properties of a tetrathiafulvalene substituted calix[4]pyrrole sensor with anions were investigated using H-1 NMR and absorption spectroscopic techniques. Visual color changes were observed upon addition of different anions (Cl-, Br-, CN-, and Ac......O-) to a solution of the sensor. (C) 2012 Elsevier Ltd. All rights reserved....

  10. Electron induced formation and stability of molecular and cluster ions in gas phase and superfluid helium nanodroplets

    International Nuclear Information System (INIS)

    Aleem, M. A.

    2010-01-01

    The present PhD thesis represents a broad range study of electron induced formation and stability of positive and negative ions in gas phase and superfluid helium nanodroplets. The molecules studied are of industrial, environmental, plasma and biological relevance. The knowledge obtained from the study provides new insight for the proper understanding and control on energetics and dynamics of the reactions involved in the formation and fragmentation processes of the studied molecules and clusters. The experiments are accomplished and investigated using mass spectrometric techniques for the formation of molecular and cluster ions using different mass spectrometers available in our laboratory. One part of the work is focused on electron-induced reactions of the molecules in gas phase. Especially focus is laid to electron attachment to the isomers of mononitrotolouene used as an additive to explosives. The fragile nature and high internal energy of these molecules has lead to extensive fragmentation following the ionisation process. Dissociative electron attachment to the three different isomers has shown different resonances and therefore this process can be utilized to explicitly distinguish these isomers. Anion efficiency curves of the isomers have been studied using effusive molecular beam source in combination with a hemispherical electron monochromator as well as a Nier-type ion source attached to a sector field mass spectrometer. The outcome of the experiment is a reliable and effective detection method highly desirable for environmental and security reasons. Secondly, dissociative electron ionization of acetylene and propene is studied and their data is directly related to the plasma modelling for plasma fusion and processing reactors. Temperature effects for dissociative electron attachment to halo-hydrocarbons are also measured using a trochoidal electron monochromator. The second part of the work is concerned with the investigation of electron

  11. Solid-state electric double layer capacitors fabricated with plastic crystal based flexible gel polymer electrolytes: Effective role of electrolyte anions

    International Nuclear Information System (INIS)

    Suleman, Mohd; Kumar, Yogesh; Hashmi, S.A.

    2015-01-01

    Flexible gel polymer electrolyte (GPE) thick films incorporated with solutions of lithium trifluoromethanesulfonate (Li-triflate or LiTf) and lithium bis trifluoromethane-sulfonimide (LiTFSI) in a plastic crystal succinonitrile (SN), entrapped in poly(vinylidine fluoride-co-hexafluoropropylene) (PVdF-HFP) have been prepared and characterized. The films have been used as electrolytes in the electrical double layer capacitors (EDLCs). Coconut-shell derived activated carbon with high specific surface area (∼2100 m 2 g −1 ) and mixed (micro- and meso-) porosity has been used as EDLC electrodes. The structural, thermal, and electrochemical characterization of the GPEs have been performed using scanning electron microscopy (SEM), X-ray diffraction (XRD), differential scanning calorimetry (DSC), impedance measurements and cyclic voltammetry. The high ionic conductivity (∼10 −3 S cm −1 at 25 °C), good electrochemical stability window (>4.0 V) and flexible nature of the free-standing films of GPEs show their competence in the fabrication of EDLCs. The EDLCs have been tested using electrochemical impedance spectroscopy, cyclic voltammetry, and charge–discharge studies. The EDLCs using LiTf based electrolyte have been found to give higher values of specific capacitance, specific energy, power density (240–280 F g −1 , ∼39 Wh kg −1 and ∼19 kW kg −1 , respectively) than the EDLC cell with LiTFSI based gel electrolyte. EDLCs have been found to show stable performance for ∼10 4 charge–discharge cycles. The comparative studies indicate the effective role of electrolyte anions on the capacitive performance of the solid-state EDLCs. - Graphical abstract: Display Omitted - Highlights: • Flexible EDLCs with succinonitrile based gel electrolyte membranes are reported. • Anionic size of salts in gel electrolytes plays important role on capacitive performance. • Li-triflate incorporated gel electrolyte shows better performance over LiTFSI-based gel.

  12. Solid-state electric double layer capacitors fabricated with plastic crystal based flexible gel polymer electrolytes: Effective role of electrolyte anions

    Energy Technology Data Exchange (ETDEWEB)

    Suleman, Mohd; Kumar, Yogesh; Hashmi, S.A., E-mail: sahashmi@physics.du.ac.in

    2015-08-01

    Flexible gel polymer electrolyte (GPE) thick films incorporated with solutions of lithium trifluoromethanesulfonate (Li-triflate or LiTf) and lithium bis trifluoromethane-sulfonimide (LiTFSI) in a plastic crystal succinonitrile (SN), entrapped in poly(vinylidine fluoride-co-hexafluoropropylene) (PVdF-HFP) have been prepared and characterized. The films have been used as electrolytes in the electrical double layer capacitors (EDLCs). Coconut-shell derived activated carbon with high specific surface area (∼2100 m{sup 2} g{sup −1}) and mixed (micro- and meso-) porosity has been used as EDLC electrodes. The structural, thermal, and electrochemical characterization of the GPEs have been performed using scanning electron microscopy (SEM), X-ray diffraction (XRD), differential scanning calorimetry (DSC), impedance measurements and cyclic voltammetry. The high ionic conductivity (∼10{sup −3} S cm{sup −1} at 25 °C), good electrochemical stability window (>4.0 V) and flexible nature of the free-standing films of GPEs show their competence in the fabrication of EDLCs. The EDLCs have been tested using electrochemical impedance spectroscopy, cyclic voltammetry, and charge–discharge studies. The EDLCs using LiTf based electrolyte have been found to give higher values of specific capacitance, specific energy, power density (240–280 F g{sup −1}, ∼39 Wh kg{sup −1} and ∼19 kW kg{sup −1}, respectively) than the EDLC cell with LiTFSI based gel electrolyte. EDLCs have been found to show stable performance for ∼10{sup 4} charge–discharge cycles. The comparative studies indicate the effective role of electrolyte anions on the capacitive performance of the solid-state EDLCs. - Graphical abstract: Display Omitted - Highlights: • Flexible EDLCs with succinonitrile based gel electrolyte membranes are reported. • Anionic size of salts in gel electrolytes plays important role on capacitive performance. • Li-triflate incorporated gel electrolyte shows better

  13. Superoxide anion production by human neutrophils activated by Trichomonas vaginalis.

    Science.gov (United States)

    Song, Hyun-Ouk; Ryu, Jae-Sook

    2013-08-01

    Neutrophils are the predominant inflammatory cells found in vaginal discharges of patients infected with Trichomonas vaginalis. In this study, we examined superoxide anion (O2 (.-)) production by neutrophils activated by T. vaginalis. Human neutrophils produced superoxide anions when stimulated with either a lysate of T. vaginalis, its membrane component (MC), or excretory-secretory product (ESP). To assess the role of trichomonad protease in production of superoxide anions by neutrophils, T. vaginalis lysate, ESP, and MC were each pretreated with a protease inhibitor cocktail before incubation with neutrophils. Superoxide anion production was significantly decreased by this treatment. Trichomonad growth was inhibited by preincubation with supernatants of neutrophils incubated for 3 hr with T. vaginalis lysate. Furthermore, myeloperoxidase (MPO) production by neutrophils was stimulated by live trichomonads. These results indicate that the production of superoxide anions and MPO by neutrophils stimulated with T. vaginalis may be a part of defense mechanisms of neutrophils in trichomoniasis.

  14. The Serum Anion Gap in the Evaluation of Acid-Base Disorders: What Are Its Limitations and Can Its Effectiveness Be Improved?

    OpenAIRE

    Kraut, Jeffrey A.; Nagami, Glenn T.

    2013-01-01

    The serum anion gap has been utilized to identify errors in the measurement of electrolytes, to detect paraproteins, and, most relevant to the nephrologist, to evaluate patients with suspected acid-base disorders. In regard to the latter purpose, traditionally an increased anion gap is identified when it exceeds the upper limit of normal for a particular clinical laboratory measurement. However, because there is a wide range of normal values (often 8–10 mEq/L), an increase in anion concentrat...

  15. Sodium citrate-assisted anion exchange strategy for construction of Bi2O2CO3/BiOI photocatalysts

    International Nuclear Information System (INIS)

    Song, Peng-Yuan; Xu, Ming; Zhang, Wei-De

    2015-01-01

    Highlights: • Heterostructured Bi 2 O 2 CO 3 /BiOI microspheres were prepared via anion exchange. • Sodium citrate-assisted anion exchange for construction of composite photocatalysts. • Bi 2 O 2 CO 3 /BiOI composites show high visible light photocatalytic activity. - Abstract: Bi 2 O 2 CO 3 /BiOI heterojuncted photocatalysts were constructed through a facile partial anion exchange strategy starting from BiOI microspheres and urea with the assistance of sodium citrate. The content of Bi 2 O 2 CO 3 in the catalysts was regulated by modulating the amount of urea as a precursor, which was decomposed to generate CO 3 2− in the hydrothermal process. Citrate anion plays a key role in controlling the morphology and composition of the products. The Bi 2 O 2 CO 3 /BiOI catalysts display much higher photocatalytic activity than pure BiOI and Bi 2 O 2 CO 3 towards the degradation of rhodamine B (RhB) and bisphenol A (BPA). The enhancement of photocatalytic activity of the heterojuncted catalysts is attributed to the formation of p–n junction between p-BiOI and n-Bi 2 O 2 CO 3 , which is favorable for retarding the recombination of photoinduced electron-hole pairs. Moreover, the holes are demonstrated to be the main active species for the degradation of RhB and BPA

  16. Cellulose Anionic Hydrogels Based on Cellulose Nanofibers As Natural Stimulants for Seed Germination and Seedling Growth.

    Science.gov (United States)

    Zhang, Hao; Yang, Minmin; Luan, Qian; Tang, Hu; Huang, Fenghong; Xiang, Xia; Yang, Chen; Bao, Yuping

    2017-05-17

    Cellulose anionic hydrogels were successfully prepared by dissolving TEMPO-oxidized cellulose nanofibers in NaOH/urea aqueous solution and being cross-linked with epichlorohydrin. The hydrogels exhibited microporous structure and high hydrophilicity, which contribute to the excellent water absorption property. The growth indexes, including the germination rate, root length, shoot length, fresh weight, and dry weight of the seedlings, were investigated. The results showed that cellulose anionic hydrogels with suitable carboxylate contents as plant growth regulators could be beneficial for seed germination and growth. Moreover, they presented preferable antifungal activity during the breeding and growth of the sesame seed breeding. Thus, the cellulose anionic hydrogels with suitable carboxylate contents could be applied as soilless culture mediums for plant growth. This research provided a simple and effective method for the fabrication of cellulose anionic hydrogel and evaluated its application in agriculture.

  17. The impact of alkali metal halide electron donor complexes in the photocatalytic degradation of pentachlorophenol

    Energy Technology Data Exchange (ETDEWEB)

    Khuzwayo, Z., E-mail: zack.khuzwayo@up.ac.za; Chirwa, E.M.N

    2017-01-05

    Highlights: • Facilitation of photocatalysis using simple metal-halides as VB hole scavengers. • Recombination prevention by coupled valence and conduction band approaches. • Determination of anions critical levels beyond which process retardation occurs. • Determination of the photocatalytic process rate of reaction kinetics. - Abstract: The performance of photocatalytic oxidation of chemical pollutants is subjected to the presence of anion complexes in natural waters. This study investigated the influence of alkali metal (Na{sup +} (sodium), K{sup +} (potassium)) halides (Cl{sup −} (chloride), Br{sup −} (bromide), F{sup −} (fluoride)) as inorganic ion sources in the photocatalytic degradation of pentachlorophenol (PCP) in batch systems. It was found that the exclusive presence of halides in the absence of an electron acceptor adequately facilitated the photocatalyst process below critical levels of anion populations, where beyond the critical point the process was significantly hindered. Below the determined critical point, the performance in some cases near matches that of the facilitation of the photocatalytic process by exclusive oxygen, acting as an electron scavenger. The coupling of halide ions and oxygenation presented significantly improved photo-oxidation of PCP, this was confirmed by the inclusion of formic acid as a comparative electron donor. The Langmuir-Hinshelwood kinetic expression was used to calculate the performance rate kinetics. The probable impact of the halide anions was discussed with regards to the process of electron hole pair recombination prevention.

  18. Photoinduced electron transfer to fullerene C70 (An in situ EPR study)

    International Nuclear Information System (INIS)

    Brezova, V.; Dvoranova, D.; Kostova, B.; Stasko, A.

    1999-01-01

    The photoexcitation of fullerene C 70 by monochromatic light (λ = 546 nm) in the presence of electron donating substrate 3,3',5,5'-tetramethyl-benzidine (TMB) resulted in the charge-transfer, quenching the fullerene triplet state and forming corresponding C 70 anion-radicals. Analogously to the photo-reduction of C 60 , two EPR signal were observed upon in situ irradiation in the cavity of EPR spectrometer. EPR singlet A characterized by g-value, g A = 2.0009 and peak-to-peak line-width, pp A = 0.013 mT was assigned to the C 70 mono-anion. Signal B (g B = 2.0011; pp B = 0.011 mT) was tentatively attributed to the C 70 di-anion or to the associated forms of mono-anions. The stabilization of photo-generated anion-radicals significantly depends on solvent polarity. (authors)

  19. Comparing and Optimizing Nitrate Adsorption from Aqueous Solution Using Fe/Pt Bimetallic Nanoparticles and Anion Exchange Resins

    International Nuclear Information System (INIS)

    Daud, M.; Khan, Z.; Ashgar, A.; Danish, M. I.; Qazi, I. A.

    2015-01-01

    This research work was carried out for the removal of nitrate from raw water for a drinking water supply. Nitrate is a widespread ground water contaminant. Methodology employed in this study included adsorption on metal based nanoparticles and ion exchange using anionic resins. Fe/Pt bimetallic nanoparticles were prepared in the laboratory, by the reduction of their respective salts using sodium borohydride. Scanning electron microscope, X-ray diffraction, energy dispersive spectrometry, and X-ray florescence techniques were utilized for characterization of bimetallic Fe/Pt nanoparticles. Optimum dose, ph, temperature, and contact time were determined for removal through batch tests, both for metal based nanoparticles and anionic exchange resin. Adsorption data fitted well the Langmuir isotherm and conformed to the pseudo first-order kinetic model. Results indicated 97% reduction in nitrate by 0.25 mg/L of Fe/Pt nanoparticles at ph 7 and 83% reduction in nitrate was observed using 0.50 mg/L anionic exchange resins at ph 4 and contact time of one hour. Overall, Fe/Pt bimetallic nanoparticles demonstrated greater removal efficiency due to the small particle size, extremely large surface area (627 m 2 /g), and high adsorption capacity.

  20. High Vacuum Techniques for Anionic Polymerization

    KAUST Repository

    Ratkanthwar, Kedar

    2015-09-01

    Anionic polymerization high vacuum techniques (HVTs) are the most suitable for the preparation of polymer samples with well-defined complex macromolecular architectures. Though HVTs require glassblowing skill for designing and making polymerization reactor, it is the best way to avoid any termination of living polymers during the number of steps for the synthesis of polymers with complex structure. In this chapter, we describe the different polymerization reactors and HVTs for the purification of monomers, solvents, and other reagents for anionic polymerization as well as few model reactions for the synthesis of polymers with simple to complex structure.

  1. Electron Effective-Attenuation-Length Database

    Science.gov (United States)

    SRD 82 NIST Electron Effective-Attenuation-Length Database (PC database, no charge)   This database provides values of electron effective attenuation lengths (EALs) in solid elements and compounds at selected electron energies between 50 eV and 2,000 eV. The database was designed mainly to provide EALs (to account for effects of elastic-eletron scattering) for applications in surface analysis by Auger-electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS).

  2. Tetrel Bonding as a Vehicle for Strong and Selective Anion Binding

    Directory of Open Access Journals (Sweden)

    Steve Scheiner

    2018-05-01

    Full Text Available Tetrel atoms T (T = Si, Ge, Sn, and Pb can engage in very strong noncovalent interactions with nucleophiles, which are commonly referred to as tetrel bonds. The ability of such bonds to bind various anions is assessed with a goal of designing an optimal receptor. The Sn atom seems to form the strongest bonds within the tetrel family. It is most effective in the context of a -SnF3 group and a further enhancement is observed when a positive charge is placed on the receptor. Connection of the -SnF3 group to either an imidazolium or triazolium provides a strong halide receptor, which can be improved if its point of attachment is changed from the C to an N atom of either ring. Aromaticity of the ring offers no advantage nor is a cyclic system superior to a simple alkyl amine of any chain length. Placing a pair of -SnF3 groups on a single molecule to form a bipodal dicationic receptor with two tetrel bonds enhances the binding, but falls short of a simple doubling. These two tetrel groups can be placed on opposite ends of an alkyl diamine chain of any length although SnF3+NH2(CH2nNH2SnF3+ with n between 2 and 4 seems to offer the strongest halide binding. Of the various anions tested, OH− binds most strongly: OH− > F− > Cl− > Br− > I−. The binding energy of the larger NO3− and HCO3− anions is more dependent upon the charge of the receptor. This pattern translates into very strong selectivity of binding one anion over another. The tetrel-bonding receptors bind far more strongly to each anion than an equivalent number of K+ counterions, which leads to equilibrium ratios in favor of the former of many orders of magnitude.

  3. Facts and views on the role of anionic impurities, crack tip chemistry and oxide films in environmentally assisted cracking

    International Nuclear Information System (INIS)

    Aaltonen, P.; Bojinov, M.; Helin, M.

    2002-01-01

    The aim of this literature study has been to evaluate the level of understanding of the role of anionic impurities in environmentally assisted cracking (EAC) of iron- and nickel-based alloys in the coolant conditions of a boiling water reactor (BWR) - type nuclear power plant, mainly under normal water chemistry (NWC). The study has been motivated by a need to find the most relevant experimental approaches that can be applied when looking for correlations between crack growth rate and measurable electrochemical and chemical parameters. Special crack tip chemistry conditions are established, when trace amounts are present in the BWR coolant and become enriched within a crack. Anions may influence both the conductivity and the pH of the coolant within the crack. In addition, they may influence the composition, structure and properties of the oxide films formed on crack walls either directly via adsorption or incorporation or indirectly via the effect of changes in pH within the crack. Based on the proposed mechanisms for EAC, oxide films formed on crack wall surfaces are likely to play a key role in determing the crack growth rate of structural materials. The prediction of the influence of anionic impurities is thus likely to be facilitated by means of understanding their effect on the films on crack walls. One of the most promising approaches to experimentally clarify this influence is based on investigating the electrochemical behaviour of oxide films Fe- and Ni-based materials in high-temperature conditions simulating the special chemistry within a stress corrosion crack. Results from such studies should be compared and combined with ex situ analytical results obtained using modern electron microscopic techniques. In addition to crack growth, currently available electro-chemical techniques should also be applied to find out whether crack initiation can be explained and modelled on the basis of the electrochemical behaviour of oxide films. (orig.)

  4. Photoelectron spectroscopy of liquid water and aqueous solution: Electron effective attenuation lengths and emission-angle anisotropy

    Energy Technology Data Exchange (ETDEWEB)

    Ottosson, Niklas [Department of Physics, Uppsala University, SE-75121 Uppsala (Sweden); Faubel, Manfred [Max-Planck-Institut fuer Dynamik und Selbstorganisation, Bunsenstrasse 10, D-37073 Goettingen (Germany); Bradforth, Stephen E. [Department of Chemistry, University of Southern California, Los Angeles, CA 90089 (United States); Jungwirth, Pavel [Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic, and Center for Biomolecules and Complex Molecular Systems, Flemingovo nam. 2, 16610 Prague 6 (Czech Republic); Winter, Bernd, E-mail: winter@bessy.d [Helmholtz-Zentrum Berlin fuer Materialien und Energie, and BESSY, Albert-Einstein-Strasse 15, D-12489 Berlin (Germany); Max-Born-Institut, Max-Born-Strasse 2A, D-12489 Berlin (Germany)

    2010-03-15

    Photoelectron (PE) spectroscopy measurements from liquid water and from a 4 m NaI aqueous solution are performed using a liquid microjet in combination with soft X-ray synchrotron radiation. From the oxygen 1s PE signal intensity from liquid water, measured as a function of photon energy (up to 1500 eV), we quantitatively determine relative electron inelastic effective attenuation lengths (EAL) for (photo)electron kinetic energies in the 70-900 eV range. In order to determine the absolute electron escape depths a calibration point is needed, which is not directly accessible by experiment. This information can instead be indirectly derived by comparing PE experiments and molecular dynamics (MD) simulations of an aqueous solution interface where density profiles of water, anions, and cations are distinctively different. We have chosen sodium iodide in water because iodide has a considerable propensity for the solution surface, whereas the sodium cation is repelled from the surface. By measuring the intensities of photoelectrons emitted from different orbitals of different symmetries from each aqueous ion we also evaluate whether gas-phase ionization cross sections and asymmetry parameters can describe the photoemission from ions at and near the aqueous solution/vapor interface. We show that gas-phase data reproduce surprisingly well the experimental observations for hydrated ions as long as the photon energy is sufficiently far above the ionization threshold. Electrons detected at the higher photon energies originate predominantly from deeper layers, suggesting that bulk-solution electron elastic scattering is relatively weak.

  5. Derivatives of Dodecahalo-Closo-Dodecaborate Di-Anion

    OpenAIRE

    Avelar, Amy Cindy

    2009-01-01

    ABSTRACT OF THE DISSERTATIONDerivatives of the Dodecahalo-Closo-Dodecaborate Di-AnionbyAmy AvelarDoctor of Philosophy, Graduate Program in ChemistryUniversity of California, Riverside, December 2009Dr. Christopher A. Reed, ChairpersonThe di-anion, dodecahalo-closo-dodecaborate, B12X122-, where the X = Cl or Br, has been determined to be a useful weakly coordinating anion, WCA. Despite the di- negative charge, several elusive and reactive cationic species were stabilized with B12X122- as the c...

  6. A combined photoelectron spectroscopy and relativistic ab initio studies of the electronic structures of UFO and UFO-

    Science.gov (United States)

    Roy, Soumendra K.; Jian, Tian; Lopez, Gary V.; Li, Wei-Li; Su, Jing; Bross, David H.; Peterson, Kirk A.; Wang, Lai-Sheng; Li, Jun

    2016-02-01

    The observation of the gaseous UFO- anion is reported, which is investigated using photoelectron spectroscopy and relativisitic ab initio calculations. Two strong photoelectron bands are observed at low binding energies due to electron detachment from the U-7sσ orbital. Numerous weak detachment bands are also observed due to the strongly correlated U-5f electrons. The electron affinity of UFO is measured to be 1.27(3) eV. High-level relativistic quantum chemical calculations have been carried out on the ground state and many low-lying excited states of UFO to help interpret the photoelectron spectra and understand the electronic structure of UFO. The ground state of UFO- is linear with an O-U-F structure and a 3H4 spectral term derived from a U 7sσ25fφ15fδ1 electron configuration, whereas the ground state of neutral UFO has a 4H7/2 spectral term with a U 7sσ15fφ15fδ1 electron configuration. Strong electron correlation effects are found in both the anionic and neutral electronic configurations. In the UFO neutral, a high density of electronic states with strong configuration mixing is observed in most of the scalar relativistic and spin-orbit coupled states. The strong electron correlation, state mixing, and spin-orbit coupling of the electronic states make the excited states of UFO very challenging for accurate quantum chemical calculations.

  7. A combined photoelectron spectroscopy and relativistic ab initio studies of the electronic structures of UFO and UFO(-).

    Science.gov (United States)

    Roy, Soumendra K; Jian, Tian; Lopez, Gary V; Li, Wei-Li; Su, Jing; Bross, David H; Peterson, Kirk A; Wang, Lai-Sheng; Li, Jun

    2016-02-28

    The observation of the gaseous UFO(-) anion is reported, which is investigated using photoelectron spectroscopy and relativisitic ab initio calculations. Two strong photoelectron bands are observed at low binding energies due to electron detachment from the U-7sσ orbital. Numerous weak detachment bands are also observed due to the strongly correlated U-5f electrons. The electron affinity of UFO is measured to be 1.27(3) eV. High-level relativistic quantum chemical calculations have been carried out on the ground state and many low-lying excited states of UFO to help interpret the photoelectron spectra and understand the electronic structure of UFO. The ground state of UFO(-) is linear with an O-U-F structure and a (3)H4 spectral term derived from a U 7sσ(2)5fφ(1)5fδ(1) electron configuration, whereas the ground state of neutral UFO has a (4)H(7/2) spectral term with a U 7sσ(1)5fφ(1)5fδ(1) electron configuration. Strong electron correlation effects are found in both the anionic and neutral electronic configurations. In the UFO neutral, a high density of electronic states with strong configuration mixing is observed in most of the scalar relativistic and spin-orbit coupled states. The strong electron correlation, state mixing, and spin-orbit coupling of the electronic states make the excited states of UFO very challenging for accurate quantum chemical calculations.

  8. Determination of Anionic Detergent Concentration of Karasu Stream in Sinop (Turkey

    Directory of Open Access Journals (Sweden)

    Ayşe Gündoğdu

    2018-02-01

    Full Text Available The study was achieved between May 2014 and April 2015 at the Karasu Creek located in the province of Sinop. It was conducted to determine anionic detergent pollution and some physicochemical properties (pH, temperature, conductivity, salinity, dissolved oxygen, total hardness, chemical oxygen demand, phosphate PO4-3, total nitrogen. The anionic detergent concentration of the stations was determined on a monthly basis. Seasonally averaged values of the anionic detergent was measured as the highest value in the autumn season. The lowest values of anionic detergent were found in stations in winter and spring. The increase in the concentration of anionic detergent is caused by population growth in residential areas, increased agricultural activities and rains, and that chemicals move to riverbed from terrestrial areas with rain water.

  9. Evidence for anionic redox activity in a tridimensional-ordered Li-rich positive electrode β-Li2IrO3.

    Science.gov (United States)

    Pearce, Paul E; Perez, Arnaud J; Rousse, Gwenaelle; Saubanère, Mathieu; Batuk, Dmitry; Foix, Dominique; McCalla, Eric; Abakumov, Artem M; Van Tendeloo, Gustaaf; Doublet, Marie-Liesse; Tarascon, Jean-Marie

    2017-05-01

    Lithium-ion battery cathode materials have relied on cationic redox reactions until the recent discovery of anionic redox activity in Li-rich layered compounds which enables capacities as high as 300 mAh g -1 . In the quest for new high-capacity electrodes with anionic redox, a still unanswered question was remaining regarding the importance of the structural dimensionality. The present manuscript provides an answer. We herein report on a β-Li 2 IrO 3 phase which, in spite of having the Ir arranged in a tridimensional (3D) framework instead of the typical two-dimensional (2D) layers seen in other Li-rich oxides, can reversibly exchange 2.5 e - per Ir, the highest value ever reported for any insertion reaction involving d-metals. We show that such a large activity results from joint reversible cationic (M n+ ) and anionic (O 2 ) n- redox processes, the latter being visualized via complementary transmission electron microscopy and neutron diffraction experiments, and confirmed by density functional theory calculations. Moreover, β-Li 2 IrO 3 presents a good cycling behaviour while showing neither cationic migration nor shearing of atomic layers as seen in 2D-layered Li-rich materials. Remarkably, the anionic redox process occurs jointly with the oxidation of Ir 4+ at potentials as low as 3.4 V versus Li + /Li 0 , as equivalently observed in the layered α-Li 2 IrO 3 polymorph. Theoretical calculations elucidate the electrochemical similarities and differences of the 3D versus 2D polymorphs in terms of structural, electronic and mechanical descriptors. Our findings free the structural dimensionality constraint and broaden the possibilities in designing high-energy-density electrodes for the next generation of Li-ion batteries.

  10. Detection of cyanide anion by zinc porphyrin-spiropyran dyad

    Energy Technology Data Exchange (ETDEWEB)

    Kho, Young Min; Hur, Dae Young; Shin, Eun Ju [Dept. of Chemistry, Sunchon National University, Suncheon (Korea, Republic of)

    2016-10-15

    Versatile methods of the sensitive and selective detection for cyanide anion to monitor toxic cyanide have been developed. These include colorimetric, colorimetric, chromatographic, and electrochemical analyses. Among those methods for cyanide detection, optical methods based on absorption and fluorescence spectroscopy are relatively simple, inexpensive, and sensitive. A number of organic sensors for cyanide anion have been designed and synthesized. Absorption and/or fluorescence spectra of these sensors are changed by forming coordination complex or bonding covalently with cyanide. Compared with other anions, cyanide anion has some characteristic properties, such as its strong nucleophilicity and high binding affinity toward metal ions, and is superior and useful for the development of the sensors. Both covalent bond-based sensors and coordination complex-based sensors have been developed for cyanide detection. The results indicate that ZnP-SP plays a role as a CN{sup -} selective, colorimetric sensor either without or with UV irradiation.

  11. Detection of cyanide anion by zinc porphyrin-spiropyran dyad

    International Nuclear Information System (INIS)

    Kho, Young Min; Hur, Dae Young; Shin, Eun Ju

    2016-01-01

    Versatile methods of the sensitive and selective detection for cyanide anion to monitor toxic cyanide have been developed. These include colorimetric, colorimetric, chromatographic, and electrochemical analyses. Among those methods for cyanide detection, optical methods based on absorption and fluorescence spectroscopy are relatively simple, inexpensive, and sensitive. A number of organic sensors for cyanide anion have been designed and synthesized. Absorption and/or fluorescence spectra of these sensors are changed by forming coordination complex or bonding covalently with cyanide. Compared with other anions, cyanide anion has some characteristic properties, such as its strong nucleophilicity and high binding affinity toward metal ions, and is superior and useful for the development of the sensors. Both covalent bond-based sensors and coordination complex-based sensors have been developed for cyanide detection. The results indicate that ZnP-SP plays a role as a CN"- selective, colorimetric sensor either without or with UV irradiation

  12. Characterization and reactivity of the weakly bound complexes of the [H, N, S]{sup −} anionic system with astrophysical and biological implications

    Energy Technology Data Exchange (ETDEWEB)

    Trabelsi, T.; Ajili, Y.; Ben Yaghlane, S.; Jaidane, N.-E. [Laboratoire de Spectroscopie Atomique, Moléculaire et Applications–LSAMA, Université de Tunis El Manar, Tunis (Tunisia); Mogren Al-Mogren, M. [Chemistry Department, Faculty of Science, King Saud University, P.O. Box 2455, Riyadh 11451 (Saudi Arabia); Francisco, J. S. [Department of Chemistry and Department of Earth and Atmospheric Sciences, Purdue University, West Lafayette, Indiana 47906 (United States); Hochlaf, M., E-mail: hochlaf@univ-mlv.fr [Laboratoire Modélisation et Simulation Multi Echelle, Université Paris-Est, MSME UMR 8208 CNRS, 5 Blvd. Descartes, 77454 Marne-la-Vallée (France)

    2015-07-21

    We investigate the lowest electronic states of doublet and quartet spin multiplicity states of HNS{sup −} and HSN{sup −} together with their parent neutral triatomic molecules. Computations were performed using highly accurate ab initio methods with a large basis set. One-dimensional cuts of the full-dimensional potential energy surfaces (PESs) along the interatomic distances and bending angle are presented for each isomer. Results show that the ground anionic states are stable with respect to the electron detachment process and that the long range parts of the PESs correlating to the SH{sup −} + N, SN{sup −} + H, SN + H{sup −}, NH + S{sup −}, and NH{sup −} + S are bound. In addition, we predict the existence of long-lived weakly bound anionic complexes that can be formed after cold collisions between SN{sup −} and H or SH{sup −} and N. The implications for the reactivity of these species are discussed; specifically, it is shown that the reactions involving SH{sup −}, SN{sup −}, and NH{sup −} lead either to the formation of HNS{sup −} or HSN{sup −} in their electronic ground states or to autodetachment processes. Thus, providing an explanation for why the anions, SH{sup −}, SN{sup −}, and NH{sup −}, have limiting detectability in astrophysical media despite the observation of their corresponding neutral species. In a biological context, we suggest that HSN{sup −} and HNS{sup −} should be incorporated into H{sub 2}S-assisted heme-catalyzed reduction mechanism of nitrites in vivo.

  13. Quantum chemical study of the interaction of elemental Hg with small neutral, anionic and cationic Aun (n = 1–6) clusters

    International Nuclear Information System (INIS)

    Siddiqui, Shamoon Ahmad; Bouarissa, Nadir; Rasheed, Tabish; Al-Assiri, M.S.

    2013-01-01

    Graphical abstract: Binding energies as a function of cluster size for Au n Hg, Au n Hg + and Au n Hg − complexes. Highlights: ► Hg adsorption of neutral and charged Au n (n = 1–6) clusters has been discussed. ► Size and charged state of cluster significantly affect the Hg adsorption. ► Transfer of electron mainly found from s orbital of Hg to s orbital of Au. - Abstract: Adsorption of elemental mercury (Hg) on small neutral, cationic and anionic gold clusters (Au n , n = 1–6) has been studied by using the density functional theory (DFT). Results of this investigation show that frontier molecular orbital theory is a useful tool to predict the selectivity of Hg adsorption. It is found that adsorption of Hg on neutral, cationic and anionic Au n (n = 1–6) clusters are thermodynamically favorable. The binding energies of Hg on the cationic Au n clusters are greater than those on the neutral and anionic clusters. Natural bond orbital (NBO) analysis indicates that the flow of electrons in the neutral and charged clusters is mainly due to the s orbitals of Hg and Au. Results of NBO analysis also indicate that the binding energy of Hg with Au n clusters is directly proportional to the charge transfer, i.e. greater is the charge transfer, higher is the binding energy

  14. Effect of Substituents on the Electronic Structure and Degradation Process in Carbazole Derivatives for Blue OLED Host Materials

    KAUST Repository

    Hong, Minki

    2016-07-25

    We investigate the dissociation mechanism of the C-N bond between carbazole and dibenzothiophene in carbazole-dibenzothiophene (Cz-DBT) positional isomers, selected as representative systems for blue host materials in organic light-emitting diodes (OLEDs). The C-N bond dissociation energies, calculated at the density functional theory level, are found to depend strongly on the charge states of the parental molecules. In particular, the anionic C-N bond dissociations resulting in a carbazole anion can have low dissociation energies (∼1.6 eV) with respect to blue emission energy. These low values are attributed to the large electron affinity of the carbazole radical, a feature that importantly can be modulated via substitution. Substitution also impacts the energies of the first excited electronic states of the Cz-DBT molecules since these states have an intramolecular charge-transfer nature due to the spatially localized character of the frontier molecular orbitals within the carbazole moiety (for the HOMO) and the dibenzothiophene moiety (for the LUMO). The implications of these results must be considered when designing blue OLED hosts since these materials must combine chemical stability and high triplet energy. © 2016 American Chemical Society.

  15. Identification of inorganic anions by gas chromatography/mass spectrometry.

    Science.gov (United States)

    Sakayanagi, Masataka; Yamada, Yaeko; Sakabe, Chikako; Watanabe, Kunio; Harigaya, Yoshihiro

    2006-03-10

    Inorganic anions were identified by using gas chromatography/mass spectrometry (GC/MS). Derivatization of the anions was achieved with pentafluorobenzyl p-toluenesulphonate (PFB-Tos) as the reaction reagent and a crown ether as a phase transfer catalyst. When PFB-Br was used as the reaction reagent, the retention time of it was close to those of the derivatized inorganic anions and interfered with the analysis. In contrast, the retention time of PFB-Tos differed greatly from the PFB derivatives of the inorganic anions and the compounds of interest could be detected without interference. Although the PFB derivatives of SO4, S2O3, CO3, ClO4, and ClO3 could not be detected, the derivatives of F, Cl, Br, I, CN, OCN, SCN, N3, NO3, and NO2 were detected using PFB-Tos as the derivatizing reagent. The inorganic anions were detectable within 30 ng approximately, which is of sufficient sensitivity for use in forensic chemistry. Accurate mass number was measured for each PFB derivative by high-resolution mass spectrometry (HRMS) within a measurement error of 2 millimass units (mmu), which allowed determination of the compositional formula from the mass number. In addition, actual analysis was performed successively by our method using trial samples of matrix.

  16. Chloride Ion Adsorption Capacity of Anion Exchange Resin in Cement Mortar

    Directory of Open Access Journals (Sweden)

    Yunsu Lee

    2018-04-01

    Full Text Available This paper presents the effect of anion exchange resin (AER on the adsorption of chloride ions in cement mortar. The kinetic and equilibrium behaviors of AER were investigated in distilled water and Ca(OH2 saturated solutions, and then the adsorption of chloride ions by the AER in the mortar specimen was determined. The AER was used as a partial replacement for sand in the mortar specimen. The mortar specimen was coated with epoxy, except for an exposed surface, and then immersed in a NaCl solution for 140 days. The chloride content in the mortar specimen was characterized by energy dispersive X-ray fluorescence analysis and electron probe microanalysis. The results showed that the AER could adsorb the chloride ions from the solution rapidly but had a relatively low performance when the pH of its surrounding environment increased. When the AER was mixed in the cement mortar, its chloride content was higher than that of the cement matrix around it, which confirms the chloride ion adsorption capacity of the AER.

  17. Probing the reactivation process of sarin-inhibited acetylcholinesterase with α-nucleophiles: hydroxylamine anion is predicted to be a better antidote with DFT calculations.

    Science.gov (United States)

    Khan, Md Abdul Shafeeuulla; Lo, Rabindranath; Bandyopadhyay, Tusar; Ganguly, Bishwajit

    2011-08-01

    Inactivation of acetylcholinesterase (AChE) due to inhibition by organophosphorus (OP) compounds is a major threat to human since AChE is a key enzyme in neurotransmission process. Oximes are used as potential reactivators of OP-inhibited AChE due to their α-effect nucleophilic reactivity. In search of more effective reactivating agents, model studies have shown that α-effect is not so important for dephosphylation reactions. We report the importance of α-effect of nucleophilic reactivity towards the reactivation of OP-inhibited AChE with hydroxylamine anion. We have demonstrated with DFT [B3LYP/6-311G(d,p)] calculations that the reactivation process of sarin-serine adduct 2 with hydroxylamine anion is more efficient than the other nucleophiles reported. The superiority of hydroxylamine anion to reactivate the sarin-inhibited AChE with sarin-serine adducts 3 and 4 compared to formoximate anion was observed in the presence and absence of hydrogen bonding interactions of Gly121 and Gly122. The calculated results show that the rates of reactivation process of adduct 4 with hydroxylamine anion are 261 and 223 times faster than the formoximate anion in the absence and presence of such hydrogen bonding interactions. The DFT calculated results shed light on the importance of the adjacent carbonyl group of Glu202 for the reactivation of sarin-serine adduct, in particular with formoximate anion. The reverse reactivation reaction between hydroxylamine anion and sarin-serine adduct was found to be higher in energy compared to the other nucleophiles, which suggests that this α-nucleophile can be a good antidote agent for the reactivation process. Copyright © 2011 Elsevier Inc. All rights reserved.

  18. Intermolecular effects on the radiogenic formation of electron-capture phosphorus-centered radicals. A single-crystal ESR study of diastereoisomeric precursors

    Energy Technology Data Exchange (ETDEWEB)

    Aagaard, O.M.; Janssen, R.A.J.; de Waal, B.F.M.; Buck, H.M. (Eindhoven Univ. of Technology (Netherlands))

    1990-01-31

    ESR experiments on X-irradiated single crystals of the 2R,4S,5R and 2S,4S,5R diastereoisomers of 2-chloro-3,4-dimethyl-5-phenyl-1,3,2-oxazaphospholidine 2-sulfide reveal that the yield of radiogenic electron-capture reactions in the solid state strongly depends on intermolecular interactions in the crystal. In the present case a high yield of P-Cl three-electron-bond phosphoranyl radical anions is found in crystals of the 2R,4S,5R isomer, whereas no radical formation can be detected for the 2S,4S,5R isomer. An analysis of nonbonded interactions with neighboring molecules reveals that the geometry relaxation necessary for the radical stabilization is easily accommodated in crystals of the 2R,4S,SR isomer but not in the 2S,4S,5R isomer, explaining the observed difference in electron-capture efficiency. Experiments on radical formation in a MeTHF host matrix give further insight into the importance of the environment on radiogenic radical formation. The possible concurrent effect of the matrix on the electronic configuration and spin density distribution of the resulting phosphoranyl radical is discussed.

  19. Intermolecular effects on the radiogenic formation of electron-capture phosphorus-centered radicals. A single-crystal ESR study of diastereoisomeric precursors

    International Nuclear Information System (INIS)

    Aagaard, O.M.; Janssen, R.A.J.; de Waal, B.F.M.; Buck, H.M.

    1990-01-01

    ESR experiments on X-irradiated single crystals of the 2R,4S,5R and 2S,4S,5R diastereoisomers of 2-chloro-3,4-dimethyl-5-phenyl-1,3,2-oxazaphospholidine 2-sulfide reveal that the yield of radiogenic electron-capture reactions in the solid state strongly depends on intermolecular interactions in the crystal. In the present case a high yield of P-Cl three-electron-bond phosphoranyl radical anions is found in crystals of the 2R,4S,5R isomer, whereas no radical formation can be detected for the 2S,4S,5R isomer. An analysis of nonbonded interactions with neighboring molecules reveals that the geometry relaxation necessary for the radical stabilization is easily accommodated in crystals of the 2R,4S,SR isomer but not in the 2S,4S,5R isomer, explaining the observed difference in electron-capture efficiency. Experiments on radical formation in a MeTHF host matrix give further insight into the importance of the environment on radiogenic radical formation. The possible concurrent effect of the matrix on the electronic configuration and spin density distribution of the resulting phosphoranyl radical is discussed

  20. Photophysical Properties of SrTaO2N Thin Films and Influence of Anion Ordering: A Joint Theoretical and Experimental Investigation

    KAUST Repository

    Ziani, Ahmed

    2017-04-10

    Converting photon energy into chemical energy using inorganic materials requires the successful capture of photons, exciton dissociation, and the charge carrier diffusion. This study reports a thorough analysis of the optoelectronic properties of visible-light-responsive SrTaON perovskites to quantify their absorption coefficient and the generated charge carriers\\' effective masses, dielectric constants, and electronic structures. The measurements on such intrinsic properties were attempted using both epitaxial and polycrystalline SrTaON films deposited by radiofrequency magnetron sputtering under N reactive plasma. Density functional theory calculations using the HSE06 functional provided reliable values of these optoelectronic properties. Such quantities obtained by both measurements and calculations gave excellent correspondence and provide possible variations that account for the small discrepancies observed. One of the significant factors determining the optical properties was found to be the anion ordering in the perovskite structure imposed by the cations. As a result, the different anion ordering has a noticeable influence on the optical properties and high sensitivity of the hole effective mass. Determination of relative band positions with respect to the water redox properties was also attempted by Mott-Schottky analysis. All these results offer the opportunity to understand why SrTaON possesses intrinsically all the ingredients needed for an efficient water splitting device.

  1. Photophysical Properties of SrTaO2N Thin Films and Influence of Anion Ordering: A Joint Theoretical and Experimental Investigation

    KAUST Repository

    Ziani, Ahmed; Le Paven, Claire; Le Gendre, Laurent; Marlec, Florent; Benzerga, Ratiba; Tessier, Franck; Cheviré , Franç ois; Hedhili, Mohamed N.; Garcia-Esparza, Angel T.; Melissen, Sigismund; Sautet, Philippe; Le Bahers, Tangui; Takanabe, Kazuhiro

    2017-01-01

    Converting photon energy into chemical energy using inorganic materials requires the successful capture of photons, exciton dissociation, and the charge carrier diffusion. This study reports a thorough analysis of the optoelectronic properties of visible-light-responsive SrTaON perovskites to quantify their absorption coefficient and the generated charge carriers' effective masses, dielectric constants, and electronic structures. The measurements on such intrinsic properties were attempted using both epitaxial and polycrystalline SrTaON films deposited by radiofrequency magnetron sputtering under N reactive plasma. Density functional theory calculations using the HSE06 functional provided reliable values of these optoelectronic properties. Such quantities obtained by both measurements and calculations gave excellent correspondence and provide possible variations that account for the small discrepancies observed. One of the significant factors determining the optical properties was found to be the anion ordering in the perovskite structure imposed by the cations. As a result, the different anion ordering has a noticeable influence on the optical properties and high sensitivity of the hole effective mass. Determination of relative band positions with respect to the water redox properties was also attempted by Mott-Schottky analysis. All these results offer the opportunity to understand why SrTaON possesses intrinsically all the ingredients needed for an efficient water splitting device.

  2. The effect of cation:anion ratio in solution on the mechanism of barite growth at constant supersaturation: Role of the desolvation process on the growth kinetics

    Science.gov (United States)

    Kowacz, M.; Putnis, C. V.; Putnis, A.

    2007-11-01

    The mechanism of barite growth has been investigated in a fluid cell of an Atomic Force Microscope by passing solutions of constant supersaturation ( Ω) but variable ion activity ratio ( r=a/a) over a barite substrate.The observed dependence of step-spreading velocity on solution stoichiometry can be explained by considering non-equivalent attachment frequency factors for the cation and anion. We show that the potential for two-dimensional nucleation changes under a constant thermodynamic driving force due to the kinetics of barium integration into the surface, and that the growth mode changes from preexisting step advancement to island spreading as the cation/anion activity ratio increases. Scanning electron microscopy studies of crystals grown in bulk solutions support our findings that matching the ion ratio in the fluid to that of the crystal lattice does not result in maximum growth and nucleation rates. Significantly more rapid rates correspond to solution stoichiometries where [Ba 2+] is in excess with respect to [ SO42-]. Experiments performed in dilute aqueous solutions of methanol show that even 0.02 molar fraction of organic cosolvent in the growth solution significantly accelerates step growth velocity and nucleation rates (while keeping Ω the same as in the reference solution in water). Our observations suggest that the effect of methanol on barite growth results first of all from reduction of the barrier that prevents the Ba 2+ from reaching the surface and corroborate the hypothesis that desolvation of the cation and of the surface is the rate limiting kinetic process for two-dimensional nucleation and for crystal growth.

  3. Changes in plasma osmolality and anion gap: potential predictors of ...

    African Journals Online (AJOL)

    Changes in plasma osmolality and anion gap: potential predictors of ... PROMOTING ACCESS TO AFRICAN RESEARCH ... Objective: To determine the relationship of mortality to plasma osmolality and anion gap inpatients on haemodialysis.

  4. Synthesis of Randomly Substituted Anionic Cyclodextrins in Ball Milling

    Directory of Open Access Journals (Sweden)

    László Jicsinszky

    2017-03-01

    Full Text Available A number of influencing factors mean that the random substitution of cyclodextrins (CD in solution is difficult to reproduce. Reaction assembly in mechanochemistry reduces the number of these factors. However, lack of water can improve the reaction outcomes by minimizing the reagent’s hydrolysis. High-energy ball milling is an efficient, green and simple method for one-step reactions and usually reduces degradation and byproduct formation. Anionic CD derivatives have successfully been synthesized in the solid state, using a planetary ball mill. Comparison with solution reactions, the solvent-free conditions strongly reduced the reagent hydrolysis and resulted in products of higher degree of substitution (DS with more homogeneous DS distribution. The synthesis of anionic CD derivatives can be effectively performed under mechanochemical activation without significant changes to the substitution pattern but the DS distributions were considerably different from the products of solution syntheses.

  5. Towards a molecular understanding of cellulose dissolution in ionic liquids: anion/cation effect, synergistic mechanism and physicochemical aspects.

    Science.gov (United States)

    Li, Yao; Wang, Jianji; Liu, Xiaomin; Zhang, Suojiang

    2018-05-07

    Cellulose is one of the most abundant bio-renewable materials on the earth and its conversion to biofuels provides an appealing way to satisfy the increasing global energy demand. However, before carrying out the process of enzymolysis to glucose or polysaccharides, cellulose needs to be pretreated to overcome its recalcitrance. In recent years, a variety of ionic liquids (ILs) have been found to be effective solvents for cellulose, providing a new, feasible pretreatment strategy. A lot of experimental and computational studies have been carried out to investigate the dissolution mechanism. However, many details are not fully understood, which highlights the necessity to overview the current knowledge of cellulose dissolution and identify the research trend in the future. This perspective summarizes the mechanistic studies and microscopic insights of cellulose dissolution in ILs. Recent investigations of the synergistic effect of cations/anions and the distinctive structural changes of cellulose microfibril in ILs are also reviewed. Besides, understanding the factors controlling the dissolution process, such as the structure of anions/cations, viscosity of ILs, pretreatment temperature, heating rate, etc. , has been discussed from a structural and physicochemical viewpoint. At the end, the existing problems are discussed and future prospects are given. We hope this article would be helpful for deeper understanding of the cellulose dissolution process in ILs and the rational design of more efficient and recyclable ILs.

  6. Diffusion, Ion Pairing and Aggregation in 1-Ethyl-3-Methylimidazolium-Based Ionic Liquids Studied by 1 H and 19 F PFG NMR: Effect of Temperature, Anion and Glucose Dissolution.

    Science.gov (United States)

    D'Agostino, Carmine; Mantle, Mick D; Mullan, Claire L; Hardacre, Christopher; Gladden, Lynn F

    2018-01-31

    In this work, using 1 H and 19 F PFG NMR, we probe the effect of temperature, ion size/type and glucose dissolution on the rate of transport in 1-ethyl-3-methylimidazolium ([EMIM] + )-based ionic liquids by measuring self-diffusion coefficients. Using such data, we are able to establish the degree of ion pairing and quantify the extent of ionic aggregation during diffusion. For the neat 1-ethyl-3-methylimidazolium acetate ([EMIM][OAc]) a strong degree of ion pairing is observed. The substitution of the [OAc] - anion with the bis{(trifluoromethyl)sulfonyl}imide ([TFSI] - ) anion reduces the pairing between the ions, which is attributed to a lower electric charge density on the [TFSI] - anion, hence a weaker electric interaction with the [EMIM] + cation. The effect of glucose, important for applications of ionic liquids as extracting media, on the strongly paired [EMIM][OAc] sample was also investigated and it is observed that the carbohydrate decreases the degree of ion pairing, which is attributed to the ability of glucose to disrupt inter-ionic interactions by forming hydrogen bonding, particularly with the [OAc] - anion. Calculations of aggregation number from diffusion data show that the [OAc] - anion diffuses as a part of larger aggregates compared to the [EMIM] + cation. The results and analysis presented here show the usefulness of PFG NMR in studies of ionic liquids, giving new insights into ion pairing and aggregation and the factors affecting these parameters. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Schlenk Techniques for Anionic Polymerization

    KAUST Repository

    Ratkanthwar, Kedar; Zhao, Junpeng; Zhang, Hefeng; Hadjichristidis, Nikolaos; Mays, Jimmy

    2015-01-01

    Anionic polymerization-high vacuum techniques (HVTs) are doubtlessly the most prominent and reliable experimental tools to prepare polymer samples with well-defined and, in many cases, complex macromolecular architectures. Due to the high demands

  8. Revisiting imidazolium based ionic liquids: Effect of the conformation bias of the [NTf2] anion studied by molecular dynamics simulations

    Science.gov (United States)

    Neumann, Jan; Golub, Benjamin; Odebrecht, Lisa-Marie; Ludwig, Ralf; Paschek, Dietmar

    2018-05-01

    We study ionic liquids composed of 1-alkyl-3-methylimidazolium cations and bis(trifluoromethyl-sulfonyl)imide anions ([CnMIm][NTf2]) with varying chain-length n = 2, 4, 6, 8 by using molecular dynamics simulations. We show that a reparametrization of the dihedral potentials as well as charges of the [NTf2] anion leads to an improvement of the force field model introduced by Köddermann, Paschek, and Ludwig [ChemPhysChem 8, 2464 (2007)] (KPL-force field). A crucial advantage of the new parameter set is that the minimum energy conformations of the anion (trans and gauche), as deduced from ab initio calculations and Raman experiments, are now both well represented by our model. In addition, the results for [CnMIm][NTf2] show that this modification leads to an even better agreement between experiment and molecular dynamics simulation as demonstrated for densities, diffusion coefficients, vaporization enthalpies, reorientational correlation times, and viscosities. Even though we focused on a better representation of the anion conformation, also the alkyl chain-length dependence of the cation behaves closer to the experiment. We strongly encourage to use the new NGOLP (Neumann, Golub, Odebrecht, Ludwig, Paschek) force field for the [NTf2] anion instead of the earlier KPL parameter set for computer simulations aiming to describe the thermodynamics, dynamics, and also structure of imidazolium-based ionic liquids.

  9. Presolvated Electron Reactions with Methyl Acetoacetate: Electron Localization, Proton-Deuteron Exchange, and H-Atom Abstraction

    Directory of Open Access Journals (Sweden)

    Alex Petrovici

    2014-09-01

    Full Text Available Radiation-produced electrons initiate various reaction processes that are important to radiation damage to biomolecules. In this work, the site of attachment of the prehydrated electrons with methyl acetoacetate (MAA, CH3-CO-CH2-COOCH3 at 77 K and subsequent reactions of the anion radical (CH3-CO•−-CH2-COOCH3 in the 77 to ca. 170 K temperature range have been investigated in homogeneous H2O and D2O aqueous glasses by electron spin resonance (ESR spectroscopy. At 77 K, the prehydrated electron attaches to MAA forming the anion radical in which the electron is delocalized over the two carbonyl groups. This species readily protonates to produce the protonated electron adduct radical CH3-C(•OH-CH2-COOCH3. The ESR spectrum of CH3-C(•OH-CH2-COOCH3 in H2O shows line components due to proton hyperfine couplings of the methyl and methylene groups. Whereas, the ESR spectrum of CH3-C(•OH-CH2-COOCH3 in D2O glass shows only the line components due to proton hyperfine couplings of CH3 group. This is expected since the methylene protons in MAA are readily exchangeable in D2O. On stepwise annealing to higher temperatures (ca. 150 to 170 K, CH3-C(•OH-CH2-COOCH3 undergoes bimolecular H-atom abstraction from MAA to form the more stable radical, CH3-CO-CH•-COOCH3. Theoretical calculations using density functional theory (DFT support the radical assignments.

  10. Presolvated electron reactions with methyl acetoacetate: electron localization, proton-deuteron exchange, and H-atom abstraction.

    Science.gov (United States)

    Petrovici, Alex; Adhikary, Amitava; Kumar, Anil; Sevilla, Michael D

    2014-09-01

    Radiation-produced electrons initiate various reaction processes that are important to radiation damage to biomolecules. In this work, the site of attachment of the prehydrated electrons with methyl acetoacetate (MAA, CH3-CO-CH2-COOCH3) at 77 K and subsequent reactions of the anion radical (CH3-CO•--CH2-COOCH3) in the 77 to ca. 170 K temperature range have been investigated in homogeneous H2O and D2O aqueous glasses by electron spin resonance (ESR) spectroscopy. At 77 K, the prehydrated electron attaches to MAA forming the anion radical in which the electron is delocalized over the two carbonyl groups. This species readily protonates to produce the protonated electron adduct radical CH3-C(•)OH-CH2-COOCH3. The ESR spectrum of CH3-C(•)OH-CH2-COOCH3 in H2O shows line components due to proton hyperfine couplings of the methyl and methylene groups. Whereas, the ESR spectrum of CH3-C(•)OH-CH2-COOCH3 in D2O glass shows only the line components due to proton hyperfine couplings of CH3 group. This is expected since the methylene protons in MAA are readily exchangeable in D2O. On stepwise annealing to higher temperatures (ca. 150 to 170 K), CH3-C(•)OH-CH2-COOCH3 undergoes bimolecular H-atom abstraction from MAA to form the more stable radical, CH3-CO-CH•-COOCH3. Theoretical calculations using density functional theory (DFT) support the radical assignments.

  11. Absorption spectrum of the firefly luciferin anion isolated in vacuo.

    Science.gov (United States)

    Støchkel, Kristian; Milne, Bruce F; Brøndsted Nielsen, Steen

    2011-03-24

    The excited-state physics of the firefly luciferin anion depends on its chemical environment, and it is therefore important to establish the intrinsic behavior of the bare ion. Here we report electronic absorption spectra of the anion isolated in vacuo obtained at an electrostatic ion storage ring and an accelerator mass spectrometer where ionic dissociation is monitored on a long time scale (from 33 μs and up to 3 ms) and on a short time scale (0-3 μs), respectively. In the ring experiment the yield of all neutrals (mainly CO(2)) as a function of wavelength was measured whereas in the single pass experiment, the abundance of daughter ions formed after loss of CO(2) was recorded to provide action spectra. We find maxima at 535 and 265 nm, and that the band shape is largely determined by the sampling time interval, which is due to the kinetics of the dissociation process. Calculations at the TD-B3LYP/TZVPP++ level predict maximum absorption at 533 and 275 nm for the carboxylate isomer in excellent agreement with the experimental findings. The phenolate isomer lies higher in energy by 0.22 eV, and also its absorption maximum is calculated to be at 463 nm, which is far away from the experimental value. Our data serve to benchmark future theoretical models for bioluminescence from fireflies.

  12. Inhibition of filiform corrosion on organic-coated AA2024-T3 by smart-release cation and anion-exchange pigments

    International Nuclear Information System (INIS)

    Williams, G.; McMurray, H.N.

    2012-01-01

    Highlights: ► Filiform corrosion (FFC) inhibition by various smart-release pigments was evaluated by SKP. ► Rare earth cation-containing pigments were ineffective at halting FFC propagation. ► Metal oxo-anions and organic copper-specific agents were exchanged into hydrotalcite. ► Effective inhibition of FFC was demonstrated by anions which stopped copper re-plating. - Abstract: In-coating cation and anion exchange pigments are studied with respect to their ability to inhibit chloride-induced filiform corrosion (FFC) on organic-coated AA2024-T3 aluminium alloy substrates. In-situ scanning Kelvin probe potentiometry is used to quantify both underfilm potentials associated with populations of propagating corrosion filaments and the kinetics of coating disbondment. Smart-release bentonite pigments containing exchangeable cerium (III) and yttrium (III) cations are shown to be largely ineffective in reducing rates of FFC propagation. The reasons for this are discussed in terms of the chemistry of the electrolyte-filled corrosion filament head. In contrast, anion-exchange hydrotalcite (HT) based pigments are highly effective inhibitors of FFC. A comparison of the extent of FFC observed for various inorganic exchangeable anions is made with as-received HT comprising carbonate anions. Of the anions evaluated, exchangeable chromate unsurprisingly provides the highest FFC inhibition efficiency. It is also demonstrated that exchanging the native carbonate ions for certain organic species which act as complexing agents for copper ions, gives rise to an equivalent level of FFC inhibition. The implication of these findings with respect to the mechanism of FFC on copper containing aluminium alloys is considered.

  13. Gamma radiation effect on gas production in anion exchange resins

    Energy Technology Data Exchange (ETDEWEB)

    Traboulsi, A. [CEA Marcoule, DEN/DTCD/SPDE/LCFI, BP 17171, 30207 Bagnols-sur-Cèze Cedex (France); E.A. LISA – METICA, Aix Marseille Université, Pôle de l’Etoile, case 451, 13397 Marseille Cedex 20 (France); Labed, V., E-mail: veronique.labed@cea.fr [CEA Marcoule, DEN/DTCD/SPDE/LCFI, BP 17171, 30207 Bagnols-sur-Cèze Cedex (France); Dauvois, V. [CEA Saclay, DEN/DANS/DPC/SECR/LSRM, 91191 Gif sur Yvette Cedex (France); Dupuy, N.; Rebufa, C. [E.A. LISA – METICA, Aix Marseille Université, Pôle de l’Etoile, case 451, 13397 Marseille Cedex 20 (France)

    2013-10-01

    Radiation-induced decomposition of Amberlite IRA400 anion exchange resin in hydroxide form by gamma radiolysis has been studied at various doses in different atmospheres (anaerobic, anaerobic with liquid water, and aerobic). The effect of these parameters on the degradation of ion exchange resins is rarely investigated in the literature. We focused on the radiolysis gases produced by resin degradation. When the resin was irradiated under anaerobic conditions with liquid water, the liquid phase over the resin was also analyzed to identify any possible water-soluble products released by degradation of the resin. The main products released are trimethylamine (TMA), molecular hydrogen (H{sub 2g}) and carbon dioxide (CO{sub 2g}). TMA and H{sub 2g} are produced in all the irradiation atmospheres. However, TMA was in gaseous form under anaerobic and aerobic conditions and in aqueous form in presence of liquid water. In the latter conditions, TMA{sub aq} was associated with aqueous dimethylamine (DMA{sub aq}), monomethylamine (MMA{sub aq}) and ammonia (NH{sub 4}{sup +}{sub aq}). CO{sub 2g} is formed in the presence of oxygen due to oxidation of organic compounds present in the system, in particular the degradation products such as TMA{sub g}.

  14. A Simple Halide-to-Anion Exchange Method for Heteroaromatic Salts and Ionic Liquids

    Directory of Open Access Journals (Sweden)

    Neus Mesquida

    2012-04-01

    Full Text Available A broad and simple method permitted halide ions in quaternary heteroaromatic and ammonium salts to be exchanged for a variety of anions using an anion exchange resin (A− form in non-aqueous media. The anion loading of the AER (OH− form was examined using two different anion sources, acids or ammonium salts, and changing the polarity of the solvents. The AER (A− form method in organic solvents was then applied to several quaternary heteroaromatic salts and ILs, and the anion exchange proceeded in excellent to quantitative yields, concomitantly removing halide impurities. Relying on the hydrophobicity of the targeted ion pair for the counteranion swap, organic solvents with variable polarity were used, such as CH3OH, CH3CN and the dipolar nonhydroxylic solvent mixture CH3CN:CH2Cl2 (3:7 and the anion exchange was equally successful with both lipophilic cations and anions.

  15. Efficiency of producing anion and relative humidity of the indigenous woody plants in Jeju islands

    Science.gov (United States)

    Son, S.-G.; Kim, K.-J.; Kim, H.-J.; Kim, C.-M.; Byun, K.-O.

    2009-04-01

    This study is to evaluate the ability of interior plants to produce anion and relative humidity that can purify polluted indoor air. Four indigenous woody plants in Jeju islands such as Sarcandra glaber (Thunb.) Nakai, Illicium anisatum L, Cleyera japonica Thunb. and Ilex rotunda Thunb. were used. Sansevieria trifasciata cv. Laurentii was also used as a comparative plant. The amount of anion and increment of relative humidity produced by five species of indoor plants was assessed by anion measurement (ITC-201A)in a sealed acryl chamber (118Ã-118Ã-119.5cm). The highest amount of anion was 515 ea/cm3produced by I. rotunda. The amounts of anion were 293 ea/cm3, 273 ea/cm3, and 211 ea/cm3 in S. glaber, I. anisatum and C. japonica, respecively while it was 220 ea/cm3 in S. trifasciata. The increment of relative humidity was highest in I. anisatum as 27.4% while it was lowest in S. trifasciata as 14.0%. This result suggested that all four indigenous plants tested were more effective to purify the indoor polluted air than S. trifasciata. Key words: interior plant, S. glaber, I. anisatum, C. japonica, I. rotunda, indoor polluted air

  16. Sorption of Pu(IV) from nitric acid by bifunctional anion-exchange resins

    International Nuclear Information System (INIS)

    Bartsch, R.A.; Zhang, Z.Y.; Elshani, S.; Zhao, W.; Jarvinen, G.D.; Barr, M.E.; Marsh, S.F.; Chamberlin, R.M.

    1999-01-01

    Anion exchange is attractive for separating plutonium because the Pu(IV) nitrate complex is very strongly sorbed and few other metal ions form competing anionic nitrate complexes. The major disadvantage of this process has been the unusually slow rate at which the Pu(IV) nitrate complex is sorbed by the resin. The paper summarizes the concept of bifunctional anion-exchange resins, proposed mechanism for Pu(IV) sorption, synthesis of the alkylating agent, calculation of K d values from Pu(IV) sorption results, and conclusions from the study of Pu(IV) sorption from 7M nitric acid by macroporous anion-exchange resins including level of crosslinking, level of alkylation, length of spacer, and bifunctional vs. monofunctional anion-exchange resins

  17. Electrochemical corrosion of grinding media and effect of anions present in industrial waters; Corrosion electroquimica de medios de molienda y efecto de aniones presentes en aguas industriales

    Energy Technology Data Exchange (ETDEWEB)

    Magne, L.; Navarro, P.; Vargas, C.; Carrasco, S.

    2001-07-01

    The steel used in the minerals processing as grinding media (balls or bars), is an important input in terms of cost of the process. Considering the importance of the steel consumption in these processes, this work is guided to evaluate to laboratory scale the effect of the anions present in the industrial waters on the electrochemical corrosion of grinding media. Tests in electrochemical cell, were accomplished measuring potential and corrosion current to four electrodes that were manufactured using sufficiently pure sample of chalcopyrite, bornite, enargite and steel ball. The ions used in the tests were chlorides, sulfates, nitrates and carbonates in concentrations from 1 to 180 ppm in individual form or in mixtures, according to the levels measurement of these in industrial waters. (Author) 10 refs.

  18. Nanotubular halloysite clay as efficient water filtration system for cationic and anionic dyes removal

    OpenAIRE

    Conference, Nanostruc; Yafei Zhao, Elshad Abdullayev and Yuri Lvov

    2014-01-01

    Halloysite clay has chemical structure similar to kaolinite but it is rolled in tubes with diameter of 50 nm and length of ca. 1000 nm. Halloysite exhibits higher adsorption capacity for both cationic and anionic dyes because it has negative SiO2 outermost and positive Al2O3 inner lumen surface. An adsorption study using cationicRhodamine 6G and anionic Chrome azurol S has shown pproximately two times better dye removal for halloysite as compared to kaolin. Halloysite filters have been effect...

  19. Ab initio study of isomerism in molecular ions Li2AB+ with 10 valence electrons

    International Nuclear Information System (INIS)

    Charkin, O.P.; Mak-Ki, M.L.; Shlojer, P.R.

    1997-01-01

    Ab initio calculations of surfaces of Li 2 AB + molecular ion potential energy with biatomic anions AB - with 10 valence electrons have been made in the framework of approximations MP2/6-31G 1 /HF/6-31G*+ZPE(HF/6-31G*) and MP4SDTQ/631G*//MP2/6-31G*+ZPE(MP2/6-31G*). Influence of electron correlation on the accuracy of calculations of their structural and vibrational characteristics is studied. The following most favourable structures have been found: linear for Li 2 BO + , Li 2 CN + , and bent one for Li 2 BS + , with cations coordinated at different anion atoms; onium one for AlOLi 2 + , AlSLi 2 + , SiNLi 2 + and SiPLi 2 + with both cations at electronegative atom of anion

  20. Ultrathin nanofibrous films prepared from cadmium hydroxide nanostrands and anionic surfactants.

    Science.gov (United States)

    Peng, Xinsheng; Karan, Santanu; Ichinose, Izumi

    2009-08-04

    We developed a simple fabrication method of ultrathin nanofibrous films from the dispersion of cadmium hydroxide nanostrands and anionic surfactants. The nanostrands were prepared in a dilute aqueous solution of cadmium chloride by using 2-aminoethanol. They were highly positively charged and gave bundlelike fibers upon mixing an aqueous solution of anionic surfactant. The nanostrand/surfactant composite fibers were filtered on an inorganic membrane filter. The resultant nanofibrous film was very uniform in the area of a few centimeters square when the thickness was not less than 60 nm. The films obtained with sodium tetradecyl sulfate (STS) had a composition close to the electroneutral complex, [Cd37(OH)68(H2O)n] x 6(STS), as confirmed by energy dispersive X-ray analysis. They were water-repellent with a contact angle of 117 degrees, and the value slightly decreased with the alkyl chain length of anionic surfactants. Ultrathin nanofibrous films were stable enough to be used for ultrafiltration at pressure difference of 90 kPa. We could effectively separate Au nanoparticles of 40 nm at an extremely high filtration rate of 14000 L/(h m2 bar).

  1. Presolvated Electron Reaction with Methylacetoacetate: Electron Localization, Proton-Deuteron Exchange, and H-atom Abstraction

    Science.gov (United States)

    Petrovici, Alex; Adhikary, Amitava; Kumar, Anil; Sevilla, Michael D.

    2015-01-01

    Radiation-produced electrons initiate various reaction processes that are important to radiation damage to biomolecules. In this work, the site of attachment of the prehydrated electrons with methylacetoacetate (MAA, CH3-CO-CH2-CO-OCH3) at 77 K and subsequent reactions of the anion radical (CH3-CO•−-CH2-CO-OCH3) in the temperature range (77 to ca. 170 K) have been investigated in homogeneous H2O and D2O aqueous glasses by electron spin resonance (ESR) spectroscopy. At 77 K, the prehydrated electron attaches to MAA forming the anion radical in which the electron is delocalized over the two carbonyl groups. This species readily protonates to produce the protonated electron adduct radical CH3-C(•)OH-CH2-CO-OCH3. The ESR spectrum of CH3-C(•)OH-CH2-CO-OCH3 in H2O shows line components due to proton hyperfine couplings of the methyl and methylene groups. Whereas, the ESR spectrum of CH3-C(•)OH-CH2-CO-OCH3 in D2O glass shows only the line components due to proton hyperfine couplings of CH3 group. This is expected since the methylen protons in MAA are readily exchangeable in D2O. On stepwise annealing to higher temperatures (ca. 150 to 170 K), CH3-C(•)OH-CH2-CO-OCH3 undergoes bimolecular H-atom abstraction from MAA to form the more stable radical, CH3-CO-CH•-CO-OCH3. Theoretical calculations using density functional theory (DFT) support the radical assignments. PMID:25255751

  2. The role of the anionic and cationic pt sites in the adsorption site preference of water and ethanol on defected Pt4/Pt(111) substrates: A density functional theory investigation within the D3 van der waals corrections

    Science.gov (United States)

    Seminovski, Yohanna; Amaral, Rafael C.; Tereshchuk, Polina; Da Silva, Juarez L. F.

    2018-01-01

    Platinum (Pt) atoms in the bulk face-centered cubic structure have neutral charge because they are equivalent by symmetry, however, in clean Pt surfaces, the effective charge on Pt atoms can turn slightly negative (anionic) or positive (cationic) while increasing substantially in magnitude for defected (low-coordinated) Pt sites. The effective charge affect the adsorption properties of molecular species on Pt surfaces and it can compete in importance with the coupling of the substrate-molecule electronic states. Although several studies have been reported due to the importance of Pt for catalysis, our understanding of the role played by low-coordinated sites is still limited. Here, we employ density functional theory within the Perdew-Burke-Ernzerhof exchange-correlation functional and the D3 van der Waals (vdW) correction to investigate the role of the cationic and anionic Pt sites on the adsorption properties of ethanol and water on defected Pt4/Pt(111) substrates. Four substrates were carefully selected, namely, two two-dimensional (2D) Pt4 configurations (2D-strand and 2D-island) and two tri-dimensional (3D) Pt4 (3D-fcc and 3D-hcp), to understand the role of coordination, effective charge, and coupling of the electronic states in the adsorption properties. From the Bader charge analysis, we identified the cationic and anionic sites among the Pt atoms exposed to the vacuum region in the Pt4/Pt(111) substrates. We found that ethanol and water bind via the anionic O atoms to the low-coordinated defected Pt sites of the substrates, where the angle PtOH is nearly 100° for most configurations. In the 3D-fcc or 3D-hcp defected configurations, the lowest-coordinated Pt atoms are anionic, hence, those Pt sites are not preferable for the adsorption of O atoms. The charge transfer from water and ethanol to the Pt substrates has similar magnitude for all cases, which implies similar Coulomb contribution to the adsorption energy. Moreover, we found a correlation of the

  3. Synthesis and characterization of cobalt ferrocyanides loaded on organic anion exchanger

    Energy Technology Data Exchange (ETDEWEB)

    Valsala, T.P. [Waste Management Division, Bhabha Atomic Research Centre, Trombay 400 085 (India)], E-mail: tpvalsala@yahoo.co.in; Joseph, Annie [Waste Management Division, Bhabha Atomic Research Centre, Trombay 400 085 (India); Shah, J.G. [Back End Technology Division, Bhabha Atomic Research Centre, Trombay 400 085 (India); Raj, Kanwar [Waste Management Division, Bhabha Atomic Research Centre, Trombay 400 085 (India); Venugopal, V. [Radiochemistry and Isotope Group, Bhabha Atomic Research Centre, Trombay 400 085 (India)

    2009-02-15

    Transition metal ferrocyanides have important applications in the selective removal of radioactive caesium from low level and intermediate level radioactive liquid waste streams. The microcrystalline nature of these materials renders them useless for application in column mode operations. Special preparation procedures have been developed to prepare granular solids by in situ precipitation of metal ferrocyanides on organic anion exchangers, which is suitable for column mode operations. The elemental compositions of the metal ferrocyanides precipitated inside the pores of anion exchanger were determined by analysing the dissolved samples using ICP-AES system and flame photometer. From the XRD and EDX analyses and the elemental composition of the synthesized materials, the nature of the compound formed inside the anion exchanger was found to be cobalt ferrocyanide. From SEM analysis of the samples, the particle size of the cobalt ferrocyanide precipitated inside the anion exchanger was found to be much less than that of cobalt ferrocyanide precipitated outside. The efficiency of these materials for removal of Cs was evaluated by measuring the distribution coefficient (Kd), ion exchange capacity and kinetics of Cs uptake. The Kd of the materials loaded on anion exchanger was found to be of the order of 10{sup 5} ml/g. The Cs uptake kinetics of the materials loaded on anion exchanger was slower than that of precipitated materials. The ion exchange capacity of the cobalt ferrocyanide loaded on anion exchanger was found to be much higher than that of the precipitated cobalt ferrocyanide.

  4. Reactions of substituted benzene anions with N and O atoms: Chemistry in Titan’s upper atmosphere and the interstellar medium

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Zhe-Chen; Bierbaum, Veronica M. [Department of Chemistry and Biochemistry, University of Colorado, Boulder, Colorado 80309 (United States)

    2016-06-07

    The likely existence of aromatic anions in many important extraterrestrial environments, from the atmosphere of Titan to the interstellar medium (ISM), is attracting increasing attention. Nitrogen and oxygen atoms are also widely observed in the ISM and in the ionospheres of planets and moons. In the current work, we extend previous studies to explore the reactivity of prototypical aromatic anions (deprotonated toluene, aniline, and phenol) with N and O atoms both experimentally and computationally. The benzyl and anilinide anions both exhibit slow associative electron detachment (AED) processes with N atom, and moderate reactivity with O atom in which AED dominates but ionic products are also formed. The reactivity of phenoxide is dramatically different; there is no measurable reaction with N atom, and the moderate reactivity with O atom produces almost exclusively ionic products. The reaction mechanisms are studied theoretically by employing density functional theory calculations, and spin conversion is found to be critical for understanding some product distributions. This work provides insight into the rich gas-phase chemistry of aromatic ion-atom reactions and their relevance to ionospheric and interstellar chemistry.

  5. Dibromine radical anion reactions with heme enzymes

    International Nuclear Information System (INIS)

    Gebicka, L.; Gebicki, J.L.

    1996-01-01

    Reactions of Br 2 radical anion with heme enzymes, catalase horseradish peroxidase, have been studied by pulse radiolysis. It has been found that Br 2 - does not react with the heme centre of investigated enzymes. Dibromine radical anion reacts with tryptophan residues of catalase without any influence on the activity of catalase. It is suggested that in pulse radiolysis studies, where horseradish peroxidase is at about tenfold excess toward Br 2 - , the enzyme is modified rather by Br 2 , than by Br 2 - . (author). 26 refs., 3 figs